catena-Poly[[[(2,2′-bipyridine-κ2N,N′)cobalt(II)]-μ-(E)-3,3′-(but-2-ene-2,3-di­yl)dibenzoato-κ4O,O′:O′′,O′′′] hemihydrate]

Li, Z.-S.; Ng, S.W.

doi:10.1107/S1600536811041699

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Page m1546

doi:10.1107/S1600536811041699

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catena-Poly[[[(2,2′-bipyridine-κ²N,N′)cobalt(II)]-μ-(E)-3,3′-(but-2-ene-2,3-diyl)dibenzoato-κ⁴O,O′:O′′,O′′′] hemihydrate]

Zong-Sheng Li ^a and Seik Weng Ng ^b,^c ^*

^aCollege of Safety and Environmental Engineering, Capital University of Economics and Business, Beijing 100070, People's Republic of China, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cChemistry Department, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 9 October 2011; accepted 10 October 2011; online 22 October 2011)

The title coordination polymer, {[Co(C₁₈H₁₄O₄)(C₁₀H₈N₂)]·0.5H₂O}_n, features a helical polymeric chain that runs along the b axis. The Co atoms are chelated by the carboxylate groups of two 3,3′-(but-2-ene-2,3-diyl)dibenzoate ligands and the N atoms of a 2,2′-bipyridine ligand. The lattice water molecule is disordered about a center of inversion and is connected to the chain by an O—H⋯O hydrogen bond. The Co^II atom shows a distorted octahedral coordination.

Related literature

For a review of the adducts of metal carboxylates with 2,2′-bipyridine-like ligands, see: Ye et al. (2005 ). For details of the synthesis, see: McMurry (1989 ).

Experimental

Crystal data

[Co(C₁₈H₁₄O₄)(C₁₀H₈N₂)]·0.5H₂O
M_r = 518.41
Monoclinic, P 2₁ /n
a = 8.7028 (9) Å
b = 19.872 (2) Å
c = 14.5181 (14) Å
β = 97.845 (2)°
V = 2487.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.73 mm⁻¹
T = 293 K
0.28 × 0.17 × 0.05 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.822, T_max = 0.965
14695 measured reflections
5667 independent reflections
3153 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.119
S = 0.96
5667 reflections
327 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1w—H11⋯O1	0.84	1.98	2.812 (5)	173

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811041699/bt5671sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811041699/bt5671Isup2.hkl

checkCIF report

Comment top

Meta(II) dicarboxylates generally adopt three-dimensional polymeric architectures as the carboxyl –CO₂ ends of the dianion are both capable of binding to more than one metal atom. The three-dimensional motifs can be altered to two-dimensional layers or even linear chains through the formation of adducts with 2,2'-bipyridine like ligands; the molecular architectures of such adducts of metal carboxylates with such α,α'-dimine ligands have been reviewed (Ye et al., 2005).

We have synthesized (E)-3,3'-(but-2-ene-2,3-diyl)dibenzoic acid in a multi-step synthesis for use in another research projecttheme; we have used this rigid dicarboxylic acid to form a coordination polymer as no derivatives of this acid have been reported. The dicarboxylate ion of the coordination polymer, [Co(C₁₀H₈N₂)(C₁₈H₁₄O₄)^.0.5H₂O]_n (Scheme I, Fig. 1), has its carboxyl –CO₂ ends each chelating a 2,2'-bipyridine chelated Co^II atom to generate a helical polymeric chain that runs along the b-axis of the monoclinic unit cell (Fig. 2). The Co^II atom shows octahedral coordination. The lattice water molecule is disordered about a center-of-inversion and is connected to the chain by an O–H···O hydrogen bond (Table 1).

Related literature top

For a review of the adducts of metal carboxylates with 2,2'-bipyridine-like ligands, see: Ye et al. (2005). For details of the synthesis, see: McMurry (1989).

Experimental top

2,3-Bis-(3-bromophenyl)-2-butene was synthesized from the cross-coupling of 3-bromoacetophenone catalyzed by low-valent titanium (McMurry, 1989).

