Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108029521/hj3085sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270108029521/hj3085Isup2.hkl |
CCDC reference: 707191
In the first step, salicylic acid sodium salt was prepared, and cobalt salicylate salt was synthesized from Na(SA) (SA = salicylic acid) salt. A solution of Co(SA)2.nH2O [In what solvent?] was left for 15 d at room temperature for crystallization. In the second step, a solution of nicotinamide (2 mmol) in distilled water (30 ml) was added dropwise to a stirred solution of Co(SA)2.nH2O (1 mmol) in hot distilled water (50 ml). The resulting solution was heated to 323 K in a temperature-controlled bath and stirred for 4 h, and then cooled to room temperature and left for 15–17 d for crystallization. The crystals which formed were filtered off, washed with cold water and acetone and dried in vacuo to give brown crystals in a yield of 84% (0.51 g). Analysis, found: C 50.38, H 4.12%; calculated for C26H28N4O10Co: C 50.86, H 4.57%.
H atoms bonded to C and N atoms were included in their expected positions and allowed to ride, with C—H and N—H distances restrained to 0.93 and 0.86 Å, respectively, and with Uiso(H) = 1.2Ueq(C,N). Water H atoms were located in a difference map and refined subject to a DFIX (SHELXL97; Sheldrick, 2008) restraint of O—H = 0.83 (2) Å. The H atoms of the hydroxy groups (O6 and O8) were allowed for with a fixed O—H distance of 0.82 Å [Uiso(H) = 1.5Ueq(O)].
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Co(C7H5O3)2(C6H6N2O)2(H2O)2] | F(000) = 634 |
Mr = 613.44 | Dx = 1.530 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P2yb | Cell parameters from 9880 reflections |
a = 7.0484 (4) Å | θ = 2.1–27.3° |
b = 19.4249 (7) Å | µ = 0.71 mm−1 |
c = 10.3331 (5) Å | T = 296 K |
β = 109.774 (4)° | Prism, brown |
V = 1331.33 (11) Å3 | 0.48 × 0.39 × 0.36 mm |
Z = 2 |
Stoe IPDSII diffractometer | 5360 independent reflections |
Radiation source: fine-focus sealed tube | 4725 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.5°, θmin = 2.1° |
ω scans | h = −8→8 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −24→24 |
Tmin = 0.549, Tmax = 0.811 | l = −12→11 |
9880 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.115 | w = 1/[σ2(Fo2) + (0.064P)2 + 0.1543P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.003 |
5360 reflections | Δρmax = 0.38 e Å−3 |
383 parameters | Δρmin = −0.67 e Å−3 |
7 restraints | Absolute structure: Flack (1983), with how many Friedel pairs? |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.012 (16) |
[Co(C7H5O3)2(C6H6N2O)2(H2O)2] | V = 1331.33 (11) Å3 |
Mr = 613.44 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.0484 (4) Å | µ = 0.71 mm−1 |
b = 19.4249 (7) Å | T = 296 K |
c = 10.3331 (5) Å | 0.48 × 0.39 × 0.36 mm |
β = 109.774 (4)° |
Stoe IPDSII diffractometer | 5360 independent reflections |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 4725 reflections with I > 2σ(I) |
Tmin = 0.549, Tmax = 0.811 | Rint = 0.061 |
