Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807020867/cv2231sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807020867/cv2231Isup2.hkl |
CCDC reference: 650530
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.005 Å
- Disorder in solvent or counterion
- R factor = 0.040
- wR factor = 0.096
- Data-to-parameter ratio = 12.3
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.98 PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 300 Ang. PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 300 Deg. PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 50.00 Perc. PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 3 N2 -CU1 -N1 -C1 166.80 0.60 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 7 N2 -CU1 -N1 -C9 -12.00 0.70 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 11 N1 -CU1 -N2 -C15 -75.00 0.70 1.555 1.555 1.555 1.555 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 15 N1 -CU1 -N2 -C19 97.90 0.70 1.555 1.555 1.555 1.555
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 16
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 9 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 6 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
2-Hydroxyaniline(1 mmol, 109.12 mg) and potassium hydroxide (1 mmol, 56.1 mg) were dissolved in hot methanol (10 ml) and added dropwise to a methanol solution of o-vanillin (1 mmol, 152.2 mg). The mixture was then stirred at 323 K for 2 h. Subsequently, an aqueous solution(2 ml) of cupric acetate monohydrate(1 mmol, 199.7 mg) was added dropwise and stirred for 2 h. An methanol solution (5 ml) of phenanthroline(1 mmol, 198.2 mg) was added dropwise and stirred for 4 h. The solution was held at room temperature for ten days, whereupon green blocky crystals suitable for X-ray diffraction analysis were obtained.
Difference Fourier maps revealed that the methanol molecule is disordered between two positions. The subsequent refinement of their occupancies gave the values of 0.566 (4) and 0.434 (4), respectively. All H atoms were placed in geometrically calculated positions (O—H = 0.82 Å, C—H = 0.93 - 0.97 Å) and allowed to ride on their parent atoms, with Uiso(H) = 1.2–1.5Ueq(parent atom).
Schiff bases still play an important role as ligands in metal coordination chemistry since their discovery [Yamada, S. (1966) Coord. Chem. Rew. 1, 415–437]. Considerable efforts have been devotedd to copper(II) complexes of tridentate Schiff base ligands of N-alkylidene or N-arylidene alkanato type due to their structural richness and a potential model for a number of important biological systems. We report here the synthesis and crystal structure of the title compound, (I), a new copper(II) complex with a tridentate Schiff base ligand derived from the condensation of o-vanillin and 2-Hydroxyaniline, and with phenanthroline.
The CuII atom is five-coordinataed in a seriously distorted square-pyramidal geometry (Fig.1), in which O1, O3, N1, and N2 locate in equatorial plane, and N3 in the apical position, and the CuII atom lies 0.1205 (12) Å above the equatorial plane. The bond distances of Cu—N2, Cu—N3 from neutral ligand phenanthroline are somewhat longer than those of Cu—N1, Cu—O1 and Cu—O2 from Schiff base anion(Table 1), similar to that reported previously (Elena et al., 1995). The apical Cu—N3 bond deviates greatly from the right position to close the Cu—N2 bond (N3—Cu1—N2 is 76.37 (9)°). The tridentate Schiff base ligand coordinated to copper atom to form two chelated rings (Cu1/O3/C9—C10/N1 and Cu1/N1/C1—C3/O1) and the two rings has dihedral angle 4.48 (34)° and 2.92 (13)° to the equatorial plane, respectively. The phenanthroline ligand almost perpendicular to the Schiff base chelating plane (dihedral angle 87.96 (7)°). As shown in Fig. 2, the ligands of 1,10-phenanthroline moiety related by centers of symmetry have a centroid-centroid separation of 3.396 (4)Å (perpendicular distance 3.282 (4) Å) for rings formed by C15—C19/N2 atoms and the slip angle is 14.89 (50)°, indicating a significant π-π interaction [Tong, M. L., Lee, H. K., Chen, X. M., Huang, R. B., Mak, T. M.C. (1999) J. Chem. Soc. Dalton. Trans. 39, 3657–3659]. The intermolecular hydrogen bond distances and bond angles were listed in table 2.
