Diaqua­bis(2,2′-biimidazole)cobalt(II) dichloride

Zhang, L.-C.; Zhu, Z.-M.; You, W.-S.; Chang, S.; Wang, E.-B.

doi:10.1107/S160053680706833X

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page m308

doi:10.1107/S160053680706833X

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Diaquabis(2,2′-biimidazole)cobalt(II) dichloride

Lan-Cui Zhang,^a,^b Zai-Ming Zhu,^b Wan-Sheng You,^c Song Chang ^a and En-Bo Wang ^a ^*

^aKey Laboratory of Polyoxometalate Science of the Ministry of Education, Faculty of Chemistry, Institute of Polyoxometalate Chemistry, Northeast Normal University, Ren Min Street No. 5268, Changchun, Jilin 130024, People's Republic of China, ^bCollege of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, People's Republic of China, and ^cInstitute of Chemistry for Functionalized Materials, College of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian 116029, People's Republic of China
^*Correspondence e-mail: wangenbo@public.cc.jl.cn

(Received 4 November 2007; accepted 24 December 2007; online 9 January 2008)

There are independent cations and four chloride anions in the crystal structure of the title complex, [Co(C₆H₆N₄)₂(H₂O)₂]Cl₂. In each cation, the Co^II cation is coordinated by four N atoms from two biimidazole and two O atoms of two water molecules; one Co atom is at a position of site symmetry m, the other at a position of site symmetry 2/m. All Cl⁻ ions and water molecules are also located on the mirror plane. Each structural unit is connected through O—H⋯Cl and N—H⋯Cl intermolecular hydrogen bonds, forming a three–dimensional supramolecular structure.

Related literature

For related literature, see: Barquin et al. (2003 ); Hirotoshi & Eisaku (2005 ); Tadokoro & Nakasuji (2000 ; Roth et al. (2000 ); Fieselmann et al. (1978 ).

Experimental

Crystal data

[Co(C₆H₆N₄)₂(H₂O)₂]Cl₂
M_r = 434.16
Monoclinic, C 2/m
a = 22.037 (3) Å
b = 12.5321 (17) Å
c = 9.6421 (13) Å
β = 95.848 (2)°
V = 2649.0 (6) Å³
Z = 6
Mo Kα radiation
μ = 1.30 mm⁻¹
T = 298 (2) K
0.16 × 0.12 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.819, T_max = 0.903
8119 measured reflections
3205 independent reflections
2291 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 0.085
S = 1.04
3205 reflections
200 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4B⋯Cl1ⁱ	0.86	2.40	3.213 (2)	157
N5—H5B⋯Cl3ⁱⁱ	0.86	2.42	3.2091 (19)	153
N6—H6B⋯Cl2ⁱ	0.86	2.42	3.210 (2)	154
O3W—H3C⋯Cl1ⁱ	0.86 (3)	2.29 (3)	3.150 (2)	175 (4)
O2W—H2B⋯Cl3ⁱⁱⁱ	0.86 (3)	2.34 (3)	3.180 (3)	166 (4)
O2W—H2C⋯Cl3^iv	0.860 (10)	2.236 (11)	3.096 (3)	178 (3)
O1W—H1A⋯Cl2	0.857 (10)	2.259 (11)	3.114 (2)	175 (3)
O1W—H1B⋯Cl1	0.857 (10)	2.285 (11)	3.139 (2)	174 (3)
O3W—H3B⋯Cl2	0.859 (10)	2.239 (11)	3.096 (2)	177 (3)
Symmetry codes: (i) x, y, z-1; (ii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (iii) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iv) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Bruker, 1997 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680706833X/rk2059sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680706833X/rk2059Isup2.hkl

checkCIF report

Comment top

The imidazole coordinated complexes have various structures and extensive uses in the field of catalysis, materials and bioactivity (Barquin et al., 2003; Hirotoshi & Eisaku, 2005). The bis(2,2'–biimidazole)dihydrate cobalt dichloride was synthesized. The 2,2'–biimidazole is an interesting dicyclo–ligand of containing four N atoms: the two N atoms forming coordinate bonds and the other two - uncoordinated N atoms of biimidazole form N—H···Cl hydrogen bonds. This crystal structure are constructed by intermolecular hydrogen bonds (Tadokoro & Nakasuji, 2000; Roth et al., 2000).

