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1523

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Chemistry of Soil Minerals. Part V11.l Synthesis, Properties, and Crystal Structures of Salt-filled Cancrinites
By R. M. Barrer," J. F. Cole, and H. Villiger, Physical Chemistry Laboratory, Imperial College of Science and
Technology, London S.W.7 Cancrinite has been synthesized in the sodalite crystallization field a t 80" by addition of sodium nitrate, chromate, or molybdate. The crystals then contain these salts as guest species in place of the carbonate often found in natural cancrinites. This promotion of the formation of cancrinite was ascribed to association of anions with certain aluminosilicate species in solution, which then yielded cancrinite nuclei. As these grow into crystallites by addition of further anion-aluminosilicate complexes, the salt i s incorporated into the 11-hedral cancrinite cages and into the wide channels enclosed by these. This behaviour was studied by investigations of conditions of synthesis and by chemical and thermal analyses, i.r. measurements, X-ray powder photography, and crystal-structure determinations based on powder data. The structure determinations were made for cancrinite nitrate ( R = 0-12) and for a basic cancrinite containing some intercalated silicate ( R = 0.07). The structures were compared with one recently determined for a natural cancrinite. In addition, partial refinement of two other cancrinites rich in sodium chromate and sodium molybdate served to locate these anions.

CANCRINITE a natural aluminosilicate having a rigid cancrinite to see how far such entrainment could be is three-dimensional framework of (Si,A1)0, tetrahedra. understood and controlled. (iii) X-Ray structural Its structure was determined by Jarchow2 and has investigations of zeolites by use of powder data can give small ll-hedral cages which are linked as in Figure 1 (a) t o give a wide channel system [Figure l(b)]. Six cations per unit cell are in this channel in front of the distorted six-ring windows opening into the cages. In natural and synthetic specimens the channel always contains salt such as sodium or calcium carbonate, and the remaining cations are in the cages, on three-fold axes near the six-rings perpendicular to the c-axis. Each cage also holds one water molecule. The structure is further described later. This work had three principal objectives: (i) It was reported that cancrinites were readily formed at 80" by hydrothermal reactions of kaolinite with aqueous sodium hydroxide plus certain sodium salts.3 Nitrate, chromate, and molybdate strongly promoted the reaction and were entrained by the crystals; in the absence of these anions, basic (or hydroxy) sodalite was formed. A template effect was suspected, which it was hoped to study in more detail. (ii) If cancrinite could be made at temperatures below 100" without inter- FIGURE Aluminosilicate framework structure of cancrinite ; 1 calated salt or stacking faults, it should be an efficient (a) ll-hedral cancrinite cages, showing method of linkage; (b) schematic view down the g3 axis showing the main channel molecular sieve sorbent of a potentially useful kind. bounded by puckered twelve-membered rings It was thus of interest to study salt entrainment by
Part VI, R. M. Barrer and J. F. Cole, preceding paper. 0. Jarchow, 2. Krist., 1965, 122, 407.
3 R. M. Barrer, J. F. Cole, and H. Sticher, J . Chem. SOC. A ) , ( 1968, 2475.

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1524
TABLE1 Characteristics of synthetic cancrinites used in this work

J. Chem. SOC. (A), 1970

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Hexagonal cell Method of synthesis Chemical analysis parameters (A) b Other characteristics a From a gel of composition c 1~19Na2O,A1,0,,2~36SiO,,-= 12.72 & 0.02 Cell volume: 728 f 3 A3 Na,O, A1,0,, 2SiO,,xH,O, 1*35H,O c = 5.19 & 0.01 Density: 2.32 f 0.02 g. 200-300% molar excess ~ m . - ~ aqueous NaOH at 390" (11) NaN0,-cancrinite From raw kaolinite and 100% Na,O,A1,O3,2.02Si0,,a = 12.67 i 0-02 Cell volume: 722 & 3 A 3 : molar excess of aqueous 0.48H,0,0.62NaN03 c = 5.19 -= 0.01 Density: 2.38 f 0.02 g. J crn.-, NaOH, plus NaNO, (7 mole kg.-l of H,O) at 190" d (111) NaN0,-cancrinite As above Na,O,Al,O,, 1.95siO2,B.E.T. surface area: 19.1 0~81H,0,0~61NaN03 m.2g.-1 Pore volume : 0.10 ml. g.-l (IV) NaN0,-cancrinite As above, except at 100"f Na,O,Al,O,, 1*96SiO,,B.E.T. surface area: 18.9 0.60H20,0.65NaNO, m.2 g.-le Pore volume: 0.13 ml. g.-l (V) Na,CrO,-cancrinite From raw kaolinite and a large Qualitative analysis for a = 12.72 & 0.02 Cell volume: 728 & 3 A3 excess of aqueous ~ M - N ~ O H Cr0,2- only; 7.5% w/w c = 5.19 4 0.01 . saturated with Na,CrO, at 80 H,O (VI) Na,MoO,-cancrinite As above, except using Na,MoO, Qualitative analysis for a = 12.75 & 0.02 Cell volume: 731 & 3 Hi3 Mo0,Z-only; 6.8% w/w c = 5-19 & 0.01 H2O a The Roman numerals are used in the text to refer to the compounds of this Table. b From Guinier photographs by leastsquares correction of observations against a lead nitrate internal standard, followed by least-squares refinement. C Specimen of In Barrer and White.ll The excess refers to NaOH added above the theoretical amount needed for the cancrinite composition. a platinum-lined stainless steel autoclave without agitation. a By N, sorption at liquid N, temperature after outgassing at 350". f I n a stirred glass reactor under N,. Q As described b y Barrer et aL3
5

Name of cancrinite and reference number (I) Basic cancrinite

valuable information, despite certain limitations.* As part of a study of the usefulness of these methods, it was hoped to apply them to cancrinite inclusion complexes. In these framework structures, problems of large water clusters and of variable locations of included molecules characteristic of very porous crystals might be reduced.
EXPERIMENTAL AND RESULTS

