Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807057091/hy2096sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807057091/hy2096Isup2.hkl |
CCDC reference: 672660
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (N-C) = 0.004 Å
- R factor = 0.052
- wR factor = 0.145
- Data-to-parameter ratio = 12.8
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT031_ALERT_4_C Refined Extinction Parameter within Range ...... 3.31 Sigma PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 3.31 PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.03
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Mn1 (2) 2.04
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 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 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For a related copper(II) complex of bistetrazolylimine, see: Friedrich et al. (2005).
A mixture of manganese chlorate tetrahydrate (0.02 g, 0.1 mmol), bistetrazolylimine (0.031 g, 0.2 mmol) and water (20 ml) was heated in a 25 ml Teflon-lined autoclave at 433 K for 3 d, followed by slowly cooling to room temperature. The resulting mixture was filtered and washed with 95% methanol, and colorless crystals were collected and dried in air. Analysis, calculated for C4H12MnN18O4: C 11.13, H 2.78, N 58.46%; found: C 10.96, H 2.93, N 58.21%.
H atoms bound to the ligand were positioned geometrically and refined as riding, with N—H = 0.86Å and Uiso(H) = 1.2Ueq(N). H atoms belonging to water molecules were located in a difference Fourier map. One H atom (H3) attached to the water molecule O1 was fixed with Uiso(H) = 1.5Ueq(O) and the other H atoms were refined isotropically. The highest residual electron density was found 0.95 Å from O1 and the deepest hole 0.23Å from Mn1.
Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).
[Mn(C2H2N9)2(H2O)2]·2H2O | F(000) = 876.0 |
Mr = 431.26 | Dx = 1.858 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 2291 reflections |
a = 14.8048 (12) Å | θ = 2.7–27.5° |
b = 6.8674 (6) Å | µ = 0.92 mm−1 |
c = 15.1623 (12) Å | T = 296 K |
V = 1541.6 (2) Å3 | Block, colorless |
Z = 4 | 0.24 × 0.19 × 0.12 mm |
Bruker SMART APEX CCD area-detector diffractometer | 1764 independent reflections |
Radiation source: fine-focus sealed tube | 1148 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.084 |
ϕ and ω scans | θmax = 27.5°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −19→19 |
Tmin = 0.798, Tmax = 0.891 | k = −8→8 |
23612 measured reflections | l = −19→19 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.052 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.145 | w = 1/[σ2(Fo2) + (0.0848P)2 + 0.1407P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
1764 reflections | Δρmax = 1.54 e Å−3 |
138 parameters | Δρmin = −0.47 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0043 (13) |
[Mn(C2H2N9)2(H2O)2]·2H2O | V = 1541.6 (2) Å3 |
Mr = 431.26 | Z = 4 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 14.8048 (12) Å | µ = 0.92 mm−1 |
b = 6.8674 (6) Å | T = 296 K |
c = 15.1623 (12) Å | 0.24 × 0.19 × 0.12 mm |
Bruker SMART APEX CCD area-detector diffractometer | 1764 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1148 reflections with I > 2σ(I) |
Tmin = 0.798, Tmax = 0.891 | Rint = 0.084 |
23612 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.145 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 1.54 e Å−3 |
1764 reflections | Δρmin = −0.47 e Å−3 |
138 parameters |
x | y | z | Uiso*/Ueq | ||
Mn1 | 0.5000 | 0.0000 | 0.5000 | 0.0220 (3) | |
