Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680704072X/hy2076sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680704072X/hy2076Isup2.hkl |
CCDC reference: 663160
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.005 Å
- R factor = 0.045
- wR factor = 0.091
- Data-to-parameter ratio = 11.8
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 200 Deg. PLAT417_ALERT_2_C Short Inter D-H..H-D H9A .. H10A .. 2.10 Ang. PLAT417_ALERT_2_C Short Inter D-H..H-D H9B .. H10A .. 2.14 Ang. PLAT432_ALERT_2_C Short Inter X...Y Contact O6 .. C12 .. 3.00 Ang.
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.26 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 11
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
The ligand was prepared according to the literature (He et al., 2002). Pyruvic acid is biochemical reagent and all other chemicals used were of analytical grade.
A solution of 2-[2-(2-hydroxybenzoyl)hydrazono]propanoic acid (0.226 g, 1 mmol) in aqua–ethanol (15 ml, v/v = 1:2) was added under stirring to a solution of CuCl2.2H2O (0.088 g, 0.5 mmol) in aqua–ethanol (5 ml, v/v = 1:2). The resulting solution was refluxed at 353 K for 2 h, then filtered. The filtrate was left to evaporate naturally for about two weeks at room temperature and green prism crystals were obtained. The results of elemental analysis are in good agreement with the title complex.
H atoms of the water molecules were located in a difference Fourier map and refined with a restraint of O—H = 0.85 (1)Å and a fixed Uiso. The other H atoms were positioned geometrically and refined as riding, with C—H = 0.93Å (CH) and N—H = 0.86 Å (NH) and Uiso(H) = 1.2Ueq(C, N), and with C—H = 0.96Å (CH3) and O—H = 0.82Å (OH) and Uiso(H) = 1.5Ueq(C, O).
Hydrazones have attracted considerable interest due to their complicated coordination behavior and pharmacological activity. Many of physiologically active hydrazone–metal complexes find applications in the treatment of several diseases such as tuberculosis, tumour and cancer (Buss et al., 2003; Rodrguez-Argelles et al., 2004). The crystal structures of five-coordinated CuII complexes with the 2-[2-(2-hydroxybenzoyl)hydrazono]propanoate ligand have been studied (He et al., 2002; 2003). However, there are no reports on the crystal structure of six-coordinated CuII complexes with such a ligand. This paper reports the crystal structure of a new CuII complexe with 2-[2-(2-hydroxybenzoyl)hydrazono]propanoic acid.
In the title complex, the CuII atom is six-coordinated by two tridentate ligands through the acyl and carboxyl O atoms and imido N atoms (Fig. 1). Thus two five-membered chelate rings sharing one edge are formed for each ligand. The atoms O1, N1, O4 and N3 are approximately coplanar, forming the equatorial plane, while the other two O atoms occupy the axial sites. The angle of the axial O5—Cu1—O7 is 150.12 (9)°, which deviates from a linear arrangement. These data indicate that the Cu1 atom is in a distorted octahedral geometry. Uncoordinated three water molecules are found in the crystal lattice. Comparing with the distances of C—O (1.42 Å) and C ?O (1.23 Å), the bond lengths of O7—C14 and O4—C4 are 1.228 (4) and 1.246 (4)Å (Table 1), respectively, indicating that they are double bonds and the ligand functions in a keto form.
There are abundant hydrogen bonds in the structure (Table 2). The intramolecular hydrogen bonds are observed between imido and hydroxyl groups. At the same time, the intermolecular hydrogen bonds exist between free water molecules and the ligands. These inter- and intramolecular hydrogen bonds result in a three-dimensional network and provide extra stability for the structure.
For related literature, see: Buss et al. (2003); He et al. (2002); He et al. (2003); Rodrguez-Argelles et al. (2004)
Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); 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 (Bruker, 2001).
