(2,9-Dimethyl-1,10-phenanthroline-κ2N,N′)bis­(2-hydroxy­benzoato)-κO;κ2O,O′-cobalt(II)

Zhao, P.-Z.; Xuan, X.-P.; Tang, Q.-H.

doi:10.1107/S1600536808012002

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 5| May 2008| Page m740

doi:10.1107/S1600536808012002

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(2,9-Dimethyl-1,10-phenanthroline-κ²N,N′)bis(2-hydroxybenzoato)-κO;κ²O,O′-cobalt(II)

Pei-Zheng Zhao,^a ^* Xiao-Peng Xuan ^a and Qing-Hu Tang ^a

^aCollege of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007, People's Republic of China
^*Correspondence e-mail: pz_zhao@hotmail.com

(Received 18 November 2007; accepted 25 April 2008; online 30 April 2008)

In the title compound, [Co(C₇H₅O₃)₂(C₁₄H₁₂N₂)], the Co^II ion is five-coordinated by two N atoms from one 2,9-dimethyl-1,10-phenanthroline (dmphen) ligand and three O atoms from two 2-hydroxybenzoate anions in a distorted trigonal bipyramidal geometry. The carboxylate group of one of the two 2-hydroxybenzoate anions is monodentate with a normal Co—O distance [1.9804 (18) Å], while the other is bidentate with two longer Co—O bonds [2.1981 (18) and 2.1359 (19) Å]. The crystal structure is stabilized by aromatic π–π stacking interactions [centroid–centroid distances of 4.0380 (3) and 3.8216 (3) Å between dmphen/dmphen and benzene/dmphen rings, respectively] and C—H⋯π(benzene) interactions.

Related literature

Experimental

Crystal data

[Co(C₇H₅O₃)₂(C₁₄H₁₂N₂)]
M_r = 541.41
Monoclinic, P 2₁ /n
a = 11.436 (1) Å
b = 16.528 (2) Å
c = 13.426 (2) Å
β = 105.856 (1)°
V = 2441.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.75 mm⁻¹
T = 293 (2) K
0.46 × 0.36 × 0.30 mm

Data collection

Bruker APEX2 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ) T_min = 0.779, T_max = 0.858 (expected range = 0.725–0.799)
20557 measured reflections
5998 independent reflections
4476 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.127
S = 1.04
5998 reflections
338 parameters
H-atom parameters constrained
Δρ_max = 0.86 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3O⋯O1	0.82	1.88	2.584 (3)	143
O6—H6O⋯O5	0.82	1.85	2.578 (3)	146
C3—H3⋯Cg1ⁱ	0.93	2.59	3.402 (3)	146
C25—H25⋯Cg2ⁱⁱ	0.93	3.06	3.989 (3)	172
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x-1, y, z. Cg1 is the centroid of the C23–C28 benzene ring and Cg2 is the centroid of the C16–C21 benzene ring.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: APEX2; data reduction: SAINT (Bruker, 2004); 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 I, global. DOI: 10.1107/S1600536808012002/lx2038sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808012002/lx2038Isup2.hkl

checkCIF report

Comment top

Metal-phenanthroline complexes have attracted much attention because of their peculiar features during recent decades (Wang et al., 1996; Wall et al., 1999; Naing et al., 1995). A number of Co(II)-phenanthroline complexes have been synthesized and structures were determined (Ding et al., 2006; Ren et al., 2007; Zhong et al., 2006; Xuan & Zhao, 2007). Herein we report the molecular and crystal structure of the title compound, (I), Bis(2-hydroxybenzoato–κO,κ²O,O')-(2,9-dimethyl-1, 10-phenanthroline-κ²N,N')-cobalt (II) (Fig. 1).

The Co atom in (I) is coordinated by a dmphen ligand and two 2-hydroxybenzoato ligands (Fig.1). The values of Co—O1 and Co—O2 distances are larger than the normal Co—O4 bond distance. The Co—O1—C15 and Co—O2—C15 bond angles [89.23 (14)°, 92.28 (15)°] appear to be compressed in order to allow Co and O atoms to approach each other. These imply the existence of genuing bonding interactions bwtween Co and O atoms, i.e. the C15-carboxylate group coordinates to the Co atom in chelating mode. The other ligand has a larger Co—O4—C22 angle of 107.71 (16)°. The values of Co···O5 distance is 2.6624 (22) Å, suggesting no bonding between the Co and O5 atoms. Therefore, the CoO₃N₂ unit forms a distorted trigonal-bipyramidal geometry.

