Diammonium tricadmium tris­(sulfate) dihydroxide dihydrate

Yin, X.

doi:10.1107/S1600536811012979

inorganic compounds

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Volume 67| Part 5| May 2011| Page i31

doi:10.1107/S1600536811012979

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Diammonium tricadmium tris(sulfate) dihydroxide dihydrate

Xin Yin ^a ^*

^aDepartment of Chemistry, East China University of Science and Technology, School of Chemistry and Molecular Engineering, Mei Long Road 130, Shanghai 200237, People's Republic of China
^*Correspondence e-mail: yoshikiyin@ecust.edu.cn

(Received 23 March 2011; accepted 7 April 2011; online 13 April 2011)

The title compound, (NH₄)₂Cd₃(SO₄)₃(OH)₂(H₂O)₂, has been obtained serendipitously. It is isotypic with the heavier alkali analogues M₂Cd₃(SO₄)₃(OH)₂(H₂O)₂ (M = K, Rb, Cs). The structure contains two Cd²⁺ ions, one in a general position and one with site symmetry m. The former Cd²⁺ ion is coordinated by three O atoms of three SO₄ groups, two hydroxide O atoms and one water O atom, the latter Cd²⁺ ion by four O atoms of four SO₄ groups and two hydroxide O atoms, both in a distorted octahedral coordination geometry. This arrangement leads to the formation of a layered framework extending parallel to (100), with the ammonium cations situated in the voids. O—H⋯O hydrogen bonds involving the water molecules, hydroxide groups and sulfate O atoms, as well as N—H⋯O hydrogen bonds between ammonium cations and sulfate O atoms consolidate the crystal packing.

Related literature

For the isotypic K and Cs analogues, see: Louer & Louer (1982 ), and for the Rb analogue, see: Swain & Guru Row (2006 ).

Experimental

Crystal data

(NH₄)₂Cd₃(SO₄)₃(OH)₂(H₂O)₂
M_r = 731.51
Orthorhombic, C m c 2₁
a = 18.906 (3) Å
b = 7.9483 (11) Å
c = 9.9809 (13) Å
V = 1499.8 (4) Å³
Z = 4
Mo Kα radiation
μ = 4.72 mm⁻¹
T = 296 K
0.12 × 0.10 × 0.08 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.601, T_max = 0.704
7060 measured reflections
1770 independent reflections
1739 reflections with I > 2σ(I)
R_int = 0.051

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.066
S = 1.08
1770 reflections
118 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.68 e Å⁻³
Δρ_min = −1.31 e Å⁻³
Absolute structure: Flack (1983 ), 825 Friedel pairs
Flack parameter: −0.07 (4)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O10—H10B⋯O7ⁱ	0.85	2.25	3.087 (5)	167
O10—H10B⋯O5ⁱⁱ	0.85	2.36	2.985 (6)	131
O9—H9A⋯O6ⁱⁱⁱ	0.85	2.18	3.029 (7)	173
O8—H8A⋯O5ⁱⁱ	0.85	2.56	3.322 (9)	150
O8—H8A⋯O5ⁱ	0.85	2.56	3.322 (9)	150
N1—H1B⋯O10^iv	0.90	2.26	2.948 (6)	133
N1—H1D⋯O4ⁱⁱ	0.90	2.18	3.077 (5)	180
N1—H1C⋯O4^v	0.90	2.19	3.074 (7)	168
N1—H1A⋯O3^vi	0.90	2.38	2.995 (6)	126
N1—H1D⋯O2ⁱⁱ	0.90	2.64	3.196 (7)	121
Symmetry codes: (i) $[-x+1, -y+1, z-{\script{1\over 2}}]$ ; (ii) $[x, -y+1, z-{\script{1\over 2}}]$ ; (iii) x, y-1, z; (iv) x, y+1, z; (v) $[-x+{\script{3\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (vi) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT-Plus (Bruker, 2003 ); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: Mercury (Macrae et al., 2006 ) and DIAMOND (Brandenburg, 2006 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811012979/wm2470sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811012979/wm2470Isup2.hkl

checkCIF report

Comment top

The title compound, (NH₄)₂Cd₃(SO₄)₃(OH)₂(H₂O)₂, (I), formed accidentally under hydrothermal reaction conditions. Our intended target product was to synthesis a coordination compound from 1H-benzimidazole-5,6-dicarboxylate and CdSO₄^.8/3H₂O. The presence of ammonium ions in the finally obtained compound points to an internal redox process that presumably has caused a (partly) reduction of the nitrogen atoms of 1H-benzimidazole-5,6-dicarboxylate or the nitrate anions. (NH₄)₂Cd₃(SO₄)₃(OH)₂(H₂O)₂ is isotypic with other M₂Cd₃(SO₄)₃(OH)₂(H₂O)₂ members (M = K, Cs (Louer & Louer, 1982); M = Rb (Swain & Guru Row, 2006)).

