Di-μ-sulfato-κ4O:O′-bis­[diaqua­(1H-imidazo[4,5-f][1,10]phenanthroline-κ2N7,N9)cobalt(II)] dihydrate

Gong, Y.; Zhou, Y.; Li, J.; Wu, X.; Qin, J.

doi:10.1107/S1600536809024295

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 8| August 2009| Pages m844-m845

doi:10.1107/S1600536809024295

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Di-μ-sulfato-κ⁴O:O′-bis[diaqua(1H-imidazo[4,5-f][1,10]phenanthroline-κ²N⁷,N⁹)cobalt(II)] dihydrate

Yun Gong,^a ^* Yuchao Zhou,^a Jinghua Li,^b Xiaoxia Wu ^b and Jianbo Qin ^a

^aDepartment of Chemistry, College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, People's Republic of China, and ^bDepartment of Pharmaceutical Chemistry, College of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044, People's Republic of China
^*Correspondence e-mail: gongyun7211@yahoo.com.cn

(Received 23 June 2009; accepted 24 June 2009; online 1 July 2009)

In the centrosymmetric dinuclear title compound, [Co₂(SO₄)₂(C₁₃H₈N₄)₂(H₂O)₄]·2H₂O, the Co^II atom is coordinated by two N atoms from two 1H-imidazo[4,5-f][1,10]phenanthroline ligands, two O atoms from two sulfate anions and two O atoms from water molecules in a distorted octahedral geometry. The Co⋯Co separation is 5.1167 (7) Å. The coordinated and uncoordinated water molecules engage in N—H⋯O and O—H⋯O hydrogen-bonding interactions.

Related literature

For related compounds, see: Jing et al. (2000 , 2004 ); Nagababu & Satyanarayana (2007 ); Selvi & Palaniandavar (2002 ); Shavaleev et al. (2007 ); Wang et al. (2008 ); Wu et al. (1997 ).

Experimental

Crystal data

[Co₂(SO₄)₂(C₁₃H₈N₄)₂(H₂O)₄]·2H₂O
M_r = 858.54
Monoclinic, P 2₁ /c
a = 10.3160 (13) Å
b = 9.0716 (10) Å
c = 16.8549 (17) Å
β = 99.1040 (10)°
V = 1557.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.29 mm⁻¹
T = 298 K
0.43 × 0.36 × 0.22 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.581, T_max = 0.754
7558 measured reflections
2742 independent reflections
2329 reflections with I > 2σ(I)
R_int = 0.020

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.073
S = 1.07
2742 reflections
235 parameters
H-atom parameters constrained
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—N1	2.124 (2)
Co1—N2	2.137 (2)
Co1—O6	2.0654 (19)
Co1—O1	2.0889 (17)
Co1—O2	2.0978 (17)
Co1—O5	2.1468 (18)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O4ⁱ	0.86	2.05	2.886 (3)	165
O5—H5A⋯O3	0.85	1.94	2.764 (2)	165
O6—H6B⋯O7ⁱⁱ	0.85	1.79	2.634 (3)	174
O7—H7B⋯O3ⁱⁱⁱ	0.85	2.00	2.843 (3)	176
Symmetry codes: (i) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) x, y-1, z; (iii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809024295/ng2604sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809024295/ng2604Isup2.hkl

checkCIF report

Comment top

Transitional metal complexes with the diimine ligands have potential applications in catalysis, molecular adsorption, magnetism, nonlinear optics, and molecular sensing. Imidazo[4,5-f]-1,10- phenanthroline (IP) ligand possesses good coordination ability due to the hetercyclic nitrogen atoms in the structure. The IP ligand is easy to prepare and modify and therefore have recently gained a lot of interest with respect to synthesis of its novel metal compounds. Most of its metal complexes are focused on Pt complexes (Shavaleev, et al., 2007) and Ru complexes (Wu, et al., 1997; Jing, et al., 2000; Jing, et al., 2004). Several Co-IP complexes have been reported in the presence of co-ligands such as 1,10-phenanthroline, 2,2'-bipyridine or ethylenediamine (Selvi, et al., 2002; Nagababu, et al., 2007). A Ni-IP complex has been reported recently (Wang, et al., 2008), which exhibits a mononuclear structure. In the present paper, we hydrothermally synthesized a novel coordination complex constructed from CoSO₄ and IP.

