Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109025293/fg3105sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109025293/fg3105Isup2.hkl |
CCDC reference: 746042
For related literature, see: Allen (2002); Bernstein et al. (1995); Cakir et al. (2003); Kozlevcar et al. (1999); Monfared et al. (2007); Sieron (2007); Valigura et al. (2006).
Copper(II) oxydiacetate hemihydrate (0.01 mol) and nicotinamide (0.02 mol) were added to a methanol–water solution (1:1, 100 ml). The mixture was heated at 333 K under stirring for 1 h, filtered and left to stand at ambient temperature. After a few days, blue crystals of the title compound were separated
H atoms attached to O atoms were found in a difference Fourier map, further idealized (O—H = 0.85 Å) and finally allowed to ride. Those attached to C and N atoms were placed at calculated positions [C—H = 0.93 (CH) and 0.97 Å (CH2), and NH2 = 0.90 Å] and allowed to ride. Uiso(H) values were taken as 1.2Ueq(C) and 1.5Ueq(N,O).
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); cell refinement: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); data reduction: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
[Cu(C4H4O5)(C6H6N2O)(H2O)2] | F(000) = 1448 |
Mr = 353.77 | Dx = 1.725 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 25 reflections |
a = 12.498 (3) Å | θ = 7.5–12.5° |
b = 20.899 (4) Å | µ = 1.65 mm−1 |
c = 10.430 (2) Å | T = 295 K |
V = 2724.2 (10) Å3 | Prism, blue |
Z = 8 | 0.22 × 0.18 × 0.12 mm |
Rigaku AFC-6 diffractometer | 2287 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.120 |
Graphite monochromator | θmax = 26.0°, θmin = 1.9° |
ω/2θ scans | h = −1→15 |
Absorption correction: ψ scan (North et al., 1968) | k = −25→25 |
Tmin = 0.68, Tmax = 0.82 | l = −12→12 |
11251 measured reflections | 3 standard reflections every 150 reflections |
2685 independent reflections | intensity decay: <2% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.119 | w = 1/[σ2(Fo2) + (0.049P)2 + 1.5316P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2685 reflections | Δρmax = 0.90 e Å−3 |
195 parameters | Δρmin = −0.66 e Å−3 |
3 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0096 (6) |
[Cu(C4H4O5)(C6H6N2O)(H2O)2] | V = 2724.2 (10) Å3 |
Mr = 353.77 | Z = 8 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 12.498 (3) Å | µ = 1.65 mm−1 |
b = 20.899 (4) Å | T = 295 K |
c = 10.430 (2) Å | 0.22 × 0.18 × 0.12 mm |
Rigaku AFC-6 diffractometer | 2287 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.120 |
Tmin = 0.68, Tmax = 0.82 | 3 standard reflections every 150 reflections |
11251 measured reflections | intensity decay: <2% |
2685 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 3 restraints |
wR(F2) = 0.119 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.90 e Å−3 |
2685 reflections | Δρmin = −0.66 e Å−3 |