N9 | 0.77109 (17) | 0.0326 (4) | 0.62014 (18) | 0.0267 (7) | |
H2 | 0.8085 | 0.0652 | 0.6610 | 0.032* | |
N1 | 0.48570 (17) | 0.0800 (4) | 0.63974 (17) | 0.0242 (7) | |
N5 | 0.63655 (18) | 0.1039 (5) | 0.69756 (17) | 0.0288 (7) | |
H1 | 0.6677 | 0.1492 | 0.7408 | 0.035* | |
N3 | 0.41468 (18) | 0.1035 (5) | 0.76371 (18) | 0.0295 (7) | |
N4 | 0.50344 (17) | 0.1154 (5) | 0.78366 (17) | 0.0272 (7) | |
N8 | 0.79321 (19) | −0.0362 (4) | 0.53957 (19) | 0.0294 (7) | |
N2 | 0.40356 (18) | 0.0821 (5) | 0.67952 (18) | 0.0310 (7) | |
N7 | 0.71908 (19) | −0.0692 (5) | 0.49821 (18) | 0.0297 (7) | |
N6 | 0.64677 (19) | −0.0217 (4) | 0.54967 (17) | 0.0253 (7) | |
C1 | 0.5441 (2) | 0.0999 (5) | 0.7061 (2) | 0.0221 (7) | |
C2 | 0.6814 (2) | 0.0412 (5) | 0.6255 (2) | 0.0244 (8) | |
O1 | 0.5313 (2) | 0.2997 (4) | 0.46099 (17) | 0.0382 (7) | |
H3 | 0.5228 | 0.3125 | 0.4079 | 0.057* | |
H4 | 0.567 (4) | 0.369 (8) | 0.483 (3) | 0.08 (2)* | |
O2 | 0.7346 (2) | 0.2913 (5) | 0.8230 (2) | 0.0491 (9) | |
H6 | 0.769 (4) | 0.248 (10) | 0.864 (4) | 0.11 (2)* | |
H5 | 0.707 (3) | 0.377 (8) | 0.850 (3) | 0.070 (18)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Mn1 | 0.0181 (4) | 0.0321 (5) | 0.0157 (4) | −0.0019 (3) | −0.0014 (3) | −0.0011 (3) |
N9 | 0.0181 (15) | 0.0419 (18) | 0.0200 (13) | 0.0020 (12) | −0.0032 (11) | −0.0026 (13) |
N1 | 0.0159 (14) | 0.0381 (17) | 0.0186 (14) | −0.0006 (12) | 0.0016 (10) | −0.0031 (13) |
N5 | 0.0165 (14) | 0.0505 (19) | 0.0194 (13) | −0.0011 (13) | −0.0022 (11) | −0.0084 (14) |
N3 | 0.0188 (15) | 0.0464 (19) | 0.0233 (14) | −0.0027 (14) | 0.0026 (11) | −0.0016 (13) |
N4 | 0.0191 (14) | 0.043 (2) | 0.0196 (13) | −0.0023 (12) | 0.0009 (11) | −0.0036 (13) |
N8 | 0.0221 (16) | 0.043 (2) | 0.0228 (15) | 0.0016 (13) | 0.0018 (12) | −0.0010 (13) |
N2 | 0.0171 (15) | 0.054 (2) | 0.0224 (15) | −0.0028 (14) | 0.0028 (11) | −0.0041 (14) |
N7 | 0.0195 (15) | 0.0431 (18) | 0.0265 (15) | 0.0040 (14) | −0.0003 (11) | −0.0043 (13) |
N6 | 0.0193 (15) | 0.0369 (18) | 0.0197 (14) | 0.0018 (12) | −0.0008 (11) | −0.0033 (12) |
C1 | 0.0196 (17) | 0.0283 (19) | 0.0185 (16) | −0.0040 (14) | 0.0013 (12) | 0.0017 (14) |
C2 | 0.0169 (16) | 0.033 (2) | 0.0230 (17) | 0.0000 (14) | −0.0005 (13) | −0.0002 (14) |
O1 | 0.0504 (18) | 0.0390 (17) | 0.0252 (13) | −0.0111 (14) | −0.0087 (14) | 0.0034 (12) |
O2 | 0.0460 (18) | 0.056 (2) | 0.0454 (18) | 0.0218 (16) | −0.0190 (14) | −0.0193 (15) |
Mn1—O1i | 2.191 (3) | N5—C1 | 1.376 (4) |
Mn1—O1 | 2.191 (3) | N5—H1 | 0.8600 |
Mn1—N1 | 2.199 (3) | N3—N2 | 1.295 (4) |
Mn1—N1i | 2.199 (3) | N3—N4 | 1.351 (4) |
Mn1—N6 | 2.304 (3) | N4—C1 | 1.325 (4) |
Mn1—N6i | 2.304 (3) | N8—N7 | 1.284 (4) |
N9—C2 | 1.332 (4) | N7—N6 | 1.364 (4) |
N9—N8 | 1.350 (4) | N6—C2 | 1.330 (4) |
N9—H2 | 0.8600 | O1—H3 | 0.8200 |
N1—C1 | 1.334 (4) | O1—H4 | 0.79 (5) |
N1—N2 | 1.357 (4) | O2—H6 | 0.85 (6) |
N5—C2 | 1.349 (4) | O2—H5 | 0.82 (5) |
O1i—Mn1—O1 | 180.00 (13) | C2—N5—C1 | 124.0 (3) |
O1i—Mn1—N1 | 87.37 (10) | C2—N5—H1 | 118.0 |
O1—Mn1—N1 | 92.63 (10) | C1—N5—H1 | 118.0 |
O1i—Mn1—N1i | 92.63 (10) | N2—N3—N4 | 110.6 (3) |
O1—Mn1—N1i | 87.37 (10) | C1—N4—N3 | 103.8 (3) |
N1—Mn1—N1i | 180.0 | N7—N8—N9 | 107.2 (3) |
O1i—Mn1—N6 | 92.90 (10) | N3—N2—N1 | 109.0 (2) |
O1—Mn1—N6 | 87.10 (11) | N8—N7—N6 | 110.4 (3) |
N1—Mn1—N6 | 78.00 (9) | C2—N6—N7 | 105.6 (3) |
N1i—Mn1—N6 | 102.00 (9) | C2—N6—Mn1 | 128.6 (2) |
O1i—Mn1—N6i | 87.10 (11) | N7—N6—Mn1 | 124.65 (19) |
O1—Mn1—N6i | 92.90 (10) | N4—C1—N1 | 112.6 (3) |
N1—Mn1—N6i | 102.00 (9) | N4—C1—N5 | 122.3 (3) |