The asymmetric unit of (I) is illustrated in Fig. 1. The crystal structure of (NH₄)₂Cd₃(SO₄)₃(OH)₂(H₂O)₂ is made up from two different Cd²⁺ ions (one on a general position (Cd1), one with site symmetry m (Cd2)), two sulfate ions (likewise one on a general position and the other with site symmetry m), two hydroxide groups, one water molecule and one NH₄⁺ cation. Both Cd²⁺ cations are six-coordinated in an octahedral coordination geometry. Cd2 is coordinated by four sulfate ions and two hydroxide ions, while Cd1 is coordinated by three sulfate ons, two hydroxide anions and one water molecule. There are four types of oxygen atoms in the crystal structure of the title compound. The O3 atom of one SO₄^2- anion is solely bound to the S atom, O8 and O9 represent the oxygen atoms of hydroxide groups shared by three Cd atoms, O10 is the water O atom bound to one Cd atom and all other O atoms represent sulfate O atoms coordinated to only one Cd atom.

As can be seen in Fig. 2, the Cd(1)O₆ polyhedra are connected by sharing edges of OH groups. Cd(2)O₆ octahedra and SO₄ tetrahedra are linked to these dimers via common corners, thus forming a two-dimensional network extending parallel to the bc plane. The NH₄⁺ cations are situated in the voids of the layers. Through formation of N—H···O and O—H···O hydrogen bonds a three-dimensional structure is formed. Since all water and hydroxide groups and most of the sulfate O atoms are involved in hydrogen bonding, the resulting network can be considered as relatively stable (Table 2, Fig. 3).

Related literature top

For the isotypic K and Cs analogues, see: Louer & Louer (1982), and for the Rb analogue, see: Swain & Guru Row (2006).

Experimental top

All reagents were obtained from commercial sources and used without further purification. A mixture of CdSO₄^.8/3H₂O (0.2565 g, 1.0 mmol), 1H-benzimidazole-5,6-dicarboxylate (0.1236 g,0.6 mmol), CH₃CN (6 ml) and 4 ml water were added to a 23 ml Teflon-lined stainless container, which was heated to 423 K and held at that temperature for 5 days. After cooling to room temperature in 24 h, colourless crystals were recovered by filtration (yield 49% based on CdSO₄^.8/3H₂O).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2006) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of (I), with displacement parameters shown at the 30% probability level.
	Fig. 2. View of the two-dimensional network structure of (I) parallel to (100) in the polyhedral representation.
	Fig. 3. Three-dimensional supramolecular structure of (I), built up through hydrogen bonding. NH₄⁺ ions have been omitted for clarity.

Diammonium tricadmium tris(sulfate) dihydroxide dihydrate top

Crystal data top

Cd₃H₆O₁₆S₃·2NH₄	F(000) = 1392
M_r = 731.51	D_x = 3.240 Mg m⁻³
Orthorhombic, Cmc2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c -2	Cell parameters from 12815 reflections
a = 18.906 (3) Å	θ = 1.7–27.5°
b = 7.9483 (11) Å	µ = 4.72 mm⁻¹
c = 9.9809 (13) Å	T = 296 K
V = 1499.8 (4) Å³	Block, colourless
Z = 4	0.12 × 0.10 × 0.08 mm

Data collection top

Bruker SMART CCD diffractometer	1770 independent reflections
Radiation source: fine-focus sealed tube	1739 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
ϕ and ω–scans	θ_max = 27.5°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −24→24
T_min = 0.601, T_max = 0.704	k = −10→10
7060 measured reflections	l = −12→12

Refinement top

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)] = 0.027	H-atom parameters constrained
wR(F²) = 0.066	w = 1/[σ²(F_o²) + (0.0328P)² + 1.1583P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
1770 reflections	Δρ_max = 0.68 e Å⁻³
118 parameters	Δρ_min = −1.31 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 825 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.07 (4)

