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Acta Crystallogr Sect E Struct Rep Online. 2008 June 1; 64(Pt 6): m772.
Published online 2008 May 3. doi:  10.1107/S1600536808012464
PMCID: PMC2961402

Tetra­aqua­bis{5-[2-(1H-tetrazol-5-yl)ethenyl]pyrazolato-κN 2}manganese(II) dihydrate

Abstract

The title compound, [Mn(C4H3N8)2(H2O)4]·2H2O, represents the first structurally characterized transition metal complex of the 1,2-bis­(tetra­zol-5-yl)ethene ligand. The complex mol­ecule occupies a special position on an inversion centre and the Mn atom has a tetra­gonally distorted octa­hedral coordination. The bis­(tetra­zolyl)ethene ligand is planar within 0.0366 (7) Å. All ‘active’ H atoms participate in hydrogen bonds, which link mol­ecules of the complex and the uncoordinated water mol­ecules into an infinite three-dimensional framework.

Related literature

For related literature, see: Huang et al. (2005 [triangle]); Demko & Sharpless (2001 [triangle]).

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Object name is e-64-0m772-scheme1.jpg

Experimental

Crystal data

  • [Mn(C4H3N8)2(H2O)4]·2H2O
  • M r = 489.32
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0m772-efi1.jpg
  • a = 6.2296 (2) Å
  • b = 7.0093 (2) Å
  • c = 12.1212 (3) Å
  • α = 84.405 (1)°
  • β = 89.457 (1)°
  • γ = 67.016 (1)°
  • V = 484.70 (2) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 0.75 mm−1
  • T = 273 (2) K
  • 0.36 × 0.28 × 0.16 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.717, T max = 0.887
  • 9107 measured reflections
  • 3246 independent reflections
  • 3149 reflections with I > 2σ(I)
  • R int = 0.015

Refinement

  • R[F 2 > 2σ(F 2)] = 0.022
  • wR(F 2) = 0.068
  • S = 1.04
  • 3246 reflections
  • 179 parameters
  • All H-atom parameters refined
  • Δρmax = 0.37 e Å−3
  • Δρmin = −0.22 e Å−3

Data collection: SMART (Bruker, 2007 [triangle]); cell refinement: SAINT-Plus (Bruker, 2007 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Selected geometric parameters (Å, °)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808012464/ya2068sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808012464/ya2068Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The author is grateful for funding from the Natural Science Foundation of Shanxi Province (2007011033), the Program of Technological Industrialization in Universities of Shanxi Province (20070308) and the Start-up Fund of the Northern University of China.

supplementary crystallographic information

Comment

The 1,2-bis(1,2,3,4-tetrazol-5-yl)ethene ligand (H2BTAE) was previously reported in its twice deprotonated form in the cystal structure of its sodium salt pentahydrate (Huang et al., 2005). The present paper provides the fist example of its structurally characterized complex with a transition metal; the ligand in this complex is monodeprotonated.

The molecule of Mn(H-BTAE)2(H2O)4 occupies a special position in the inversion centre (Fig. 1); the Mn1 atom has a tetragonally distorted octahedral coordination (Table 1). The H-BTAE ligand has essentailly planar conformation, the maximum deviation of the N6 atom from its mean plane being 0.0366 (7) Å. The geometry of the ligand is similar to the one observed in Huang et al. (2005).

All "active" hydrogen atoms in the structure participate in the H-bonding (Table 2); the extensive H-bond system links molecules of the complex and non-coordinated water molecules into three-dimensional infinite network (Fig. 2).

Experimental

MnCl2.4H2O (0.5 mmol, 99 mg) and 1,2-bis(1,2,3,4-tetrazol-5-yl)ethene (1 mmol, 192 mg) (Demko & Sharpless, 2001) were added to 30 ml of water:MeOH (1:1) mixture. After stirring for 30 min at room temperature, the pH value was adjusted to 7 by 1M NaOH, and clear solution was allowed to evaporate in the air. Nice prism-shaped crystals of the title compound were obtained after 3 days. The crystals were filtered, washed by EtOH and dried in the air.