2,3-Bis-(3-bromophenyl)-2-butene (17.3 g, 0.048 mol) was added to a solution of n-butyllithium (2.5 M in hexane, 40 ml, 0.10 mol) in ether (400 ml) at 200 K. The reaction was carried out under nitrogen. The mixture was warmed to room temperature and then stirred overnight. The reaction was quenched with water (100 ml) and the organic compounds were extracted with ether. The aqueous phase was adjusted to a pH of 1 by the addition of concentrated hydrochloric acid. The precipitate was collected, washed with ethyl acetate and dried to yield 3,3'-(but-2-ene-2,3-diyl)dibenzoic acid (yield 9.8 g, 70%) as a mixture of E and Z isomers.

3,3'-(But-2-ene-2,3-diyl)dibenzoic acid (10 g, 0.034 mol), thionyl chloride (12.0 ml) and methanol (150 ml) were heated for 2 h. The solvent was evaporated and the residue was purified by silica gel chromatography to yield 2.2 g of (Z)-dimethyl 3,3'-(but-2-ene-2,3-diyl)dibenzoate and 6.6 g of (E)-dimethyl 3,3'-(but-2-ene-2,3-diyl)dibenzoate.

To (E)-dimethyl 3,3'-(but-2-ene-2,3-diyl)dibenzoate (5.0 g,15.4 mmol) in THF (30 ml) was added lithium hydroxide (1.48 g, 61.6 mmol) in water (30 ml). The mixture was stirred overnight. The solvent was removed and then acidified with concentrated hydrochloric acid; the reaction was carried out at 273 K. The precipitate was collected, washed with ethyl acetate and dried to give to (E)-3,3'-(but-2-ene-2,3-diyl)dibenzoic acid (yield 4.3 g, 95%) as a white solid.

(E)-3,3'-(But-2-ene-2,3-diyl)dibenzoic acid (15.3 mg, 0.05 mmol), sodium hydroxide (4.1 mg, 0.10 mmol), cobalt(II) chloride hexahydrate (11.8 mg, 0.05 mmol) and 2,2'-bipyridine (7.8 mg, 0.05 mol) were mixed in water (4 ml). This was transferred to a 25-mLTeflon-lined stainless-steel Parr bomb. The bomb was heated at 408 K for 3 days. The bomb was cooled slowly to room temperature. Red block-shaped crystals were obtained; yield: 10.8 mg (40% based on the acid). CH&N elemental analysis. Calcd. (%): C, 65.00; H, 4.22; N, 5.33. Found (%): C, 65.29; H, 4.05; N, 5.32.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. Anisotropic ellipsoid plot (Barbour, 2001) of a portion of polymeric Co(C₁₀H₈N₂)(C₁₈H₁₄O₄)^.0.5H₂O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.
	Fig. 2. Chain structure; the lattice water molecules are not shown.

catena-Poly[[[(2,2'-bipyridine-κ²N,N')cobalt(II)]- µ-(E)-3,3'-(but-2-ene-2,3-diyl)dibenzoato- κ⁴O,O':O'',O'''] hemihydrate] top

Crystal data top

[Co(C₁₈H₁₄O₄)(C₁₀H₈N₂)]·0.5H₂O	F(000) = 1072
M_r = 518.41	D_x = 1.384 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2090 reflections
a = 8.7028 (9) Å	θ = 2.6–21.1°
b = 19.872 (2) Å	µ = 0.73 mm⁻¹
c = 14.5181 (14) Å	T = 293 K
β = 97.845 (2)°	Plate, red
V = 2487.2 (4) Å³	0.28 × 0.17 × 0.05 mm
Z = 4

Data collection top

Bruker SMART APEX diffractometer	5667 independent reflections
Radiation source: fine-focus sealed tube	3153 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ω scans	θ_max = 27.5°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→11
T_min = 0.822, T_max = 0.965	k = −23→25
14695 measured reflections	l = −18→14

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.119	H-atom parameters constrained
S = 0.96	w = 1/[σ²(F_o²) + (0.0535P)²] where P = (F_o² + 2F_c²)/3
5667 reflections	(Δ/σ)_max = 0.001
327 parameters	Δρ_max = 0.23 e Å⁻³
6 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

