Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807033338/bi2200sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807033338/bi2200Isup2.hkl |
CCDC reference: 1277974
All chemicals were used as purchased from Shanghai Sci & Tec Co. Ltd. A solution of cobalt(II) acetate (0.5 mmol) and N-(2-hydroxy-benzoyl)-N-(2-hydroxy-3-methoxo-benzoylidene)hydrazine (0.5 mmol) in DMF (10 ml) was refluxed for 2 h then filtered. Red crystals were obtained after a few days standing at room temperature with a yield of 25%. Elemental analysis calculated: C 51.89, H 4.56, N 10.09%; found: C 51.82, H 4.60, N 10.01%.
H atoms were placed geometrically and refined as riding with C—H = 0.93, N—H = 0.86 and O—H = 0.82 Å, and with Uiso(H) = 1.2Ueq(C/N) or 1.5Ueq(O).
Owing to their biological activity and chemical/industrial versatility, metal-hydrazine complexes have received considerable attention. For instance, Schiff base hydrazine and its analogues have been well studied in order to understand better the mechanism of enzymes containing vitamin B6 (Maghler et al., 1982; Rath et al., 1997; Rath et al., 1998)
Herein, we report the structure of the title compound, [Co4(C15H12N2O4)4].4C3H7NO. As shown in Fig. 1, the asymmetric unit comprises one N-(2-hydroxy-benzoyl)-N-(2-hydroxy-3-methoxo-benzoylidene)hydrazine anion and one CoII cation. These are linked into tetrameric complexes about positions of 4 point symmetry. Each CoII cation adopts a distorted 6-coordinate geometry through one N and three O atoms lying in the equatorial plane, with the Co1—O3 bond lying to one side of this plane and the longer Co1—O4 bond lying on the opposite side.
One motivation to study the Schiff base hydrazine and its analogues is to understand better the mechanism of enzymes containing vitamin B6. For related literature, see: Maghler et al. (1982); Rath et al. (1997, 1998).
Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2001); software used to prepare material for publication: SHELXTL.
[Co4(C15H12N2O4)4]·4C3H7NO | Dx = 1.460 Mg m−3 |
Mr = 1665.17 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/a | Cell parameters from 3308 reflections |
Hall symbol: -I 4ad | θ = 1.7–25.0° |
a = 23.996 (2) Å | µ = 0.94 mm−1 |
c = 13.1605 (10) Å | T = 298 K |
V = 7578.0 (11) Å3 | Cube, red |
Z = 4 | 0.10 × 0.10 × 0.10 mm |
F(000) = 3440 |
Bruker APEXII CCD diffractometer | 2180 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.060 |
Graphite monochromator | θmax = 25.0°, θmin = 1.7° |
φ and ω scans | h = −28→25 |
18342 measured reflections | k = −26→28 |
3308 independent reflections | l = −15→15 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0641P)2 + 15.4281P] where P = (Fo2 + 2Fc2)/3 |