Refinement

All H atoms were located in the difference map and refined isotropically [O—H 0.79 (2)–0.83 (2) Å; C—H 0.91 (1) and 0.96 (1) Å; N—H 0.93 (2) Å].

Figures

Fig. 1.
Molecular structure showing 50% probability displacement ellipsoids. The unlabeled atoms are derived from the reference atoms by means of the (1 - x, -y, 1 - z) symmetry transformation..
Fig. 2.
Packing diagram viewed down the a axis, The hydrogen bonds are shown as dotted lines.

Crystal data

[Mn(C4H3N8)2(H2O)4]·2H2OZ = 1
Mr = 489.32F000 = 251
Triclinic, P1Dx = 1.676 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 6.2296 (2) ÅCell parameters from 7983 reflections
b = 7.0093 (2) Åθ = 3.2–33.5º
c = 12.1212 (3) ŵ = 0.75 mm1
α = 84.405 (1)ºT = 273 (2) K
β = 89.457 (1)ºPrism, brown
γ = 67.016 (1)º0.36 × 0.28 × 0.16 mm
V = 484.70 (2) Å3

Data collection

Bruker SMART CCD area-detector diffractometer3246 independent reflections
Radiation source: fine-focus sealed tube3149 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.015
T = 273(2) Kθmax = 33.5º
[var phi] and ω scansθmin = 3.2º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −9→9
Tmin = 0.717, Tmax = 0.887k = −10→10
9107 measured reflectionsl = −16→18

Refinement

Refinement on F2Hydrogen site location: difference Fourier map
Least-squares matrix: fullAll H-atom parameters refined
R[F2 > 2σ(F2)] = 0.022  w = 1/[σ2(Fo2) + (0.039P)2 + 0.093P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.068(Δ/σ)max < 0.001
S = 1.05Δρmax = 0.37 e Å3
3246 reflectionsΔρmin = −0.22 e Å3
179 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.022 (3)
Secondary atom site location: difference Fourier map

