400 C R Y S T A L D A T A

mOtres de la maille monoclinique:

a = 8,427 (2); b = 5,690 (2); c = 7,935 (2) A, f l= 108,90 (2) U=359,93/~3; Z = 2

Dm = 6,45 ; D~ = 6,60.

Le diagramme de poudre a 6t6 index6 (Tableau 3). Des essais sont actuellement en cours pour obtenir de

meilleurs monocristaux de cette phase. Cependant en alliant la technique des recuits au refroidissement lent, une autre phase triclinique (dont les param6tres ont 6t6 d6termin6s sur monocristal) s'est manifest6e; sa formulation est en- core incertaine. Ces r6sultats montrent/~ la fois la complexit6 et la vari6t6 des enchainements Mo-O pouvant exister dans les polymolybdates. II est /~ noter qu'aucune isotypie n'a pu 6tre relev6e entre les polymolybdates alcalins d6j/t identifi6s et les compos6s du T1 ~ de formulation analogue alors qu'entre les compos6s du K et du Rb elle a 6t6 con- stat6e (Gatehouse & Leverett, 1971). Aussi une 6tude structurale a-t-elle 6t6 entreprise.

R6f6rences

BELYAEV, I. N., DOROSHENKO, A. K. & NESTEROV, A. A. (1971). Russ. J. Inorg. Chem. 16, 1389-1390.

BROWER, W. S., PARKET, H. S., ROTH, R. S. & WARING, J. L. (1972). J. Cryst. Growth, 16, 115-120.

GATEHOUSE, B. M. & LEVERETT, P. (1968). J. Chem. Soc. (A), pp. 1398-1405.

GATEHOUSE, B. M. & LEVERETT, P. (1971). J. Chem. Soc. (A), pp. 2107-2112.

GATEHOUSE, B. M., LLOYD, D. J. & MISKIN, B. K. (1972). Proc. 5th Materials Research Symposium-Natl. Bur. Stand. Publ. 364, 15-27.

HOEKSTaA, H. R. (1973). hwrg. Nucl. Chem. Lett. 9, 1291-1301.

RAGHUCHANDRA KINI, M., UDUPA, M. R. & ARAVAMUDAN, G. (1973). Curr. Sci. 42, 536-537.

TOUBOUL, M., TOLEDANO, P. & PEREZ, G. (1974). C. R. Acad. Sci. Paris. Sdr. C, 278, 417-419.

J. Appl. Cryst. (1975). 8, 400

Crystal data for two dihydrated compounds of methanesulphonic acid with Mn(H) and Cd(II): M n ( C H 3 S O 3 ) z . 2 H 2 0 and C d ( C H 3 S O 3 ) 2 . 2 H 2 0 . By F. CHARBONYIER, Laboratoire de Synthbse Mindrale, Univer- sitd Claude Bernard-Lyon I, 69621-Villeurbanne, France and R. FAURE et H. LOISELEUR, Laboratoire de Chimie Analytique II, Universitd Claude Bernard-Lyon I, 69621-Villeurbanne, France

(Received 28 January 1975; accepted 28 January 1975)

The unit-cell parameters and indexed powder patterns are reported for the title compounds. Both these compounds are new; they crystallize in the triclinic system.

Origin of specimens

The compounds were obtained from metathesis of barium methanesulphonate and manganese(II) or cadmium(II) sulphate solutions. After elimination of the barium sulphate by filtration, the solutions were slowly evaporated at room temperature and single crystals isolated.

Chemical characterization

The compounds were analysed for metal content by a volumetric method (EDTA titration) and for sulphur con- tent by a gravimetric method previously described (Char- bonnier, 1973). Water of crystallization was determined by drying in an oven set at 120 ° and the results conformed with the mass loss on the thermobalance. Table 1 gives the results of the chemical analysis.

Table 1. Results of the chemical analysis

Mn(CH3SO3). 2H20 Cd(CH3SO3)2.2H20 Mn % S % HzO % Cd % S % HzO %

Theor. 19"53 2 2 - 8 3 1 2 - 8 3 3 3 " 1 9 1 8 " 9 4 10"64 Found 19 .46 22.70 12.94 3 3 - 2 1 1 8 - 8 0 10"60

Crystal geometry

Weissenberg and precession X-ray photographs, obtained with Cu K~ (2= 1.5418 A,) and Mo K~ (A=0.7107 /~) ra- diations respectively, showed the examinated crystals were triclinic. The unit-cell data were refined from the indexed powder diffraction patterns by a classical least-squares method, minimizing ~(sin 2 0o-Sin 2 0c) 2. The parameter values are given with errors calculated for a probability of 0-1% according to the Student distribution.

