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metal-organic compounds
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Bis(2-aminopyridine-κN1)bis(benzoato-κO)cobalt(II)
aInstitute of Coordination Catalysis, Yichun University, Yichun, Jiangxi, 336000, People's Republic of China, bCollege of Chemistry and Chemical Engineering, Anyang Normal University, Anyang, Henan, 455000, People's Republic of China, and cSchool of Chemistry and Materials Engineering, Huangshi Institute of Technology, Huangshi, 435003, People's Republic of China
*Correspondence e-mail: zhong_dichang@yahoo.com.cn
In the title compound, [Co(C7H5O2)2(C5H6N2)2], the CoII atom is hexacoordinated by four O atoms from two benzoate anions, and two N atoms from two 2-aminopyridine molecules, resulting in a distorted octahedral geometry. Both benzoate anions act as bidentate ligands and both 2-aminopyridine molecules are coordinated to the metal through their pyridyl N atoms. The crystal packing is stabilized by intermolecular N—H⋯O hydrogen bonds, C—H⋯π, and π–π stacking interactions involving benzoate anions and 2-aminopyridine molecules.
Related literature
For related literature, see: Benbellat et al. (2006); Brechin et al. (2000
); Dirnitrou et al. (1995
); Kozlevčar et al. (2001
); Zhu, Shao et al. (2003
); Zhu, Usman et al. (2003
).
Experimental
Crystal data
|
Refinement
|
|
|
|
Data collection: SMART (Bruker, 2004); cell SAINT (Bruker, 2004
); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a
); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a
); molecular graphics: SHELXTL (Sheldrick, 1997b
); software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536807063933/kp2149sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807063933/kp2149Isup2.hkl
The reagents available commercially were used without further purification. Co(NO3)2.6H2O (0.5 mmol), benzoate sodium (1 mmol) and 2-aminopyridine (1 mmol) were mixed in solution containing 8 ml of ethanol and 8 ml of water. After stirring 1.5 h, the mixture was placed in 25 ml Teflon-lined reactor and heated at 383 K in an oven for 7 days. The resulting solution was filtered and the filtrate was allowed to stay at ambience temperature. Well shaped purple crystals suitable for X-rays diffraction were obtained after two weeks. Yield: 78%.
All the H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with N—H, C—H distances of 0.86 Å, 0.93 Å and with Uiso(H) = 1.2Ueq(C or N).
In recent years the study of crystal structures and properties of cobalt complexes based on carboxyl ligand, owing to their novel geometries and magnetic behaviours, have attracted chemists (Tan et al., 2003; Zheng et al., 2004; Wang et al., 2004; Shi et al., 2004) to explore their use. The structures of the mixed ligand complexes containing benzoate as the most simple aromatic carboxyl compoud with well antibacterial activity and 2-aminopyridine reported by (Kozlevčar et al., 2001; Zhu, Usman et al., 2003; Zhu, Shao et al., 2004). Herein, we report the synthesis and
of mixed ligands cobalt(II) complex.The stucture of the title compound (I) is isostructural with the nickel (I) complex (Zhu, Shao et al., 2003) with the CoII atom hexa-coordinated by four O atoms of two benzoato anions, and two independent pyridine N atoms from two 2-aminopyridine molecules in distorted octahedral geometry (Fig. 1). The Co—N bond lengths of 2.1030 (14) Å and 2.1054 (14) Å, the Co—O distances ranging from 2.0363 (13) to 2.4016 (15) Å, are in the normal range. The close carboxylato distances O1—C8 and O2—C8, 1.260 (2) Å and 1.250 (2) Å, O3—C1 and O4—C1, 1.241 (2) Å and 1.274 (2) Å reveal the bidentate benzoato function. The molecules are held together by intramolecular and intermolecular hydrogen bonds, C—H···π and π–π stacking interactions generating three-dimensional supramolecular network.The amide N2 and N4 donate H atoms to the carboxyl O atoms O1and O4 in intramolecular N2—H2A···O1 and N4—H4A···O4 hydrogen bonds. The N2 and N4 also donate H atoms to O2 and O3 to form intermolecular N2—H2B···O2 and N4—H4B···O3 hydrogen bonds. Intermolecular C—H···π interation is pronounced in this involving methyl group C13 of the benzoato and the pyridyl rings N1→C24, with the distance 2.95 Å between the methyl hydrogen and the centroid of the nearest aromatic ring. In addition, π–π stacking interactions are also observed; the distance between centroids of the pyridyl ring N3→C19 and the aromatic ring C2→C7 is 3.7145 (16) Å (Table 1, Fig. 2).
