Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807024579/wm2112sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807024579/wm2112Isup2.hkl |
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.
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.
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°).
For isostructures, see: Prout & Powell, 1961; Parkins et al., 2001; Srinivasan et al., 2006; Srinivasan et al., 2007.
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.
Mn(N2H5)2(SO4)2 | V = 222.81 (7) Å3 |
Mr = 313.18 | Z = 1 |
Triclinic, P1 | F(000) = 159 |
Hall symbol: -P 1 | Dx = 2.334 Mg m−3 |
a = 5.391 (1) Å | Synchrotron radiation, λ = 0.69050 Å |
b = 5.8678 (11) Å | µ = 1.99 mm−1 |
c = 7.3954 (14) Å | T = 120 K |
α = 92.651 (2)° | Plate, colourless |
β = 104.332 (2)° | 0.02 × 0.02 × 0.001 mm |
γ = 99.249 (2)° |
Bruker SMART 1000 CCD diffractometer | 881 independent reflections |
Radiation source: beam line 9.8 at Daresbury synchrotron | 852 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
ω scans | θmax = 29.7°, θmin = 3.9° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −7→7 |
Tmin = 0.961, Tmax = 0.998 | k = −8→8 |
1414 measured reflections | l = −10→10 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.082 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.248 | H-atom parameters constrained |
S = 1.23 | w = 1/[σ2(Fo2) + (0.2P)2] where P = (Fo2 + 2Fc2)/3 |
881 reflections | (Δ/σ)max < 0.001 |
71 parameters | Δρmax = 0.73 e Å−3 |
0 restraints | Δρmin = −1.06 e Å−3 |
Mn(N2H5)2(SO4)2 | γ = 99.249 (2)° |
Mr = 313.18 | V = 222.81 (7) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.391 (1) Å | Synchrotron radiation, λ = 0.69050 Å |
b = 5.8678 (11) Å | µ = 1.99 mm−1 |
c = 7.3954 (14) Å | T = 120 K |
α = 92.651 (2)° | 0.02 × 0.02 × 0.001 mm |
β = 104.332 (2)° |
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 = 0.998 | Rint = 0.027 |
1414 measured reflections |
R[F2 > 2σ(F2)] = 0.082 | 0 restraints |
wR(F2) = 0.248 | H-atom parameters constrained |
S = 1.23 | Δρmax = 0.73 e Å−3 |
881 reflections | Δρmin = −1.06 e Å−3 |
71 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Mn1 | 0.0000 | 0.0000 | 0.0000 | 0.0057 (5) | |
S1 | 0.63753 (11) | 0.24939 (10) | 0.22017 (8) | 0.0049 (5) | |
O1 | 0.3752 (4) | 0.2300 (3) | 0.0925 (3) | 0.0112 (6) | |
O2 | 0.8345 (4) | 0.2732 (3) | 0.1091 (3) | 0.0082 (6) | |
O3 | 0.6580 (4) | 0.0439 (3) | 0.3271 (3) | 0.0098 (6) | |
O4 | 0.6915 (4) | 0.4609 (3) | 0.3504 (3) | 0.0081 (6) | |
N1 | 0.0682 (4) | −0.1820 (4) | 0.2659 (3) | 0.0073 (6) | |
H1A | 0.1181 | −0.0716 | 0.3665 | 0.009* | |
H1B | −0.0870 | −0.2701 | 0.2709 | 0.009* | |
N2 | 0.2616 (5) | −0.3304 (4) | 0.2857 (3) | 0.0089 (6) | |
H2A | 0.2730 | −0.3998 | 0.3943 | 0.011* | |
H2B | 0.4187 | −0.2440 | 0.2883 | 0.011* | |
H2C | 0.2146 | −0.4408 | 0.1871 | 0.011* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0062 (6) | 0.0061 (6) | 0.0046 (6) | 0.0002 (4) | 0.0013 (4) | 0.0010 (3) |
S1 | 0.0056 (6) | 0.0052 (6) | 0.0039 (7) | −0.0009 (4) | 0.0023 (4) | 0.0001 (4) |
O1 | 0.0065 (10) | 0.0126 (10) | 0.0115 (12) | −0.0026 (7) | −0.0006 (8) | 0.0011 (8) |
O2 | 0.0095 (9) | 0.0097 (10) | 0.0075 (10) | −0.0005 (7) | 0.0075 (7) | 0.0011 (7) |
O3 | 0.0131 (10) | 0.0075 (10) | 0.0090 (11) | 0.0002 (7) | 0.0035 (8) | 0.0037 (7) |
O4 | 0.0115 (9) | 0.0070 (10) | 0.0055 (10) | 0.0000 (7) | 0.0029 (7) | −0.0005 (7) |
N1 | 0.0071 (10) | 0.0084 (11) | 0.0081 (11) | 0.0022 (8) | 0.0042 (8) | 0.0018 (8) |
