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

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ISSN: 2056-9890

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

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[Hand, D. W. & Prout, C. K. (1966). J. Chem. Soc. A, pp. 168-171.]). 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[Prout, C. K. & Powell, H. M. (1961). J. Chem. Soc. pp. 4177-4182.]). More recently, chromous hydrazinium sulfate, [Cr(N2H5)2](SO4)2, was fortuitously isolated as single crystals from a well tried reaction (Palmer, 1954[Palmer, W. G. (1954). Experimental Inorganic Chemistry, p. 381. Cambridge University Press.]) that usually generates a powder, and its crystal structure was subsequently determined (Parkins et al., 2001[Parkins, A. W., Prince, P. D., Smith, R. A. L. & Steed, J. W. (2001). Acta Cryst. C57, 670-671.]). 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[Prout, C. K. & Powell, H. M. (1961). J. Chem. Soc. pp. 4177-4182.]) and [Cr(N2H5)2](SO4)2 (Parkins et al., 2001[Parkins, A. W., Prince, P. D., Smith, R. A. L. & Steed, J. W. (2001). Acta Cryst. C57, 670-671.]).

Compound (I) contains trans-CdN2O4 octa­hedra (Fig. 1[link]), 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[link]). 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[Parkins, A. W., Prince, P. D., Smith, R. A. L. & Steed, J. W. (2001). Acta Cryst. C57, 670-671.]).

The crystal packing in (I) is influenced by N—H⋯O hydrogen bonds (Table 2[link]). 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[link]); 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[link]).

[Figure 1]
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]
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[link].
[Figure 3]
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 [MII(N2H5)2](SO4)2 compounds.

Crystal data
  • [Cd(SO4)2(N2H5)2]

  • Mr = 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

  • Dx = 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[Bruker (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.314, Tmax = 0.595 (expected range = 0.296–0.560)

  • 5260 measured reflections

  • 1036 independent reflections

  • 1032 reflections with I > 2σ(I)

  • Rint = 0.023

  • θmax = 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(Fo2) + (0.002P)2 + 0.3006P] where P = (Fo2 + 2Fc2)/3

  • (Δ/σ)max = 0.001

  • Δρmax = 0.38 e Å−3

  • Δρmin = −0.52 e Å−3

  • Extinction correction: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.])

  • 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 DA D—H⋯A
N1—H1A⋯O3iii 0.93 (3) 2.17 (3) 2.988 (2) 146 (2)
N1—H1B⋯O4iv 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⋯O2v 0.83 (3) 2.34 (3) 2.876 (2) 123 (2)
N2—H2C⋯O2iv 0.83 (3) 2.44 (3) 2.964 (2) 121 (2)
N2—H2C⋯O1vi 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 Uiso values were freely refined. N—H distances are listed in Table 2[link].

Data collection: COLLECT (Nonius, 1998[Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: SCALEPACK (Otwinowski & Minor, 1997[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.]); data reduction: SCALEPACK, DENZO (Otwinowski & Minor, 1997[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.]) and SORTAV (Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-38.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); software used to prepare material for publication: SHELXL97.

Supporting information


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.

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 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 [MII(N2H5)2](SO4)2 compounds.

Refinement top

The H atoms were located in difference maps and their positions and Uiso values were freely refined. [Range of refined N—H distances?]