For related literature, see: Elena et al. (1995).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
Fig. 1. The structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme. | |
Fig. 2. Packing diagram of the title compound. |
[Cu(C14H11NO3)(C12H8N2)]·CH4O | Z = 2 |
Mr = 517.02 | F(000) = 534 |
Triclinic, P1 | Dx = 1.482 Mg m−3 |
a = 9.905 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 10.335 (3) Å | Cell parameters from 2789 reflections |
c = 12.094 (3) Å | θ = 2.3–27.6° |
α = 82.701 (3)° | µ = 0.98 mm−1 |
β = 70.742 (3)° | T = 298 K |
γ = 89.236 (3)° | Block, blue |
V = 1158.8 (6) Å3 | 0.21 × 0.18 × 0.07 mm |
Siemens SMART CCD area-detector diffractometer | 4012 independent reflections |
Radiation source: fine-focus sealed tube | 3134 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.018 |
φ and ω scans | θmax = 25.0°, θmin = 1.8° |
Absorption correction: multi-scan (SABADS; Sheldrick, 1996) | h = −11→8 |
Tmin = 0.820, Tmax = 0.934 | k = −11→12 |
5996 measured reflections | l = −14→14 |
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) = 0.096 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0438P)2 + 0.4525P] where P = (Fo2 + 2Fc2)/3 |
4012 reflections | (Δ/σ)max < 0.001 |
325 parameters | Δρmax = 0.48 e Å−3 |
16 restraints | Δρmin = −0.47 e Å−3 |
[Cu(C14H11NO3)(C12H8N2)]·CH4O | γ = 89.236 (3)° |
Mr = 517.02 | V = 1158.8 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.905 (3) Å | Mo Kα radiation |
b = 10.335 (3) Å | µ = 0.98 mm−1 |
c = 12.094 (3) Å | T = 298 K |
α = 82.701 (3)° | 0.21 × 0.18 × 0.07 mm |
β = 70.742 (3)° |
Siemens SMART CCD area-detector diffractometer | 4012 independent reflections |
Absorption correction: multi-scan (SABADS; Sheldrick, 1996) | 3134 reflections with I > 2σ(I) |
Tmin = 0.820, Tmax = 0.934 | Rint = 0.018 |
5996 measured reflections |
R[F2 > 2σ(F2)] = 0.040 | 16 restraints |
wR(F2) = 0.096 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.48 e Å−3 |
4012 reflections | Δρmin = −0.47 e Å−3 |
325 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) | |
Cu1 | −0.06105 (4) | 0.81675 (4) | 0.73686 (3) | 0.03642 (14) | |
N1 | −0.0446 (2) | 0.7433 (2) | 0.5923 (2) | 0.0349 (6) | |
N2 | −0.1087 (3) | 0.8788 (2) | 0.8987 (2) | 0.0346 (6) | |
N3 | 0.0767 (3) | 0.6863 (2) | 0.8276 (2) | 0.0416 (6) | |
O1 | 0.0849 (2) | 0.9503 (2) | 0.65842 (16) | 0.0433 (5) | |
O2 | 0.2853 (3) | 1.1329 (2) | 0.5911 (2) | 0.0594 (7) | |
O3 | −0.2347 (2) | 0.7071 (2) | 0.80315 (17) | 0.0447 (5) | |
O4 | 0.5173 (6) | 0.8061 (5) | −0.0646 (4) | 0.0833 (13) | 0.566 (4) |
H4 | 0.5785 | 0.7648 | −0.1087 | 0.125* | 0.566 (4) |
O4' | 0.5881 (8) | 0.6913 (7) | 0.0324 (5) | 0.0833 (13) | 0.434 (4) |
H4' | 0.6469 | 0.6899 | −0.0335 | 0.125* | 0.434 (4) |
C1 | 0.0500 (3) | 0.7797 (3) | 0.4913 (3) | 0.0395 (7) | |
H1 | 0.0473 | 0.7368 | 0.4289 | 0.047* | |