3308 reflections | (Δ/σ)max < 0.001 |
249 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
[Co4(C15H12N2O4)4]·4C3H7NO | Z = 4 |
Mr = 1665.17 | Mo Kα radiation |
Tetragonal, I41/a | µ = 0.94 mm−1 |
a = 23.996 (2) Å | T = 298 K |
c = 13.1605 (10) Å | 0.10 × 0.10 × 0.10 mm |
V = 7578.0 (11) Å3 |
Bruker APEXII CCD diffractometer | 2180 reflections with I > 2σ(I) |
18342 measured reflections | Rint = 0.060 |
3308 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.136 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0641P)2 + 15.4281P] where P = (Fo2 + 2Fc2)/3 |
3308 reflections | Δρmax = 0.36 e Å−3 |
249 parameters | Δρmin = −0.28 e Å−3 |
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 | 0.48657 (2) | 0.81667 (2) | 1.03441 (3) | 0.0390 (2) | |
C13 | 0.5884 (2) | 0.8962 (2) | 0.7148 (4) | 0.0729 (14) | |
C14 | 0.6317 (3) | 0.9226 (3) | 0.6646 (6) | 0.099 (2) | |
H14 | 0.6337 | 0.9224 | 0.5940 | 0.118* | |
C15 | 0.6710 (3) | 0.9486 (3) | 0.7205 (7) | 0.105 (2) | |
H15 | 0.7005 | 0.9660 | 0.6873 | 0.126* | |
C16 | 0.6689 (2) | 0.9502 (2) | 0.8288 (7) | 0.098 (2) | |
H16 | 0.6961 | 0.9694 | 0.8651 | 0.117* | |
C17 | 0.6263 (2) | 0.9231 (2) | 0.8797 (5) | 0.0736 (14) | |
H17 | 0.6248 | 0.9235 | 0.9503 | 0.088* | |
C12 | 0.58614 (19) | 0.89558 (18) | 0.8248 (4) | 0.0572 (11) | |
C11 | 0.54300 (18) | 0.86555 (17) | 0.8812 (3) | 0.0516 (10) | |
C10 | 0.42641 (18) | 0.79092 (18) | 0.8447 (3) | 0.0547 (11) | |
H10 | 0.4223 | 0.7953 | 0.7749 | 0.066* | |
C8 | 0.38607 (17) | 0.75893 (18) | 0.8983 (3) | 0.0517 (10) | |
C7 | 0.3406 (2) | 0.7401 (2) | 0.8402 (4) | 0.0681 (13) | |
H7 | 0.3380 | 0.7495 | 0.7717 | 0.082* | |
C6 | 0.3005 (2) | 0.7085 (2) | 0.8840 (4) | 0.0723 (14) | |
H6 | 0.2702 | 0.6966 | 0.8458 | 0.087* | |
C5 | 0.3047 (2) | 0.6933 (2) | 0.9878 (4) | 0.0668 (13) | |
H5 | 0.2767 | 0.6717 | 1.0168 | 0.080* | |
C4 | 0.34892 (18) | 0.70962 (18) | 1.0463 (3) | 0.0528 (10) | |
C9 | 0.39024 (17) | 0.74385 (17) | 1.0048 (3) | 0.0478 (10) | |
C3 | 0.3125 (3) | 0.6763 (3) | 1.2083 (5) | 0.125 (3) | |
H3A | 0.2843 | 0.7046 | 1.2079 | 0.188* | |
H3B | 0.3249 | 0.6701 | 1.2767 | 0.188* | |
H3C | 0.2973 | 0.6423 | 1.1815 | 0.188* | |
C18 | 0.2797 (4) | 0.8669 (4) | 0.8818 (8) | 0.121 (2) | |
H2 | 0.2621 | 0.8535 | 0.8238 | 0.41 (11)* | |
N1 | 0.2578 (3) | 0.8534 (3) | 0.9732 (5) | 0.124 (2) | |
N3 | 0.50473 (15) | 0.84230 (15) | 0.8251 (3) | 0.0571 (9) | |
N2 | 0.46821 (15) | 0.81391 (14) | 0.8886 (3) | 0.0526 (9) | |
O1 | 0.3210 (3) | 0.8956 (3) | 0.8710 (5) | 0.174 (3) | |
O6 | 0.55073 (19) | 0.87083 (19) | 0.6544 (3) | 0.0981 (13) | |