N1i—Mn1—N6i | 78.00 (9) | N1—C1—N5 | 125.2 (3) |
N6—Mn1—N6i | 180.0 | N6—C2—N9 | 108.5 (3) |
C2—N9—N8 | 108.2 (3) | N6—C2—N5 | 127.9 (3) |
C2—N9—H2 | 125.9 | N9—C2—N5 | 123.6 (3) |
N8—N9—H2 | 125.9 | Mn1—O1—H3 | 109.5 |
C1—N1—N2 | 104.1 (2) | Mn1—O1—H4 | 127 (4) |
C1—N1—Mn1 | 133.7 (2) | H3—O1—H4 | 116.8 |
N2—N1—Mn1 | 121.14 (19) | H6—O2—H5 | 101 (5) |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N9—H2···N3ii | 0.86 | 1.96 | 2.803 (4) | 166 |
N5—H1···O2 | 0.86 | 1.87 | 2.716 (4) | 169 |
O1—H3···N4iii | 0.82 | 1.97 | 2.782 (4) | 172 |
O1—H4···N8iv | 0.79 (5) | 2.33 (6) | 3.072 (4) | 157 (6) |
O2—H5···N2v | 0.82 (5) | 2.21 (5) | 2.859 (5) | 136 (4) |
O2—H5···N7vi | 0.82 (5) | 2.62 (5) | 3.280 (4) | 139 (4) |
O2—H6···N7vii | 0.85 (6) | 2.39 (7) | 3.140 (4) | 148 (5) |
O2—H6···N2ii | 0.85 (6) | 2.39 (6) | 2.885 (4) | 118 (5) |
Symmetry codes: (ii) x+1/2, y, −z+3/2; (iii) x, −y+1/2, z−1/2; (iv) −x+3/2, y+1/2, z; (v) −x+1, y+1/2, −z+3/2; (vi) x, −y+1/2, z+1/2; (vii) −x+3/2, −y, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Mn(C2H2N9)2(H2O)2]·2H2O |
Mr | 431.26 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 296 |
a, b, c (Å) | 14.8048 (12), 6.8674 (6), 15.1623 (12) |
V (Å3) | 1541.6 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.92 |
Crystal size (mm) | 0.24 × 0.19 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.798, 0.891 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 23612, 1764, 1148 |
Rint | 0.084 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.145, 1.03 |
No. of reflections | 1764 |
No. of parameters | 138 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.54, −0.47 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT (Bruker, 2001, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).
Mn1—O1 | 2.191 (3) | Mn1—N6 | 2.304 (3) |
Mn1—N1 | 2.199 (3) | ||
O1i—Mn1—N1 | 87.37 (10) | O1—Mn1—N6 | 87.10 (11) |
O1—Mn1—N1 | 92.63 (10) | N1—Mn1—N6 | 78.00 (9) |
O1i—Mn1—N6 | 92.90 (10) | N1i—Mn1—N6 | 102.00 (9) |
Symmetry code: (i) −x+1, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N9—H2···N3ii | 0.86 | 1.96 | 2.803 (4) | 166 |
N5—H1···O2 | 0.86 | 1.87 | 2.716 (4) | 169 |
O1—H3···N4iii | 0.82 | 1.97 | 2.782 (4) | 172 |
O1—H4···N8iv | 0.79 (5) | 2.33 (6) | 3.072 (4) | 157 (6) |
O2—H5···N2v | 0.82 (5) | 2.21 (5) | 2.859 (5) | 136 (4) |
O2—H5···N7vi | 0.82 (5) | 2.62 (5) | 3.280 (4) | 139 (4) |
O2—H6···N7vii | 0.85 (6) | 2.39 (7) | 3.140 (4) | 148 (5) |
O2—H6···N2ii | 0.85 (6) | 2.39 (6) | 2.885 (4) | 118 (5) |
Symmetry codes: (ii) x+1/2, y, −z+3/2; (iii) x, −y+1/2, z−1/2; (iv) −x+3/2, y+1/2, z; (v) −x+1, y+1/2, −z+3/2; (vi) x, −y+1/2, z+1/2; (vii) −x+3/2, −y, z+1/2. |
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The metal complexes of bistetrazolylimine, containing nine electron-donating nitrogen atoms, have not been aroused sufficient attention (Friedrich et al., 2005). The bistetrazolylimine and its deprotonated anions can show a number of different coordinating or bridging modes. The title complex consists of a MnII atom lying on an inversion center, two bistetrazolylimine ligands, two coordinated water molecules and two free water molecules (Table 1; Fig. 1). The ligand acts as chelating bidentate and the MnII atom is coordinated by four N atoms from two ligands and two water molecules in an octahedral geometry with the axial O—Mn—O bond angle of 180.0 (1)°. A three-dimensional network is constructed through O—H···N, N—H···O and N—H···N hydrogen bonds between the water molecules and the ligands (Table 2; Fig. 2).