9880 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.115 | Δρmax = 0.38 e Å−3 |
S = 1.05 | Δρmin = −0.67 e Å−3 |
5360 reflections | Absolute structure: Flack (1983), with how many Friedel pairs? |
383 parameters | Absolute structure parameter: 0.012 (16) |
7 restraints |
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 | ||
C1 | 0.4559 (7) | 0.1501 (2) | 0.4983 (4) | 0.0507 (9) | |
H1 | 0.5545 | 0.1413 | 0.4592 | 0.061* | |
C2 | 0.4618 (8) | 0.1144 (2) | 0.6136 (5) | 0.0651 (12) | |
H2 | 0.5614 | 0.0817 | 0.6514 | 0.078* | |
C3 | 0.3163 (7) | 0.1279 (2) | 0.6735 (4) | 0.0575 (10) | |
H3 | 0.3165 | 0.1040 | 0.7516 | 0.069* | |
C4 | 0.1726 (6) | 0.17694 (19) | 0.6160 (4) | 0.0454 (8) | |
C5 | 0.1756 (6) | 0.2094 (2) | 0.4974 (4) | 0.0464 (8) | |
H5 | 0.0756 | 0.2416 | 0.4562 | 0.056* | |
C6 | 0.0127 (7) | 0.1981 (2) | 0.6706 (4) | 0.0504 (9) | |
C7 | 0.1489 (6) | 0.3403 (2) | −0.0040 (4) | 0.0485 (8) | |
H7 | 0.0509 | 0.3517 | 0.0341 | 0.058* | |
C8 | 0.1330 (7) | 0.3674 (2) | −0.1314 (4) | 0.0553 (10) | |
H8 | 0.0261 | 0.3961 | −0.1779 | 0.066* | |
C9 | 0.2786 (7) | 0.3509 (2) | −0.1876 (4) | 0.0559 (10) | |
H9 | 0.2709 | 0.3682 | −0.2731 | 0.067* | |
C10 | 0.4367 (6) | 0.3083 (2) | −0.1158 (4) | 0.0451 (8) | |
C11 | 0.4400 (6) | 0.2837 (2) | 0.0116 (4) | 0.0462 (8) | |
H11 | 0.5461 | 0.2554 | 0.0612 | 0.055* | |
C12 | 0.6042 (6) | 0.2856 (2) | −0.1645 (4) | 0.0504 (9) | |
C13 | 0.3227 (6) | 0.10799 (19) | 0.1328 (4) | 0.0482 (9) | |
C14 | 0.4161 (6) | 0.06376 (19) | 0.0500 (4) | 0.0457 (8) | |
C15 | 0.5935 (7) | 0.0848 (2) | 0.0293 (4) | 0.0513 (9) | |
H15 | 0.6570 | 0.1251 | 0.0706 | 0.062* | |
C16 | 0.6751 (8) | 0.0470 (2) | −0.0509 (5) | 0.0605 (10) | |
H16 | 0.7913 | 0.0620 | −0.0658 | 0.073* | |
C17 | 0.5833 (8) | −0.0134 (2) | −0.1092 (5) | 0.0653 (12) | |
H17 | 0.6402 | −0.0395 | −0.1621 | 0.078* | |
C18 | 0.4109 (9) | −0.0358 (2) | −0.0912 (5) | 0.0682 (13) | |
H18 | 0.3490 | −0.0760 | −0.1337 | 0.082* | |
C19 | 0.3271 (7) | 0.0020 (2) | −0.0086 (5) | 0.0584 (10) | |
C20 | 0.0543 (6) | 0.36403 (18) | 0.3307 (4) | 0.0434 (8) | |
C21 | 0.0796 (6) | 0.42063 (19) | 0.4346 (4) | 0.0472 (8) | |
C22 | −0.0864 (7) | 0.4443 (2) | 0.4651 (5) | 0.0613 (11) | |
H22 | −0.2129 | 0.4256 | 0.4194 | 0.074* | |
C23 | −0.0667 (9) | 0.4950 (3) | 0.5620 (5) | 0.0748 (14) | |
H23 | −0.1787 | 0.5097 | 0.5826 | 0.090* | |
C24 | 0.1183 (11) | 0.5234 (3) | 0.6277 (6) | 0.0817 (16) | |
H24 | 0.1306 | 0.5583 | 0.6916 | 0.098* | |
C25 | 0.2865 (9) | 0.5013 (2) | 0.6009 (5) | 0.0704 (13) | |
H25 | 0.4119 | 0.5206 | 0.6474 | 0.085* | |
C26 | 0.2676 (7) | 0.4494 (2) | 0.5030 (4) | 0.0518 (9) | |
N1 | 0.3147 (5) | 0.19697 (16) | 0.4394 (3) | 0.0457 (7) | |
N2 | 0.2978 (5) | 0.29893 (16) | 0.0659 (3) | 0.0446 (7) | |
N3 | 0.0194 (6) | 0.1745 (2) | 0.7931 (4) | 0.0692 (11) | |
H3A | −0.0706 | 0.1871 | 0.8274 | 0.083* | |
H3B | 0.1138 | 0.1467 | 0.8379 | 0.083* | |
N4 | 0.6131 (6) | 0.3132 (2) | −0.2798 (4) | 0.0673 (10) | |
H4A | 0.7043 | 0.2999 | −0.3125 | 0.081* | |