[Co(C₁₈H₁₄O₄)(C₁₀H₈N₂)]·0.5H₂O	V = 2487.2 (4) Å³
M_r = 518.41	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.7028 (9) Å	µ = 0.73 mm⁻¹
b = 19.872 (2) Å	T = 293 K
c = 14.5181 (14) Å	0.28 × 0.17 × 0.05 mm
β = 97.845 (2)°

Data collection top

Bruker SMART APEX diffractometer	5667 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3153 reflections with I > 2σ(I)
T_min = 0.822, T_max = 0.965	R_int = 0.046
14695 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	6 restraints
wR(F²) = 0.119	H-atom parameters constrained
S = 0.96	Δρ_max = 0.23 e Å⁻³
5667 reflections	Δρ_min = −0.20 e Å⁻³
327 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Co1	0.72581 (4)	0.433780 (19)	0.65569 (3)	0.05411 (15)
O1	0.6416 (2)	0.49163 (10)	0.76819 (13)	0.0630 (5)
O2	0.6521 (2)	0.53304 (10)	0.63038 (14)	0.0648 (6)
O3	−0.0199 (2)	0.88087 (10)	0.90530 (14)	0.0629 (5)
O4	−0.2047 (2)	0.83205 (10)	0.81231 (14)	0.0659 (6)
O1W	0.6236 (8)	0.4682 (3)	0.9574 (3)	0.125 (2)	0.50
H11	0.6219	0.4775	0.9009	0.188*	0.50
H12	0.5499	0.4883	0.9774	0.188*	0.50
N1	0.9576 (3)	0.44197 (11)	0.71738 (18)	0.0564 (6)
N2	0.8468 (3)	0.41977 (11)	0.54323 (17)	0.0555 (6)
C1	0.6243 (3)	0.54056 (14)	0.7128 (2)	0.0507 (7)
C2	0.5758 (3)	0.60753 (14)	0.74361 (19)	0.0468 (6)
C3	0.5469 (3)	0.66010 (15)	0.68050 (19)	0.0526 (7)
H3	0.5576	0.6534	0.6183	0.063*
C4	0.5025 (3)	0.72181 (15)	0.7100 (2)	0.0590 (8)
H4	0.4817	0.7567	0.6674	0.071*
C5	0.4887 (3)	0.73232 (15)	0.8025 (2)	0.0571 (7)
H5	0.4581	0.7744	0.8215	0.069*
C6	0.5193 (3)	0.68143 (14)	0.86754 (18)	0.0497 (7)
C7	0.5619 (3)	0.61921 (14)	0.83632 (18)	0.0490 (7)
H7	0.5817	0.5842	0.8788	0.059*
C8	0.5183 (3)	0.69319 (14)	0.96955 (19)	0.0547 (7)
C9	0.6782 (4)	0.69610 (19)	1.0248 (2)	0.0845 (11)
H9A	0.7295	0.7366	1.0096	0.127*
H9B	0.7373	0.6577	1.0100	0.127*
H9C	0.6696	0.6958	1.0900	0.127*
C10	0.3872 (4)	0.70120 (14)	1.00524 (19)	0.0569 (7)
C11	0.3799 (4)	0.71311 (19)	1.1077 (2)	0.0856 (11)
H11A	0.3364	0.6743	1.1338	0.128*
H11B	0.3160	0.7516	1.1148	0.128*
