catena-Poly[[dihydrazinecadmium(II)]-di-μ-sulfato-κ4O:O′]

Srinivasan, K.; Govindarajan, S.; Harrison, W.T.A.

doi:10.1107/S1600536806039511

inorganic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 62| Part 11| November 2006| Pages i219-i221

doi:10.1107/S1600536806039511

catena-Poly[[dihydrazinecadmium(II)]-di-μ-sulfato-κ⁴O:O′]

Krishnan Srinivasan,^a Subbaiah Govindarajan ^a and William T. A. Harrison ^b ^*

^aDepartment of Chemistry, Bharathiar University, Coimbatore 641 046, India, and ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 19 September 2006; accepted 26 September 2006; online 4 October 2006)

The title compound, {[Cd(SO₄)₂(N₂H₅)₂]}_n, contains fairly regular trans-CdN₂O₄ octahedra. The Cd atoms (site symmetry $[\overline{1}]$ ) are bridged by pairs of sulfate groups into infinite chains. A network of N—H⋯O hydrogen bonds, including a well defined trifurcated N—H⋯(O,O,O) link, completes the structure, which is isostructural with its zinc(II) and chromium(II) analogues.

Comment

The divalent-metal–hydrazinium sulfates of general formula [M(N₂H₅)₂](SO₄)₂, where M = Cr, Mn, Fe, Co, Ni, Cu, Zn and Cd, are readily prepared by reacting a salt of the respective metal with hydrazinium sulfate in dilute sulfuric acid (Hand & Prout, 1966 ). This method usually results in the formation of microcrystalline solids unsuitable for single-crystal X-ray studies, except for the zinc compound, which was obtained as twinned crystals (Prout & Powell, 1961 ). More recently, chromous hydrazinium sulfate, [Cr(N₂H₅)₂](SO₄)₂, was fortuitously isolated as single crystals from a well tried reaction (Palmer, 1954 ) that usually generates a powder, and its crystal structure was subsequently determined (Parkins et al., 2001 ). The title compound, (I), arose unexpectedly during our attempts to prepare metal complexes with the hydrazinoacetate (NH₂—NH—CH₂—COO⁻) anion. It is isostructural with [Zn(N₂H₅)₂](SO₄)₂ (Prout & Powell, 1961) and [Cr(N₂H₅)₂](SO₄)₂ (Parkins et al., 2001).

Compound (I) contains trans-CdN₂O₄ octahedra (Fig. 1), where the N atom is part of a hydrazinium (N₂H₅⁺) cation. The Cd atoms (site symmetry $[\overline{1}]$ ) are connected by pairs of sulfate groups into infinite chains that propagate in the [100] direction. In the previously studied compounds, a different setting of the triclinic cell was used and the equivalent chains in these materials propagate in the [010] direction. The separation of the Cd nodes in (I) is equal to the a unit-cell dimension, i.e. 5.4835 (2) Å. The equivalent metal⋯metal separations for the Zn and Cr compounds are 5.33 and 5.4568 (5) Å, respectively.

Unlike the situation in the zinc and chromium analogues, where there is a substantial asymmetry in the two distinct M—O bond lengths [2.10 and 2.38 Å for Zn, and 2.0535 (17) and 2.3791 (19) Å for Cr], the two distinct Cd—O bond lengths in (I) are very similar (Table 1). The N—N bond length in (I) of 1.450 (2) Å is much shorter than the equivalent value of 1.56 Å reported for the Zn compound, but is almost identical to the value of 1.453 (3) Å found for [Cr(N₂H₅)₂](SO₄)₂ (Parkins et al., 2001).

The crystal packing in (I) is influenced by N—H⋯O hydrogen bonds (Table 2). It appears to be similar to the scheme proposed for [Zn(N₂H₅)₂](SO₄)₂ and is the same as that observed in [Cr(N₂H₅)₂](SO₄)₂. Four of the N—H bonds participate in simple N—H⋯O interactions [mean N—H = 0.88 (3), mean H⋯O = 2.03 (3) and mean N⋯O = 2.853 (3) Å; mean N—H⋯O = 159 (3)°]. The other H atom, H2C, is involved in a well defined trifurcated (four-centre) N—H⋯(O,O,O) bond (Fig. 2); the bond-angle sum about H2C is 107°. The packing for (I) involves the Cd/sulfate chains propagating in the [100] direction, with crosslinking in the [010] and [001] directions via the N—H⋯O hydrogen bonds (Fig. 3).

