Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807057509/bg2125sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807057509/bg2125Isup2.hkl |
CCDC reference: 672655
To a solution of 2,9-dimethyl-1,10-phenanthroline (C14H12N2.0.5H2O, 0.1096 g, 0.5 mmol), 3-hydroxy-benzoate (0.1382 g, 1 mmol) and sodium hydroxide (0.03820 g, 1 mmol) in ethanol/water (v:v=1:1, 20 ml) was added a solution of Co(NO3)2.6H2O (0.1458 g, 0.5 mmol) in distilled water (10 ml). The resulting solution was stirred for 5 h at 323 K and then a pink precipitate was filtered. Brown single crystals of (I) were obtained by slow evaporation of the filtrate over two weeks.
The OH group of the benzoate anion is disordered over two symmetry-related positions with equal occupancy. The carbon-bound H atoms were placed in calculated positions and were included in the refinement in the riding model approximation, with d(C—H) = 0.93 Å, Uiso=1.2Ueq(C) for aromatic and 0.96 Å, Uiso = 1.5Ueq(C) for CH3 atoms. The hydroxyl H atoms were placed in calculated positions (O—H =0.82 Å) and refined with free torsion angles to fit the electron density; water H atoms were found in a difference Fourier and allowed to ride. For all O—H's, Uiso(H) = 1.5 Ueq(O).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
[Co(C7H5O3)(C14H12N2)(H2O)2]NO3 | F(000) = 1032 |
Mr = 501.33 | Dx = 1.518 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 5273 reflections |
a = 10.9405 (14) Å | θ = 2.3–28.0° |
b = 28.750 (4) Å | µ = 0.84 mm−1 |
c = 7.967 (1) Å | T = 298 K |
β = 119.142 (1)° | Block, brown |
V = 2188.7 (5) Å3 | 0.49 × 0.40 × 0.37 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 2040 independent reflections |
Radiation source: fine-focus sealed tube | 1878 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ϕ and ω scans | θmax = 25.5°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = −13→13 |
Tmin = 0.67, Tmax = 0.73 | k = −34→34 |
8035 measured reflections | l = −9→9 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0659P)2 + 2.1796P] where P = (Fo2 + 2Fc2)/3 |
2040 reflections | (Δ/σ)max < 0.001 |
159 parameters | Δρmax = 0.50 e Å−3 |
33 restraints | Δρmin = −0.39 e Å−3 |
[Co(C7H5O3)(C14H12N2)(H2O)2]NO3 | V = 2188.7 (5) Å3 |
Mr = 501.33 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 10.9405 (14) Å | µ = 0.84 mm−1 |
b = 28.750 (4) Å | T = 298 K |
c = 7.967 (1) Å | 0.49 × 0.40 × 0.37 mm |
β = 119.142 (1)° |
