Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106013242/gd3011sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106013242/gd3011Isup2.hkl |
CCDC reference: 609408
Compound (I) was synthesized by adding an ethanol solution (15 ml) of E-2-(2-hydroxybenzylideneamino)benzoic acid (0.120 g) to an aqueous solution (5 ml) of Cu(C2H3O2)2·H2O (0.102 g). The mixed solution was refluxed at 333 K for 2 h; the pH was then adjusted to 7 with 0.1 mol dm−3 NaOH and the solution was filtered while it cooled to room temperature. Dark-blue needle-shaped crystals of (I) were obtained from the filtrate at room temperature after two weeks.
H atoms attached to C atoms were placed in geometrically idealized positions, with C—H = 0.93 Å, and refined with Uiso(H) values of 1.2Ueq(C). H atoms attached to O atoms were located from difference Fourier maps and refined as riding in their as-found positions with Uiso(H) values of 1.2Ueq(O). The O—H distances are in the range 0.82–0.91 Å. Examination of the refined structure using PLATON (Spek, 2003) revealed the presence of voids having a total volume of 1518.3 Å3 per unit cell, arranged into three channels along the c axis with the centres at approximately (0, 0, 0), (1/3, 2/3, 4/5), and (2/3, 1/3, 1/2). No electron density greater than 0.63 e Å3 could be found in the area of the void, and so no definitive solvent molecule could be found. Since the electron count per void is 51 from SQUEEZE (Spek, 2003) results and, considering the symmetry of the voids, six water molecules per void may be reasonable; these voids are certainly large enough. The large voids also slightly increased the final Rvalue.
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1999); software used to prepare material for publication: SHELXTL/PC.
[Cu(C14H9NO3)(H2O)2] | Dx = 1.517 Mg m−3 |
Mr = 338.81 | Mo Kα radiation, λ = 0.71073 Å |
Trigonal, R3 | Cell parameters from 1391 reflections |
Hall symbol: -R 3 | θ = 2.3–17.0° |
a = 46.263 (2) Å | µ = 1.49 mm−1 |
c = 7.2030 (7) Å | T = 298 K |
V = 13350.9 (15) Å3 | Needles, dark-blue |
Z = 36 | 0.24 × 0.09 × 0.01 mm |
F(000) = 6228 |
Bruker SMART 1K CCD area-detector diffractometer | 5220 independent reflections |
Radiation source: fine-focus sealed tube | 3659 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.000 |
ω scans | θmax = 25.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | h = −54→26 |
Tmin = 0.715, Tmax = 0.985 | k = 0→55 |
5220 measured reflections | l = 0→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)] = 0.072 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.160 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0697P)2 + 7.9408P] where P = (Fo2 + 2Fc2)/3 |
5220 reflections | (Δ/σ)max = 0.001 |
379 parameters | Δρmax = 0.63 e Å−3 |