Special details

Experimental. H atoms were located on intermediate difference Fourier map
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Mn10.50000.00000.50000.02323 (6)
O10.13139 (12)0.18659 (13)0.45633 (6)0.03342 (15)
O20.48182 (15)0.26842 (14)0.58308 (6)0.03732 (17)
O30.15295 (14)0.60925 (13)0.38023 (6)0.03452 (15)
H3A0.108 (4)0.639 (3)0.3151 (17)0.063 (5)*
H3B0.180 (4)0.488 (3)0.3935 (17)0.068 (6)*
N10.80858 (13)0.13919 (13)0.30839 (6)0.02546 (14)
N20.60467 (13)0.13162 (13)0.34123 (6)0.02647 (14)
N30.46087 (14)0.17201 (14)0.25572 (6)0.02953 (16)
N40.56698 (13)0.20725 (13)0.16459 (6)0.02663 (15)
N51.08450 (14)0.30165 (13)−0.16586 (6)0.02657 (14)
N61.28887 (14)0.30586 (14)−0.20234 (6)0.02983 (16)
N71.43373 (14)0.27581 (14)−0.12043 (6)0.03067 (16)
N81.32424 (13)0.25048 (12)−0.02771 (6)0.02534 (14)
C10.78023 (14)0.18638 (13)0.19858 (6)0.02208 (14)
C20.96111 (15)0.20610 (14)0.12755 (7)0.02469 (15)
C30.93208 (15)0.24900 (14)0.01755 (7)0.02401 (15)
C41.11010 (14)0.26607 (13)−0.05597 (6)0.02185 (14)
H30.794 (2)0.271 (2)−0.0175 (12)0.035 (3)*
H21.104 (3)0.186 (2)0.1658 (12)0.039 (4)*
H81.405 (3)0.232 (3)0.0389 (15)0.057 (5)*
H1A0.047 (3)0.239 (3)0.5070 (15)0.046 (4)*
H1B0.050 (3)0.155 (3)0.4134 (15)0.055 (5)*
H2B0.587 (3)0.304 (3)0.5865 (15)0.052 (4)*
H2A0.417 (3)0.280 (3)0.6422 (17)0.057 (5)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Mn10.02135 (10)0.03467 (10)0.01477 (8)−0.01276 (7)0.00178 (6)−0.00004 (6)
O10.0225 (3)0.0535 (4)0.0236 (3)−0.0133 (3)−0.0009 (2)−0.0078 (3)
O20.0443 (4)0.0551 (5)0.0264 (3)−0.0324 (4)0.0122 (3)−0.0141 (3)
O30.0370 (4)0.0392 (4)0.0279 (3)−0.0154 (3)−0.0016 (3)−0.0036 (3)
N10.0241 (3)0.0396 (4)0.0164 (3)−0.0169 (3)0.0007 (2)−0.0007 (2)
N20.0249 (3)0.0414 (4)0.0161 (3)−0.0170 (3)0.0019 (2)0.0003 (3)
N30.0255 (3)0.0484 (4)0.0179 (3)−0.0190 (3)0.0011 (2)0.0012 (3)
N40.0250 (3)0.0419 (4)0.0161 (3)−0.0174 (3)0.0002 (2)0.0011 (3)
N50.0283 (3)0.0380 (4)0.0167 (3)−0.0167 (3)0.0015 (2)−0.0020 (3)
N60.0302 (4)0.0437 (4)0.0185 (3)−0.0178 (3)0.0051 (3)−0.0027 (3)
N70.0268 (4)0.0464 (4)0.0213 (3)−0.0174 (3)0.0052 (3)−0.0024 (3)
N80.0230 (3)0.0373 (4)0.0172 (3)−0.0138 (3)0.0015 (2)−0.0006 (3)
C10.0232 (3)0.0296 (3)0.0159 (3)−0.0133 (3)0.0014 (2)−0.0012 (2)
C20.0236 (4)0.0351 (4)0.0190 (3)−0.0158 (3)0.0024 (3)−0.0014 (3)
C30.0234 (4)0.0332 (4)0.0189 (3)−0.0150 (3)0.0025 (3)−0.0019 (3)
C40.0234 (3)0.0277 (3)0.0164 (3)−0.0122 (3)0.0017 (2)−0.0021 (2)

Geometric parameters (Å, °)