Figure 1
A view of part of the chain stucture in (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 70% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) −x, −y, −z; (ii) 1 − x, −y, −z; (iii) x − 1, y, z; (iv) x + 1, y, z.]

Figure 2
Detail of (I), showing the trifurcated N2—H2C⋯(O,O,O) hydrogen bonds as dashed lines. Displacement ellipsoids are drawn at the 70% probability level and H atoms are shown as small spheres of arbitrary radii. Symmetry codes are as in Table 2

Figure 3
The packing in (I) in a polyhedral representation, with N—H⋯O hydrogen bonds indicated by dashed lines. Colour key: CdN₂O₄ octahedra are blue–grey, SO₄ tetrahedra green, N atoms blue, O atoms beige and H atoms dark grey.

Experimental

In an attempt to synthesize ethyl hydrazinoacetate, 99%+ hydrazine hydrate (N₂H₄·H₂O; 0.50 g, 10 mmol) and ethyl bromoacetate (1.671 g, 10 mmol) were reacted together in dry ethanol (5 ml), resulting in a white solid. The white solid (0.236 g, 2 mmol) was dissolved in water (30 ml) and mixed with an aqueous solution (30 ml) of 3CdSO₄·8H₂O (0.769 g, 1 mmol). The resulting clear solution, with a pH of 3, was kept for crystallization at room temperature. Within 1 d, many faceted block-shaped crystals of (I) were visible. These were recovered by filtration, washed with cold water and dried in air. Later analysis of the previously obtained white solid suggested the presence of hydrazinium bromide as well as ethyl hydrazinoacetate. The detailed mechanism that results in the formation of large single crystals of (I) rather than the usual powder is unknown, but the reaction is reproducible and may also be used to prepare single crystals of other [M^II(N₂H₅)₂](SO₄)₂ compounds.

Crystal data

[Cd(SO₄)₂(N₂H₅)₂]
M_r = 370.64
Triclinic, $[P \overline 1]$
a = 5.4835 (2) Å
b = 5.9034 (1) Å
c = 7.3624 (2) Å
α = 92.116 (2)°
β = 103.5206 (16)°
γ = 99.7984 (18)°
V = 227.61 (1) Å³
Z = 1
D_x = 2.704 Mg m⁻³
Mo Kα radiation
μ = 2.90 mm⁻¹
T = 120 (2) K
Block, colourless
0.52 × 0.38 × 0.20 mm

Data collection

Nonius KappaCCD area-detector diffractometer
φ and ω scans
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.314, T_max = 0.595 (expected range = 0.296–0.560)
5260 measured reflections
1036 independent reflections
1032 reflections with I > 2σ(I)
R_int = 0.023
θ_max = 27.5°

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.013
wR(F²) = 0.032
S = 1.14
1036 reflections
91 parameters
All H-atom parameters refined
w = 1/[σ²(F_o²) + (0.002P)² + 0.3006P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max = 0.001
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.52 e Å⁻³
Extinction correction: SHELXL97 (Sheldrick, 1997 )
Extinction coefficient: 0.176 (5)

Table 1
Selected geometric parameters (Å, °)

Cd1—O2ⁱ	2.2890 (12)
Cd1—N1	2.3018 (15)
Cd1—O1	2.3058 (12)

S1—O1—Cd1	141.72 (8)
S1—O2—Cd1ⁱⁱ	123.18 (7)
Symmetry codes: (i) x-1, y, z; (ii) x+1, y, z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3ⁱⁱⁱ	0.93 (3)	2.17 (3)	2.988 (2)	146 (2)
N1—H1B⋯O4^iv	0.82 (3)	2.09 (3)	2.8949 (19)	167 (3)
N2—H2A⋯O4ⁱⁱⁱ	0.88 (3)	1.92 (3)	2.776 (2)	164 (2)
N2—H2B⋯O3	0.87 (3)	1.93 (3)	2.753 (2)	158 (2)
N2—H2C⋯O2^v	0.83 (3)	2.34 (3)	2.876 (2)	123 (2)
N2—H2C⋯O2^iv	0.83 (3)	2.44 (3)	2.964 (2)	121 (2)
N2—H2C⋯O1^vi	0.83 (3)	2.47 (3)	3.127 (2)	136 (2)
Symmetry codes: (iii) -x+1, -y, -z+1; (iv) x-1, y-1, z; (v) -x+1, -y, -z; (vi) x, y-1, z.

