Triaqua-dichlorido[5-(4-pyridinio)tetra-zolato-κN]cobalt(II) monohydrate.

The title compound, [CoCl(2)(C(6)H(5)N(5))(H(2)O)(3)]·H(2)O, was synthesized by hydro-thermal reaction of CoCl(2) with 4-(2H-tetra-zol-5-yl)pyridine. The Co(II) cation is coordinated by two Cl(-) ions, one N atom from the 5-(4-pyridinio)tetra-zolate zwitterion and three O atoms from three water mol-ecules in a distorted octa-hedral geometry. In the crystal, mol-ecules are linked into a three-dimensional network by N-H⋯Cl hydrogen bonds and O-H⋯O/N/Cl hydrogen bonds involv-ing both coordinated and uncoordinated water mol-ecules. Strong π-π stacking is present between parallel pyridinium and tetra-zolate rings [centroid-centroid distances = 3.411 (2) and 3.436 (2) Å].

Related literature

For general background to the chemistry of tetra­zole derivatives, see: Fu et al. (2007 ▶, 2008 ▶); Huang et al. (1999 ▶); Liu et al. (1999 ▶); Wang et al. (2005 ▶). For the crystal structures of related compounds, see: Dai & Fu (2008 ▶); Wen (2008 ▶); Wittenberger & Donner (1993 ▶).

Experimental

Crystal data

[CoCl2(C6H5N5)(H2O)3]·H2O

M = 349.04

Triclinic,

a = 6.4900 (13) Å

b = 9.842 (2) Å

c = 11.159 (2) Å

α = 110.72 (3)°

β = 97.05 (3)°

γ = 106.27 (3)°

V = 620.1 (3) Å3

Z = 2

Mo Kα radiation

μ = 1.83 mm−1

T = 298 K

0.15 × 0.15 × 0.10 mm

Data collection

Rigaku Mercury2 diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.762, T max = 0.841

6551 measured reflections

2842 independent reflections

2619 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.080

S = 1.18

2842 reflections

163 parameters

H-atom parameters constrained

Δρmax = 0.34 e Å−3

Δρmin = −0.49 e Å−3

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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 I, global. DOI: 10.1107/S1600536809024337/ci2831sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809024337/ci2831Isup2.hkl

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

[CoCl2(C6H5N5)(H2O)3]·H2O	Z = 2
Mr = 349.04	F(000) = 354
Triclinic, P1	Dx = 1.869 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.4900 (13) Å	Cell parameters from 2619 reflections
b = 9.842 (2) Å	θ = 3.4–27.5°
c = 11.159 (2) Å	µ = 1.83 mm−1
α = 110.72 (3)°	T = 298 K
β = 97.05 (3)°	Block, pink
γ = 106.27 (3)°	0.15 × 0.15 × 0.10 mm
V = 620.1 (3) Å3

Rigaku Mercury2 diffractometer	2842 independent reflections
Radiation source: fine-focus sealed tube	2619 reflections with I > 2σ(I)
graphite	Rint = 0.019
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.4°
CCD profile fitting scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −12→12
Tmin = 0.762, Tmax = 0.841	l = −14→14
6551 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.080	H-atom parameters constrained
S = 1.18	w = 1/[σ2(Fo2) + (0.0344P)2 + 0.391P] where P = (Fo2 + 2Fc2)/3
2842 reflections	(Δ/σ)max = 0.001
163 parameters	Δρmax = 0.34 e Å−3
0 restraints	Δρmin = −0.49 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
N5	0.6736 (3)	0.84317 (19)	0.28889 (17)	0.0224 (4)
C6	0.6810 (3)	0.8500 (2)	0.41148 (19)	0.0188 (4)
N1	0.8708 (3)	1.2651 (2)	0.74897 (19)	0.0281 (4)
H1A	0.9098	1.3503	0.8183	0.034*
N2	0.6143 (3)	0.70917 (18)	0.41274 (16)	0.0192 (3)
N4	0.5984 (3)	0.69178 (19)	0.21085 (16)	0.0224 (4)
C3	0.7487 (3)	0.9955 (2)	0.52968 (19)	0.0183 (4)
C5	0.8008 (4)	1.1310 (3)	0.7624 (2)	0.0301 (5)
H5	0.7952	1.1308	0.8452	0.036*
N3	0.5635 (3)	0.61292 (18)	0.28545 (16)	0.0197 (3)
C2	0.8224 (3)	1.1378 (2)	0.5204 (2)	0.0243 (4)
H2	0.8309	1.1419	0.4391	0.029*
C4	0.7372 (4)	0.9933 (2)	0.6525 (2)	0.0253 (4)
H4	0.6868	0.8994	0.6605	0.030*
C1	0.8826 (4)	1.2725 (2)	0.6330 (2)	0.0282 (5)
H1	0.9312	1.3682	0.6280	0.034*
Co1A	0.41776 (4)	0.36866 (3)	0.20745 (2)	0.01763 (9)
Cl2	0.08900 (9)	0.38823 (6)	0.08079 (5)	0.02643 (13)
Cl1	0.73776 (8)	0.35040 (6)	0.33499 (5)	0.02677 (13)
O1W	0.5652 (3)	0.33958 (19)	0.04986 (14)	0.0285 (3)
H1WA	0.7173	0.3570	0.0656	0.043*
H1WB	0.5254	0.3583	−0.0197	0.043*
O2W	0.2585 (3)	0.37067 (19)	0.35990 (15)	0.0296 (3)
H2WA	0.3037	0.3809	0.4362	0.044*
H2WB	0.1266	0.3867	0.3566	0.044*
O3W	0.2553 (3)	0.12646 (16)	0.12299 (15)	0.0266 (3)
H3WA	0.1036	0.0973	0.1231	0.040*
H3WB	0.2462	0.0857	0.0400	0.040*
O4W	0.1925 (3)	0.96192 (19)	0.85528 (16)	0.0363 (4)
H4WA	0.2306	1.0107	0.8093	0.054*
H4WB	0.2283	0.8803	0.8140	0.054*

