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Acta Cryst. (2007). E63, i152    [ doi:10.1107/S1600536807024579 ]

catena-Poly[[dihydraziniummanganese(II)]-di-[mu]-sulfato-[kappa]4O:O'] from synchrotron data

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

Abstract top

The title compound, [Mn(N2H5)2(SO4)2]n, contains fairly regular trans-MnN2O4 octahedra. The Mn atoms (site symmetry \overline{1}) are bridged by pairs of sulfate groups into infinite [100] chains, which are cross-linked by a network of N-H...O hydrogen bonds arising from the hydrazinium groups. Mn(N2H5)2(SO4)2 is isostructural with its iron, zinc, chromium and cadmium-containing analogues.

Comment top

The title compound, (I), was prepared as part of our ongoing structural studies of the MII(N2H5)2(SO4)2 family of compounds. It is isostructural with its iron (Srinivasan et al., 2007), cadmium (Srinivasan et al., 2006), chromium (Parkins et al., 2001) and zinc (Prout & Powell, 1961) analogues. The extremely thin plates of (I) necessitated the use of synchrotron radiation for the data collection.

Compound (I) contains trans-MnN2O4 octahedra (Fig. 1, Table 1), where the bonded N atom is part of a hydrazinium (N2H5+) cation. The Mn atoms (site symmetry 1) are connected by pairs of sulfate groups into infinite chains that propagate in [100]. The intra-chain Mn···Mn separation in (I) is equal to 5.391 (1) Å, the a unit-cell dimension.

The manganese-sulfate chains in (I) are crosslinked by N—H···O hydrogen bonds (Table 2) to result in the same hydrogen bonding network as that seen in the analogues noted above, including a trifurcated N2—H3c···(O,O,O) link (mean bond angle about H3c = 108°).

Related literature top

For isostructures, see: Prout & Powell, 1961; Parkins et al., 2001; Srinivasan et al., 2006; Srinivasan et al., 2007.

Experimental top

The reaction of hydrazine hydrate (N2H4·H2O; 0.50 g, 10 mmol) and ethyl bromoacetate (1.671 g, 10 mmol) in 5 ml of dry ethanol resulted in the formation of a white solid containing hydrazinium bromide and ethyl hydrazinoacetate, as reported earliear (Srinivasan et al., 2006). This white solid (0.236 g) was dissolved in water (30 ml) and mixed with an aqueous solution (30 ml) of MnSO4·H2O (0.169 g, 1 mmol) in few drops of conc. H2SO4. The resulting clear solution, with a pH of 2, was concentrated over a water bath to 20 ml and kept for crystallization at room temperature. After 5 days, colourless clumps of very thin plates of (I) were formed. These were recovered by filtration, washed with cold water and dried in air.