H6A | 0.5288 | 0.8530 | 0.6895 | 0.147* | |
O5 | 0.54502 (12) | 0.86371 (12) | 0.9823 (2) | 0.0579 (8) | |
O4 | 0.43272 (11) | 0.75891 (12) | 1.0661 (2) | 0.0503 (7) | |
O3 | 0.35778 (12) | 0.69341 (13) | 1.1480 (2) | 0.0643 (8) | |
C1 | 0.2100 (4) | 0.8200 (4) | 0.9791 (7) | 0.146 (3) | |
H1A | 0.1977 | 0.8106 | 0.9118 | 0.219* | |
H1B | 0.1810 | 0.8400 | 1.0137 | 0.219* | |
H1C | 0.2184 | 0.7865 | 1.0159 | 0.219* | |
C2 | 0.2841 (5) | 0.8651 (5) | 1.0693 (8) | 0.205 (5) | |
H2A | 0.3212 | 0.8786 | 1.0578 | 0.308* | |
H2B | 0.2856 | 0.8317 | 1.1092 | 0.308* | |
H2C | 0.2629 | 0.8929 | 1.1048 | 0.308* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Co1 | 0.0497 (3) | 0.0468 (3) | 0.0207 (3) | −0.0024 (2) | −0.0030 (2) | 0.0027 (2) |
C13 | 0.079 (3) | 0.076 (3) | 0.064 (3) | 0.009 (3) | 0.020 (3) | 0.019 (3) |
C14 | 0.104 (5) | 0.095 (4) | 0.097 (5) | 0.007 (4) | 0.041 (4) | 0.031 (4) |
C15 | 0.086 (5) | 0.088 (4) | 0.140 (7) | 0.001 (4) | 0.036 (5) | 0.039 (5) |
C16 | 0.069 (4) | 0.083 (4) | 0.141 (7) | −0.009 (3) | −0.003 (4) | 0.032 (4) |
C17 | 0.064 (3) | 0.065 (3) | 0.092 (4) | −0.003 (3) | 0.000 (3) | 0.019 (3) |
C12 | 0.060 (3) | 0.053 (2) | 0.059 (3) | 0.006 (2) | 0.004 (2) | 0.014 (2) |
C11 | 0.060 (3) | 0.054 (2) | 0.040 (3) | 0.006 (2) | 0.000 (2) | 0.011 (2) |
C10 | 0.064 (3) | 0.066 (3) | 0.034 (2) | −0.002 (2) | −0.012 (2) | 0.005 (2) |
C8 | 0.055 (2) | 0.060 (3) | 0.040 (2) | −0.004 (2) | −0.006 (2) | 0.002 (2) |
C7 | 0.071 (3) | 0.088 (3) | 0.044 (3) | −0.005 (3) | −0.016 (2) | 0.003 (2) |
C6 | 0.065 (3) | 0.087 (4) | 0.064 (3) | −0.018 (3) | −0.015 (3) | 0.001 (3) |
C5 | 0.061 (3) | 0.075 (3) | 0.064 (3) | −0.014 (2) | −0.004 (2) | 0.003 (3) |
C4 | 0.058 (3) | 0.060 (3) | 0.041 (2) | −0.001 (2) | −0.002 (2) | 0.001 (2) |
C9 | 0.050 (2) | 0.054 (2) | 0.040 (2) | 0.0002 (19) | −0.0044 (19) | −0.0029 (18) |
C3 | 0.102 (5) | 0.189 (8) | 0.085 (5) | −0.056 (5) | 0.000 (4) | 0.053 (5) |
C18 | 0.107 (6) | 0.137 (7) | 0.117 (7) | 0.011 (5) | 0.013 (6) | −0.005 (6) |
N1 | 0.106 (5) | 0.167 (6) | 0.099 (5) | −0.006 (4) | 0.019 (4) | −0.012 (4) |
N3 | 0.063 (2) | 0.072 (2) | 0.037 (2) | −0.0066 (19) | −0.0005 (17) | 0.0081 (18) |
N2 | 0.062 (2) | 0.062 (2) | 0.0328 (19) | −0.0019 (17) | −0.0020 (17) | 0.0070 (16) |
O1 | 0.149 (5) | 0.215 (7) | 0.157 (6) | −0.027 (5) | 0.030 (5) | 0.007 (5) |
O6 | 0.122 (3) | 0.125 (3) | 0.048 (2) | −0.025 (3) | 0.013 (2) | 0.010 (2) |
O5 | 0.0687 (19) | 0.0638 (18) | 0.0412 (18) | −0.0062 (15) | −0.0044 (14) | 0.0044 (14) |
O4 | 0.0575 (17) | 0.0633 (17) | 0.0302 (14) | −0.0054 (13) | −0.0032 (13) | 0.0038 (13) |
O3 | 0.0636 (19) | 0.082 (2) | 0.0475 (19) | −0.0145 (16) | 0.0005 (15) | 0.0124 (16) |