195 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. The ether oxygen in ODA appeared disordered at both sides of the least squares plane defined by the remaning ODA atoms, with occupation factors which refined to 0.900/0.100 (6). Similarity restraints were applied to bond distances and displacement factors involving the disordered atoms. The p3ca ring dispalys a vibration scheme compatible with a flapping rigid group, showing smaller amplitudes at the pivoting (N12) and substituted (C22) sites, and much larger ones at the unclamped ones opposing them (particularly C42). There were a number of concurrent indications (e.g.: a rather large Rint, many (slight) violations in the expected space group. systematic absences, etc) that the centrosymmetric space group chosen (Pbcn) might have been a compromise describing just an "average" symmetry. However, none of the many refinements performed with a relaxed symmetry resulted in a lower R, nor any improvement in the disordered model could be made, for what Pbcn was finally chosen as the space group which best describes the overall symmetry of the structure. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.13944 (3) | 0.172238 (14) | 0.06749 (3) | 0.03269 (18) | |
O11 | 0.13018 (15) | 0.14930 (9) | −0.11483 (18) | 0.0359 (5) | |
O21 | 0.12349 (16) | 0.19096 (10) | −0.31125 (18) | 0.0388 (5) | |
O31A | 0.0945 (2) | 0.25659 (8) | −0.00246 (16) | 0.0303 (6) | 0.900 (6) |
O31B | 0.1527 (16) | 0.2594 (4) | −0.0050 (8) | 0.0303 (6) | 0.100 (6) |
O41 | 0.12439 (17) | 0.32090 (9) | 0.30576 (19) | 0.0379 (5) | |
O51 | 0.13350 (14) | 0.22173 (9) | 0.22904 (16) | 0.0328 (4) | |
C11 | 0.12408 (19) | 0.19524 (13) | −0.1929 (2) | 0.0300 (5) | |
C21 | 0.1210 (2) | 0.26262 (12) | −0.1357 (2) | 0.0320 (6) | |
H21A | 0.1903 | 0.2830 | −0.1451 | 0.038* | 0.900 (6) |
H21B | 0.0680 | 0.2885 | −0.1797 | 0.038* | 0.900 (6) |
H21C | 0.1691 | 0.2904 | −0.1828 | 0.038* | 0.100 (6) |
H21D | 0.0492 | 0.2801 | −0.1417 | 0.038* | 0.100 (6) |
C31 | 0.1202 (2) | 0.30905 (14) | 0.0812 (2) | 0.0324 (6) | |
H31A | 0.0657 | 0.3420 | 0.0758 | 0.039* | 0.900 (6) |
H31B | 0.1885 | 0.3276 | 0.0570 | 0.039* | 0.900 (6) |
H31C | 0.0477 | 0.3223 | 0.0612 | 0.039* | 0.100 (6) |
H31D | 0.1670 | 0.3458 | 0.0728 | 0.039* | 0.100 (6) |
C41 | 0.12600 (19) | 0.28223 (12) | 0.2161 (2) | 0.0285 (5) | |
N12 | 0.1774 (2) | 0.08670 (10) | 0.1377 (2) | 0.0352 (5) | |
N22 | 0.4082 (3) | −0.04453 (12) | 0.3959 (3) | 0.0672 (10) | |
H22A | 0.3839 | −0.0798 | 0.3559 | 0.101* | |
H22B | 0.4624 | −0.0505 | 0.4515 | 0.101* | |
O12 | 0.4133 (3) | 0.06228 (10) | 0.4105 (3) | 0.0748 (9) | |
C12 | 0.2580 (2) | 0.07750 (11) | 0.2192 (2) | 0.0371 (6) | |
H12 | 0.2979 | 0.1128 | 0.2450 | 0.045* | |
C22 | 0.2853 (2) | 0.01792 (12) | 0.2673 (2) | 0.0363 (6) | |
C32 | 0.2267 (3) | −0.03374 (14) | 0.2281 (4) | 0.0600 (10) | |
H32 | 0.2428 | −0.0746 | 0.2578 | 0.072* | |
C42 | 0.1428 (4) | −0.02424 (17) | 0.1433 (6) | 0.097 (2) | |
H42 | 0.1020 | −0.0588 | 0.1154 | 0.117* | |
C52 | 0.1206 (3) | 0.03570 (16) | 0.1012 (5) | 0.0688 (12) | |
H52 | 0.0637 | 0.0415 | 0.0449 | 0.083* | |
C62 | 0.3753 (3) | 0.01375 (13) | 0.3642 (3) | 0.0471 (8) | |