H4B | 0.5278 | 0.3443 | −0.3219 | 0.081* | |
O1 | 0.6036 (4) | 0.28346 (16) | 0.3536 (3) | 0.0541 (7) | |
H1A | 0.696 (6) | 0.297 (3) | 0.327 (5) | 0.081* | |
H1B | 0.654 (6) | 0.255 (2) | 0.413 (4) | 0.081* | |
O2 | 0.0064 (5) | 0.21115 (18) | 0.1713 (3) | 0.0585 (7) | |
H2A | 0.023 (8) | 0.1710 (14) | 0.149 (6) | 0.088* | |
H2B | −0.107 (5) | 0.222 (2) | 0.121 (5) | 0.088* | |
O3 | 0.4119 (4) | 0.16219 (13) | 0.1839 (3) | 0.0490 (6) | |
O4 | 0.2184 (4) | 0.34197 (14) | 0.3174 (3) | 0.0490 (6) | |
O5 | −0.1124 (4) | 0.34022 (15) | 0.2679 (3) | 0.0541 (6) | |
O6 | 0.4403 (5) | 0.42729 (19) | 0.4848 (4) | 0.0740 (9) | |
H6 | 0.4140 | 0.3956 | 0.4291 | 0.111* | |
O7 | 0.1586 (6) | 0.08797 (17) | 0.1435 (4) | 0.0811 (11) | |
O8 | 0.1580 (6) | −0.02228 (19) | 0.0089 (5) | 0.0892 (12) | |
H8A | 0.1231 | 0.0040 | 0.0589 | 0.134* | |
O9 | 0.7238 (5) | 0.2410 (2) | −0.1014 (3) | 0.0636 (8) | |
O10 | −0.1223 (4) | 0.2379 (2) | 0.6058 (3) | 0.0665 (9) | |
Co1 | 0.30510 (7) | 0.24951 (2) | 0.25339 (4) | 0.04027 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.060 (2) | 0.051 (2) | 0.051 (2) | 0.0054 (17) | 0.0324 (19) | 0.0034 (17) |
C2 | 0.078 (3) | 0.065 (3) | 0.064 (3) | 0.023 (2) | 0.039 (2) | 0.018 (2) |
C3 | 0.067 (3) | 0.065 (3) | 0.050 (2) | 0.009 (2) | 0.031 (2) | 0.0169 (19) |
C4 | 0.054 (2) | 0.050 (2) | 0.0399 (17) | −0.0034 (16) | 0.0256 (17) | 0.0005 (15) |
C5 | 0.056 (2) | 0.050 (2) | 0.0399 (17) | 0.0080 (17) | 0.0253 (17) | 0.0086 (15) |
C6 | 0.056 (2) | 0.060 (2) | 0.0411 (19) | −0.0030 (18) | 0.0241 (18) | 0.0041 (17) |
C7 | 0.055 (2) | 0.051 (2) | 0.0478 (19) | 0.0017 (17) | 0.0276 (18) | 0.0010 (16) |
C8 | 0.063 (3) | 0.057 (2) | 0.049 (2) | 0.011 (2) | 0.023 (2) | 0.0087 (18) |
C9 | 0.069 (3) | 0.062 (2) | 0.0425 (19) | 0.003 (2) | 0.027 (2) | 0.0114 (18) |
C10 | 0.053 (2) | 0.050 (2) | 0.0391 (17) | −0.0033 (16) | 0.0253 (16) | 0.0000 (15) |
C11 | 0.056 (2) | 0.0516 (19) | 0.0408 (18) | −0.0016 (17) | 0.0299 (17) | 0.0014 (15) |
C12 | 0.063 (2) | 0.058 (2) | 0.0424 (19) | −0.003 (2) | 0.0338 (19) | −0.0010 (17) |
C13 | 0.058 (2) | 0.046 (2) | 0.052 (2) | 0.0017 (17) | 0.0331 (19) | 0.0050 (16) |
C14 | 0.055 (2) | 0.0384 (18) | 0.049 (2) | 0.0025 (16) | 0.0254 (18) | 0.0001 (15) |
C15 | 0.060 (2) | 0.047 (2) | 0.054 (2) | 0.0014 (17) | 0.0286 (19) | −0.0014 (16) |
C16 | 0.071 (3) | 0.061 (3) | 0.057 (2) | 0.007 (2) | 0.032 (2) | 0.002 (2) |
C17 | 0.090 (4) | 0.056 (3) | 0.054 (2) | 0.020 (2) | 0.029 (2) | −0.0035 (19) |
C18 | 0.087 (4) | 0.045 (2) | 0.066 (3) | 0.003 (2) | 0.017 (3) | −0.010 (2) |
C19 | 0.063 (3) | 0.045 (2) | 0.068 (3) | 0.0025 (19) | 0.024 (2) | −0.0014 (19) |
C20 | 0.052 (2) | 0.0411 (18) | 0.0450 (18) | 0.0007 (15) | 0.0264 (17) | 0.0051 (14) |
C21 | 0.060 (2) | 0.0447 (19) | 0.0442 (19) | 0.0038 (17) | 0.0273 (18) | 0.0024 (15) |
C22 | 0.067 (3) | 0.066 (3) | 0.058 (2) | 0.011 (2) | 0.030 (2) | −0.007 (2) |
C23 | 0.088 (4) | 0.081 (3) | 0.064 (3) | 0.020 (3) | 0.037 (3) | −0.013 (2) |