H11C	0.4825	0.7210	1.1393	0.128*
C12	0.2327 (3)	0.70095 (14)	0.94623 (19)	0.0528 (7)
C13	0.1647 (4)	0.64333 (16)	0.9054 (2)	0.0682 (9)
H13	0.2170	0.6025	0.9137	0.082*
C14	0.0202 (4)	0.64560 (16)	0.8527 (2)	0.0714 (9)
H14	−0.0243	0.6062	0.8268	0.086*
C15	−0.0583 (3)	0.70517 (15)	0.83819 (19)	0.0570 (7)
H15	−0.1548	0.7063	0.8017	0.068*
C16	0.0063 (3)	0.76353 (14)	0.87795 (18)	0.0494 (7)
C17	−0.0770 (3)	0.82881 (14)	0.8639 (2)	0.0516 (7)
C18	0.1496 (3)	0.76036 (14)	0.93232 (19)	0.0522 (7)
H18	0.1916	0.7995	0.9605	0.063*
C19	1.0053 (4)	0.45294 (16)	0.8071 (3)	0.0727 (9)
H19	0.9311	0.4587	0.8468	0.087*
C20	1.1591 (4)	0.45614 (18)	0.8438 (3)	0.0845 (11)
H20	1.1881	0.4646	0.9068	0.101*
C21	1.2687 (4)	0.44668 (18)	0.7861 (4)	0.0916 (12)
H21	1.3736	0.4483	0.8094	0.110*
C22	1.2228 (4)	0.43482 (16)	0.6937 (3)	0.0752 (10)
H22	1.2961	0.4282	0.6536	0.090*
C23	1.0648 (3)	0.43281 (13)	0.6601 (2)	0.0560 (7)
C24	1.0024 (3)	0.42047 (12)	0.5620 (2)	0.0534 (7)
C25	1.0942 (4)	0.41078 (15)	0.4925 (3)	0.0668 (9)
H25	1.2017	0.4130	0.5057	0.080*
C26	1.0246 (4)	0.39784 (16)	0.4041 (3)	0.0786 (10)
H26	1.0850	0.3902	0.3570	0.094*
C27	0.8642 (4)	0.39610 (17)	0.3846 (2)	0.0772 (10)
H27	0.8151	0.3868	0.3250	0.093*
C28	0.7805 (4)	0.40859 (16)	0.4565 (2)	0.0690 (9)
H28	0.6728	0.4093	0.4440	0.083*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0452 (2)	0.0561 (3)	0.0637 (3)	−0.00109 (18)	0.01649 (18)	−0.00717 (19)
O1	0.0733 (14)	0.0552 (13)	0.0637 (13)	0.0107 (10)	0.0214 (10)	−0.0004 (10)
O2	0.0729 (14)	0.0641 (13)	0.0623 (13)	0.0021 (11)	0.0270 (11)	−0.0056 (10)
O3	0.0502 (11)	0.0490 (12)	0.0899 (15)	−0.0008 (9)	0.0108 (10)	−0.0069 (11)
O4	0.0546 (13)	0.0654 (14)	0.0750 (14)	0.0052 (10)	−0.0008 (11)	−0.0053 (11)
O1W	0.195 (6)	0.101 (4)	0.076 (3)	0.032 (4)	0.004 (4)	0.017 (3)
N1	0.0516 (14)	0.0506 (15)	0.0675 (17)	0.0005 (11)	0.0100 (13)	−0.0047 (12)
N2	0.0477 (14)	0.0553 (15)	0.0660 (17)	−0.0051 (11)	0.0173 (12)	−0.0059 (12)
C1	0.0376 (14)	0.0565 (18)	0.060 (2)	−0.0061 (12)	0.0143 (13)	−0.0038 (15)