For related literature, see: Benbellat et al. (2006); Brechin et al. (2000); Dirnitrou et al. (1995); Kozlevčar et al. (2001); Zhu, Shao et al. (2003); Zhu, Usman et al. (2003).
Data collection: APEX2 (Bruker, 2004); cell
APEX2 (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).[Co(C7H5O2)2(C5H6N2)2] | F(000) = 1012 |
Mr = 489.39 | Dx = 1.420 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 7256 reflections |
a = 9.0230 (9) Å | θ = 2.4–27.2° |
b = 11.3787 (12) Å | µ = 0.79 mm−1 |
c = 22.451 (2) Å | T = 296 K |
β = 96.765 (1)° | Block, purple |
V = 2288.9 (4) Å3 | 0.36 × 0.28 × 0.22 mm |
Z = 4 |
Bruker APEXII CCD area-detector diffractometer | 5288 independent reflections |
Radiation source: fine-focus sealed tube | 4198 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
phi and ω scans | θmax = 27.7°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→11 |
Tmin = 0.770, Tmax = 0.835 | k = −14→14 |
19674 measured reflections | l = −29→25 |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0416P)2 + 0.6259P] where P = (Fo2 + 2Fc2)/3 |
5288 reflections | (Δ/σ)max = 0.050 |
298 parameters | Δρmax = 0.32 e Å−3 |
357 restraints | Δρmin = −0.27 e Å−3 |
[Co(C7H5O2)2(C5H6N2)2] | V = 2288.9 (4) Å3 |
Mr = 489.39 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.0230 (9) Å | µ = 0.79 mm−1 |
b = 11.3787 (12) Å | T = 296 K |
c = 22.451 (2) Å | 0.36 × 0.28 × 0.22 mm |
β = 96.765 (1)° |
Bruker APEXII CCD area-detector diffractometer | 5288 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4198 reflections with I > 2σ(I) |
Tmin = 0.770, Tmax = 0.835 | Rint = 0.027 |
19674 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 357 restraints |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.32 e Å−3 |
5288 reflections | Δρmin = −0.27 e Å−3 |
298 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Co1 | 0.29899 (3) | 0.42895 (2) | 0.123207 (11) | 0.04251 (10) | |
N1 | 0.37446 (18) | 0.31734 (14) | 0.05834 (7) | 0.0434 (4) | |
N2 | 0.3314 (2) | 0.44408 (15) | −0.02241 (8) | 0.0520 (4) | |
H2A | 0.2773 | 0.4869 | −0.0019 | 0.062* | |
H2B | 0.3439 | 0.4640 | −0.0584 | 0.062* | |
N3 | 0.11106 (18) | 0.33308 (14) | 0.14242 (7) | 0.0429 (4) | |
N4 | 0.2282 (2) | 0.2407 (2) | 0.22706 (9) | 0.0745 (6) | |
H4A | 0.3108 | 0.2736 | 0.2208 | 0.089* | |
H4B | 0.2254 | 0.1949 | 0.2574 | 0.089* | |
O1 | 0.1750 (2) | 0.55468 (13) | 0.06636 (7) | 0.0651 (5) | |
O2 | 0.2427 (2) | 0.60479 (15) | 0.15868 (8) | 0.0698 (5) | |
O3 | 0.54634 (19) | 0.51020 (15) | 0.13357 (6) | 0.0602 (4) | |