Crystal data top

Cd₃H₆O₁₆S₃·2NH₄	V = 1499.8 (4) Å³
M_r = 731.51	Z = 4
Orthorhombic, Cmc2₁	Mo Kα radiation
a = 18.906 (3) Å	µ = 4.72 mm⁻¹
b = 7.9483 (11) Å	T = 296 K
c = 9.9809 (13) Å	0.12 × 0.10 × 0.08 mm

Data collection top

Bruker SMART CCD diffractometer	1770 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	1739 reflections with I > 2σ(I)
T_min = 0.601, T_max = 0.704	R_int = 0.051
7060 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.066	Δρ_max = 0.68 e Å⁻³
S = 1.08	Δρ_min = −1.31 e Å⁻³
1770 reflections	Absolute structure: Flack (1983), 825 Friedel pairs
118 parameters	Absolute structure parameter: −0.07 (4)
1 restraint

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cd1	0.588435 (18)	0.46065 (4)	0.29502 (5)	0.01981 (11)
Cd2	0.5000	0.19102 (5)	0.58110 (4)	0.01744 (12)
S1	0.67635 (6)	0.30002 (13)	0.57340 (14)	0.0184 (2)
S2	0.5000	0.8103 (2)	0.41513 (16)	0.0192 (4)
O1	0.6589 (3)	0.4252 (6)	0.4718 (4)	0.0387 (11)
O2	0.6223 (2)	0.1661 (4)	0.5730 (5)	0.0299 (8)
O3	0.7446 (2)	0.2229 (5)	0.5454 (5)	0.0357 (11)
O4	0.6794 (2)	0.3814 (5)	0.7053 (4)	0.0299 (9)
O5	0.5621 (3)	0.7036 (8)	0.4165 (6)	0.0583 (18)
O6	0.5000	0.9205 (6)	0.3000 (7)	0.0500 (19)
O7	0.5000	0.9098 (6)	0.5395 (5)	0.0303 (13)
O8	0.5000	0.5445 (5)	0.1571 (5)	0.0192 (11)
H8A	0.5000	0.4922	0.0828	0.029*
O9	0.5000	0.2910 (6)	0.3712 (5)	0.0201 (10)
H9A	0.5000	0.1896	0.3440	0.030*
O10	0.6329 (2)	0.2327 (5)	0.1789 (4)	0.0293 (8)
H10A	0.6695	0.2468	0.1308	0.044*
H10B	0.5985	0.2025	0.1297	0.044*
N1	0.6921 (3)	0.9615 (4)	0.3464 (5)	0.0238 (10)
H1A	0.6950	0.9457	0.4356	0.029*
H1B	0.6538	1.0244	0.3276	0.029*
H1C	0.7312	1.0147	0.3174	0.029*
H1D	0.6883	0.8612	0.3052	0.029*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.02190 (18)	0.01799 (18)	0.01954 (18)	0.00123 (11)	−0.00023 (14)	0.00305 (13)
Cd2	0.0246 (3)	0.0116 (2)	0.0161 (2)	0.000	0.000	−0.00027 (18)
S1	0.0206 (6)	0.0174 (5)	0.0172 (5)	0.0020 (4)	−0.0014 (5)	0.0002 (4)
S2	0.0299 (10)	0.0120 (7)	0.0157 (8)	0.000	0.000	−0.0020 (5)
O1	0.051 (3)	0.034 (2)	0.032 (2)	−0.014 (2)	−0.024 (2)	0.0156 (18)
O2	0.028 (2)	0.0217 (15)	0.040 (2)	−0.0028 (14)	−0.0029 (18)	−0.0014 (18)
O3	0.027 (2)	0.036 (3)	0.045 (2)	0.0036 (19)	0.0040 (16)	−0.0123 (17)
O4	0.036 (2)	0.034 (2)	0.0201 (17)	0.0036 (18)	−0.0002 (15)	−0.0073 (15)
O5	0.059 (4)	0.066 (3)	0.051 (3)	0.042 (3)	−0.027 (3)	−0.034 (3)
O6	0.120 (6)	0.016 (2)	0.014 (2)	0.000	0.000	−0.001 (3)
O7	0.063 (4)	0.011 (2)	0.016 (2)	0.000	0.000	−0.0070 (19)
O8	0.031 (3)	0.014 (2)	0.012 (2)	0.000	0.000	−0.0018 (16)
O9	0.023 (3)	0.016 (2)	0.021 (2)	0.000	0.000	0.0034 (17)
O10	0.024 (2)	0.0293 (19)	0.034 (2)	0.0021 (16)	−0.0009 (16)	−0.0066 (17)
N1	0.034 (3)	0.016 (2)	0.022 (2)	0.0022 (15)	−0.0038 (19)	−0.0032 (17)