C1 | 0.122 (7) | 0.136 (7) | 0.181 (10) | −0.001 (6) | 0.019 (6) | 0.009 (6) |
C2 | 0.219 (11) | 0.282 (15) | 0.115 (8) | −0.050 (11) | 0.010 (8) | −0.015 (9) |
Co1—N2 | 1.970 (3) | C6—C5 | 1.417 (7) |
Co1—O4 | 1.941 (3) | C6—H6 | 0.930 |
Co1—O5 | 1.927 (3) | C5—C4 | 1.369 (6) |
Co1—O4i | 2.039 (3) | C5—H5 | 0.930 |
Co1—O3i | 2.270 (3) | C4—C9 | 1.399 (6) |
Co1—O4ii | 2.686 (3) | C4—O3 | 1.409 (5) |
C13—O6 | 1.349 (6) | C9—O4 | 1.350 (5) |
C13—C14 | 1.385 (8) | C3—O3 | 1.408 (6) |
C13—C12 | 1.450 (7) | C3—H3A | 0.960 |
C14—C15 | 1.349 (9) | C3—H3B | 0.960 |
C14—H14 | 0.930 | C3—H3C | 0.960 |
C15—C16 | 1.427 (10) | C18—O1 | 1.214 (9) |
C15—H15 | 0.930 | C18—N1 | 1.352 (10) |
C16—C17 | 1.386 (7) | C18—H2 | 0.930 |
C16—H16 | 0.930 | N1—C1 | 1.403 (9) |
C17—C12 | 1.373 (7) | N1—C2 | 1.441 (11) |
C17—H17 | 0.930 | N3—N2 | 1.390 (5) |
C12—C11 | 1.463 (6) | O6—H6A | 0.820 |
C11—N3 | 1.304 (5) | O4—Co1iii | 2.039 (3) |
C11—O5 | 1.332 (5) | O3—Co1iii | 2.270 (3) |
C10—N2 | 1.282 (5) | C1—H1A | 0.960 |
C10—C8 | 1.423 (6) | C1—H1B | 0.960 |
C10—H10 | 0.930 | C1—H1C | 0.960 |
C8—C7 | 1.408 (6) | C2—H2A | 0.960 |
C8—C9 | 1.450 (6) | C2—H2B | 0.960 |
C7—C6 | 1.354 (7) | C2—H2C | 0.960 |
C7—H7 | 0.930 | ||
O5—Co1—O4 | 168.50 (12) | C4—C5—H5 | 119.2 |
O5—Co1—N2 | 80.55 (13) | C6—C5—H5 | 119.2 |
O4—Co1—N2 | 92.10 (13) | C5—C4—C9 | 119.8 (4) |
O5—Co1—O4i | 98.51 (12) | C5—C4—O3 | 124.9 (4) |
O4—Co1—O4i | 88.43 (11) | C9—C4—O3 | 115.2 (4) |
N2—Co1—O4i | 177.24 (13) | O4—C9—C4 | 117.3 (4) |
O5—Co1—O3i | 90.22 (12) | O4—C9—C8 | 124.3 (4) |
O4—Co1—O3i | 100.50 (12) | C4—C9—C8 | 118.4 (4) |
N2—Co1—O3i | 107.87 (13) | O3—C3—H3A | 109.5 |
O4i—Co1—O3i | 74.68 (11) | O3—C3—H3B | 109.5 |
O6—C13—C14 | 115.4 (6) | H3A—C3—H3B | 109.5 |
O6—C13—C12 | 124.0 (4) | O3—C3—H3C | 109.5 |
C14—C13—C12 | 120.6 (6) | H3A—C3—H3C | 109.5 |
C15—C14—C13 | 118.4 (7) | H3B—C3—H3C | 109.5 |
C15—C14—H14 | 120.8 | O1—C18—N1 | 123.8 (10) |
C13—C14—H14 | 120.8 | O1—C18—H2 | 118.1 |
C14—C15—C16 | 122.3 (6) | N1—C18—H2 | 118.1 |
C14—C15—H15 | 118.9 | C18—N1—C1 | 120.3 (8) |
C16—C15—H15 | 118.9 | C18—N1—C2 | 124.4 (8) |
C17—C16—C15 | 119.7 (6) | C1—N1—C2 | 114.9 (8) |
C17—C16—H16 | 120.1 | C11—N3—N2 | 108.3 (3) |
C15—C16—H16 | 120.2 | C10—N2—N3 | 115.7 (3) |
C12—C17—C16 | 119.3 (6) | C10—N2—Co1 | 128.9 (3) |
C12—C17—H17 | 120.3 | N3—N2—Co1 | 115.4 (3) |
C16—C17—H17 | 120.3 | C13—O6—H6A | 109.5 |
C17—C12—C13 | 119.6 (5) | C11—O5—Co1 | 110.4 (3) |
C17—C12—C11 | 117.8 (5) | C9—O4—Co1 | 124.4 (3) |
C13—C12—C11 | 122.5 (4) | C9—O4—Co1iii | 120.8 (2) |
N3—C11—O5 | 125.3 (4) | Co1—O4—Co1iii | 112.99 (13) |
N3—C11—C12 | 115.0 (4) | C4—O3—C3 | 120.0 (4) |