O4 | 0.45109 (17) | 0.39318 (15) | 0.19532 (6) | 0.0566 (4) | |
C1 | 0.5594 (2) | 0.45573 (18) | 0.18175 (9) | 0.0444 (4) | |
C2 | 0.6981 (2) | 0.4610 (2) | 0.22510 (10) | 0.0504 (5) | |
C3 | 0.7083 (3) | 0.3990 (3) | 0.27797 (11) | 0.0690 (7) | |
H3 | 0.6284 | 0.3539 | 0.2875 | 0.083* | |
C4 | 0.8401 (4) | 0.4045 (3) | 0.31715 (15) | 0.0957 (10) | |
H4 | 0.8483 | 0.3637 | 0.3533 | 0.115* | |
C5 | 0.9565 (4) | 0.4697 (4) | 0.30237 (19) | 0.1039 (11) | |
H5 | 1.0446 | 0.4716 | 0.3284 | 0.125* | |
C6 | 0.9476 (3) | 0.5316 (4) | 0.2510 (2) | 0.1015 (11) | |
H6 | 1.0283 | 0.5765 | 0.2421 | 0.122* | |
C7 | 0.8173 (3) | 0.5283 (3) | 0.21134 (14) | 0.0760 (7) | |
H7 | 0.8102 | 0.5710 | 0.1758 | 0.091* | |
C8 | 0.1784 (2) | 0.62950 (18) | 0.10788 (10) | 0.0520 (5) | |
C9 | 0.1044 (2) | 0.74580 (18) | 0.09538 (10) | 0.0499 (5) | |
C10 | 0.1555 (3) | 0.8438 (2) | 0.12792 (12) | 0.0667 (6) | |
H10 | 0.2364 | 0.8373 | 0.1575 | 0.080* | |
C11 | 0.0872 (4) | 0.9512 (2) | 0.11675 (15) | 0.0842 (8) | |
H11 | 0.1236 | 1.0173 | 0.1381 | 0.101* | |
C12 | −0.0346 (4) | 0.9607 (3) | 0.07410 (16) | 0.0886 (9) | |
H12 | −0.0813 | 1.0331 | 0.0670 | 0.106* | |
C13 | −0.0872 (4) | 0.8644 (3) | 0.04219 (15) | 0.0880 (8) | |
H13 | −0.1706 | 0.8709 | 0.0138 | 0.106* | |
C14 | −0.0171 (3) | 0.7572 (2) | 0.05190 (12) | 0.0696 (7) | |
H14 | −0.0515 | 0.6923 | 0.0292 | 0.084* | |
C15 | −0.0147 (2) | 0.3464 (2) | 0.10357 (10) | 0.0529 (5) | |
H15 | −0.0106 | 0.3956 | 0.0707 | 0.063* | |
C16 | −0.1465 (3) | 0.2924 (2) | 0.10970 (12) | 0.0634 (6) | |
H16 | −0.2295 | 0.3033 | 0.0815 | 0.076* | |
C17 | −0.1537 (3) | 0.2207 (2) | 0.15906 (12) | 0.0643 (6) | |
H17 | −0.2426 | 0.1834 | 0.1648 | 0.077* | |
C18 | −0.0309 (3) | 0.2052 (2) | 0.19887 (11) | 0.0594 (6) | |
H18 | −0.0353 | 0.1578 | 0.2324 | 0.071* | |
C19 | 0.1036 (2) | 0.26105 (18) | 0.18948 (9) | 0.0479 (5) | |
C20 | 0.3961 (2) | 0.34636 (17) | 0.00178 (8) | 0.0426 (4) | |
C21 | 0.4848 (3) | 0.27532 (19) | −0.03144 (10) | 0.0532 (5) | |
H21 | 0.5028 | 0.2980 | −0.0697 | 0.064* | |
C22 | 0.5438 (3) | 0.1739 (2) | −0.00744 (11) | 0.0610 (6) | |
H22 | 0.6025 | 0.1268 | −0.0291 | 0.073* | |
C23 | 0.5157 (3) | 0.1407 (2) | 0.05002 (11) | 0.0614 (6) | |
H23 | 0.5525 | 0.0704 | 0.0669 | 0.074* | |
C24 | 0.4331 (3) | 0.21426 (19) | 0.08048 (10) | 0.0548 (5) | |
H24 | 0.4156 | 0.1926 | 0.1190 | 0.066* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.04193 (16) | 0.05067 (17) | 0.03496 (15) | −0.00377 (11) | 0.00463 (10) | 0.00284 (11) |