Mn(CH3SOz)2.2H20 a=5-146+0"008, b=5"675+0"012, c=9-20+0"03/~ ~= 114-83+0.18, fl= 103.21 +0.20, y= 90.93 + 0.20 ° U=235+_2/~3; Z = I D,,,= 2.00 g cm-3; Dx= 1.98 g cm -3 Cd(CH3SO3)2.2H20 a=4-773 +_0.003, b=6.08+0.01 , c=9-965_+0.019 ,~

-- 124"63 _+ 0.12, fl= 91-94_+ 0-12, ),= 94.34 + 0.12 ° U=236_+2 A?; Z = 1 Din=2"31 g cm-3; Dx=2"38 g cm -3.

Powder data

The powder patterns were obtained with a Guinier camera (114.6 mm in diameter) with Cu Kax radiation (2= 1.54051

C R Y S T A L D A T A 401

/~). Intensities were measured with a Nonius microdensi- tometer. Resulting powder diffraction data are reported on Tables 2 and 3 for manganese and cadmium methanesul- phonates respectively.

Table 2. Powder diffraction dataforMn(CH3SO3)~.2H20

dobs dealt hkl HA 8.08 8.06 001 70 5"541 5"541 011 3 5"110 5-108 010 85 4.980 4"969 100 3 4"168 4"166 0T2 1 4.031 4"030 002 13 3"814 { 3.812 1T0 } 42

3.811 101 3.785 3"776 i-ll 7 3"660 3"655 011 40 3.628 {3"627 1T1}

3"623 TO2 100 3"489 3"488 i]'2 77 3"356 3"355 110 12 3.286 3"290 111 4 2-967 2-969 0T3 35 2.826 2.827 1-]-3 3 2"795 2.795 102 10 2"775 2"771 0~2 22 2"688 { 2.689 111 }

2-687 003 7 2.652 2-652 012 4 2-576 2"569 201 45 2"553 2.554 020 6 2.502 2-501 121 7 2.485 2.485 200 3 2"462 { 2.463 i 2 2 }

2.462 023 3 2.398 2-398 1"21 17

Table 3. Powder diffracthgndataforCd(CH3SO3)2.2H20

dobs dealt hkl H~ 8"18 8"16 001 98 6"062 6"057 0T1 58 4.973 4.970 010 87 4.786 4.765 012 3 4.735 4.738 100 3 4-277 4.276 101 41 4.077 4.082 002 1 3.946 3.941 101 32 3-874 3-868 111 50 3.613 3.609 iT1 38 3.459 3.456 011 24

Table 3 (cont.)

~obs dcale hkl HA 3-364 {3.362 112}

3.358 ] i2 100 3-323 3.318 0T3 31 3-249 { 3-247 110 }

3.247 T02 40 2.960 2.958 102 57 2.881 2.881 021 18 2-802 2.800 023 6 2.767 2.767 i-]-3 20 2.672 2.672 113 30 2.641 { 2.645 111 }

2.639 1~2 34 2.579 2-580 121 40 2.523 2.524 012 4 2.486 2.485 020 25 2.472 2.473 122 30 2.442 2.442 014 14 2.381 2.383 024 10 2-375 2-376 123 44 2.345 2.344 T12 22 2.313 2.313 120 20 2.270 2.270 103 26 2.242 2.241 210 15 2-220 2.220 201 30 2.155 2.155 211 19 2.131 2.130 124 30 2.122 2.122 2T2 30 2.070 2-070 021 17 2.049 2.049 210 22 2-041 2.041 004 8 2"020 2-019 033 6 1"981 { 1"981 0~5 } 19

1"980 032 1"961 1"960 013 10 1"940 1-940 034 12 1"927 1"928 221 4 1"908 { 1"909 015 } 7

1-907 133 1"890 1"891 112 19 1"876 1"876 203 9 1"853 1-853 211 12 1"841 1"839 223 22 1"823 1"823 220 18

Conclusion

Work is in progress to determine the crystal structures of these new compounds.

Reference

CHARBONNIER, F. (1973). Thermochim. Acta, 7, 217-224.