O1W | 0.3225 (2) | 0.19898 (11) | 0.05550 (19) | 0.0495 (6) | |
H1WA | 0.3352 | 0.2305 | 0.1047 | 0.074* | |
H1WB | 0.3439 | 0.1993 | −0.0219 | 0.074* | |
O2W | −0.05471 (19) | 0.14692 (10) | 0.06669 (18) | 0.0462 (5) | |
H2WA | −0.0607 | 0.1565 | −0.0122 | 0.069* | |
H2WB | −0.0742 | 0.1733 | 0.1243 | 0.069* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0514 (3) | 0.0209 (2) | 0.0258 (2) | 0.00238 (13) | −0.00323 (12) | 0.00238 (11) |
O11 | 0.0493 (12) | 0.0287 (9) | 0.0298 (9) | 0.0010 (8) | −0.0021 (8) | −0.0017 (8) |
O21 | 0.0472 (11) | 0.0406 (10) | 0.0285 (10) | −0.0064 (9) | −0.0010 (8) | −0.0015 (9) |
O31A | 0.0404 (16) | 0.0264 (9) | 0.0242 (9) | −0.0009 (9) | −0.0011 (9) | 0.0018 (7) |
O31B | 0.0404 (16) | 0.0264 (9) | 0.0242 (9) | −0.0009 (9) | −0.0011 (9) | 0.0018 (7) |
O41 | 0.0505 (12) | 0.0329 (9) | 0.0304 (9) | 0.0021 (8) | −0.0017 (8) | −0.0054 (8) |
O51 | 0.0462 (11) | 0.0261 (8) | 0.0262 (9) | −0.0006 (8) | −0.0011 (7) | 0.0023 (7) |
C11 | 0.0300 (12) | 0.0320 (13) | 0.0279 (12) | −0.0044 (11) | −0.0017 (9) | 0.0009 (11) |
C21 | 0.0445 (15) | 0.0282 (12) | 0.0234 (12) | −0.0017 (11) | −0.0018 (10) | 0.0047 (10) |
C31 | 0.0438 (15) | 0.0234 (12) | 0.0300 (12) | 0.0024 (12) | −0.0018 (10) | 0.0003 (10) |
C41 | 0.0270 (12) | 0.0299 (12) | 0.0286 (12) | 0.0004 (10) | 0.0004 (9) | 0.0006 (10) |
N12 | 0.0465 (13) | 0.0226 (10) | 0.0364 (11) | −0.0014 (9) | −0.0079 (10) | 0.0016 (9) |
N22 | 0.097 (2) | 0.0265 (12) | 0.0783 (19) | 0.0120 (15) | −0.051 (2) | −0.0037 (13) |
O12 | 0.104 (2) | 0.0315 (11) | 0.0892 (18) | 0.0075 (13) | −0.0606 (17) | −0.0104 (12) |
C12 | 0.0507 (17) | 0.0231 (11) | 0.0376 (13) | −0.0023 (12) | −0.0090 (12) | −0.0016 (10) |
C22 | 0.0472 (15) | 0.0263 (12) | 0.0356 (12) | 0.0028 (11) | −0.0077 (12) | 0.0016 (10) |
C32 | 0.068 (2) | 0.0236 (13) | 0.088 (2) | −0.0064 (14) | −0.035 (2) | 0.0116 (15) |
C42 | 0.105 (4) | 0.0263 (15) | 0.160 (5) | −0.0143 (18) | −0.089 (4) | 0.010 (2) |
C52 | 0.078 (3) | 0.0307 (15) | 0.097 (3) | −0.0076 (16) | −0.054 (2) | 0.0056 (19) |
C62 | 0.066 (2) | 0.0290 (14) | 0.0461 (16) | 0.0070 (13) | −0.0203 (14) | −0.0039 (13) |
O1W | 0.0651 (14) | 0.0471 (13) | 0.0363 (10) | −0.0165 (12) | 0.0116 (10) | −0.0085 (9) |
O2W | 0.0582 (14) | 0.0446 (12) | 0.0360 (10) | 0.0087 (10) | 0.0011 (9) | −0.0038 (8) |
Cu1—O11 | 1.964 (2) | C31—H31B | 0.9700 |
Cu1—O51 | 1.978 (2) | C31—H31C | 0.9700 |
Cu1—O31B | 1.979 (9) | C31—H31D | 0.9700 |
Cu1—O31A | 1.989 (2) | N12—C12 | 1.332 (3) |
Cu1—N12 | 1.989 (2) | N12—C52 | 1.336 (4) |
Cu1—O1W | 2.359 (3) | N22—C62 | 1.328 (4) |
Cu1—O2W | 2.483 (2) | N22—H22A | 0.9001 |
O11—C11 | 1.261 (3) | N22—H22B | 0.9000 |
O21—C11 | 1.238 (3) | O12—C62 | 1.219 (4) |
O31A—C21 | 1.434 (3) | C12—C22 | 1.385 (3) |
O31A—C31 | 1.437 (3) | C12—H12 | 0.9300 |
O31B—C21 | 1.421 (9) | C22—C32 | 1.367 (4) |
O31B—C31 | 1.431 (9) | C22—C62 | 1.515 (4) |
O41—C41 | 1.236 (3) | C32—C42 | 1.385 (5) |
O51—C41 | 1.275 (3) | C32—H32 | 0.9300 |