	U11	U22	U33	U12	U13	U23
N5	0.0273 (9)	0.0172 (8)	0.0214 (8)	0.0062 (7)	0.0062 (7)	0.0075 (7)
C6	0.0169 (9)	0.0168 (9)	0.0209 (9)	0.0050 (7)	0.0041 (7)	0.0066 (7)
N1	0.0271 (9)	0.0175 (8)	0.0273 (9)	0.0062 (7)	0.0015 (7)	−0.0020 (7)
N2	0.0221 (8)	0.0155 (7)	0.0161 (8)	0.0052 (6)	0.0026 (6)	0.0040 (6)
N4	0.0280 (9)	0.0182 (8)	0.0191 (8)	0.0063 (7)	0.0049 (7)	0.0071 (7)
C3	0.0140 (8)	0.0161 (9)	0.0216 (9)	0.0056 (7)	0.0001 (7)	0.0053 (7)
C5	0.0356 (12)	0.0251 (11)	0.0225 (10)	0.0083 (9)	0.0043 (9)	0.0045 (9)
N3	0.0235 (8)	0.0161 (8)	0.0173 (8)	0.0058 (7)	0.0045 (7)	0.0054 (6)
C2	0.0254 (10)	0.0200 (10)	0.0282 (11)	0.0077 (8)	0.0066 (8)	0.0107 (8)
C4	0.0319 (11)	0.0189 (9)	0.0231 (10)	0.0082 (8)	0.0042 (8)	0.0075 (8)
C1	0.0247 (10)	0.0163 (9)	0.0405 (13)	0.0064 (8)	0.0065 (9)	0.0093 (9)
Co1A	0.02082 (15)	0.01475 (14)	0.01550 (15)	0.00521 (11)	0.00386 (11)	0.00507 (11)
Cl2	0.0265 (3)	0.0249 (3)	0.0237 (3)	0.0102 (2)	−0.0001 (2)	0.0064 (2)
Cl1	0.0260 (3)	0.0286 (3)	0.0274 (3)	0.0105 (2)	0.0033 (2)	0.0135 (2)
O1W	0.0259 (8)	0.0419 (9)	0.0191 (7)	0.0127 (7)	0.0067 (6)	0.0131 (7)
O2W	0.0331 (9)	0.0381 (9)	0.0230 (8)	0.0158 (7)	0.0124 (7)	0.0140 (7)
O3W	0.0318 (8)	0.0187 (7)	0.0218 (7)	0.0030 (6)	0.0043 (6)	0.0050 (6)
O4W	0.0518 (11)	0.0262 (8)	0.0300 (9)	0.0106 (8)	0.0174 (8)	0.0104 (7)