Fig. 1. The molecular structure of the title compoud. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. |
[Cu(C10H9N2O4)2]·3H2O | Z = 2 |
Mr = 559.97 | F(000) = 578 |
Triclinic, P1 | Dx = 1.588 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.3787 (12) Å | Cell parameters from 4104 reflections |
b = 10.7935 (14) Å | θ = 1.9–25.1° |
c = 11.8795 (15) Å | µ = 1.00 mm−1 |
α = 86.447 (2)° | T = 298 K |
β = 81.805 (2)° | Block, green |
γ = 79.847 (2)° | 0.32 × 0.27 × 0.14 mm |
V = 1170.8 (3) Å3 |
Bruker SMART APEX CCD area-detector diffractometer | 4104 independent reflections |
Radiation source: fine-focus sealed tube | 3173 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
φ and ω scans | θmax = 25.1°, θmin = 1.9° |
Absorption correction: multi-scan (SAINT-Plus; Bruker, 2001) | h = −10→11 |
Tmin = 0.740, Tmax = 0.871 | k = −12→12 |
5974 measured reflections | l = −14→8 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.87 | w = 1/[σ2(Fo2) + (0.004P)2 + 3.5P] where P = (Fo2 + 2Fc2)/3 |
4104 reflections | (Δ/σ)max = 0.001 |
347 parameters | Δρmax = 0.46 e Å−3 |
11 restraints | Δρmin = −0.38 e Å−3 |
[Cu(C10H9N2O4)2]·3H2O | γ = 79.847 (2)° |
Mr = 559.97 | V = 1170.8 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.3787 (12) Å | Mo Kα radiation |
b = 10.7935 (14) Å | µ = 1.00 mm−1 |
c = 11.8795 (15) Å | T = 298 K |
α = 86.447 (2)° | 0.32 × 0.27 × 0.14 mm |
β = 81.805 (2)° |
Bruker SMART APEX CCD area-detector diffractometer | 4104 independent reflections |
Absorption correction: multi-scan (SAINT-Plus; Bruker, 2001) | 3173 reflections with I > 2σ(I) |
Tmin = 0.740, Tmax = 0.871 | Rint = 0.017 |
5974 measured reflections |
R[F2 > 2σ(F2)] = 0.045 | 11 restraints |
wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.87 | Δρmax = 0.46 e Å−3 |
4104 reflections | Δρmin = −0.38 e Å−3 |
347 parameters |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.96365 (5) | 0.75181 (4) | 0.26010 (4) | 0.04285 (14) | |
N1 | 0.9839 (3) | 0.7462 (3) | 0.4209 (2) | 0.0375 (7) | |
N3 | 0.9562 (3) | 0.7491 (2) | 0.0943 (2) | 0.0355 (7) | |
O5 | 1.1161 (3) | 0.8770 (2) | 0.1822 (2) | 0.0486 (7) | |
O3 | 0.8437 (3) | 1.0082 (2) | 0.6413 (2) | 0.0497 (7) | |
H3 | 0.8400 | 1.0384 | 0.7036 | 0.075* | |
O8 | 0.8088 (3) | 0.5336 (2) | −0.0892 (2) | 0.0450 (6) | |
H8 | 0.8197 | 0.4948 | −0.1478 | 0.068* | |
O4 | 0.8153 (3) | 0.9105 (2) | 0.3181 (2) | 0.0510 (7) | |
O1 | 1.1185 (3) | 0.5939 (2) | 0.2717 (2) | 0.0479 (7) | |
O7 | 0.7917 (3) | 0.6310 (2) | 0.2436 (2) | 0.0498 (7) | |
N4 | 0.8732 (3) | 0.6699 (3) | 0.0602 (2) | 0.0397 (7) | |
H4 | 0.8714 | 0.6592 | −0.0106 | 0.048* | |
N2 | 0.8996 (3) | 0.8420 (3) | 0.4821 (2) | 0.0411 (7) | |
