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Acta Cryst. (2007). E63, m3017    [ doi:10.1107/S1600536807057091 ]

Diaquabis[5-(1H-tetrazol-5-ylamino-[kappa]N4)tetrazolato-[kappa]N1]manganese(II) dihydrate

J.-M. Lin, Y.-F. Guan and W. Dong

Abstract top

The title compound, [Mn(C2H2N9)2(H2O)2]·2H2O, has been prepared under hydrothermal conditions. The MnII atom, lying on an inversion center, is coordinated in an octahedral geometry defined by four N atoms from two di-1H-tetrazol-5-ylaminate ligands in the equatorial plane and two water molecules in the axial positions. The complex molecules are linked into a three-dimensional network through O-H...N, N-H...O and N-H...N hydrogen bonds.

Comment top

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).

Related literature top

For a related copper(II) complex of bistetrazolylimine, see: Friedrich et al. (2005).

Experimental top

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%.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry code: (i) −x + 1, −y, −z + 1.]
[Figure 2] Fig. 2. The packing diagram of the title compound, showing a three-dimensional network connected by O—H···N, N—H···O and N—H···N hydrogen bonds (dashed lines).
Diaquabis[5-(1H-tetrazol-5-ylamino-κN4)tetrazolato- κN1]manganese(II) dihydrate top
Crystal data top
[Mn(C2H2N9)2(H2O)2]·2H2OF000 = 876.0
Mr = 431.26Dx = 1.858 Mg m−3
Orthorhombic, PbcaMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 2291 reflections
a = 14.8048 (12) Åθ = 2.7–27.5º
b = 6.8674 (6) ŵ = 0.92 mm−1
c = 15.1623 (12) ÅT = 296 (2) K
V = 1541.6 (2) Å3Block, colorless
Z = 40.24 × 0.19 × 0.12 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer		1764 independent reflections
Radiation source: fine-focus sealed tube1148 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.084
T = 296(2) Kθmax = 27.5º
φ and ω scansθmin = 2.7º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −19→19
Tmin = 0.798, Tmax = 0.891k = −8→8
23612 measured reflectionsl = −19→19
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH atoms treated by a mixture of
independent and constrained refinement
R[F2 > 2σ(F2)] = 0.052  w = 1/[σ2(Fo2) + (0.0848P)2 + 0.1407P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.145(Δ/σ)max < 0.001
S = 1.03Δρmax = 1.54 e Å−3
1764 reflectionsΔρmin = −0.47 e Å−3
138 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0043 (13)
Secondary atom site location: difference Fourier map
Crystal data top
[Mn(C2H2N9)2(H2O)2]·2H2OV = 1541.6 (2) Å3
Mr = 431.26Z = 4
Orthorhombic, PbcaMo Kα
a = 14.8048 (12) ŵ = 0.92 mm−1
b = 6.8674 (6) ÅT = 296 (2) K
c = 15.1623 (12) Å0.24 × 0.19 × 0.12 mm
Data collection top
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 = 0.891Rint = 0.084
23612 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.052138 parameters
wR(F2) = 0.145H atoms treated by a mixture of
independent and constrained refinement
S = 1.03Δρmax = 1.54 e Å−3
1764 reflectionsΔρmin = −0.47 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Mn10.50000.00000.50000.0220 (3)
N90.77109 (17)0.0326 (4)0.62014 (18)0.0267 (7)
H20.80850.06520.66100.032*
N10.48570 (17)0.0800 (4)0.63974 (17)0.0242 (7)
N50.63655 (18)0.1039 (5)0.69756 (17)0.0288 (7)
H10.66770.14920.74080.035*
N30.41468 (18)0.1035 (5)0.76371 (18)0.0295 (7)
N40.50344 (17)0.1154 (5)0.78366 (17)0.0272 (7)
N80.79321 (19)−0.0362 (4)0.53957 (19)0.0294 (7)
N20.40356 (18)0.0821 (5)0.67952 (18)0.0310 (7)
N70.71908 (19)−0.0692 (5)0.49821 (18)0.0297 (7)
N60.64677 (19)−0.0217 (4)0.54967 (17)0.0253 (7)
C10.5441 (2)0.0999 (5)0.7061 (2)0.0221 (7)
C20.6814 (2)0.0412 (5)0.6255 (2)0.0244 (8)
O10.5313 (2)0.2997 (4)0.46099 (17)0.0382 (7)
H30.52280.31250.40790.057*
H40.567 (4)0.369 (8)0.483 (3)0.08 (2)*
O20.7346 (2)0.2913 (5)0.8230 (2)0.0491 (9)
H60.769 (4)0.248 (10)0.864 (4)0.11 (2)*