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
[Figure 1] 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.]
[Figure 2] 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.
[Figure 3] 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
Mr = 370.64F(000) = 182
Triclinic, P1Dx = 2.704 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 5.4835 (2) ÅCell parameters from 1033 reflections
b = 5.9034 (1) Åθ = 1.0–27.5°
c = 7.3624 (2) ŵ = 2.90 mm1
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 tube1032 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
ϕ and ω scansθmax = 27.5°, θmin = 3.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2003)
h = 77
Tmin = 0.314, Tmax = 0.595k = 77
5260 measured reflectionsl = 99
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.013All H-atom parameters refined
wR(F2) = 0.032 w = 1/[σ2(Fo2) + (0.002P)2 + 0.3006P]
where P = (Fo2 + 2Fc2)/3
S = 1.14(Δ/σ)max = 0.001
1036 reflectionsΔρmax = 0.38 e Å3
91 parametersΔρmin = 0.52 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.176 (5)
Crystal data top
[Cd(SO4)2(N2H5)2]γ = 99.7984 (18)°
Mr = 370.64V = 227.61 (1) Å3
Triclinic, P1Z = 1
a = 5.4835 (2) ÅMo Kα radiation
b = 5.9034 (1) ŵ = 2.90 mm1
c = 7.3624 (2) ÅT = 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)
Tmin = 0.314, Tmax = 0.595Rint = 0.023
5260 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0130 restraints
wR(F2) = 0.032All H-atom parameters refined
S = 1.14Δρmax = 0.38 e Å3
1036 reflectionsΔρmin = 0.52 e Å3
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
xyzUiso*/Ueq
Cd10.00000.00000.00000.00581 (10)
S10.64505 (7)0.26136 (7)0.22259 (6)0.00434 (11)
O10.3921 (2)0.2413 (2)0.09232 (19)0.0115 (3)
O20.8452 (2)0.2967 (2)0.11515 (17)0.0078 (3)
O30.6639 (2)0.0524 (2)0.32514 (18)0.0091 (3)
O40.6894 (2)0.4654 (2)0.35697 (17)0.0074 (2)
N10.0764 (3)0.1853 (3)0.2717 (2)0.0067 (3)
H1A0.129 (5)0.089 (4)0.382 (4)0.017 (6)*
H1B0.049 (5)0.275 (5)0.284 (4)0.020 (6)*
N20.2749 (3)0.3221 (3)0.2844 (2)0.0073 (3)
H2A0.293 (5)0.392 (4)0.389 (4)0.013 (6)*
H2B0.418 (5)0.231 (5)0.287 (4)0.019 (6)*
H2C0.238 (5)0.415 (5)0.190 (4)0.014 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cd10.00511 (12)0.00545 (12)0.00648 (12)0.00149 (6)0.00025 (7)0.00081 (6)
S10.0034 (2)0.0045 (2)0.0050 (2)0.00012 (15)0.00116 (15)0.00009 (15)
O10.0054 (6)0.0120 (6)0.0139 (6)0.0008 (5)0.0023 (5)0.0016 (5)
O20.0081 (6)0.0072 (6)0.0098 (6)0.0010 (5)0.0058 (5)0.0005 (5)
O30.0111 (6)0.0062 (6)0.0099 (6)0.0009 (5)0.0026 (5)0.0027 (5)
O40.0097 (6)0.0060 (6)0.0067 (6)0.0013 (5)0.0030 (5)0.0014 (4)
N10.0042 (7)0.0069 (7)0.0092 (8)0.0012 (6)0.0023 (6)0.0011 (6)
N20.0076 (7)0.0070 (7)0.0075 (8)0.0027 (6)0.0011 (6)0.0014 (6)
Geometric parameters (Å, º) top
Cd1—O2i2.2890 (12)S1—O21.4880 (12)
Cd1—O2ii2.2890 (12)O2—Cd1iv2.2890 (12)
Cd1—N12.3018 (15)N1—N21.450 (2)
Cd1—N1iii2.3018 (15)N1—H1A0.93 (3)
Cd1—O1iii2.3058 (12)N1—H1B0.82 (3)
Cd1—O12.3058 (12)N2—H2A0.88 (3)
S1—O11.4735 (13)N2—H2B0.87 (3)
S1—O31.4759 (13)N2—H2C0.83 (3)
S1—O41.4793 (12)
O2i—Cd1—O2ii180.0O1—S1—O2109.26 (8)
O2i—Cd1—N196.98 (5)O3—S1—O2109.43 (7)
O2ii—Cd1—N183.02 (5)O4—S1—O2107.98 (7)
O2i—Cd1—N1iii83.02 (5)S1—O1—Cd1141.72 (8)
O2ii—Cd1—N1iii96.98 (5)S1—O2—Cd1iv123.18 (7)
N1—Cd1—N1iii180.0N2—N1—Cd1113.54 (10)
O2i—Cd1—O1iii94.68 (5)N2—N1—H1A103.8 (16)
O2ii—Cd1—O1iii85.32 (5)Cd1—N1—H1A115.3 (16)
N1—Cd1—O1iii88.39 (5)N2—N1—H1B105.4 (18)
N1iii—Cd1—O1iii91.61 (5)Cd1—N1—H1B112.8 (19)
O2i—Cd1—O185.32 (5)H1A—N1—H1B105 (2)
O2ii—Cd1—O194.68 (5)N1—N2—H2A109.8 (15)
N1—Cd1—O191.61 (5)N1—N2—H2B108.9 (17)
N1iii—Cd1—O188.39 (5)H2A—N2—H2B108 (2)
O1iii—Cd1—O1180.0N1—N2—H2C108.8 (17)
O1—S1—O3111.11 (8)H2A—N2—H2C112 (2)
O1—S1—O4109.22 (8)H2B—N2—H2C109 (2)
O3—S1—O4109.79 (7)
O3—S1—O1—Cd14.06 (16)O1—S1—O2—Cd1iv92.03 (9)
O4—S1—O1—Cd1117.19 (13)O3—S1—O2—Cd1iv29.82 (10)
O2—S1—O1—Cd1124.90 (12)O4—S1—O2—Cd1iv149.29 (8)
O2i—Cd1—O1—S1116.20 (14)O2i—Cd1—N1—N2154.09 (11)
O2ii—Cd1—O1—S163.80 (14)O2ii—Cd1—N1—N225.91 (11)
N1—Cd1—O1—S119.33 (14)O1iii—Cd1—N1—N2111.39 (12)
N1iii—Cd1—O1—S1160.67 (14)O1—Cd1—N1—N268.61 (12)
Symmetry codes: (i) x1, y, z; (ii) x+1, y, z; (iii) x, y, z; (iv) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3v0.93 (3)2.17 (3)2.988 (2)146 (2)
N1—H1B···O4vi0.82 (3)2.09 (3)2.8949 (19)167 (3)
N2—H2A···O4v0.88 (3)1.92 (3)2.776 (2)164 (2)
N2—H2B···O30.87 (3)1.93 (3)2.753 (2)158 (2)
N2—H2C···O2ii0.83 (3)2.34 (3)2.876 (2)123 (2)
N2—H2C···O2vi0.83 (3)2.44 (3)2.964 (2)121 (2)
N2—H2C···O1vii0.83 (3)2.47 (3)3.127 (2)136 (2)
Symmetry codes: (ii) x+1, y, z; (v) x+1, y, z+1; (vi) x1, y1, z; (vii) x, y1, z.

