Cadmium sulfite hexahydrate revisited.

The present structural revision of the title compound, tetra-cadmium tetra-sulfite hexa-hydrate, [Cd(4)(SO(3))(4)(H(2)O)(5)]·H(2)O, is a low-temperature upgrade (T = 100 K and R = 0.017) of the original room-temperature structure reported by Kiers & Vos [Cryst. Struct. Commun. (1978). 7, 399-403; T = 293 K and R = 0.080). The compound is a three-dimensional polymer with four independent cadmium centres, four sulfite anions and six water mol-ecules, five of them coordinated to two cadmium centres and the remaining one an unbound solvent mol-ecule which completes the asymmetric unit. There are two types of cadmium environment: CdO(8) (through four chelating sulfite ligands) and CdO(6) (by way of six monocoordinated ligands). The former groups form planar arrays [parallel to (001) and separated by half a unit cell translation along c], made up of chains running along [110] and [10], respectively. These chains are, in turn, inter-connected both in an intra-planar as well as in an inter-planar fashion by the latter CdO(6) polyhedra into a tight three-dimensional framework. There is, in addition, an extensive network of hydrogen bonds, in which all 12 water H atoms act as donors and eight O atoms from all four sulfite groups and two water mol-ecules act as acceptors.

Related literature

For related literature, see: Agre et al. (1981 ▶); Brown & Altermatt (1985 ▶); Elder et al. (1978 ▶); Harvey et al. (2006 ▶); Kiers & Vos (1978 ▶); Larsson & Kierkegaard (1969 ▶).

Experimental

Crystal data

[Cd4(SO3)4(H2O)5]·H2O

M = 877.94

Monoclinic,

a = 12.1406 (3) Å

b = 10.5485 (3) Å

c = 13.9329 (4) Å

β = 103.93 (1)°

V = 1731.82 (11) Å3

Z = 4

Mo Kα radiation

μ = 5.41 mm−1

T = 150 (2) K

0.24 × 0.12 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2001 ▶) T min = 0.40, T max = 0.64

31336 measured reflections

3959 independent reflections

3922 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.017

wR(F 2) = 0.040

S = 1.26

3959 reflections

284 parameters

18 restraints

All H-atom parameters refined

Δρmax = 0.70 e Å−3

Δρmin = −0.56 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808011409/br2070sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808011409/br2070Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cd4(SO3)4(H2O)5]·H2O	F000 = 1648
Mr = 877.94	Dx = 3.367 Mg m−3
Monoclinic, P21/c	Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9999 reflections
a = 12.1406 (3) Å	θ = 1.9–27.2º
b = 10.5485 (3) Å	µ = 5.41 mm−1
c = 13.9329 (4) Å	T = 150 (2) K
β = 103.93 (1)º	Prisms, colourless
V = 1731.82 (11) Å3	0.24 × 0.12 × 0.08 mm
Z = 4

Bruker CCD area-detector diffractometer	3959 independent reflections
Radiation source: fine-focus sealed tube	3922 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.021
T = 150(2) K	θmax = 27.8º
φ and ω scans	θmin = 1.7º
Absorption correction: multi-scan(SADABS; Sheldrick, 2001)	h = −15→15
Tmin = 0.40, Tmax = 0.64	k = −13→13
31336 measured reflections	l = −18→18

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.017	All H-atom parameters refined
wR(F2) = 0.040	w = 1/[σ2(Fo2) + (0.0143P)2 + 2.6649P] where P = (Fo2 + 2Fc2)/3
S = 1.26	(Δ/σ)max = 0.001
3959 reflections	Δρmax = 0.70 e Å−3
284 parameters	Δρmin = −0.56 e Å−3
18 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00228 (6)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