The molecular structure of the complex (I) (Fig. 1) has one Co(II), one IP, two coordinated water molecules, one sulfuric anion and one dissociated water molecule in its asymmetric unit. The Co(II) center is six-coordinated by two nitrogen atoms from two IP ligands, two oxygen atoms from water and two oxygen atoms from two sulfuric anions in a distorted octahedral geometry. Each IP ligand is chelate-coordinated to one Co(II) with two nitrogen atoms uncoordinated (Fig.1). Two sulfuric anions bridge two Co(II) centers to form a dinuclear cobalt clusters with the Co···Co separation of 5.1167 (7) Å (Fig. 1). Strong hydrogen bonds exist in the structure (Table 2).

Strong π–π stacking interactions are observed in the structure. For example: Aromatic phenyl rings 1 and 2 are composed of C4, C5, C6, C7, C11, C12 and C4A, C5A, C6A, C7A, C11A, C12A (atom with additional label A refers to the symmetry operation: 2- x, - y, - z). The perpendicular distance and the centroid-centroid distance are 3.41Å, and 4.251 (6)Å, respectively.

Related literature top

For related compounds, see: Jing et al. (2000, 2004); Nagababu et al. (2007); Selvi et al. (2002); Shavaleev et al. (2007); Wang et al. (2008); Wu et al. (1997).

Experimental top

The ligand IP was synthesised according to the procedure published already (Wu, et al., 1997). Yield: 87%. HNMR (DMSO-d6): 9.06(dd, 2H), 8.87(d, 2H), 8.50(s, 1H), 7.83(dd, 2H).

A mixture of IP (0.05 mmol, 0.011 g), CoSO₄7H₂O (0.1 mmol, 0.028 g), KSCN (0.1mmol, 0.010g ) and water (8 ml) was put into a Teflon-lined autoclave. The reaction mixture was heated at 120 centigrade for two day, followed by slow cooling to room temperatrue and brown single crystals were collected. Elemental analyse found: C, 36.36; H, 3.26; N, 13.05%.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. The structure of (I), with the atomic numbering scheme and displacement ellipsoids at the 30% probability level (H atoms omitted for clarity). [Symmetry codes: (i) -1-x,1-y,-z.]
	Fig. 2. Three dimensional supramolecular architecture constructed by intermolecular hydrogen bonds. The dotted lines indicate the hydrogen bonds.

Di-µ-sulfato-κ⁴O:O'-bis[diaqua(imidazo[4,5- f][1,10]phenanthroline-κ²N⁷,N⁹)cobalt(II)] dihydrate top

Crystal data top

[Co₂(SO₄)₂(C₁₃H₈N₄)₂(H₂O)₄]·2H₂O	F(000) = 876
M_r = 858.54	D_x = 1.831 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 7558 reflections
a = 10.3160 (13) Å	θ = 2.0–25.0°
b = 9.0716 (10) Å	µ = 1.29 mm⁻¹
c = 16.8549 (17) Å	T = 298 K
β = 99.104 (1)°	Block, brown
V = 1557.5 (3) Å³	0.43 × 0.36 × 0.22 mm
Z = 2

Data collection top

Siemens SMART CCD area-detector diffractometer	2742 independent reflections
Radiation source: fine-focus sealed tube	2329 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→8
T_min = 0.581, T_max = 0.754	k = −10→10
7558 measured reflections	l = −19→20

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.073	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0289P)² + 1.5148P] where P = (F_o² + 2F_c²)/3
2742 reflections	(Δ/σ)_max < 0.001
235 parameters	Δρ_max = 0.63 e Å⁻³
0 restraints	Δρ_min = −0.36 e Å⁻³