H50.707 (3)0.377 (8)0.850 (3)0.070 (18)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Mn10.0181 (4)0.0321 (5)0.0157 (4)−0.0019 (3)−0.0014 (3)−0.0011 (3)
N90.0181 (15)0.0419 (18)0.0200 (13)0.0020 (12)−0.0032 (11)−0.0026 (13)
N10.0159 (14)0.0381 (17)0.0186 (14)−0.0006 (12)0.0016 (10)−0.0031 (13)
N50.0165 (14)0.0505 (19)0.0194 (13)−0.0011 (13)−0.0022 (11)−0.0084 (14)
N30.0188 (15)0.0464 (19)0.0233 (14)−0.0027 (14)0.0026 (11)−0.0016 (13)
N40.0191 (14)0.043 (2)0.0196 (13)−0.0023 (12)0.0009 (11)−0.0036 (13)
N80.0221 (16)0.043 (2)0.0228 (15)0.0016 (13)0.0018 (12)−0.0010 (13)
N20.0171 (15)0.054 (2)0.0224 (15)−0.0028 (14)0.0028 (11)−0.0041 (14)
N70.0195 (15)0.0431 (18)0.0265 (15)0.0040 (14)−0.0003 (11)−0.0043 (13)
N60.0193 (15)0.0369 (18)0.0197 (14)0.0018 (12)−0.0008 (11)−0.0033 (12)
C10.0196 (17)0.0283 (19)0.0185 (16)−0.0040 (14)0.0013 (12)0.0017 (14)
C20.0169 (16)0.033 (2)0.0230 (17)0.0000 (14)−0.0005 (13)−0.0002 (14)
O10.0504 (18)0.0390 (17)0.0252 (13)−0.0111 (14)−0.0087 (14)0.0034 (12)
O20.0460 (18)0.056 (2)0.0454 (18)0.0218 (16)−0.0190 (14)−0.0193 (15)
Geometric parameters (Å, °) top
Mn1—O1i2.191 (3)N5—C11.376 (4)
Mn1—O12.191 (3)N5—H10.8600
Mn1—N12.199 (3)N3—N21.295 (4)
Mn1—N1i2.199 (3)N3—N41.351 (4)
Mn1—N62.304 (3)N4—C11.325 (4)
Mn1—N6i2.304 (3)N8—N71.284 (4)
N9—C21.332 (4)N7—N61.364 (4)
N9—N81.350 (4)N6—C21.330 (4)
N9—H20.8600O1—H30.8200
N1—C11.334 (4)O1—H40.79 (5)
N1—N21.357 (4)O2—H60.85 (6)
N5—C21.349 (4)O2—H50.82 (5)
O1i—Mn1—O1180.00 (13)C2—N5—C1124.0 (3)
O1i—Mn1—N187.37 (10)C2—N5—H1118.0
O1—Mn1—N192.63 (10)C1—N5—H1118.0
O1i—Mn1—N1i92.63 (10)N2—N3—N4110.6 (3)
O1—Mn1—N1i87.37 (10)C1—N4—N3103.8 (3)
N1—Mn1—N1i180.0N7—N8—N9107.2 (3)
O1i—Mn1—N692.90 (10)N3—N2—N1109.0 (2)
O1—Mn1—N687.10 (11)N8—N7—N6110.4 (3)
N1—Mn1—N678.00 (9)C2—N6—N7105.6 (3)
N1i—Mn1—N6102.00 (9)C2—N6—Mn1128.6 (2)
O1i—Mn1—N6i87.10 (11)N7—N6—Mn1124.65 (19)
O1—Mn1—N6i92.90 (10)N4—C1—N1112.6 (3)
N1—Mn1—N6i102.00 (9)N4—C1—N5122.3 (3)
N1i—Mn1—N6i78.00 (9)N1—C1—N5125.2 (3)
N6—Mn1—N6i180.0N6—C2—N9108.5 (3)
C2—N9—N8108.2 (3)N6—C2—N5127.9 (3)
C2—N9—H2125.9N9—C2—N5123.6 (3)
N8—N9—H2125.9Mn1—O1—H3109.5
C1—N1—N2104.1 (2)Mn1—O1—H4127 (4)
C1—N1—Mn1133.7 (2)H3—O1—H4116.8
N2—N1—Mn1121.14 (19)H6—O2—H5101 (5)
Symmetry codes: (i) −x+1, −y, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N9—H2···N3ii0.861.962.803 (4)166
N5—H1···O20.861.872.716 (4)169
O1—H3···N4iii0.821.972.782 (4)172
O1—H4···N8iv0.79 (5)2.33 (6)3.072 (4)157 (6)
O2—H5···N2v0.82 (5)2.21 (5)2.859 (5)136 (4)
O2—H5···N7vi0.82 (5)2.62 (5)3.280 (4)139 (4)
O2—H6···N7vii0.85 (6)2.39 (7)3.140 (4)148 (5)
O2—H6···N2ii0.85 (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.
Table 1
Selected geometric parameters (Å, °) top
Mn1—O12.191 (3)Mn1—N62.304 (3)
Mn1—N12.199 (3)
O1i—Mn1—N187.37 (10)O1—Mn1—N687.10 (11)
O1—Mn1—N192.63 (10)N1—Mn1—N678.00 (9)
O1i—Mn1—N692.90 (10)N1i—Mn1—N6102.00 (9)
Symmetry codes: (i) −x+1, −y, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N9—H2···N3ii0.861.962.803 (4)166
N5—H1···O20.861.872.716 (4)169
O1—H3···N4iii0.821.972.782 (4)172
O1—H4···N8iv0.79 (5)2.33 (6)3.072 (4)157 (6)
O2—H5···N2v0.82 (5)2.21 (5)2.859 (5)136 (4)
O2—H5···N7vi0.82 (5)2.62 (5)3.280 (4)139 (4)
O2—H6···N7vii0.85 (6)2.39 (7)3.140 (4)148 (5)
O2—H6···N2ii0.85 (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.
Acknowledgements top

We acknowledge financial support from the National Natural Science Foundation of China (grant No. 206710214) and the Science and Technology Program Foundation of Guangzhou, China (grant No. 2007 J1-co381).

references
References top

Bruker (2001). SMART, SAINT and SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

Friedrich, M., Gólvez-Ruiz, J. C., Klapötke, T. M., Mayer, P., Weber, R. & Weigand, J. J. (2005). Inorg. Chem. 44, 8044–8052.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

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