The average bond distance Co—N is of 2.1563 (18) Å, the average bond angle N—Co—N is 101.50 (8)°, the average bond distance Co—O is 2.091 (2) Å. These parameters show, that the polihedron configuration is distorted octahedron (Fig. 1.). The biimidazole moieties and Cl atoms are linked by N—H···Cl and the water molecules and Cl atoms are linked by O—H···Cl hydrogen bonds, which shown on Fig. 2.

Related literature top

For related literature, see: Barquin et al., 2003; Hirotoshi & Eisaku, 2005; Tadokoro & Nakasuji, 2000; Roth et al., 2000; Fieselmann et al., 1978.

Experimental top

The 2,2'–biimidazole was prepared according to (Fieselmann et al., 1978). 2,2'–Biimidazole (0.1 mmol) was mixed with 0.1 mmol CoCl₂^.6H₂O in solution. After 10 min of stirring, the precipitate was filtered off, the resulting clear solution was allowed to stand at room temperature, after a few days yellow block–shaped crystals were obtained.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL (Bruker, 1997).

Figures top

	Fig. 1. The molecular structure of the title complex with the atom labeling scheme. Displacement ellipsoids are drawn at 50% probability level. H atoms are presented as small spheres of arbitrary radius.
	Fig. 2. The packing diagram of title complex - viewed down the b axis. Dashed lines show hydrogen bonds.

Diaquabis(2,2'-biimidazole)cobalt(II) dichloride top

Crystal data top

[Co(C₆H₆N₄)₂(H₂O)₂]Cl₂	F(000) = 1326
M_r = 434.16	D_x = 1.633 Mg m⁻³
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 2062 reflections
a = 22.037 (3) Å	θ = 2.7–26.7°
b = 12.5321 (17) Å	µ = 1.30 mm⁻¹
c = 9.6421 (13) Å	T = 298 K
β = 95.848 (2)°	Block, yellow
V = 2649.0 (6) Å³	0.16 × 0.12 × 0.08 mm
Z = 6

Data collection top

Bruker SMART CCD area-detector diffractometer	3205 independent reflections
Radiation source: fine–focus sealed tube	2291 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ϕ and ω scans	θ_max = 27.7°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −24→28
T_min = 0.819, T_max = 0.903	k = −16→15
8119 measured reflections	l = −11→12

Refinement top

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0613P)²] where P = (F_o² + 2F_c²)/3
3205 reflections	(Δ/σ)_max = 0.001
200 parameters	Δρ_max = 0.29 e Å⁻³
6 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

[Co(C₆H₆N₄)₂(H₂O)₂]Cl₂	V = 2649.0 (6) Å³
M_r = 434.16	Z = 6
Monoclinic, C2/m	Mo Kα radiation
a = 22.037 (3) Å	µ = 1.30 mm⁻¹
b = 12.5321 (17) Å	T = 298 K
c = 9.6421 (13) Å	0.16 × 0.12 × 0.08 mm
β = 95.848 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3205 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	2291 reflections with I > 2σ(I)
T_min = 0.819, T_max = 0.903	R_int = 0.026
8119 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	6 restraints
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.29 e Å⁻³
3205 reflections	Δρ_min = −0.24 e Å⁻³
200 parameters