C24 | 0.129 (5) | 0.058 (3) | 0.061 (3) | 0.016 (3) | 0.037 (3) | −0.014 (2) |
C25 | 0.098 (4) | 0.055 (2) | 0.057 (2) | −0.009 (2) | 0.023 (3) | −0.011 (2) |
C26 | 0.063 (2) | 0.051 (2) | 0.049 (2) | −0.0010 (18) | 0.029 (2) | 0.0022 (17) |
N1 | 0.0539 (19) | 0.0493 (17) | 0.0427 (15) | 0.0043 (14) | 0.0280 (14) | 0.0061 (13) |
N2 | 0.0513 (18) | 0.0483 (17) | 0.0426 (15) | 0.0005 (14) | 0.0270 (14) | 0.0016 (13) |
N3 | 0.074 (3) | 0.098 (3) | 0.051 (2) | 0.017 (2) | 0.042 (2) | 0.0243 (19) |
N4 | 0.078 (3) | 0.088 (3) | 0.0505 (19) | 0.016 (2) | 0.0406 (19) | 0.0195 (18) |
O1 | 0.0514 (16) | 0.0644 (17) | 0.0521 (16) | −0.0047 (14) | 0.0248 (13) | 0.0077 (13) |
O2 | 0.0491 (16) | 0.0667 (18) | 0.0598 (17) | 0.0000 (14) | 0.0186 (13) | −0.0014 (15) |
O3 | 0.0603 (17) | 0.0454 (14) | 0.0523 (15) | −0.0019 (12) | 0.0332 (13) | −0.0053 (11) |
O4 | 0.0527 (15) | 0.0508 (14) | 0.0528 (15) | 0.0008 (12) | 0.0300 (12) | −0.0075 (12) |
O5 | 0.0536 (16) | 0.0557 (15) | 0.0600 (16) | −0.0026 (13) | 0.0283 (14) | −0.0040 (13) |
O6 | 0.0613 (19) | 0.086 (2) | 0.077 (2) | −0.0092 (17) | 0.0274 (18) | −0.0200 (18) |
O7 | 0.082 (2) | 0.0589 (18) | 0.129 (3) | −0.0129 (17) | 0.070 (2) | −0.015 (2) |
O8 | 0.083 (3) | 0.061 (2) | 0.139 (4) | −0.0217 (18) | 0.058 (3) | −0.022 (2) |
O9 | 0.0727 (18) | 0.079 (2) | 0.0546 (14) | 0.0161 (18) | 0.0420 (14) | 0.0117 (16) |
O10 | 0.0638 (17) | 0.099 (3) | 0.0460 (13) | 0.0195 (18) | 0.0305 (13) | 0.0125 (16) |
Co1 | 0.0497 (2) | 0.0426 (2) | 0.03727 (19) | 0.0004 (2) | 0.02618 (17) | 0.0007 (2) |
C1—N1 | 1.334 (5) | C17—C18 | 1.361 (7) |
C1—C2 | 1.367 (6) | C17—H17 | 0.9300 |
C1—H1 | 0.9300 | C18—C19 | 1.399 (6) |
C2—C3 | 1.390 (6) | C18—H18 | 0.9300 |
C2—H2 | 0.9300 | C19—O8 | 1.350 (5) |
C3—C4 | 1.370 (6) | C20—O5 | 1.225 (5) |
C3—H3 | 0.9300 | C20—O4 | 1.283 (4) |
C4—C5 | 1.385 (5) | C20—C21 | 1.504 (5) |
C4—C6 | 1.479 (5) | C21—C22 | 1.389 (6) |
C5—N1 | 1.333 (4) | C21—C26 | 1.391 (6) |
C5—H5 | 0.9300 | C22—C23 | 1.376 (6) |
C6—O10 | 1.233 (5) | C22—H22 | 0.9300 |
C6—N3 | 1.332 (5) | C23—C24 | 1.367 (9) |
C7—N2 | 1.326 (5) | C23—H23 | 0.9300 |
C7—C8 | 1.386 (5) | C24—C25 | 1.374 (8) |
C7—H7 | 0.9300 | C24—H24 | 0.9300 |
C8—C9 | 1.377 (6) | C25—C26 | 1.402 (6) |
C8—H8 | 0.9300 | C25—H25 | 0.9300 |
C9—C10 | 1.385 (6) | C26—O6 | 1.363 (5) |
C9—H9 | 0.9300 | N1—Co1 | 2.157 (3) |
C10—C11 | 1.393 (5) | N2—Co1 | 2.147 (3) |
C10—C12 | 1.499 (5) | N3—H3A | 0.8600 |
C11—N2 | 1.337 (4) | N3—H3B | 0.8600 |
C11—H11 | 0.9300 | N4—H4A | 0.8600 |
C12—O9 | 1.231 (5) | N4—H4B | 0.8600 |
C12—N4 | 1.327 (5) | O1—Co1 | 2.112 (3) |
C13—O3 | 1.248 (5) | O1—H1A | 0.83 (5) |
C13—O7 | 1.260 (5) | O1—H1B | 0.81 (4) |
C13—C14 | 1.512 (5) | O2—Co1 | 2.121 (3) |
C14—C19 | 1.393 (6) | O2—H2A | 0.834 (19) |
C14—C15 | 1.399 (5) | O2—H2B | 0.82 (4) |
C15—C16 | 1.371 (6) | O3—Co1 | 2.079 (3) |
C15—H15 | 0.9300 | O4—Co1 | 2.076 (3) |
C16—C17 | 1.376 (7) | O6—H6 | 0.8200 |
C16—H16 | 0.9300 | O8—H8A | 0.8200 |
N1—C1—C2 | 122.8 (4) | O5—C20—C21 | 121.0 (3) |
N1—C1—H1 | 118.6 | O4—C20—C21 | 115.2 (3) |