Mn1—O2i2.1835 (8)N2—N31.3112 (10)
Mn1—O12.1923 (7)N3—N41.3336 (9)
Mn1—O22.1835 (8)N4—C11.3427 (11)
Mn1—O1i2.1923 (7)N5—C41.3304 (10)
Mn1—N2i2.2538 (7)N5—N61.3541 (10)
Mn1—N22.2538 (7)N6—N71.2931 (11)
O1—H1A0.823 (18)N7—N81.3420 (10)
O1—H1B0.833 (18)N8—C41.3403 (11)
O2—H2B0.790 (18)N8—H80.926 (18)
O2—H2A0.81 (2)C1—C21.4526 (11)
O3—H3A0.82 (2)C2—C31.3360 (11)
O3—H3B0.80 (2)C2—H20.963 (15)
N1—C11.3361 (10)C3—C41.4499 (11)
N1—N21.3468 (10)C3—H30.914 (14)
O2i—Mn1—O2180.0N3—N2—N1110.34 (6)
O2i—Mn1—O195.43 (3)N3—N2—Mn1115.77 (5)
O2—Mn1—O184.57 (3)N1—N2—Mn1132.31 (6)
O2i—Mn1—O1i84.57 (3)N2—N3—N4108.57 (7)
O2—Mn1—O1i95.43 (3)N3—N4—C1105.93 (7)
O1—Mn1—O1i180.0C4—N5—N6105.63 (7)
O2i—Mn1—N2i91.07 (3)N7—N6—N5111.07 (7)
O2—Mn1—N2i88.93 (3)N6—N7—N8106.55 (7)
O1—Mn1—N2i89.76 (3)C4—N8—N7108.63 (7)
O1i—Mn1—N2i90.24 (3)C4—N8—H8134.5 (11)
O2i—Mn1—N288.93 (3)N7—N8—H8116.8 (11)
O2—Mn1—N291.07 (3)N1—C1—N4110.73 (7)
O1—Mn1—N290.24 (3)N1—C1—C2123.47 (7)
O1i—Mn1—N289.76 (3)N4—C1—C2125.79 (7)
N2i—Mn1—N2179.999 (2)C3—C2—C1122.84 (8)
Mn1—O1—H1A116.9 (11)C3—C2—H2122.3 (9)
Mn1—O1—H1B125.3 (12)C1—C2—H2114.9 (9)
H1A—O1—H1B106.3 (16)C2—C3—C4124.29 (8)
Mn1—O2—H2B123.3 (13)C2—C3—H3121.3 (9)
Mn1—O2—H2A114.9 (13)C4—C3—H3114.4 (9)
H2B—O2—H2A109.2 (17)N5—C4—N8108.11 (7)
H3A—O3—H3B105.6 (18)N5—C4—C3124.43 (8)
C1—N1—N2104.43 (7)N8—C4—C3127.46 (7)
C1—N1—N2—N30.04 (10)N6—N7—N8—C4−0.01 (10)
C1—N1—N2—Mn1164.68 (7)N2—N1—C1—N4−0.02 (10)
O2i—Mn1—N2—N361.58 (7)N2—N1—C1—C2−178.57 (8)
O2—Mn1—N2—N3−118.42 (7)N3—N4—C1—N1−0.01 (10)
O1—Mn1—N2—N3−33.84 (7)N3—N4—C1—C2178.50 (8)
O1i—Mn1—N2—N3146.16 (7)N1—C1—C2—C3178.52 (9)
O2i—Mn1—N2—N1−102.42 (8)N4—C1—C2—C30.19 (14)
O2—Mn1—N2—N177.58 (8)C1—C2—C3—C4−178.84 (8)
O1—Mn1—N2—N1162.16 (8)N6—N5—C4—N80.29 (10)
O1i—Mn1—N2—N1−17.84 (8)N6—N5—C4—C3−179.93 (8)
N1—N2—N3—N4−0.05 (11)N7—N8—C4—N5−0.18 (10)
Mn1—N2—N3—N4−167.49 (6)N7—N8—C4—C3−179.96 (8)
N2—N3—N4—C10.03 (10)C2—C3—C4—N5177.57 (9)
C4—N5—N6—N7−0.30 (10)C2—C3—C4—N8−2.68 (15)
N5—N6—N7—N80.19 (11)

Symmetry codes: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1—H1B···N1ii0.833 (18)2.021 (18)2.8419 (10)168.8 (17)
O1—H1A···O3iii0.823 (18)1.940 (18)2.7599 (11)174.0 (16)
O2—H2B···O3iv0.790 (18)1.996 (19)2.7797 (11)171.4 (18)
O2—H2A···N6v0.81 (2)2.04 (2)2.8472 (10)173.7 (18)
O3—H3A···N5vi0.82 (2)2.09 (2)2.8922 (11)164.2 (19)
O3—H3B···O10.80 (2)2.30 (2)3.0693 (12)160 (2)
N8—H8···N4vii0.926 (18)1.792 (18)2.7171 (10)176.6 (16)

Symmetry codes: (ii) x−1, y, z; (iii) −x, −y+1, −z+1; (iv) −x+1, −y+1, −z+1; (v) x−1, y, z+1; (vi) −x+1, −y+1, −z; (vii) x+1, y, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: YA2068).

References

  • Bruker (2007). SMART and SAINT-Plus Bruker AXS Inc., Madison, Wisconsin, USA.
  • Demko, Z. P. & Sharpless, K. B. (2001). J. Org. Chem.66, 7945–7950. [PubMed]
  • Huang, X. F., Song, Y. M., Wu, Q., Ye, Q., Chen, X. B., Xiong, R. G. & You, X. Z. (2005). Inorg. Chem. Commun.8, 58–60.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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