C11—C21 | 1.530 (4) | C42—C52 | 1.356 (5) |
C21—H21A | 0.9700 | C42—H42 | 0.9300 |
C21—H21B | 0.9699 | C52—H52 | 0.9300 |
C21—H21C | 0.9701 | O1W—H1WA | 0.8500 |
C21—H21D | 0.9700 | O1W—H1WB | 0.8500 |
C31—C41 | 1.517 (3) | O2W—H2WA | 0.8501 |
C31—H31A | 0.9700 | O2W—H2WB | 0.8500 |
O11—Cu1—O51 | 161.75 (8) | O31A—C31—H31A | 110.4 |
O11—Cu1—O31B | 81.9 (2) | C41—C31—H31A | 110.4 |
O51—Cu1—O31B | 81.2 (2) | O31A—C31—H31B | 110.1 |
O11—Cu1—O31A | 81.06 (7) | C41—C31—H31B | 110.3 |
O51—Cu1—O31A | 80.70 (7) | H31A—C31—H31B | 108.6 |
O11—Cu1—N12 | 98.69 (8) | O31B—C31—H31C | 109.7 |
O51—Cu1—N12 | 99.52 (8) | C41—C31—H31C | 110.4 |
O31B—Cu1—N12 | 161.4 (6) | H31B—C31—H31C | 130.7 |
O31A—Cu1—N12 | 177.38 (10) | O31B—C31—H31D | 110.3 |
O11—Cu1—O1W | 93.65 (8) | O31A—C31—H31D | 133.2 |
O51—Cu1—O1W | 87.57 (7) | C41—C31—H31D | 110.3 |
O31B—Cu1—O1W | 71.4 (6) | H31C—C31—H31D | 108.6 |
O31A—Cu1—O1W | 92.55 (10) | O41—C41—O51 | 124.7 (2) |
N12—Cu1—O1W | 90.06 (9) | O41—C41—C31 | 117.4 (2) |
O11—Cu1—O2W | 83.53 (7) | O51—C41—C31 | 117.9 (2) |
O51—Cu1—O2W | 94.45 (7) | C12—N12—C52 | 117.9 (2) |
O31B—Cu1—O2W | 106.1 (6) | C12—N12—Cu1 | 123.02 (17) |
O31A—Cu1—O2W | 84.93 (9) | C52—N12—Cu1 | 119.1 (2) |
N12—Cu1—O2W | 92.45 (9) | C62—N22—H22A | 122.1 |
O1W—Cu1—O2W | 176.47 (7) | C62—N22—H22B | 121.3 |
C11—O11—Cu1 | 116.28 (17) | H22A—N22—H22B | 116.1 |
C21—O31A—C31 | 118.0 (2) | N12—C12—C22 | 123.2 (2) |
C21—O31A—Cu1 | 111.61 (15) | N12—C12—H12 | 118.4 |
C31—O31A—Cu1 | 112.97 (15) | C22—C12—H12 | 118.4 |
C21—O31B—C31 | 119.3 (8) | C32—C22—C12 | 118.0 (3) |
C21—O31B—Cu1 | 112.7 (6) | C32—C22—C62 | 123.5 (2) |
C31—O31B—Cu1 | 113.8 (6) | C12—C22—C62 | 118.4 (2) |
C41—O51—Cu1 | 115.55 (16) | C22—C32—C42 | 118.9 (3) |
O21—C11—O11 | 126.1 (3) | C22—C32—H32 | 120.6 |
O21—C11—C21 | 117.1 (2) | C42—C32—H32 | 120.6 |
O11—C11—C21 | 116.8 (2) | C52—C42—C32 | 119.6 (3) |
O31B—C21—C11 | 108.9 (4) | C52—C42—H42 | 120.2 |
O31A—C21—C11 | 107.62 (19) | C32—C42—H42 | 120.2 |
O31A—C21—H21A | 110.0 | N12—C52—C42 | 122.4 (3) |
C11—C21—H21A | 110.0 | N12—C52—H52 | 118.8 |
O31A—C21—H21B | 110.5 | C42—C52—H52 | 118.8 |
C11—C21—H21B | 110.2 | O12—C62—N22 | 122.9 (3) |
H21A—C21—H21B | 108.5 | O12—C62—C22 | 120.4 (3) |
O31B—C21—H21C | 110.0 | N22—C62—C22 | 116.7 (3) |
C11—C21—H21C | 109.8 | Cu1—O1W—H1WA | 109.4 |
O31B—C21—H21D | 109.7 | Cu1—O1W—H1WB | 110.9 |
C11—C21—H21D | 110.2 | H1WA—O1W—H1WB | 120.6 |
H21A—C21—H21D | 130.8 | Cu1—O2W—H2WA | 92.2 |
H21C—C21—H21D | 108.4 | Cu1—O2W—H2WB | 98.0 |
O31B—C31—C41 | 107.5 (4) | H2WA—O2W—H2WB | 120.4 |
O31A—C31—C41 | 107.0 (2) | ||
O51—Cu1—O11—C11 | 15.2 (4) | O21—C11—C21—O31B | −163.5 (9) |
O31B—Cu1—O11—C11 | −7.5 (6) | O11—C11—C21—O31B | 14.5 (9) |
O31A—Cu1—O11—C11 | 13.88 (19) | O21—C11—C21—O31A | 165.3 (2) |
N12—Cu1—O11—C11 | −168.75 (18) | O11—C11—C21—O31A | −16.7 (3) |
O1W—Cu1—O11—C11 | −78.13 (19) | C21—O31B—C31—O31A | 64.8 (12) |
O2W—Cu1—O11—C11 | 99.75 (18) | Cu1—O31B—C31—O31A | −72.2 (10) |
O11—Cu1—O31A—C21 | −22.96 (18) | C21—O31B—C31—C41 | 158.4 (10) |