H2 | 0.9011 | 0.8481 | 0.5537 | 0.049* | |
C14 | 0.7938 (4) | 0.6088 (3) | 0.1432 (3) | 0.0386 (8) | |
O6 | 1.1890 (3) | 0.9618 (2) | 0.0119 (2) | 0.0526 (7) | |
C12 | 1.0356 (4) | 0.8087 (3) | 0.0209 (3) | 0.0373 (8) | |
C1 | 1.1542 (4) | 0.5673 (3) | 0.3714 (3) | 0.0410 (9) | |
C4 | 0.8137 (4) | 0.9265 (3) | 0.4213 (3) | 0.0392 (8) | |
C6 | 0.7345 (4) | 1.0711 (3) | 0.5872 (3) | 0.0406 (8) | |
C2 | 1.0792 (4) | 0.6613 (3) | 0.4607 (3) | 0.0381 (8) | |
O2 | 1.2374 (3) | 0.4751 (3) | 0.3998 (2) | 0.0646 (8) | |
C16 | 0.7262 (4) | 0.4758 (3) | −0.0055 (3) | 0.0358 (8) | |
C17 | 0.6531 (4) | 0.3818 (3) | −0.0294 (3) | 0.0437 (9) | |
H17 | 0.6607 | 0.3570 | −0.1039 | 0.052* | |
C13 | 1.0480 (4) | 0.8025 (3) | −0.1052 (3) | 0.0441 (9) | |
H13A | 1.1011 | 0.7217 | −0.1284 | 0.066* | |
H13B | 1.0990 | 0.8674 | −0.1407 | 0.066* | |
H13C | 0.9521 | 0.8143 | −0.1277 | 0.066* | |
C15 | 0.7146 (4) | 0.5144 (3) | 0.1066 (3) | 0.0376 (8) | |
C11 | 1.1221 (4) | 0.8899 (3) | 0.0752 (3) | 0.0399 (8) | |
C3 | 1.1214 (5) | 0.6499 (4) | 0.5772 (3) | 0.0527 (10) | |
H3A | 1.2145 | 0.6759 | 0.5753 | 0.079* | |
H3B | 1.1279 | 0.5638 | 0.6048 | 0.079* | |
H3C | 1.0491 | 0.7025 | 0.6268 | 0.079* | |
C5 | 0.7198 (4) | 1.0345 (3) | 0.4785 (3) | 0.0384 (8) | |
C20 | 0.6267 (4) | 0.4558 (4) | 0.1915 (3) | 0.0486 (10) | |
H20 | 0.6165 | 0.4805 | 0.2662 | 0.058* | |
C10 | 0.6092 (4) | 1.1031 (4) | 0.4218 (3) | 0.0527 (10) | |
H10 | 0.6000 | 1.0808 | 0.3491 | 0.063* | |
C19 | 0.5554 (4) | 0.3626 (4) | 0.1663 (4) | 0.0561 (11) | |
H19 | 0.4975 | 0.3247 | 0.2237 | 0.067* | |
C9 | 0.5136 (5) | 1.2027 (4) | 0.4704 (4) | 0.0628 (12) | |
H9 | 0.4402 | 1.2469 | 0.4313 | 0.075* | |
C7 | 0.6369 (4) | 1.1726 (4) | 0.6355 (3) | 0.0534 (10) | |
H7 | 0.6456 | 1.1973 | 0.7075 | 0.064* | |
C18 | 0.5696 (4) | 0.3249 (4) | 0.0556 (4) | 0.0543 (11) | |
H18 | 0.5224 | 0.2608 | 0.0387 | 0.065* | |
C8 | 0.5277 (5) | 1.2365 (4) | 0.5776 (4) | 0.0626 (12) | |
H8A | 0.4625 | 1.3033 | 0.6112 | 0.075* | |
O11 | 0.8000 (4) | 0.7508 (3) | 0.7027 (3) | 0.0812 (10) | |
O9 | 0.3526 (4) | 0.0972 (4) | 0.1281 (4) | 0.0952 (12) | |
O10 | 0.3972 (5) | 0.0687 (7) | 0.8498 (4) | 0.152 (2) | |
H11A | 0.744 (7) | 0.788 (6) | 0.758 (4) | 0.183* | |
H9B | 0.309 (6) | 0.059 (6) | 0.086 (6) | 0.183* | |
H10B | 0.344 (6) | 0.088 (8) | 0.796 (4) | 0.183* | |
H11B | 0.774 (7) | 0.680 (3) | 0.696 (6) | 0.183* | |
H9A | 0.435 (4) | 0.049 (5) | 0.136 (6) | 0.183* | |
H10A | 0.347 (4) | 0.037 (5) | 0.906 (4) | 0.183* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0542 (3) | 0.0390 (3) | 0.0353 (3) | −0.0025 (2) | −0.0089 (2) | −0.00926 (19) |
N1 | 0.0452 (18) | 0.0367 (16) | 0.0308 (15) | −0.0068 (14) | −0.0024 (13) | −0.0107 (13) |