Special details top

Geometry. All s.u.'s (except the s.u.'s in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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) top

	x	y	z	U_iso*/U_eq
Co1	0.0000	0.0000	0.5000	0.03508 (16)
Co2	0.332770 (17)	0.0000	0.08867 (4)	0.03888 (14)
O1W	0.09155 (10)	0.0000	0.5815 (2)	0.0493 (6)
H1A	0.1231 (9)	0.0000	0.536 (3)	0.049 (10)*
H1B	0.0984 (16)	0.0000	0.6706 (11)	0.071 (12)*
O2W	0.42387 (11)	0.0000	0.0446 (2)	0.0836 (10)
H2B	0.4517 (13)	0.0000	0.114 (3)	0.090 (14)*
H2C	0.4321 (16)	0.0000	−0.0407 (16)	0.074 (12)*
O3W	0.24136 (10)	0.0000	0.1289 (2)	0.0544 (6)
H3B	0.2314 (15)	0.0000	0.2127 (16)	0.065 (12)*
H3C	0.2115 (12)	0.0000	0.064 (3)	0.083 (13)*
N1	0.01986 (7)	0.10903 (15)	0.33535 (16)	0.0378 (4)
N2	0.35622 (8)	0.10868 (16)	0.25695 (16)	0.0413 (4)
N3	0.30994 (8)	0.10867 (16)	−0.07959 (16)	0.0420 (4)
N4	0.05671 (8)	0.12463 (16)	0.13273 (17)	0.0458 (5)
H4B	0.0719	0.1074	0.0571	0.055*
N5	0.38823 (8)	0.12580 (16)	0.47968 (18)	0.0471 (5)
H5B	0.4007	0.1093	0.5644	0.056*
N6	0.27788 (8)	0.12601 (17)	−0.30166 (17)	0.0494 (5)
H6B	0.2653	0.1097	−0.3864	0.059*
C1	0.04173 (8)	0.05762 (17)	0.23184 (19)	0.0363 (5)
C2	0.02053 (10)	0.2150 (2)	0.2986 (2)	0.0446 (5)
H2A	0.0073	0.2710	0.3511	0.054*
C3	0.04345 (11)	0.2251 (2)	0.1741 (2)	0.0516 (6)
H3A	0.0490	0.2883	0.1264	0.062*
C4	0.37410 (9)	0.05749 (18)	0.37374 (19)	0.0379 (5)
C5	0.35969 (10)	0.2148 (2)	0.2901 (2)	0.0509 (6)
H5A	0.3502	0.2704	0.2277	0.061*
C6	0.37892 (11)	0.2268 (2)	0.4267 (2)	0.0546 (6)
H6A	0.3847	0.2907	0.4752	0.066*
C7	0.29209 (9)	0.05720 (19)	−0.19698 (19)	0.0397 (5)
C8	0.30664 (10)	0.2147 (2)	−0.1125 (2)	0.0526 (6)
H8A	0.3164	0.2702	−0.0501	0.063*
C9	0.28699 (10)	0.2271 (2)	−0.2492 (3)	0.0564 (6)
H9A	0.2809	0.2910	−0.2976	0.068*
Cl1	0.12670 (4)	0.0000	0.90521 (8)	0.0602 (3)
Cl2	0.21127 (4)	0.0000	0.43563 (7)	0.0551 (2)
Cl3	0.04319 (4)	0.5000	0.25997 (7)	0.0501 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0382 (3)	0.0427 (4)	0.0243 (3)	0.000	0.0025 (2)	0.000
Co2	0.0385 (2)	0.0531 (3)	0.0243 (2)	0.000	−0.00013 (16)	0.000
O1W	0.0386 (13)	0.0814 (19)	0.0279 (12)	0.000	0.0031 (10)	0.000
O2W	0.0386 (14)	0.181 (3)	0.0307 (14)	0.000	0.0011 (11)	0.000
O3W	0.0406 (13)	0.093 (2)	0.0289 (12)	0.000	0.0017 (10)	0.000
N1	0.0417 (10)	0.0429 (12)	0.0285 (8)	−0.0017 (8)	0.0025 (7)	−0.0009 (8)
N2	0.0435 (10)	0.0495 (13)	0.0293 (9)	−0.0028 (9)	−0.0034 (7)	0.0027 (8)
N3	0.0447 (10)	0.0503 (13)	0.0304 (9)	−0.0030 (9)	0.0008 (7)	0.0019 (8)
N4	0.0582 (12)	0.0493 (13)	0.0309 (9)	−0.0039 (10)	0.0096 (8)	0.0030 (8)
N5	0.0574 (12)	0.0506 (13)	0.0307 (9)	−0.0015 (10)	−0.0080 (8)	−0.0006 (9)
N6	0.0546 (12)	0.0630 (15)	0.0296 (9)	−0.0007 (10)	−0.0002 (8)	0.0054 (9)
C1	0.0365 (11)	0.0453 (13)	0.0265 (10)	−0.0024 (9)	0.0003 (8)	0.0024 (9)
C2	0.0488 (13)	0.0448 (15)	0.0397 (12)	−0.0014 (11)	0.0018 (9)	−0.0037 (10)
C3	0.0629 (15)	0.0451 (16)	0.0468 (14)	−0.0034 (13)	0.0055 (11)	0.0066 (11)
C4	0.0372 (11)	0.0476 (13)	0.0283 (10)	−0.0022 (10)	−0.0003 (8)	−0.0015 (9)
C5	0.0551 (14)	0.0509 (16)	0.0445 (13)	−0.0044 (12)	−0.0059 (10)	0.0076 (11)
C6	0.0637 (15)	0.0473 (16)	0.0504 (14)	−0.0053 (13)	−0.0066 (11)	−0.0051 (12)
C7	0.0364 (11)	0.0540 (14)	0.0287 (10)	0.0006 (10)	0.0030 (8)	0.0037 (9)
C8	0.0546 (14)	0.0570 (18)	0.0459 (13)	−0.0091 (12)	0.0040 (11)	0.0014 (12)
C9	0.0639 (16)	0.0559 (18)	0.0489 (14)	−0.0009 (13)	0.0032 (12)	0.0097 (12)
Cl1	0.0536 (5)	0.0994 (8)	0.0274 (4)	0.000	0.0029 (3)	0.000
Cl2	0.0528 (5)	0.0848 (7)	0.0280 (4)	0.000	0.0056 (3)	0.000
Cl3	0.0622 (5)	0.0554 (6)	0.0305 (4)	0.000	−0.0065 (3)	0.000

