Tetra-aqua-bis{5-[2-(1H-tetrazol-5-yl)ethenyl]pyrazolato-κN}manganese(II) dihydrate.

The title compound, [Mn(C(4)H(3)N(8))(2)(H(2)O)(4)]·2H(2)O, represents the first structurally characterized transition metal complex of the 1,2-bis-(tetra-zol-5-yl)ethene ligand. The complex mol-ecule occupies a special position on an inversion centre and the Mn atom has a tetra-gonally distorted octa-hedral coordination. The bis-(tetra-zolyl)ethene ligand is planar within 0.0366 (7) Å. All 'active' H atoms participate in hydrogen bonds, which link mol-ecules of the complex and the uncoordinated water mol-ecules into an infinite three-dimensional framework.

Related literature

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

Experimental

Crystal data

[Mn(C4H3N8)2(H2O)4]·2H2O

M = 489.32

Triclinic,

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

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

[Mn(C4H3N8)2(H2O)4]·2H2O	Z = 1
Mr = 489.32	F000 = 251
Triclinic, P1	Dx = 1.676 Mg m−3
Hall symbol: -P 1	Mo Kα radiation λ = 0.71073 Å
a = 6.2296 (2) Å	Cell parameters from 7983 reflections
b = 7.0093 (2) Å	θ = 3.2–33.5º
c = 12.1212 (3) Å	µ = 0.75 mm−1
α = 84.405 (1)º	T = 273 (2) K
β = 89.457 (1)º	Prism, brown
γ = 67.016 (1)º	0.36 × 0.28 × 0.16 mm
V = 484.70 (2) Å3

Bruker SMART CCD area-detector diffractometer	3246 independent reflections
Radiation source: fine-focus sealed tube	3149 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.015
T = 273(2) K	θmax = 33.5º
φ and ω scans	θmin = 3.2º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.717, Tmax = 0.887	k = −10→10
9107 measured reflections	l = −16→18

Refinement on F2	Hydrogen site location: difference Fourier map
Least-squares matrix: full	All 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 = 1.05	Δρmax = 0.37 e Å−3
3246 reflections	Δρmin = −0.22 e Å−3
179 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.022 (3)
Secondary atom site location: difference Fourier map

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.

	x	y	z	Uiso*/Ueq
Mn1	0.5000	0.0000	0.5000	0.02323 (6)
O1	0.13139 (12)	0.18659 (13)	0.45633 (6)	0.03342 (15)
O2	0.48182 (15)	0.26842 (14)	0.58308 (6)	0.03732 (17)
O3	0.15295 (14)	0.60925 (13)	0.38023 (6)	0.03452 (15)
H3A	0.108 (4)	0.639 (3)	0.3151 (17)	0.063 (5)*
H3B	0.180 (4)	0.488 (3)	0.3935 (17)	0.068 (6)*
N1	0.80858 (13)	0.13919 (13)	0.30839 (6)	0.02546 (14)
N2	0.60467 (13)	0.13162 (13)	0.34123 (6)	0.02647 (14)
N3	0.46087 (14)	0.17201 (14)	0.25572 (6)	0.02953 (16)
N4	0.56698 (13)	0.20725 (13)	0.16459 (6)	0.02663 (15)
N5	1.08450 (14)	0.30165 (13)	−0.16586 (6)	0.02657 (14)
N6	1.28887 (14)	0.30586 (14)	−0.20234 (6)	0.02983 (16)
N7	1.43373 (14)	0.27581 (14)	−0.12043 (6)	0.03067 (16)
N8	1.32424 (13)	0.25048 (12)	−0.02771 (6)	0.02534 (14)
C1	0.78023 (14)	0.18638 (13)	0.19858 (6)	0.02208 (14)
C2	0.96111 (15)	0.20610 (14)	0.12755 (7)	0.02469 (15)
C3	0.93208 (15)	0.24900 (14)	0.01755 (7)	0.02401 (15)
C4	1.11010 (14)	0.26607 (13)	−0.05597 (6)	0.02185 (14)
H3	0.794 (2)	0.271 (2)	−0.0175 (12)	0.035 (3)*
H2	1.104 (3)	0.186 (2)	0.1658 (12)	0.039 (4)*
H8	1.405 (3)	0.232 (3)	0.0389 (15)	0.057 (5)*
H1A	0.047 (3)	0.239 (3)	0.5070 (15)	0.046 (4)*
H1B	0.050 (3)	0.155 (3)	0.4134 (15)	0.055 (5)*
H2B	0.587 (3)	0.304 (3)	0.5865 (15)	0.052 (4)*
H2A	0.417 (3)	0.280 (3)	0.6422 (17)	0.057 (5)*