N1 | 0.0453 (9) | 0.0461 (9) | 0.0388 (8) | −0.0058 (7) | 0.0051 (7) | 0.0010 (7) |
N2 | 0.0644 (11) | 0.0542 (10) | 0.0393 (9) | 0.0026 (8) | 0.0141 (8) | 0.0041 (7) |
N3 | 0.0430 (9) | 0.0459 (9) | 0.0404 (8) | −0.0037 (7) | 0.0080 (7) | −0.0016 (7) |
N4 | 0.0630 (13) | 0.0910 (16) | 0.0676 (13) | −0.0130 (11) | 0.0000 (10) | 0.0383 (12) |
O1 | 0.0964 (13) | 0.0450 (8) | 0.0594 (10) | −0.0035 (8) | 0.0324 (9) | −0.0087 (7) |
O2 | 0.0713 (11) | 0.0598 (10) | 0.0745 (11) | 0.0096 (8) | −0.0071 (9) | −0.0133 (9) |
O3 | 0.0701 (10) | 0.0665 (10) | 0.0455 (8) | −0.0001 (8) | 0.0132 (7) | 0.0081 (7) |
O4 | 0.0462 (8) | 0.0740 (10) | 0.0483 (8) | −0.0136 (7) | 0.0003 (6) | 0.0080 (7) |
C1 | 0.0448 (11) | 0.0493 (10) | 0.0399 (10) | 0.0008 (8) | 0.0088 (8) | −0.0041 (8) |
C2 | 0.0403 (10) | 0.0578 (12) | 0.0537 (12) | 0.0024 (9) | 0.0082 (9) | −0.0181 (10) |
C3 | 0.0601 (14) | 0.0847 (16) | 0.0591 (14) | 0.0156 (12) | −0.0058 (11) | −0.0075 (12) |
C4 | 0.083 (2) | 0.119 (2) | 0.0781 (18) | 0.0320 (18) | −0.0214 (16) | −0.0218 (17) |
C5 | 0.0558 (17) | 0.136 (3) | 0.113 (2) | 0.0282 (18) | −0.0207 (17) | −0.062 (2) |
C6 | 0.0519 (15) | 0.125 (2) | 0.128 (3) | −0.0153 (16) | 0.0137 (17) | −0.060 (2) |
C7 | 0.0550 (14) | 0.0890 (17) | 0.0862 (17) | −0.0142 (13) | 0.0174 (13) | −0.0327 (15) |
C8 | 0.0520 (12) | 0.0452 (11) | 0.0625 (13) | −0.0078 (9) | 0.0225 (10) | −0.0096 (10) |
C9 | 0.0507 (12) | 0.0462 (10) | 0.0556 (12) | −0.0041 (9) | 0.0179 (9) | −0.0073 (9) |
C10 | 0.0746 (16) | 0.0515 (12) | 0.0732 (15) | −0.0025 (11) | 0.0052 (12) | −0.0129 (11) |
C11 | 0.108 (2) | 0.0492 (13) | 0.097 (2) | 0.0020 (14) | 0.0172 (18) | −0.0177 (13) |
C12 | 0.098 (2) | 0.0639 (16) | 0.106 (2) | 0.0221 (15) | 0.0193 (18) | 0.0063 (16) |
C13 | 0.0807 (19) | 0.0802 (19) | 0.100 (2) | 0.0087 (15) | −0.0046 (16) | 0.0101 (16) |
C14 | 0.0707 (16) | 0.0606 (14) | 0.0754 (16) | −0.0063 (12) | −0.0003 (13) | −0.0067 (12) |
C15 | 0.0504 (12) | 0.0540 (12) | 0.0530 (12) | −0.0063 (9) | 0.0013 (9) | 0.0007 (10) |
C16 | 0.0467 (12) | 0.0608 (13) | 0.0809 (16) | −0.0081 (10) | −0.0001 (11) | −0.0041 (12) |
C17 | 0.0498 (13) | 0.0555 (13) | 0.0900 (17) | −0.0121 (10) | 0.0191 (12) | −0.0067 (12) |
C18 | 0.0655 (14) | 0.0483 (11) | 0.0686 (14) | −0.0083 (10) | 0.0257 (12) | 0.0039 (10) |
C19 | 0.0511 (11) | 0.0451 (10) | 0.0495 (11) | −0.0017 (9) | 0.0146 (9) | −0.0001 (9) |
C20 | 0.0412 (10) | 0.0454 (10) | 0.0412 (9) | −0.0104 (8) | 0.0050 (8) | −0.0040 (8) |
