Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803012236/ob6257sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803012236/ob6257Isup2.hkl |
CCDC reference: 217365
Methanolic solution of potassium ((2-(2-hydroxyphenyl)ethylidene)amino)acetate (Dakternieks et al., 1998) was added dropwise to the stirred aqueous solution of Cu(OAc)2·H2O containing few drops of acetic acid (1:1). The filtered solution upon slow evaporation afforded green crystals of the title compound (I). M.p. 520 (1) K, analysis found: C 41.27, H. 4.47, N 4.80%; calc. for C10H13NO5Cu: C 41.31, H. 4.51, N 4.82%; IR (KBr): 1630 ν(OCO), 1599 ν(C=N), 1237 ν[Ph(C=O)].
All H atoms attached to C were geometrically fixed with C—H 0.93–0.97 Å. Though the H atoms attached to the O1W were calculated and isotropically refined with OW—H 0.84 (6)–1.02 (7) Å, those attached to the O2W were located from difference maps with OW—H 1.04 Å and treated as riding atoms.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).
C10H11CuNO4·H2O | F(000) = 1192 |
Mr = 290.75 | Dx = 1.759 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 20.2250 (3) Å | Cell parameters from 3297 reflections |
b = 10.6741 (3) Å | θ = 2.8–28.3° |
c = 14.2089 (3) Å | µ = 2.00 mm−1 |
β = 134.294 (1)° | T = 293 K |
V = 2195.59 (9) Å3 | Block, green |
Z = 8 | 0.20 × 0.12 × 0.10 mm |
Siemens SMART CCD area detector diffractometer | 2718 independent reflections |
Radiation source: fine-focus sealed tube | 1739 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.080 |
Detector resolution: 8.33 pixels mm-1 | θmax = 28.3°, θmin = 2.8° |
ω scans | h = −26→20 |
Absorption correction: empirical (using intensity measurements) SADABS (Sheldrick, 1996) | k = −12→14 |
Tmin = 0.691, Tmax = 0.825 | l = −14→18 |
7657 measured reflections |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.95 | w = 1/[σ2(Fo2) + (0.0475P)2] where P = (Fo2 + 2Fc2)/3 |
2718 reflections | (Δ/σ)max < 0.001 |
163 parameters | Δρmax = 0.97 e Å−3 |
0 restraints | Δρmin = −0.73 e Å−3 |
C10H11CuNO4·H2O | V = 2195.59 (9) Å3 |
Mr = 290.75 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 20.2250 (3) Å | µ = 2.00 mm−1 |
b = 10.6741 (3) Å | T = 293 K |
c = 14.2089 (3) Å | 0.20 × 0.12 × 0.10 mm |
β = 134.294 (1)° |
Siemens SMART CCD area detector diffractometer | 2718 independent reflections |
Absorption correction: empirical (using intensity measurements) SADABS (Sheldrick, 1996) | 1739 reflections with I > 2σ(I) |
Tmin = 0.691, Tmax = 0.825 | Rint = 0.080 |