O51—Cu1—O31A—C21 | 157.45 (19) | Cu1—O31B—C31—C41 | 21.4 (12) |
O31B—Cu1—O31A—C21 | 67.8 (6) | C21—O31A—C31—O31B | −62.4 (7) |
O1W—Cu1—O31A—C21 | 70.33 (18) | Cu1—O31A—C31—O31B | 70.3 (7) |
O2W—Cu1—O31A—C21 | −107.18 (18) | C21—O31A—C31—C41 | −158.1 (2) |
O11—Cu1—O31A—C31 | −158.7 (2) | Cu1—O31A—C31—C41 | −25.4 (3) |
O51—Cu1—O31A—C31 | 21.73 (19) | Cu1—O51—C41—O41 | −177.84 (19) |
O31B—Cu1—O31A—C31 | −67.9 (6) | Cu1—O51—C41—C31 | 1.2 (3) |
O1W—Cu1—O31A—C31 | −65.39 (19) | O31B—C31—C41—O41 | 164.2 (8) |
O2W—Cu1—O31A—C31 | 117.09 (19) | O31A—C31—C41—O41 | −164.8 (2) |
O11—Cu1—O31B—C21 | 15.7 (10) | O31B—C31—C41—O51 | −14.9 (9) |
O51—Cu1—O31B—C21 | −157.3 (11) | O31A—C31—C41—O51 | 16.0 (3) |
O31A—Cu1—O31B—C21 | −70.3 (11) | O11—Cu1—N12—C12 | 131.1 (2) |
N12—Cu1—O31B—C21 | 109.0 (12) | O51—Cu1—N12—C12 | −50.2 (2) |
O1W—Cu1—O31B—C21 | 112.3 (11) | O31B—Cu1—N12—C12 | 40.5 (8) |
O2W—Cu1—O31B—C21 | −65.2 (11) | O1W—Cu1—N12—C12 | 37.4 (2) |
O11—Cu1—O31B—C31 | 155.5 (11) | O2W—Cu1—N12—C12 | −145.1 (2) |
O51—Cu1—O31B—C31 | −17.4 (10) | O11—Cu1—N12—C52 | −48.3 (3) |
N12—Cu1—O31B—C31 | −111.2 (12) | O51—Cu1—N12—C52 | 130.4 (3) |
O1W—Cu1—O31B—C31 | −107.8 (11) | O31B—Cu1—N12—C52 | −138.9 (8) |
O2W—Cu1—O31B—C31 | 74.7 (11) | O1W—Cu1—N12—C52 | −142.0 (3) |
O11—Cu1—O51—C41 | −13.9 (4) | O2W—Cu1—N12—C52 | 35.5 (3) |
O31B—Cu1—O51—C41 | 8.8 (6) | C52—N12—C12—C22 | 0.0 (5) |
O31A—Cu1—O51—C41 | −12.62 (18) | Cu1—N12—C12—C22 | −179.4 (2) |
N12—Cu1—O51—C41 | 170.02 (18) | N12—C12—C22—C32 | 0.5 (5) |
O1W—Cu1—O51—C41 | 80.36 (18) | N12—C12—C22—C62 | −177.2 (3) |
O2W—Cu1—O51—C41 | −96.74 (18) | C12—C22—C32—C42 | −0.4 (6) |
Cu1—O11—C11—O21 | 175.8 (2) | C62—C22—C32—C42 | 177.1 (4) |
Cu1—O11—C11—C21 | −1.9 (3) | C22—C32—C42—C52 | 0.0 (8) |
C31—O31B—C21—O31A | −64.6 (12) | C12—N12—C52—C42 | −0.5 (7) |
Cu1—O31B—C21—O31A | 72.9 (10) | Cu1—N12—C52—C42 | 178.9 (5) |
C31—O31B—C21—C11 | −157.2 (10) | C32—C42—C52—N12 | 0.6 (9) |
Cu1—O31B—C21—C11 | −19.8 (12) | C32—C22—C62—O12 | −168.4 (4) |
C31—O31A—C21—O31B | 62.7 (7) | C12—C22—C62—O12 | 9.1 (5) |
Cu1—O31A—C21—O31B | −70.6 (7) | C32—C22—C62—N22 | 10.8 (5) |
C31—O31A—C21—C11 | 160.0 (2) | C12—C22—C62—N22 | −171.7 (3) |
Cu1—O31A—C21—C11 | 26.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N22—H22B···O12i | 0.90 | 2.13 | 3.031 (4) | 177 |
N22—H22A···O41ii | 0.90 | 2.14 | 2.993 (3) | 157 |
O1W—H1WA···O21iii | 0.85 | 1.93 | 2.771 (3) | 169 |
O1W—H1WB···O41iv | 0.85 | 1.89 | 2.720 (3) | 166 |
O2W—H2WA···O21v | 0.85 | 2.13 | 2.947 (3) | 163 |
O2W—H2WB···O51vi | 0.85 | 1.98 | 2.820 (3) | 170 |
C21—H21A···O51iv | 0.97 | 2.57 | 3.393 (3) | 143 |
C32—H32···O11vii | 0.93 | 2.49 | 3.158 (4) | 129 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1/2, y−1/2, z; (iii) −x+1/2, −y+1/2, z+1/2; (iv) −x+1/2, −y+1/2, z−1/2; (v) −x, y, −z−1/2; (vi) −x, y, −z+1/2; (vii) x, −y, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C4H4O5)(C6H6N2O)(H2O)2] |
Mr | 353.77 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 295 |