C21 | 0.0579 (13) | 0.0544 (12) | 0.0493 (11) | −0.0079 (10) | 0.0151 (9) | −0.0079 (9) |
C22 | 0.0602 (14) | 0.0558 (13) | 0.0685 (14) | −0.0024 (10) | 0.0141 (11) | −0.0156 (11) |
C23 | 0.0654 (14) | 0.0489 (12) | 0.0683 (14) | 0.0016 (10) | 0.0015 (11) | −0.0004 (11) |
C24 | 0.0614 (13) | 0.0525 (12) | 0.0503 (12) | −0.0043 (10) | 0.0058 (10) | 0.0039 (10) |
Co1—O4 | 2.0364 (15) | C6—H6 | 0.9300 |
Co1—N3 | 2.1033 (16) | C7—H7 | 0.9300 |
Co1—N1 | 2.1050 (16) | C8—C9 | 1.494 (3) |
Co1—O1 | 2.1426 (18) | C9—C10 | 1.383 (3) |
Co1—O2 | 2.2340 (17) | C9—C14 | 1.386 (3) |
Co1—O3 | 2.4016 (17) | C10—C11 | 1.378 (4) |
N1—C20 | 1.348 (2) | C10—H10 | 0.9300 |
N1—C24 | 1.357 (3) | C11—C12 | 1.374 (4) |
N2—C20 | 1.341 (3) | C11—H11 | 0.9300 |
N2—H2A | 0.8600 | C12—C13 | 1.364 (5) |
N2—H2B | 0.8600 | C12—H12 | 0.9300 |
N3—C19 | 1.345 (3) | C13—C14 | 1.379 (4) |
N3—C15 | 1.356 (3) | C13—H13 | 0.9300 |
N4—C19 | 1.344 (3) | C14—H14 | 0.9300 |
N4—H4A | 0.8600 | C15—C16 | 1.360 (3) |
N4—H4B | 0.8600 | C15—H15 | 0.9300 |
O1—C8 | 1.260 (3) | C16—C17 | 1.384 (4) |
O2—C8 | 1.249 (3) | C16—H16 | 0.9300 |
O3—C1 | 1.240 (2) | C17—C18 | 1.350 (4) |
O4—C1 | 1.274 (2) | C17—H17 | 0.9300 |
C1—C2 | 1.493 (3) | C18—C19 | 1.408 (3) |
C2—C3 | 1.375 (3) | C18—H18 | 0.9300 |
C2—C7 | 1.385 (3) | C20—C21 | 1.411 (3) |
C3—C4 | 1.395 (4) | C21—C22 | 1.355 (3) |
C3—H3 | 0.9300 | C21—H21 | 0.9300 |
C4—C5 | 1.359 (6) | C22—C23 | 1.396 (3) |
C4—H4 | 0.9300 | C22—H22 | 0.9300 |
C5—C6 | 1.345 (5) | C23—C24 | 1.358 (3) |
C5—H5 | 0.9300 | C23—H23 | 0.9300 |
C6—C7 | 1.389 (4) | C24—H24 | 0.9300 |
O4—Co1—N3 | 102.55 (6) | O2—C8—O1 | 119.5 (2) |
O4—Co1—N1 | 100.77 (7) | O2—C8—C9 | 121.34 (19) |
N3—Co1—N1 | 99.40 (6) | O1—C8—C9 | 119.2 (2) |
O4—Co1—O1 | 149.63 (7) | C10—C9—C14 | 118.9 (2) |
N3—Co1—O1 | 95.25 (7) | C10—C9—C8 | 120.1 (2) |
N1—Co1—O1 | 100.34 (6) | C14—C9—C8 | 121.0 (2) |
O4—Co1—O2 | 93.20 (7) | C11—C10—C9 | 120.3 (3) |
N3—Co1—O2 | 99.72 (7) | C11—C10—H10 | 119.8 |
N1—Co1—O2 | 153.21 (7) | C9—C10—H10 | 119.8 |
O1—Co1—O2 | 59.31 (6) | C12—C11—C10 | 120.1 (3) |
O4—Co1—O3 | 57.88 (5) | C12—C11—H11 | 120.0 |
N3—Co1—O3 | 160.43 (6) | C10—C11—H11 | 120.0 |
N1—Co1—O3 | 85.79 (6) | C13—C12—C11 | 120.2 (3) |
O1—Co1—O3 | 102.40 (6) | C13—C12—H12 | 119.9 |
O2—Co1—O3 | 82.44 (6) | C11—C12—H12 | 119.9 |
C20—N1—C24 | 117.60 (18) | C12—C13—C14 | 120.2 (3) |
C20—N1—Co1 | 126.75 (13) | C12—C13—H13 | 119.9 |
C24—N1—Co1 | 114.33 (13) | C14—C13—H13 | 119.9 |
C20—N2—H2A | 120.0 | C13—C14—C9 | 120.3 (3) |
C20—N2—H2B | 120.0 | C13—C14—H14 | 119.8 |