Refinement top

Although more than a hemisphere of intensity data was scanned, the low data completion is thought to have arisen from as-yet unresolved problems in the data-reduction software. The H atoms were positioned geometrically (N—H = 0.91–0.92 Å) and refined as riding with Uiso(H) = 1.2Ueq(N). The deepest difference hole is 1.49Å from H2a.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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. View of the molecular structure of (I) expanded to show the manganese coordination sphere (50% displacement ellipsoids; arbitrary spheres for the H atoms). Symmetry codes: (i) −x, −y, −z; (ii) x − 1, y, z; (iii) 1 − x, −y, −z. The double-dashed line represents the hydrogen bond.
catena-poly[[dihydraziniummanganese(II)]-di-µ-sulfato-κ4O:O'] top
Crystal data top
Mn(N2H5)2(SO4)2V = 222.81 (7) Å3
Mr = 313.18Z = 1
Triclinic, P1F000 = 159
Hall symbol: -P 1Dx = 2.334 Mg m−3
a = 5.391 (1) ÅSynchrotron radiation
λ = 0.69050 Å
b = 5.8678 (11) ŵ = 1.99 mm−1
c = 7.3954 (14) ÅT = 120 (2) K
α = 92.651 (2)ºPlate, colourless
β = 104.332 (2)º0.02 × 0.02 × 0.001 mm
γ = 99.249 (2)º
Data collection top
Bruker SMART 1000 CCD
diffractometer		881 independent reflections
Radiation source: beam line 9.8 at Daresbury synchrotron852 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.027
T = 120(2) Kθmax = 29.7º
ω scansθmin = 3.9º
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		h = −7→7
Tmin = 0.961, Tmax = 0.998k = −8→8
1414 measured reflectionsl = −10→10
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.082H-atom parameters constrained
wR(F2) = 0.248  w = 1/[σ2(Fo2) + (0.2P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.23(Δ/σ)max < 0.001
881 reflectionsΔρmax = 0.73 e Å−3
71 parametersΔρmin = −1.06 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
Mn(N2H5)2(SO4)2γ = 99.249 (2)º
Mr = 313.18V = 222.81 (7) Å3
Triclinic, P1Z = 1
a = 5.391 (1) ÅSynchrotron radiation
λ = 0.69050 Å
b = 5.8678 (11) ŵ = 1.99 mm−1
c = 7.3954 (14) ÅT = 120 (2) K
α = 92.651 (2)º0.02 × 0.02 × 0.001 mm
β = 104.332 (2)º
Data collection top
Bruker SMART 1000 CCD
diffractometer		881 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2004)		852 reflections with I > 2σ(I)
Tmin = 0.961, Tmax = 0.998Rint = 0.027
1414 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.08271 parameters
wR(F2) = 0.248H-atom parameters constrained
S = 1.23Δρmax = 0.73 e Å−3
881 reflectionsΔρmin = −1.06 e Å−3
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
Mn10.00000.00000.00000.0057 (5)
S10.63753 (11)0.24939 (10)0.22017 (8)0.0049 (5)
O10.3752 (4)0.2300 (3)0.0925 (3)0.0112 (6)
O20.8345 (4)0.2732 (3)0.1091 (3)0.0082 (6)
O30.6580 (4)0.0439 (3)0.3271 (3)0.0098 (6)
O40.6915 (4)0.4609 (3)0.3504 (3)0.0081 (6)
N10.0682 (4)−0.1820 (4)0.2659 (3)0.0073 (6)
H1A0.1181−0.07160.36650.009*
H1B−0.0870−0.27010.27090.009*
N20.2616 (5)−0.3304 (4)0.2857 (3)0.0089 (6)
H2A0.2730−0.39980.39430.011*
H2B0.4187−0.24400.28830.011*
H2C0.2146−0.44080.18710.011*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0062 (6)0.0061 (6)0.0046 (6)0.0002 (4)0.0013 (4)0.0010 (3)
S10.0056 (6)0.0052 (6)0.0039 (7)−0.0009 (4)0.0023 (4)0.0001 (4)
O10.0065 (10)0.0126 (10)0.0115 (12)−0.0026 (7)−0.0006 (8)0.0011 (8)
