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Acta Cryst. (2008). E64, m327    [ doi:10.1107/S1600536807068080 ]

Bis(benzoato-[kappa]2O,O')(2,9-dimethyl-1,10-phenanthroline-[kappa]2N,N')cobalt(II)

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

Abstract top

In the title compound, [Co(C7H5O2)2(C14H12N2)], the CoII ion is located on a twofold rotation axis and is chelated by a 2,9-dimethyl-1,10-phenanthroline (dmphen) ligand and two benzoate anions in a distorted octahedral geometry. The crystal packing is stabilized by [pi]-[pi] interactions between parallel dmphen ligands of neighbouring molecules, with a face-to-face distance of 3.411 (2) Å.

Comment top

Metal-phenanthroline complexes and their detivatives 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) complexes have been synthesized and structures determined (Wu et al., 2003; Su et al., 2005; Ding et al., 2006; Ren et al., 2007; Zhong et al., 2006; Li et al., 2007). The title complex, (I), was recently prepared and its crystal structure is reported here.

Each CoII ion is located on a twofold rotation axis and six-coordinated by two N atoms from a dmphen ligand and four carbonyl O atoms from two benzoate ligands (Fig. 1) with a distorted octahedral geometry (Table 1).

In the crystal structure, molecules are linked into a one dimensional network by π-π interactions between the dmphen ring systems (Fig. 2). These intermolecular interaction occur between the parallel rings within offset face-to-face packing. The face-to-face distance of neighboring parallel rings is 3.411 (2) Å.

Related literature top

For background information on cobalt coordination chemistry, see: Wang et al. (1996); Wall et al. (1999); Naing et al. (1995). For related structures, see: Wu et al. (2003); Su et al. (2005); Ding et al. (2006); Ren et al. (2007); Zhong et al. (2006); Li et al. (2007).

Experimental top

Sodium benzoate (0.1455 g, 1 mmol) and Co(NO3)2.6H2O (0.1456 g, 0.5 mmol) were dissolved in distilled water (15 ml). This solution was added to a solution of 2,9-dimethyl-1,10-phenanthroline hemihydrate (C14H12N2.0.5H2O, 0.1090 g, 0.5 mmol) in ethanol (10 ml). The mixture was refluxed for 4 h. After cooling to room temperature the mixture was filtered. Brown single crystals were obtained by slow evaporation at room temperature after 1 d.

Refinement top

The benzene ring of benzoate ligand is disordered over two positions, site occupancy factors were refined and converged to 0.452 (14) and 0.548 (14), respectively. H atoms were placed in calculated positions and refined in riding model approximation, with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic, and 0.96 Å, Uiso(H) = 1.5Ueq(C) for methyl.