A partially overlapped arrangement of neighboring parallel C3-dmphen and C3^v-dmphen rings[symmetry code: (v) -x + 2, -y + 1, -z + 1] is observed in the structure of (I) (Fig. 2). The shorter face-to-face separation of 3.3881 (5) Å clearly indicates the existence of π—π stacking between the dmphen ligands. In addition, the distance between the ring centroids Cg3 (C2—C5/C13/N1) and Cg2ⁱⁱⁱ (C16ⁱⁱⁱ—C21ⁱⁱⁱ) is 3.8216 (3) Å. This value is indentical to van der Waals thickness of the π—π stacking interaction between the nearly parallel dmphen and benzene ligands [dihedral angle 0.208 (68)°], although dmphen and benzene rings are well overlapped with respect to each other (Fig. 2).

The interaction of C—H···π and hydrogen bond intrains in the compound. The crystal structure is further stablilized by C—H···π interactions between the H atom of C3-dmphen ring and C23ⁱ-benzene ring, with a C3—H3···Cg1ⁱ separation of 2.5914 (4) Å (Fig.2 and Table 1; Cg1ⁱ is the centroid of C23ⁱ—C28ⁱ benzene ring, symmmetry code as in Fig. 2).

Related literature top

For related literature, see: Naing et al. (1995); Wang et al. (1996); Wall et al. (1999). For related structures, see: Ding et al. (2006); Ren et al. (2007); Xuan & Zhao (2007); Zhong et al. (2006). Cg1 is the centroid of the C23–C28 benzene ring and Cg2 is the centroid of the C16–C21 benzene ring.

Experimental top

2-hydroxybenzoic acid (0.1396 g, 1 mmol) and NaOH (0.0377 g, 1 mmol) were dissolved in distilled water(15 ml) and Co(NO₃)₂.6H₂O (0.1460 g, 0.5 mmol) were added. This solution was added to a solution of 2,9-dimethyl-1,10-phenanthroline hemihydrate (C₁₄H₁₂N₂.0.5H₂O, 0.1087 g, 0.5 mmol) in ethanol (10 ml). The mixture was stirred at 323 K and then refluxed for 4 h, cooled to room temperature and filtered. Brown single crystals of (I) were appeared over a period of one day by slow evaporation at room temperature.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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 molecular structure of the title complex(I), with atom labels and 30% probability displacement ellipsoids.
	Fig. 2. π—π and C—H···π interactions of neighboring molecules and hydrogen bond intrains in the crystal structure of (I). [symmetry code: (i) -x + 1, -y + 1, -z + 1; (ii) x - 1, y, z; (iii) -x + 3/2, y - 1/2, -z + 1/2; (iv)-x + 1/2, y - 1/2, -z + 1/2; (v) -x + 2, -y + 1, -z + 1; (vi) x + 1/2, -y + 3/2, z + 1/2; (vii) x + 1, y, z; (viii) x + 3/2, -y + 3/2, z + 1/2]

(2,9-Dimethyl-1,10-phenanthroline-κ²N,N')bis(2- hydroxybenzoato)-κO;κ²O,O'-cobalt(II) top

Crystal data top

[Co(C₇H₅O₃)₂(C₁₄H₁₂N₂)]	F(000) = 1116
M_r = 541.41	D_x = 1.473 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6265 reflections
a = 11.436 (1) Å	θ = 2.4–26.2°
b = 16.528 (2) Å	µ = 0.75 mm⁻¹
c = 13.426 (2) Å	T = 293 K
β = 105.856 (1)°	Block, brown
V = 2441.1 (5) Å³	0.46 × 0.36 × 0.30 mm
Z = 4