The H atoms were located in difference maps and their positions and U_iso values were freely refined. N—H distances are listed in Table 2.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK, DENZO (Otwinowski & Minor, 1997) and SORTAV (Blessing, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536806039511/wm2054sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536806039511/wm2054Isup2.hkl

Comment top

The divalent-metal–hydrazinium sulfates of general formula [M(N₂H₅)₂](SO₄)₂, where M = Cr, Mn, Fe, Co, Ni, Cu, Zn and Cd, are readily prepared by reacting a salt of the respective metal with hydrazinium sulfate in dilute sulfuric acid (Hand & Prout, 1966). This method usually results in the formation of microcrystalline solids unsuitable for single-crystal X-ray studies, except for the zinc compound, which was obtained as twinned crystals (Prout & Powell, 1961). More recently, chromous hydrazinium sulfate, [Cr(N₂H₅)₂](SO₄)₂, was fortuitously isolated as single crystals from a well tried reaction (Palmer, 1954) that usually generates a powder, and its crystal structure was subsequently determined (Parkins et al., 2001). The title compound, (I), arose unexpectedly during our attempts to prepare metal complexes with the hydrazinoacetate (NH₂—NH—CH₂—COO⁻) anion. It is isostructural with [Zn(N₂H₅)₂](SO₄)₂ (Prout & Powell, 1961)and [Cr(N₂H₅)₂](SO₄)₂ (Parkins et al., 2001).

Compound (I) contains trans-CdN₂O₄ octahedra (Fig. 1), where the N atom is part of a hydrazinium (N₂H₅⁺) cation. The Cd atoms (site symmetry 1) are connected by pairs of sulfate groups into infinite chains that propagate in the [100] direction. In the previously studied compounds, a different setting of the triclinic cell was used and the equivalent chains in these materials propagate in the [010] direction. The separation of the Cd nodes in (I) is equal to the a unit-cell dimension, i.e. 5.4835 (2) Å. The equivalent metal···metal separations for the Zn and Cr compounds are 5.33 and 5.4568 (5) Å, respectively.

The crystal packing in (I) is influenced by N—H···O hydrogen bonds (Table 2). It appears to be similar to the scheme proposed for [Zn(N₂H₅)₂](SO₄)₂ and is the same as that observed in [Cr(N₂H₅)₂](SO₄)₂. Four of the N—H vertices participate in simple N—H···O interactions [mean N—H = 0.88 (3), mean H···O = 2.03 (3) and mean N···O = 2.853 (3) Å; mean N—H···O = 159 (3)°]. The other H atom, H2C, is involved in a well defined trifurcated (four-centre) N—H···(O,O,O) bond (Fig. 2); the bond-angle sum about H2C is 107.1°. The unit-cell packing for (I) involves the Cd/sulfate chains propagating in the [100] direction, with crosslinking in the [010] and [001] directions via the N—H···O hydrogen bonds (Fig. 3).

Experimental top

In an attempt to synthesize ethyl hydrazinoacetate, hydrazine hydrate (N₂H₄·H₂O; 0.50 g, 10 mmol) and ethyl bromoacetate (1.671 g, 10 mmol) were reacted together in dry ethanol (Volume?), resulting in a white solid. The white solid (0.236 g, 2 mmol) was dissolved in water (30 ml) and mixed with an aqueous solution (30 ml) of 3 CdSO₄·8H₂O (0.769 g, 1 mmol). The resulting clear solution, with a pH of 3, was kept for crystallization at room temperature. Within 1 d, many faceted block-shaped crystals of (I) were visible. These were recovered by filtration, washed with cold water and dried in air. Later analysis of the previously obtained white solid suggested the presence of hydrazinium bromide as well as ethyl hydrazinoacetate. The detailed mechanism that results in the formation of large single crystals of (I) rather than the usual powder is unknown, but the reaction is reproducible and may also be used to prepare single crystals of other [M^II(N₂H₅)₂](SO₄)₂ compounds.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK, DENZO (Otwinowski & Minor, 1997) and SORTAV (Blessing, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. A view of part of the chain stucture in (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 70% probability level and H atoms are shown as small spheres of arbitrary radii. Hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) −x, −y, −z; (ii) 1 − x, −y, −z; (iii) x − 1, y, z; (iv) x + 1, y, z.]
	Fig. 2. Detail of (I), showing the trifurcated N2—H2C···(O,O,O) hydrogen bond as dashed lines. Displacement ellipsoids are drawn at the 70% probability level and H atoms are shown as small spheres of arbitrary radii. Symmetry codes are as in Table 2.
	Fig. 3. The unit-cell packing in (I) in a polyhedral representation, with N—H···O hydrogen bonds indicated by dashed lines. Colour key: CdN₂O₄ octahedra are blue–grey, SO₄ tetrahedra green, N atoms blue, O atoms beige and H atoms dark grey.