0 restraints | Δρmin = −0.61 e Å−3 |
[Cu(C14H9NO3)(H2O)2] | Z = 36 |
Mr = 338.81 | Mo Kα radiation |
Trigonal, R3 | µ = 1.49 mm−1 |
a = 46.263 (2) Å | T = 298 K |
c = 7.2030 (7) Å | 0.24 × 0.09 × 0.01 mm |
V = 13350.9 (15) Å3 |
Bruker SMART 1K CCD area-detector diffractometer | 5220 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 3659 reflections with I > 2σ(I) |
Tmin = 0.715, Tmax = 0.985 | Rint = 0.000 |
5220 measured reflections |
R[F2 > 2σ(F2)] = 0.072 | 0 restraints |
wR(F2) = 0.160 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.63 e Å−3 |
5220 reflections | Δρmin = −0.61 e Å−3 |
379 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 | ||
Cu1 | 0.190904 (18) | 0.222020 (19) | 0.97110 (10) | 0.0251 (2) | |
O1 | 0.16768 (10) | 0.19144 (11) | 0.7725 (5) | 0.0314 (10) | |
O2 | 0.20649 (10) | 0.24159 (10) | 1.2173 (5) | 0.0270 (10) | |
O3 | 0.24209 (11) | 0.26156 (13) | 1.4501 (6) | 0.0452 (13) | |
O4 | 0.14922 (10) | 0.22217 (11) | 1.0221 (6) | 0.0380 (12) | |
H4A | 0.1359 | 0.2177 | 0.9311 | 0.046* | |
H4B | 0.1484 | 0.2372 | 1.0862 | 0.046* | |
O5 | 0.21484 (11) | 0.26883 (10) | 0.7888 (6) | 0.0380 (11) | |
H5A | 0.2364 | 0.2791 | 0.7510 | 0.046* | |
H5B | 0.2012 | 0.2604 | 0.6882 | 0.046* | |
N1 | 0.22883 (11) | 0.21479 (12) | 0.9458 (6) | 0.0214 (11) | |
C1 | 0.16729 (16) | 0.16270 (15) | 0.7572 (8) | 0.0277 (15) | |
C2 | 0.13990 (17) | 0.13477 (18) | 0.6774 (8) | 0.0374 (17) | |
H2 | 0.1214 | 0.1362 | 0.6404 | 0.045* | |
C3 | 0.14000 (19) | 0.10532 (17) | 0.6530 (9) | 0.0438 (19) | |
H3 | 0.1218 | 0.0873 | 0.5969 | 0.053* | |
C4 | 0.1666 (2) | 0.10199 (17) | 0.7100 (9) | 0.0433 (19) | |
H4 | 0.1663 | 0.0819 | 0.6935 | 0.052* | |
C5 | 0.19330 (18) | 0.12825 (16) | 0.7903 (8) | 0.0347 (17) | |
H5 | 0.2108 | 0.1255 | 0.8321 | 0.042* | |
C6 | 0.19551 (16) | 0.15991 (16) | 0.8131 (8) | 0.0284 (15) | |
C7 | 0.22537 (16) | 0.18693 (15) | 0.8888 (8) | 0.0271 (14) | |
H7 | 0.2439 | 0.1841 | 0.8975 | 0.033* | |
C8 | 0.26063 (14) | 0.24078 (14) | 1.0005 (8) | 0.0235 (13) | |
C9 | 0.28862 (16) | 0.24834 (16) | 0.8928 (9) | 0.0331 (16) | |
H9 | 0.2861 | 0.2362 | 0.7850 | 0.040* | |
C10 | 0.32002 (16) | 0.27355 (17) | 0.9435 (10) | 0.0416 (18) | |
H10 | 0.3385 | 0.2782 | 0.8708 | 0.050* | |
C11 | 0.32391 (16) | 0.29177 (17) | 1.1018 (10) | 0.0417 (18) | |
H11 | 0.3450 | 0.3086 | 1.1375 | 0.050* | |
C12 | 0.29639 (16) | 0.28499 (17) | 1.2072 (9) | 0.0363 (16) | |
H12 | 0.2993 | 0.2975 | 1.3136 | 0.044* | |
C13 | 0.26453 (15) | 0.26009 (15) | 1.1598 (8) | 0.0260 (14) | |
C14 | 0.23604 (16) | 0.25394 (15) | 1.2861 (8) | 0.0274 (14) | |
Cu2 | 0.125236 (18) | 0.237059 (19) | 0.53174 (10) | 0.0265 (2) | |
O6 | 0.10684 (10) | 0.20564 (11) | 0.7302 (5) | 0.0344 (11) | |
O7 | 0.13891 (10) | 0.25999 (10) | 0.2926 (5) | 0.0274 (10) | |