Data collection top

Bruker APEX2 CCD area-detector diffractometer	5998 independent reflections
Radiation source: fine-focus sealed tube	4476 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 10.0 pixels mm^-1	θ_max = 28.4°, θ_min = 2.4°
ϕ and ω scans	h = −15→15
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	k = −21→22
T_min = 0.779, T_max = 0.858	l = −16→17
20557 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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0698P)² + 0.571P] where P = (F_o² + 2F_c²)/3
5998 reflections	(Δ/σ)_max < 0.001
338 parameters	Δρ_max = 0.86 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

[Co(C₇H₅O₃)₂(C₁₄H₁₂N₂)]	V = 2441.1 (5) Å³
M_r = 541.41	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.436 (1) Å	µ = 0.75 mm⁻¹
b = 16.528 (2) Å	T = 293 K
c = 13.426 (2) Å	0.46 × 0.36 × 0.30 mm
β = 105.856 (1)°

Data collection top

Bruker APEX2 CCD area-detector diffractometer	5998 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	4476 reflections with I > 2σ(I)
T_min = 0.779, T_max = 0.858	R_int = 0.023
20557 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.04	Δρ_max = 0.86 e Å⁻³
5998 reflections	Δρ_min = −0.39 e Å⁻³
338 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
Co	0.66347 (2)	0.522121 (17)	0.26226 (2)	0.04340 (11)
O1	0.65059 (16)	0.59650 (10)	0.12395 (14)	0.0649 (5)
O2	0.77931 (16)	0.62474 (11)	0.27073 (14)	0.0671 (5)
O3	0.6514 (3)	0.67759 (15)	−0.04042 (18)	0.0985 (7)
H3O	0.6371	0.6376	−0.0095	0.148*
O4	0.49377 (15)	0.48299 (12)	0.23285 (17)	0.0713 (5)
O5	0.47135 (18)	0.61052 (14)	0.26953 (17)	0.0841 (6)
O6	0.2585 (2)	0.67472 (13)	0.2052 (2)	0.0926 (7)
H6O	0.3315	0.6732	0.2343	0.139*
N1	0.76714 (15)	0.48305 (10)	0.40730 (13)	0.0422 (4)
N2	0.74922 (14)	0.42206 (10)	0.21681 (13)	0.0397 (4)
C1	0.6828 (2)	0.57760 (19)	0.5073 (2)	0.0727 (8)
H1A	0.6606	0.6079	0.4439	0.109*
H1B	0.7191	0.6132	0.5638	0.109*
H1C	0.6115	0.5532	0.5190	0.109*
C2	0.7717 (2)	0.51308 (14)	0.50009 (18)	0.0492 (5)
C3	0.8578 (2)	0.48496 (15)	0.58982 (18)	0.0546 (6)
H3	0.8597	0.5068	0.6541	0.066*
C4	0.9379 (2)	0.42604 (15)	0.58278 (18)	0.0544 (6)
H4	0.9953	0.4080	0.6419	0.065*
C5	0.93361 (18)	0.39243 (14)	0.48552 (16)	0.0471 (5)