Geometric parameters (Å, º) top

Co1—O1W	2.089 (2)	N3—C8	1.366 (3)
Co1—O1Wⁱ	2.089 (2)	N4—C1	1.338 (3)
Co1—N1ⁱⁱ	2.1727 (17)	N4—C3	1.362 (3)
Co1—N1ⁱ	2.1727 (17)	N4—H4B	0.8600
Co1—N1ⁱⁱⁱ	2.1727 (17)	N5—C4	1.345 (3)
Co1—N1	2.1727 (17)	N5—C6	1.372 (3)
Co2—O3W	2.090 (2)	N5—H5B	0.8600
Co2—O2W	2.094 (2)	N6—C7	1.340 (3)
Co2—N3ⁱⁱⁱ	2.1386 (18)	N6—C9	1.371 (3)
Co2—N3	2.1386 (18)	N6—H6B	0.8600
Co2—N2	2.1410 (18)	C1—C1ⁱⁱⁱ	1.444 (4)
Co2—N2ⁱⁱⁱ	2.1410 (18)	C2—C3	1.355 (3)
O1W—H1A	0.857 (10)	C2—H2A	0.9300
O1W—H1B	0.857 (10)	C3—H3A	0.9300
O2W—H2B	0.86 (3)	C4—C4ⁱⁱⁱ	1.441 (4)
O2W—H2C	0.860 (10)	C5—C6	1.351 (3)
O3W—H3B	0.859 (10)	C5—H5A	0.9300
O3W—H3C	0.86 (3)	C6—H6A	0.9300
N1—C1	1.320 (2)	C7—C7ⁱⁱⁱ	1.434 (5)
N1—C2	1.374 (3)	C8—C9	1.354 (3)
N2—C4	1.321 (3)	C8—H8A	0.9300
N2—C5	1.368 (3)	C9—H9A	0.9300
N3—C7	1.327 (3)