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL (Bruker, 2001); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL (Bruker, 2001).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title complex with 30% probability displacement ellipsoids, one disordered component has been omitted for clarity. Symmetry code: (A) -x + 1, y, -z + 3/2.
[Figure 2] Fig. 2. The π-π interaction between the dmphen rings of neighboring molecules in the crystal structure.
Bis(benzoato-κ2O,O')(2,9-dimethyl-1,10-phenanthroline-κ2N,N')cobalt(II) top
Crystal data top
[Co(C7H5O2)2(C14H12N2)]F000 = 1052
Mr = 509.41Dx = 1.398 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2433 reflections
a = 17.632 (3) Åθ = 2.3–22.5º
b = 14.410 (2) ŵ = 0.75 mm−1
c = 9.5282 (15) ÅT = 293 (2) K
β = 90.796 (2)ºBlock, brown
V = 2420.6 (7) Å30.30 × 0.22 × 0.22 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		2253 independent reflections
Radiation source: fine-focus sealed tube1840 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.026
T = 293(2) Kθmax = 25.5º
φ and ω scansθmin = 2.3º
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −21→21
Tmin = 0.805, Tmax = 0.856k = −17→17
8882 measured reflectionsl = −11→11
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.111  w = 1/[σ2(Fo2) + (0.0507P)2 + 2.0726P]
where P = (Fo2 + 2Fc2)/3
S = 1.06(Δ/σ)max < 0.001
2253 reflectionsΔρmax = 0.49 e Å−3
180 parametersΔρmin = −0.37 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Co(C7H5O2)2(C14H12N2)]V = 2420.6 (7) Å3
Mr = 509.41Z = 4
Monoclinic, C2/cMo Kα
a = 17.632 (3) ŵ = 0.75 mm−1
b = 14.410 (2) ÅT = 293 (2) K
c = 9.5282 (15) Å0.30 × 0.22 × 0.22 mm
β = 90.796 (2)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		2253 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		1840 reflections with I > 2σ(I)
Tmin = 0.805, Tmax = 0.856Rint = 0.026
8882 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.041180 parameters
wR(F2) = 0.111H-atom parameters constrained
S = 1.06Δρmax = 0.49 e Å−3
2253 reflectionsΔρmin = −0.37 e Å−3
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
xyzUiso*/UeqOcc. (<1)
Co10.50000.76395 (3)0.75000.0542 (2)
C10.63842 (19)0.7820 (2)0.9976 (4)0.0839 (10)
H1A0.59750.74721.03730.126*
H1B0.67760.79061.06730.126*
H1C0.65850.74880.91910.126*
C20.60968 (14)0.8746 (2)0.9496 (3)0.0593 (7)
C30.63991 (16)0.9577 (2)1.0038 (3)0.0678 (8)
H30.67820.95521.07190.081*
C40.61443 (17)1.0410 (2)0.9589 (3)0.0651 (8)
H40.63451.09530.99660.078*