7657 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.123 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.95 | Δρmax = 0.97 e Å−3 |
2718 reflections | Δρmin = −0.73 e Å−3 |
163 parameters |
Experimental. The data collection covered over a hemisphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle (0, 88 and 180°) for the crystal and each exposure of 30 s covered 0.3° in ω. The crystal-to-detector distance was 5 cm and the detector swing angle was −35°. Crystal decay was monitored by repeating fifty initial frames at the end of data collection and analysing the intensity of duplicate reflections, and was found to be negligible. |
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 | 0.07427 (3) | 0.63653 (4) | 0.42731 (5) | 0.02928 (17) | |
O1 | 0.1025 (2) | 0.6112 (3) | 0.3276 (3) | 0.0410 (8) | |
O2 | 0.0380 (2) | 0.8136 (3) | 0.6311 (3) | 0.0516 (9) | |
O3 | 0.04290 (19) | 0.6636 (3) | 0.5279 (3) | 0.0346 (7) | |
N1 | 0.0922 (2) | 0.8160 (3) | 0.4386 (3) | 0.0265 (7) | |
C1 | 0.1412 (3) | 0.6939 (4) | 0.3098 (4) | 0.0289 (9) | |
C2 | 0.1670 (3) | 0.6498 (4) | 0.2452 (4) | 0.0357 (10) | |
H2 | 0.1556 | 0.5667 | 0.2181 | 0.043* | |
C3 | 0.2083 (3) | 0.7265 (5) | 0.2216 (4) | 0.0412 (11) | |
H3 | 0.2249 | 0.6948 | 0.1796 | 0.049* | |
C4 | 0.2253 (3) | 0.8505 (5) | 0.2595 (4) | 0.0443 (11) | |
H4 | 0.2542 | 0.9020 | 0.2444 | 0.053* | |
C5 | 0.1995 (3) | 0.8972 (4) | 0.3194 (4) | 0.0373 (10) | |
H5 | 0.2114 | 0.9810 | 0.3445 | 0.045* | |
C6 | 0.1552 (3) | 0.8223 (4) | 0.3447 (4) | 0.0271 (8) | |
C7 | 0.1258 (3) | 0.8819 (4) | 0.4035 (4) | 0.0267 (8) | |
C8 | 0.0653 (3) | 0.8751 (4) | 0.5011 (4) | 0.0323 (9) | |
H8A | 0.0099 | 0.9247 | 0.4365 | 0.039* | |
H8B | 0.1141 | 0.9310 | 0.5703 | 0.039* | |
C9 | 0.0474 (3) | 0.7781 (4) | 0.5588 (4) | 0.0318 (9) | |
C10 | 0.1340 (4) | 1.0211 (4) | 0.4199 (5) | 0.0505 (12) | |
H10A | 0.0939 | 1.0505 | 0.4291 | 0.076* | |
H10B | 0.1167 | 1.0593 | 0.3441 | 0.076* | |
H10C | 0.1967 | 1.0430 | 0.4969 | 0.076* | |
O1W | 0.0698 (3) | 0.4558 (3) | 0.4463 (3) | 0.0436 (8) | |
H1W1 | 0.092 (4) | 0.402 (7) | 0.414 (6) | 0.10 (2)* | |
H2W1 | 0.039 (3) | 0.413 (5) | 0.454 (5) | 0.056 (16)* | |
O2W | 0.1302 (3) | 0.3495 (4) | 0.3495 (4) | 0.0805 (13) | |
H2W2 | 0.0958 | 0.2798 | 0.2778 | 0.121* | |
H1W2 | 0.1822 | 0.3018 | 0.4368 | 0.121* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0418 (3) | 0.0246 (3) | 0.0375 (3) | −0.0046 (2) | 0.0335 (3) | −0.0033 (2) |
O1 | 0.0608 (19) | 0.0301 (17) | 0.064 (2) | −0.0155 (14) | 0.0549 (18) | −0.0160 (14) |
O2 | 0.091 (2) | 0.0433 (19) | 0.061 (2) | 0.0008 (18) | 0.068 (2) | −0.0024 (16) |