N5—N4	1.337 (2)	C4—H4	0.93
N5—C6	1.340 (3)	C1—H1	0.93
C6—N2	1.337 (2)	Co1A—O1W	2.0738 (16)
C6—C3	1.467 (3)	Co1A—O2W	2.0933 (16)
N1—C1	1.332 (3)	Co1A—O3W	2.1071 (17)
N1—C5	1.339 (3)	Co1A—Cl1	2.4568 (9)
N1—H1A	0.86	Co1A—Cl2	2.5041 (9)
N2—N3	1.335 (2)	O1W—H1WA	0.94
N4—N3	1.323 (2)	O1W—H1WB	0.88
C3—C4	1.389 (3)	O2W—H2WA	0.83
C3—C2	1.393 (3)	O2W—H2WB	0.91
C5—C4	1.377 (3)	O3W—H3WA	0.94
C5—H5	0.93	O3W—H3WB	0.86
N3—Co1A	2.1153 (18)	O4W—H4WA	0.83
C2—C1	1.379 (3)	O4W—H4WB	0.88
C2—H2	0.93
N4—N5—C6	104.78 (16)	C2—C1—H1	120.1
N2—C6—N5	112.14 (17)	O1W—Co1A—O2W	173.47 (6)
N2—C6—C3	124.23 (18)	O1W—Co1A—O3W	87.50 (7)
N5—C6—C3	123.61 (17)	O2W—Co1A—O3W	86.15 (7)
C1—N1—C5	122.93 (19)	O1W—Co1A—N3	92.57 (7)
C1—N1—H1A	118.5	O2W—Co1A—N3	93.86 (7)
C5—N1—H1A	118.5	O3W—Co1A—N3	176.39 (6)
N3—N2—C6	103.82 (16)	O1W—Co1A—Cl1	89.28 (5)
N3—N4—N5	108.68 (16)	O2W—Co1A—Cl1	89.42 (5)
C4—C3—C2	118.98 (19)	O3W—Co1A—Cl1	92.27 (6)
C4—C3—C6	120.36 (18)	N3—Co1A—Cl1	91.34 (6)
C2—C3—C6	120.65 (19)	O1W—Co1A—Cl2	91.67 (5)
N1—C5—C4	119.4 (2)	O2W—Co1A—Cl2	89.64 (5)
N1—C5—H5	120.3	O3W—Co1A—Cl2	87.85 (6)
C4—C5—H5	120.3	N3—Co1A—Cl2	88.54 (6)
N4—N3—N2	110.58 (15)	Cl1—Co1A—Cl2	179.04 (2)
N4—N3—Co1A	123.34 (12)	Co1A—O1W—H1WA	118.8
N2—N3—Co1A	125.83 (13)	Co1A—O1W—H1WB	125.5
C1—C2—C3	119.3 (2)	H1WA—O1W—H1WB	108.6
C1—C2—H2	120.4	Co1A—O2W—H2WA	131.9
C3—C2—H2	120.4	Co1A—O2W—H2WB	120.0
C5—C4—C3	119.6 (2)	H2WA—O2W—H2WB	106.3
C5—C4—H4	120.2	Co1A—O3W—H3WA	112.7
C3—C4—H4	120.2	Co1A—O3W—H3WB	112.6
N1—C1—C2	119.8 (2)	H3WA—O3W—H3WB	100.6
N1—C1—H1	120.1	H4WA—O4W—H4WB	98.3

D—H···A	D—H	H···A	D···A	D—H···A
O3W—H3WA···O4Wi	0.95	1.92	2.858 (3)	173
O3W—H3WB···O4Wii	0.86	1.91	2.761 (2)	170
O1W—H1WB···N4iii	0.88	2.01	2.848 (2)	157
O2W—H2WA···N2iv	0.83	2.24	2.999 (2)	153
O4W—H4WA···N5v	0.83	2.11	2.935 (3)	173
N1—H1A···Cl2v	0.86	2.41	3.180 (2)	149
O1W—H1WA···Cl2vi	0.94	2.32	3.254 (2)	174
O2W—H2WB···Cl1vii	0.91	2.42	3.300 (2)	163
O4W—H4WB···Cl1iv	0.88	2.38	3.249 (2)	168

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3W—H3WA⋯O4Wi	0.95	1.92	2.858 (3)	173
O3W—H3WB⋯O4Wii	0.86	1.91	2.761 (2)	170
O1W—H1WB⋯N4iii	0.88	2.01	2.848 (2)	157
O2W—H2WA⋯N2iv	0.83	2.24	2.999 (2)	153
O4W—H4WA⋯N5v	0.83	2.11	2.935 (3)	173
N1—H1A⋯Cl2v	0.86	2.41	3.180 (2)	149
O1W—H1WA⋯Cl2vi	0.94	2.32	3.254 (2)	174
O2W—H2WB⋯Cl1vii	0.91	2.42	3.300 (2)	163
O4W—H4WB⋯Cl1iv	0.88	2.38	3.249 (2)	168

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