Synthesis of Cancrinite.-Cancrinites were made with imbibed silicate, NaNO,, Na,CrO,, and Na,MoO,. The
TABLE2 Inclusion compositions of some NaN0,-rich cancrinites
Inclusion composition * H,O NaNO, (% wlw) ( Y o w/w) Synthesis conditions 3-02 14.02 0.1-7-0 mole kg.-l NaNO, in H,O, 100% 2-75 14.60 excess of aqueous NaOH a t SOo, in 4 08 13 05 plastic bottles, agitated 4.03 14.23 2.34 14-30 3.98 13-42 2.0-14-0 moles kg.-1 NaNO, in H,O, 3.53 13-90 100% excess of aqueous NaOH at 190", 3.48 15-53 in Pt-lined autoclaves, static, under 4.42 13-34 autogenous pressure 3.99 14-04 3-98 13-92 2-38 14-52 0.40 15.55 Excess of solid NaNO,, O-lOO% excess 0.60 14.97 of aqueous NaOH a t 420, in Pt-lined 0.20 14-33 autoclaves, static, under autogenous Not 15-79 pressure detected * Wet basis, samples equilibrated over saturated aq. Ca(NO,), (56% R.H. at 20"). t Untreated kaolinite feedstock in all cases ; see Table 1. $ Thermogravimetric analyses : see p. 1525. 9 These extreme conditions gave sodalites instead of cancrinites.

methods of synthesis and the characteristics of the samples are in Table 1. Roman numerals in Table 1 will be used in the text for reference. Barrer and Cole measured salt inclusion isotherms in sodalite and found that these had the form of Langmuir's isotherm equation. Attempts were made in the present work to obtain similar isotherms for NaNO, in cancrinite, and to see whether the nitrate contents of samples (11),(111), and (IV) could be increased. Representative results are in Table 2, which shows that no significant increase in nitrate content is possible. Under the conditions stated, the nitrate content approached a limit which was scarcely affected by temperature, pressure, or the concentration of NaNO, in the aqueous phase. If the amount of NaNO, was decreased in the hope of obtaining an inclusion isotherm, mixtures of cancrinite with sodalite appeared. Further decreases led, at the limit, to formation of basic sodalite (cf. ref. 3). TABLE 3 Effect of additions of sodium chromate on reaction product from 2 g. of kaolinite in 200 ml. of NaOH (4 moles bg.-l in H,O) a t 80" in plastic bottles with agitation
Amount of Na,CrO, added Crystalline product according (moles per kg. H,O) t o X-ray powder analysis 0.0308 Sodalite Mixtures of sodalite with 0.061 7 cancrinite * 0.1543 0.309 Cancrinite 0.617 1.235 * Cancrinite becoming dominant as the amount of Na,CrO, increases.

The effect of sodium chromate on the reactions was next studied and it was found (Table 3) that this salt behaved like nitrate but was a less active promoter of cancrinite
H. Villiger, Ph.D. Thesis, University of London, 1969.

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crystallization, more chromate than nitrate being required to produce cancrinite without sodalite under similar conditions (cf. ref. 3). Attempts to Crystallize Cancrinite-Sodalite Intergr0wths.In the earlier experiments cited above, salts such as NaClO, and NaBr were shown to be strong promoters of sodalite crystallization. It was therefore of interest to examine crystallizations in the presence of two salts, one a strong promoter of sodalite, and the other, of cancrinite. It is possible in principle to obtain ordered and disordered intergrowths of these two minerals, since cancrinite can be represented as an AB sequence of aluminosilicate layers and sodalite as an ABC sequence of the same layers. Table 4 gives the results for a number of crystallizations in presence of salt mixtures. Always, however, sodalite and cancrinite appeared in admixture and examination of Guinier powder photographs did not give any evidence for the existence of intergrowths. Table 4 also gives an indication of the 800" is significantly different for samples (111) and (IV) (prepared a t 190' and 100' respectively) despite the fact that they have nearly the same nitrate content (Table 1). Part of the thermogravimetric trace for sample (111)(Figure 2) is included for comparison. The heat effects between 7 0 and 900' are obviously connected with the degradation 0' of NaNO, to Na,O, but the differences between samples (111)and (IV) are not yet clear.

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c
1'

TABLE 4
Crystallizations in the presence of equimolar salt mixtures. Salt mixture as indicated, 0 . 1 ~ each component; of 2 g. of kaolinite; 200 ml. of NaOH (4 moles kg.-l in H,O) ; 80" in plastic bottles, agitated
Anions present
(Na+ was cation)

Cl-/Cr042Cl-/NO,ct-ts: C1-/Mo042 st + c : Br-/Cr0,2S+C$ Br-/NO,st+c: Br As above C104-/Cr0,2S C104-/N0,st+c: As above C~O,-/RIOO,~WO42-/Cr0,2C W042-/N0,As above W0,2-/Mo042S -4s above C0,2-/Cr0,2C032-/N0,As above y+c: C0,2-/Mo0,2C10,-/Cr0,2C103-/NO,st+c C1O3-/Mo0,2S N0,-/Cr0,2C XO,-/MOO,~As above * S = Sodalite, C = cancrinite; major phase marked minor (trace) phase marked $.