	x	y	z	Uiso*/Ueq
Cd1	0.374818 (15)	0.126886 (17)	0.512881 (12)	0.01034 (5)
Cd2	0.126635 (15)	0.392254 (17)	0.488405 (12)	0.00985 (5)
Cd3	0.651371 (15)	0.304514 (17)	0.535886 (13)	0.01196 (5)
Cd4	0.251030 (14)	0.282648 (17)	0.748125 (12)	0.00938 (5)
S1	0.39723 (5)	0.40991 (6)	0.57849 (4)	0.00932 (11)
O11	0.30501 (15)	0.49090 (17)	0.51101 (13)	0.0124 (4)
O21	0.33019 (15)	0.29972 (16)	0.60990 (13)	0.0126 (4)
O31	0.45766 (15)	0.34041 (17)	0.50750 (13)	0.0126 (3)
S2	0.58417 (5)	0.04129 (6)	0.66523 (4)	0.01119 (12)
O12	0.58184 (16)	0.10397 (17)	0.56483 (13)	0.0151 (4)
O22	0.45763 (15)	0.03386 (19)	0.66270 (13)	0.0167 (4)
O32	0.61638 (16)	−0.09653 (17)	0.64740 (13)	0.0139 (4)
S3	0.11611 (5)	0.11583 (6)	0.42209 (4)	0.01077 (12)
O13	0.20348 (15)	0.03728 (17)	0.49607 (13)	0.0142 (4)
O23	0.19010 (15)	0.22405 (17)	0.39362 (13)	0.0131 (4)
O33	0.04828 (15)	0.18855 (17)	0.48327 (13)	0.0146 (4)
S4	0.01096 (5)	0.43144 (6)	0.66480 (4)	0.01148 (12)
O14	−0.05477 (15)	0.40529 (17)	0.55726 (13)	0.0144 (4)
O24	−0.01213 (16)	0.57150 (18)	0.67606 (13)	0.0166 (4)
O34	0.13592 (15)	0.42562 (18)	0.65556 (13)	0.0137 (4)
O1W	0.81699 (17)	0.20277 (19)	0.57164 (16)	0.0197 (4)
H1WA	0.814 (3)	0.1330 (18)	0.546 (3)	0.045 (12)*
H1WB	0.868 (2)	0.246 (3)	0.559 (3)	0.030 (10)*
O2W	0.7011 (2)	0.3753 (2)	0.68995 (16)	0.0286 (5)
H2WA	0.693 (3)	0.4504 (13)	0.700 (3)	0.045 (12)*
H2WB	0.760 (2)	0.347 (3)	0.725 (2)	0.037 (11)*
O3W	0.61491 (18)	0.2464 (2)	0.37382 (15)	0.0203 (4)
H3WA	0.6757 (19)	0.249 (4)	0.358 (3)	0.046 (12)*
H3WB	0.586 (3)	0.1767 (18)	0.359 (3)	0.034 (11)*
O4W	0.36903 (15)	0.11969 (18)	0.80645 (13)	0.0133 (4)
H4WA	0.411 (2)	0.101 (4)	0.7709 (19)	0.032 (11)*
H4WB	0.405 (2)	0.133 (4)	0.8633 (11)	0.034 (11)*
O5W	0.12980 (17)	0.1237 (2)	0.68645 (14)	0.0186 (4)
H5WA	0.100 (3)	0.132 (4)	0.6275 (9)	0.033 (10)*
H5WB	0.082 (2)	0.113 (4)	0.718 (2)	0.047 (13)*
O6W	0.83535 (18)	0.2464 (2)	0.83907 (16)	0.0233 (4)
H6WA	0.861 (3)	0.180 (2)	0.822 (3)	0.058 (15)*
H6WB	0.885 (3)	0.284 (3)	0.879 (3)	0.052 (14)*