O20.0095 (9)0.0097 (10)0.0075 (10)−0.0005 (7)0.0075 (7)0.0011 (7)
O30.0131 (10)0.0075 (10)0.0090 (11)0.0002 (7)0.0035 (8)0.0037 (7)
O40.0115 (9)0.0070 (10)0.0055 (10)0.0000 (7)0.0029 (7)−0.0005 (7)
N10.0071 (10)0.0084 (11)0.0081 (11)0.0022 (8)0.0042 (8)0.0018 (8)
N20.0111 (11)0.0087 (11)0.0070 (12)0.0018 (8)0.0026 (8)0.0014 (7)
Geometric parameters (Å, °) top
Mn1—O2i2.1712 (19)S1—O21.489 (2)
Mn1—O2ii2.1712 (19)O2—Mn1iv2.1712 (19)
Mn1—O1iii2.1752 (18)N1—N21.447 (3)
Mn1—O12.1752 (18)N1—H1A0.9200
Mn1—N12.259 (2)N1—H1B0.9200
Mn1—N1iii2.259 (2)N2—H2A0.9100
S1—O31.4765 (19)N2—H2B0.9100
S1—O11.4772 (19)N2—H2C0.9100
S1—O41.4787 (19)
O2i—Mn1—O2ii180.0O3—S1—O2109.51 (11)
O2i—Mn1—O1iii87.22 (7)O1—S1—O2109.35 (12)
O2ii—Mn1—O1iii92.78 (7)O4—S1—O2107.99 (11)
O2i—Mn1—O192.78 (7)S1—O1—Mn1142.28 (13)
O2ii—Mn1—O187.22 (7)S1—O2—Mn1iv127.72 (11)
O1iii—Mn1—O1180.0N2—N1—Mn1115.31 (15)
O2i—Mn1—N184.77 (8)N2—N1—H1A108.4
O2ii—Mn1—N195.23 (8)Mn1—N1—H1A108.4
O1iii—Mn1—N187.42 (8)N2—N1—H1B108.4
O1—Mn1—N192.58 (8)Mn1—N1—H1B108.4
O2i—Mn1—N1iii95.23 (8)H1A—N1—H1B107.5
O2ii—Mn1—N1iii84.77 (8)N1—N2—H2A109.5
O1iii—Mn1—N1iii92.58 (8)N1—N2—H2B109.5
O1—Mn1—N1iii87.42 (8)H2A—N2—H2B109.5
N1—Mn1—N1iii180.0N1—N2—H2C109.5
O3—S1—O1111.04 (11)H2A—N2—H2C109.5
O3—S1—O4109.90 (11)H2B—N2—H2C109.5
O1—S1—O4108.98 (13)
O3—S1—O1—Mn1−1.2 (3)O3—S1—O2—Mn1iv27.96 (18)
O4—S1—O1—Mn1−122.4 (2)O1—S1—O2—Mn1iv−93.92 (16)
O2—S1—O1—Mn1119.8 (2)O4—S1—O2—Mn1iv147.62 (14)
O2i—Mn1—O1—S1−61.4 (2)O2i—Mn1—N1—N221.43 (16)
O2ii—Mn1—O1—S1118.6 (2)O2ii—Mn1—N1—N2−158.57 (16)
N1—Mn1—O1—S123.5 (2)O1iii—Mn1—N1—N2108.87 (17)
N1iii—Mn1—O1—S1−156.5 (2)O1—Mn1—N1—N2−71.13 (17)
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, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3v0.922.273.014 (3)137
N1—H1B···O4vi0.922.022.879 (3)154
N2—H2A···O4v0.911.912.794 (3)165
N2—H2B···O30.911.922.755 (3)152
N2—H2C···O2i0.912.412.882 (3)112
N2—H2C···O2vi0.912.362.988 (3)126
N2—H2C···O1vii0.912.383.110 (3)137
Symmetry codes: (v) −x+1, −y, −z+1; (vi) x−1, y−1, z; (i) −x+1, −y, −z; (vii) x, y−1, z.
Table 1
Selected geometric parameters (Å) top
Mn1—O2i2.1712 (19)Mn1—N12.259 (2)
Mn1—O12.1752 (18)
Symmetry codes: (i) −x+1, −y, −z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O3ii0.922.273.014 (3)137
N1—H1B···O4iii0.922.022.879 (3)154
N2—H2A···O4ii0.911.912.794 (3)165
N2—H2B···O30.911.922.755 (3)152
N2—H2C···O2i0.912.412.882 (3)112
N2—H2C···O2iii0.912.362.988 (3)126
N2—H2C···O1iv0.912.383.110 (3)137
Symmetry codes: (ii) −x+1, −y, −z+1; (iii) x−1, y−1, z; (i) −x+1, −y, −z; (iv) x, y−1, z.
Acknowledgements top

We thank Professor Bill Clegg (University of Newcastle and Daresbury Laboratory) for the data collection and initial data processing.

references
References top

Bruker (2004). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Parkins, A. W., Prince, P. D., Smith, R. A. L. & Steed, J. W. (2001). Acta Cryst. C57, 670–671.

Prout, C. K. & Powell, H. M. (1961). J. Chem. Soc. pp. 4177–4182.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Srinivasan, K., Govindarajan, S. & Harrison, W. T. A. (2006). Acta Cryst. E62, i219–i221.

Srinivasan, K., Govindarajan, S. & Harrison, W. T. A. (2007). Acta Cryst. E63, i41–i42.