O8 | 0.13426 (14) | 0.28805 (15) | 0.0616 (6) | 0.0645 (17) | |
O9 | 0.15570 (10) | 0.22038 (11) | 0.4856 (6) | 0.0390 (12) | |
H9A | 0.1603 | 0.2095 | 0.5632 | 0.047* | |
H9B | 0.1700 | 0.2268 | 0.3992 | 0.047* | |
O10 | 0.16392 (12) | 0.28662 (14) | 0.7373 (6) | 0.0585 (15) | |
H10A | 0.1579 | 0.2912 | 0.8344 | 0.070* | |
H10B | 0.1857 | 0.2986 | 0.7308 | 0.070* | |
N2 | 0.09147 (12) | 0.24974 (13) | 0.5646 (6) | 0.0252 (12) | |
C15 | 0.07471 (16) | 0.18645 (16) | 0.7482 (8) | 0.0294 (15) | |
C16 | 0.06151 (19) | 0.15433 (17) | 0.8259 (8) | 0.0402 (18) | |
H16 | 0.0761 | 0.1469 | 0.8608 | 0.048* | |
C17 | 0.0279 (2) | 0.13366 (17) | 0.8517 (9) | 0.0436 (19) | |
H17 | 0.0202 | 0.1126 | 0.9030 | 0.052* | |
C18 | 0.0051 (2) | 0.14340 (18) | 0.8032 (9) | 0.047 (2) | |
H18 | −0.0176 | 0.1291 | 0.8219 | 0.057* | |
C19 | 0.01661 (15) | 0.17468 (17) | 0.7265 (8) | 0.0354 (17) | |
H19 | 0.0015 | 0.1816 | 0.6937 | 0.042* | |
C20 | 0.05135 (15) | 0.19640 (16) | 0.6975 (8) | 0.0276 (15) | |
C21 | 0.06180 (15) | 0.22910 (16) | 0.6232 (7) | 0.0255 (14) | |
H21 | 0.0459 | 0.2358 | 0.6170 | 0.031* | |
C22 | 0.09928 (15) | 0.28254 (15) | 0.5119 (8) | 0.0265 (14) | |
C23 | 0.08879 (17) | 0.30033 (18) | 0.6227 (10) | 0.0455 (19) | |
H23 | 0.0766 | 0.2906 | 0.7300 | 0.055* | |
C24 | 0.09639 (19) | 0.3322 (2) | 0.5743 (12) | 0.060 (2) | |
H24 | 0.0892 | 0.3439 | 0.6478 | 0.072* | |
C25 | 0.11456 (18) | 0.34640 (19) | 0.4175 (13) | 0.055 (2) | |
H25 | 0.1201 | 0.3680 | 0.3852 | 0.066* | |
C26 | 0.12476 (17) | 0.32898 (18) | 0.3072 (11) | 0.0458 (19) | |
H26 | 0.1365 | 0.3388 | 0.1989 | 0.055* | |
C27 | 0.11800 (14) | 0.29691 (15) | 0.3530 (8) | 0.0264 (14) | |
C28 | 0.13100 (15) | 0.28052 (16) | 0.2270 (8) | 0.0306 (15) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0258 (4) | 0.0341 (5) | 0.0223 (4) | 0.0202 (4) | −0.0012 (3) | −0.0043 (3) |
O1 | 0.040 (3) | 0.038 (3) | 0.024 (2) | 0.025 (2) | −0.009 (2) | −0.010 (2) |
O2 | 0.027 (2) | 0.034 (3) | 0.023 (2) | 0.017 (2) | 0.0033 (18) | −0.0045 (19) |
O3 | 0.037 (3) | 0.072 (4) | 0.027 (3) | 0.027 (3) | −0.005 (2) | −0.016 (2) |
O4 | 0.032 (3) | 0.059 (3) | 0.035 (3) | 0.032 (2) | −0.009 (2) | −0.016 (2) |
O5 | 0.038 (3) | 0.040 (3) | 0.030 (3) | 0.015 (2) | 0.001 (2) | 0.000 (2) |
N1 | 0.021 (3) | 0.026 (3) | 0.021 (3) | 0.015 (2) | 0.003 (2) | −0.002 (2) |
C1 | 0.039 (4) | 0.031 (4) | 0.012 (3) | 0.016 (3) | 0.006 (3) | −0.003 (3) |
C2 | 0.043 (4) | 0.049 (5) | 0.018 (3) | 0.021 (4) | −0.004 (3) | −0.005 (3) |
C3 | 0.046 (5) | 0.031 (4) | 0.034 (4) | 0.004 (4) | 0.002 (3) | −0.012 (3) |
C4 | 0.073 (6) | 0.024 (4) | 0.030 (4) | 0.023 (4) | 0.008 (4) | −0.002 (3) |
C5 | 0.062 (5) | 0.031 (4) | 0.025 (3) | 0.033 (4) | 0.012 (3) | 0.006 (3) |