	U11	U22	U33	U12	U13	U23
Cd1	0.00977 (9)	0.01060 (9)	0.01059 (9)	0.00073 (6)	0.00235 (7)	0.00000 (6)
Cd2	0.00950 (9)	0.00952 (9)	0.01055 (9)	0.00085 (6)	0.00243 (6)	0.00000 (6)
Cd3	0.01045 (9)	0.01000 (9)	0.01560 (9)	0.00038 (6)	0.00346 (7)	0.00120 (6)
Cd4	0.00934 (9)	0.00987 (9)	0.00873 (9)	0.00011 (6)	0.00176 (7)	0.00026 (6)
S1	0.0086 (3)	0.0090 (3)	0.0101 (3)	0.0010 (2)	0.0019 (2)	0.0000 (2)
O11	0.0097 (8)	0.0102 (8)	0.0169 (9)	0.0021 (7)	0.0027 (7)	0.0033 (7)
O21	0.0167 (9)	0.0100 (8)	0.0131 (8)	0.0000 (7)	0.0071 (7)	0.0011 (6)
O31	0.0110 (8)	0.0147 (9)	0.0130 (8)	0.0020 (7)	0.0047 (7)	0.0004 (7)
S2	0.0119 (3)	0.0101 (3)	0.0110 (3)	0.0023 (2)	0.0015 (2)	−0.0009 (2)
O12	0.0159 (9)	0.0134 (9)	0.0150 (9)	−0.0016 (7)	0.0019 (7)	0.0036 (7)
O22	0.0130 (9)	0.0238 (10)	0.0145 (9)	0.0067 (8)	0.0054 (7)	0.0030 (7)
O32	0.0172 (9)	0.0101 (8)	0.0136 (8)	0.0053 (7)	0.0022 (7)	0.0003 (7)
S3	0.0099 (3)	0.0109 (3)	0.0115 (3)	0.0002 (2)	0.0025 (2)	−0.0015 (2)
O13	0.0128 (9)	0.0107 (9)	0.0186 (9)	0.0004 (7)	0.0029 (7)	0.0019 (7)
O23	0.0143 (9)	0.0129 (9)	0.0135 (8)	0.0006 (7)	0.0060 (7)	0.0003 (7)
O33	0.0134 (9)	0.0148 (9)	0.0179 (9)	0.0012 (7)	0.0082 (7)	−0.0013 (7)
S4	0.0106 (3)	0.0121 (3)	0.0123 (3)	0.0021 (2)	0.0038 (2)	0.0015 (2)
O14	0.0138 (9)	0.0145 (9)	0.0139 (8)	−0.0008 (7)	0.0010 (7)	−0.0009 (7)
O24	0.0201 (10)	0.0140 (9)	0.0164 (9)	0.0065 (8)	0.0057 (7)	−0.0001 (7)
O34	0.0096 (8)	0.0172 (9)	0.0144 (8)	0.0029 (7)	0.0033 (7)	0.0025 (7)
O1W	0.0131 (10)	0.0123 (9)	0.0336 (11)	−0.0006 (8)	0.0052 (8)	−0.0019 (8)
O2W	0.0419 (14)	0.0186 (11)	0.0201 (10)	0.0122 (10)	−0.0027 (9)	−0.0021 (8)
O3W	0.0221 (11)	0.0204 (10)	0.0206 (10)	−0.0038 (8)	0.0094 (8)	−0.0028 (8)
O4W	0.0134 (9)	0.0144 (9)	0.0119 (8)	0.0023 (7)	0.0028 (7)	−0.0005 (7)
O5W	0.0201 (10)	0.0231 (10)	0.0129 (9)	−0.0100 (8)	0.0046 (8)	−0.0013 (8)
O6W	0.0177 (10)	0.0271 (12)	0.0230 (10)	0.0056 (9)	0.0006 (8)	−0.0002 (9)