Geometric parameters (Å, º) top

Cd1—O1	2.228 (4)	S2—O6	1.444 (6)
Cd1—O8	2.266 (3)	S2—O5ⁱⁱ	1.449 (5)
Cd1—O9	2.278 (3)	S2—O5	1.449 (5)
Cd1—O10	2.309 (4)	S2—O7	1.472 (5)
Cd1—O4ⁱ	2.310 (4)	O4—Cd1^v	2.310 (4)
Cd1—O5	2.333 (5)	O6—Cd2^vi	2.358 (6)
Cd1—Cd1ⁱⁱ	3.3439 (8)	O7—Cd2^vii	2.274 (5)
Cd2—O8ⁱⁱⁱ	2.235 (4)	O8—Cd2^vi	2.235 (4)
Cd2—O9	2.241 (5)	O8—Cd1ⁱⁱ	2.266 (3)
Cd2—O7^iv	2.274 (5)	O8—H8A	0.8500
Cd2—O2	2.323 (4)	O9—Cd1ⁱⁱ	2.278 (3)
Cd2—O2ⁱⁱ	2.323 (4)	O9—H9A	0.8501
Cd2—O6ⁱⁱⁱ	2.358 (6)	O10—H10A	0.8500
Cd2—H9A	2.3665	O10—H10B	0.8501
S1—O3	1.456 (4)	N1—H1A	0.9000
S1—O1	1.459 (4)	N1—H1B	0.9001
S1—O4	1.468 (4)	N1—H1C	0.9001
S1—O2	1.475 (4)	N1—H1D	0.9000