Bruker SMART CCD area-detector diffractometer | 2040 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1997) | 1878 reflections with I > 2σ(I) |
Tmin = 0.67, Tmax = 0.73 | Rint = 0.023 |
8035 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 33 restraints |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.50 e Å−3 |
2040 reflections | Δρmin = −0.39 e Å−3 |
159 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 | Occ. (<1) | |
Co1 | 0.5000 | 0.294272 (13) | 0.7500 | 0.03386 (17) | |
O1 | 0.39631 (16) | 0.22788 (5) | 0.7385 (2) | 0.0405 (4) | |
O2 | 0.3140 (5) | 0.05502 (14) | 0.7959 (10) | 0.0861 (17) | 0.50 |
H2 | 0.2760 | 0.0705 | 0.8442 | 0.129* | 0.50 |
O3 | 0.38785 (18) | 0.29149 (5) | 0.4529 (2) | 0.0451 (4) | |
H1W | 0.3041 | 0.2893 | 0.4180 | 0.068* | |
H2W | 0.4025 | 0.3083 | 0.3795 | 0.068* | |
O4 | 0.4231 (3) | 0.39849 (12) | 0.2935 (4) | 0.1120 (11) | |
O5 | 0.5000 | 0.33543 (12) | 0.2500 | 0.0923 (12) | |
N1 | 0.6166 (2) | 0.35148 (7) | 0.7293 (3) | 0.0416 (4) | |
N2 | 0.5000 | 0.37833 (10) | 0.2500 | 0.0461 (6) | |
C1 | 0.7857 (3) | 0.30542 (11) | 0.6842 (6) | 0.0720 (9) | |
H1A | 0.8586 | 0.2953 | 0.8074 | 0.108* | |
H1B | 0.8228 | 0.3089 | 0.5978 | 0.108* | |
H1C | 0.7119 | 0.2828 | 0.6337 | 0.108* | |
C2 | 0.7295 (3) | 0.35093 (10) | 0.7058 (4) | 0.0528 (6) | |
C3 | 0.7935 (3) | 0.39298 (12) | 0.6971 (5) | 0.0717 (9) | |
H3A | 0.8724 | 0.3920 | 0.6817 | 0.086* | |
C4 | 0.7413 (4) | 0.43432 (12) | 0.7110 (5) | 0.0786 (10) | |
H4 | 0.7846 | 0.4617 | 0.7062 | 0.094* | |
C5 | 0.6219 (4) | 0.43603 (10) | 0.7327 (4) | 0.0647 (8) | |
C6 | 0.5623 (3) | 0.39312 (8) | 0.7410 (3) | 0.0465 (6) | |
C7 | 0.5582 (5) | 0.47851 (10) | 0.7418 (6) | 0.0882 (12) | |
H7 | 0.5979 | 0.5067 | 0.7362 | 0.106* | |
C8 | 0.5000 | 0.20572 (10) | 0.7500 | 0.0358 (7) | |
C9 | 0.5000 | 0.15334 (11) | 0.7500 | 0.0415 (7) | |
C10 | 0.3986 (3) | 0.12923 (9) | 0.7701 (4) | 0.0521 (6) | |
H10 | 0.3304 | 0.1454 | 0.7840 | 0.063* | |
C11 | 0.3985 (3) | 0.08081 (10) | 0.7696 (5) | 0.0672 (8) | |
C12 | 0.5000 | 0.05691 (14) | 0.7500 | 0.0799 (15) | |
H12 | 0.5000 | 0.0246 | 0.7500 | 0.096* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0271 (2) | 0.0265 (2) | 0.0455 (3) | 0.000 | 0.01572 (19) | 0.000 |
O1 | 0.0319 (8) | 0.0312 (8) | 0.0581 (10) | 0.0011 (6) | 0.0218 (7) | 0.0000 (7) |
O2 | 0.080 (3) | 0.036 (2) | 0.176 (6) | −0.006 (2) | 0.088 (4) | 0.004 (3) |
O3 | 0.0371 (9) | 0.0482 (10) | 0.0452 (9) | −0.0074 (7) | 0.0162 (7) | 0.0025 (7) |
O4 | 0.105 (2) | 0.146 (3) | 0.0908 (18) | 0.065 (2) | 0.0517 (16) | 0.0036 (17) |