C50.55731 (15)1.04513 (18)0.8547 (3)0.0560 (6)
C60.52910 (13)0.96006 (17)0.8040 (2)0.0471 (6)
C70.52756 (18)1.1299 (2)0.8001 (3)0.0693 (8)
H70.54631.18610.83380.083*
C80.57021 (17)0.68233 (18)0.5604 (3)0.0602 (7)
C90.6070 (2)0.6373 (2)0.4415 (3)0.054 (4)0.452 (14)
C100.68276 (16)0.6552 (3)0.4177 (4)0.066 (3)0.452 (14)
H100.70950.69540.47660.079*0.452 (14)
C110.71880 (15)0.6135 (3)0.3065 (4)0.078 (6)0.452 (14)
H110.76980.62550.29050.094*0.452 (14)
C120.6791 (3)0.5537 (4)0.2190 (5)0.096 (4)0.452 (14)
H120.70340.52560.14410.115*0.452 (14)
C130.6034 (3)0.5358 (6)0.2427 (7)0.111 (4)0.452 (14)
H130.57670.49560.18380.133*0.452 (14)
C140.5674 (3)0.5776 (6)0.3540 (6)0.084 (3)0.452 (14)
H140.51640.56550.37000.100*0.452 (14)
C9'0.6177 (2)0.63122 (19)0.4495 (3)0.056 (3)0.548 (14)
C10'0.68099 (17)0.6701 (2)0.3936 (5)0.064 (3)0.548 (14)
H10'0.69700.72840.42360.077*0.548 (14)
C11'0.72124 (15)0.6236 (2)0.2934 (4)0.083 (5)0.548 (14)
H11'0.76430.65050.25530.100*0.548 (14)
C12'0.6981 (3)0.5377 (2)0.2495 (5)0.084 (3)0.548 (14)
H12'0.72570.50590.18230.101*0.548 (14)
C13'0.6347 (5)0.4987 (3)0.3043 (9)0.090 (3)0.548 (14)
H13'0.61850.44070.27340.108*0.548 (14)
C14'0.5949 (4)0.5449 (3)0.4048 (7)0.072 (2)0.548 (14)
H14'0.55210.51770.44310.087*0.548 (14)
N10.55395 (11)0.87653 (14)0.8526 (2)0.0496 (5)
O10.60107 (14)0.74637 (15)0.6274 (3)0.0847 (5)
O20.50361 (13)0.65984 (16)0.5879 (2)0.0847 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0625 (3)0.0494 (3)0.0509 (3)0.0000.0041 (2)0.000
C10.076 (2)0.098 (3)0.077 (2)0.0292 (18)−0.0178 (17)0.0002 (18)
C20.0486 (14)0.0791 (19)0.0502 (15)0.0093 (13)0.0026 (11)−0.0044 (13)
C30.0521 (16)0.098 (2)0.0530 (16)−0.0035 (15)−0.0033 (12)−0.0160 (15)
C40.0679 (18)0.075 (2)0.0522 (16)−0.0159 (15)0.0081 (13)−0.0161 (14)
C50.0638 (16)0.0613 (16)0.0433 (13)−0.0074 (12)0.0138 (12)−0.0070 (11)
C60.0506 (14)0.0547 (14)0.0363 (12)0.0007 (11)0.0101 (10)−0.0017 (10)
C70.099 (2)0.0540 (16)0.0549 (17)−0.0078 (14)0.0167 (14)−0.0058 (12)
C80.0749 (18)0.0479 (15)0.0579 (16)−0.0033 (13)0.0010 (14)0.0031 (12)
C90.059 (5)0.049 (7)0.055 (7)0.002 (5)0.015 (5)0.007 (5)
C100.066 (8)0.075 (6)0.056 (5)−0.008 (5)−0.008 (5)−0.001 (4)
C110.051 (9)0.105 (12)0.079 (10)0.001 (8)0.001 (7)0.006 (10)
C120.096 (7)0.120 (9)0.072 (6)0.012 (6)0.010 (5)−0.035 (5)
C130.103 (7)0.129 (9)0.103 (7)−0.024 (7)0.017 (6)−0.059 (7)
C140.074 (5)0.089 (6)0.088 (6)−0.014 (5)0.013 (5)−0.034 (5)
C9'0.062 (5)0.058 (6)0.047 (6)−0.003 (4)−0.004 (4)−0.006 (4)
