metal-organic compounds
(2,9-Dimethyl-1,10-phenanthroline-κ2N,N′)bis(2-hydroxybenzoato)-κO;κ2O,O′-cobalt(II)
aCollege of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007, People's Republic of China
*Correspondence e-mail: pz_zhao@hotmail.com
In the title compound, [Co(C7H5O3)2(C14H12N2)], the CoII 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 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
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).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2004); cell 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
10.1107/S1600536808012002/lx2038sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808012002/lx2038Isup2.hkl
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.
Methyl H and hydroxy H atoms were placed in calculated positions,with C—H=0.96 and O—H=0.82 Å, and refined with free torsion angles to fit the electron density; Uiso(H) = 1.5Ueq(carrier). Other H atoms were placed in calculated positions, with C—H=0.93 Å, and refined in the riding-model approximation with Uiso(H) = 1.2Ueq(C).
Data collection: APEX2 (Bruker, 2004); cell
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).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] |
[Co(C7H5O3)2(C14H12N2)] | F(000) = 1116 |
Mr = 541.41 | Dx = 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 |
Bruker APEX2 CCD area-detector diffractometer | 5998 independent reflections |
Radiation source: fine-focus sealed tube | 4476 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
Detector resolution: 10.0 pixels mm-1 | θmax = 28.4°, θmin = 2.4° |
ϕ and ω scans | h = −15→15 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | k = −21→22 |
Tmin = 0.779, Tmax = 0.858 | l = −16→17 |
20557 measured reflections |
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(Fo2) + (0.0698P)2 + 0.571P] where P = (Fo2 + 2Fc2)/3 |
5998 reflections | (Δ/σ)max < 0.001 |
338 parameters | Δρmax = 0.86 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
[Co(C7H5O3)2(C14H12N2)] | V = 2441.1 (5) Å3 |
Mr = 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)° |
Bruker APEX2 CCD area-detector diffractometer | 5998 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 4476 reflections with I > 2σ(I) |
Tmin = 0.779, Tmax = 0.858 | Rint = 0.023 |
20557 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 0 restraints |
wR(F2) = 0.127 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.86 e Å−3 |
5998 reflections | Δρmin = −0.39 e Å−3 |
338 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 | ||
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* |
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) |
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) |
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)] |
Mr | 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) |
Tmin, Tmax | 0.779, 0.858 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20557, 5998, 4476 |
Rint | 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 |
Δρmax, Δρmin (e Å−3) | 0.86, −0.39 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
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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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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 C3v-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).