O3 | 0.0496 (16) | 0.0288 (16) | 0.0478 (18) | −0.0084 (13) | 0.0423 (15) | −0.0050 (13) |
N1 | 0.0338 (18) | 0.0275 (17) | 0.0298 (18) | −0.0002 (13) | 0.0265 (16) | −0.0012 (14) |
C1 | 0.029 (2) | 0.033 (2) | 0.029 (2) | −0.0019 (17) | 0.0217 (18) | 0.0027 (17) |
C2 | 0.042 (2) | 0.038 (3) | 0.042 (2) | 0.0004 (19) | 0.035 (2) | −0.005 (2) |
C3 | 0.045 (3) | 0.054 (3) | 0.043 (3) | 0.002 (2) | 0.037 (2) | 0.002 (2) |
C4 | 0.050 (3) | 0.054 (3) | 0.051 (3) | 0.000 (2) | 0.043 (2) | 0.008 (2) |
C5 | 0.046 (2) | 0.036 (2) | 0.043 (3) | −0.0058 (19) | 0.036 (2) | 0.0009 (19) |
C6 | 0.032 (2) | 0.030 (2) | 0.025 (2) | 0.0003 (16) | 0.0220 (18) | 0.0028 (16) |
C7 | 0.031 (2) | 0.027 (2) | 0.0268 (19) | −0.0016 (15) | 0.0217 (17) | 0.0008 (16) |
C8 | 0.047 (2) | 0.024 (2) | 0.040 (2) | −0.0006 (17) | 0.036 (2) | −0.0014 (18) |
C9 | 0.037 (2) | 0.035 (2) | 0.035 (2) | −0.0008 (18) | 0.029 (2) | −0.0001 (18) |
C10 | 0.082 (3) | 0.027 (2) | 0.065 (3) | −0.001 (2) | 0.059 (3) | 0.002 (2) |
O1W | 0.072 (2) | 0.0278 (17) | 0.059 (2) | −0.0065 (16) | 0.056 (2) | −0.0011 (14) |
O2W | 0.111 (3) | 0.067 (3) | 0.093 (3) | 0.001 (2) | 0.082 (3) | −0.009 (2) |
Cu1—O1 | 1.881 (3) | C4—C5 | 1.366 (6) |
Cu1—N1 | 1.936 (3) | C4—H4 | 0.9300 |
Cu1—O3 | 1.948 (3) | C5—C6 | 1.422 (6) |
Cu1—O1W | 1.959 (3) | C5—H5 | 0.9300 |
Cu1—O1i | 2.809 (3) | C6—C7 | 1.466 (5) |
O1—C1 | 1.317 (5) | C7—C10 | 1.495 (6) |
O2—C9 | 1.228 (5) | C8—C9 | 1.514 (6) |
O3—C9 | 1.280 (5) | C8—H8A | 0.9700 |
N1—C7 | 1.296 (5) | C8—H8B | 0.9700 |
N1—C8 | 1.469 (5) | C10—H10A | 0.9600 |
C1—C2 | 1.416 (5) | C10—H10B | 0.9600 |
C1—C6 | 1.418 (5) | C10—H10C | 0.9600 |
C2—C3 | 1.367 (6) | O1W—H1W1 | 1.02 (7) |
C2—H2 | 0.9300 | O1W—H2W1 | 0.84 (6) |
C3—C4 | 1.379 (6) | O2W—H2W2 | 1.0425 |
C3—H3 | 0.9300 | O2W—H1W2 | 1.0401 |
O1—Cu1—N1 | 93.9 (1) | C4—C5—H5 | 118.8 |
O1—Cu1—O3 | 179.0 (1) | C6—C5—H5 | 118.8 |
N1—Cu1—O3 | 86.0 (1) | C1—C6—C5 | 117.5 (4) |
O1—Cu1—O1W | 91.7 (1) | C1—C6—C7 | 123.9 (3) |
N1—Cu1—O1W | 170.9 (1) | C5—C6—C7 | 118.6 (4) |
O3—Cu1—O1W | 88.6 (1) | N1—C7—C6 | 120.9 (4) |
O1—Cu1—O1i | 78.3 (1) | N1—C7—C10 | 120.7 (4) |
N1—Cu1—O1i | 101.4 (2) | C6—C7—C10 | 118.4 (3) |
O3—Cu1—O1i | 100.8 (2) | N1—C8—C9 | 111.3 (3) |
O1W—Cu1—O1i | 86.7 (1) | N1—C8—H8A | 109.4 |
C1—O1—Cu1 | 125.6 (3) | C9—C8—H8A | 109.4 |
C9—O3—Cu1 | 114.4 (2) | N1—C8—H8B | 109.4 |
C7—N1—C8 | 121.0 (3) | C9—C8—H8B | 109.4 |
C7—N1—Cu1 | 128.6 (3) | H8A—C8—H8B | 108.0 |
C8—N1—Cu1 | 110.4 (2) | O2—C9—O3 | 124.5 (4) |
O1—C1—C2 | 116.1 (4) | O2—C9—C8 | 118.5 (4) |
O1—C1—C6 | 125.5 (4) | O3—C9—C8 | 117.0 (4) |