C2—C1—H1 | 118.6 | C22—C21—C26 | 118.8 (4) |
C1—C2—C3 | 118.9 (4) | C22—C21—C20 | 119.9 (4) |
C1—C2—H2 | 120.6 | C26—C21—C20 | 121.3 (3) |
C3—C2—H2 | 120.6 | C23—C22—C21 | 121.1 (5) |
C4—C3—C2 | 119.1 (4) | C23—C22—H22 | 119.5 |
C4—C3—H3 | 120.5 | C21—C22—H22 | 119.5 |
C2—C3—H3 | 120.5 | C24—C23—C22 | 119.6 (5) |
C3—C4—C5 | 118.0 (3) | C24—C23—H23 | 120.2 |
C3—C4—C6 | 125.0 (3) | C22—C23—H23 | 120.2 |
C5—C4—C6 | 116.9 (4) | C23—C24—C25 | 121.1 (4) |
N1—C5—C4 | 123.3 (4) | C23—C24—H24 | 119.4 |
N1—C5—H5 | 118.4 | C25—C24—H24 | 119.4 |
C4—C5—H5 | 118.4 | C24—C25—C26 | 119.4 (5) |
O10—C6—N3 | 120.3 (4) | C24—C25—H25 | 120.3 |
O10—C6—C4 | 121.0 (3) | C26—C25—H25 | 120.3 |
N3—C6—C4 | 118.7 (4) | O6—C26—C21 | 123.0 (4) |
N2—C7—C8 | 122.8 (3) | O6—C26—C25 | 117.1 (4) |
N2—C7—H7 | 118.6 | C21—C26—C25 | 119.9 (4) |
C8—C7—H7 | 118.6 | C5—N1—C1 | 117.9 (3) |
C9—C8—C7 | 118.7 (4) | C5—N1—Co1 | 120.6 (3) |
C9—C8—H8 | 120.7 | C1—N1—Co1 | 121.5 (2) |
C7—C8—H8 | 120.7 | C7—N2—C11 | 118.3 (3) |
C8—C9—C10 | 119.5 (3) | C7—N2—Co1 | 122.4 (2) |
C8—C9—H9 | 120.3 | C11—N2—Co1 | 119.2 (3) |
C10—C9—H9 | 120.3 | C6—N3—H3A | 120.0 |
C9—C10—C11 | 117.7 (3) | C6—N3—H3B | 120.0 |
C9—C10—C12 | 125.3 (3) | H3A—N3—H3B | 120.0 |
C11—C10—C12 | 117.0 (4) | C12—N4—H4A | 120.0 |
N2—C11—C10 | 123.0 (4) | C12—N4—H4B | 120.0 |
N2—C11—H11 | 118.5 | H4A—N4—H4B | 120.0 |
C10—C11—H11 | 118.5 | Co1—O1—H1A | 134 (4) |
O9—C12—N4 | 121.9 (3) | Co1—O1—H1B | 105 (3) |
O9—C12—C10 | 120.3 (3) | H1A—O1—H1B | 106 (3) |
N4—C12—C10 | 117.7 (4) | Co1—O2—H2A | 103 (4) |
O3—C13—O7 | 124.7 (3) | Co1—O2—H2B | 142 (4) |
O3—C13—C14 | 117.7 (3) | H2A—O2—H2B | 105 (3) |
O7—C13—C14 | 117.5 (4) | C13—O3—Co1 | 130.1 (3) |
C19—C14—C15 | 118.7 (4) | C20—O4—Co1 | 134.1 (3) |
C19—C14—C13 | 121.1 (4) | C26—O6—H6 | 109.5 |
C15—C14—C13 | 120.2 (3) | C19—O8—H8A | 109.5 |
C16—C15—C14 | 121.0 (4) | O4—Co1—O3 | 174.58 (11) |
C16—C15—H15 | 119.5 | O4—Co1—O1 | 85.72 (12) |
C14—C15—H15 | 119.5 | O3—Co1—O1 | 90.40 (12) |
C15—C16—C17 | 119.3 (5) | O4—Co1—O2 | 94.12 (12) |
C15—C16—H16 | 120.3 | O3—Co1—O2 | 90.11 (12) |
C17—C16—H16 | 120.3 | O1—Co1—O2 | 174.40 (12) |
C18—C17—C16 | 121.4 (4) | O4—Co1—N2 | 88.92 (11) |
C18—C17—H17 | 119.3 | O3—Co1—N2 | 87.38 (11) |
C16—C17—H17 | 119.3 | O1—Co1—N2 | 91.06 (11) |
C17—C18—C19 | 119.8 (4) | O2—Co1—N2 | 94.53 (12) |
C17—C18—H18 | 120.1 | O4—Co1—N1 | 92.82 (11) |
C19—C18—H18 | 120.1 | O3—Co1—N1 | 90.90 (11) |
O8—C19—C14 | 122.1 (4) | O1—Co1—N1 | 89.14 (12) |
O8—C19—C18 | 118.2 (4) | O2—Co1—N1 | 85.28 (13) |
C14—C19—C18 | 119.7 (4) | N2—Co1—N1 | 178.26 (12) |
O5—C20—O4 | 123.7 (3) | ||
N1—C1—C2—C3 | −0.8 (7) | C23—C24—C25—C26 | 1.0 (8) |
C1—C2—C3—C4 | −0.6 (7) | C22—C21—C26—O6 | 176.7 (4) |
C2—C3—C4—C5 | 2.0 (7) | C20—C21—C26—O6 | −2.3 (6) |
C2—C3—C4—C6 | −178.2 (4) | C22—C21—C26—C25 | 0.1 (6) |
C3—C4—C5—N1 | −2.2 (6) | C20—C21—C26—C25 | −178.9 (4) |
C6—C4—C5—N1 | 177.9 (4) | C24—C25—C26—O6 | −177.1 (5) |
C3—C4—C6—O10 | −173.1 (4) | C24—C25—C26—C21 | −0.4 (7) |
C5—C4—C6—O10 | 6.7 (6) | C4—C5—N1—C1 | 0.9 (6) |