C6 | 0.035 (4) | 0.035 (4) | 0.016 (3) | 0.019 (3) | 0.003 (3) | −0.002 (3) |
C7 | 0.033 (4) | 0.036 (4) | 0.020 (3) | 0.023 (3) | 0.006 (3) | 0.002 (3) |
C8 | 0.018 (3) | 0.026 (3) | 0.024 (3) | 0.009 (3) | 0.001 (3) | 0.003 (3) |
C9 | 0.033 (4) | 0.038 (4) | 0.033 (4) | 0.022 (3) | 0.007 (3) | 0.003 (3) |
C10 | 0.019 (4) | 0.042 (4) | 0.059 (5) | 0.011 (3) | 0.016 (3) | 0.005 (4) |
C11 | 0.023 (4) | 0.029 (4) | 0.062 (5) | 0.005 (3) | 0.000 (3) | −0.001 (4) |
C12 | 0.033 (4) | 0.041 (4) | 0.040 (4) | 0.021 (4) | −0.007 (3) | −0.013 (3) |
C13 | 0.031 (4) | 0.030 (4) | 0.022 (3) | 0.019 (3) | −0.001 (3) | 0.006 (3) |
C14 | 0.029 (4) | 0.025 (4) | 0.029 (4) | 0.015 (3) | −0.003 (3) | −0.001 (3) |
Cu2 | 0.0258 (4) | 0.0380 (5) | 0.0230 (4) | 0.0214 (4) | 0.0040 (3) | 0.0041 (3) |
O6 | 0.027 (3) | 0.057 (3) | 0.026 (2) | 0.025 (2) | 0.0041 (19) | 0.013 (2) |
O7 | 0.031 (2) | 0.033 (3) | 0.024 (2) | 0.020 (2) | 0.0059 (19) | 0.0051 (19) |
O8 | 0.092 (5) | 0.111 (5) | 0.032 (3) | 0.082 (4) | 0.021 (3) | 0.026 (3) |
O9 | 0.042 (3) | 0.067 (3) | 0.031 (3) | 0.044 (3) | 0.014 (2) | 0.018 (2) |
O10 | 0.052 (3) | 0.105 (5) | 0.032 (3) | 0.049 (3) | 0.014 (2) | 0.008 (3) |
N2 | 0.023 (3) | 0.035 (3) | 0.021 (3) | 0.018 (3) | 0.009 (2) | 0.002 (2) |
C15 | 0.033 (4) | 0.039 (4) | 0.016 (3) | 0.019 (3) | 0.004 (3) | −0.001 (3) |
C16 | 0.054 (5) | 0.040 (4) | 0.027 (4) | 0.023 (4) | 0.002 (3) | 0.007 (3) |
C17 | 0.057 (5) | 0.029 (4) | 0.031 (4) | 0.010 (4) | 0.009 (4) | 0.007 (3) |
C18 | 0.050 (5) | 0.040 (5) | 0.031 (4) | 0.007 (4) | 0.004 (4) | −0.009 (3) |
C19 | 0.023 (4) | 0.049 (5) | 0.019 (3) | 0.006 (3) | 0.002 (3) | −0.014 (3) |
C20 | 0.031 (4) | 0.041 (4) | 0.013 (3) | 0.020 (3) | 0.000 (3) | −0.004 (3) |
C21 | 0.026 (4) | 0.043 (4) | 0.017 (3) | 0.024 (3) | −0.001 (3) | −0.004 (3) |
C22 | 0.031 (4) | 0.028 (4) | 0.031 (4) | 0.023 (3) | −0.010 (3) | −0.010 (3) |
C23 | 0.040 (4) | 0.038 (5) | 0.052 (5) | 0.015 (4) | 0.011 (4) | −0.014 (4) |
C24 | 0.051 (5) | 0.046 (5) | 0.089 (7) | 0.028 (4) | 0.008 (5) | −0.023 (5) |
C25 | 0.038 (5) | 0.031 (4) | 0.103 (7) | 0.022 (4) | 0.005 (5) | 0.004 (4) |
C26 | 0.034 (4) | 0.043 (5) | 0.057 (5) | 0.017 (4) | 0.012 (4) | 0.015 (4) |
C27 | 0.018 (3) | 0.031 (4) | 0.032 (3) | 0.014 (3) | 0.003 (3) | 0.003 (3) |
C28 | 0.027 (4) | 0.039 (4) | 0.025 (4) | 0.016 (3) | 0.009 (3) | 0.009 (3) |
Cu1—O1 | 1.919 (4) | Cu2—O6 | 1.909 (4) |
Cu1—N1 | 1.952 (4) | Cu2—N2 | 1.938 (5) |
Cu1—O2 | 1.957 (4) | Cu2—O9 | 1.944 (4) |
Cu1—O4 | 1.967 (4) | Cu2—O7 | 1.955 (4) |
Cu1—O5 | 2.290 (4) | Cu2—O10 | 2.559 (5) |
Cu1—Cu2 | 4.674 (1) | O6—C15 | 1.302 (7) |
O1—C1 | 1.325 (7) | O7—C28 | 1.267 (7) |
O2—C14 | 1.288 (7) | O8—C28 | 1.229 (7) |
O3—C14 | 1.225 (7) | O9—H9A | 0.8480 |
O4—H4A | 0.8505 | O9—H9B | 0.8458 |