C2	0.0357 (14)	0.0509 (17)	0.0553 (18)	−0.0017 (12)	0.0121 (12)	−0.0022 (13)
C3	0.0452 (15)	0.063 (2)	0.0500 (17)	−0.0050 (13)	0.0085 (13)	−0.0020 (14)
C4	0.0589 (18)	0.0581 (19)	0.059 (2)	0.0031 (14)	0.0046 (15)	0.0098 (15)
C5	0.0559 (18)	0.0522 (18)	0.063 (2)	0.0081 (13)	0.0087 (15)	−0.0016 (15)
C6	0.0432 (15)	0.0542 (18)	0.0518 (17)	0.0053 (13)	0.0074 (13)	−0.0008 (14)
C7	0.0447 (15)	0.0525 (17)	0.0504 (18)	0.0053 (12)	0.0085 (13)	0.0065 (13)
C8	0.0573 (18)	0.0546 (18)	0.0519 (18)	0.0078 (14)	0.0069 (14)	−0.0023 (13)
C9	0.071 (2)	0.111 (3)	0.069 (2)	0.020 (2)	−0.0006 (18)	−0.007 (2)
C10	0.0654 (19)	0.0571 (18)	0.0490 (17)	0.0085 (15)	0.0102 (15)	−0.0058 (14)
C11	0.092 (3)	0.112 (3)	0.054 (2)	0.021 (2)	0.0129 (18)	−0.0125 (19)
C12	0.0551 (17)	0.0531 (18)	0.0540 (18)	0.0050 (14)	0.0212 (14)	−0.0063 (14)
C13	0.072 (2)	0.056 (2)	0.078 (2)	0.0121 (16)	0.0171 (18)	−0.0117 (16)
C14	0.073 (2)	0.054 (2)	0.086 (2)	−0.0048 (16)	0.0092 (19)	−0.0178 (17)
C15	0.0517 (17)	0.061 (2)	0.0591 (19)	−0.0024 (14)	0.0079 (14)	−0.0079 (15)
C16	0.0511 (16)	0.0510 (17)	0.0499 (17)	−0.0044 (13)	0.0203 (13)	−0.0050 (13)
C17	0.0474 (17)	0.0536 (18)	0.0587 (19)	−0.0001 (14)	0.0242 (14)	−0.0004 (14)
C18	0.0505 (16)	0.0525 (18)	0.0560 (17)	−0.0027 (13)	0.0156 (14)	−0.0093 (13)
C19	0.067 (2)	0.071 (2)	0.079 (3)	0.0006 (16)	0.0034 (19)	−0.0085 (18)
C20	0.076 (3)	0.082 (3)	0.089 (3)	−0.0013 (19)	−0.011 (2)	−0.004 (2)
C21	0.058 (2)	0.087 (3)	0.123 (4)	−0.0026 (19)	−0.011 (2)	0.010 (2)
C22	0.0490 (18)	0.068 (2)	0.110 (3)	0.0052 (16)	0.0142 (19)	0.009 (2)
C23	0.0467 (16)	0.0398 (15)	0.083 (2)	0.0018 (12)	0.0147 (16)	0.0018 (15)
C24	0.0496 (16)	0.0379 (16)	0.077 (2)	0.0009 (12)	0.0226 (15)	0.0019 (13)
C25	0.063 (2)	0.0564 (19)	0.087 (3)	0.0040 (15)	0.0340 (19)	0.0061 (17)
C26	0.090 (3)	0.067 (2)	0.090 (3)	0.0024 (19)	0.052 (2)	0.0011 (19)
C27	0.089 (3)	0.080 (2)	0.068 (2)	−0.013 (2)	0.030 (2)	−0.0066 (18)
C28	0.063 (2)	0.075 (2)	0.073 (2)	−0.0135 (16)	0.0221 (18)	−0.0075 (18)