Crystalline product according to X-ray powder analysis * St3.C::

800 LOO Tempera!ure C"c1

FIGURE Thermogravimetric analysis of nitrate cancrinite 2 sample (111) conditions : heating rate 4" mim-1 in air; 627.5 ; mg. sample in platinum microcrucible; Stanton TR/1 instrument

'3%
Y

-s
0

t,
0
LOO Temperature ('c)

800

relative efficiencies of structural promotion by particular FIGURE Differential thermal analyses of nitrate cancrinites : 3 anions. (A) 2.95 mg. of sample ( 1 ) (B) 2.92 mg. of sample (IV) ; con1 1; Thermogravimetric Study of Nitrate Cancrinite Sam$le (111). ditions heating rate loo rnin.-' in air flow of 1 1. h.-1; reference -Figure 2 shows a thermogravimetric trace for this comwas 3.05 mg. cr-Al,O,. Platinum thimbles, Bureau de Liaisons instrument; inset is part of Figure 2 pound which is representative of traces for all the nitrate cancrinites examined. Decomposition of nitrate was assumed to follow equation (1) and nitrate contents were D.t.a. traces for samples (V) and (VI) are shown in Figure 4. These indicate that some thermal rearrangement T > 780' of chromate and molybdate ions takes place during removal 2NaN0, Na,O NO NO, 0, (1) of zeolitic water. Only about 50% of the latter could be calculated from the thermogravimetric traces in the region replaced by storing the dehydrated specimens over saturated above ca. 450". Wet chemical determinations of NO," aqueous Ca(NO,), for 14 days. with nitron reagent confirmed that the thermoanalytical Infrared S#ectroscopy of Nitrate Ions in Cancrinite method was quite accurate, and it was frequently used Samples (111) and (IV).-Measurements are recorded in for checking nitrate uptake (Table 2). Zeolitic water was Table 5, together with the data for crystalline NaNO,. It determined simultaneously. appears from the frequencies that there are two main Differential Thermal A na1yses.-The decomposition of locations for NO3- in cancrinite, both of which are occupied imbibed nitrate was studied by differential thermal analysis in both samples. One location (v = ca. 1420 cm.-l) is (d.t.a.). Results in Figure 3 show that the behaviour near more restricted than the other (v = ca. 1380 cm.-l) and is

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1526
evidently more highly occupied in samples synthesized a t 80-100". The reverse is true for samples synthesized at 160--190. Thus, while the overall nitrate content does not change much with synthesis conditions, the distribution

J. Chem. SOC. (A), 1970

of the observations (ii) and (iv) above. Point R is in the range (v). Crystal Structure Analyses.-Four synthetic cancrinites were selected from Table 1 for structure determinations, namely samples (I), (11), (V), and (VI). The X-ray powder 1 lines of the above four materials showed marked differences in relative intensities, and i t was decided that structural investigations could be successful. Also, the nitrate ion seemed to be particularly suitable because of its high point symmetry and the fact that oxygen is a stronger scatterer than nitrogen, which could help in determination of the nitrate orientation. It was also hoped that the heavy chromate and molybdate atoms would appear clearly in Fourier syntheses. Compositions, unit cells, and space-group. The unit cells for all samples and the chemical analyses and densities Temperature ("c) FIGURE4 Differential thermal analyses of molybdate and for samples (I)and (11)are in Table 1. Particular attention chromate cancrinites: (A) 2.88 mg. sample (VI); (B) 2.75 mg. was paid to the latter samples. The unit cell contents for 1.O8SiO2,samples (I) and (11)are accordingly 6(NaA1Si04), sample (V) ; conditions as for Figure 3 0.57Na20,4.05H20 [basic cancrinite, sample (I)] with a TABLE5 calculated density of 2.34 g. ~ m . - and 6(NaA1Si04),1.86~, NaNO,, 1.44H20 [nitrate cancrinite, sample (11) with a J 1.r. analysis of NO3- in cancrinite measured in air a t calculated density of 2.38 g. crn.-,. It was not possible to 20" between K I plates establish in what form the excess of silica was present in Specimen v2 (cm.-l) v3 (cm.-l) basic cancrinite. Clearly, i t cannot be part of the frameNaNO,, pure AnalaR salt 837 1387 822 1387m; 1427s; NO3--cancrinite, prepared a t 80work since in such a case the unit-cell content ought to be 100" * 1438v.w written as (12 tetrahedra per unit cell) 5.5(NaA1O2,l.18NO3--cancrinite prepared a t 160838 1382s; 1420m; SO,) ,0.52Na20,3.72H20 with a calculated density of 2.15 190" $ 1436w g. ~ m . - ~On grounds of the composition the excess of * D.t.a. trace B of Figure 3, sample (IV). t D.t.a. trace A silica might. have been present as NaH,SiO, since any of Figure 3, sample (111). condensed species such as an (Si30J6- ring would be too of NO3- ions between the two sites does. The vibrations large to fit in the channel of cancrinite. It is interesting to arrived a t a similar conclusion which was note that Guth v1 and v2 refer to the modes (A) and (B) respectively. based on density and comparison of unit cells of various salt-filled cancrinites. +O On the basis of spatial considerations alone, one would O+ expect four nitrates per unit cell, two in the channel and two +O (A1 in the cancrinite cages. However attempts to increase the amount above the composition already given did not X-Ray Powder Study of Nitrate Cancrinite Sample (111) succeed. For the four cancrinites, the intensities of about in a Guinier-Lenne Camera.-Continuous recording of the 66 powder lines were collected below the angle 28 = 80". X-ray powder diffractions during heating gave interesting The instrument was a General Electric XRD6 diffractoinformation regarding changes in nitrate cancrinite. The meter using Cu-K, radiation, with a proportional counter sample temperature was monitored on a chart recorder and and chart recording. No systematic absences were detected tests on the a+@ quartz transition showed that the and the 001 line in particular was clearly observable, which temperature-indicating spots on the film were accurate to indicated that the 2,-screw axis had been destroyed. The &3O. The specimen was X-rayed in air a t a film velocity true space-group is possibly P3, which gives 35 positional of 1.5 mm./hr. The temperature range studied was 20framework variables. Because of the limited data, it was 770" which was equivalent to 73 mm. of exposed film. decided t o assume the pseudo-space-group P63, with 17 The observations may be summarized as follows: (i) range positional framework variables. Jarchow refined the 20-530": a slow continuous increase occurred in the a structure of a natural cancrinite assuming this space group. and G axes, which accelerated above 350"; (ii) 530" f 10": Even the determination of the structure based on this a sudden discontinuity in spacings was seen; (iii) range space-group seemed to be a difficult undertaking, owing 530-694": the cancrinite pattern had been replaced by to the exact overlapping of hkl and khl lines, in addition another pattern whichappeared to be a highly expanded. to the absence of centrosymmetry. The co-ordinates of nepheline; (iv) 594" f 10': contraction of the nephline framework atoms for the idealised structure in P63 were phase began; (v) range 694-7'70": the pattern was still very close to the figures quoted for the refined structure. that of nepheline, but less expanded than previously It was therefore thought justifiable to hold the framework [GJ (iii)]. As the temperature increased to 770' a slow co-ordinates constant during the initial stages of the Fourier continuous contraction was noted. and least-squares refinement as a constraint, which could The residue was heated to 800", cooled t o Z O O , and shown help to achieve convergence. by its X-ray powder pattern to be normal (i.e., non-expanded) nepheline. No other unusual crystalline phases 5 J. L. Guth, Ph.D. Thesis, University of Strasbourg, 1964. were detected during the thermal study. In Figure 3, J. L. Guth. Rev. Chim. minerale, 1965, 2, 127. d.t.a. trace A, the points P and Q designate temperatures W. M. Meier and H. Villiger, 2.Krist., 1969, 124,411.
5y6