C2 | 0.1585 (3) | 0.8789 (3) | 0.4651 (2) | 0.0353 (7) | |
C3 | 0.1689 (3) | 0.9587 (3) | 0.5493 (2) | 0.0359 (7) | |
C4 | 0.2815 (3) | 1.0569 (3) | 0.5073 (3) | 0.0406 (7) | |
C5 | 0.3739 (3) | 1.0715 (3) | 0.3943 (3) | 0.0482 (8) | |
H5 | 0.4456 | 1.1363 | 0.3703 | 0.058* | |
C6 | 0.3617 (4) | 0.9898 (3) | 0.3138 (3) | 0.0531 (9) | |
H6 | 0.4253 | 0.9998 | 0.2369 | 0.064* | |
C7 | 0.2572 (3) | 0.8969 (3) | 0.3489 (3) | 0.0473 (8) | |
H7 | 0.2496 | 0.8429 | 0.2952 | 0.057* | |
C8 | 0.4035 (4) | 1.2217 (4) | 0.5636 (3) | 0.0674 (11) | |
H8A | 0.4909 | 1.1752 | 0.5408 | 0.101* | |
H8B | 0.3971 | 1.2633 | 0.6317 | 0.101* | |
H8C | 0.4024 | 1.2866 | 0.4997 | 0.101* | |
C9 | −0.1522 (3) | 0.6459 (3) | 0.6113 (3) | 0.0358 (7) | |
C10 | −0.2511 (3) | 0.6329 (3) | 0.7263 (3) | 0.0391 (7) | |
C11 | −0.3634 (4) | 0.5416 (3) | 0.7559 (3) | 0.0535 (9) | |
H11 | −0.4313 | 0.5328 | 0.8311 | 0.064* | |
C12 | −0.3746 (4) | 0.4638 (3) | 0.6740 (3) | 0.0601 (10) | |
H12 | −0.4495 | 0.4024 | 0.6950 | 0.072* | |
C13 | −0.2762 (4) | 0.4765 (3) | 0.5618 (3) | 0.0561 (9) | |
H13 | −0.2846 | 0.4236 | 0.5075 | 0.067* | |
C14 | −0.1655 (4) | 0.5674 (3) | 0.5301 (3) | 0.0467 (8) | |
H14 | −0.0993 | 0.5763 | 0.4541 | 0.056* | |
C15 | −0.2009 (3) | 0.9712 (3) | 0.9343 (3) | 0.0411 (8) | |
H15 | −0.2401 | 1.0152 | 0.8807 | 0.049* | |
C16 | −0.2419 (3) | 1.0055 (3) | 1.0479 (3) | 0.0454 (8) | |
H16 | −0.3066 | 1.0715 | 1.0690 | 0.054* | |
C17 | −0.1867 (3) | 0.9419 (3) | 1.1279 (3) | 0.0456 (8) | |
H17 | −0.2122 | 0.9646 | 1.2039 | 0.055* | |
C18 | −0.0906 (3) | 0.8415 (3) | 1.0944 (3) | 0.0402 (7) | |
C19 | −0.0542 (3) | 0.8127 (3) | 0.9781 (2) | 0.0335 (7) | |
C20 | 0.0459 (3) | 0.7120 (3) | 0.9396 (3) | 0.0371 (7) | |
C21 | 0.1055 (3) | 0.6438 (3) | 1.0203 (3) | 0.0438 (8) | |
C22 | 0.2003 (4) | 0.5448 (4) | 0.9792 (3) | 0.0552 (9) | |
H22 | 0.2415 | 0.4962 | 1.0293 | 0.066* | |
C23 | 0.2313 (4) | 0.5208 (4) | 0.8663 (3) | 0.0601 (10) | |
H23 | 0.2950 | 0.4563 | 0.8380 | 0.072* | |
C24 | 0.1679 (4) | 0.5926 (3) | 0.7929 (3) | 0.0519 (9) | |
H24 | 0.1904 | 0.5741 | 0.7156 | 0.062* | |
C25 | −0.0268 (4) | 0.7709 (3) | 1.1735 (3) | 0.0492 (9) | |
H25 | −0.0500 | 0.7906 | 1.2504 | 0.059* | |
C26 | 0.0663 (4) | 0.6767 (4) | 1.1375 (3) | 0.0537 (9) | |
H26 | 0.1060 | 0.6318 | 1.1904 | 0.064* | |
C27 | 0.4951 (14) | 0.7539 (17) | 0.0535 (10) | 0.071 (3) | 0.566 (4) |
H27A | 0.5828 | 0.7600 | 0.0702 | 0.106* | 0.566 (4) |
H27B | 0.4640 | 0.6641 | 0.0657 | 0.106* | 0.566 (4) |
H27C | 0.4231 | 0.8021 | 0.1051 | 0.106* | 0.566 (4) |
C27' | 0.4749 (19) | 0.763 (2) | 0.0235 (16) | 0.071 (3) | 0.434 (4) |
H27D | 0.3924 | 0.7384 | 0.0917 | 0.106* | 0.434 (4) |
H27E | 0.4550 | 0.7481 | −0.0464 | 0.106* | 0.434 (4) |