O5—C11—C12 | 119.8 (4) | C4—O3—Co1iii | 111.5 (2) |
N2—C10—C8 | 122.7 (4) | C3—O3—Co1iii | 121.9 (3) |
N2—C10—H10 | 118.6 | N1—C1—H1A | 109.5 |
C8—C10—H10 | 118.6 | N1—C1—H1B | 109.5 |
C7—C8—C10 | 115.5 (4) | H1A—C1—H1B | 109.5 |
C7—C8—C9 | 119.9 (4) | N1—C1—H1C | 109.5 |
C10—C8—C9 | 124.5 (4) | H1A—C1—H1C | 109.5 |
C6—C7—C8 | 119.9 (5) | H1B—C1—H1C | 109.5 |
C6—C7—H7 | 120.1 | N1—C2—H2A | 109.5 |
C8—C7—H7 | 120.1 | N1—C2—H2B | 109.5 |
C7—C6—C5 | 120.4 (4) | H2A—C2—H2B | 109.5 |
C7—C6—H6 | 119.8 | N1—C2—H2C | 109.5 |
C5—C6—H6 | 119.8 | H2A—C2—H2C | 109.5 |
C4—C5—C6 | 121.5 (4) | H2B—C2—H2C | 109.5 |
Symmetry codes: (i) y−1/4, −x+5/4, −z+9/4; (ii) −x+1, −y+3/2, z; (iii) −y+5/4, x+1/4, −z+9/4. |
Experimental details
Crystal data | |
Chemical formula | [Co4(C15H12N2O4)4]·4C3H7NO |
Mr | 1665.17 |
Crystal system, space group | Tetragonal, I41/a |
Temperature (K) | 298 |
a, c (Å) | 23.996 (2), 13.1605 (10) |
V (Å3) | 7578.0 (11) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.94 |
Crystal size (mm) | 0.10 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker APEXII CCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18342, 3308, 2180 |
Rint | 0.060 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.136, 1.00 |
No. of reflections | 3308 |
No. of parameters | 249 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0641P)2 + 15.4281P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.36, −0.28 |
Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SAINT-Plus, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXTL.
Co1—N2 | 1.970 (3) | Co1—O4i | 2.039 (3) |
Co1—O4 | 1.941 (3) | Co1—O3i | 2.270 (3) |
Co1—O5 | 1.927 (3) | Co1—O4ii | 2.686 (3) |
Symmetry codes: (i) y−1/4, −x+5/4, −z+9/4; (ii) −x+1, −y+3/2, z. |
Owing to their biological activity and chemical/industrial versatility, metal-hydrazine complexes have received considerable attention. For instance, Schiff base hydrazine and its analogues have been well studied in order to understand better the mechanism of enzymes containing vitamin B6 (Maghler et al., 1982; Rath et al., 1997; Rath et al., 1998)
Herein, we report the structure of the title compound, [Co4(C15H12N2O4)4].4C3H7NO. As shown in Fig. 1, the asymmetric unit comprises one N-(2-hydroxy-benzoyl)-N-(2-hydroxy-3-methoxo-benzoylidene)hydrazine anion and one CoII cation. These are linked into tetrameric complexes about positions of 4 point symmetry. Each CoII cation adopts a distorted 6-coordinate geometry through one N and three O atoms lying in the equatorial plane, with the Co1—O3 bond lying to one side of this plane and the longer Co1—O4 bond lying on the opposite side.