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>--

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Inorg. Phys. Theor.

ReJinement of basic and nitrate cancrinite [samples (I) and (II)]. Both structures were refined simultaneously,
starting with three-dimensional Fourier maps based on parameters of framework atoms as given by Jarchow.2 The scattering factors applied were those in the International Tables for X-ray Crystallography, 1952. Silicon, aluminium, and oxygen were assumed to be half-ionised. The cations inserted during the later stages of refinement were taken to be fully ionised whereas the water molecules were inserted with the same scattering power assumed for the framework oxygens. The residual R values quoted are defined as in equation (2), where the symbols have the

1527
atoms were held fixed a t their initial positions as long as possible. Attempts to refine these co-ordinates caused the framework oxygens to move and the interatomic distances a t this intermediate stage indicated a disordered distribution of silicon and aluminium tetrahedra. Final parameters are in Table 7 and selected interatomic distances in Table 8. TABLE7 Parameters of basic cancrinite (estimated standard deviations in parentheses)
Position Fracbased on tional x P63 occupancy 0.0765 1.000 6c (0.0048) 0.3285 1.000 6C (0.0051) 0.2070 6c 1.000 (0.0060) 0.1228 1.000 6c (0.0032) 0.0287 1.000 6c (0.0054) 0.3168 1.000 6c (0.0046) 0.49 0~000 2a (0.05) 0.44 0.1184 6c (0.0073) (0-03) 0.36 0.063 6c (0.03) (0.037) 0.91 2b 0.3333 (0.07) 0.1410 0.70 6c (0.02) (0-0050) 0.25 0.115 6c (0.02) (0.015) 2b 0.72 0-3333 (0.06)

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R(l) =

(cllobs

- Icalc[)/xIobs;
Iobs

R(F)

= (xIIFobs[

- ISFcalcll)/xFobs

(2)

following meanings :
= intensity; Icalc
i=l

= uncorrected observed relative

Mi.Lpi.(sFi)2; number of nonn=

equivalent reflections contributing to a powder line ; Mi = multiplicity factor for each reflection; Lpi = Lorentz polarization (Lp) correction factor for each reflection ; sFi = scaled structure factor; the scale factor is included here because of the requirements of the computer programmes available. The application of the Lp-correction to the calculated values (sFJz leads to an artificially high initial R ( I ) value. This procedure however makes it possible to treat reflection coincidences properly even if the observed ' powder line ' consists of a number of unresolved reflections. It also enables one to ascribe individual leastsquares (LS) weights inversely proportional to the standard deviations of the observed intensities without applying an artificial weighting scheme. The function minimized in the least squares refinement was (3) where CJ denotes the
(3)

Y 2 0.4147 0.750 (0.0028) 0.740 0.41 10 (0.0036) (0.018) 0.642 0.4009 (0.0027) (0.011) 0.5698 0.703 (0.0073) (0.016) 0.051 0.3638 (0.0048) (0-016) 0.034 0.3558 (0.0047) (0.012) o*oooo 0.426 (0.053) 0.452 0.1061 (0.0080) (0.028) 0.608 0.0809 (0.0088) (0.030) 0-176 0.6667 (0.026) 0.2930 0.259 (0*0024) (0.013) 0.1933 0.228 (0.0094) (0.052) 0.628 0.6667 (0.022)

standard deviation and the summation was made over all powder - lines. For purposes of Fourier synthesis, Fobs values were assigned proportional to the calculated structure amplitudes and the R(F)values were calculated accordingly.8 Table 6 shows the progress of refinement as TABLE6 Progress of structure analyses of basic and nitrate cancrinit es
Basic cancrinite Nitrate cancrinite

TABLE8 Interatomic distances of basic cancrinite (A) (estimated standard deviations in units of the last figure)
A1-0 ( 1) 1.85(10) A1-0 (2) 11) 1-77( A 1 0 (3) 1*69( 10) A1-0 (4) 1 77 (07) Mean 1.77 O(1)-0(4) O(2)-0(3) 0(2)-0 (4) 0(3)-0(4) Mean

~ ( ( : \ 2.98(07)~ \ l~
2*82(08) 2*91(07) 2.96(07) 2-80(09) 2-89

2-86(11)

W)
Initial co-ordinates After first Fourier cycle After second Fourier cycle Final parameters 0.83 0.66 0-41 0.07

R(F) 0.32 0.26 0.19 0.07

R(4 0.73
0.48

0-38 0.13

R(F) 0.31 0.24 0.17 0.12

1-57(09) Si-0 (1) Si-0(2) 1.63(11) Si-0 (3) 1*59(08) Si-0(4) 1* 66 ( 10) Mean 1-61

264(12) 2.57 (08) 2*69(07) o@j-o(sj 2.59(07j 0(2)-0 (4) 2.78 (09) 0(3)-0 (4) 2-62(10) Mean 2-63 Na (2)-0 (4) Na(2)-0 ( 5 ) Na (2)-0 ( 5 ) Na (2)-0 (7) Na(3)-O( 1) Na(3)-O(2) Na(3)-O(8) 2.57 (19) 2.38 (22) 2.66 (24) 2-1 (49) 5 2-94( 03) $-fold: 2.36(04) 3-fold 2-35(14) 1-fold