H27F | 0.4976 | 0.8543 | 0.0189 | 0.106* | 0.434 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0389 (2) | 0.0426 (2) | 0.0274 (2) | −0.00479 (16) | −0.00977 (15) | −0.00596 (15) |
N1 | 0.0341 (14) | 0.0396 (15) | 0.0318 (13) | −0.0005 (11) | −0.0120 (11) | −0.0050 (11) |
N2 | 0.0365 (14) | 0.0348 (14) | 0.0334 (13) | −0.0032 (12) | −0.0124 (11) | −0.0045 (11) |
N3 | 0.0432 (15) | 0.0452 (16) | 0.0351 (14) | 0.0008 (13) | −0.0100 (12) | −0.0088 (12) |
O1 | 0.0475 (13) | 0.0502 (13) | 0.0290 (11) | −0.0100 (11) | −0.0069 (10) | −0.0080 (9) |
O2 | 0.0668 (16) | 0.0581 (15) | 0.0511 (14) | −0.0235 (13) | −0.0146 (12) | −0.0098 (12) |
O3 | 0.0424 (12) | 0.0521 (14) | 0.0361 (12) | −0.0118 (10) | −0.0054 (10) | −0.0125 (10) |
O4 | 0.071 (3) | 0.095 (3) | 0.061 (3) | 0.031 (2) | 0.000 (2) | 0.012 (2) |
O4' | 0.071 (3) | 0.095 (3) | 0.061 (3) | 0.031 (2) | 0.000 (2) | 0.012 (2) |
C1 | 0.0439 (18) | 0.0439 (19) | 0.0333 (17) | 0.0040 (15) | −0.0154 (15) | −0.0077 (14) |
C2 | 0.0377 (16) | 0.0393 (18) | 0.0281 (15) | 0.0018 (14) | −0.0113 (13) | −0.0001 (13) |
C3 | 0.0363 (17) | 0.0404 (18) | 0.0316 (16) | 0.0018 (14) | −0.0141 (14) | 0.0004 (13) |
C4 | 0.0427 (18) | 0.0424 (19) | 0.0383 (17) | 0.0005 (15) | −0.0165 (15) | −0.0025 (14) |
C5 | 0.0424 (19) | 0.050 (2) | 0.0457 (19) | −0.0093 (16) | −0.0114 (16) | 0.0078 (16) |
C6 | 0.051 (2) | 0.067 (2) | 0.0314 (17) | −0.0069 (18) | −0.0030 (15) | 0.0005 (16) |
C7 | 0.049 (2) | 0.059 (2) | 0.0321 (17) | −0.0061 (17) | −0.0113 (15) | −0.0047 (15) |
C8 | 0.065 (3) | 0.060 (3) | 0.080 (3) | −0.019 (2) | −0.027 (2) | −0.009 (2) |
C9 | 0.0352 (16) | 0.0359 (17) | 0.0388 (16) | 0.0027 (13) | −0.0156 (13) | −0.0054 (13) |
C10 | 0.0364 (17) | 0.0404 (18) | 0.0414 (17) | −0.0006 (14) | −0.0144 (14) | −0.0049 (14) |
C11 | 0.046 (2) | 0.056 (2) | 0.053 (2) | −0.0122 (17) | −0.0077 (16) | −0.0098 (17) |
C12 | 0.056 (2) | 0.053 (2) | 0.071 (3) | −0.0169 (18) | −0.020 (2) | −0.0122 (19) |
C13 | 0.062 (2) | 0.053 (2) | 0.060 (2) | −0.0067 (18) | −0.0230 (19) | −0.0223 (18) |
C14 | 0.049 (2) | 0.048 (2) | 0.0442 (18) | −0.0016 (16) | −0.0146 (16) | −0.0132 (15) |
C15 | 0.0434 (19) | 0.0426 (19) | 0.0400 (17) | −0.0030 (16) | −0.0182 (15) | −0.0026 (14) |
C16 | 0.048 (2) | 0.0427 (19) | 0.0454 (19) | 0.0051 (16) | −0.0133 (16) | −0.0131 (15) |
C17 | 0.053 (2) | 0.050 (2) | 0.0331 (17) | −0.0025 (17) | −0.0111 (15) | −0.0115 (15) |
C18 | 0.0444 (18) | 0.0441 (19) | 0.0340 (16) | −0.0045 (15) | −0.0153 (14) | −0.0055 (14) |
C19 | 0.0333 (16) | 0.0381 (17) | 0.0303 (15) | −0.0062 (13) | −0.0129 (13) | −0.0015 (13) |
C20 | 0.0345 (17) | 0.0398 (18) | 0.0368 (17) | −0.0032 (14) | −0.0123 (14) | −0.0028 (14) |
C21 | 0.0383 (18) | 0.049 (2) | 0.0465 (19) | −0.0011 (16) | −0.0181 (15) | −0.0021 (15) |
C22 | 0.047 (2) | 0.061 (2) | 0.063 (2) | 0.0084 (18) | −0.0269 (18) | −0.0029 (19) |