O4—H4B | 0.8536 | O10—H10A | 0.8187 |
O5—H5A | 0.9042 | O10—H10B | 0.8742 |
O5—H5B | 0.9097 | N2—C21 | 1.290 (7) |
N1—C7 | 1.284 (7) | N2—C22 | 1.424 (7) |
N1—C8 | 1.413 (7) | C15—C16 | 1.410 (9) |
C1—C2 | 1.403 (9) | C15—C20 | 1.418 (8) |
C1—C6 | 1.433 (9) | C16—C17 | 1.372 (10) |
C2—C3 | 1.376 (9) | C16—H16 | 0.9300 |
C2—H2 | 0.9300 | C17—C18 | 1.382 (10) |
C3—C4 | 1.379 (10) | C17—H17 | 0.9300 |
C3—H3 | 0.9300 | C18—C19 | 1.383 (9) |
C4—C5 | 1.354 (9) | C18—H18 | 0.9300 |
C4—H4 | 0.9300 | C19—C20 | 1.422 (8) |
C5—C6 | 1.426 (8) | C19—H19 | 0.9300 |
C5—H5 | 0.9300 | C20—C21 | 1.442 (8) |
C6—C7 | 1.429 (9) | C21—H21 | 0.9300 |
C7—H7 | 0.9300 | C22—C27 | 1.388 (8) |
C8—C9 | 1.396 (8) | C22—C23 | 1.396 (8) |
C8—C13 | 1.409 (8) | C23—C24 | 1.379 (10) |
C9—C10 | 1.382 (9) | C23—H23 | 0.9300 |
C9—H9 | 0.9300 | C24—C25 | 1.364 (11) |
C10—C11 | 1.376 (9) | C24—H24 | 0.9300 |
C10—H10 | 0.9300 | C25—C26 | 1.373 (10) |
C11—C12 | 1.377 (9) | C25—H25 | 0.9300 |
C11—H11 | 0.9300 | C26—C27 | 1.394 (9) |
C12—C13 | 1.385 (8) | C26—H26 | 0.9300 |
C12—H12 | 0.9300 | C27—C28 | 1.489 (8) |
C13—C14 | 1.507 (8) | ||
O1—Cu1—N1 | 91.36 (18) | O6—Cu2—N2 | 91.10 (19) |
O1—Cu1—O2 | 163.21 (18) | O6—Cu2—O9 | 87.79 (17) |
N1—Cu1—O2 | 90.52 (18) | N2—Cu2—O9 | 174.2 (2) |
O1—Cu1—O4 | 87.33 (18) | O6—Cu2—O7 | 166.71 (19) |
N1—Cu1—O4 | 170.10 (19) | N2—Cu2—O7 | 91.97 (18) |
O2—Cu1—O4 | 87.96 (17) | O9—Cu2—O7 | 87.86 (17) |
O1—Cu1—O5 | 95.59 (17) | O6—Cu2—O10 | 95.44 (17) |
N1—Cu1—O5 | 93.28 (18) | N2—Cu2—O10 | 88.08 (18) |
O2—Cu1—O5 | 100.96 (16) | O9—Cu2—O10 | 97.68 (17) |
O4—Cu1—O5 | 96.62 (17) | O7—Cu2—O10 | 97.59 (16) |
C1—O1—Cu1 | 121.6 (4) | C15—O6—Cu2 | 121.1 (4) |
C14—O2—Cu1 | 128.1 (4) | C28—O7—Cu2 | 126.8 (4) |
Cu1—O4—H4A | 116.5 | Cu2—O9—H9A | 124.7 |
Cu1—O4—H4B | 123.4 | Cu2—O9—H9B | 125.3 |
H4A—O4—H4B | 107.0 | H9A—O9—H9B | 108.2 |
Cu1—O5—H5A | 123.6 | Cu2—O10—H10A | 123.4 |
Cu1—O5—H5B | 98.6 | Cu2—O10—H10B | 127.2 |
H5A—O5—H5B | 109.2 | H10A—O10—H10B | 108.3 |
C7—N1—C8 | 119.8 (5) | C21—N2—C22 | 119.0 (5) |
C7—N1—Cu1 | 122.0 (4) | C21—N2—Cu2 | 122.4 (4) |
C8—N1—Cu1 | 118.1 (4) | C22—N2—Cu2 | 118.5 (4) |
O1—C1—C2 | 120.7 (6) | O6—C15—C16 | 120.2 (6) |
O1—C1—C6 | 120.8 (5) | O6—C15—C20 | 123.3 (6) |
C2—C1—C6 | 118.4 (6) | C16—C15—C20 | 116.5 (6) |
C3—C2—C1 | 121.0 (7) | C17—C16—C15 | 122.1 (7) |
C3—C2—H2 | 119.5 | C17—C16—H16 | 119.0 |
C1—C2—H2 | 119.5 | C15—C16—H16 | 119.0 |
C2—C3—C4 | 121.2 (6) | C16—C17—C18 | 121.5 (7) |
C2—C3—H3 | 119.4 | C16—C17—H17 | 119.2 |
C4—C3—H3 | 119.4 | C18—C17—H17 | 119.2 |
C5—C4—C3 | 119.4 (7) | C17—C18—C19 | 119.0 (7) |
C5—C4—H4 | 120.3 | C17—C18—H18 | 120.5 |
C3—C4—H4 | 120.3 | C19—C18—H18 | 120.5 |
C4—C5—C6 | 122.4 (7) | C18—C19—C20 | 120.4 (7) |
C4—C5—H5 | 118.8 | C18—C19—H19 | 119.8 |