0(1)-0 (2) 0 (1)-0(3) O(1)-O(4)

indicated by the R-values. Evaluation of the third and fourth set of Fourier maps did not yield appreciably improved R-values and the LS-refinement was then commenced. A more detailed description of the subsequent course of the structure determination is given below. Basic cancrinite. The first Fourier map showed the positions Na(l), Na(3), and 0 ( 8 ) , and in the second one 0 ( 5 ) , 0 ( 6 ) , 0 ( 7 ) , and Na(2), the divided part of Na(l), were found. On the next two maps a few more peaks were encountered which, owing to their short distances from framework atoms, were removed during the subsequent LS-refinement. As mentioned earlier, the framework

Na(1)-O(1) Na( 1)-0(3) Na (1)-0(3) Na(1)-O(4) Na(1)-O(4) Na( 1)-0(6) Na(l)-0(7)

2.32(06) 2.31 (08) 3.02(08) 2.29(08) 2-85(08) 2.46(13) 2-71(45)

Nitrate cancrinite. Refinement of this structure was a more difficult and lengthy procedure than that of basic cancrinite. The first Fourier map showed Na(l), and Na(3), and on the second one all the remaining atoms in
8 L. Broussard and D. P. Shoemaker, J. Amer. Chem. SOC. 1960, 82, 1041.

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J. Chem. SOC. (A), 1970

Table 9 were found. I n addition, a peak appeared inside the small cavity of Figure l(a) and was thought to represent a nitrate oxygen. Its distance from the three-fold axis was 1.6 A, a value between 1.2 and 2.1 A, the N-0 and 0-0 very well refined. The distinction between Si and A1 was retained for purposes of comparison with basic cancrinite, although ordering of Si and A1 is not certain considering the serious variations in bond lengths. The observed and calculated powder line intensities are in Tables 11 and 12. In these Tables, the multiplicity factors and Lorentzpolarization corrections have been aplied to Icalc.
1

TABLE 9 Parameters of nitrate cancrinite (estimated standard deviations in parentheses)

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Position Fracbased on tional P6, occupancy x 6c 1.000 0.0733

(0.0050)

t
1

Y
0.4097 (0.0045) 0.4139 (0.0034) 0.4030 (0.0046) 0.5646 (0.0068) 0.3164 (0*0040) 0.3442 (0.0053) 0.031 (0.0 10) 0.6667

0.7500

6c

1.000 1.000 1.000

6c 6c 6c 6c 6c 2b 2b 6c 2a 2b

1.000
1.000 0.42 (0-04) 0.81 (0.17) 0-44 (0.15) 0.87 (0.03) 0.90 (0.09) 0.57 (0.07)

0.762 (0.017) 0.644 (0.015) 0.689 (0.0 15 ) 0.014 (0-018) 0.028 (0.017) 0.290 (0.033) 0.437 (0.030) 0-168 0.3333 0.6667 (0.079) 0.1231 0.2676 0-268 (0.0048) (0.0027) (0,013) 0~0000 0~0000 0.407 (0.023) 0-860 0-3333 0.6667 (0*026)

0.3332 (0.0052) 0.2 170 (0.0065) 0.1231 (0.0052) 0-0340 (0.0044 0.3279 (0.0059) 0.112 (0.009) 0,3333

(C)

(d)

FIGURE Schematic drawing of four likely highly-sym6 metric arrangements o a nitrate ion inside a cancrinite cage f

distances in sodium nitrate.B It was hoped that LSrefinement would shift this peak to a position compatible with a nitrate anion having its three-fold axis in common with that of the cavity. However, the presence of certain elements of symmetry does not necessarily mean that a guest molecule will conform to this symmetry. Apart from the most symmetric arrangement mentioned, three additional orientations are likely, all of them having a t least one atom on the three-fold axis. Any of these arrangements, depicted in Figure 5, should be detectable if each cavity were fully occupied by one nitrate anion. Half-occupancy was the most one could expect according to the chemical analysis and the fact that nitrate had already been observed in the large channel. Partial occupancy, and the presence of other included constituents such as water and cations, would inevitably obscure the Fourier map. The aforementioned peak moved to a position 1-75 away from the axis which would be arrangement c of Figure 5. However, owing to its z-co-ordinate of 0.35, the distance t o O(2) of the framework was too small (ca. 2 A) and it was thought that placing the inclusion atoms into positions corresponding to the enantiomorphic pair (i.e. , replacement of z-co-ordinates by Q - z ) could help t o overcome this difficulty. The replacement of these coordinates caused the subsequent refinement to diverge rapidly and it was therefore decided to disregard this peak since its electron density corresponded to less than 3e/A3. The refinement then proceeded reasonably well but the final Fourier maps still indicated this peak to be in exactly the same position as before. The resulting structural parameters are in Table 9, and the interatomic distances in Table 10 show that even the framework oxygens are not

TABLE 10 Interatomic distances of nitrate cancrinite (estimated standard deviations in units of the last figure)
A1-0 -41-0 A1-0 A1-0
( 1) 1-89( 11) (2) 1* 78(1 2) (3) 1 6 4 (12) 1-64(11) (4) Mean 1.71

:zI;[:

%84( 2.82(11) 2.68(11) %96(14) O(2)-0(4) 2*84(13) 0(3)-0 (4) 2.63 (08) Mean 2-80 O(1)-0(2) O(1)-0(3) O(1)-0(4) O(2)-0(3) 2*65(11) 2.45( 1I) 2.76(14) 2.91 (11) 2-65(12) 2.69(07) Mean 2-67 2.34(17) 3-fold 2.48(07) 3-fold 2.12(20) 1-fold

E [ ~ { z ~ [ ~ ~10)

Si-0 ( 1) 1-53( 10) Si-0 (2) 1.65( 10) Si-0 (3) 1.83(09) Si-0(4) 1.62(10) Mean 1.66