C23 | 0.048 (2) | 0.061 (2) | 0.070 (3) | 0.0153 (19) | −0.0162 (19) | −0.017 (2) |
C24 | 0.051 (2) | 0.060 (2) | 0.0423 (19) | 0.0034 (19) | −0.0092 (17) | −0.0137 (17) |
C25 | 0.058 (2) | 0.060 (2) | 0.0344 (17) | 0.0011 (19) | −0.0217 (16) | −0.0050 (16) |
C26 | 0.060 (2) | 0.066 (2) | 0.0429 (19) | 0.002 (2) | −0.0297 (18) | 0.0011 (17) |
C27 | 0.051 (4) | 0.087 (4) | 0.065 (6) | 0.004 (4) | −0.017 (4) | 0.011 (5) |
C27' | 0.051 (4) | 0.087 (4) | 0.065 (6) | 0.004 (4) | −0.017 (4) | 0.011 (5) |
Cu1—O1 | 1.926 (2) | C10—C11 | 1.391 (4) |
Cu1—O3 | 1.949 (2) | C11—C12 | 1.385 (4) |
Cu1—N1 | 1.950 (2) | C11—H11 | 0.9300 |
Cu1—N2 | 2.041 (2) | C12—C13 | 1.376 (5) |
Cu1—N3 | 2.333 (3) | C12—H12 | 0.9300 |
N1—C1 | 1.284 (4) | C13—C14 | 1.375 (4) |
N1—C9 | 1.419 (3) | C13—H13 | 0.9300 |
N2—C15 | 1.324 (4) | C14—H14 | 0.9300 |
N2—C19 | 1.359 (4) | C15—C16 | 1.389 (4) |
N3—C24 | 1.327 (4) | C15—H15 | 0.9300 |
N3—C20 | 1.347 (4) | C16—C17 | 1.359 (4) |
O1—C3 | 1.300 (3) | C16—H16 | 0.9300 |
O2—C4 | 1.369 (3) | C17—C18 | 1.404 (4) |
O2—C8 | 1.421 (4) | C17—H17 | 0.9300 |
O3—C10 | 1.328 (3) | C18—C19 | 1.402 (4) |
O4—C27 | 1.407 (11) | C18—C25 | 1.434 (4) |
O4—H4 | 0.8200 | C19—C20 | 1.440 (4) |
O4'—C27' | 1.364 (15) | C20—C21 | 1.412 (4) |
O4'—H4' | 0.8200 | C21—C22 | 1.404 (5) |
C1—C2 | 1.425 (4) | C21—C26 | 1.425 (4) |
C1—H1 | 0.9300 | C22—C23 | 1.352 (5) |
C2—C7 | 1.413 (4) | C22—H22 | 0.9300 |
C2—C3 | 1.418 (4) | C23—C24 | 1.386 (5) |
C3—C4 | 1.434 (4) | C23—H23 | 0.9300 |
C4—C5 | 1.361 (4) | C24—H24 | 0.9300 |
C5—C6 | 1.401 (4) | C25—C26 | 1.345 (5) |
C5—H5 | 0.9300 | C25—H25 | 0.9300 |
C6—C7 | 1.344 (4) | C26—H26 | 0.9300 |
C6—H6 | 0.9300 | C27—H27A | 0.9600 |
C7—H7 | 0.9300 | C27—H27B | 0.9600 |
C8—H8A | 0.9600 | C27—H27C | 0.9600 |
C8—H8B | 0.9600 | C27'—H27D | 0.9600 |
C8—H8C | 0.9600 | C27'—H27E | 0.9600 |
C9—C14 | 1.390 (4) | C27'—H27F | 0.9600 |
C9—C10 | 1.403 (4) | ||
O1—Cu1—O3 | 167.67 (9) | C10—C11—H11 | 119.8 |
O1—Cu1—N1 | 94.04 (9) | C13—C12—C11 | 120.7 (3) |
O3—Cu1—N1 | 83.92 (9) | C13—C12—H12 | 119.6 |
O1—Cu1—N2 | 94.42 (8) | C11—C12—H12 | 119.6 |
O3—Cu1—N2 | 87.19 (9) | C14—C13—C12 | 119.9 (3) |
N1—Cu1—N2 | 171.06 (9) | C14—C13—H13 | 120.0 |
O1—Cu1—N3 | 96.12 (9) | C12—C13—H13 | 120.0 |
O3—Cu1—N3 | 96.14 (9) | C13—C14—C9 | 120.1 (3) |
N1—Cu1—N3 | 105.59 (9) | C13—C14—H14 | 119.9 |
N2—Cu1—N3 | 76.37 (9) | C9—C14—H14 | 119.9 |
C1—N1—C9 | 123.6 (2) | N2—C15—C16 | 123.2 (3) |
C1—N1—Cu1 | 124.6 (2) | N2—C15—H15 | 118.4 |
C9—N1—Cu1 | 111.79 (18) | C16—C15—H15 | 118.4 |
C15—N2—C19 | 118.2 (3) | C17—C16—C15 | 119.4 (3) |
C15—N2—Cu1 | 123.4 (2) | C17—C16—H16 | 120.3 |
C19—N2—Cu1 | 118.0 (2) | C15—C16—H16 | 120.3 |
C24—N3—C20 | 117.6 (3) | C16—C17—C18 | 119.3 (3) |
C24—N3—Cu1 | 133.2 (2) | C16—C17—H17 | 120.4 |
C20—N3—Cu1 | 109.1 (2) | C18—C17—H17 | 120.4 |
C3—O1—Cu1 | 125.68 (18) | C19—C18—C17 | 118.0 (3) |