C3—C4—C6—N3 | 8.4 (7) | C4—C5—N1—Co1 | 179.4 (3) |
C5—C4—C6—N3 | −171.7 (4) | C2—C1—N1—C5 | 0.6 (6) |
N2—C7—C8—C9 | −0.3 (7) | C2—C1—N1—Co1 | −177.8 (4) |
C7—C8—C9—C10 | −0.3 (7) | C8—C7—N2—C11 | 1.1 (6) |
C8—C9—C10—C11 | 0.2 (6) | C8—C7—N2—Co1 | −173.8 (3) |
C8—C9—C10—C12 | 179.5 (4) | C10—C11—N2—C7 | −1.2 (6) |
C9—C10—C11—N2 | 0.6 (6) | C10—C11—N2—Co1 | 173.9 (3) |
C12—C10—C11—N2 | −178.7 (4) | O7—C13—O3—Co1 | −18.6 (6) |
C9—C10—C12—O9 | −170.9 (4) | C14—C13—O3—Co1 | 160.2 (3) |
C11—C10—C12—O9 | 8.4 (6) | O5—C20—O4—Co1 | −23.3 (6) |
C9—C10—C12—N4 | 6.4 (6) | C21—C20—O4—Co1 | 154.5 (2) |
C11—C10—C12—N4 | −174.3 (4) | C20—O4—Co1—O1 | −161.6 (3) |
O3—C13—C14—C19 | 179.0 (4) | C20—O4—Co1—O2 | 12.8 (3) |
O7—C13—C14—C19 | −2.0 (6) | C20—O4—Co1—N2 | 107.2 (3) |
O3—C13—C14—C15 | −1.8 (6) | C20—O4—Co1—N1 | −72.7 (3) |
O7—C13—C14—C15 | 177.1 (4) | C13—O3—Co1—O1 | 166.1 (3) |
C19—C14—C15—C16 | 2.3 (6) | C13—O3—Co1—O2 | −8.3 (3) |
C13—C14—C15—C16 | −176.9 (4) | C13—O3—Co1—N2 | −102.9 (3) |
C14—C15—C16—C17 | −1.5 (7) | C13—O3—Co1—N1 | 76.9 (3) |
C15—C16—C17—C18 | 1.3 (7) | C7—N2—Co1—O4 | −44.2 (3) |
C16—C17—C18—C19 | −1.9 (7) | C11—N2—Co1—O4 | 140.9 (3) |
C15—C14—C19—O8 | 178.8 (4) | C7—N2—Co1—O3 | 139.7 (3) |
C13—C14—C19—O8 | −2.0 (7) | C11—N2—Co1—O3 | −35.1 (3) |
C15—C14—C19—C18 | −2.9 (6) | C7—N2—Co1—O1 | −129.9 (3) |
C13—C14—C19—C18 | 176.4 (4) | C11—N2—Co1—O1 | 55.2 (3) |
C17—C18—C19—O8 | −178.9 (5) | C7—N2—Co1—O2 | 49.8 (3) |
C17—C18—C19—C14 | 2.7 (7) | C11—N2—Co1—O2 | −125.0 (3) |
O5—C20—C21—C22 | 3.1 (6) | C5—N1—Co1—O4 | 39.2 (3) |
O4—C20—C21—C22 | −174.7 (4) | C1—N1—Co1—O4 | −142.3 (3) |
O5—C20—C21—C26 | −177.9 (4) | C5—N1—Co1—O3 | −144.7 (3) |
O4—C20—C21—C26 | 4.3 (5) | C1—N1—Co1—O3 | 33.7 (3) |
C26—C21—C22—C23 | −0.5 (7) | C5—N1—Co1—O1 | 124.9 (3) |
C20—C21—C22—C23 | 178.5 (4) | C1—N1—Co1—O1 | −56.7 (3) |
C21—C22—C23—C24 | 1.2 (8) | C5—N1—Co1—O2 | −54.7 (3) |
C22—C23—C24—C25 | −1.4 (8) | C1—N1—Co1—O2 | 123.8 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···O9i | 0.86 | 2.11 | 2.955 (4) | 167 |
N4—H4A···O10ii | 0.86 | 2.09 | 2.916 (5) | 162 |
N4—H4B···O6iii | 0.86 | 2.48 | 3.210 (6) | 144 |
O6—H6···O4 | 0.82 | 1.80 | 2.521 (4) | 146 |
O8—H8A···O7 | 0.82 | 1.83 | 2.553 (5) | 147 |
O1—H1A···O5iv | 0.83 (5) | 1.86 (5) | 2.684 (4) | 172 (5) |
O1—H1B···O10iv | 0.81 (4) | 2.11 (4) | 2.810 (4) | 145 (5) |
O2—H2A···O7 | 0.83 (2) | 1.88 (2) | 2.677 (5) | 158 (5) |
O2—H2B···O9v | 0.82 (4) | 2.23 (4) | 2.906 (4) | 140 (5) |
C18—H18···O5vi | 0.93 | 2.41 | 3.311 (6) | 165 |
C3—H3···Cg1vii | 0.93 | 2.68 | 3.520 (4) | 151 |
C9—H9···Cg2iii | 0.93 | 2.82 | 3.614 (4) | 144 |
Symmetry codes: (i) x−1, y, z+1; (ii) x+1, y, z−1; (iii) x, y, z−1; (iv) x+1, y, z; (v) x−1, y, z; (vi) −x, y−1/2, −z; (vii) x, y, z+1. |
Experimental details
Crystal data | |
Chemical formula | [Co(C7H5O3)2(C6H6N2O)2(H2O)2] |
Mr | 613.44 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 296 |
a, b, c (Å) | 7.0484 (4), 19.4249 (7), 10.3331 (5) |
β (°) | 109.774 (4) |