N2 | 0.0111 (11) | 0.0087 (11) | 0.0070 (12) | 0.0018 (8) | 0.0026 (8) | 0.0014 (7) |
Mn1—O2i | 2.1712 (19) | S1—O2 | 1.489 (2) |
Mn1—O2ii | 2.1712 (19) | O2—Mn1iv | 2.1712 (19) |
Mn1—O1iii | 2.1752 (18) | N1—N2 | 1.447 (3) |
Mn1—O1 | 2.1752 (18) | N1—H1A | 0.9200 |
Mn1—N1 | 2.259 (2) | N1—H1B | 0.9200 |
Mn1—N1iii | 2.259 (2) | N2—H2A | 0.9100 |
S1—O3 | 1.4765 (19) | N2—H2B | 0.9100 |
S1—O1 | 1.4772 (19) | N2—H2C | 0.9100 |
S1—O4 | 1.4787 (19) | ||
O2i—Mn1—O2ii | 180.0 | O3—S1—O2 | 109.51 (11) |
O2i—Mn1—O1iii | 87.22 (7) | O1—S1—O2 | 109.35 (12) |
O2ii—Mn1—O1iii | 92.78 (7) | O4—S1—O2 | 107.99 (11) |
O2i—Mn1—O1 | 92.78 (7) | S1—O1—Mn1 | 142.28 (13) |
O2ii—Mn1—O1 | 87.22 (7) | S1—O2—Mn1iv | 127.72 (11) |
O1iii—Mn1—O1 | 180.0 | N2—N1—Mn1 | 115.31 (15) |
O2i—Mn1—N1 | 84.77 (8) | N2—N1—H1A | 108.4 |
O2ii—Mn1—N1 | 95.23 (8) | Mn1—N1—H1A | 108.4 |
O1iii—Mn1—N1 | 87.42 (8) | N2—N1—H1B | 108.4 |
O1—Mn1—N1 | 92.58 (8) | Mn1—N1—H1B | 108.4 |
O2i—Mn1—N1iii | 95.23 (8) | H1A—N1—H1B | 107.5 |
O2ii—Mn1—N1iii | 84.77 (8) | N1—N2—H2A | 109.5 |
O1iii—Mn1—N1iii | 92.58 (8) | N1—N2—H2B | 109.5 |
O1—Mn1—N1iii | 87.42 (8) | H2A—N2—H2B | 109.5 |
N1—Mn1—N1iii | 180.0 | N1—N2—H2C | 109.5 |
O3—S1—O1 | 111.04 (11) | H2A—N2—H2C | 109.5 |
O3—S1—O4 | 109.90 (11) | H2B—N2—H2C | 109.5 |
O1—S1—O4 | 108.98 (13) | ||
O3—S1—O1—Mn1 | −1.2 (3) | O3—S1—O2—Mn1iv | 27.96 (18) |
O4—S1—O1—Mn1 | −122.4 (2) | O1—S1—O2—Mn1iv | −93.92 (16) |
O2—S1—O1—Mn1 | 119.8 (2) | O4—S1—O2—Mn1iv | 147.62 (14) |
O2i—Mn1—O1—S1 | −61.4 (2) | O2i—Mn1—N1—N2 | 21.43 (16) |
O2ii—Mn1—O1—S1 | 118.6 (2) | O2ii—Mn1—N1—N2 | −158.57 (16) |
N1—Mn1—O1—S1 | 23.5 (2) | O1iii—Mn1—N1—N2 | 108.87 (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. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O3v | 0.92 | 2.27 | 3.014 (3) | 137 |
N1—H1B···O4vi | 0.92 | 2.02 | 2.879 (3) | 154 |
N2—H2A···O4v | 0.91 | 1.91 | 2.794 (3) | 165 |
N2—H2B···O3 | 0.91 | 1.92 | 2.755 (3) | 152 |
N2—H2C···O2i | 0.91 | 2.41 | 2.882 (3) | 112 |
N2—H2C···O2vi | 0.91 | 2.36 | 2.988 (3) | 126 |
N2—H2C···O1vii | 0.91 | 2.38 | 3.110 (3) | 137 |
Symmetry codes: (i) −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 | Mn(N2H5)2(SO4)2 |
Mr | 313.18 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 120 |
a, b, c (Å) | 5.391 (1), 5.8678 (11), 7.3954 (14) |
α, β, γ (°) | 92.651 (2), 104.332 (2), 99.249 (2) |
V (Å3) | 222.81 (7) |
Z | 1 |
Radiation type | Synchrotron, λ = 0.69050 Å |
µ (mm−1) | 1.99 |
Crystal size (mm) | 0.02 × 0.02 × 0.001 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2004) |
Tmin, Tmax | 0.961, 0.998 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1414, 881, 852 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.718 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.082, 0.248, 1.23 |
No. of reflections | 881 |
No. of parameters | 71 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.73, −1.06 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
Mn1—O2i | 2.1712 (19) | Mn1—N1 | 2.259 (2) |
Mn1—O1 | 2.1752 (18) |
Symmetry code: (i) −x+1, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O3ii | 0.92 | 2.27 | 3.014 (3) | 137 |
N1—H1B···O4iii | 0.92 | 2.02 | 2.879 (3) | 154 |
N2—H2A···O4ii | 0.91 | 1.91 | 2.794 (3) | 165 |
N2—H2B···O3 | 0.91 | 1.92 | 2.755 (3) | 152 |
N2—H2C···O2i | 0.91 | 2.41 | 2.882 (3) | 112 |
N2—H2C···O2iii | 0.91 | 2.36 | 2.988 (3) | 126 |
N2—H2C···O1iv | 0.91 | 2.38 | 3.110 (3) | 137 |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x+1, −y, −z+1; (iii) x−1, y−1, z; (iv) x, y−1, z. |
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°).