C4—O2—C8 | 117.9 (3) | C19—C18—C25 | 119.5 (3) |
C10—O3—Cu1 | 111.84 (18) | C17—C18—C25 | 122.5 (3) |
C27'—O4'—H4' | 109.5 | N2—C19—C18 | 121.9 (3) |
N1—C1—C2 | 126.6 (3) | N2—C19—C20 | 118.3 (2) |
N1—C1—H1 | 116.7 | C18—C19—C20 | 119.8 (3) |
C2—C1—H1 | 116.7 | N3—C20—C21 | 123.0 (3) |
C7—C2—C3 | 120.2 (3) | N3—C20—C19 | 117.9 (3) |
C7—C2—C1 | 116.9 (3) | C21—C20—C19 | 119.1 (3) |
C3—C2—C1 | 122.9 (3) | C22—C21—C20 | 116.9 (3) |
O1—C3—C2 | 125.4 (3) | C22—C21—C26 | 123.7 (3) |
O1—C3—C4 | 118.8 (3) | C20—C21—C26 | 119.4 (3) |
C2—C3—C4 | 115.8 (3) | C23—C22—C21 | 119.4 (3) |
C5—C4—O2 | 124.3 (3) | C23—C22—H22 | 120.3 |
C5—C4—C3 | 122.2 (3) | C21—C22—H22 | 120.3 |
O2—C4—C3 | 113.5 (3) | C22—C23—C24 | 119.9 (3) |
C4—C5—C6 | 120.6 (3) | C22—C23—H23 | 120.1 |
C4—C5—H5 | 119.7 | C24—C23—H23 | 120.1 |
C6—C5—H5 | 119.7 | N3—C24—C23 | 123.1 (3) |
C7—C6—C5 | 119.4 (3) | N3—C24—H24 | 118.5 |
C7—C6—H6 | 120.3 | C23—C24—H24 | 118.5 |
C5—C6—H6 | 120.3 | C26—C25—C18 | 120.6 (3) |
C6—C7—C2 | 121.9 (3) | C26—C25—H25 | 119.7 |
C6—C7—H7 | 119.0 | C18—C25—H25 | 119.7 |
C2—C7—H7 | 119.0 | C25—C26—C21 | 121.6 (3) |
O2—C8—H8A | 109.5 | C25—C26—H26 | 119.2 |
O2—C8—H8B | 109.5 | C21—C26—H26 | 119.2 |
H8A—C8—H8B | 109.5 | O4—C27—H27A | 109.5 |
O2—C8—H8C | 109.5 | O4—C27—H27B | 109.5 |
H8A—C8—H8C | 109.5 | H27A—C27—H27B | 109.5 |
H8B—C8—H8C | 109.5 | O4—C27—H27C | 109.5 |
C14—C9—C10 | 120.4 (3) | H27A—C27—H27C | 109.5 |
C14—C9—N1 | 126.9 (3) | H27B—C27—H27C | 109.5 |
C10—C9—N1 | 112.7 (2) | O4'—C27'—H27D | 109.5 |
O3—C10—C11 | 122.2 (3) | O4'—C27'—H27E | 109.5 |
O3—C10—C9 | 119.4 (3) | H27D—C27'—H27E | 109.5 |
C11—C10—C9 | 118.4 (3) | O4'—C27'—H27F | 109.5 |
C12—C11—C10 | 120.4 (3) | H27D—C27'—H27F | 109.5 |
C12—C11—H11 | 119.8 | H27E—C27'—H27F | 109.5 |
O1—Cu1—N1—C1 | 5.8 (3) | C1—N1—C9—C14 | 6.3 (5) |
O3—Cu1—N1—C1 | 173.6 (3) | Cu1—N1—C9—C14 | −174.9 (3) |
N2—Cu1—N1—C1 | 166.8 (6) | C1—N1—C9—C10 | −174.0 (3) |
N3—Cu1—N1—C1 | −91.7 (3) | Cu1—N1—C9—C10 | 4.8 (3) |
O1—Cu1—N1—C9 | −172.97 (19) | Cu1—O3—C10—C11 | 176.6 (3) |
O3—Cu1—N1—C9 | −5.18 (19) | Cu1—O3—C10—C9 | −3.3 (3) |
N2—Cu1—N1—C9 | −12.0 (7) | C14—C9—C10—O3 | 178.7 (3) |
N3—Cu1—N1—C9 | 89.52 (19) | N1—C9—C10—O3 | −1.0 (4) |
O1—Cu1—N2—C15 | 86.0 (2) | C14—C9—C10—C11 | −1.2 (5) |
O3—Cu1—N2—C15 | −81.8 (2) | N1—C9—C10—C11 | 179.1 (3) |
N1—Cu1—N2—C15 | −75.0 (7) | O3—C10—C11—C12 | −178.4 (3) |
N3—Cu1—N2—C15 | −178.8 (2) | C9—C10—C11—C12 | 1.4 (5) |
O1—Cu1—N2—C19 | −101.1 (2) | C10—C11—C12—C13 | −0.8 (6) |
O3—Cu1—N2—C19 | 91.2 (2) | C11—C12—C13—C14 | −0.1 (6) |
N1—Cu1—N2—C19 | 97.9 (7) | C12—C13—C14—C9 | 0.4 (5) |
N3—Cu1—N2—C19 | −5.86 (19) | C10—C9—C14—C13 | 0.2 (5) |
O1—Cu1—N3—C24 | −86.5 (3) | N1—C9—C14—C13 | 179.9 (3) |
O3—Cu1—N3—C24 | 94.8 (3) | C19—N2—C15—C16 | 1.5 (4) |
N1—Cu1—N3—C24 | 9.4 (3) | Cu1—N2—C15—C16 | 174.5 (2) |
