Diaqua­bis[5-(1H-tetrazol-5-ylamino-κN⁴)tetrazolato-κN¹]manganese(II) dihydrate

The title compound, [Mn(C₂H₂N₉)₂(H₂O)₂]·2H₂O, has been prepared under hydro­thermal conditions. The Mn^II 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.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](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

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S1. Comment

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 Mn^II 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 Mn^II 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

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

S2. Experimental

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%.

S3. Refinement

H atoms bound to the ligand were positioned geometrically and refined as riding, with N—H = 0.86Å and U_iso(H) = 1.2U_eq(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 U_iso(H) = 1.5U_eq(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

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

	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.]
	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

Crystal data

[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) Å^3	Block, colorless
Z = 4	0.24 × 0.19 × 0.12 mm

Data collection

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

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.052	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.145	w = 1/[σ^2(Fo^2) + (0.0848P)^2 + 0.1407P] where P = (Fo^2 + 2Fc^2)/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+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0043 (13)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

Mn1—O1^i	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—N1^i	2.199 (3)	N3—N4	1.351 (4)
Mn1—N6	2.304 (3)	N4—C1	1.325 (4)
Mn1—N6^i	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)
O1^i—Mn1—O1	180.00 (13)	C2—N5—C1	124.0 (3)
O1^i—Mn1—N1	87.37 (10)	C2—N5—H1	118.0
O1—Mn1—N1	92.63 (10)	C1—N5—H1	118.0
O1^i—Mn1—N1^i	92.63 (10)	N2—N3—N4	110.6 (3)
O1—Mn1—N1^i	87.37 (10)	C1—N4—N3	103.8 (3)
N1—Mn1—N1^i	180.0	N7—N8—N9	107.2 (3)
O1^i—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)
N1^i—Mn1—N6	102.00 (9)	C2—N6—Mn1	128.6 (2)
O1^i—Mn1—N6^i	87.10 (11)	N7—N6—Mn1	124.65 (19)
O1—Mn1—N6^i	92.90 (10)	N4—C1—N1	112.6 (3)
N1—Mn1—N6^i	102.00 (9)	N4—C1—N5	122.3 (3)
N1^i—Mn1—N6^i	78.00 (9)	N1—C1—N5	125.2 (3)
N6—Mn1—N6^i	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.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N9—H2···N3^ii	0.86	1.96	2.803 (4)	166
N5—H1···O2	0.86	1.87	2.716 (4)	169
O1—H3···N4^iii	0.82	1.97	2.782 (4)	172
O1—H4···N8^iv	0.79 (5)	2.33 (6)	3.072 (4)	157 (6)
O2—H5···N2^v	0.82 (5)	2.21 (5)	2.859 (5)	136 (4)
O2—H5···N7^vi	0.82 (5)	2.62 (5)	3.280 (4)	139 (4)
O2—H6···N7^vii	0.85 (6)	2.39 (7)	3.140 (4)	148 (5)
O2—H6···N2^ii	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.