catena-Poly[[dihydrazinecadmium(II)]-di-µ-sulfato-κ²O:O'] top

Crystal data top

[Cd(SO₄)₂(N₂H₅)₂]	Z = 1
M_r = 370.64	F(000) = 182
Triclinic, P1	D_x = 2.704 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.4835 (2) Å	Cell parameters from 1033 reflections
b = 5.9034 (1) Å	θ = 1.0–27.5°
c = 7.3624 (2) Å	µ = 2.90 mm⁻¹
α = 92.116 (2)°	T = 120 K
β = 103.5206 (16)°	Block, colourless
γ = 99.7984 (18)°	0.52 × 0.38 × 0.20 mm
V = 227.61 (1) Å³

Data collection top

Nonius KappaCCD area-detector diffractometer	1036 independent reflections
Radiation source: fine-focus sealed tube	1032 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 27.5°, θ_min = 3.9°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −7→7
T_min = 0.314, T_max = 0.595	k = −7→7
5260 measured reflections	l = −9→9

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F² > 2σ(F²)] = 0.013	All H-atom parameters refined
wR(F²) = 0.032	w = 1/[σ²(F_o²) + (0.002P)² + 0.3006P] where P = (F_o² + 2F_c²)/3
S = 1.14	(Δ/σ)_max = 0.001
1036 reflections	Δρ_max = 0.38 e Å⁻³
91 parameters	Δρ_min = −0.52 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.176 (5)

Crystal data top

[Cd(SO₄)₂(N₂H₅)₂]	γ = 99.7984 (18)°
M_r = 370.64	V = 227.61 (1) Å³
Triclinic, P1	Z = 1
a = 5.4835 (2) Å	Mo Kα radiation
b = 5.9034 (1) Å	µ = 2.90 mm⁻¹
c = 7.3624 (2) Å	T = 120 K
α = 92.116 (2)°	0.52 × 0.38 × 0.20 mm
β = 103.5206 (16)°

Data collection top

Nonius KappaCCD area-detector diffractometer	1036 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	1032 reflections with I > 2σ(I)
T_min = 0.314, T_max = 0.595	R_int = 0.023
5260 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.013	0 restraints
wR(F²) = 0.032	All H-atom parameters refined
S = 1.14	Δρ_max = 0.38 e Å⁻³
1036 reflections	Δρ_min = −0.52 e Å⁻³
91 parameters

Special details top

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.

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	0.0000	0.0000	0.0000	0.00581 (10)
S1	0.64505 (7)	0.26136 (7)	0.22259 (6)	0.00434 (11)
O1	0.3921 (2)	0.2413 (2)	0.09232 (19)	0.0115 (3)
O2	0.8452 (2)	0.2967 (2)	0.11515 (17)	0.0078 (3)
O3	0.6639 (2)	0.0524 (2)	0.32514 (18)	0.0091 (3)
O4	0.6894 (2)	0.4654 (2)	0.35697 (17)	0.0074 (2)
N1	0.0764 (3)	−0.1853 (3)	0.2717 (2)	0.0067 (3)
H1A	0.129 (5)	−0.089 (4)	0.382 (4)	0.017 (6)*
H1B	−0.049 (5)	−0.275 (5)	0.284 (4)	0.020 (6)*
N2	0.2749 (3)	−0.3221 (3)	0.2844 (2)	0.0073 (3)
H2A	0.293 (5)	−0.392 (4)	0.389 (4)	0.013 (6)*
H2B	0.418 (5)	−0.231 (5)	0.287 (4)	0.019 (6)*
H2C	0.238 (5)	−0.415 (5)	0.190 (4)	0.014 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cd1	0.00511 (12)	0.00545 (12)	0.00648 (12)	0.00149 (6)	0.00025 (7)	0.00081 (6)
S1	0.0034 (2)	0.0045 (2)	0.0050 (2)	0.00012 (15)	0.00116 (15)	0.00009 (15)
O1	0.0054 (6)	0.0120 (6)	0.0139 (6)	−0.0008 (5)	−0.0023 (5)	0.0016 (5)
O2	0.0081 (6)	0.0072 (6)	0.0098 (6)	0.0010 (5)	0.0058 (5)	−0.0005 (5)
O3	0.0111 (6)	0.0062 (6)	0.0099 (6)	0.0009 (5)	0.0026 (5)	0.0027 (5)
O4	0.0097 (6)	0.0060 (6)	0.0067 (6)	0.0013 (5)	0.0030 (5)	−0.0014 (4)
N1	0.0042 (7)	0.0069 (7)	0.0092 (8)	0.0012 (6)	0.0023 (6)	0.0011 (6)
N2	0.0076 (7)	0.0070 (7)	0.0075 (8)	0.0027 (6)	0.0011 (6)	0.0014 (6)