N2—Cu1—N3—C24 | −179.6 (3) | N2—C15—C16—C17 | −0.4 (5) |
O1—Cu1—N3—C20 | 97.58 (19) | C15—C16—C17—C18 | −0.8 (5) |
O3—Cu1—N3—C20 | −81.09 (19) | C16—C17—C18—C19 | 0.9 (4) |
N1—Cu1—N3—C20 | −166.48 (19) | C16—C17—C18—C25 | 179.3 (3) |
N2—Cu1—N3—C20 | 4.50 (18) | C15—N2—C19—C18 | −1.4 (4) |
O3—Cu1—O1—C3 | −88.9 (5) | Cu1—N2—C19—C18 | −174.7 (2) |
N1—Cu1—O1—C3 | −8.9 (2) | C15—N2—C19—C20 | 179.9 (3) |
N2—Cu1—O1—C3 | 174.0 (2) | Cu1—N2—C19—C20 | 6.6 (3) |
N3—Cu1—O1—C3 | 97.3 (2) | C17—C18—C19—N2 | 0.2 (4) |
O1—Cu1—O3—C10 | 85.7 (4) | C25—C18—C19—N2 | −178.3 (3) |
N1—Cu1—O3—C10 | 4.7 (2) | C17—C18—C19—C20 | 178.9 (3) |
N2—Cu1—O3—C10 | −176.4 (2) | C25—C18—C19—C20 | 0.4 (4) |
N3—Cu1—O3—C10 | −100.4 (2) | C24—N3—C20—C21 | −0.3 (4) |
C9—N1—C1—C2 | 178.3 (3) | Cu1—N3—C20—C21 | 176.3 (2) |
Cu1—N1—C1—C2 | −0.4 (4) | C24—N3—C20—C19 | −179.3 (3) |
N1—C1—C2—C7 | 176.1 (3) | Cu1—N3—C20—C19 | −2.7 (3) |
N1—C1—C2—C3 | −4.8 (5) | N2—C19—C20—N3 | −2.0 (4) |
Cu1—O1—C3—C2 | 6.7 (4) | C18—C19—C20—N3 | 179.2 (3) |
Cu1—O1—C3—C4 | −174.0 (2) | N2—C19—C20—C21 | 178.9 (2) |
C7—C2—C3—O1 | −179.5 (3) | C18—C19—C20—C21 | 0.2 (4) |
C1—C2—C3—O1 | 1.4 (5) | N3—C20—C21—C22 | −0.3 (4) |
C7—C2—C3—C4 | 1.2 (4) | C19—C20—C21—C22 | 178.7 (3) |
C1—C2—C3—C4 | −177.9 (3) | N3—C20—C21—C26 | −179.5 (3) |
C8—O2—C4—C5 | −8.3 (5) | C19—C20—C21—C26 | −0.5 (4) |
C8—O2—C4—C3 | 172.0 (3) | C20—C21—C22—C23 | 0.9 (5) |
O1—C3—C4—C5 | 179.9 (3) | C26—C21—C22—C23 | −179.9 (3) |
C2—C3—C4—C5 | −0.8 (4) | C21—C22—C23—C24 | −0.9 (5) |
O1—C3—C4—O2 | −0.5 (4) | C20—N3—C24—C23 | 0.3 (5) |
C2—C3—C4—O2 | 178.9 (3) | Cu1—N3—C24—C23 | −175.3 (2) |
O2—C4—C5—C6 | −179.6 (3) | C22—C23—C24—N3 | 0.3 (5) |
C3—C4—C5—C6 | 0.0 (5) | C19—C18—C25—C26 | −0.7 (5) |
C4—C5—C6—C7 | 0.4 (5) | C17—C18—C25—C26 | −179.1 (3) |
C5—C6—C7—C2 | 0.0 (5) | C18—C25—C26—C21 | 0.3 (5) |
C3—C2—C7—C6 | −0.8 (5) | C22—C21—C26—C25 | −178.9 (3) |
C1—C2—C7—C6 | 178.3 (3) | C20—C21—C26—C25 | 0.3 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O3i | 0.82 | 1.93 | 2.719 (5) | 160 |
O4′—H4′···O3i | 0.82 | 1.92 | 2.735 (6) | 171 |
C17—H17···O2ii | 0.93 | 2.43 | 3.204 (4) | 141 |
Symmetry codes: (i) x+1, y, z−1; (ii) −x, −y+2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C14H11NO3)(C12H8N2)]·CH4O |
Mr | 517.02 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 9.905 (3), 10.335 (3), 12.094 (3) |
α, β, γ (°) | 82.701 (3), 70.742 (3), 89.236 (3) |
V (Å3) | 1158.8 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.98 |
Crystal size (mm) | 0.21 × 0.18 × 0.07 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector |
Absorption correction | Multi-scan (SABADS; Sheldrick, 1996) |
Tmin, Tmax | 0.820, 0.934 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5996, 4012, 3134 |
Rint | 0.018 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.096, 1.03 |
No. of reflections | 4012 |