N3 | 0.0411 (17) | 0.0307 (15) | 0.0368 (16) | −0.0049 (13) | −0.0105 (13) | −0.0081 (13) |
O5 | 0.0694 (18) | 0.0443 (15) | 0.0376 (15) | −0.0159 (13) | −0.0152 (13) | −0.0087 (12) |
O3 | 0.0675 (18) | 0.0472 (15) | 0.0355 (14) | −0.0017 (13) | −0.0149 (13) | −0.0144 (12) |
O8 | 0.0606 (17) | 0.0456 (15) | 0.0311 (13) | −0.0153 (13) | −0.0011 (12) | −0.0125 (11) |
O4 | 0.0654 (18) | 0.0534 (16) | 0.0326 (14) | 0.0010 (14) | −0.0104 (13) | −0.0122 (12) |
O1 | 0.0664 (18) | 0.0430 (15) | 0.0320 (14) | 0.0030 (13) | −0.0106 (13) | −0.0087 (11) |
O7 | 0.0625 (18) | 0.0601 (17) | 0.0292 (14) | −0.0143 (14) | −0.0053 (12) | −0.0101 (12) |
N4 | 0.0514 (19) | 0.0398 (17) | 0.0308 (16) | −0.0105 (14) | −0.0093 (14) | −0.0061 (13) |
N2 | 0.0511 (19) | 0.0415 (17) | 0.0284 (15) | 0.0019 (14) | −0.0057 (14) | −0.0098 (13) |
C14 | 0.040 (2) | 0.040 (2) | 0.034 (2) | 0.0002 (16) | −0.0056 (16) | −0.0037 (16) |
O6 | 0.0636 (18) | 0.0486 (16) | 0.0491 (16) | −0.0199 (14) | −0.0062 (14) | −0.0009 (13) |
C12 | 0.043 (2) | 0.0320 (18) | 0.037 (2) | 0.0011 (16) | −0.0108 (16) | −0.0052 (15) |
C1 | 0.048 (2) | 0.036 (2) | 0.040 (2) | −0.0056 (17) | −0.0097 (18) | −0.0058 (16) |
C4 | 0.044 (2) | 0.042 (2) | 0.0331 (19) | −0.0087 (17) | −0.0049 (16) | −0.0085 (16) |
C6 | 0.046 (2) | 0.040 (2) | 0.037 (2) | −0.0087 (17) | −0.0055 (17) | −0.0036 (16) |
C2 | 0.047 (2) | 0.0353 (19) | 0.0326 (19) | −0.0075 (16) | −0.0070 (16) | −0.0034 (15) |
O2 | 0.080 (2) | 0.0516 (17) | 0.0554 (18) | 0.0195 (16) | −0.0218 (16) | −0.0109 (14) |
C16 | 0.0342 (19) | 0.0338 (18) | 0.0368 (19) | 0.0013 (15) | −0.0054 (15) | 0.0001 (15) |
C17 | 0.041 (2) | 0.040 (2) | 0.050 (2) | −0.0022 (17) | −0.0102 (18) | −0.0076 (18) |
C13 | 0.054 (2) | 0.044 (2) | 0.035 (2) | −0.0016 (18) | −0.0127 (17) | −0.0056 (16) |
C15 | 0.039 (2) | 0.0374 (19) | 0.0353 (19) | −0.0028 (15) | −0.0047 (16) | −0.0036 (16) |
C11 | 0.047 (2) | 0.0333 (19) | 0.039 (2) | −0.0014 (17) | −0.0079 (17) | −0.0050 (16) |
C3 | 0.065 (3) | 0.055 (2) | 0.038 (2) | −0.004 (2) | −0.0120 (19) | −0.0066 (18) |
C5 | 0.040 (2) | 0.042 (2) | 0.0330 (19) | −0.0070 (16) | −0.0025 (16) | −0.0039 (16) |
C20 | 0.049 (2) | 0.055 (2) | 0.040 (2) | −0.0030 (19) | −0.0065 (18) | 0.0032 (18) |
C10 | 0.056 (3) | 0.060 (3) | 0.041 (2) | 0.000 (2) | −0.0130 (19) | −0.0068 (19) |
C19 | 0.049 (2) | 0.054 (3) | 0.064 (3) | −0.016 (2) | 0.000 (2) | 0.011 (2) |
C9 | 0.054 (3) | 0.066 (3) | 0.063 (3) | 0.008 (2) | −0.010 (2) | −0.006 (2) |
C7 | 0.060 (3) | 0.052 (2) | 0.045 (2) | −0.004 (2) | 0.003 (2) | −0.0166 (19) |
C18 | 0.047 (2) | 0.043 (2) | 0.075 (3) | −0.0110 (19) | −0.014 (2) | −0.002 (2) |
C8 | 0.055 (3) | 0.058 (3) | 0.066 (3) | 0.011 (2) | 0.003 (2) | −0.015 (2) |