Geometric parameters (Å, º) top

Co1—N2	2.079 (2)	C10—C12	1.492 (4)
Co1—O4ⁱ	2.088 (2)	C10—C11	1.515 (4)
Co1—O2	2.091 (2)	C11—H11A	0.9600
Co1—N1	2.099 (2)	C11—H11B	0.9600
Co1—O3ⁱ	2.1602 (18)	C11—H11C	0.9600
Co1—O1	2.2030 (19)	C12—C13	1.385 (4)
O1—C1	1.257 (3)	C12—C18	1.385 (4)
O2—C1	1.262 (3)	C13—C14	1.381 (4)
O3—C17	1.264 (3)	C13—H13	0.9300
O3—Co1ⁱⁱ	2.1602 (18)	C14—C15	1.369 (4)
O4—C17	1.254 (3)	C14—H14	0.9300
O4—Co1ⁱⁱ	2.088 (2)	C15—C16	1.381 (3)
O1W—H11	0.8400	C15—H15	0.9300
O1W—H12	0.8401	C16—C18	1.383 (4)
N1—C19	1.330 (4)	C16—C17	1.487 (4)
N1—C23	1.344 (4)	C17—Co1ⁱⁱ	2.451 (3)
N2—C28	1.330 (3)	C18—H18	0.9300
N2—C24	1.345 (3)	C19—C20	1.372 (4)
C1—C2	1.483 (4)	C19—H19	0.9300
C2—C7	1.387 (3)	C20—C21	1.366 (5)
C2—C3	1.390 (4)	C20—H20	0.9300
C3—C4	1.371 (4)	C21—C22	1.367 (5)
C3—H3	0.9300	C21—H21	0.9300
C4—C5	1.382 (4)	C22—C23	1.395 (4)
C4—H4	0.9300	C22—H22	0.9300
C5—C6	1.384 (4)	C23—C24	1.473 (4)
C5—H5	0.9300	C24—C25	1.384 (4)
C6—C7	1.385 (4)	C25—C26	1.366 (4)
C6—C8	1.501 (4)	C25—H25	0.9300
C7—H7	0.9300	C26—C27	1.387 (5)
C8—C10	1.325 (4)	C26—H26	0.9300
C8—C9	1.510 (4)	C27—C28	1.375 (4)
C9—H9A	0.9600	C27—H27	0.9300
C9—H9B	0.9600	C28—H28	0.9300
C9—H9C	0.9600