Cd1—O13	2.2452 (18)	Cd3—O12	2.3482 (18)
Cd1—O32i	2.2839 (18)	Cd3—O11iii	2.3518 (18)
Cd1—O22	2.3065 (18)	Cd4—O34	2.2412 (18)
Cd1—O21	2.4078 (17)	Cd4—O4W	2.2599 (18)
Cd1—O12	2.4542 (18)	Cd4—O5W	2.2601 (19)
Cd1—O31	2.4752 (18)	Cd4—O32iv	2.2816 (18)
Cd1—O23	2.6544 (18)	Cd4—O23v	2.3203 (17)
Cd1—O12i	2.7665 (19)	Cd4—O21	2.3571 (17)
Cd2—O34	2.3311 (18)	S1—O11	1.5364 (18)
Cd2—O14ii	2.3365 (18)	S1—O21	1.5416 (18)
Cd2—O33	2.3440 (18)	S1—O31	1.5504 (18)
Cd2—O11	2.3545 (18)	S2—O22	1.5302 (19)
Cd2—O24ii	2.4074 (18)	S2—O32	1.5410 (18)
Cd2—O23	2.4446 (18)	S2—O12	1.5413 (18)
Cd2—O14	2.6091 (18)	S3—O33	1.5269 (18)
Cd2—O21	2.8126 (18)	S3—O13	1.5323 (18)
Cd3—O2W	2.215 (2)	S3—O23	1.5618 (18)
Cd3—O1W	2.2272 (19)	S4—O24	1.5189 (19)
Cd3—O3W	2.278 (2)	S4—O14	1.5435 (18)
Cd3—O31	2.3201 (17)	S4—O34	1.5544 (18)
O13—Cd1—O32i	95.70 (7)	O34—Cd2—O21	68.10 (6)
O13—Cd1—O22	96.10 (7)	O14ii—Cd2—O21	134.22 (6)
O32i—Cd1—O22	135.43 (6)	O33—Cd2—O21	89.52 (6)
O13—Cd1—O21	92.82 (6)	O11—Cd2—O21	54.99 (5)
O32i—Cd1—O21	136.46 (6)	O24ii—Cd2—O21	148.24 (6)
O22—Cd1—O21	85.53 (6)	O23—Cd2—O21	74.20 (6)
O13—Cd1—O12	147.85 (6)	O14—Cd2—O21	119.61 (5)
O32i—Cd1—O12	89.36 (6)	O2W—Cd3—O1W	85.69 (8)
O22—Cd1—O12	59.93 (6)	O2W—Cd3—O3W	173.70 (9)
O21—Cd1—O12	105.18 (6)	O1W—Cd3—O3W	92.38 (8)
O13—Cd1—O31	138.85 (6)	O2W—Cd3—O31	97.98 (8)
O32i—Cd1—O31	89.02 (6)	O1W—Cd3—O31	160.09 (7)
O22—Cd1—O31	108.83 (7)	O3W—Cd3—O31	85.86 (7)
O21—Cd1—O31	58.40 (6)	O2W—Cd3—O12	99.36 (8)
O12—Cd1—O31	72.77 (6)	O1W—Cd3—O12	82.53 (7)
O13—Cd1—O23	58.36 (6)	O3W—Cd3—O12	86.31 (7)
O32i—Cd1—O23	70.94 (6)	O31—Cd3—O12	77.57 (6)
O22—Cd1—O23	148.13 (6)	O2W—Cd3—O11iii	86.15 (8)
O21—Cd1—O23	77.80 (6)	O1W—Cd3—O11iii	104.64 (7)
O12—Cd1—O23	150.86 (6)	O3W—Cd3—O11iii	88.54 (7)
O31—Cd1—O23	85.29 (6)	O31—Cd3—O11iii	95.15 (6)
O13—Cd1—O12i	81.22 (6)	O12—Cd3—O11iii	171.36 (6)
O32i—Cd1—O12i	55.66 (6)	O34—Cd4—O4W	166.47 (7)
O22—Cd1—O12i	84.10 (6)	O34—Cd4—O5W	91.25 (7)
O21—Cd1—O12i	167.41 (6)	O4W—Cd4—O5W	82.57 (8)
O12—Cd1—O12i	75.58 (6)	O34—Cd4—O32iv	103.74 (7)
O31—Cd1—O12i	132.23 (5)	O4W—Cd4—O32iv	84.65 (7)
O23—Cd1—O12i	107.85 (5)	O5W—Cd4—O32iv	162.15 (7)
O34—Cd2—O14ii	93.39 (6)	O34—Cd4—O23v	103.74 (6)
O34—Cd2—O33	95.19 (6)	O4W—Cd4—O23v	88.31 (6)
O14ii—Cd2—O33	135.02 (6)	O5W—Cd4—O23v	89.67 (7)
O34—Cd2—O11	88.74 (6)	O32iv—Cd4—O23v	77.53 (6)
O14ii—Cd2—O11	84.47 (6)	O34—Cd4—O21	78.39 (6)
O33—Cd2—O11	139.70 (6)	O4W—Cd4—O21	90.23 (6)
O34—Cd2—O24ii	143.60 (6)	O5W—Cd4—O21	95.87 (7)
O14ii—Cd2—O24ii	60.23 (6)	O32iv—Cd4—O21	96.59 (6)
O33—Cd2—O24ii	88.82 (7)	O23v—Cd4—O21	174.04 (6)
O11—Cd2—O24ii	111.03 (6)	O11—S1—O21	103.67 (10)
O34—Cd2—O23	134.72 (6)	O11—S1—O31	105.04 (10)
O14ii—Cd2—O23	131.44 (6)	O21—S1—O31	100.83 (10)
O33—Cd2—O23	59.77 (6)	O22—S2—O32	103.91 (11)
O11—Cd2—O23	89.63 (6)	O22—S2—O12	101.66 (10)
O24ii—Cd2—O23	77.64 (6)	O32—S2—O12	102.03 (10)
O34—Cd2—O14	57.77 (6)	O33—S3—O13	105.97 (10)
O14ii—Cd2—O14	76.06 (7)	O33—S3—O23	101.25 (10)
O33—Cd2—O14	71.77 (6)	O13—S3—O23	102.63 (10)
O11—Cd2—O14	139.30 (6)	O24—S4—O14	102.06 (10)
O24ii—Cd2—O14	89.80 (6)	O24—S4—O34	104.78 (11)
O23—Cd2—O14	129.84 (6)	O14—S4—O34	101.50 (10)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O13i	0.82 (3)	1.88 (2)	2.693 (3)	170 (4)
O1W—H1WB···O14vi	0.82 (3)	1.93 (2)	2.679 (3)	151 (3)
O2W—H2WA···O4Wiv	0.82 (3)	1.93 (2)	2.719 (3)	162 (4)
O2W—H2WB···O6W	0.82 (3)	1.95 (2)	2.681 (3)	149 (4)
O3W—H3WA···O6Wvii	0.82 (3)	2.02 (2)	2.833 (3)	172 (4)
O3W—H3WB···O22i	0.82 (3)	2.29 (2)	3.092 (3)	168 (4)
O4W—H4WA···O22	0.82 (3)	1.87 (2)	2.651 (3)	159 (3)
O4W—H4WB···O31v	0.82 (3)	1.98 (2)	2.780 (3)	167 (3)
O5W—H5WA···O33	0.82 (3)	2.05 (2)	2.848 (3)	167 (4)
O5W—H5WB···O24viii	0.82 (3)	1.92 (2)	2.708 (3)	162 (4)
O6W—H6WA···O24ix	0.82 (3)	2.16 (2)	2.876 (3)	146 (4)
O6W—H6WB···O33x	0.82 (3)	2.18 (2)	2.948 (3)	157 (4)