O11 | 0.104 (3) | 0.070 (2) | 0.069 (2) | −0.025 (2) | 0.006 (2) | −0.0090 (18) |
O9 | 0.092 (3) | 0.098 (3) | 0.101 (3) | −0.034 (2) | 0.004 (2) | −0.037 (2) |
O10 | 0.107 (4) | 0.260 (7) | 0.079 (3) | −0.017 (4) | −0.007 (3) | 0.027 (4) |
Cu1—N1 | 1.942 (3) | C2—C3 | 1.485 (5) |
Cu1—N3 | 1.982 (3) | C16—C17 | 1.385 (5) |
Cu1—O1 | 2.047 (2) | C16—C15 | 1.404 (5) |
Cu1—O4 | 2.092 (3) | C17—C18 | 1.370 (5) |
Cu1—O5 | 2.208 (3) | C17—H17 | 0.9300 |
Cu1—O7 | 2.281 (3) | C13—H13A | 0.9600 |
N1—C2 | 1.281 (4) | C13—H13B | 0.9600 |
N1—N2 | 1.365 (4) | C13—H13C | 0.9600 |
N3—C12 | 1.282 (4) | C15—C20 | 1.402 (5) |
N3—N4 | 1.367 (4) | C3—H3A | 0.9600 |
O5—C11 | 1.264 (4) | C3—H3B | 0.9600 |
O3—C6 | 1.346 (4) | C3—H3C | 0.9600 |
O3—H3 | 0.8200 | C5—C10 | 1.394 (5) |
O8—C16 | 1.361 (4) | C20—C19 | 1.371 (5) |
O8—H8 | 0.8200 | C20—H20 | 0.9300 |
O4—C4 | 1.246 (4) | C10—C9 | 1.372 (5) |
O1—C1 | 1.279 (4) | C10—H10 | 0.9300 |
O7—C14 | 1.228 (4) | C19—C18 | 1.382 (6) |
N4—C14 | 1.358 (4) | C19—H19 | 0.9300 |
N4—H4 | 0.8600 | C9—C8 | 1.376 (6) |
N2—C4 | 1.352 (4) | C9—H9 | 0.9300 |
N2—H2 | 0.8600 | C7—C8 | 1.375 (6) |
C14—C15 | 1.481 (5) | C7—H7 | 0.9300 |
O6—C11 | 1.235 (4) | C18—H18 | 0.9300 |
C12—C13 | 1.491 (5) | C8—H8A | 0.9300 |
C12—C11 | 1.521 (5) | O11—H11A | 0.85 (6) |
C1—O2 | 1.213 (4) | O11—H11B | 0.85 (4) |
C1—C2 | 1.523 (5) | O9—H9B | 0.86 (6) |
C4—C5 | 1.470 (5) | O9—H9A | 0.87 (5) |
C6—C7 | 1.394 (5) | O10—H10B | 0.86 (5) |
C6—C5 | 1.406 (5) | O10—H10A | 0.85 (5) |
N1—Cu1—N3 | 175.97 (12) | O8—C16—C17 | 121.3 (3) |
N1—Cu1—O1 | 78.90 (11) | O8—C16—C15 | 118.6 (3) |
N3—Cu1—O1 | 97.23 (10) | C17—C16—C15 | 120.1 (3) |
N1—Cu1—O4 | 77.76 (11) | C18—C17—C16 | 120.7 (4) |
N3—Cu1—O4 | 106.09 (10) | C18—C17—H17 | 119.7 |
O1—Cu1—O4 | 156.66 (10) | C16—C17—H17 | 119.7 |
N1—Cu1—O5 | 103.78 (11) | C12—C13—H13A | 109.5 |
N3—Cu1—O5 | 75.37 (10) | C12—C13—H13B | 109.5 |
O1—Cu1—O5 | 96.24 (11) | H13A—C13—H13B | 109.5 |
O4—Cu1—O5 | 89.13 (10) | C12—C13—H13C | 109.5 |
N1—Cu1—O7 | 106.07 (11) | H13A—C13—H13C | 109.5 |
N3—Cu1—O7 | 74.94 (10) | H13B—C13—H13C | 109.5 |
O1—Cu1—O7 | 90.73 (10) | C20—C15—C16 | 117.9 (3) |
O4—Cu1—O7 | 95.86 (10) | C20—C15—C14 | 117.2 (3) |
O5—Cu1—O7 | 150.12 (9) | C16—C15—C14 | 124.8 (3) |
C2—N1—N2 | 124.5 (3) | O6—C11—O5 | 126.8 (3) |
C2—N1—Cu1 | 119.8 (2) | O6—C11—C12 | 117.7 (3) |
N2—N1—Cu1 | 115.6 (2) | O5—C11—C12 | 115.5 (3) |
C12—N3—N4 | 120.6 (3) | C2—C3—H3A | 109.5 |
C12—N3—Cu1 | 122.3 (2) | C2—C3—H3B | 109.5 |
N4—N3—Cu1 | 116.7 (2) | H3A—C3—H3B | 109.5 |
C11—O5—Cu1 | 113.5 (2) | C2—C3—H3C | 109.5 |
C6—O3—H3 | 109.5 | H3A—C3—H3C | 109.5 |
C16—O8—H8 | 109.5 | H3B—C3—H3C | 109.5 |