	U11	U22	U33	U12	U13	U23
Mn1	0.02135 (10)	0.03467 (10)	0.01477 (8)	−0.01276 (7)	0.00178 (6)	−0.00004 (6)
O1	0.0225 (3)	0.0535 (4)	0.0236 (3)	−0.0133 (3)	−0.0009 (2)	−0.0078 (3)
O2	0.0443 (4)	0.0551 (5)	0.0264 (3)	−0.0324 (4)	0.0122 (3)	−0.0141 (3)
O3	0.0370 (4)	0.0392 (4)	0.0279 (3)	−0.0154 (3)	−0.0016 (3)	−0.0036 (3)
N1	0.0241 (3)	0.0396 (4)	0.0164 (3)	−0.0169 (3)	0.0007 (2)	−0.0007 (2)
N2	0.0249 (3)	0.0414 (4)	0.0161 (3)	−0.0170 (3)	0.0019 (2)	0.0003 (3)
N3	0.0255 (3)	0.0484 (4)	0.0179 (3)	−0.0190 (3)	0.0011 (2)	0.0012 (3)
N4	0.0250 (3)	0.0419 (4)	0.0161 (3)	−0.0174 (3)	0.0002 (2)	0.0011 (3)
N5	0.0283 (3)	0.0380 (4)	0.0167 (3)	−0.0167 (3)	0.0015 (2)	−0.0020 (3)
N6	0.0302 (4)	0.0437 (4)	0.0185 (3)	−0.0178 (3)	0.0051 (3)	−0.0027 (3)
N7	0.0268 (4)	0.0464 (4)	0.0213 (3)	−0.0174 (3)	0.0052 (3)	−0.0024 (3)
N8	0.0230 (3)	0.0373 (4)	0.0172 (3)	−0.0138 (3)	0.0015 (2)	−0.0006 (3)
C1	0.0232 (3)	0.0296 (3)	0.0159 (3)	−0.0133 (3)	0.0014 (2)	−0.0012 (2)
C2	0.0236 (4)	0.0351 (4)	0.0190 (3)	−0.0158 (3)	0.0024 (3)	−0.0014 (3)
C3	0.0234 (4)	0.0332 (4)	0.0189 (3)	−0.0150 (3)	0.0025 (3)	−0.0019 (3)
C4	0.0234 (3)	0.0277 (3)	0.0164 (3)	−0.0122 (3)	0.0017 (2)	−0.0021 (2)