O5 | 0.167 (4) | 0.0530 (17) | 0.086 (2) | 0.000 | 0.084 (2) | 0.000 |
N1 | 0.0362 (10) | 0.0363 (10) | 0.0437 (10) | −0.0056 (8) | 0.0127 (8) | 0.0036 (8) |
N2 | 0.0463 (15) | 0.0445 (15) | 0.0519 (16) | 0.000 | 0.0273 (13) | 0.000 |
C1 | 0.0526 (17) | 0.0655 (18) | 0.114 (3) | 0.0096 (14) | 0.0531 (19) | 0.0277 (18) |
C2 | 0.0387 (13) | 0.0547 (15) | 0.0579 (15) | −0.0092 (11) | 0.0180 (11) | 0.0106 (12) |
C3 | 0.0554 (17) | 0.073 (2) | 0.083 (2) | −0.0241 (15) | 0.0304 (16) | 0.0104 (16) |
C4 | 0.087 (2) | 0.0552 (19) | 0.088 (2) | −0.0352 (17) | 0.039 (2) | −0.0023 (16) |
C5 | 0.088 (2) | 0.0371 (14) | 0.0630 (17) | −0.0181 (14) | 0.0315 (16) | −0.0035 (12) |
C6 | 0.0547 (14) | 0.0333 (12) | 0.0405 (12) | −0.0067 (10) | 0.0146 (11) | 0.0000 (9) |
C7 | 0.137 (4) | 0.0310 (14) | 0.101 (3) | −0.0160 (16) | 0.061 (3) | −0.0025 (15) |
C8 | 0.0318 (16) | 0.0290 (15) | 0.0423 (16) | 0.000 | 0.0147 (13) | 0.000 |
C9 | 0.0371 (16) | 0.0296 (16) | 0.0519 (18) | 0.000 | 0.0171 (14) | 0.000 |
C10 | 0.0468 (14) | 0.0344 (12) | 0.0782 (18) | 0.0014 (10) | 0.0328 (13) | 0.0044 (11) |
C11 | 0.0629 (18) | 0.0359 (14) | 0.110 (2) | −0.0060 (12) | 0.0478 (18) | 0.0052 (14) |
C12 | 0.083 (3) | 0.0279 (18) | 0.140 (5) | 0.000 | 0.063 (3) | 0.000 |
Co1—O3 | 2.0706 (17) | C1—H1C | 0.9600 |
Co1—O3i | 2.0706 (17) | C2—C3 | 1.415 (4) |
Co1—N1i | 2.1361 (19) | C3—C4 | 1.346 (5) |
Co1—N1 | 2.1363 (19) | C3—H3A | 0.9300 |
Co1—O1 | 2.1993 (16) | C4—C5 | 1.400 (5) |
Co1—O1i | 2.1993 (16) | C4—H4 | 0.9300 |
O1—C8 | 1.265 (2) | C5—C6 | 1.412 (4) |
O2—C11 | 1.280 (5) | C5—C7 | 1.425 (5) |
O2—H2 | 0.8200 | C6—C6i | 1.439 (6) |
O3—H1W | 0.8200 | C7—C7i | 1.341 (9) |
O3—H2W | 0.8313 | C7—H7 | 0.9300 |
O4—N2 | 1.204 (3) | C8—C9 | 1.506 (4) |
O5—N2 | 1.233 (4) | C9—C10i | 1.382 (3) |
N1—C2 | 1.337 (3) | C9—C10 | 1.382 (3) |
N1—C6 | 1.360 (3) | C10—C11 | 1.392 (4) |
C1—C2 | 1.490 (4) | C10—H10 | 0.9300 |
C1—H1A | 0.9600 | C11—C12 | 1.378 (4) |
C1—H1B | 0.9600 | C12—H12 | 0.9300 |
O3—Co1—O3i | 175.57 (9) | N1—C2—C1 | 119.2 (2) |
O3—Co1—N1i | 94.26 (7) | C3—C2—C1 | 120.2 (3) |
O3i—Co1—N1i | 89.15 (7) | C4—C3—C2 | 120.7 (3) |
O3—Co1—N1 | 89.15 (7) | C4—C3—H3A | 119.6 |
O3i—Co1—N1 | 94.27 (7) | C2—C3—H3A | 119.6 |
N1i—Co1—N1 | 79.32 (11) | C3—C4—C5 | 120.0 (3) |
O3—Co1—O1 | 84.97 (6) | C3—C4—H4 | 120.0 |
O3i—Co1—O1 | 91.18 (6) | C5—C4—H4 | 120.0 |
N1i—Co1—O1 | 110.87 (7) | C4—C5—C6 | 117.1 (3) |
N1—Co1—O1 | 168.55 (7) | C4—C5—C7 | 123.1 (3) |
O3—Co1—O1i | 91.18 (6) | C6—C5—C7 | 119.9 (3) |