:rI:[:

Na(1)-O(1) Na( 1)-0(3) Na(1)-O(3) Na(1)-O(4) Na( 1)-0(4) Na(1)-O(5)

2.47(07) 2.26( 11) 2.83(10) 2-64(10) 2-72(11) 2.23(17)

Na(2)-O(5) Na(3)-O(2) Na(3)-O(7)

Description and Discussion of the Structures.-Framework. The aluminosilicate framework common to both structures is shown in Figure 1. The large channels parallel to the c-axis are circumscribed by puckered twelve-membered rings with free diameters of ca. 6.2 A. They are liable to be blocked by faulty stacking so that C-layers may sometimes intrude into the AB sequence of the layers of six-membered rings. The other openings are insignificant as diffusion paths, except for ion exchange a t high temperatures, since they are either too small (4-rings) or partly blocked by cations (6-rings). The co-ordinates of Si and
E. Sturm and W. Lodding, Acta Cryst. (A), 1968, 24, 650.

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Inorg. Phys. Theor.

TABLE 11 Observed and calculated powder line intensities for basic cancrinite
h k l

1529
1 (obs) I (calc)

I (obs) I (calc) 35.0

I (obs) I (calc)
382.0 407.2 38.9

I (obs) I (calc)

1 0 0 57.2 1 1 0 2210.0 2261.4 2 0 0 535.0 1 0 1 3970.0 3791.2 1 2 0 2 1 0 1208.0 1322.2 471.9

3 2 1 691.0 5 0 0 1 2 2 2 1 2
77.0
--r
I

la1

4 3 ; 1 0 s 1 6 0 6 1 0

1 7 2 5

7 1 5 2

0 0 2 2 971-0 996.2 275.5

k I 1 8 0 8 1 0 1 0 4
5

I (obs) I (caIc)

72.3 343.1 5 2 5 1 0 5 2 1 2 1 1 3

43.0

1 4 1 4 1 1 373-0 3 3 0 3 0 2 1163.0 1019.2 2 4 0 4 2 0

5.0

2 3 3 3 2 3 329.0 4 5 1 6 1 7 1 4 5 4 6 1 7 1 4 1 0 0 2 2 1 1 3 3 84.0 3 6 0 6 3 0 36.0 8 0 0

7 i-0

I 2 ; 1 2 1 1 4 213.0 4 6 0 6 4 0 2 0 4 15.0
G O 3

5.0

6.8

234.0

450.0 2 0 3 3 3 2 417.0 13-0 111.1 57.3 1 6 1 2 4 3 5 1 5

3

415.6 405.4 29.8

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1 1 1 83.0 2 0 1 194.0 3 0 0 3.538.0 3275.2 1 2 1 2 1 1 5465.0 5075.0 2 2 0

50.0

83.0 196.6

19.0 3.2

5 0 1 1064 2 2 2 58.0 2.6 150.7 153,4 1 5 ; a 5 1 3 1 0

0

2 4 2 4 2 2 39.0 6 1 2 1 4 5 3 6 1
0

5.0 96.9 43.1 78.2

7 0 7 3 0
3

1 3 0 3 1 0 125.0 3 0 1 111.0 4 0 0 2162.0 2107.5 2 2 1 49.0

1

2 2 110.0 118.4 25.1 12.8

58.0

1 : 3 3 0 l2X.0 1380.8 0 0 2 2 92.0

3

;;;
252.0 97.0 4 5 1 2 5 2 5 4 6 9 6 3 5 4 2 1 5 5 2 2 2 4 4 1 3 3 10.0 26.1 251.0 31.7

1 8 1 8 1 1

5 0 0

3 3 1 2 4 1 4 2 1
5.0

4 5 5 4 2 7 3 5 7 3 6 3 8 2 4

5 4 0 4 7 2 5 3 0 6 3 3 0 4 2

1 1 3 2 729.0 707.2 0 0 2 2 2 196.0 124.4 1 1 3 1 i s 716.0 565.1 11.0

95.4 1.0

4 0 2 637.0 1 5 1 5 1 1 405.0 6 0 0
5.0

50.6 856.9

612.3 331.2 11.8

7 0 1

5.0 2 6 4 2 3 5 ; 0 6 6 2 4 2 5 3 3 1 0 0 0 1 3
77.0

1 3 1 1
3

6 1 4 1
0

597.0

0 0 2

6 2 3

;;:
1 0 2 4 0 1 1 4 0 4 1 0 1 1 2

1320.0 1274.7 3 4 2 3 2 5 1 4 4 3 3 2 5 2 4 1 0 0 2 2

80.7

420.0

431.8

452.0 0 0 2 2 838.0 6 0 1
5.0

493.6

1830.0 1626.0

1 1 3 3 2
750.0

3 0 4 8 0 2 448.0 3 7 1
7 3 1

474.6

2 6 2 6 2 2 722.5 31.4 2 7 1 5 0 7 2 5 1 0 1 1 3 3 4 419.0 415.9 5.0

3 4 2 4 3 2 829.6 4.0 3 6 1 6 2 1 4 0 3 15.0

1 6 3 6 1 3 8 2 2 8 0 2 2 4 213.0 304.3

200.0
2 0 2

210.2 28.2 3 4 1

32.0 2 3 1

TABLE 12 Observed and calculated powder line intensities for nitrate cancrinite
h k 1 0
1

I (obs) I (calc)
50.0

h k l 5 0 0

I (obs) I (calc)

Z (obs) I (calc)

I (obs) I (calc)

53.8

1 1 0 2438.0 2437.8 2 0 0 234.0 1 0 1 3409.0 3916.8 1 2 0 2 1 0 830.0 1 1 1 60.0 2 0 1 339.0 3 0 0 4624.0 42594 1 2 1 2 1 1 4491.0 4739.3 2 2 0
15.0