Geometric parameters (Å, º) top

Cd1—O2ⁱ	2.2890 (12)	S1—O2	1.4880 (12)
Cd1—O2ⁱⁱ	2.2890 (12)	O2—Cd1^iv	2.2890 (12)
Cd1—N1	2.3018 (15)	N1—N2	1.450 (2)
Cd1—N1ⁱⁱⁱ	2.3018 (15)	N1—H1A	0.93 (3)
Cd1—O1ⁱⁱⁱ	2.3058 (12)	N1—H1B	0.82 (3)
Cd1—O1	2.3058 (12)	N2—H2A	0.88 (3)
S1—O1	1.4735 (13)	N2—H2B	0.87 (3)
S1—O3	1.4759 (13)	N2—H2C	0.83 (3)
S1—O4	1.4793 (12)

O2ⁱ—Cd1—O2ⁱⁱ	180.0	O1—S1—O2	109.26 (8)
O2ⁱ—Cd1—N1	96.98 (5)	O3—S1—O2	109.43 (7)
O2ⁱⁱ—Cd1—N1	83.02 (5)	O4—S1—O2	107.98 (7)
O2ⁱ—Cd1—N1ⁱⁱⁱ	83.02 (5)	S1—O1—Cd1	141.72 (8)
O2ⁱⁱ—Cd1—N1ⁱⁱⁱ	96.98 (5)	S1—O2—Cd1^iv	123.18 (7)
N1—Cd1—N1ⁱⁱⁱ	180.0	N2—N1—Cd1	113.54 (10)
O2ⁱ—Cd1—O1ⁱⁱⁱ	94.68 (5)	N2—N1—H1A	103.8 (16)
O2ⁱⁱ—Cd1—O1ⁱⁱⁱ	85.32 (5)	Cd1—N1—H1A	115.3 (16)
N1—Cd1—O1ⁱⁱⁱ	88.39 (5)	N2—N1—H1B	105.4 (18)
N1ⁱⁱⁱ—Cd1—O1ⁱⁱⁱ	91.61 (5)	Cd1—N1—H1B	112.8 (19)
O2ⁱ—Cd1—O1	85.32 (5)	H1A—N1—H1B	105 (2)
O2ⁱⁱ—Cd1—O1	94.68 (5)	N1—N2—H2A	109.8 (15)
N1—Cd1—O1	91.61 (5)	N1—N2—H2B	108.9 (17)
N1ⁱⁱⁱ—Cd1—O1	88.39 (5)	H2A—N2—H2B	108 (2)
O1ⁱⁱⁱ—Cd1—O1	180.0	N1—N2—H2C	108.8 (17)
O1—S1—O3	111.11 (8)	H2A—N2—H2C	112 (2)
O1—S1—O4	109.22 (8)	H2B—N2—H2C	109 (2)
O3—S1—O4	109.79 (7)

O3—S1—O1—Cd1	4.06 (16)	O1—S1—O2—Cd1^iv	−92.03 (9)
O4—S1—O1—Cd1	−117.19 (13)	O3—S1—O2—Cd1^iv	29.82 (10)
O2—S1—O1—Cd1	124.90 (12)	O4—S1—O2—Cd1^iv	149.29 (8)
O2ⁱ—Cd1—O1—S1	116.20 (14)	O2ⁱ—Cd1—N1—N2	−154.09 (11)
O2ⁱⁱ—Cd1—O1—S1	−63.80 (14)	O2ⁱⁱ—Cd1—N1—N2	25.91 (11)
N1—Cd1—O1—S1	19.33 (14)	O1ⁱⁱⁱ—Cd1—N1—N2	111.39 (12)
N1ⁱⁱⁱ—Cd1—O1—S1	−160.67 (14)	O1—Cd1—N1—N2	−68.61 (12)