C10'0.062 (6)0.059 (4)0.073 (4)0.000 (4)0.004 (4)0.009 (4)
C11'0.071 (9)0.099 (9)0.080 (9)0.007 (7)0.028 (7)0.012 (8)
C12'0.076 (4)0.110 (6)0.067 (4)0.015 (5)0.016 (4)−0.010 (5)
C13'0.097 (6)0.086 (5)0.086 (5)−0.018 (4)0.010 (4)−0.039 (4)
C14'0.068 (4)0.073 (4)0.077 (4)−0.020 (3)0.016 (4)−0.014 (3)
N10.0488 (12)0.0589 (13)0.0412 (11)0.0050 (9)0.0029 (9)−0.0033 (9)
O10.0876 (11)0.0800 (11)0.0870 (11)−0.0088 (8)0.0221 (9)−0.0209 (8)
O20.0876 (11)0.0800 (11)0.0870 (11)−0.0088 (8)0.0221 (9)−0.0209 (8)
Geometric parameters (Å, °) top
Co1—N12.114 (2)C8—C91.465 (4)
Co1—N1i2.114 (2)C8—C9'1.544 (4)
Co1—O12.159 (2)C9—C101.3816 (16)
Co1—O1i2.159 (2)C9—C141.3816 (16)
Co1—O2i2.154 (2)C10—C111.3815 (16)
Co1—O22.154 (2)C10—H100.9300
Co1—C8i2.498 (3)C11—C121.3816 (16)
C1—C21.497 (4)C11—H110.9300
C1—H1A0.9600C12—C131.3816 (16)
C1—H1B0.9600C12—H120.9300
C1—H1C0.9600C13—C141.3816 (16)
C2—N11.339 (3)C13—H130.9300
C2—C31.406 (4)C14—H140.9300
C3—C41.349 (4)C9'—C10'1.3643 (16)
C3—H30.9300C9'—C14'1.3726 (16)
C4—C51.406 (4)C10'—C11'1.3726 (16)
C4—H40.9300C10'—H10'0.9300
C5—C61.406 (3)C11'—C12'1.3660 (16)
C5—C71.425 (4)C11'—H11'0.9300
C6—N11.360 (3)C12'—C13'1.3619 (15)
C6—C6i1.444 (5)C12'—H12'0.9300
C7—C7i1.353 (6)C13'—C14'1.3685 (16)
C7—H70.9300C13'—H13'0.9300
C8—O11.243 (3)C14'—H14'0.9300
C8—O21.249 (3)
N1—Co1—N1i79.73 (11)O1—C8—C9122.0 (3)
N1—Co1—O2i102.73 (9)O2—C8—C9118.4 (3)
N1i—Co1—O2i148.05 (8)O1—C8—C9'117.9 (3)
N1—Co1—O2148.05 (8)O2—C8—C9'122.7 (3)
N1i—Co1—O2102.73 (9)C10—C9—C14120.0
O2i—Co1—O291.74 (13)C10—C9—C8118.9 (2)
N1—Co1—O188.33 (8)C14—C9—C8121.1 (2)
N1i—Co1—O1102.08 (9)C11—C10—C9120.0
O2i—Co1—O1109.81 (9)C11—C10—H10120.0
O2—Co1—O159.85 (8)C9—C10—H10120.0
N1—Co1—O1i102.08 (9)C10—C11—C12120.0
N1i—Co1—O1i88.33 (8)C10—C11—H11120.0
O2i—Co1—O1i59.85 (8)C12—C11—H11120.0
O2—Co1—O1i109.81 (9)C11—C12—C13120.0
O1—Co1—O1i166.53 (12)C11—C12—H12120.0
N1—Co1—C8i104.54 (8)C13—C12—H12120.0
N1i—Co1—C8i118.14 (8)C12—C13—C14120.0
O2i—Co1—C8i30.01 (8)C12—C13—H13120.0
O2—Co1—C8i102.14 (9)C14—C13—H13120.0
O1—Co1—C8i139.20 (10)C9—C14—C13120.0
O1i—Co1—C8i29.84 (8)C9—C14—H14120.0
C2—C1—H1A109.5C13—C14—H14120.0
C2—C1—H1B109.5C10'—C9'—C14'119.2
H1A—C1—H1B109.5C10'—C9'—C8121.72 (19)
C2—C1—H1C109.5C14'—C9'—C8119.06 (19)
H1A—C1—H1C109.5C9'—C10'—C11'120.3
H1B—C1—H1C109.5C9'—C10'—H10'119.8
N1—C2—C3120.4 (3)C11'—C10'—H10'119.8
N1—C2—C1118.1 (3)C12'—C11'—C10'120.0
C3—C2—C1121.4 (3)C12'—C11'—H11'120.0
C4—C3—C2121.2 (3)C10'—C11'—H11'120.0
C4—C3—H3119.4C13'—C12'—C11'120.0