O1—Cd1—O8	163.57 (18)	O2—Cd2—Cd1ⁱⁱⁱ	120.64 (10)
O1—Cd1—O9	95.73 (17)	O2ⁱⁱ—Cd2—Cd1ⁱⁱⁱ	69.55 (10)
O8—Cd1—O9	80.52 (14)	O6ⁱⁱⁱ—Cd2—Cd1ⁱⁱⁱ	76.00 (12)
O1—Cd1—O10	94.62 (17)	Cd1^v—Cd2—Cd1ⁱⁱⁱ	51.115 (14)
O8—Cd1—O10	101.21 (15)	O8ⁱⁱⁱ—Cd2—H9A	110.1
O9—Cd1—O10	88.27 (16)	O9—Cd2—H9A	21.0
O1—Cd1—O4ⁱ	86.03 (15)	O7^iv—Cd2—H9A	79.2
O8—Cd1—O4ⁱ	98.85 (13)	O2—Cd2—H9A	88.0
O9—Cd1—O4ⁱ	175.79 (16)	O2ⁱⁱ—Cd2—H9A	88.0
O10—Cd1—O4ⁱ	87.77 (15)	O6ⁱⁱⁱ—Cd2—H9A	157.7
O1—Cd1—O5	79.68 (19)	Cd1^v—Cd2—H9A	123.7
O8—Cd1—O5	85.11 (16)	Cd1ⁱⁱⁱ—Cd2—H9A	123.7
O9—Cd1—O5	99.2 (2)	O3—S1—O1	110.7 (3)
O10—Cd1—O5	171.0 (2)	O3—S1—O4	108.8 (3)
O4ⁱ—Cd1—O5	84.9 (2)	O1—S1—O4	109.4 (3)
O1—Cd1—Cd1ⁱⁱ	126.71 (14)	O3—S1—O2	108.0 (2)
O8—Cd1—Cd1ⁱⁱ	42.45 (9)	O1—S1—O2	109.5 (3)
O9—Cd1—Cd1ⁱⁱ	42.79 (8)	O4—S1—O2	110.3 (3)
O10—Cd1—Cd1ⁱⁱ	111.34 (10)	O6—S2—O5ⁱⁱ	111.2 (3)
O4ⁱ—Cd1—Cd1ⁱⁱ	138.11 (10)	O6—S2—O5	111.2 (3)
O5—Cd1—Cd1ⁱⁱ	77.68 (16)	O5ⁱⁱ—S2—O5	108.3 (6)
O1—Cd1—Cd2^vi	141.66 (12)	O6—S2—O7	110.2 (3)
O8—Cd1—Cd2^vi	30.33 (10)	O5ⁱⁱ—S2—O7	107.9 (2)
O9—Cd1—Cd2^vi	106.86 (9)	O5—S2—O7	107.9 (2)
O10—Cd1—Cd2^vi	116.18 (10)	S1—O1—Cd1	140.5 (3)
O4ⁱ—Cd1—Cd2^vi	73.69 (10)	S1—O2—Cd2	128.9 (2)
O5—Cd1—Cd2^vi	66.61 (14)	S1—O4—Cd1^v	123.9 (2)
Cd1ⁱⁱ—Cd1—Cd2^vi	64.443 (7)	S2—O5—Cd1	130.8 (3)
O8ⁱⁱⁱ—Cd2—O9	89.07 (18)	S2—O6—Cd2^vi	120.6 (3)
O8ⁱⁱⁱ—Cd2—O7^iv	170.68 (18)	S2—O7—Cd2^vii	133.0 (3)
O9—Cd2—O7^iv	100.25 (17)	Cd2^vi—O8—Cd1ⁱⁱ	118.87 (13)
O8ⁱⁱⁱ—Cd2—O2	95.29 (9)	Cd2^vi—O8—Cd1	118.87 (13)
O9—Cd2—O2	89.88 (12)	Cd1ⁱⁱ—O8—Cd1	95.09 (18)
O7^iv—Cd2—O2	84.82 (8)	Cd2^vi—O8—H8A	99.4
O8ⁱⁱⁱ—Cd2—O2ⁱⁱ	95.29 (9)	Cd1ⁱⁱ—O8—H8A	112.7
O9—Cd2—O2ⁱⁱ	89.88 (12)	Cd1—O8—H8A	112.7
O7^iv—Cd2—O2ⁱⁱ	84.82 (9)	Cd2—O9—Cd1ⁱⁱ	121.45 (15)
O2—Cd2—O2ⁱⁱ	169.42 (18)	Cd2—O9—Cd1	121.45 (15)
O8ⁱⁱⁱ—Cd2—O6ⁱⁱⁱ	92.24 (18)	Cd1ⁱⁱ—O9—Cd1	94.41 (17)
O9—Cd2—O6ⁱⁱⁱ	178.69 (19)	Cd2—O9—H9A	87.8
O7^iv—Cd2—O6ⁱⁱⁱ	78.44 (18)	Cd1ⁱⁱ—O9—H9A	117.0
O2—Cd2—O6ⁱⁱⁱ	90.00 (12)	Cd1—O9—H9A	117.0
O2ⁱⁱ—Cd2—O6ⁱⁱⁱ	90.00 (12)	Cd1—O10—H10A	118.4
O8ⁱⁱⁱ—Cd2—Cd1^v	30.80 (7)	Cd1—O10—H10B	103.5
O9—Cd2—Cd1^v	105.18 (11)	H10A—O10—H10B	109.5
O7^iv—Cd2—Cd1^v	143.41 (9)	H1A—N1—H1B	109.5
O2—Cd2—Cd1^v	69.55 (10)	H1A—N1—H1C	109.5
O2ⁱⁱ—Cd2—Cd1^v	120.64 (10)	H1B—N1—H1C	109.5
O6ⁱⁱⁱ—Cd2—Cd1^v	76.00 (12)	H1A—N1—H1D	109.5
O8ⁱⁱⁱ—Cd2—Cd1ⁱⁱⁱ	30.80 (7)	H1B—N1—H1D	109.5
O9—Cd2—Cd1ⁱⁱⁱ	105.18 (11)	H1C—N1—H1D	109.5
O7^iv—Cd2—Cd1ⁱⁱⁱ	143.41 (9)