N2—Co1—O4ⁱ	96.57 (8)	C10—C11—H11B	109.5
N2—Co1—O2	99.46 (8)	H11A—C11—H11B	109.5
O4ⁱ—Co1—O2	156.66 (8)	C10—C11—H11C	109.5
N2—Co1—N1	77.60 (10)	H11A—C11—H11C	109.5
O4ⁱ—Co1—N1	95.09 (8)	H11B—C11—H11C	109.5
O2—Co1—N1	104.82 (8)	C13—C12—C18	117.3 (3)
N2—Co1—O3ⁱ	95.36 (9)	C13—C12—C10	123.2 (3)
O4ⁱ—Co1—O3ⁱ	61.75 (7)	C18—C12—C10	119.5 (3)
O2—Co1—O3ⁱ	99.77 (8)	C12—C13—C14	120.9 (3)
N1—Co1—O3ⁱ	155.20 (8)	C12—C13—H13	119.5
N2—Co1—O1	155.19 (8)	C14—C13—H13	119.5
O4ⁱ—Co1—O1	106.98 (8)	C15—C14—C13	120.8 (3)
O2—Co1—O1	60.85 (7)	C15—C14—H14	119.6
N1—Co1—O1	92.34 (9)	C13—C14—H14	119.6
O3ⁱ—Co1—O1	102.51 (8)	C14—C15—C16	119.7 (3)
C1—O1—Co1	87.29 (16)	C14—C15—H15	120.1
C1—O2—Co1	92.23 (17)	C16—C15—H15	120.1
C17—O3—Co1ⁱⁱ	87.33 (16)	C15—C16—C18	119.0 (3)
C17—O4—Co1ⁱⁱ	90.83 (16)	C15—C16—C17	120.8 (3)
H11—O1W—H12	108.6	C18—C16—C17	120.2 (3)
C19—N1—C23	118.5 (3)	O4—C17—O3	120.0 (3)
C19—N1—Co1	125.8 (2)	O4—C17—C16	120.2 (3)
C23—N1—Co1	115.7 (2)	O3—C17—C16	119.8 (3)
C28—N2—C24	119.2 (3)	O4—C17—Co1ⁱⁱ	58.40 (14)
C28—N2—Co1	124.42 (19)	O3—C17—Co1ⁱⁱ	61.68 (14)
C24—N2—Co1	116.3 (2)	C16—C17—Co1ⁱⁱ	177.01 (19)
O1—C1—O2	119.5 (3)	C16—C18—C12	122.3 (3)
O1—C1—C2	121.0 (3)	C16—C18—H18	118.9
O2—C1—C2	119.4 (3)	C12—C18—H18	118.9
C7—C2—C3	118.8 (3)	N1—C19—C20	123.1 (4)
C7—C2—C1	120.5 (3)	N1—C19—H19	118.5
C3—C2—C1	120.6 (2)	C20—C19—H19	118.5
C4—C3—C2	120.0 (3)	C21—C20—C19	118.7 (4)
C4—C3—H3	120.0	C21—C20—H20	120.6
C2—C3—H3	120.0	C19—C20—H20	120.6
C3—C4—C5	120.3 (3)	C22—C21—C20	119.4 (3)
C3—C4—H4	119.9	C22—C21—H21	120.3
C5—C4—H4	119.9	C20—C21—H21	120.3
C4—C5—C6	121.2 (3)	C21—C22—C23	119.3 (3)
C4—C5—H5	119.4	C21—C22—H22	120.3
C6—C5—H5	119.4	C23—C22—H22	120.3
C5—C6—C7	117.7 (3)	N1—C23—C22	120.9 (3)
C5—C6—C8	122.2 (3)	N1—C23—C24	115.2 (2)
C7—C6—C8	120.0 (2)	C22—C23—C24	123.9 (3)
C6—C7—C2	122.0 (3)	N2—C24—C25	121.1 (3)
C6—C7—H7	119.0	N2—C24—C23	115.2 (2)
C2—C7—H7	119.0	C25—C24—C23	123.7 (3)
C10—C8—C6	121.8 (3)	C26—C25—C24	119.1 (3)
C10—C8—C9	124.6 (3)	C26—C25—H25	120.5
C6—C8—C9	113.6 (2)	C24—C25—H25	120.5
C8—C9—H9A	109.5	C25—C26—C27	120.1 (3)
C8—C9—H9B	109.5	C25—C26—H26	119.9
H9A—C9—H9B	109.5	C27—C26—H26	119.9
C8—C9—H9C	109.5	C28—C27—C26	117.6 (3)
H9A—C9—H9C	109.5	C28—C27—H27	121.2
H9B—C9—H9C	109.5	C26—C27—H27	121.2
C8—C10—C12	122.1 (2)	N2—C28—C27	122.9 (3)
C8—C10—C11	123.8 (3)	N2—C28—H28	118.6
C12—C10—C11	114.1 (3)	C27—C28—H28	118.6
C10—C11—H11A	109.5