V (Å3) | 1331.33 (11) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.71 |
Crystal size (mm) | 0.48 × 0.39 × 0.36 |
Data collection | |
Diffractometer | Stoe IPDSII diffractometer |
Absorption correction | Integration (X-RED32; Stoe & Cie, 2002) |
Tmin, Tmax | 0.549, 0.811 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9880, 5360, 4725 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.628 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.115, 1.05 |
No. of reflections | 5360 |
No. of parameters | 383 |
No. of restraints | 7 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.38, −0.67 |
Absolute structure | Flack (1983), with how many Friedel pairs? |
Absolute structure parameter | 0.012 (16) |
Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
N1—Co1 | 2.157 (3) | O2—Co1 | 2.121 (3) |
N2—Co1 | 2.147 (3) | O3—Co1 | 2.079 (3) |
O1—Co1 | 2.112 (3) | O4—Co1 | 2.076 (3) |
C13—O3—Co1 | 130.1 (3) | O1—Co1—O2 | 174.40 (12) |
C20—O4—Co1 | 134.1 (3) | N2—Co1—N1 | 178.26 (12) |
O4—Co1—O3 | 174.58 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3A···O9i | 0.86 | 2.11 | 2.955 (4) | 166.7 |
N4—H4A···O10ii | 0.86 | 2.09 | 2.916 (5) | 161.6 |
N4—H4B···O6iii | 0.86 | 2.48 | 3.210 (6) | 143.7 |
O6—H6···O4 | 0.82 | 1.80 | 2.521 (4) | 145.8 |
O8—H8A···O7 | 0.82 | 1.83 | 2.553 (5) | 146.5 |
O1—H1A···O5iv | 0.83 (5) | 1.86 (5) | 2.684 (4) | 172 (5) |
O1—H1B···O10iv | 0.81 (4) | 2.11 (4) | 2.810 (4) | 145 (5) |
O2—H2A···O7 | 0.834 (19) | 1.88 (2) | 2.677 (5) | 158 (5) |
O2—H2B···O9v | 0.82 (4) | 2.23 (4) | 2.906 (4) | 140 (5) |
C18—H18···O5vi | 0.93 | 2.41 | 3.311 (6) | 164.5 |
C3—H3···Cg1vii | 0.93 | 2.68 | 3.520 (4) | 151 |
C9—H9···Cg2iii | 0.93 | 2.82 | 3.614 (4) | 144 |
Symmetry codes: (i) x−1, y, z+1; (ii) x+1, y, z−1; (iii) x, y, z−1; (iv) x+1, y, z; (v) x−1, y, z; (vi) −x, y−1/2, −z; (vii) x, y, z+1. |
Metal–organic supramolecular complexes with various fascinating topologies have been studied widely for their versatile chemical and physical properties and potential applications as functional materials (Janiak, 2003; Kitagawa et al., 2004; Yaghi et al., 2003). Self-assembly based on molecular building blocks has become an effective approach to construct these functional materials. In the development of supramolecular chemistry, hydrogen-bonding and π–π interactions, acting as the two main driving forces, play an important role in the self-assembly of multi-dimensional metal–organic supramolecular frameworks or networks (Graham & Pike, 2000; Mitzi et al., 1995). Some interesting coordination polymers assembled with 4,4'-bipyridine (bipy) have been reported, showing various structural motifs, including two-dimensional layers (Carlucci et al., 1997; Tong et al., 1998) and three-dimensional nets (Lu et al., 1998; Hagrman et al., 1998; Kondo et al., 1999; Greve et al., 2003; Zhang et al., 1999; Şahin et al., 2007). We report here the structure of the title complex, (I), in which hydrogen-bond interactions lead to a three-dimensional supramolecular network.