1 2 2 2 1 2 81.0 1 4 1 4 1 1 533.0 3 3 0 3 0 2 1644.0 1795.3 2 4 0 4 2 0 26.0 5 0 1 228.0 2 2 2 48.0 1 5 0 3 1 2 86.8 22-4 197.6 549.8 93.1

1 6 0 6 1 0 5 0 2

7 1 0 2 5 2 5 2 2 43.0 86.3

k I 8 1 0 1 0 4 h

I (obs) I [calc) 19.0

10.8

2194

1 5 2 1 1 1 3
5

;;;
4 5 1 6 1 7 1 4 5 4 6 1 7 1 4 1 0 0 2 2 1 ; a 3

976.0 81.0

828-0 80-3

220.0 2 0 3 103.0 3 3 2 142.0 2 4 2 4 2 2 12.0 1 6 1 2 6 1 2 1 1 1 3 5 420.0 4 4 0 s1.0

52.7

216.9 103.7 153.4 20.0

5 1 7 1 4 6

5 7 1 1 6 4

0 2 2 4 0 0 322.0 333.3 14.8

717.4 57.9 228.5

9.0

14.2

2 0 4 6 0 3 56.0 1 8 3 4
8 7

12.0 3 6 0 6 3 0 466.4 8 0 0 542.0 203-2 a a 5 4 84.0 10i.1

8.8

28.6 3.0 23.3

8 1 4 3
7

1 1 3 3 210.0 125.4
0 0

18.0 12.0 5 4 0 4 7 2 0 5 3 6 3 3 1 1 3 2
468.0

0.1 3 3 1 46.9 107.6 4 0 2 1 5 1 5 1 1 2 4 1 4 2 1

1 3 0 3 1 0
80.0

7 0 0

6.0 121.0
16.0

1.6 42.4 478.2

78.0

3 0 1 4 0 0 1512.0 1300.0 2 2 1
101.0

3 5 1 5

5 3 5 1

0 0 2 2
9.0

4 5 1 2

3 5 4 2 1

2 2 4 4 15.0 26.0

318.1

433.0 52.0 6 0 0

3 0 3 2 6 0 6 2 0 20.0 4 4 1 2 2 3 2.54
25.5

114.0 819.8

1 3 1 3 1 1 650.0 0 0 2 1722.0 1922.9 2 3 0 3 2 0 1 0 2 281.0 4 1 4 1 0 4 1 1 1 0 0 2 1925.0 2167.3 2 0 2 48.0 2 3 1 3 2 1

486.0

21.6

37.0 3 4 2 3 4 3 3 2 0 0 2 2 608.0

30.0

2 7 7 3 5 3 6 3

0 0 2 2 2 1 1 3 222.0 132.5

5 5 1 2 5 3 5 2 3 15.0 4 6 1 6 4 1 36.0
9 0 0

26.5 40.2

516.8

323.0

2 5 0

a 2 0 1 4 2 4 1 2 911.0 6 0 1 10.0 54.8 521.5 3 4 1 4 3 1 1 0 3 268.0 303.6 13.5 589.6

7 3 5 1 3 6

0 5 3 3 1 0

1 1 1 3 3 2 816.0 843.9 101.1

8 0 1 2 4 3 4 2 3 430.0 2 6 2 6 2 2 12.0 2 7 1 5 0 7 2 5 1 0 1 1 3 3 4 336.0

8 0

3 6 5 8 3 7 1 6 2 8 2

6 3 0 0 7 3 6 1 8 2 2

2 2 4 2 1 1 3 3 0 0 4

332.0 26.0

348.9
8.8

250.9 13.3

3 4 2 4 3 2 103.0 2 6 4 1 6 2 0 7 1 1 3 0

139.0 244.5

156.4

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1530
A1 are the same as those given by Jarchow for natural cancrinite within the limits o error. The positions of f framework oxygens are different and show the influence of the guest molecules. According to the interatomic distances for basic cancrinite it appears that the ordered distribution of silicon and aluminium is maintained. However, the large standard deviations do not permit a further discussion of these bond lengths. Cations and guest species. Basic cancrinite. The probable cation distribution proved to be a most interesting feature of basic cancrinite. Jarchow found two cation positions, but basic cancrinite clearly possesses three sites. The site found by Jarchow in front of the 6-ring opening to the main channel [Jarchows designation Na,(Ca)] is in basic cancrinite divided into two positions, Na(1) and Na(2). Na(3) has almost the same location as given by Jarchow [his designation Na,(Ca)], and the occupancy factors for the three sodium positions lead to 7.15Na per unit cell, a value which compares very well with the chemical analysis (Table 1). The distances in Table 8 give some idea of the mode of framework charge compensation. Na( 1) is closely bound (2.3 A) to 0(1),0(3), and 0(4),while Na(3) is nearest to three O(2). The position denoted 0(8) is most probably a f water molecule attached to Na(3). I i t were an hydroxyl ion there would be no cation left for the intercalated silicate anions. Also there would be no clear reason for the division already mentioned of one of Jarchows cation sites. Na(2), the cation near the centre of the main channel, could well balance the charge of the silicate anion (cf. distances in Table 8). Nevertheless i t was not possible to find a satisfactory explanation of the arrangement of peaks * 0 ( 5 ) ,0(6), and O(7) with their respective occupancy factors. In the main channels are two water molecules and some kind of silicate anion, but any suggested structure would be hypothetical. Chemical analysis and the structure determination of basic cancrinite strongly indicate that silicate anions are present in the main channel. These anions and associated cations will prevent the diffusion of sorbates into the outgassed crystals even in absence of stacking faults. There is accordingly no difficulty in understanding why basic cancrinites are not useful molecular sieve sorbents. Nitrate cancrinite. Although the structure is not refined as well as one might wish, several valid statements can be made. As with basic cancrinite the position of Na(1) is not fully occupied, but no division of the position into two as in basic cancrinite was found. The distances of the oxygen neighbours (Table 10) are reasonable. Na(3) appears to have an environment similar to that in basic cancrinite, although the co-ordinates (Table 9) are slightly different and the occupancy factor of the assumed water molecule [ 0 ( 8 ) in basic cancrinite and O(7) in nitrate cancrinite] is certainly smaller. Apart from this, the actual arrangement of guests species in the small cavity is quite uncertain. For two reasons it is very likely that some of the small cavities contain nitrate. First, less than half of the 1.9N0,- ions per unit cell are located in the main channel; and secondly, if there were no nitrate in the cancrinite cavities the organisation of guest species in the complex should be the same as in basic cancrinite. Oxygen O ( 5 ) in the main channel clearly belongs to a
lo