O3i—Co1—O1i | 84.96 (6) | N1—C6—C5 | 122.6 (3) |
N1i—Co1—O1i | 168.55 (7) | N1—C6—C6i | 118.26 (14) |
N1—Co1—O1i | 110.87 (7) | C5—C6—C6i | 119.10 (19) |
O1—Co1—O1i | 59.57 (8) | C7i—C7—C5 | 121.0 (2) |
C8—O1—Co1 | 90.46 (14) | C7i—C7—H7 | 119.5 |
C11—O2—H2 | 109.5 | C5—C7—H7 | 119.5 |
Co1—O3—H1W | 109.4 | O1i—C8—O1 | 119.5 (3) |
Co1—O3—H2W | 124.9 | O1i—C8—C9 | 120.25 (13) |
H1W—O3—H2W | 111.9 | O1—C8—C9 | 120.25 (13) |
C2—N1—C6 | 119.0 (2) | C10i—C9—C10 | 119.8 (3) |
C2—N1—Co1 | 128.97 (18) | C10i—C9—C8 | 120.10 (16) |
C6—N1—Co1 | 112.06 (16) | C10—C9—C8 | 120.10 (16) |
O4—N2—O4ii | 122.4 (5) | C9—C10—C11 | 120.1 (3) |
O4—N2—O5 | 118.8 (2) | C9—C10—H10 | 120.0 |
O4ii—N2—O5 | 118.8 (2) | C11—C10—H10 | 120.0 |
C2—C1—H1A | 109.5 | O2—C11—C12 | 114.6 (3) |
C2—C1—H1B | 109.5 | O2—C11—C10 | 125.4 (3) |
H1A—C1—H1B | 109.5 | C12—C11—C10 | 119.9 (3) |
C2—C1—H1C | 109.5 | C11i—C12—C11 | 120.2 (4) |
H1A—C1—H1C | 109.5 | C11i—C12—H12 | 119.9 |
H1B—C1—H1C | 109.5 | C11—C12—H12 | 119.9 |
N1—C2—C3 | 120.6 (3) | ||
O3—Co1—O1—C8 | 94.35 (9) | C3—C4—C5—C7 | −177.8 (3) |
O3i—Co1—O1—C8 | −83.46 (9) | C2—N1—C6—C5 | −1.1 (4) |
N1i—Co1—O1—C8 | −173.00 (8) | Co1—N1—C6—C5 | 179.4 (2) |
N1—Co1—O1—C8 | 35.0 (4) | C2—N1—C6—C6i | 177.7 (3) |
O1i—Co1—O1—C8 | 0.0 | Co1—N1—C6—C6i | −1.8 (3) |
O3—Co1—N1—C2 | −84.2 (2) | C4—C5—C6—N1 | 0.2 (4) |
O3i—Co1—N1—C2 | 92.9 (2) | C7—C5—C6—N1 | 178.7 (3) |
N1i—Co1—N1—C2 | −178.7 (3) | C4—C5—C6—C6i | −178.6 (3) |
O1—Co1—N1—C2 | −25.3 (4) | C7—C5—C6—C6i | −0.1 (5) |
O1i—Co1—N1—C2 | 6.7 (2) | C4—C5—C7—C7i | 178.4 (5) |
O3—Co1—N1—C6 | 95.12 (16) | C6—C5—C7—C7i | 0.0 (7) |
O3i—Co1—N1—C6 | −87.70 (16) | Co1—O1—C8—O1i | 0.0 |
N1i—Co1—N1—C6 | 0.62 (12) | Co1—O1—C8—C9 | 180.0 |
O1—Co1—N1—C6 | 154.1 (3) | O1i—C8—C9—C10i | −10.93 (16) |
O1i—Co1—N1—C6 | −173.93 (15) | O1—C8—C9—C10i | 169.07 (16) |
C6—N1—C2—C3 | 1.3 (4) | O1i—C8—C9—C10 | 169.07 (16) |
Co1—N1—C2—C3 | −179.4 (2) | O1—C8—C9—C10 | −10.93 (16) |
C6—N1—C2—C1 | −177.4 (3) | C10i—C9—C10—C11 | −0.2 (2) |
Co1—N1—C2—C1 | 2.0 (4) | C8—C9—C10—C11 | 179.8 (2) |
N1—C2—C3—C4 | −0.5 (5) | C9—C10—C11—O2 | 176.6 (5) |
C1—C2—C3—C4 | 178.1 (3) | C9—C10—C11—C12 | 0.3 (5) |
C2—C3—C4—C5 | −0.5 (5) | O2—C11—C12—C11i | −176.8 (5) |
C3—C4—C5—C6 | 0.7 (5) | C10—C11—C12—C11i | −0.2 (2) |
Symmetry codes: (i) −x+1, y, −z+3/2; (ii) −x+1, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H1W···O1iii | 0.82 | 1.99 | 2.772 (3) | 160 |
O2—H2···O4iii | 0.82 | 2.10 | 2.688 (7) | 128 |
O3—H2W···O5 | 0.83 | 1.97 | 2.765 (2) | 159 |