a, b, c (Å) | 12.498 (3), 20.899 (4), 10.430 (2) |
V (Å3) | 2724.2 (10) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.65 |
Crystal size (mm) | 0.22 × 0.18 × 0.12 |
Data collection | |
Diffractometer | Rigaku AFC-6 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.68, 0.82 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11251, 2685, 2287 |
Rint | 0.120 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.119, 1.05 |
No. of reflections | 2685 |
No. of parameters | 195 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.90, −0.66 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1988), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N22—H22B···O12i | 0.90 | 2.13 | 3.031 (4) | 177 |
N22—H22A···O41ii | 0.90 | 2.14 | 2.993 (3) | 157 |
O1W—H1WA···O21iii | 0.85 | 1.93 | 2.771 (3) | 169 |
O1W—H1WB···O41iv | 0.85 | 1.89 | 2.720 (3) | 166 |
O2W—H2WA···O21v | 0.85 | 2.13 | 2.947 (3) | 163 |
O2W—H2WB···O51vi | 0.85 | 1.98 | 2.820 (3) | 170 |
C21—H21A···O51iv | 0.97 | 2.57 | 3.393 (3) | 143 |
C32—H32···O11vii | 0.93 | 2.49 | 3.158 (4) | 129 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1/2, y−1/2, z; (iii) −x+1/2, −y+1/2, z+1/2; (iv) −x+1/2, −y+1/2, z−1/2; (v) −x, y, −z−1/2; (vi) −x, y, −z+1/2; (vii) x, −y, z+1/2. |
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The coordination chemistry of CuII is a topic of current interest because of the relevance of such complexes as structural and spectroscopic models in biological systems and molecular-based magnet materials. In the monomeric title compound, [Cu(C4H4O5)(C6H6N2O)(H2O)2] (Fig 1), the copper cation is bound to a κ3O,O',O" chelating oxydiacetate (ODA) ligand, a κ1N monodentate pyridine-3-carboxamide unit (p3ca) and two water molecules, defining an octahedral coordination where the former two ligands form the equatorial plane and the latter two occupy the apical sites. The basal atoms span a very tight range of coordination distances [1.964 (2)–1.989 (2) Å; Table 1]; the apical water molecules, instead, show a 5% difference in their Cu—O bondss. In general terms, however, and in spite of chelation the average geometry of the octahedron is rather regular (Table 1). The oxydiacetate (ODA) ligand is slightly disordered at its O31 central atom, split at both sides [0.36 (1) Å above/below] of the plane through the remaining atoms (the mean deviation from the least squares plane is < 0.001 Å). The p3ca unit shows a rotation around the C22—C62 bond of 10.1 (1)° between the pyridyl and amide planar groups
The availability of efficient donors and ready acceptors for hydrogen bonding, represented by water and amine H atoms on one side and carboxylate and amide O atoms on the other, results in a complex interaction scheme where each monomer links to six different similar units to define a well-connected three-dimensional structure. Fig. 2(a) shows a full packing view depicting the most conspicuous characteristics of this packing; the copper coordination polyhedra and the p3ca units (which