C2—C3—H3119.4C13'—C12'—H12'120.0
C3—C4—C5119.6 (3)C11'—C12'—H12'120.0
C3—C4—H4120.2C12'—C13'—C14'119.9
C5—C4—H4120.2C12'—C13'—H13'120.0
C4—C5—C6116.9 (3)C14'—C13'—H13'120.0
C4—C5—C7123.4 (3)C13'—C14'—C9'120.5
C6—C5—C7119.7 (2)C13'—C14'—H14'119.8
N1—C6—C5123.0 (2)C9'—C14'—H14'119.8
N1—C6—C6i117.74 (13)C2—N1—C6118.9 (2)
C5—C6—C6i119.30 (15)C2—N1—Co1128.61 (18)
C7i—C7—C5120.99 (16)C6—N1—Co1112.39 (15)
C7i—C7—H7119.5C8—O1—Co190.36 (19)
C5—C7—H7119.5C8—O2—Co190.41 (17)
O1—C8—O2119.4 (3)
N1—C2—C3—C4−0.8 (4)C3—C2—N1—C62.3 (4)
C1—C2—C3—C4179.2 (3)C1—C2—N1—C6−177.6 (2)
C2—C3—C4—C5−0.8 (4)C3—C2—N1—Co1178.41 (18)
C3—C4—C5—C60.8 (4)C1—C2—N1—Co1−1.5 (4)
C3—C4—C5—C7−179.4 (3)C5—C6—N1—C2−2.4 (3)
C4—C5—C6—N10.9 (4)C6i—C6—N1—C2177.8 (2)
C7—C5—C6—N1−179.0 (2)C5—C6—N1—Co1−179.10 (18)
C4—C5—C6—C6i−179.4 (2)C6i—C6—N1—Co11.2 (3)
C7—C5—C6—C6i0.8 (4)N1i—Co1—N1—C2−176.7 (3)
C4—C5—C7—C7i−179.9 (3)O2i—Co1—N1—C235.9 (2)
C6—C5—C7—C7i0.0 (5)O2—Co1—N1—C2−79.0 (3)
O1—C8—C9—C1011.2 (5)O1—Co1—N1—C2−74.1 (2)
O2—C8—C9—C10−174.2 (4)O1i—Co1—N1—C297.3 (2)
C9'—C8—C9—C10−49.13 (12)C8i—Co1—N1—C266.7 (2)
O1—C8—C9—C14−169.0 (5)N1i—Co1—N1—C6−0.41 (11)
O2—C8—C9—C145.7 (5)O2i—Co1—N1—C6−147.88 (16)
C9'—C8—C9—C14130.70 (19)O2—Co1—N1—C697.2 (2)
C14—C9—C10—C110.0O1—Co1—N1—C6102.19 (17)
C8—C9—C10—C11179.8 (3)O1i—Co1—N1—C6−86.45 (17)
C9—C10—C11—C120.0C8i—Co1—N1—C6−117.03 (16)
C10—C11—C12—C130.0O2—C8—O1—Co10.7 (3)
C11—C12—C13—C140.0C9—C8—O1—Co1175.3 (3)
C10—C9—C14—C130.0C9'—C8—O1—Co1−177.0 (2)
C8—C9—C14—C13−179.8 (3)N1—Co1—O1—C8−177.35 (18)
C12—C13—C14—C90.0N1i—Co1—O1—C8−98.22 (18)
O1—C8—C9'—C10'−20.3 (5)O2i—Co1—O1—C879.71 (19)
O2—C8—C9'—C10'162.1 (4)O2—Co1—O1—C8−0.39 (17)
C9—C8—C9'—C10'103.27 (16)O1i—Co1—O1—C841.69 (17)
O1—C8—C9'—C14'160.6 (4)C8i—Co1—O1—C872.1 (3)
O2—C8—C9'—C14'−17.0 (5)O1—C8—O2—Co1−0.7 (3)
C9—C8—C9'—C14'−75.85 (18)C9—C8—O2—Co1−175.5 (3)
C14'—C9'—C10'—C11'0.3C9'—C8—O2—Co1176.9 (3)
C8—C9'—C10'—C11'−178.9 (3)N1—Co1—O2—C86.1 (3)
C9'—C10'—C11'—C12'−0.3N1i—Co1—O2—C897.09 (18)
C10'—C11'—C12'—C13'0.6O2i—Co1—O2—C8−111.61 (19)
C11'—C12'—C13'—C14'−1.0O1—Co1—O2—C80.38 (17)
C12'—C13'—C14'—C9'1.0O1i—Co1—O2—C8−170.06 (17)
C10'—C9'—C14'—C13'−0.6C8i—Co1—O2—C8−140.01 (16)
C8—C9'—C14'—C13'178.5 (3)
Symmetry codes: (i) −x+1, y, −z+3/2.
Table 1
Selected geometric parameters (Å) top
Co1—N12.114 (2)Co1—O22.154 (2)
Co1—O12.159 (2)
Acknowledgements top

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

references
References top

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