C6—C5—H5 | 118.8 | C20—C19—H19 | 119.8 |
C5—C6—C7 | 119.0 (6) | C15—C20—C19 | 120.6 (6) |
C5—C6—C1 | 117.4 (6) | C15—C20—C21 | 121.8 (6) |
C7—C6—C1 | 123.7 (6) | C19—C20—C21 | 117.6 (6) |
N1—C7—C6 | 125.5 (6) | N2—C21—C20 | 124.9 (5) |
N1—C7—H7 | 117.2 | N2—C21—H21 | 117.5 |
C6—C7—H7 | 117.2 | C20—C21—H21 | 117.5 |
C9—C8—C13 | 119.0 (6) | C27—C22—C23 | 120.4 (6) |
C9—C8—N1 | 119.9 (5) | C27—C22—N2 | 119.7 (5) |
C13—C8—N1 | 121.0 (5) | C23—C22—N2 | 119.9 (6) |
C10—C9—C8 | 121.1 (6) | C24—C23—C22 | 120.6 (7) |
C10—C9—H9 | 119.4 | C24—C23—H23 | 119.7 |
C8—C9—H9 | 119.4 | C22—C23—H23 | 119.7 |
C11—C10—C9 | 119.8 (6) | C25—C24—C23 | 119.4 (7) |
C11—C10—H10 | 120.1 | C25—C24—H24 | 120.3 |
C9—C10—H10 | 120.1 | C23—C24—H24 | 120.3 |
C10—C11—C12 | 119.7 (6) | C24—C25—C26 | 120.4 (7) |
C10—C11—H11 | 120.2 | C24—C25—H25 | 119.8 |
C12—C11—H11 | 120.2 | C26—C25—H25 | 119.8 |
C11—C12—C13 | 122.1 (6) | C25—C26—C27 | 121.9 (7) |
C11—C12—H12 | 118.9 | C25—C26—H26 | 119.1 |
C13—C12—H12 | 118.9 | C27—C26—H26 | 119.1 |
C12—C13—C8 | 118.3 (6) | C22—C27—C26 | 117.3 (6) |
C12—C13—C14 | 118.3 (5) | C22—C27—C28 | 125.0 (5) |
C8—C13—C14 | 123.3 (5) | C26—C27—C28 | 117.7 (6) |
O3—C14—O2 | 122.5 (6) | O8—C28—O7 | 122.2 (6) |
O3—C14—C13 | 118.4 (6) | O8—C28—C27 | 118.0 (6) |
O2—C14—C13 | 119.0 (5) | O7—C28—C27 | 119.7 (5) |
N1—Cu1—O1—C1 | 42.3 (4) | N2—Cu2—O6—C15 | 42.2 (5) |
O2—Cu1—O1—C1 | −54.0 (8) | O9—Cu2—O6—C15 | −132.1 (5) |
O4—Cu1—O1—C1 | −127.8 (4) | O7—Cu2—O6—C15 | −61.1 (9) |
O5—Cu1—O1—C1 | 135.8 (4) | O10—Cu2—O6—C15 | 130.4 (4) |
O1—Cu1—O2—C14 | 116.5 (7) | O6—Cu2—O7—C28 | 116.2 (8) |
N1—Cu1—O2—C14 | 20.0 (5) | N2—Cu2—O7—C28 | 12.9 (5) |
O4—Cu1—O2—C14 | −169.8 (5) | O9—Cu2—O7—C28 | −172.9 (5) |
O5—Cu1—O2—C14 | −73.4 (5) | O10—Cu2—O7—C28 | −75.4 (5) |
O1—Cu1—N1—C7 | −30.0 (5) | O6—Cu2—N2—C21 | −31.0 (5) |
O2—Cu1—N1—C7 | 133.3 (5) | O7—Cu2—N2—C21 | 136.1 (5) |
O5—Cu1—N1—C7 | −125.7 (5) | O10—Cu2—N2—C21 | −126.4 (5) |
O1—Cu1—N1—C8 | 152.9 (4) | O6—Cu2—N2—C22 | 152.6 (4) |
O2—Cu1—N1—C8 | −43.8 (4) | O7—Cu2—N2—C22 | −40.3 (4) |
O5—Cu1—N1—C8 | 57.2 (4) | O10—Cu2—N2—C22 | 57.2 (4) |
Cu1—O1—C1—C2 | 149.6 (4) | Cu2—O6—C15—C16 | 148.9 (5) |
Cu1—O1—C1—C6 | −33.6 (7) | Cu2—O6—C15—C20 | −32.9 (7) |
O1—C1—C2—C3 | 176.9 (6) | O6—C15—C16—C17 | 178.3 (6) |
C6—C1—C2—C3 | 0.0 (9) | C20—C15—C16—C17 | −0.1 (9) |
C1—C2—C3—C4 | 1.6 (10) | C15—C16—C17—C18 | −0.3 (10) |
C2—C3—C4—C5 | −0.5 (10) | C16—C17—C18—C19 | 0.2 (10) |
C3—C4—C5—C6 | −2.1 (10) | C17—C18—C19—C20 | 0.2 (9) |
C4—C5—C6—C7 | −176.2 (6) | O6—C15—C20—C19 | −177.9 (5) |
C4—C5—C6—C1 | 3.6 (9) | C16—C15—C20—C19 | 0.5 (8) |
O1—C1—C6—C5 | −179.3 (5) | O6—C15—C20—C21 | −0.7 (9) |
C2—C1—C6—C5 | −2.4 (8) | C16—C15—C20—C21 | 177.6 (5) |
O1—C1—C6—C7 | 0.4 (9) | C18—C19—C20—C15 | −0.6 (9) |