O3—S1—O1—Cd1	105.4 (5)	O5—S2—O7—Cd2^vii	121.6 (4)
O4—S1—O1—Cd1	−134.6 (5)	O1—Cd1—O8—Cd2^vi	72.2 (6)
O2—S1—O1—Cd1	−13.6 (6)	O9—Cd1—O8—Cd2^vi	150.2 (2)
O8—Cd1—O1—S1	106.0 (6)	O10—Cd1—O8—Cd2^vi	−123.5 (2)
O9—Cd1—O1—S1	30.2 (6)	O4ⁱ—Cd1—O8—Cd2^vi	−34.0 (2)
O10—Cd1—O1—S1	−58.5 (6)	O5—Cd1—O8—Cd2^vi	50.0 (3)
O4ⁱ—Cd1—O1—S1	−146.0 (6)	Cd1ⁱⁱ—Cd1—O8—Cd2^vi	127.1 (3)
O5—Cd1—O1—S1	128.5 (6)	O1—Cd1—O8—Cd1ⁱⁱ	−54.8 (6)
Cd1ⁱⁱ—Cd1—O1—S1	62.5 (6)	O9—Cd1—O8—Cd1ⁱⁱ	23.12 (17)
Cd2^vi—Cd1—O1—S1	156.8 (4)	O10—Cd1—O8—Cd1ⁱⁱ	109.44 (16)
O3—S1—O2—Cd2	−171.0 (3)	O4ⁱ—Cd1—O8—Cd1ⁱⁱ	−161.09 (15)
O1—S1—O2—Cd2	−50.3 (4)	O5—Cd1—O8—Cd1ⁱⁱ	−77.1 (2)
O4—S1—O2—Cd2	70.2 (4)	Cd2^vi—Cd1—O8—Cd1ⁱⁱ	−127.1 (3)
O8ⁱⁱⁱ—Cd2—O2—S1	−18.0 (4)	O8ⁱⁱⁱ—Cd2—O9—Cd1ⁱⁱ	−59.33 (18)
O9—Cd2—O2—S1	71.1 (4)	O7^iv—Cd2—O9—Cd1ⁱⁱ	120.67 (18)
O7^iv—Cd2—O2—S1	171.4 (4)	O2—Cd2—O9—Cd1ⁱⁱ	−154.6 (2)
O2ⁱⁱ—Cd2—O2—S1	159.8 (9)	O2ⁱⁱ—Cd2—O9—Cd1ⁱⁱ	36.0 (2)
O6ⁱⁱⁱ—Cd2—O2—S1	−110.2 (4)	Cd1^v—Cd2—O9—Cd1ⁱⁱ	−85.89 (17)
Cd1^v—Cd2—O2—S1	−35.2 (3)	Cd1ⁱⁱⁱ—Cd2—O9—Cd1ⁱⁱ	−32.8 (2)
Cd1ⁱⁱⁱ—Cd2—O2—S1	−36.5 (4)	O8ⁱⁱⁱ—Cd2—O9—Cd1	59.33 (18)
O3—S1—O4—Cd1^v	175.6 (3)	O7^iv—Cd2—O9—Cd1	−120.67 (18)
O1—S1—O4—Cd1^v	54.5 (3)	O2—Cd2—O9—Cd1	−36.0 (2)
O2—S1—O4—Cd1^v	−66.0 (3)	O2ⁱⁱ—Cd2—O9—Cd1	154.6 (2)
O6—S2—O5—Cd1	−77.9 (6)	Cd1^v—Cd2—O9—Cd1	32.8 (2)
O5ⁱⁱ—S2—O5—Cd1	44.7 (8)	Cd1ⁱⁱⁱ—Cd2—O9—Cd1	85.89 (17)
O7—S2—O5—Cd1	161.1 (5)	O1—Cd1—O9—Cd2	9.6 (2)
O1—Cd1—O5—S2	−156.4 (6)	O8—Cd1—O9—Cd2	−154.3 (2)
O8—Cd1—O5—S2	17.4 (6)	O10—Cd1—O9—Cd2	104.0 (2)
O9—Cd1—O5—S2	−62.2 (6)	O5—Cd1—O9—Cd2	−70.9 (2)
O4ⁱ—Cd1—O5—S2	116.8 (6)	Cd1ⁱⁱ—Cd1—O9—Cd2	−131.3 (3)
Cd1ⁱⁱ—Cd1—O5—S2	−24.9 (5)	Cd2^vi—Cd1—O9—Cd2	−139.10 (15)
Cd2^vi—Cd1—O5—S2	42.3 (5)	O1—Cd1—O9—Cd1ⁱⁱ	140.89 (19)
O5ⁱⁱ—S2—O6—Cd2^vi	−60.4 (3)	O8—Cd1—O9—Cd1ⁱⁱ	−22.97 (17)
O5—S2—O6—Cd2^vi	60.4 (3)	O10—Cd1—O9—Cd1ⁱⁱ	−124.63 (17)
O7—S2—O6—Cd2^vi	180.0	O5—Cd1—O9—Cd1ⁱⁱ	60.45 (19)
O6—S2—O7—Cd2^vii	0.000 (2)	Cd2^vi—Cd1—O9—Cd1ⁱⁱ	−7.76 (18)
O5ⁱⁱ—S2—O7—Cd2^vii	−121.6 (4)