Crystal data top

[Co₂(SO₄)₂(C₁₃H₈N₄)₂(H₂O)₄]·2H₂O	V = 1557.5 (3) Å³
M_r = 858.54	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.3160 (13) Å	µ = 1.29 mm⁻¹
b = 9.0716 (10) Å	T = 298 K
c = 16.8549 (17) Å	0.43 × 0.36 × 0.22 mm
β = 99.104 (1)°

Data collection top

Siemens SMART CCD area-detector diffractometer	2742 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2329 reflections with I > 2σ(I)
T_min = 0.581, T_max = 0.754	R_int = 0.020
7558 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.073	H-atom parameters constrained
S = 1.07	Δρ_max = 0.63 e Å⁻³
2742 reflections	Δρ_min = −0.36 e Å⁻³
235 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Co1	0.68903 (3)	0.31926 (4)	0.04124 (2)	0.02494 (12)
N1	0.8745 (2)	0.3237 (2)	0.11677 (12)	0.0266 (5)
N2	0.75649 (19)	0.0980 (2)	0.03284 (12)	0.0254 (5)
N3	1.2464 (2)	−0.0127 (2)	0.20274 (13)	0.0326 (5)
H3	1.3069	0.0380	0.2315	0.039*
N4	1.1436 (2)	−0.2056 (2)	0.13930 (13)	0.0339 (5)
O1	0.53904 (16)	0.29041 (18)	−0.05637 (10)	0.0302 (4)
O2	0.63548 (17)	0.53058 (18)	0.07489 (11)	0.0339 (4)
O3	0.56078 (16)	0.51259 (19)	−0.13340 (10)	0.0307 (4)
O4	0.40919 (19)	0.3224 (2)	−0.18590 (11)	0.0399 (5)
O5	0.79510 (17)	0.4343 (2)	−0.03947 (10)	0.0323 (4)
H5A	0.7307	0.4726	−0.0703	0.039*
H5B	0.8276	0.3690	−0.0667	0.039*
O6	0.5767 (2)	0.2368 (2)	0.12221 (12)	0.0472 (5)
H6A	0.5151	0.2917	0.1330	0.057*
H6B	0.5745	0.1555	0.1470	0.057*
O7	0.5866 (3)	0.9854 (2)	0.20115 (13)	0.0658 (7)
H7A	0.5836	0.8952	0.1873	0.079*
H7B	0.5822	0.9896	0.2510	0.079*
S1	0.46794 (6)	0.39915 (6)	−0.11220 (4)	0.02442 (15)
C1	0.9322 (3)	0.4409 (3)	0.15383 (16)	0.0312 (6)
H1	0.8867	0.5298	0.1501	0.037*
C2	1.0586 (3)	0.4365 (3)	0.19832 (16)	0.0335 (6)
H2	1.0963	0.5212	0.2232	0.040*
C3	1.1263 (3)	0.3062 (3)	0.20491 (16)	0.0322 (6)
H3A	1.2097	0.3008	0.2352	0.039*
C4	1.0685 (2)	0.1811 (3)	0.16548 (14)	0.0255 (5)
C5	0.9415 (2)	0.1946 (3)	0.12104 (14)	0.0239 (5)
C6	0.8762 (2)	0.0708 (3)	0.07713 (14)	0.0231 (5)
C7	0.9348 (2)	−0.0701 (3)	0.08041 (14)	0.0247 (5)
C8	0.8635 (3)	−0.1852 (3)	0.03828 (16)	0.0304 (6)
H8	0.8987	−0.2797	0.0390	0.036*
C9	0.7410 (3)	−0.1567 (3)	−0.00397 (16)	0.0333 (6)
H9	0.6916	−0.2323	−0.0310	0.040*
C10	0.6914 (2)	−0.0137 (3)	−0.00605 (15)	0.0305 (6)