C2—C1—C6—C7 | 177.3 (6) | C18—C19—C20—C21 | −177.8 (6) |
C8—N1—C7—C6 | −173.7 (5) | C22—N2—C21—C20 | −173.7 (5) |
Cu1—N1—C7—C6 | 9.3 (8) | Cu2—N2—C21—C20 | 9.9 (8) |
C5—C6—C7—N1 | −167.6 (6) | C15—C20—C21—N2 | 13.2 (9) |
C1—C6—C7—N1 | 12.7 (9) | C19—C20—C21—N2 | −169.6 (5) |
C7—N1—C8—C9 | 44.1 (8) | C21—N2—C22—C27 | −137.8 (6) |
Cu1—N1—C8—C9 | −138.7 (5) | Cu2—N2—C22—C27 | 38.8 (7) |
C7—N1—C8—C13 | −138.0 (6) | C21—N2—C22—C23 | 43.8 (8) |
Cu1—N1—C8—C13 | 39.1 (7) | Cu2—N2—C22—C23 | −139.7 (5) |
C13—C8—C9—C10 | 2.3 (9) | C27—C22—C23—C24 | 1.0 (10) |
N1—C8—C9—C10 | −179.8 (6) | N2—C22—C23—C24 | 179.5 (6) |
C8—C9—C10—C11 | −0.5 (11) | C22—C23—C24—C25 | −0.5 (12) |
C9—C10—C11—C12 | −0.8 (11) | C23—C24—C25—C26 | 1.0 (12) |
C10—C11—C12—C13 | 0.3 (11) | C24—C25—C26—C27 | −2.0 (12) |
C11—C12—C13—C8 | 1.5 (10) | C23—C22—C27—C26 | −1.9 (9) |
C11—C12—C13—C14 | 178.5 (6) | N2—C22—C27—C26 | 179.6 (6) |
C9—C8—C13—C12 | −2.8 (9) | C23—C22—C27—C28 | 178.8 (6) |
N1—C8—C13—C12 | 179.4 (5) | N2—C22—C27—C28 | 0.4 (9) |
C9—C8—C13—C14 | −179.7 (5) | C25—C26—C27—C22 | 2.5 (10) |
N1—C8—C13—C14 | 2.5 (9) | C25—C26—C27—C28 | −178.3 (6) |
Cu1—O2—C14—O3 | −170.2 (5) | Cu2—O7—C28—O8 | −163.3 (5) |
Cu1—O2—C14—C13 | 11.4 (8) | Cu2—O7—C28—C27 | 18.1 (8) |
C12—C13—C14—O3 | −25.6 (9) | C22—C27—C28—O8 | 149.7 (7) |
C8—C13—C14—O3 | 151.3 (6) | C26—C27—C28—O8 | −29.5 (9) |
C12—C13—C14—O2 | 152.9 (6) | C22—C27—C28—O7 | −31.7 (9) |
C8—C13—C14—O2 | −30.2 (9) | C26—C27—C28—O7 | 149.1 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
O10—H10B···O5 | 0.87 | 2.40 | 2.882 (7) | 115 |
O10—H10A···O8i | 0.82 | 1.93 | 2.727 (6) | 163 |
O9—H9B···O2ii | 0.85 | 1.97 | 2.813 (5) | 174 |
O9—H9A···O1 | 0.85 | 1.84 | 2.667 (6) | 166 |
O5—H5A···O3ii | 0.90 | 2.37 | 2.842 (6) | 112 |
O4—H4B···O7i | 0.85 | 1.99 | 2.814 (6) | 161 |
O4—H4A···O6 | 0.85 | 1.86 | 2.711 (6) | 177 |
C23—H23···Cg3iii | 0.93 | 2.87 | 3.618 (9) | 139 |
Symmetry codes: (i) x, y, z+1; (ii) x, y, z−1; (iii) x−y, x, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C14H9NO3)(H2O)2] |
Mr | 338.81 |
Crystal system, space group | Trigonal, R3 |
Temperature (K) | 298 |
a, c (Å) | 46.263 (2), 7.2030 (7) |
V (Å3) | 13350.9 (15) |
Z | 36 |
Radiation type | Mo Kα |
µ (mm−1) | 1.49 |
Crystal size (mm) | 0.24 × 0.09 × 0.01 |
Data collection | |
Diffractometer | Bruker SMART 1K CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2000) |
Tmin, Tmax | 0.715, 0.985 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5220, 5220, 3659 |
Rint | 0.000 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.072, 0.160, 1.04 |
No. of reflections | 5220 |
No. of parameters | 379 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.63, −0.61 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Sheldrick, 1999), SHELXTL/PC.