C6	1.0126 (2)	0.32887 (15)	0.4708 (2)	0.0589 (6)
H6	1.0714	0.3087	0.5276	0.071*
C7	1.0031 (2)	0.29808 (15)	0.3768 (2)	0.0588 (6)
H7	1.0553	0.2568	0.3694	0.071*
C8	0.91380 (19)	0.32754 (13)	0.28708 (18)	0.0482 (5)
C9	0.8954 (2)	0.29494 (14)	0.18696 (19)	0.0557 (6)
H9	0.9441	0.2527	0.1757	0.067*
C10	0.8064 (2)	0.32529 (14)	0.10690 (19)	0.0562 (6)
H10	0.7941	0.3038	0.0408	0.067*
C11	0.73282 (19)	0.38898 (13)	0.12356 (17)	0.0468 (5)
C12	0.83719 (17)	0.39055 (12)	0.29830 (15)	0.0397 (4)
C13	0.84636 (16)	0.42332 (12)	0.39942 (15)	0.0402 (4)
C14	0.6317 (2)	0.42116 (17)	0.03642 (19)	0.0638 (6)
H14A	0.5637	0.4351	0.0620	0.096*
H14B	0.6075	0.3806	−0.0163	0.096*
H14C	0.6592	0.4684	0.0078	0.096*
C15	0.7372 (2)	0.63949 (13)	0.17593 (19)	0.0505 (5)
C16	0.7892 (2)	0.70419 (13)	0.12395 (19)	0.0506 (5)
C17	0.7452 (3)	0.71637 (15)	0.0181 (2)	0.0635 (6)
C18	0.7973 (4)	0.7736 (2)	−0.0324 (3)	0.0966 (12)
H18	0.7680	0.7806	−0.1036	0.116*
C19	0.8899 (4)	0.8184 (2)	0.0225 (5)	0.1149 (17)
H19	0.9248	0.8564	−0.0116	0.138*
C20	0.9356 (3)	0.8098 (2)	0.1287 (5)	0.1114 (15)
H20	0.9999	0.8423	0.1643	0.134*
C21	0.8862 (2)	0.75258 (15)	0.1836 (3)	0.0800 (9)
H21	0.9153	0.7468	0.2550	0.096*
C22	0.4271 (2)	0.54319 (17)	0.23779 (18)	0.0539 (6)
C23	0.29299 (19)	0.53232 (13)	0.20118 (16)	0.0454 (5)
C24	0.2156 (2)	0.59876 (17)	0.18600 (19)	0.0593 (6)
C25	0.0897 (3)	0.5876 (2)	0.1481 (2)	0.0805 (9)
H25	0.0374	0.6319	0.1366	0.097*
C26	0.0446 (3)	0.5104 (3)	0.1281 (2)	0.0905 (11)
H26	−0.0390	0.5028	0.1048	0.109*
C27	0.1191 (3)	0.4451 (2)	0.1415 (2)	0.0792 (9)
H27	0.0867	0.3934	0.1265	0.095*
C28	0.2427 (2)	0.45565 (17)	0.17743 (19)	0.0583 (6)
H28	0.2936	0.4108	0.1860	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co	0.03569 (16)	0.04799 (18)	0.04465 (18)	0.00305 (11)	0.00781 (12)	0.00426 (11)
O1	0.0620 (10)	0.0564 (9)	0.0732 (12)	−0.0129 (8)	0.0131 (9)	0.0073 (8)
O2	0.0662 (11)	0.0710 (11)	0.0597 (11)	0.0084 (9)	0.0098 (9)	0.0131 (9)
O3	0.134 (2)	0.0891 (16)	0.0711 (14)	−0.0045 (15)	0.0268 (14)	−0.0029 (12)
O4	0.0378 (8)	0.0865 (14)	0.0891 (14)	0.0078 (8)	0.0163 (9)	0.0230 (10)
O5	0.0729 (12)	0.0987 (16)	0.0775 (13)	−0.0393 (12)	0.0150 (10)	−0.0125 (11)
O6	0.1171 (18)	0.0672 (13)	0.1017 (18)	0.0126 (12)	0.0439 (16)	−0.0003 (11)