O1W—Co1—O1Wⁱ	180.00 (4)	C4—N2—C5	105.57 (17)
O1W—Co1—N1ⁱⁱ	89.08 (6)	C4—N2—Co2	111.42 (15)
O1Wⁱ—Co1—N1ⁱⁱ	90.92 (6)	C5—N2—Co2	143.01 (14)
O1W—Co1—N1ⁱ	89.08 (6)	C7—N3—C8	105.70 (18)
O1Wⁱ—Co1—N1ⁱ	90.92 (6)	C7—N3—Co2	111.34 (16)
N1ⁱⁱ—Co1—N1ⁱ	77.93 (9)	C8—N3—Co2	142.96 (15)
O1W—Co1—N1ⁱⁱⁱ	90.92 (6)	C1—N4—C3	107.16 (18)
O1Wⁱ—Co1—N1ⁱⁱⁱ	89.08 (6)	C1—N4—H4B	126.4
N1ⁱⁱ—Co1—N1ⁱⁱⁱ	180.0	C3—N4—H4B	126.4
N1ⁱ—Co1—N1ⁱⁱⁱ	102.07 (9)	C4—N5—C6	106.87 (18)
O1W—Co1—N1	90.92 (6)	C4—N5—H5B	126.6
O1Wⁱ—Co1—N1	89.08 (6)	C6—N5—H5B	126.6
N1ⁱⁱ—Co1—N1	102.07 (9)	C7—N6—C9	107.62 (19)
N1ⁱ—Co1—N1	180.0	C7—N6—H6B	126.2
N1ⁱⁱⁱ—Co1—N1	77.93 (9)	C9—N6—H6B	126.2
O3W—Co2—O2W	179.00 (9)	N1—C1—N4	111.7 (2)
O3W—Co2—N3ⁱⁱⁱ	89.09 (6)	N1—C1—C1ⁱⁱⁱ	119.22 (12)
O2W—Co2—N3ⁱⁱⁱ	90.14 (7)	N4—C1—C1ⁱⁱⁱ	128.86 (12)
O3W—Co2—N3	89.09 (6)	C3—C2—N1	109.5 (2)
O2W—Co2—N3	90.14 (7)	C3—C2—H2A	125.2
N3ⁱⁱⁱ—Co2—N3	79.11 (10)	N1—C2—H2A	125.2
O3W—Co2—N2	91.27 (7)	C2—C3—N4	106.4 (2)
O2W—Co2—N2	89.50 (7)	C2—C3—H3A	126.8
N3ⁱⁱⁱ—Co2—N2	179.64 (7)	N4—C3—H3A	126.8
N3—Co2—N2	100.94 (7)	N2—C4—N5	111.4 (2)
O3W—Co2—N2ⁱⁱⁱ	91.27 (7)	N2—C4—C4ⁱⁱⁱ	119.06 (12)
O2W—Co2—N2ⁱⁱⁱ	89.50 (7)	N5—C4—C4ⁱⁱⁱ	129.54 (12)
N3ⁱⁱⁱ—Co2—N2ⁱⁱⁱ	100.94 (7)	C6—C5—N2	109.9 (2)
N3—Co2—N2ⁱⁱⁱ	179.64 (7)	C6—C5—H5A	125.0
N2—Co2—N2ⁱⁱⁱ	79.01 (10)	N2—C5—H5A	125.0
Co1—O1W—H1A	128 (2)	C5—C6—N5	106.3 (2)
Co1—O1W—H1B	116 (2)	C5—C6—H6A	126.9
H1A—O1W—H1B	116 (3)	N5—C6—H6A	126.9
Co2—O2W—H2B	118 (3)	N3—C7—N6	110.8 (2)
Co2—O2W—H2C	120 (2)	N3—C7—C7ⁱⁱⁱ	119.08 (13)
H2B—O2W—H2C	123 (4)	N6—C7—C7ⁱⁱⁱ	130.05 (13)
Co2—O3W—H3B	121 (2)	C9—C8—N3	110.0 (2)
Co2—O3W—H3C	123 (3)	C9—C8—H8A	125.0
H3B—O3W—H3C	116 (3)	N3—C8—H8A	125.0
C1—N1—C2	105.19 (17)	C8—C9—N6	105.8 (2)
C1—N1—Co1	111.22 (14)	C8—C9—H9A	127.1
C2—N1—Co1	143.52 (14)	N6—C9—H9A	127.1