C4—O4—Cu1 | 112.8 (2) | C10—C5—C6 | 118.5 (3) |
C1—O1—Cu1 | 114.6 (2) | C10—C5—C4 | 117.8 (3) |
C14—O7—Cu1 | 109.9 (2) | C6—C5—C4 | 123.6 (3) |
C14—N4—N3 | 117.1 (3) | C19—C20—C15 | 121.2 (4) |
C14—N4—H4 | 121.5 | C19—C20—H20 | 119.4 |
N3—N4—H4 | 121.5 | C15—C20—H20 | 119.4 |
C4—N2—N1 | 114.8 (3) | C9—C10—C5 | 121.7 (4) |
C4—N2—H2 | 122.6 | C9—C10—H10 | 119.1 |
N1—N2—H2 | 122.6 | C5—C10—H10 | 119.1 |
O7—C14—N4 | 120.2 (3) | C20—C19—C18 | 120.0 (4) |
O7—C14—C15 | 122.8 (3) | C20—C19—H19 | 120.0 |
N4—C14—C15 | 117.0 (3) | C18—C19—H19 | 120.0 |
N3—C12—C13 | 126.1 (3) | C10—C9—C8 | 119.2 (4) |
N3—C12—C11 | 112.9 (3) | C10—C9—H9 | 120.4 |
C13—C12—C11 | 121.0 (3) | C8—C9—H9 | 120.4 |
O2—C1—O1 | 126.2 (3) | C8—C7—C6 | 120.5 (4) |
O2—C1—C2 | 119.1 (3) | C8—C7—H7 | 119.8 |
O1—C1—C2 | 114.7 (3) | C6—C7—H7 | 119.8 |
O4—C4—N2 | 119.1 (3) | C17—C18—C19 | 120.1 (4) |
O4—C4—C5 | 121.6 (3) | C17—C18—H18 | 119.9 |
N2—C4—C5 | 119.3 (3) | C19—C18—H18 | 119.9 |
O3—C6—C7 | 121.7 (3) | C7—C8—C9 | 120.8 (4) |
O3—C6—C5 | 119.1 (3) | C7—C8—H8A | 119.6 |
C7—C6—C5 | 119.2 (4) | C9—C8—H8A | 119.6 |
N1—C2—C3 | 127.6 (3) | H11A—O11—H11B | 108 (6) |
N1—C2—C1 | 111.8 (3) | H9B—O9—H9A | 107 (6) |
C3—C2—C1 | 120.6 (3) | H10B—O10—H10A | 109 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11B···O2i | 0.82 (3) | 2.11 (5) | 2.888 (5) | 154 (7) |
O9—H9B···O6ii | 0.87 (4) | 1.99 (6) | 2.836 (5) | 171 (7) |
O11—H11A···O9iii | 0.85 (6) | 1.91 (6) | 2.752 (6) | 167 (6) |
O9—H9A···O10iv | 0.87 (5) | 1.86 (5) | 2.724 (7) | 177 (6) |
N2—H2···O11 | 0.86 | 2.19 | 2.830 (5) | 131 |
N2—H2···O3 | 0.86 | 2.02 | 2.623 (4) | 126 |
N4—H4···O8 | 0.86 | 1.91 | 2.573 (4) | 133 |
O8—H8···O1v | 0.82 | 1.77 | 2.584 (3) | 168 |
O3—H3···O5vi | 0.82 | 1.81 | 2.605 (3) | 162 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x−1, y−1, z; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y, −z+1; (v) −x+2, −y+1, −z; (vi) −x+2, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C10H9N2O4)2]·3H2O |
Mr | 559.97 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 9.3787 (12), 10.7935 (14), 11.8795 (15) |
α, β, γ (°) | 86.447 (2), 81.805 (2), 79.847 (2) |
V (Å3) | 1170.8 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.00 |
Crystal size (mm) | 0.32 × 0.27 × 0.14 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SAINT-Plus; Bruker, 2001) |
Tmin, Tmax | 0.740, 0.871 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5974, 4104, 3173 |
Rint | 0.017 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.091, 0.87 |
No. of reflections | 4104 |
No. of parameters | 347 |
No. of restraints | 11 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.46, −0.38 |
Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001).