N1	0.0362 (8)	0.0499 (10)	0.0402 (9)	0.0024 (7)	0.0100 (7)	0.0020 (7)
N2	0.0345 (8)	0.0428 (9)	0.0402 (9)	−0.0003 (6)	0.0077 (6)	0.0051 (7)
C1	0.0637 (15)	0.094 (2)	0.0591 (16)	0.0221 (15)	0.0149 (12)	−0.0129 (14)
C2	0.0433 (11)	0.0600 (13)	0.0440 (12)	0.0001 (10)	0.0114 (9)	−0.0001 (10)
C3	0.0538 (13)	0.0711 (15)	0.0383 (12)	−0.0012 (11)	0.0115 (10)	0.0013 (10)
C4	0.0472 (12)	0.0689 (15)	0.0432 (12)	0.0018 (11)	0.0058 (9)	0.0131 (10)
C5	0.0395 (10)	0.0559 (12)	0.0448 (12)	0.0024 (9)	0.0096 (9)	0.0129 (9)
C6	0.0502 (12)	0.0646 (14)	0.0575 (14)	0.0168 (11)	0.0074 (11)	0.0210 (12)
C7	0.0540 (13)	0.0560 (13)	0.0672 (16)	0.0204 (11)	0.0179 (11)	0.0156 (12)
C8	0.0461 (11)	0.0439 (11)	0.0572 (13)	0.0060 (9)	0.0185 (10)	0.0076 (9)
C9	0.0601 (13)	0.0472 (12)	0.0628 (15)	0.0092 (10)	0.0219 (11)	0.0001 (10)
C10	0.0671 (15)	0.0512 (13)	0.0520 (13)	−0.0003 (11)	0.0191 (11)	−0.0069 (10)
C11	0.0478 (11)	0.0475 (11)	0.0448 (12)	−0.0044 (9)	0.0120 (9)	−0.0018 (9)
C12	0.0361 (9)	0.0409 (10)	0.0432 (11)	0.0001 (8)	0.0127 (8)	0.0085 (8)
C13	0.0332 (9)	0.0456 (10)	0.0419 (11)	0.0000 (8)	0.0103 (8)	0.0087 (8)
C14	0.0659 (15)	0.0730 (16)	0.0438 (13)	0.0047 (13)	−0.0001 (11)	−0.0063 (11)
C15	0.0470 (11)	0.0449 (11)	0.0622 (15)	0.0111 (9)	0.0193 (10)	0.0061 (10)
C16	0.0477 (11)	0.0380 (10)	0.0717 (15)	0.0054 (9)	0.0259 (11)	0.0007 (10)
C17	0.0734 (16)	0.0531 (13)	0.0745 (18)	0.0071 (12)	0.0379 (14)	0.0058 (12)
C18	0.112 (3)	0.084 (2)	0.119 (3)	0.022 (2)	0.075 (2)	0.036 (2)
C19	0.104 (3)	0.067 (2)	0.205 (5)	0.007 (2)	0.096 (4)	0.030 (3)
C20	0.068 (2)	0.0577 (18)	0.219 (5)	−0.0157 (15)	0.057 (3)	−0.025 (3)
C21	0.0525 (14)	0.0464 (13)	0.148 (3)	−0.0021 (11)	0.0390 (17)	−0.0123 (16)
C22	0.0408 (11)	0.0775 (16)	0.0422 (12)	−0.0063 (11)	0.0094 (9)	0.0102 (11)
C23	0.0381 (10)	0.0631 (13)	0.0357 (10)	0.0005 (9)	0.0111 (8)	0.0002 (9)
C24	0.0634 (14)	0.0708 (16)	0.0483 (13)	0.0131 (12)	0.0227 (11)	0.0034 (11)
C25	0.0564 (15)	0.130 (3)	0.0573 (16)	0.0379 (18)	0.0187 (13)	0.0141 (17)
C26	0.0416 (14)	0.170 (4)	0.0562 (18)	−0.0097 (19)	0.0079 (12)	−0.012 (2)
C27	0.0581 (16)	0.113 (2)	0.0666 (18)	−0.0316 (17)	0.0173 (13)	−0.0227 (17)
C28	0.0507 (13)	0.0715 (15)	0.0546 (14)	−0.0070 (11)	0.0177 (11)	−0.0093 (11)