H2A—N2—H2B | 120.0 | C9—C14—H14 | 119.8 |
C19—N3—C15 | 117.26 (17) | N3—C15—C16 | 124.0 (2) |
C19—N3—Co1 | 126.38 (14) | N3—C15—H15 | 118.0 |
C15—N3—Co1 | 116.35 (13) | C16—C15—H15 | 118.0 |
C19—N4—H4A | 120.0 | C15—C16—C17 | 118.2 (2) |
C19—N4—H4B | 120.0 | C15—C16—H16 | 120.9 |
H4A—N4—H4B | 120.0 | C17—C16—H16 | 120.9 |
C8—O1—Co1 | 92.57 (15) | C18—C17—C16 | 119.7 (2) |
C8—O2—Co1 | 88.66 (13) | C18—C17—H17 | 120.2 |
C1—O3—Co1 | 83.32 (13) | C16—C17—H17 | 120.2 |
C1—O4—Co1 | 99.33 (12) | C17—C18—C19 | 119.8 (2) |
O3—C1—O4 | 119.41 (19) | C17—C18—H18 | 120.1 |
O3—C1—C2 | 122.31 (19) | C19—C18—H18 | 120.1 |
O4—C1—C2 | 118.28 (18) | N4—C19—N3 | 118.84 (18) |
C3—C2—C7 | 120.1 (2) | N4—C19—C18 | 120.1 (2) |
C3—C2—C1 | 120.5 (2) | N3—C19—C18 | 121.1 (2) |
C7—C2—C1 | 119.4 (2) | N2—C20—N1 | 118.69 (18) |
C2—C3—C4 | 119.1 (3) | N2—C20—C21 | 120.54 (18) |
C2—C3—H3 | 120.4 | N1—C20—C21 | 120.77 (19) |
C4—C3—H3 | 120.4 | C22—C21—C20 | 119.9 (2) |
C5—C4—C3 | 119.8 (4) | C22—C21—H21 | 120.1 |
C5—C4—H4 | 120.1 | C20—C21—H21 | 120.1 |
C3—C4—H4 | 120.1 | C21—C22—C23 | 119.5 (2) |
C4—C5—C6 | 121.7 (3) | C21—C22—H22 | 120.3 |
C4—C5—H5 | 119.1 | C23—C22—H22 | 120.3 |
C6—C5—H5 | 119.2 | C24—C23—C22 | 118.0 (2) |
C5—C6—C7 | 119.7 (3) | C24—C23—H23 | 121.0 |
C5—C6—H6 | 120.1 | C22—C23—H23 | 121.0 |
C7—C6—H6 | 120.1 | C23—C24—N1 | 124.2 (2) |
C2—C7—C6 | 119.5 (3) | C23—C24—H24 | 117.9 |
C2—C7—H7 | 120.2 | N1—C24—H24 | 117.9 |
C6—C7—H7 | 120.2 |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1 | 0.86 | 2.03 | 2.866 (2) | 163 |
N2—H2B···O3i | 0.86 | 2.07 | 2.891 (2) | 158 |
N4—H4A···O4 | 0.86 | 1.99 | 2.810 (2) | 160 |
N4—H4B···O2ii | 0.86 | 2.14 | 2.980 (2) | 167 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1/2, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Co(C7H5O2)2(C5H6N2)2] |
Mr | 489.39 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 296 |
a, b, c (Å) | 9.0230 (9), 11.3787 (12), 22.451 (2) |
β (°) | 96.765 (1) |
V (Å3) | 2288.9 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.79 |
Crystal size (mm) | 0.36 × 0.28 × 0.22 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.770, 0.835 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19674, 5288, 4198 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.653 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.092, 1.05 |
No. of reflections | 5288 |
No. of parameters | 298 |
No. of restraints | 357 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.27 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).