Cu1—N1 | 1.942 (3) | Cu1—O5 | 2.208 (3) |
Cu1—N3 | 1.982 (3) | Cu1—O7 | 2.281 (3) |
Cu1—O1 | 2.047 (2) | O4—C4 | 1.246 (4) |
Cu1—O4 | 2.092 (3) | O7—C14 | 1.228 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
O11—H11B···O2i | 0.82 (3) | 2.11 (5) | 2.888 (5) | 154 (7) |
O9—H9B···O6ii | 0.87 (4) | 1.99 (6) | 2.836 (5) | 171 (7) |
O11—H11A···O9iii | 0.85 (6) | 1.91 (6) | 2.752 (6) | 167 (6) |
O9—H9A···O10iv | 0.87 (5) | 1.86 (5) | 2.724 (7) | 177 (6) |
N2—H2···O11 | 0.86 | 2.19 | 2.830 (5) | 131.4 |
N2—H2···O3 | 0.86 | 2.02 | 2.623 (4) | 125.9 |
N4—H4···O8 | 0.86 | 1.91 | 2.573 (4) | 132.9 |
O8—H8···O1v | 0.82 | 1.77 | 2.584 (3) | 168.00 |
O3—H3···O5vi | 0.82 | 1.81 | 2.605 (3) | 161.7 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x−1, y−1, z; (iii) −x+1, −y+1, −z+1; (iv) −x+1, −y, −z+1; (v) −x+2, −y+1, −z; (vi) −x+2, −y+2, −z+1. |
Hydrazones have attracted considerable interest due to their complicated coordination behavior and pharmacological activity. Many of physiologically active hydrazone–metal complexes find applications in the treatment of several diseases such as tuberculosis, tumour and cancer (Buss et al., 2003; Rodrguez-Argelles et al., 2004). The crystal structures of five-coordinated CuII complexes with the 2-[2-(2-hydroxybenzoyl)hydrazono]propanoate ligand have been studied (He et al., 2002; 2003). However, there are no reports on the crystal structure of six-coordinated CuII complexes with such a ligand. This paper reports the crystal structure of a new CuII complexe with 2-[2-(2-hydroxybenzoyl)hydrazono]propanoic acid.
In the title complex, the CuII atom is six-coordinated by two tridentate ligands through the acyl and carboxyl O atoms and imido N atoms (Fig. 1). Thus two five-membered chelate rings sharing one edge are formed for each ligand. The atoms O1, N1, O4 and N3 are approximately coplanar, forming the equatorial plane, while the other two O atoms occupy the axial sites. The angle of the axial O5—Cu1—O7 is 150.12 (9)°, which deviates from a linear arrangement. These data indicate that the Cu1 atom is in a distorted octahedral geometry. Uncoordinated three water molecules are found in the crystal lattice. Comparing with the distances of C—O (1.42 Å) and C ?O (1.23 Å), the bond lengths of O7—C14 and O4—C4 are 1.228 (4) and 1.246 (4)Å (Table 1), respectively, indicating that they are double bonds and the ligand functions in a keto form.
There are abundant hydrogen bonds in the structure (Table 2). The intramolecular hydrogen bonds are observed between imido and hydroxyl groups. At the same time, the intermolecular hydrogen bonds exist between free water molecules and the ligands. These inter- and intramolecular hydrogen bonds result in a three-dimensional network and provide extra stability for the structure.