N2—Co1—O1—C1	38.9 (3)	C6—C8—C10—C12	−1.7 (4)
O4ⁱ—Co1—O1—C1	−160.09 (16)	C9—C8—C10—C12	177.1 (3)
O2—Co1—O1—C1	−1.82 (15)	C6—C8—C10—C11	179.9 (3)
N1—Co1—O1—C1	103.86 (16)	C9—C8—C10—C11	−1.3 (5)
O3ⁱ—Co1—O1—C1	−96.14 (16)	C8—C10—C12—C13	72.2 (4)
N2—Co1—O2—C1	−162.06 (17)	C11—C10—C12—C13	−109.3 (3)
O4ⁱ—Co1—O2—C1	65.2 (3)	C8—C10—C12—C18	−109.3 (3)
N1—Co1—O2—C1	−82.50 (18)	C11—C10—C12—C18	69.2 (4)
O3ⁱ—Co1—O2—C1	100.77 (17)	C18—C12—C13—C14	0.4 (4)
O1—Co1—O2—C1	1.81 (15)	C10—C12—C13—C14	178.9 (3)
N2—Co1—N1—C19	−179.5 (2)	C12—C13—C14—C15	1.1 (5)
O4ⁱ—Co1—N1—C19	−83.9 (2)	C13—C14—C15—C16	−1.1 (5)
O2—Co1—N1—C19	83.8 (2)	C14—C15—C16—C18	−0.3 (4)
O3ⁱ—Co1—N1—C19	−103.9 (3)	C14—C15—C16—C17	−179.5 (3)
O1—Co1—N1—C19	23.4 (2)	Co1ⁱⁱ—O4—C17—O3	−2.0 (3)
N2—Co1—N1—C23	−1.95 (18)	Co1ⁱⁱ—O4—C17—C16	176.9 (2)
O4ⁱ—Co1—N1—C23	93.68 (19)	Co1ⁱⁱ—O3—C17—O4	2.0 (3)
O2—Co1—N1—C23	−98.61 (19)	Co1ⁱⁱ—O3—C17—C16	−177.0 (2)
O3ⁱ—Co1—N1—C23	73.7 (3)	C15—C16—C17—O4	−3.1 (4)
O1—Co1—N1—C23	−159.04 (19)	C18—C16—C17—O4	177.8 (3)
O4ⁱ—Co1—N2—C28	86.1 (2)	C15—C16—C17—O3	175.9 (2)
O2—Co1—N2—C28	−76.9 (2)	C18—C16—C17—O3	−3.3 (4)
N1—Co1—N2—C28	179.9 (2)	C15—C16—C18—C12	1.8 (4)
O3ⁱ—Co1—N2—C28	24.0 (2)	C17—C16—C18—C12	−179.0 (2)
O1—Co1—N2—C28	−112.2 (3)	C13—C12—C18—C16	−1.8 (4)
O4ⁱ—Co1—N2—C24	−91.99 (19)	C10—C12—C18—C16	179.6 (3)
O2—Co1—N2—C24	105.04 (19)	C23—N1—C19—C20	0.8 (4)
N1—Co1—N2—C24	1.81 (18)	Co1—N1—C19—C20	178.3 (2)
O3ⁱ—Co1—N2—C24	−154.10 (19)	N1—C19—C20—C21	−1.0 (5)
O1—Co1—N2—C24	69.7 (3)	C19—C20—C21—C22	0.5 (5)
Co1—O1—C1—O2	3.0 (3)	C20—C21—C22—C23	0.2 (5)
Co1—O1—C1—C2	−175.3 (2)	C19—N1—C23—C22	−0.1 (4)
Co1—O2—C1—O1	−3.2 (3)	Co1—N1—C23—C22	−177.9 (2)
Co1—O2—C1—C2	175.1 (2)	C19—N1—C23—C24	179.6 (2)
O1—C1—C2—C7	5.8 (4)	Co1—N1—C23—C24	1.8 (3)
O2—C1—C2—C7	−172.5 (2)	C21—C22—C23—N1	−0.4 (4)
O1—C1—C2—C3	−175.7 (2)	C21—C22—C23—C24	180.0 (3)
O2—C1—C2—C3	6.0 (4)	C28—N2—C24—C25	1.0 (4)
C7—C2—C3—C4	−1.3 (4)	Co1—N2—C24—C25	179.2 (2)
C1—C2—C3—C4	−179.8 (2)	C28—N2—C24—C23	−179.6 (2)
C2—C3—C4—C5	1.0 (4)	Co1—N2—C24—C23	−1.4 (3)
C3—C4—C5—C6	0.2 (4)	N1—C23—C24—N2	−0.3 (3)
C4—C5—C6—C7	−1.1 (4)	C22—C23—C24—N2	179.4 (3)
C4—C5—C6—C8	174.7 (3)	N1—C23—C24—C25	179.1 (3)
C5—C6—C7—C2	0.8 (4)	C22—C23—C24—C25	−1.2 (4)
C8—C6—C7—C2	−175.1 (2)	N2—C24—C25—C26	−2.5 (4)
C3—C2—C7—C6	0.4 (4)	C23—C24—C25—C26	178.2 (3)
C1—C2—C7—C6	178.9 (2)	C24—C25—C26—C27	1.5 (5)
C5—C6—C8—C10	74.1 (4)	C25—C26—C27—C28	0.8 (5)
C7—C6—C8—C10	−110.3 (3)	C24—N2—C28—C27	1.5 (4)
C5—C6—C8—C9	−104.9 (3)	Co1—N2—C28—C27	−176.5 (2)
C7—C6—C8—C9	70.8 (3)	C26—C27—C28—N2	−2.4 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H11···O1	0.84	1.98	2.812 (5)	173

Experimental details

Crystal data
Chemical formula	[Co(C₁₈H₁₄O₄)(C₁₀H₈N₂)]·0.5H₂O
M_r	518.41
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	8.7028 (9), 19.872 (2), 14.5181 (14)
β (°)	97.845 (2)
V (Å³)	2487.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.73
Crystal size (mm)	0.28 × 0.17 × 0.05

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.822, 0.965
No. of measured, independent and observed [I > 2σ(I)] reflections	14695, 5667, 3153
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.119, 0.96
No. of reflections	5667
No. of parameters	327
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.20

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1w—H11···O1	0.84	1.98	2.812 (5)	173

Acknowledgements

We thank the Beijing Municipal Commission of Educational S&T Development Foundation (KM201010038002) and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
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Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Ye, B.-H., Tong, M.-L. & Chen, X.-M. (2005). Coord. Chem. Rev. 249, 545–565. Web of Science CrossRef CAS Google Scholar

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