Geometric parameters (Å, º) top

Co—O4	1.9804 (18)	C8—C9	1.410 (3)
Co—N1	2.0863 (17)	C9—C10	1.359 (3)
Co—N2	2.0967 (17)	C9—H9	0.9300
Co—O2	2.1359 (19)	C10—C11	1.403 (3)
Co—O1	2.1981 (18)	C10—H10	0.9300
O1—C15	1.263 (3)	C11—C14	1.500 (3)
O2—C15	1.256 (3)	C12—C13	1.439 (3)
O3—C17	1.311 (4)	C14—H14A	0.9600
O3—H3O	0.8200	C14—H14B	0.9600
O4—C22	1.266 (3)	C14—H14C	0.9600
O5—C22	1.248 (3)	C15—C16	1.487 (3)
O6—C24	1.347 (3)	C16—C17	1.386 (4)
O6—H6O	0.8200	C16—C21	1.423 (4)
N1—C2	1.329 (3)	C17—C18	1.389 (4)
N1—C13	1.363 (3)	C18—C19	1.337 (6)
N2—C11	1.332 (3)	C18—H18	0.9300
N2—C12	1.371 (2)	C19—C20	1.384 (6)
C1—C2	1.495 (3)	C19—H19	0.9300
C1—H1A	0.9600	C20—C21	1.409 (5)
C1—H1B	0.9600	C20—H20	0.9300
C1—H1C	0.9600	C21—H21	0.9300
C2—C3	1.410 (3)	C22—C23	1.488 (3)
C3—C4	1.358 (3)	C23—C24	1.390 (3)
C3—H3	0.9300	C23—C28	1.392 (3)
C4—C5	1.407 (3)	C24—C25	1.402 (4)
C4—H4	0.9300	C25—C26	1.376 (5)
C5—C13	1.401 (3)	C25—H25	0.9300
C5—C6	1.434 (3)	C26—C27	1.356 (5)
C6—C7	1.337 (4)	C26—H26	0.9300
C6—H6	0.9300	C27—C28	1.375 (4)
C7—C8	1.435 (3)	C27—H27	0.9300
C7—H7	0.9300	C28—H28	0.9300
C8—C12	1.395 (3)

O4—Co—N1	111.16 (8)	C10—C11—C14	120.6 (2)
O4—Co—N2	101.25 (8)	N2—C12—C8	122.88 (19)
N1—Co—N2	80.55 (7)	N2—C12—C13	117.29 (17)
O4—Co—O2	146.07 (7)	C8—C12—C13	119.79 (18)
N1—Co—O2	90.58 (7)	N1—C13—C5	122.59 (19)
N2—Co—O2	108.01 (7)	N1—C13—C12	117.85 (17)
O4—Co—O1	100.27 (7)	C5—C13—C12	119.56 (18)
N1—Co—O1	148.37 (7)	C11—C14—H14A	109.5
N2—Co—O1	97.12 (7)	C11—C14—H14B	109.5
O2—Co—O1	59.89 (6)	H14A—C14—H14B	109.5
C15—O1—Co	89.23 (14)	C11—C14—H14C	109.5
C15—O2—Co	92.28 (15)	H14A—C14—H14C	109.5
C17—O3—H3O	109.5	H14B—C14—H14C	109.5
C22—O4—Co	107.71 (16)	O2—C15—O1	118.4 (2)
C24—O6—H6O	109.5	O2—C15—C16	121.6 (2)
C2—N1—C13	119.10 (18)	O1—C15—C16	119.9 (2)
C2—N1—Co	128.77 (15)	C17—C16—C21	120.3 (2)
C13—N1—Co	111.84 (13)	C17—C16—C15	120.4 (2)
C11—N2—C12	118.60 (18)	C21—C16—C15	119.4 (2)
C11—N2—Co	129.83 (14)	O3—C17—C16	123.5 (2)
C12—N2—Co	111.53 (13)	O3—C17—C18	115.4 (3)
C2—C1—H1A	109.5	C16—C17—C18	121.0 (3)
C2—C1—H1B	109.5	C19—C18—C17	119.3 (4)
H1A—C1—H1B	109.5	C19—C18—H18	120.4
C2—C1—H1C	109.5	C17—C18—H18	120.4
H1A—C1—H1C	109.5	C18—C19—C20	122.0 (3)
H1B—C1—H1C	109.5	C18—C19—H19	119.0
N1—C2—C3	121.2 (2)	C20—C19—H19	119.0
N1—C2—C1	118.3 (2)	C19—C20—C21	121.0 (4)
C3—C2—C1	120.5 (2)	C19—C20—H20	119.5
C4—C3—C2	120.2 (2)	C21—C20—H20	119.5
C4—C3—H3	119.9	C20—C21—C16	116.5 (4)
C2—C3—H3	119.9	C20—C21—H21	121.8
C3—C4—C5	119.6 (2)	C16—C21—H21	121.8
C3—C4—H4	120.2	O5—C22—O4	121.6 (2)
C5—C4—H4	120.2	O5—C22—C23	120.4 (2)
C13—C5—C4	117.3 (2)	O4—C22—C23	118.0 (2)
C13—C5—C6	119.1 (2)	C24—C23—C28	118.6 (2)
C4—C5—C6	123.6 (2)	C24—C23—C22	120.7 (2)
C7—C6—C5	121.1 (2)	C28—C23—C22	120.6 (2)
C7—C6—H6	119.4	O6—C24—C23	121.6 (2)
C5—C6—H6	119.4	O6—C24—C25	118.4 (3)
C6—C7—C8	121.3 (2)	C23—C24—C25	119.9 (3)
C6—C7—H7	119.4	C26—C25—C24	119.0 (3)
C8—C7—H7	119.4	C26—C25—H25	120.5
C12—C8—C9	117.0 (2)	C24—C25—H25	120.5
C12—C8—C7	119.1 (2)	C27—C26—C25	121.6 (3)
C9—C8—C7	123.9 (2)	C27—C26—H26	119.2
C10—C9—C8	119.9 (2)	C25—C26—H26	119.2
C10—C9—H9	120.1	C26—C27—C28	119.6 (3)
C8—C9—H9	120.1	C26—C27—H27	120.2
C9—C10—C11	120.2 (2)	C28—C27—H27	120.2
C9—C10—H10	119.9	C27—C28—C23	121.2 (3)
C11—C10—H10	119.9	C27—C28—H28	119.4
N2—C11—C10	121.4 (2)	C23—C28—H28	119.4
N2—C11—C14	117.9 (2)