Cu1—O1 | 1.919 (4) | Cu2—O6 | 1.909 (4) |
Cu1—N1 | 1.952 (4) | Cu2—N2 | 1.938 (5) |
Cu1—O2 | 1.957 (4) | Cu2—O9 | 1.944 (4) |
Cu1—O4 | 1.967 (4) | Cu2—O7 | 1.955 (4) |
Cu1—O5 | 2.290 (4) | Cu2—O10 | 2.559 (5) |
Cu1—Cu2 | 4.674 (1) | ||
O1—Cu1—N1 | 91.36 (18) | O6—Cu2—N2 | 91.10 (19) |
O1—Cu1—O2 | 163.21 (18) | O6—Cu2—O9 | 87.79 (17) |
N1—Cu1—O2 | 90.52 (18) | N2—Cu2—O9 | 174.2 (2) |
O1—Cu1—O4 | 87.33 (18) | O6—Cu2—O7 | 166.71 (19) |
N1—Cu1—O4 | 170.10 (19) | N2—Cu2—O7 | 91.97 (18) |
O2—Cu1—O4 | 87.96 (17) | O9—Cu2—O7 | 87.86 (17) |
O1—Cu1—O5 | 95.59 (17) | O6—Cu2—O10 | 95.44 (17) |
N1—Cu1—O5 | 93.28 (18) | N2—Cu2—O10 | 88.08 (18) |
O2—Cu1—O5 | 100.96 (16) | O9—Cu2—O10 | 97.68 (17) |
O4—Cu1—O5 | 96.62 (17) | O7—Cu2—O10 | 97.59 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
O10—H10B···O5 | 0.87 | 2.40 | 2.882 (7) | 115 |
O10—H10A···O8i | 0.82 | 1.93 | 2.727 (6) | 163 |
O9—H9B···O2ii | 0.85 | 1.97 | 2.813 (5) | 174 |
O9—H9A···O1 | 0.85 | 1.84 | 2.667 (6) | 166 |
O5—H5A···O3ii | 0.90 | 2.37 | 2.842 (6) | 112 |
O4—H4B···O7i | 0.85 | 1.99 | 2.814 (6) | 161 |
O4—H4A···O6 | 0.85 | 1.86 | 2.711 (6) | 177 |
C23—H23···Cg3iii | 0.93 | 2.87 | 3.618 (9) | 139 |
Symmetry codes: (i) x, y, z+1; (ii) x, y, z−1; (iii) x−y, x, −z+2. |
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(E)-2-(2-Hydroxybenzylideneamino)benzoic acid is a tridentate ligand, many of whose metal complexes have been studied (Clague et al., 1993; Asgedom et al., 1997; Dey et al., 1999; Redshaw & Elsegood, 2001; Rosair et al., 2002; Shan et al., 2003). As the result of our interest in Schiff base metal complexes as model compounds for the study of the active sites of metalloenzymes, we have investigated the title compound, (I), and we report here its structure.
Compound (I) (Fig. 1) crystallizes with Z = 18 in space group R3, and consists of two independent Cu(C14H9NO3) complexes. In each complex, the Cu atom is coordinated by one N atom and four O atoms from two water molecules and one E-2-(2-hydroxybenzylideneamino)benzoic acid molecule, adopting square-pyramidal geometry, similar to that in [Cu(C14H9NO3)(C5H5N)2]·H2O (Li et al.,1995) but n contrast to [Cu(C14H9NO3)(C3H4N2)], in which the Cu atom is four-coordinate with a square geometry (Gao et al., 2000). Although the two complexes have the same coordination spheres, the corresponding bonds around atoms Cu1 and Cu2 are significantly different (Table 1), especially the Cu—O distances between the Cu atom and the apical water ligands. The two aryl rings in each complex make dihedral angles of 58.7 (2) and 58.4 (2)°, respectively. The two complexes are connected to each other by three strong O—H···O hydrogen bonds to form a dimer in which the Cu···Cu distance is 4.674 (1) Å.
The supramolecular interactions (Table 2) are illustrated in Figs. 2 and 3. Four intermolecular O—H···O hydrogen bonds, with two coordinated water molecules as hydrogen-bond donors and two carboxyl O atoms of the ligand as acceptors, link the dimers to one-dimensional chains along the c axis (Fig. 2). Because of the relatively strong intermolecular hydrogen bonding, neighbouring dimers are connected closely, the Cu1···Cu2(x, y, 1 + z) separation being 5.304 (1) Å, leaving atoms Cu1 and Cu2 arranged in a zigzag shape in the chains. Six such chains, related to each other by a rotation of 60° in the (001) plane, are connected through π–πstacking interactions between the C1–C6 and C15–C20 aryl rings, with Cg1···Cg2(y, −x + y, 1 − z) (Cg1 is the centroid of the C1–C6 ring and Cg2 is the centroid of the C15—C20 ring), Cg1···Cg2(y, −x + y, 2 − z), Cg2···Cg1(x-y, x, 1 − z) and Cg2···Cg1(x-y, x, 2 − z) distances of 3.677 (3), 3.548 (3), 3.677 (4) and 3.548 (4) Å, and interplanar spacings of 3.250, 3.263, 3.279 and 3.302 Å, respectively, assembling the six chains into a tube (Fig. 3). Additionally, a C—H···π interaction (Fig. 3a) between the C23/H23 group and the C9–C13 aryl ring (centroid Cg3) in a neighbouring chain, with a C23···Cg3(x − y, x, 2 − z) separation of 3.618 (9) Å, also takes part in the stabilization of the tubes.
Large voids in the structure were examined using PLATON (Spek, 2003). In the three-dimensional structure of (I), there are three channels along the c axis (Fig. 3), accounting in total for 1518.3 Å3 per unit cell, i.e. some 11.4% of the total volume. The channels lie along a threefold inversion centre with an average cross-sectional area of ca 70.6 Å2 and an average diameter of ca 9.5 Å. The channels in (I) appear to be occupied by water molecules; their behaviour is intractable, possibly due to dynamic disorder.