Symmetry codes: (i) x, −y+1, z−1/2; (ii) −x+1, y, z; (iii) −x+1, −y+1, z+1/2; (iv) x, y−1, z; (v) x, −y+1, z+1/2; (vi) −x+1, −y+1, z−1/2; (vii) x, y+1, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10B···O7^vi	0.85	2.25	3.087 (5)	167
O10—H10B···O5ⁱ	0.85	2.36	2.985 (6)	131
O9—H9A···O6^iv	0.85	2.18	3.029 (7)	173
O8—H8A···O5ⁱ	0.85	2.56	3.322 (9)	150
O8—H8A···O5^vi	0.85	2.56	3.322 (9)	150
N1—H1B···O10^vii	0.90	2.26	2.948 (6)	133
N1—H1D···O4ⁱ	0.90	2.18	3.077 (5)	180
N1—H1C···O4^viii	0.90	2.19	3.074 (7)	168
N1—H1A···O3^ix	0.90	2.38	2.995 (6)	126
N1—H1D···O2ⁱ	0.90	2.64	3.196 (7)	121

Symmetry codes: (i) x, −y+1, z−1/2; (iv) x, y−1, z; (vi) −x+1, −y+1, z−1/2; (vii) x, y+1, z; (viii) −x+3/2, −y+3/2, z−1/2; (ix) −x+3/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula	Cd₃H₆O₁₆S₃·2NH₄
M_r	731.51
Crystal system, space group	Orthorhombic, Cmc2₁
Temperature (K)	296
a, b, c (Å)	18.906 (3), 7.9483 (11), 9.9809 (13)
V (Å³)	1499.8 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	4.72
Crystal size (mm)	0.12 × 0.10 × 0.08

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.601, 0.704
No. of measured, independent and observed [I > 2σ(I)] reflections	7060, 1770, 1739
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.066, 1.08
No. of reflections	1770
No. of parameters	118
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.68, −1.31
Absolute structure	Flack (1983), 825 Friedel pairs
Absolute structure parameter	−0.07 (4)

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2003), SHELXTL (Sheldrick, 2008), Mercury (Macrae et al., 2006) and DIAMOND (Brandenburg, 2006).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O10—H10B···O7ⁱ	0.85	2.25	3.087 (5)	167
O10—H10B···O5ⁱⁱ	0.85	2.36	2.985 (6)	131
O9—H9A···O6ⁱⁱⁱ	0.85	2.18	3.029 (7)	173
O8—H8A···O5ⁱⁱ	0.85	2.56	3.322 (9)	150
O8—H8A···O5ⁱ	0.85	2.56	3.322 (9)	150
N1—H1B···O10^iv	0.90	2.26	2.948 (6)	133
N1—H1D···O4ⁱⁱ	0.90	2.18	3.077 (5)	180
N1—H1C···O4^v	0.90	2.19	3.074 (7)	168
N1—H1A···O3^vi	0.90	2.38	2.995 (6)	126
N1—H1D···O2ⁱⁱ	0.90	2.64	3.196 (7)	121

Symmetry codes: (i) −x+1, −y+1, z−1/2; (ii) x, −y+1, z−1/2; (iii) x, y−1, z; (iv) x, y+1, z; (v) −x+3/2, −y+3/2, z−1/2; (vi) −x+3/2, y+1/2, z.

References

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2001). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2003). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Louer, M. & Louer, D. (1982). Rev. Chim. Miner.19, 162-171. Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2003). SADABS. University of Gοttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Swain, D. & Guru Row, T. N. (2006). Acta Cryst. E62, i74–i76. Web of Science CrossRef IUCr Journals Google Scholar

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Volume 67| Part 5| May 2011| Page i31

doi:10.1107/S1600536811012979

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