O4—Co—O1—C15	152.70 (14)	Co—N2—C12—C13	6.9 (2)
N1—Co—O1—C15	−20.9 (2)	C9—C8—C12—N2	−1.6 (3)
N2—Co—O1—C15	−104.45 (14)	C7—C8—C12—N2	−179.73 (19)
O2—Co—O1—C15	2.28 (13)	C9—C8—C12—C13	176.34 (19)
O4—Co—O2—C15	−62.8 (2)	C7—C8—C12—C13	−1.8 (3)
N1—Co—O2—C15	165.78 (14)	C2—N1—C13—C5	−0.5 (3)
N2—Co—O2—C15	85.54 (14)	Co—N1—C13—C5	173.88 (16)
O1—Co—O2—C15	−2.30 (13)	C2—N1—C13—C12	178.44 (18)
N1—Co—O4—C22	108.46 (16)	Co—N1—C13—C12	−7.2 (2)
N2—Co—O4—C22	−167.43 (16)	C4—C5—C13—N1	−0.5 (3)
O2—Co—O4—C22	−18.0 (3)	C6—C5—C13—N1	179.22 (19)
O1—Co—O4—C22	−67.95 (17)	C4—C5—C13—C12	−179.36 (18)
O4—Co—N1—C2	−79.6 (2)	C6—C5—C13—C12	0.3 (3)
N2—Co—N1—C2	−178.06 (19)	N2—C12—C13—N1	0.1 (3)
O2—Co—N1—C2	73.77 (19)	C8—C12—C13—N1	−177.93 (17)
O1—Co—N1—C2	93.7 (2)	N2—C12—C13—C5	179.10 (17)
O4—Co—N1—C13	106.75 (14)	C8—C12—C13—C5	1.0 (3)
N2—Co—N1—C13	8.26 (13)	Co—O2—C15—O1	3.9 (2)
O2—Co—N1—C13	−99.91 (14)	Co—O2—C15—C16	−174.31 (17)
O1—Co—N1—C13	−79.99 (19)	Co—O1—C15—O2	−3.8 (2)
O4—Co—N2—C11	64.42 (19)	Co—O1—C15—C16	174.45 (17)
N1—Co—N2—C11	174.30 (18)	O2—C15—C16—C17	176.6 (2)
O2—Co—N2—C11	−98.18 (18)	O1—C15—C16—C17	−1.6 (3)
O1—Co—N2—C11	−37.59 (18)	O2—C15—C16—C21	−2.3 (3)
O4—Co—N2—C12	−118.05 (13)	O1—C15—C16—C21	179.5 (2)
N1—Co—N2—C12	−8.17 (13)	C21—C16—C17—O3	−175.6 (2)
O2—Co—N2—C12	79.35 (13)	C15—C16—C17—O3	5.6 (4)
O1—Co—N2—C12	139.94 (13)	C21—C16—C17—C18	2.4 (4)
C13—N1—C2—C3	0.8 (3)	C15—C16—C17—C18	−176.4 (2)
Co—N1—C2—C3	−172.49 (16)	O3—C17—C18—C19	177.0 (3)
C13—N1—C2—C1	−179.0 (2)	C16—C17—C18—C19	−1.1 (4)
Co—N1—C2—C1	7.7 (3)	C17—C18—C19—C20	−0.3 (5)
N1—C2—C3—C4	−0.1 (4)	C18—C19—C20—C21	0.4 (6)
C1—C2—C3—C4	179.7 (2)	C19—C20—C21—C16	0.9 (4)
C2—C3—C4—C5	−0.8 (4)	C17—C16—C21—C20	−2.2 (3)
C3—C4—C5—C13	1.1 (3)	C15—C16—C21—C20	176.6 (2)
C3—C4—C5—C6	−178.6 (2)	Co—O4—C22—O5	−8.2 (3)
C13—C5—C6—C7	−0.9 (3)	Co—O4—C22—C23	169.81 (15)
C4—C5—C6—C7	178.7 (2)	O5—C22—C23—C24	10.4 (3)
C5—C6—C7—C8	0.2 (4)	O4—C22—C23—C24	−167.7 (2)
C6—C7—C8—C12	1.2 (4)	O5—C22—C23—C28	−172.3 (2)
C6—C7—C8—C9	−176.8 (2)	O4—C22—C23—C28	9.7 (3)