The molecular structure of (I) and the atom-labelling scheme are shown in Fig. 1. The CoII ion is coordinated by two O atoms from two identical carboxylate groups, two O atoms from two water molecules and two pyridyl N atoms. The geometry around the CoII ion (Table 1) is that of a slightly distorted octahedron. The distortion arises from the N1—Co1—N2 axis, which is not perfectly perpendicular to the coordination plane (O1/O2/O3/O4/Co1). The significant difference between the Co—O bond distances in the equatorial plane and the Co—N bond distances in the axial positions has also been observed in another cobalt complex (Şahin et al., 2007).
Molecules are linked by intermolecular hydrogen bonding, and we employ graph-set notation (Bernstein et al., 1995) to describe the patterns of hydrogen bonding. Molecules of (I) are linked into sheets by a combination of C—H···O, O—H···O and N—H···O hydrogen bonds (Table 2). Within the selected asymmetric unit, intramolecular O—H···O hydrogen bonds define S21(10) and S(6) motifs (Fig. 1). Water atom O1 in the molecule at (x, y, z) acts as hydrogen-bond donor, via atoms H1A and H1B, respectively, to atom O5 at (x + 1, y, z) and atom O10 at (x + 1, y, z), so forming a C(6)C(8)[R22(12)] chain of rings running parallel to the [100] direction. Similarly, water atom O2 in the reference molecule at (x, y, z) acts as hydrogen-bond donor, via atom H2B, to atom O9 in the molecule at (x - 1, y, z), so forming a C(8) chain running parallel to the [100] direction. The combination of the C(6) and C(8) chains generates a chain of edge-fused R22(14) rings running parallel to the [100] direction (Fig. 2). Amino atom N4 in the reference molecule at (x, y, z) acts as hydrogen-bond donor, via atom H4A, to atom O10 in the molecule at (x + 1, y, z - 1), so forming a C(12) chain running parallel to the [101] direction (Fig. 3). Amino atom N3 in the molecule at (x, y, z) acts as hydrogen-bond donor, via atom H3A, to atom O9 in the molecule at (x - 1, y, z + 1), so forming a C(12) chain running parallel to the [101] direction. The combination of C(12) chains generates a chain of edge-fused R22(8) rings running parallel to the [101] direction (Fig. 3).
Fig. 4 shows the way in which amino atom N4, hydroxyl atom O6, atom C18 and carboxylate atom O5 enter into intermolecular hydrogen-bonding interactions. As a result, amino atom N4 in the reference molecule at (x, y, z) acts as hydrogen-bond donor, via atom H4B, to atom O6 in the molecule at (x, y, z - 1), so forming a C(12) chain running parallel to the [001] direction. At the same time, atom C18 in the reference molecule at (x, y, z) acts as hydrogen-bond donor, via atom H18, to atom O5 in the molecule at (-x, y - 1/2, -z), so forming a C(10) chain running parallel to the [010] direction. The combination of the C(10) and C(12) chains generates a chain of edge-fused R44(40) rings parallel to the bc plane (Fig. 4).
Compound (I) also contains two intermolecular C—H···π interactions. In the first, atom C9 in the molecule at (x, y, z) acts as hydrogen-bond donor to the C21–C26 benzene ring in the molecule at (x, y, z - 1), so forming a chain running parallel to the [001] direction. In the second, atom C3 in the molecule at (x, y, z) acts as hydrogen-bond donor to the C14–C19 benzene ring in the molecule at (x, y, z + 1), so forming a chain running parallel to the [001] direction. Details of these interactions are given in Table 2. The combination of C—H···π interactions defines an R22(20) ring pattern (Fig. 5).
The combination of the chains along [100], [101], [010] and [001] suffices to generate a three-dimensional structure of considerable complexity.