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y, −z; (iii) −x, −y, −z; (iv) x+1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3^v	0.93 (3)	2.17 (3)	2.988 (2)	146 (2)
N1—H1B···O4^vi	0.82 (3)	2.09 (3)	2.8949 (19)	167 (3)
N2—H2A···O4^v	0.88 (3)	1.92 (3)	2.776 (2)	164 (2)
N2—H2B···O3	0.87 (3)	1.93 (3)	2.753 (2)	158 (2)
N2—H2C···O2ⁱⁱ	0.83 (3)	2.34 (3)	2.876 (2)	123 (2)
N2—H2C···O2^vi	0.83 (3)	2.44 (3)	2.964 (2)	121 (2)
N2—H2C···O1^vii	0.83 (3)	2.47 (3)	3.127 (2)	136 (2)

Symmetry codes: (ii) −x+1, −y, −z; (v) −x+1, −y, −z+1; (vi) x−1, y−1, z; (vii) x, y−1, z.

Experimental details

Crystal data
Chemical formula	[Cd(SO₄)₂(N₂H₅)₂]
M_r	370.64
Crystal system, space group	Triclinic, P1
Temperature (K)	120
a, b, c (Å)	5.4835 (2), 5.9034 (1), 7.3624 (2)
α, β, γ (°)	92.116 (2), 103.5206 (16), 99.7984 (18)
V (Å³)	227.61 (1)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	2.90
Crystal size (mm)	0.52 × 0.38 × 0.20

Data collection
Diffractometer	Nonius KappaCCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.314, 0.595
No. of measured, independent and observed [I > 2σ(I)] reflections	5260, 1036, 1032
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.013, 0.032, 1.14
No. of reflections	1036
No. of parameters	91
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.52

Computer programs: COLLECT (Nonius, 1998), SCALEPACK (Otwinowski & Minor, 1997), SCALEPACK, DENZO (Otwinowski & Minor, 1997) and SORTAV (Blessing, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.

Selected geometric parameters (Å, º) top

Cd1—O2ⁱ	2.2890 (12)	Cd1—O1	2.3058 (12)
Cd1—N1	2.3018 (15)

S1—O1—Cd1	141.72 (8)	S1—O2—Cd1ⁱⁱ	123.18 (7)

Symmetry codes: (i) x−1, y, z; (ii) x+1, y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱⁱⁱ	0.93 (3)	2.17 (3)	2.988 (2)	146 (2)
N1—H1B···O4^iv	0.82 (3)	2.09 (3)	2.8949 (19)	167 (3)
N2—H2A···O4ⁱⁱⁱ	0.88 (3)	1.92 (3)	2.776 (2)	164 (2)
N2—H2B···O3	0.87 (3)	1.93 (3)	2.753 (2)	158 (2)
N2—H2C···O2^v	0.83 (3)	2.34 (3)	2.876 (2)	123 (2)
N2—H2C···O2^iv	0.83 (3)	2.44 (3)	2.964 (2)	121 (2)
N2—H2C···O1^vi	0.83 (3)	2.47 (3)	3.127 (2)	136 (2)

Symmetry codes: (iii) −x+1, −y, −z+1; (iv) x−1, y−1, z; (v) −x+1, −y, −z; (vi) x, y−1, z.

Acknowledgements

We thank the EPSRC National Crystallography Service (University of Southampton) for the data collection.

References

Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Bruker (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Hand, D. W. & Prout, C. K. (1966). J. Chem. Soc. A, pp. 168–171. CrossRef Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Palmer, W. G. (1954). Experimental Inorganic Chemistry, p. 381. Cambridge University Press. Google Scholar
Parkins, A. W., Prince, P. D., Smith, R. A. L. & Steed, J. W. (2001). Acta Cryst. C57, 670–671. CrossRef CAS IUCr Journals Google Scholar
Prout, C. K. & Powell, H. M. (1961). J. Chem. Soc. pp. 4177–4182. CrossRef Web of Science Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar

© International Union of Crystallography. Prior permission is not required to reproduce short quotations, tables and figures from this article, provided the original authors and source are cited. For more information, click here.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 62| Part 11| November 2006| Pages i219-i221

doi:10.1107/S1600536806039511

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

inorganic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)