C2—C1—C6 | 118.3 (3) | C7—C10—H10A | 109.5 |
C3—C2—C1 | 121.6 (4) | C7—C10—H10B | 109.5 |
C3—C2—H2 | 119.2 | H10A—C10—H10B | 109.5 |
C1—C2—H2 | 119.2 | C7—C10—H10C | 109.5 |
C2—C3—C4 | 120.6 (4) | H10A—C10—H10C | 109.5 |
C2—C3—H3 | 119.7 | H10B—C10—H10C | 109.5 |
C4—C3—H3 | 119.7 | Cu1—O1W—H1W1 | 115 (4) |
C5—C4—C3 | 119.5 (4) | Cu1—O1W—H2W1 | 131 (4) |
C5—C4—H4 | 120.2 | H1W1—O1W—H2W1 | 111 (5) |
C3—C4—H4 | 120.2 | H2W2—O2W—H1W2 | 104.2 |
C4—C5—C6 | 122.3 (4) | ||
N1—Cu1—O1—C1 | 13.4 (3) | C2—C1—C6—C7 | 175.6 (4) |
O1W—Cu1—O1—C1 | −159.4 (3) | C4—C5—C6—C1 | 2.3 (6) |
N1—Cu1—O3—C9 | −0.6 (3) | C4—C5—C6—C7 | −177.0 (4) |
O1W—Cu1—O3—C9 | 172.1 (3) | C8—N1—C7—C6 | 178.2 (3) |
O1—Cu1—N1—C7 | −8.9 (3) | Cu1—N1—C7—C6 | 0.9 (5) |
O3—Cu1—N1—C7 | 172.1 (3) | C8—N1—C7—C10 | −2.9 (6) |
O1—Cu1—N1—C8 | 173.6 (3) | Cu1—N1—C7—C10 | 179.8 (3) |
O3—Cu1—N1—C8 | −5.4 (3) | C1—C6—C7—N1 | 6.5 (6) |
Cu1—O1—C1—C2 | 172.2 (3) | C5—C6—C7—N1 | −174.2 (4) |
Cu1—O1—C1—C6 | −10.6 (6) | C1—C6—C7—C10 | −172.4 (4) |
O1—C1—C2—C3 | −179.7 (4) | C5—C6—C7—C10 | 6.9 (5) |
C6—C1—C2—C3 | 2.9 (6) | C7—N1—C8—C9 | −168.0 (4) |
C1—C2—C3—C4 | −0.6 (7) | Cu1—N1—C8—C9 | 9.7 (4) |
C2—C3—C4—C5 | −1.0 (7) | Cu1—O3—C9—O2 | −173.5 (4) |
C3—C4—C5—C6 | 0.0 (7) | Cu1—O3—C9—C8 | 6.6 (4) |
O1—C1—C6—C5 | 179.2 (4) | N1—C8—C9—O2 | 169.1 (4) |
C2—C1—C6—C5 | −3.7 (5) | N1—C8—C9—O3 | −11.0 (5) |
O1—C1—C6—C7 | −1.5 (6) |
Symmetry code: (i) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···O2W | 1.02 (9) | 1.65 (9) | 2.649 (9) | 164 (7) |
O1W—H2W1···O3ii | 0.83 (7) | 2.02 (7) | 2.850 (8) | 172 (6) |
O2W—H2W2···O2iii | 1.04 | 1.82 | 2.838 (5) | 166 |
Symmetry codes: (ii) −x, −y+1, −z+1; (iii) x, −y+1, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C10H11CuNO4·H2O |
Mr | 290.75 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 20.2250 (3), 10.6741 (3), 14.2089 (3) |
β (°) | 134.294 (1) |
V (Å3) | 2195.59 (9) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 2.00 |
Crystal size (mm) | 0.20 × 0.12 × 0.10 |
Data collection | |
Diffractometer | Siemens SMART CCD area detector diffractometer |
Absorption correction | Empirical (using intensity measurements) SADABS (Sheldrick, 1996) |
Tmin, Tmax | 0.691, 0.825 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7657, 2718, 1739 |
Rint | 0.080 |
(sin θ/λ)max (Å−1) | 0.667 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.123, 0.95 |
No. of reflections | 2718 |
No. of parameters | 163 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.97, −0.73 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2003).