No. of parameters | 325 |
No. of restraints | 16 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.48, −0.47 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
Cu1—O1 | 1.926 (2) | Cu1—N2 | 2.041 (2) |
Cu1—O3 | 1.949 (2) | Cu1—N3 | 2.333 (3) |
Cu1—N1 | 1.950 (2) | ||
O1—Cu1—O3 | 167.67 (9) | N1—Cu1—N2 | 171.06 (9) |
O1—Cu1—N1 | 94.04 (9) | O1—Cu1—N3 | 96.12 (9) |
O3—Cu1—N1 | 83.92 (9) | O3—Cu1—N3 | 96.14 (9) |
O1—Cu1—N2 | 94.42 (8) | N1—Cu1—N3 | 105.59 (9) |
O3—Cu1—N2 | 87.19 (9) | N2—Cu1—N3 | 76.37 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O3i | 0.82 | 1.93 | 2.719 (5) | 159.8 |
O4'—H4'···O3i | 0.82 | 1.92 | 2.735 (6) | 170.6 |
C17—H17···O2ii | 0.93 | 2.43 | 3.204 (4) | 141.2 |
Symmetry codes: (i) x+1, y, z−1; (ii) −x, −y+2, −z+2. |
Schiff bases still play an important role as ligands in metal coordination chemistry since their discovery [Yamada, S. (1966) Coord. Chem. Rew. 1, 415–437]. Considerable efforts have been devotedd to copper(II) complexes of tridentate Schiff base ligands of N-alkylidene or N-arylidene alkanato type due to their structural richness and a potential model for a number of important biological systems. We report here the synthesis and crystal structure of the title compound, (I), a new copper(II) complex with a tridentate Schiff base ligand derived from the condensation of o-vanillin and 2-Hydroxyaniline, and with phenanthroline.
The CuII atom is five-coordinataed in a seriously distorted square-pyramidal geometry (Fig.1), in which O1, O3, N1, and N2 locate in equatorial plane, and N3 in the apical position, and the CuII atom lies 0.1205 (12) Å above the equatorial plane. The bond distances of Cu—N2, Cu—N3 from neutral ligand phenanthroline are somewhat longer than those of Cu—N1, Cu—O1 and Cu—O2 from Schiff base anion(Table 1), similar to that reported previously (Elena et al., 1995). The apical Cu—N3 bond deviates greatly from the right position to close the Cu—N2 bond (N3—Cu1—N2 is 76.37 (9)°). The tridentate Schiff base ligand coordinated to copper atom to form two chelated rings (Cu1/O3/C9—C10/N1 and Cu1/N1/C1—C3/O1) and the two rings has dihedral angle 4.48 (34)° and 2.92 (13)° to the equatorial plane, respectively. The phenanthroline ligand almost perpendicular to the Schiff base chelating plane (dihedral angle 87.96 (7)°). As shown in Fig. 2, the ligands of 1,10-phenanthroline moiety related by centers of symmetry have a centroid-centroid separation of 3.396 (4)Å (perpendicular distance 3.282 (4) Å) for rings formed by C15—C19/N2 atoms and the slip angle is 14.89 (50)°, indicating a significant π-π interaction [Tong, M. L., Lee, H. K., Chen, X. M., Huang, R. B., Mak, T. M.C. (1999) J. Chem. Soc. Dalton. Trans. 39, 3657–3659]. The intermolecular hydrogen bond distances and bond angles were listed in table 2.