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 |
Key indicators
- Single-crystal synchrotron study
- T = 120 K
- Mean (N-N) = 0.003 Å
- R factor = 0.082
- wR factor = 0.248
- Data-to-parameter ratio = 12.4
checkCIF/PLATON results
No syntax errors found
Alert level A REFLT03_ALERT_3_A Reflection count < 85% complete (theta max?) From the CIF: _diffrn_reflns_theta_max 29.73 From the CIF: _diffrn_reflns_theta_full 29.73 From the CIF: _reflns_number_total 881 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 1390 Completeness (_total/calc) 63.38%
Author Response: we believe this arose due to as-yet unresolved problems with the data-reduction software. |
PLAT029_ALERT_3_A _diffrn_measured_fraction_theta_full Low ....... 0.63
Author Response: see above... |
Alert level C PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 200 Deg. PLAT213_ALERT_2_C Atom O2 has ADP max/min Ratio ............. 3.70 oblat
Alert level G ABSMU_01 Radiation type not identified. Calculation of _exptl_absorpt_correction_mu not performed. PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1 (2) 2.08
2 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 2 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For isostructures, see: Prout & Powell, 1961; Parkins et al., 2001; Srinivasan et al., 2006; Srinivasan et al., 2007.
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. |
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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°).