Cu1—O1 | 1.881 (3) | Cu1—O1W | 1.959 (3) |
Cu1—N1 | 1.936 (3) | Cu1—O1i | 2.809 (3) |
Cu1—O3 | 1.948 (3) | ||
O1—Cu1—N1 | 93.9 (1) | O3—Cu1—O1W | 88.6 (1) |
O1—Cu1—O3 | 179.0 (1) | O1—Cu1—O1i | 78.3 (1) |
N1—Cu1—O3 | 86.0 (1) | N1—Cu1—O1i | 101.4 (2) |
O1—Cu1—O1W | 91.7 (1) | O3—Cu1—O1i | 100.8 (2) |
N1—Cu1—O1W | 170.9 (1) | O1W—Cu1—O1i | 86.7 (1) |
Symmetry code: (i) −x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1W1···O2W | 1.02 (9) | 1.65 (9) | 2.649 (9) | 164 (7) |
O1W—H2W1···O3ii | 0.83 (7) | 2.02 (7) | 2.850 (8) | 172 (6) |
O2W—H2W2···O2iii | 1.04 | 1.82 | 2.838 (5) | 166 |
Symmetry codes: (ii) −x, −y+1, −z+1; (iii) x, −y+1, z−1/2. |
Considerable attention has been paid to the structures of Cu complexes with Schiff bases formed from salicylaldehyde-amino acid (Ueki et al., 1967, 1969; Bkouche-Waksman et al., 1988). These complexes are expected to be a catalytic intermediate in the non-enzymatic transamination reactions (Eichhorn & Marchand, 1956; Longenecker & Snell, 1957). Recently, X-ray structural studies on tin complexes with such ligands exhibited a variety of coordination and bonding towards the tinIV ion (Dakternieks et al., 1998; Basu Baul et al., 1999, 2001, 2002). The usefulness of such systems have in turn prompted research into the chemistry of Cu since the bond distances concerning the N atoms are of interest. In this study, we report the X-ray structural analysis of the title Cu complex, (I).
The asymmetric unit comprises a ligand-coordinated CuII cation, a coordinated water molecule, and a free water molecule. The Cu1 atom is tetracoordinated by two O atoms and one N atom from the O,N,O-tridentate ligand and by one O atom of a water molecule. The Cu—O and Cu—N bond distances are in the range of 1.881 (3)–1.959 (3) Å, which are agreeable with the values [1.892 (2)–1.993 (2) Å Warda, 1997a,b; Warda & Friebel et al., 1997, Warda, 1998a,b)]. The Cu1 atom also facilitates an intermolecular Cu···O1i short contact (Table 1). The two symmetrically related CuO4N coordinations form mutual distorted square pyramids with the atom O1i occupying the apices. The basal plane is formed by the Cu1/O1/N1/O3/O1W. The bond angles around the Cu1 are listed in Table 1.
The ligand and Cu1 atom form two nearly planar rings, a five-membered Cu1—O3—C9—C8—N1 [Q2 puckering amplitude 0.090 (5) Å] and a six-membered Cu1—O1—C1—C6—C7—N1 [QT puckering amplitude 0.184 (4) Å]. These two rings adopt envelope conformations with atoms C8 and Cu1 deviating by 0.134 (1) Å and 0.222 (1) Å from the N1/Cu1/O3/C9 and O1/C1/C6/C7/N1 planes, respectively. The three rings; the six-membered, five-membered and aromatic rings are nearly coplanar with the first one making dihedral angles of 7.1 (2)° and 4.8 (2)° with the 2nd and 3rd, respectively.
In the asymmetric unit, the CuII complex cation and the free water molecule are interconnected by O1W-H1W1···O2W hydrogen bond. In the crystal packing, the two water molecules also play an important role in the intermolecular hydrogen bonding scheme, in which there are two types of intermolecular O—H···O bonds, O1W-H2W1···O3i and O2W-H2W2···O2ii (Table 2 and Fig. 2), involving the water molecules. Two molecules are interconnected by the two intermolecular hydrogen bonds into molecular chains.