Co1—O4 | 2.0364 (15) | Co1—O3 | 2.4016 (17) |
Co1—N3 | 2.1033 (16) | O1—C8 | 1.260 (3) |
Co1—N1 | 2.1050 (16) | O2—C8 | 1.249 (3) |
Co1—O1 | 2.1426 (18) | O3—C1 | 1.240 (2) |
Co1—O2 | 2.2340 (17) | O4—C1 | 1.274 (2) |
O4—Co1—N3 | 102.55 (6) | N1—Co1—O2 | 153.21 (7) |
O4—Co1—N1 | 100.77 (7) | O1—Co1—O2 | 59.31 (6) |
N3—Co1—N1 | 99.40 (6) | O4—Co1—O3 | 57.88 (5) |
N3—Co1—O1 | 95.25 (7) | N3—Co1—O3 | 160.43 (6) |
N1—Co1—O1 | 100.34 (6) | N1—Co1—O3 | 85.79 (6) |
O4—Co1—O2 | 93.20 (7) | O1—Co1—O3 | 102.40 (6) |
N3—Co1—O2 | 99.72 (7) | O2—Co1—O3 | 82.44 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O1 | 0.86 | 2.03 | 2.866 (2) | 163 |
N2—H2B···O3i | 0.86 | 2.07 | 2.891 (2) | 158 |
N4—H4A···O4 | 0.86 | 1.99 | 2.810 (2) | 160 |
N4—H4B···O2ii | 0.86 | 2.14 | 2.980 (2) | 167 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+1/2, y−1/2, −z+1/2. |
C—H···Cga | H···Cg | C···Cg | γb | C—H···Cg |
C13—H13···Cg(N1→C24)iii | 2.95 | 3.719 (3) | 6.07 | 141 |
Notes: Cga = centre of gravity of the six-membered ring. γb = angle defined by a line connecting centre of gravity of the six-membered ring with H atom and the normal to the six-membered ring. Symmetry code: (iii) -x, 1 - y, -z. |
π–π contacts | Cg···Cg | αa( | βb | Cg···Plane |
Cg(N3→C19)···Cg(C2→C7)iv | 3.7145 (16) | 6.30 | 16.02 | 3.535 |
Cg(C2→C7)···Cg(N3→C19)v | 3.7145 (16) | 6.30 | 17.87 | 3.570 |
Notes: αa = angle between planes of two aromatic rings. βb = angle between Cg···Cg line and normal to the plane of the first aromatic ring. Symmetry codes: (iv) -1 + x, y, z; (v) 1 + x, y, z. |
Acknowledgements
The authors thank the National Natural Science Foundation of China (Nos. 20361002 and 30460153), 973 Plan of China (2007CB516805).
References
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In recent years the study of crystal structures and properties of cobalt complexes based on carboxyl ligand, owing to their novel geometries and magnetic behaviours, have attracted chemists (Tan et al., 2003; Zheng et al., 2004; Wang et al., 2004; Shi et al., 2004) to explore their use. The structures of the mixed ligand complexes containing benzoate as the most simple aromatic carboxyl compoud with well antibacterial activity and 2-aminopyridine reported by (Kozlevčar et al., 2001; Zhu, Usman et al., 2003; Zhu, Shao et al., 2004). Herein, we report the synthesis and crystal structure of mixed ligands cobalt(II) complex.
The stucture of the title compound (I) is isostructural with the nickel (I) complex (Zhu, Shao et al., 2003) with the CoII atom hexa-coordinated by four O atoms of two benzoato anions, and two independent pyridine N atoms from two 2-aminopyridine molecules in distorted octahedral geometry (Fig. 1). The Co—N bond lengths of 2.1030 (14) Å and 2.1054 (14) Å, the Co—O distances ranging from 2.0363 (13) to 2.4016 (15) Å, are in the normal range. The close carboxylato distances O1—C8 and O2—C8, 1.260 (2) Å and 1.250 (2) Å, O3—C1 and O4—C1, 1.241 (2) Å and 1.274 (2) Å reveal the bidentate benzoato function. The molecules are held together by intramolecular and intermolecular hydrogen bonds, C—H···π and π–π stacking interactions generating three-dimensional supramolecular network.The amide N2 and N4 donate H atoms to the carboxyl O atoms O1and O4 in intramolecular N2—H2A···O1 and N4—H4A···O4 hydrogen bonds. The N2 and N4 also donate H atoms to O2 and O3 to form intermolecular N2—H2B···O2 and N4—H4B···O3 hydrogen bonds. Intermolecular C—H···π interation is pronounced in this crystal structure involving methyl group C13 of the benzoato and the pyridyl rings N1→C24, with the distance 2.95 Å between the methyl hydrogen and the centroid of the nearest aromatic ring. In addition, π–π stacking interactions are also observed; the distance between centroids of the pyridyl ring N3→C19 and the aromatic ring C2→C7 is 3.7145 (16) Å (Table 1, Fig. 2).