H10	0.6092	0.0044	−0.0359	0.037*
C11	1.1259 (2)	0.0376 (3)	0.16564 (15)	0.0265 (5)
C12	1.0637 (2)	−0.0818 (3)	0.12648 (15)	0.0260 (5)
C13	1.2505 (3)	−0.1568 (3)	0.18502 (17)	0.0378 (7)
H13	1.3222	−0.2167	0.2033	0.045*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.02401 (19)	0.02377 (19)	0.0260 (2)	0.00539 (14)	0.00088 (13)	0.00188 (14)
N1	0.0291 (11)	0.0243 (11)	0.0257 (11)	0.0054 (9)	0.0026 (9)	0.0006 (9)
N2	0.0233 (11)	0.0275 (11)	0.0246 (11)	0.0037 (9)	0.0015 (8)	0.0013 (9)
N3	0.0276 (11)	0.0378 (12)	0.0288 (12)	0.0042 (10)	−0.0068 (9)	−0.0011 (10)
N4	0.0355 (12)	0.0316 (12)	0.0328 (13)	0.0118 (10)	0.0004 (10)	0.0020 (10)
O1	0.0297 (9)	0.0255 (9)	0.0323 (10)	0.0025 (7)	−0.0046 (8)	0.0043 (8)
O2	0.0317 (10)	0.0241 (9)	0.0478 (11)	0.0049 (8)	0.0117 (8)	−0.0021 (8)
O3	0.0310 (9)	0.0289 (9)	0.0325 (10)	0.0035 (8)	0.0061 (8)	0.0049 (8)
O4	0.0504 (12)	0.0338 (10)	0.0302 (10)	0.0044 (9)	−0.0102 (9)	−0.0075 (8)
O5	0.0311 (10)	0.0350 (10)	0.0307 (10)	0.0052 (8)	0.0044 (8)	0.0005 (8)
O6	0.0587 (13)	0.0317 (10)	0.0586 (14)	0.0165 (10)	0.0318 (11)	0.0167 (10)
O7	0.129 (2)	0.0306 (11)	0.0426 (13)	0.0143 (13)	0.0287 (14)	0.0071 (10)
S1	0.0258 (3)	0.0217 (3)	0.0239 (3)	0.0051 (2)	−0.0016 (2)	−0.0010 (2)
C1	0.0388 (15)	0.0237 (13)	0.0308 (14)	0.0034 (11)	0.0046 (11)	−0.0012 (11)
C2	0.0372 (15)	0.0291 (14)	0.0335 (15)	−0.0045 (12)	0.0029 (12)	−0.0052 (11)
C3	0.0273 (13)	0.0356 (15)	0.0315 (15)	−0.0006 (11)	−0.0023 (11)	−0.0032 (12)
C4	0.0254 (13)	0.0284 (13)	0.0224 (13)	0.0026 (11)	0.0025 (10)	0.0003 (10)
C5	0.0257 (13)	0.0232 (12)	0.0228 (13)	0.0039 (10)	0.0037 (10)	0.0014 (10)
C6	0.0246 (12)	0.0233 (12)	0.0211 (12)	0.0029 (10)	0.0029 (10)	0.0020 (10)
C7	0.0275 (13)	0.0249 (12)	0.0219 (13)	0.0021 (10)	0.0046 (10)	0.0035 (10)
C8	0.0370 (14)	0.0219 (13)	0.0320 (14)	0.0029 (11)	0.0051 (11)	0.0001 (11)
C9	0.0349 (15)	0.0283 (14)	0.0349 (15)	−0.0056 (11)	0.0002 (12)	−0.0039 (12)
C10	0.0245 (13)	0.0341 (14)	0.0309 (14)	0.0003 (11)	−0.0015 (10)	−0.0023 (12)
C11	0.0245 (12)	0.0303 (13)	0.0240 (13)	0.0058 (11)	0.0014 (10)	0.0030 (11)
C12	0.0284 (13)	0.0267 (13)	0.0230 (13)	0.0071 (10)	0.0047 (10)	0.0029 (10)
C13	0.0368 (16)	0.0401 (16)	0.0341 (16)	0.0169 (13)	−0.0021 (12)	0.0036 (12)

Geometric parameters (Å, º) top

Co1—N1	2.124 (2)	O7—H7A	0.8500
Co1—N2	2.137 (2)	O7—H7B	0.8500
Co1—O6	2.0654 (19)	S1—O2ⁱ	1.4671 (18)
Co1—O1	2.0889 (17)	C1—C2	1.398 (4)
Co1—O2	2.0978 (17)	C1—H1	0.9300
Co1—O5	2.1468 (18)	C2—C3	1.369 (4)
N1—C1	1.326 (3)	C2—H2	0.9300
N1—C5	1.356 (3)	C3—C4	1.400 (3)
N2—C10	1.330 (3)	C3—H3A	0.9300
N2—C6	1.360 (3)	C4—C5	1.408 (3)
N3—C13	1.343 (3)	C4—C11	1.430 (3)
N3—C11	1.378 (3)	C5—C6	1.451 (3)
N3—H3	0.8600	C6—C7	1.411 (3)
N4—C13	1.318 (4)	C7—C8	1.404 (3)
N4—C12	1.390 (3)	C7—C12	1.433 (3)
O1—S1	1.4758 (17)	C8—C9	1.373 (4)
O2—S1ⁱ	1.4671 (18)	C8—H8	0.9300
O3—S1	1.4873 (18)	C9—C10	1.393 (4)
O4—S1	1.4689 (18)	C9—H9	0.9300
O5—H5A	0.8500	C10—H10	0.9300
O5—H5B	0.8501	C11—C12	1.374 (3)
O6—H6A	0.8499	C13—H13	0.9300
O6—H6B	0.8499

O6—Co1—O1	92.97 (8)	N1—C1—C2	122.7 (2)
O6—Co1—O2	87.31 (7)	N1—C1—H1	118.6
O1—Co1—O2	97.67 (7)	C2—C1—H1	118.6
O6—Co1—N1	99.04 (8)	C3—C2—C1	119.3 (2)
O1—Co1—N1	163.56 (8)	C3—C2—H2	120.4
O2—Co1—N1	94.09 (7)	C1—C2—H2	120.4
O6—Co1—N2	85.76 (8)	C2—C3—C4	119.2 (2)
O1—Co1—N2	92.21 (7)	C2—C3—H3A	120.4
O2—Co1—N2	168.21 (8)	C4—C3—H3A	120.4
N1—Co1—N2	77.62 (7)	C3—C4—C5	118.2 (2)
O6—Co1—O5	172.06 (7)	C3—C4—C11	126.3 (2)
O1—Co1—O5	87.15 (7)	C5—C4—C11	115.5 (2)
O2—Co1—O5	84.80 (7)	N1—C5—C4	121.8 (2)
N1—Co1—O5	82.50 (7)	N1—C5—C6	116.8 (2)
N2—Co1—O5	102.17 (7)	C4—C5—C6	121.4 (2)
C1—N1—C5	118.7 (2)	N2—C6—C7	122.1 (2)
C1—N1—Co1	126.32 (17)	N2—C6—C5	116.6 (2)
C5—N1—Co1	114.74 (16)	C7—C6—C5	121.3 (2)
C10—N2—C6	118.4 (2)	C8—C7—C6	117.8 (2)
C10—N2—Co1	127.18 (16)	C8—C7—C12	125.9 (2)
C6—N2—Co1	114.27 (16)	C6—C7—C12	116.3 (2)
C13—N3—C11	106.2 (2)	C9—C8—C7	119.2 (2)
C13—N3—H3	126.9	C9—C8—H8	120.4
C11—N3—H3	126.9	C7—C8—H8	120.4
C13—N4—C12	103.9 (2)	C8—C9—C10	119.6 (2)
S1—O1—Co1	130.53 (10)	C8—C9—H9	120.2
S1ⁱ—O2—Co1	138.89 (11)	C10—C9—H9	120.2
Co1—O5—H5A	99.1	N2—C10—C9	122.8 (2)
Co1—O5—H5B	106.7	N2—C10—H10	118.6
H5A—O5—H5B	107.0	C9—C10—H10	118.6
Co1—O6—H6A	116.5	C12—C11—N3	106.0 (2)
Co1—O6—H6B	134.5	C12—C11—C4	123.7 (2)
H6A—O6—H6B	108.9	N3—C11—C4	130.2 (2)
H7A—O7—H7B	108.0	C11—C12—N4	110.0 (2)
O2ⁱ—S1—O4	109.74 (11)	C11—C12—C7	121.7 (2)
O2ⁱ—S1—O1	109.81 (11)	N4—C12—C7	128.4 (2)
O4—S1—O1	108.62 (10)	N4—C13—N3	113.8 (2)
O2ⁱ—S1—O3	109.99 (10)	N4—C13—H13	123.1
O4—S1—O3	108.67 (11)	N3—C13—H13	123.1
O1—S1—O3	109.98 (10)

O6—Co1—N1—C1	−100.4 (2)	Co1—N1—C5—C6	−2.7 (3)
O1—Co1—N1—C1	123.2 (3)	C3—C4—C5—N1	−1.0 (4)
O2—Co1—N1—C1	−12.5 (2)	C11—C4—C5—N1	178.9 (2)
N2—Co1—N1—C1	176.0 (2)	C3—C4—C5—C6	178.7 (2)
O5—Co1—N1—C1	71.7 (2)	C11—C4—C5—C6	−1.5 (4)
O6—Co1—N1—C5	84.93 (18)	C10—N2—C6—C7	2.5 (4)
O1—Co1—N1—C5	−51.5 (3)	Co1—N2—C6—C7	178.45 (18)
O2—Co1—N1—C5	172.86 (17)	C10—N2—C6—C5	−177.7 (2)
N2—Co1—N1—C5	1.34 (17)	Co1—N2—C6—C5	−1.7 (3)
O5—Co1—N1—C5	−102.94 (18)	N1—C5—C6—N2	3.0 (3)
O6—Co1—N2—C10	75.6 (2)	C4—C5—C6—N2	−176.7 (2)
O1—Co1—N2—C10	−17.2 (2)	N1—C5—C6—C7	−177.2 (2)
O2—Co1—N2—C10	129.8 (3)	C4—C5—C6—C7	3.1 (4)
N1—Co1—N2—C10	175.8 (2)	N2—C6—C7—C8	−2.2 (4)
O5—Co1—N2—C10	−104.8 (2)	C5—C6—C7—C8	178.0 (2)
O6—Co1—N2—C6	−99.96 (17)	N2—C6—C7—C12	177.3 (2)
O1—Co1—N2—C6	167.22 (17)	C5—C6—C7—C12	−2.5 (3)
O2—Co1—N2—C6	−45.8 (4)	C6—C7—C8—C9	0.0 (4)
N1—Co1—N2—C6	0.26 (16)	C12—C7—C8—C9	−179.4 (3)
O5—Co1—N2—C6	79.66 (17)	C7—C8—C9—C10	1.7 (4)
O6—Co1—O1—S1	117.94 (15)	C6—N2—C10—C9	−0.6 (4)
O2—Co1—O1—S1	30.25 (15)	Co1—N2—C10—C9	−176.0 (2)
N1—Co1—O1—S1	−105.0 (3)	C8—C9—C10—N2	−1.5 (4)
N2—Co1—O1—S1	−156.20 (15)	C13—N3—C11—C12	−0.4 (3)
O5—Co1—O1—S1	−54.11 (15)	C13—N3—C11—C4	178.7 (3)
O6—Co1—O2—S1ⁱ	−21.15 (18)	C3—C4—C11—C12	179.2 (3)
O1—Co1—O2—S1ⁱ	71.49 (18)	C5—C4—C11—C12	−0.7 (4)
N1—Co1—O2—S1ⁱ	−120.03 (18)	C3—C4—C11—N3	0.2 (5)
N2—Co1—O2—S1ⁱ	−75.2 (4)	C5—C4—C11—N3	−179.7 (2)
O5—Co1—O2—S1ⁱ	157.89 (18)	N3—C11—C12—N4	0.4 (3)
Co1—O1—S1—O2ⁱ	−80.84 (16)	C4—C11—C12—N4	−178.8 (2)
Co1—O1—S1—O4	159.15 (14)	N3—C11—C12—C7	−179.6 (2)
Co1—O1—S1—O3	40.34 (17)	C4—C11—C12—C7	1.2 (4)
C5—N1—C1—C2	−1.1 (4)	C13—N4—C12—C11	−0.2 (3)
Co1—N1—C1—C2	−175.59 (19)	C13—N4—C12—C7	179.7 (3)
N1—C1—C2—C3	−0.5 (4)	C8—C7—C12—C11	179.9 (2)
C1—C2—C3—C4	1.4 (4)	C6—C7—C12—C11	0.4 (4)
C2—C3—C4—C5	−0.7 (4)	C8—C7—C12—N4	−0.1 (4)
C2—C3—C4—C11	179.5 (3)	C6—C7—C12—N4	−179.5 (2)
C1—N1—C5—C4	1.8 (4)	C12—N4—C13—N3	0.0 (3)
Co1—N1—C5—C4	176.97 (18)	C11—N3—C13—N4	0.3 (3)
C1—N1—C5—C6	−177.8 (2)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O4ⁱⁱ	0.86	2.05	2.886 (3)	165
N3—H3···S1ⁱⁱ	0.86	2.94	3.709 (2)	150
O5—H5A···O3	0.85	1.94	2.764 (2)	165
O5—H5A···S1	0.85	2.77	3.4184 (19)	134
O6—H6B···O7ⁱⁱⁱ	0.85	1.79	2.634 (3)	174
O7—H7B···O3^iv	0.85	2.00	2.843 (3)	176
O7—H7B···S1^iv	0.85	2.93	3.703 (3)	152

Symmetry codes: (ii) x+1, −y+1/2, z+1/2; (iii) x, y−1, z; (iv) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[Co₂(SO₄)₂(C₁₃H₈N₄)₂(H₂O)₄]·2H₂O
M_r	858.54
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	10.3160 (13), 9.0716 (10), 16.8549 (17)
β (°)	99.104 (1)
V (Å³)	1557.5 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.29
Crystal size (mm)	0.43 × 0.36 × 0.22

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.581, 0.754
No. of measured, independent and observed [I > 2σ(I)] reflections	7558, 2742, 2329
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.073, 1.07
No. of reflections	2742
No. of parameters	235
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.63, −0.36

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Co1—N1	2.124 (2)	Co1—O1	2.0889 (17)
Co1—N2	2.137 (2)	Co1—O2	2.0978 (17)
Co1—O6	2.0654 (19)	Co1—O5	2.1468 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O4ⁱ	0.86	2.048	2.886 (3)	165
N3—H3···S1ⁱ	0.86	2.940	3.709 (2)	150
O5—H5A···O3	0.85	1.935	2.764 (2)	165
O5—H5A···S1	0.85	2.772	3.4184 (19)	134
O6—H6B···O7ⁱⁱ	0.85	1.786	2.634 (3)	174
O7—H7B···O3ⁱⁱⁱ	0.85	1.995	2.843 (3)	176
O7—H7B···S1ⁱⁱⁱ	0.85	2.929	3.703 (3)	152

Symmetry codes: (i) x+1, −y+1/2, z+1/2; (ii) x, y−1, z; (iii) x, −y+3/2, z+1/2.

Acknowledgements

This work was supported by the Natural Science Young Scholars Foundation of Chongqing University, the Large-scale Instrument and Equipment Open Foundation of Chongqing University, the Scientific Research Start-up Foundation of Chongqing University, the Innovative Talent Training Project of the Third Stage of the `211 project' of Chongqing University (No. S-09103) and Chongqing University Postgraduate Science and Innovation Fund.

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