Experimental details

Crystal data
Chemical formula[Cd(SO4)2(N2H5)2]
Mr370.64
Crystal system, space groupTriclinic, 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)
V3)227.61 (1)
Z1
Radiation typeMo Kα
µ (mm1)2.90
Crystal size (mm)0.52 × 0.38 × 0.20
Data collection
DiffractometerNonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2003)
Tmin, Tmax0.314, 0.595
No. of measured, independent and
observed [I > 2σ(I)] reflections
5260, 1036, 1032
Rint0.023
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.013, 0.032, 1.14
No. of reflections1036
No. of parameters91
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)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—O2i2.2890 (12)Cd1—O12.3058 (12)
Cd1—N12.3018 (15)
S1—O1—Cd1141.72 (8)S1—O2—Cd1ii123.18 (7)
Symmetry codes: (i) x1, y, z; (ii) x+1, y, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3iii0.93 (3)2.17 (3)2.988 (2)146 (2)
N1—H1B···O4iv0.82 (3)2.09 (3)2.8949 (19)167 (3)
N2—H2A···O4iii0.88 (3)1.92 (3)2.776 (2)164 (2)
N2—H2B···O30.87 (3)1.93 (3)2.753 (2)158 (2)
N2—H2C···O2v0.83 (3)2.34 (3)2.876 (2)123 (2)
N2—H2C···O2iv0.83 (3)2.44 (3)2.964 (2)121 (2)
N2—H2C···O1vi0.83 (3)2.47 (3)3.127 (2)136 (2)
Symmetry codes: (iii) x+1, y, z+1; (iv) x1, y1, z; (v) x+1, y, z; (vi) x, y1, z.
 

Acknowledgements

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

References

First citationBlessing, R. H. (1995). Acta Cryst. A51, 33–38.  CrossRef CAS Web of Science IUCr Journals Google Scholar
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First citationOtwinowski, 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
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