Symmetry codes: (i) −x, −y, −z+1; (ii) −x, y, −z+1; (iii) x, −y, z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···Cl1^iv	0.86	2.40	3.213 (2)	157
N5—H5B···Cl3^v	0.86	2.42	3.2091 (19)	153
N6—H6B···Cl2^iv	0.86	2.42	3.210 (2)	154
O3W—H3C···Cl1^iv	0.86 (3)	2.29 (3)	3.150 (2)	175 (4)
O2W—H2B···Cl3^vi	0.86 (3)	2.34 (3)	3.180 (3)	166 (4)
O2W—H2C···Cl3^vii	0.86 (1)	2.24 (1)	3.096 (3)	178 (3)
O1W—H1A···Cl2	0.86 (1)	2.26 (1)	3.114 (2)	175 (3)
O1W—H1B···Cl1	0.86 (1)	2.29 (1)	3.139 (2)	174 (3)
O3W—H3B···Cl2	0.86 (1)	2.24 (1)	3.096 (2)	177 (3)

Symmetry codes: (iv) x, y, z−1; (v) −x+1/2, −y+1/2, −z+1; (vi) x+1/2, y−1/2, z; (vii) −x+1/2, −y+1/2, −z.

Experimental details

Crystal data
Chemical formula	[Co(C₆H₆N₄)₂(H₂O)₂]Cl₂
M_r	434.16
Crystal system, space group	Monoclinic, C2/m
Temperature (K)	298
a, b, c (Å)	22.037 (3), 12.5321 (17), 9.6421 (13)
β (°)	95.848 (2)
V (Å³)	2649.0 (6)
Z	6
Radiation type	Mo Kα
µ (mm⁻¹)	1.30
Crystal size (mm)	0.16 × 0.12 × 0.08

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2003)
T_min, T_max	0.819, 0.903
No. of measured, independent and observed [I > 2σ(I)] reflections	8119, 3205, 2291
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.655

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.085, 1.05
No. of reflections	3205
No. of parameters	200
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.24

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Bruker, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4B···Cl1ⁱ	0.86	2.40	3.213 (2)	156.9
N5—H5B···Cl3ⁱⁱ	0.86	2.42	3.2091 (19)	153.2
N6—H6B···Cl2ⁱ	0.86	2.42	3.210 (2)	153.8
O3W—H3C···Cl1ⁱ	0.86 (3)	2.29 (3)	3.150 (2)	175 (4)
O2W—H2B···Cl3ⁱⁱⁱ	0.86 (3)	2.34 (3)	3.180 (3)	166 (4)
O2W—H2C···Cl3^iv	0.860 (10)	2.236 (11)	3.096 (3)	178 (3)
O1W—H1A···Cl2	0.857 (10)	2.259 (11)	3.114 (2)	175 (3)
O1W—H1B···Cl1	0.857 (10)	2.285 (11)	3.139 (2)	174 (3)
O3W—H3B···Cl2	0.859 (10)	2.239 (11)	3.096 (2)	177 (3)

Symmetry codes: (i) x, y, z−1; (ii) −x+1/2, −y+1/2, −z+1; (iii) x+1/2, y−1/2, z; (iv) −x+1/2, −y+1/2, −z.

Acknowledgements

The authors are grateful to Professor Guang-Ning Zhang for his selfless help with our work.

References

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