Table 1

Selected bond lengths (Å)

Cd1—O13	2.2452 (18)
Cd1—O32i	2.2839 (18)
Cd1—O22	2.3065 (18)
Cd1—O21	2.4078 (17)
Cd1—O12	2.4542 (18)
Cd1—O31	2.4752 (18)
Cd1—O23	2.6544 (18)
Cd1—O12i	2.7665 (19)
Cd2—O34	2.3311 (18)
Cd2—O14ii	2.3365 (18)
Cd2—O33	2.3440 (18)
Cd2—O11	2.3545 (18)
Cd2—O24ii	2.4074 (18)
Cd2—O23	2.4446 (18)
Cd2—O14	2.6091 (18)
Cd2—O21	2.8126 (18)
Cd3—O2W	2.215 (2)
Cd3—O1W	2.2272 (19)
Cd3—O3W	2.278 (2)
Cd3—O31	2.3201 (17)
Cd3—O12	2.3482 (18)
Cd3—O11iii	2.3518 (18)
Cd4—O34	2.2412 (18)
Cd4—O4W	2.2599 (18)
Cd4—O5W	2.2601 (19)
Cd4—O32iv	2.2816 (18)
Cd4—O23v	2.3203 (17)
Cd4—O21	2.3571 (17)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O13i	0.82 (3)	1.88 (2)	2.693 (3)	170 (4)
O1W—H1WB⋯O14vi	0.82 (3)	1.93 (2)	2.679 (3)	151 (3)
O2W—H2WA⋯O4Wiv	0.82 (3)	1.93 (2)	2.719 (3)	162 (4)
O2W—H2WB⋯O6W	0.82 (3)	1.95 (2)	2.681 (3)	149 (4)
O3W—H3WA⋯O6Wvii	0.82 (3)	2.02 (2)	2.833 (3)	172 (4)
O3W—H3WB⋯O22i	0.82 (3)	2.29 (2)	3.092 (3)	168 (4)
O4W—H4WA⋯O22	0.82 (3)	1.87 (2)	2.651 (3)	159 (3)
O4W—H4WB⋯O31v	0.82 (3)	1.98 (2)	2.780 (3)	167 (3)
O5W—H5WA⋯O33	0.82 (3)	2.05 (2)	2.848 (3)	167 (4)
O5W—H5WB⋯O24viii	0.82 (3)	1.92 (2)	2.708 (3)	162 (4)
O6W—H6WA⋯O24ix	0.82 (3)	2.16 (2)	2.876 (3)	146 (4)
O6W—H6WB⋯O33x	0.82 (3)	2.18 (2)	2.948 (3)	157 (4)

Symmetry codes: (i) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) ; (ix) ; (x) .