C12—C8—C9—C10	0.2 (3)	C28—C23—C24—O6	−178.5 (2)
C7—C8—C9—C10	178.2 (2)	C22—C23—C24—O6	−1.0 (3)
C8—C9—C10—C11	0.0 (4)	C28—C23—C24—C25	0.4 (3)
C12—N2—C11—C10	−2.5 (3)	C22—C23—C24—C25	177.8 (2)
Co—N2—C11—C10	174.90 (16)	O6—C24—C25—C26	180.0 (3)
C12—N2—C11—C14	176.70 (19)	C23—C24—C25—C26	1.1 (4)
Co—N2—C11—C14	−5.9 (3)	C24—C25—C26—C27	−1.8 (5)
C9—C10—C11—N2	1.1 (3)	C25—C26—C27—C28	1.0 (5)
C9—C10—C11—C14	−178.0 (2)	C26—C27—C28—C23	0.5 (4)
C11—N2—C12—C8	2.8 (3)	C24—C23—C28—C27	−1.2 (4)
Co—N2—C12—C8	−175.06 (15)	C22—C23—C28—C27	−178.6 (2)
C11—N2—C12—C13	−175.23 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O1	0.82	1.88	2.584 (3)	143
O6—H6O···O5	0.82	1.86	2.578 (3)	146
C3—H3···Cg1ⁱ	0.93	2.59	3.402 (3)	146
C25—H25···Cg2ⁱⁱ	0.93	3.07	3.989 (3)	172

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

Experimental details

Crystal data
Chemical formula	[Co(C₇H₅O₃)₂(C₁₄H₁₂N₂)]
M_r	541.41
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	11.436 (1), 16.528 (2), 13.426 (2)
β (°)	105.856 (1)
V (Å³)	2441.1 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.75
Crystal size (mm)	0.46 × 0.36 × 0.30

Data collection
Diffractometer	Bruker APEX2 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2004)
T_min, T_max	0.779, 0.858
No. of measured, independent and observed [I > 2σ(I)] reflections	20557, 5998, 4476
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.127, 1.04
No. of reflections	5998
No. of parameters	338
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.86, −0.39

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3O···O1	0.82	1.883	2.584 (3)	142.9
O6—H6O···O5	0.82	1.855	2.578 (3)	146.4
C3—H3···Cg1ⁱ	0.9300	2.591	3.402 (3)	145.7
C25—H25···Cg2ⁱⁱ	0.9300	3.065	3.989 (3)	171.6

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

Acknowledgements

Financial support from the Science Fund of Henan Province for Distinguished Young Scholars (No. 074100510005) is gratefully acknowledged.

References

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