J. Chem. SOC. (A), 1970

nitrate anion. The anion is lying on the 6,-axis, as ex0-21 pected, and has an oxygen-oxygen distance of 2.16 which compares favourably with 2.14 A for oxygens in nitrate ions.lO Within the limits of error the three oxygens O ( 5 ) are in the plane of the three Na(1). The nitrogen belonging to this NO3- could not be separately refined because i t was too close to Na(2). The corresponding Fourier peak was slightly distorted owing to the additional electron density of the unresolved nitrogen peak. For the same reason i t is thought that the occupancy factor is too high. The most probable arrangement therefore is the alternation of Na(2) with nitrate anions along c, which explains the destruction of the 6,-axis. On examining the locations found for the nitrate ions and water molecules, one realises that in order to pack maximum amounts of guest species, only eight cations can be accommodated per unit cell. Six of these are in the main channel in front of the 6-ring openings to the small cavities, and two are near the 6-rings perpendicular to the c-axis. The remaining space can then be filled by two nitrates and about two water molecules, or by four nitrates alone. The latter possibility, however, leads to 10 cations per unit cell, 6 for the framework and 4 for the salt inclusion. Only if the Si : A ratio became 2 : 1, corresponding to a framework 1 composition 4NaAlO,, SSiO,, would the overall number of cations be lowered to the required 8. Such a ratio is not observed, and accordingly the limit to the amount of nitrate which was observed in the preparations is also underst andable. Chromate and Molybdate Cancrinite [Samples (V) and (VI). -The same procedures were applied as outlined for samples (I) and (11). The first Fourier maps showed outstandingly large peaks in the cancrinite cages of both structures, as well as a complicated mixture of peaks in and near the wide channel. The cage peaks were attributed to chromate and molybdate ions, and persisted throughout the refinement. Although these anions were also present in the channel, i t was noted that the Fourier maps always indicated their much greater occupancy of the cages. Sodium ions were located, and after several cycles of slow Fourier refinement the R ( I ) factors had been lowered from initial values around 0.95 to ca. 0.35. A t this point all the distances were reasonable and the structure chemically sensible and similar to that of nitrate cancrinite. However no further Fourier or least-squares refinement could be achieved , despite considerable efforts which involved starting afresh three times. A characteristic of these structures was the appearance of severe disturbances in the Fourier maps near the heavy atoms. It was thought that inclusion disorder in the specimens and series termination effects were responsible for slow initial refinement and ultimate limit to R ( I ) . Despite this, it was clear that the anions had entered the cancrinite cages, and that the amount of salt in the cages was higher than in the channel.

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DISCUSSION

P. Cherin, W. C. Hamilton, and B. Post, Acta Cryst., 1967,

23,455.

The structural, physicochemical, and chemical study reported in this paper indicates that in inclusion complexes of cancrinite containing nitrate, chromate, or molybdate, these anions are found both in the wide channels parallel to the c-axis and in the ll-hedral cavities which lie between these channels. Lowtemperature syntheses appear to favour complexes with

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Inorg. Phys. Theor.

more nitrate in the ll-hedra than in the channels while a t high temperatures the reverse tends to be the case. The maximum uptake of NO,- approaches two anions per unit cell. For a cancrinite in which SiO,: A1,0, = 2 : 1 an explanation can be found in terms of the framework charge, corresponding numbers of cations, and their locations. Particular salts induce the formation of cancrinite a t low temperatures, under conditions which in absence of these salts or in the presence of other salts yield sodalite. This suggests that salts may catalyse cancrinite synthesis by a template action. One way in which such an effect could arise involves association of salt with specific aluminosilicate anions in solution. These complexes may then be precursors to nucleation and crystal growth. At higher temperatures the cancrinite structure can grow in the absence of salts, as basic cancrinite.ll It has yet to be established how far salts still exert a template action and whether this action is in the same direction as in low-temperature synthesis. It is also possible that the inability of cancrinite and sodalite to form intergrowths a t low temperatures may be modified a t sufficiently high temperatures. Regardless of how cancrinites are made, a t low temperatures simple sorbate molecules do not have access to the intracrystalline channels, as evidenced by the low surface areas found by the B.E.T. method for samples (111) and (IV) (Table 1). Washing the crystals

1531
in an attempt to remove entrained salt or sodium hydroxide did not change this. At high pressures and temperatures, however, limited intracrystalline sorption of certain gases can occur in basic cancrinite.12 Two other features are of interest. First, extreme reaction conditions (Table 2) gave nearly anhydrous nitrate-rich sodalites instead of cancrinites, and secondly, during the thermal decomposition of nitrate cancrinite, an expanded nepheline intermediate was detected. Of the original objectives of this work the template action of salts has been investigated and discussed. It has further been demonstrated that the determination of the structures of inclusion complexes by X-ray powder methods can sometimes be very successful, while in other cases, although refinement may fail for various reasons, valuable information may be obtained without complete strucfure determination. There is so far, however, no method available for producing unblocked cancrinite molecular sieve sorbents in the soda system.
We thank Mrs. K. Cole and Mrs. G. Villiger-Jaggi for help in measuring intensities and evaluating Fourier shifts, and G. F. Cole for a gift of two computer tapes. One of us (J. F. C.) was supported by the Agricultural Research Council, and another (H. V.) by the S.R.C.
[9/1254 Received, July 23rd, 19691
l1
l2

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R. M. Barrer and E. A. D. White, J . Chem. SOC.,1952, 1561. R. 31. Barrer and D. E. TV. Vaughan, to be published.