C1—H1C···O1i | 0.96 | 2.47 | 3.242 (4) | 137 |
C7—H7···O2iv | 0.93 | 2.58 | 3.418 (8) | 150 |
Symmetry codes: (i) −x+1, y, −z+3/2; (iii) −x+1/2, −y+1/2, −z+1; (iv) x+1/2, y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | [Co(C7H5O3)(C14H12N2)(H2O)2]NO3 |
Mr | 501.33 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 10.9405 (14), 28.750 (4), 7.967 (1) |
β (°) | 119.142 (1) |
V (Å3) | 2188.7 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.84 |
Crystal size (mm) | 0.49 × 0.40 × 0.37 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
Tmin, Tmax | 0.67, 0.73 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8035, 2040, 1878 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.102, 1.02 |
No. of reflections | 2040 |
No. of parameters | 159 |
No. of restraints | 33 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.50, −0.39 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H1W···O1i | 0.8200 | 1.9900 | 2.772 (3) | 160.00 |
O2—H2···O4i | 0.8200 | 2.1000 | 2.688 (7) | 128.00 |
O3—H2W···O5 | 0.8300 | 1.9700 | 2.765 (2) | 159.00 |
C1—H1C···O1ii | 0.9600 | 2.4700 | 3.242 (4) | 137.00 |
C7—H7···O2iii | 0.9300 | 2.5800 | 3.418 (8) | 150.00 |
Symmetry codes: (i) −x+1/2, −y+1/2, −z+1; (ii) −x+1, y, −z+3/2; (iii) x+1/2, y+1/2, z. |
We have recently reported the structure of diaqua(3-hydroxy-benzoato-κ2O,O')(2,9-dimethyl-1,10-phenanthroline-κ2N,N')nickel(II) nitrate (Xuan et al. 2007). We report herein the isomorphous cobalt analogue,Co(C7H5O3)(C14H12N2)(H2O)2].NO3, (I).
The asymmetric unit of the title compound is composed of one half of the CoII complex cation and one half of the non-coordinated nitrate anion: a twofold rotation axis passes through the central CoII atom, N atom and one O atom of the nitrate anion. The metal is in a distorted octahedral environment, being six-coordinated by two N atoms from the dmphen ligand and two O atoms from the carboxyl group of the 3-hydroxy-benzoate anion, defining the equatorial plane, and two O atoms from two water molecules in the apical position (Table 1). The OH group on the 3-hydroxybenzoate ligand is disordered over two symmetry-related positions with equal site occupancy.
The crystal structure is stabilized by a network of O—H···O and C—H···O hydrogen bonds (Table 2 and Figure 2). The former interactions link molecules into two-dimensional networks parallel to (010) while the latter ones join them along the [010] direction generating a three-dimensional framework.