Mn1—O2i	2.1835 (8)	N2—N3	1.3112 (10)
Mn1—O1	2.1923 (7)	N3—N4	1.3336 (9)
Mn1—O2	2.1835 (8)	N4—C1	1.3427 (11)
Mn1—O1i	2.1923 (7)	N5—C4	1.3304 (10)
Mn1—N2i	2.2538 (7)	N5—N6	1.3541 (10)
Mn1—N2	2.2538 (7)	N6—N7	1.2931 (11)
O1—H1A	0.823 (18)	N7—N8	1.3420 (10)
O1—H1B	0.833 (18)	N8—C4	1.3403 (11)
O2—H2B	0.790 (18)	N8—H8	0.926 (18)
O2—H2A	0.81 (2)	C1—C2	1.4526 (11)
O3—H3A	0.82 (2)	C2—C3	1.3360 (11)
O3—H3B	0.80 (2)	C2—H2	0.963 (15)
N1—C1	1.3361 (10)	C3—C4	1.4499 (11)
N1—N2	1.3468 (10)	C3—H3	0.914 (14)
O2i—Mn1—O2	180.0	N3—N2—N1	110.34 (6)
O2i—Mn1—O1	95.43 (3)	N3—N2—Mn1	115.77 (5)
O2—Mn1—O1	84.57 (3)	N1—N2—Mn1	132.31 (6)
O2i—Mn1—O1i	84.57 (3)	N2—N3—N4	108.57 (7)
O2—Mn1—O1i	95.43 (3)	N3—N4—C1	105.93 (7)
O1—Mn1—O1i	180.0	C4—N5—N6	105.63 (7)
O2i—Mn1—N2i	91.07 (3)	N7—N6—N5	111.07 (7)
O2—Mn1—N2i	88.93 (3)	N6—N7—N8	106.55 (7)
O1—Mn1—N2i	89.76 (3)	C4—N8—N7	108.63 (7)
O1i—Mn1—N2i	90.24 (3)	C4—N8—H8	134.5 (11)
O2i—Mn1—N2	88.93 (3)	N7—N8—H8	116.8 (11)
O2—Mn1—N2	91.07 (3)	N1—C1—N4	110.73 (7)
O1—Mn1—N2	90.24 (3)	N1—C1—C2	123.47 (7)
O1i—Mn1—N2	89.76 (3)	N4—C1—C2	125.79 (7)
N2i—Mn1—N2	179.999 (2)	C3—C2—C1	122.84 (8)
Mn1—O1—H1A	116.9 (11)	C3—C2—H2	122.3 (9)
Mn1—O1—H1B	125.3 (12)	C1—C2—H2	114.9 (9)
H1A—O1—H1B	106.3 (16)	C2—C3—C4	124.29 (8)
Mn1—O2—H2B	123.3 (13)	C2—C3—H3	121.3 (9)
Mn1—O2—H2A	114.9 (13)	C4—C3—H3	114.4 (9)
H2B—O2—H2A	109.2 (17)	N5—C4—N8	108.11 (7)
H3A—O3—H3B	105.6 (18)	N5—C4—C3	124.43 (8)
C1—N1—N2	104.43 (7)	N8—C4—C3	127.46 (7)
C1—N1—N2—N3	0.04 (10)	N6—N7—N8—C4	−0.01 (10)
C1—N1—N2—Mn1	164.68 (7)	N2—N1—C1—N4	−0.02 (10)
O2i—Mn1—N2—N3	61.58 (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—C2	178.50 (8)
O1i—Mn1—N2—N3	146.16 (7)	N1—C1—C2—C3	178.52 (9)
O2i—Mn1—N2—N1	−102.42 (8)	N4—C1—C2—C3	0.19 (14)
O2—Mn1—N2—N1	77.58 (8)	C1—C2—C3—C4	−178.84 (8)
O1—Mn1—N2—N1	162.16 (8)	N6—N5—C4—N8	0.29 (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—C1	0.03 (10)	C2—C3—C4—N5	177.57 (9)
C4—N5—N6—N7	−0.30 (10)	C2—C3—C4—N8	−2.68 (15)
N5—N6—N7—N8	0.19 (11)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1B···N1ii	0.833 (18)	2.021 (18)	2.8419 (10)	168.8 (17)
O1—H1A···O3iii	0.823 (18)	1.940 (18)	2.7599 (11)	174.0 (16)
O2—H2B···O3iv	0.790 (18)	1.996 (19)	2.7797 (11)	171.4 (18)
O2—H2A···N6v	0.81 (2)	2.04 (2)	2.8472 (10)	173.7 (18)
O3—H3A···N5vi	0.82 (2)	2.09 (2)	2.8922 (11)	164.2 (19)
O3—H3B···O1	0.80 (2)	2.30 (2)	3.0693 (12)	160 (2)
N8—H8···N4vii	0.926 (18)	1.792 (18)	2.7171 (10)	176.6 (16)

Mn1—O1	2.1923 (7)
Mn1—O2	2.1835 (8)
Mn1—N2	2.2538 (7)

O2—Mn1—O1	84.57 (3)
O2—Mn1—N2	91.07 (3)
O1—Mn1—N2	90.24 (3)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯N1i	0.833 (18)	2.021 (18)	2.8419 (10)	168.8 (17)
O1—H1A⋯O3ii	0.823 (18)	1.940 (18)	2.7599 (11)	174.0 (16)
O2—H2B⋯O3iii	0.790 (18)	1.996 (19)	2.7797 (11)	171.4 (18)
O2—H2A⋯N6iv	0.81 (2)	2.04 (2)	2.8472 (10)	173.7 (18)
O3—H3A⋯N5v	0.82 (2)	2.09 (2)	2.8922 (11)	164.2 (19)
O3—H3B⋯O1	0.80 (2)	2.30 (2)	3.0693 (12)	160 (2)
N8—H8⋯N4vi	0.926 (18)	1.792 (18)	2.7171 (10)	176.6 (16)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .