Bis(1,10-phenanthroline-κ2N,N′)(sulfato-κ2O,O′)cobalt(II) butane-2,3-diol monosolvate

Wang, S.-J.; Zhong, K.-L.

doi:10.1107/S1600536811009147

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 4| April 2011| Page m446

doi:10.1107/S1600536811009147

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Bis(1,10-phenanthroline-κ²N,N′)(sulfato-κ²O,O′)cobalt(II) butane-2,3-diol monosolvate

Shi-Juan Wang ^a and Kai-Long Zhong ^a ^*

^aDepartment of Applied Chemistry, Nanjing College of Chemical Technology, Nanjing 210048, People's Republic of China
^*Correspondence e-mail: zklong@tom.com

(Received 27 February 2011; accepted 10 March 2011; online 15 March 2011)

In the title compound, [Co(SO₄)(C₁₂H₈N₂)₂]·C₄H₁₀O₂, the Co²⁺ ion has a distorted octahedral coordination environment composed of four N atoms from two chelating 1,10-phenanthroline ligands and two O atoms from an O,O′-bidentate sulfate anion. The dihedral angle between the two chelating N₂C₂ groups is 83.48 (1)°. The Co²⁺ ion, the S atom and the mid-point of the central C—C bond of the butane-2,3-diol solvent molecule are situated on twofold rotation axes. The molecules of the complex and the solvent molecules are held together by pairs of symmetry-related O—H⋯O hydrogen bonds with the uncoordinated O atoms of the sulfate ions as acceptors. The solvent molecule is disordered over two sets of sites with site occupancies of 0.40 and 0.60.

Related literature

For the ethane-1,2-diol solvate of the title complex, see: Zhong et al. (2006 ). For the propane-1,3-diol solvate of the title complex, see: Zhong (2010 ). For background to coordination polymers, see: Batten & Robson (1998 ); Lu et al. (2006 ); Zhang et al. (2010 ); Zhong et al. (2011 ).

Experimental

Crystal data

[Co(SO₄)(C₁₂H₈N₂)₂]·C₄H₁₀O₂
M_r = 605.52
Monoclinic, C 2/c
a = 18.184 (4) Å
b = 13.009 (3) Å
c = 13.112 (3) Å
β = 122.13 (3)°
V = 2626.6 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.79 mm⁻¹
T = 223 K
0.40 × 0.20 × 0.10 mm

Data collection

Rigaku Mercury CCD diffractometer
Absorption correction: multi-scan (REQAB; Jacobson, 1998 ) T_min = 0.763, T_max = 1.000
7651 measured reflections
2316 independent reflections
2079 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.109
S = 1.12
2316 reflections
209 parameters
50 restraints
H-atom parameters constrained
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Selected bond lengths (Å)

Co1—O1	2.124 (2)
Co1—N1	2.128 (3)
Co1—N2	2.146 (2)
S1—O2	1.455 (2)
S1—O1	1.492 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O2	0.82	2.07	2.779 (8)	145
O3′—H3′⋯O2	0.82	1.94	2.709 (7)	155

Data collection: CrystalClear (Rigaku, 2007 ); 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: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811009147/wm2463sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811009147/wm2463Isup2.hkl

checkCIF report

Comment top

The self-assembly of coordination polymers and the crystal engineering of metal-organic coordination frameworks have recently attracted great interest, owing to their interesting structural topologies and their potential applications as functional materials (Batten & Robson, 1998; Lu et al., 2006; Zhang et al., 2010; Zhong et al., 2011). 1,10-phenanthroline (phen) has been widely used as an auxiliary ligands in constructing interesting coordination polymers. During attempts to synthesize mixed-ligand coordination polymers of transition metals with phen as second ligand via solvothermal reactions, we obtained compounds with a structure composed of a bidentate-chelating sulfate ligand, e.g. [CoSO₄(C₁₂H₈N₂)₂].C₂H₆O₂ (Zhong et al., 2006), (II) and [CoSO₄(C₁₂H₈N₂)₂].C₃H₈O₂ (Zhong, 2010), (III).

We here report the new title compound, [CoSO₄(C₁₂H₈N₂)₂].C₄H₁₀O₂, (I), as part of our systematic investigation of transition metal complexes with bidentate bridging sulfate ligands. The crystal structure of the title compound consist of a neutral [CoSO₄(C₁₀H₈N₂)₂] complex and a solvent butane-2,3-diol molecule. Twofold rotation axes pass through the Co and S atoms and the mid-point of the central C—C bond of the butane-2,3-diol solvent molecule. In the complex molecule, the Co^II ion is sixfold coordinated by four N atoms from two phen ligands and two O atoms from an O,O'-bidentate sulfate ion, giving rise to a distorted CoN₄O₂ octahedral environment (Fig. 1). The dihedral angle between the two chelating N₂C₂ groups is 83.48 (1)°, which is much larger that found in the structure of (II) and (III) (70.16 (6)° and 80.06 (8)°, respectively). The Co—O bond length [2.124 (2) Å], the O—Co—O bite angle [66.83 (12)°], the Co—N bond lenghts [2.128 (3)–2.146 (2) Å], and the N—Co—N bite angle [77.82 (10)°] are in good agreement with those observed in (II) [2.131 (1) Å, 66.32 (7)°, 2.126 (2)–2.137 (2) Å, 78.10 (6)°] and (III) [2.132 (2) Å, 66.54 (8)°, 2.123 (2)–2.134 (2) Å, and 77.99 (6)°].

The neutral metal complex and the solvent molecule are held together by pairs of symmetry-related O—H···O hydrogen bonds (Fig.1).

Related literature top

For the ethane-1,2-diol solvate of the title complex, see: Zhong et al. (2006). For the propane-1,3-diol solvate of the title complex, see: Zhong (2010). For background to coordination polymers, see: Batten & Robson (1998); Lu et al. (2006); Zhang et al. (2010); Zhong et al. (2011).

For related literature, see: Ni et al. (2010).

Experimental top

0.2 mmol 1,10-phenanthroline (phen), 0.1 mmol melamine, 0.1 mmol CoSO₄.7H₂O, 2.0 ml butane-2,3-diol and 1.0 ml water were mixed and placed in a thick Pyrex tube, which was sealed and heated to 423 K for 96 h. The tube was cooled to ambient temperature spontaneously and orange prism-shaped single crystals of the title compound were obtained.

Computing details top

Data collection: CrystalClear (Rigaku, 2007); cell refinement: CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular entities of the title compound, showing the atom-numbering scheme and with displacement ellipsoids drawn at the 35% probability level. The light broken lines depict O—H···O interactions. Unlabelled atoms are related to the labelled atoms by the symmetry operator (-x + 1, y, -z + 1/2). Note that only one orientation of the disordered solvent molecule is shown.

Bis(1,10-phenanthroline-κ²N,N')(sulfato- κ²O,O')cobalt(II) butane-2,3-diol monosolvate top

Crystal data top

[Co(SO₄)(C₁₂H₈N₂)₂]·C₄H₁₀O₂	F(000) = 1252
M_r = 605.52	D_x = 1.531 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4290 reflections
a = 18.184 (4) Å	θ = 3.1–27.5°
b = 13.009 (3) Å	µ = 0.79 mm⁻¹
c = 13.112 (3) Å	T = 223 K
β = 122.13 (3)°	Prism, orange
V = 2626.6 (13) Å³	0.40 × 0.20 × 0.10 mm
Z = 4

Data collection top

Rigaku Mercury CCD diffractometer	2316 independent reflections
Radiation source: fine-focus sealed tube	2079 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
Detector resolution: 28.5714 pixels mm^-1	θ_max = 25.0°, θ_min = 3.2°
ω scans	h = −19→21
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	k = −15→13
T_min = 0.763, T_max = 1.000	l = −15→14
7651 measured reflections

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.049P)² + 4.2601P] where P = (F_o² + 2F_c²)/3
2316 reflections	(Δ/σ)_max = 0.001
209 parameters	Δρ_max = 0.49 e Å⁻³
50 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

[Co(SO₄)(C₁₂H₈N₂)₂]·C₄H₁₀O₂	V = 2626.6 (13) Å³
M_r = 605.52	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 18.184 (4) Å	µ = 0.79 mm⁻¹
b = 13.009 (3) Å	T = 223 K
c = 13.112 (3) Å	0.40 × 0.20 × 0.10 mm
β = 122.13 (3)°

Data collection top

Rigaku Mercury CCD diffractometer	2316 independent reflections
Absorption correction: multi-scan (REQAB; Jacobson, 1998)	2079 reflections with I > 2σ(I)
T_min = 0.763, T_max = 1.000	R_int = 0.033
7651 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	50 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.12	Δρ_max = 0.49 e Å⁻³
2316 reflections	Δρ_min = −0.39 e Å⁻³
209 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.5000	0.67718 (4)	0.2500	0.0274 (2)
S1	0.5000	0.46963 (8)	0.2500	0.0289 (3)
O1	0.44423 (14)	0.54091 (16)	0.14832 (19)	0.0389 (6)
N2	0.40247 (16)	0.78032 (18)	0.1216 (2)	0.0284 (6)
C10	0.3905 (2)	0.8150 (2)	0.0182 (3)	0.0356 (7)
H10A	0.4292	0.7942	−0.0037	0.043*
O2	0.55262 (15)	0.40620 (18)	0.2215 (2)	0.0461 (6)
C11	0.34456 (19)	0.8101 (2)	0.1512 (3)	0.0280 (7)
C7	0.27533 (19)	0.8780 (2)	0.0798 (3)	0.0324 (7)
C9	0.3233 (2)	0.8808 (3)	−0.0584 (3)	0.0401 (8)
H9A	0.3173	0.9027	−0.1299	0.048*
C8	0.2657 (2)	0.9131 (2)	−0.0276 (3)	0.0391 (8)
H8A	0.2209	0.9578	−0.0775	0.047*
C6	0.2174 (2)	0.9049 (3)	0.1186 (3)	0.0400 (8)
H6A	0.1723	0.9506	0.0726	0.048*
C12	0.35381 (18)	0.7670 (2)	0.2586 (3)	0.0288 (7)
C4	0.2945 (2)	0.7931 (3)	0.2918 (3)	0.0348 (8)
C5	0.2268 (2)	0.8654 (3)	0.2200 (3)	0.0422 (9)
H5A	0.1889	0.8853	0.2436	0.051*
N1	0.41924 (16)	0.69769 (19)	0.3205 (2)	0.0303 (6)
C2	0.3687 (2)	0.6731 (3)	0.4543 (3)	0.0462 (9)
H2A	0.3747	0.6391	0.5207	0.055*
C1	0.4256 (2)	0.6524 (3)	0.4161 (3)	0.0385 (8)
H1A	0.4698	0.6050	0.4592	0.046*
C3	0.3041 (2)	0.7438 (3)	0.3930 (3)	0.0458 (9)
H3A	0.2665	0.7592	0.4186	0.055*
C13	0.5467 (3)	0.1136 (6)	0.2621 (9)	0.042 (2)	0.40
H13	0.5819	0.0562	0.3132	0.050*	0.40
O3	0.5935 (6)	0.2007 (6)	0.2842 (8)	0.066 (2)	0.40
H3	0.5605	0.2492	0.2500	0.098*	0.40
C14	0.4923 (11)	0.0849 (17)	0.1279 (9)	0.107 (6)	0.40
H14A	0.4601	0.0232	0.1180	0.161*	0.40
H14B	0.5300	0.0737	0.0986	0.161*	0.40
H14C	0.4527	0.1398	0.0834	0.161*	0.40
C13'	0.5031 (6)	0.1256 (6)	0.1915 (8)	0.081 (3)	0.60
H13'	0.4457	0.1395	0.1200	0.098*	0.60
O3'	0.5627 (6)	0.2002 (5)	0.2013 (8)	0.108 (3)	0.60
H3'	0.5454	0.2576	0.2046	0.161*	0.60
C14'	0.5388 (6)	0.0259 (6)	0.1741 (8)	0.073 (2)	0.60
H14D	0.5066	−0.0311	0.1771	0.110*	0.60
H14E	0.5989	0.0190	0.2368	0.110*	0.60
H14F	0.5336	0.0270	0.0972	0.110*	0.60

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0229 (3)	0.0270 (3)	0.0300 (3)	0.000	0.0127 (3)	0.000
S1	0.0217 (5)	0.0260 (5)	0.0365 (6)	0.000	0.0137 (5)	0.000
O1	0.0324 (12)	0.0314 (12)	0.0327 (12)	−0.0003 (9)	0.0036 (10)	−0.0013 (9)
N2	0.0268 (13)	0.0261 (13)	0.0323 (14)	−0.0019 (10)	0.0156 (11)	0.0016 (10)
C10	0.0346 (17)	0.0382 (18)	0.0388 (18)	−0.0013 (14)	0.0228 (15)	0.0036 (14)
O2	0.0431 (13)	0.0377 (13)	0.0724 (17)	0.0066 (11)	0.0407 (13)	−0.0007 (12)
C11	0.0243 (15)	0.0262 (15)	0.0305 (15)	−0.0025 (12)	0.0125 (13)	−0.0010 (12)
C7	0.0262 (15)	0.0294 (16)	0.0320 (16)	0.0001 (13)	0.0090 (13)	−0.0022 (13)
C9	0.0383 (18)	0.045 (2)	0.0320 (17)	−0.0023 (15)	0.0150 (15)	0.0097 (15)
C8	0.0316 (17)	0.0344 (18)	0.0360 (18)	0.0010 (14)	0.0077 (15)	0.0082 (14)
C6	0.0263 (16)	0.0421 (19)	0.0406 (19)	0.0105 (14)	0.0103 (15)	0.0000 (15)
C12	0.0258 (15)	0.0287 (16)	0.0282 (15)	−0.0033 (12)	0.0119 (13)	−0.0027 (12)
C4	0.0297 (16)	0.0431 (19)	0.0307 (17)	0.0015 (14)	0.0155 (14)	−0.0028 (13)
C5	0.0289 (17)	0.056 (2)	0.0408 (19)	0.0083 (16)	0.0176 (15)	−0.0063 (16)
N1	0.0277 (13)	0.0300 (14)	0.0307 (13)	0.0016 (11)	0.0138 (11)	0.0022 (11)
C2	0.049 (2)	0.055 (2)	0.0374 (19)	−0.0005 (18)	0.0252 (17)	0.0071 (16)
C1	0.0388 (18)	0.0420 (19)	0.0346 (17)	0.0031 (15)	0.0195 (15)	0.0077 (14)
C3	0.0413 (19)	0.065 (2)	0.0401 (19)	0.0044 (18)	0.0276 (17)	0.0001 (18)
C13	0.035 (5)	0.028 (4)	0.060 (6)	0.004 (4)	0.024 (4)	0.000 (4)
O3	0.069 (5)	0.045 (4)	0.084 (5)	0.006 (3)	0.042 (4)	0.012 (4)
C14	0.116 (10)	0.148 (11)	0.090 (8)	−0.006 (8)	0.077 (8)	0.007 (8)
C13'	0.095 (6)	0.065 (5)	0.100 (7)	−0.003 (5)	0.062 (6)	0.015 (5)
O3'	0.148 (6)	0.052 (3)	0.178 (7)	−0.009 (4)	0.123 (6)	−0.015 (5)
C14'	0.089 (5)	0.068 (5)	0.081 (5)	−0.011 (4)	0.057 (4)	−0.007 (4)

Geometric parameters (Å, º) top

Co1—O1	2.124 (2)	C4—C3	1.399 (5)
Co1—O1ⁱ	2.124 (2)	C4—C5	1.434 (5)
Co1—N1	2.128 (3)	C5—H5A	0.9300
Co1—N1ⁱ	2.128 (3)	N1—C1	1.334 (4)
Co1—N2ⁱ	2.146 (2)	C2—C3	1.367 (5)
Co1—N2	2.146 (2)	C2—C1	1.392 (5)
S1—O2ⁱ	1.455 (2)	C2—H2A	0.9300
S1—O2	1.455 (2)	C1—H1A	0.9300
S1—O1ⁱ	1.492 (2)	C3—H3A	0.9300
S1—O1	1.492 (2)	C13—O3	1.353 (8)
N2—C10	1.332 (4)	C13—C14	1.537 (4)
N2—C11	1.359 (4)	C13—C13ⁱ	1.553 (5)
C10—C9	1.389 (5)	C13—H13	0.9800
C10—H10A	0.9300	O3—H3	0.8200
C11—C7	1.410 (4)	C14—H14A	0.9600
C11—C12	1.440 (4)	C14—H14B	0.9600
C7—C8	1.400 (5)	C14—H14C	0.9600
C7—C6	1.435 (5)	C13'—O3'	1.410 (4)
C9—C8	1.373 (5)	C13'—C14'	1.522 (8)
C9—H9A	0.9300	C13'—C13'ⁱ	1.596 (13)
C8—H8A	0.9300	C13'—H13'	0.9800
C6—C5	1.349 (5)	O3'—H3'	0.8200
C6—H6A	0.9300	C14'—H14D	0.9600
C12—N1	1.364 (4)	C14'—H14E	0.9600
C12—C4	1.402 (5)	C14'—H14F	0.9600

O1—Co1—O1ⁱ	66.83 (12)	C5—C6—C7	121.7 (3)
O1—Co1—N1	99.67 (10)	C5—C6—H6A	119.2
O1ⁱ—Co1—N1	92.38 (10)	C7—C6—H6A	119.2
O1—Co1—N1ⁱ	92.38 (10)	N1—C12—C4	123.2 (3)
O1ⁱ—Co1—N1ⁱ	99.67 (10)	N1—C12—C11	116.8 (3)
N1—Co1—N1ⁱ	165.59 (14)	C4—C12—C11	120.0 (3)
O1—Co1—N2ⁱ	159.07 (9)	C3—C4—C12	117.0 (3)
O1ⁱ—Co1—N2ⁱ	96.31 (9)	C3—C4—C5	123.6 (3)
N1—Co1—N2ⁱ	93.10 (10)	C12—C4—C5	119.4 (3)
N1ⁱ—Co1—N2ⁱ	77.82 (10)	C6—C5—C4	120.7 (3)
O1—Co1—N2	96.31 (9)	C6—C5—H5A	119.7
O1ⁱ—Co1—N2	159.07 (9)	C4—C5—H5A	119.7
N1—Co1—N2	77.82 (10)	C1—N1—C12	117.6 (3)
N1ⁱ—Co1—N2	93.10 (10)	C1—N1—Co1	128.2 (2)
N2ⁱ—Co1—N2	102.59 (13)	C12—N1—Co1	114.2 (2)
O1—Co1—S1	33.41 (6)	C3—C2—C1	119.3 (3)
O1ⁱ—Co1—S1	33.41 (6)	C3—C2—H2A	120.4
N1—Co1—S1	97.21 (7)	C1—C2—H2A	120.4
N1ⁱ—Co1—S1	97.21 (7)	N1—C1—C2	122.9 (3)
N2ⁱ—Co1—S1	128.71 (7)	N1—C1—H1A	118.6
N2—Co1—S1	128.71 (7)	C2—C1—H1A	118.6
O2ⁱ—S1—O2	110.9 (2)	C2—C3—C4	120.0 (3)
O2ⁱ—S1—O1ⁱ	110.50 (14)	C2—C3—H3A	120.0
O2—S1—O1ⁱ	110.77 (14)	C4—C3—H3A	120.0
O2ⁱ—S1—O1	110.77 (14)	O3—C13—C14	113.4 (11)
O2—S1—O1	110.50 (14)	O3—C13—C13ⁱ	122.6 (5)
O1ⁱ—S1—O1	103.17 (17)	C14—C13—C13ⁱ	78.3 (9)
O2ⁱ—S1—Co1	124.56 (10)	O3—C13—H13	112.7
O2—S1—Co1	124.56 (10)	C14—C13—H13	112.7
O1ⁱ—S1—Co1	51.59 (9)	C13ⁱ—C13—H13	112.7
O1—S1—Co1	51.59 (9)	C13—O3—H3	109.5
S1—O1—Co1	95.00 (11)	C13—C14—H14A	109.5
C10—N2—C11	117.6 (3)	C13—C14—H14B	109.5
C10—N2—Co1	129.0 (2)	H14A—C14—H14B	109.5
C11—N2—Co1	113.38 (19)	C13—C14—H14C	109.5
N2—C10—C9	123.3 (3)	H14A—C14—H14C	109.5
N2—C10—H10A	118.4	H14B—C14—H14C	109.5
C9—C10—H10A	118.4	O3'—C13'—C14'	103.3 (7)
N2—C11—C7	122.9 (3)	O3'—C13'—C13'ⁱ	110.9 (8)
N2—C11—C12	117.6 (3)	C14'—C13'—C13'ⁱ	113.5 (6)
C7—C11—C12	119.5 (3)	O3'—C13'—H13'	109.7
C8—C7—C11	117.5 (3)	C14'—C13'—H13'	109.7
C8—C7—C6	123.7 (3)	C13'ⁱ—C13'—H13'	109.7
C11—C7—C6	118.8 (3)	C13'—O3'—H3'	109.5
C8—C9—C10	119.4 (3)	C13'—C14'—H14D	109.5
C8—C9—H9A	120.3	C13'—C14'—H14E	109.5
C10—C9—H9A	120.3	H14D—C14'—H14E	109.5
C9—C8—C7	119.3 (3)	C13'—C14'—H14F	109.5
C9—C8—H8A	120.3	H14D—C14'—H14F	109.5
C7—C8—H8A	120.3	H14E—C14'—H14F	109.5

O1—Co1—S1—O2ⁱ	−90.19 (18)	C10—N2—C11—C12	175.8 (3)
O1ⁱ—Co1—S1—O2ⁱ	89.81 (18)	Co1—N2—C11—C12	−2.3 (3)
N1—Co1—S1—O2ⁱ	6.45 (14)	N2—C11—C7—C8	1.8 (4)
N1ⁱ—Co1—S1—O2ⁱ	−173.55 (14)	C12—C11—C7—C8	−176.2 (3)
N2ⁱ—Co1—S1—O2ⁱ	106.30 (16)	N2—C11—C7—C6	179.9 (3)
N2—Co1—S1—O2ⁱ	−73.70 (16)	C12—C11—C7—C6	2.0 (4)
O1—Co1—S1—O2	89.81 (18)	N2—C10—C9—C8	0.4 (5)
O1ⁱ—Co1—S1—O2	−90.19 (18)	C10—C9—C8—C7	−0.8 (5)
N1—Co1—S1—O2	−173.55 (14)	C11—C7—C8—C9	−0.2 (5)
N1ⁱ—Co1—S1—O2	6.45 (14)	C6—C7—C8—C9	−178.2 (3)
N2ⁱ—Co1—S1—O2	−73.70 (16)	C8—C7—C6—C5	176.8 (3)
N2—Co1—S1—O2	106.30 (16)	C11—C7—C6—C5	−1.2 (5)
O1—Co1—S1—O1ⁱ	180.0	N2—C11—C12—N1	−1.4 (4)
N1—Co1—S1—O1ⁱ	−83.36 (14)	C7—C11—C12—N1	176.7 (3)
N1ⁱ—Co1—S1—O1ⁱ	96.64 (14)	N2—C11—C12—C4	−178.4 (3)
N2ⁱ—Co1—S1—O1ⁱ	16.50 (15)	C7—C11—C12—C4	−0.4 (4)
N2—Co1—S1—O1ⁱ	−163.50 (15)	N1—C12—C4—C3	−0.6 (5)
O1ⁱ—Co1—S1—O1	180.0	C11—C12—C4—C3	176.3 (3)
N1—Co1—S1—O1	96.64 (14)	N1—C12—C4—C5	−178.8 (3)
N1ⁱ—Co1—S1—O1	−83.36 (14)	C11—C12—C4—C5	−2.0 (4)
N2ⁱ—Co1—S1—O1	−163.50 (15)	C7—C6—C5—C4	−1.2 (5)
N2—Co1—S1—O1	16.50 (15)	C3—C4—C5—C6	−175.3 (3)
O2ⁱ—S1—O1—Co1	118.26 (13)	C12—C4—C5—C6	2.8 (5)
O2—S1—O1—Co1	−118.45 (13)	C4—C12—N1—C1	0.8 (4)
O1ⁱ—S1—O1—Co1	0.0	C11—C12—N1—C1	−176.1 (3)
O1ⁱ—Co1—O1—S1	0.0	C4—C12—N1—Co1	−178.7 (2)
N1—Co1—O1—S1	−88.45 (12)	C11—C12—N1—Co1	4.4 (3)
N1ⁱ—Co1—O1—S1	99.50 (12)	O1—Co1—N1—C1	81.9 (3)
N2ⁱ—Co1—O1—S1	38.3 (3)	O1ⁱ—Co1—N1—C1	15.0 (3)
N2—Co1—O1—S1	−167.12 (12)	N1ⁱ—Co1—N1—C1	−131.8 (3)
O1—Co1—N2—C10	−75.8 (3)	N2ⁱ—Co1—N1—C1	−81.4 (3)
O1ⁱ—Co1—N2—C10	−110.8 (3)	N2—Co1—N1—C1	176.4 (3)
N1—Co1—N2—C10	−174.3 (3)	S1—Co1—N1—C1	48.2 (3)
N1ⁱ—Co1—N2—C10	17.0 (3)	O1—Co1—N1—C12	−98.7 (2)
N2ⁱ—Co1—N2—C10	95.2 (3)	O1ⁱ—Co1—N1—C12	−165.5 (2)
S1—Co1—N2—C10	−84.8 (3)	N1ⁱ—Co1—N1—C12	47.65 (19)
O1—Co1—N2—C11	102.0 (2)	N2ⁱ—Co1—N1—C12	98.0 (2)
O1ⁱ—Co1—N2—C11	67.0 (3)	N2—Co1—N1—C12	−4.2 (2)
N1—Co1—N2—C11	3.46 (19)	S1—Co1—N1—C12	−132.35 (19)
N1ⁱ—Co1—N2—C11	−165.2 (2)	C12—N1—C1—C2	0.0 (5)
N2ⁱ—Co1—N2—C11	−87.0 (2)	Co1—N1—C1—C2	179.4 (3)
S1—Co1—N2—C11	93.0 (2)	C3—C2—C1—N1	−1.0 (6)
C11—N2—C10—C9	1.1 (5)	C1—C2—C3—C4	1.3 (6)
Co1—N2—C10—C9	178.8 (2)	C12—C4—C3—C2	−0.5 (5)
C10—N2—C11—C7	−2.2 (4)	C5—C4—C3—C2	177.7 (3)
Co1—N2—C11—C7	179.7 (2)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.82	2.07	2.779 (8)	145
O3′—H3′···O2	0.82	1.94	2.709 (7)	155

Experimental details

Crystal data
Chemical formula	[Co(SO₄)(C₁₂H₈N₂)₂]·C₄H₁₀O₂
M_r	605.52
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	223
a, b, c (Å)	18.184 (4), 13.009 (3), 13.112 (3)
β (°)	122.13 (3)
V (Å³)	2626.6 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.79
Crystal size (mm)	0.40 × 0.20 × 0.10

Data collection
Diffractometer	Rigaku Mercury CCD diffractometer
Absorption correction	Multi-scan (REQAB; Jacobson, 1998)
T_min, T_max	0.763, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7651, 2316, 2079
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.109, 1.12
No. of reflections	2316
No. of parameters	209
No. of restraints	50
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.39

Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Co1—O1	2.124 (2)	S1—O2	1.455 (2)
Co1—N1	2.128 (3)	S1—O1	1.492 (2)
Co1—N2	2.146 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O2	0.82	2.07	2.779 (8)	145.0
O3'—H3'···O2	0.82	1.94	2.709 (7)	155.2

Acknowledgements

This work was partially supported by the Scientific Research Foundation of Nanjing College of Chemical Technology (grant No. NHKY-2010-17).

References

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