stretch out from them) associate into two well differentiated types of planar arrays, which dispose parallel to (010) and are shown sideways in Fig. 2(a), labelled as A and B, respectively. The B planes are formed by a conglomerate of p3ca units, which interact with each other in pairs through an N—H···O hydrogen bond (Table 1, first entry) around a symmetry center defining a classical R22(8) loop (Bernstein et al., 1995). The interaction is marked as (1) in Fig. 2(b). The same figure shows how the two types of arrays (A and B) interconnect through a second N—H···O hydrogen bond [Table 1, second entry, and Fig. 2(b), site marked (2)].
An interesting feature of the packing is the way in which type A planes build up through the interaction of CuO3N(H2O)2 units, interwoven into a two-dimensional network of large R44(10) loops, shown as (3) in Fig. 3, and where both types of water molecules participate with all their H atoms (Table 1, entries 3–6). There are also some weak C—H···O contacts completing the interaction scheme.
A search of the 2009 version of the Cambridge Structural Database (CSD; Allen, 2002) showed a closely related structure to (I), viz. aqua(ODA-κ3O,O',O")(p2ca-κ2N,O)copper(II), (II) (Sieroń, 2007), where the only a priori difference between intervening units resides in the position of the carboxamide sustituent. In (I) the group is bound to pyridine at site 3, the next nearest neighbour to the coordinated N atom, and the result is that the amide O atom appears in a position too far appart to make chelation feasible; in (II), instead, the group attaches at site 2, nearest neighbour to N, thus configuring an adequate geometry for a bidentate coordination. This results in two completely different coordination modes for the pca ligands, κ1N monodentate (p3ca) in (I) and κ2N,O chelating (p2ca) in (II) (see scheme). However, this has also a profound influence on the remaining ligands, viz. the ODA group, which in (I) adopts its usual planar, meridional coordination mode, in (II) `breaks' around the central Oether—Cu bond into two quasi perpendicular `butterfly' wings binding in a facial mode, a fact that positions the ether O atom in one apical coordination site. The remaining apical site is occupied by the unique water molecule in the structure.
The simultaneous reduction of the number of potential hydrogen-bonding donors (now the amine group and only one water molecule) and acceptors (through the involvement of the amide O atom in coordination) drastically modifies the noncovalent interaction scheme by decreasing the number of strong hydrogen bonds in (II) to basically three.
The coordination modes to copper discussed herein appear to be quite typical for both cpa groups; all entries found in the CSD for Cu–c2pa complexes (15 in all) show the ligand behaving in a chelating manner; on the other side, 41 out of a total of 45 Cu–p3ca complexes show the ligand acting in monocoordinated mode, the exceptions [entries BENQAM (Kozlevcar et al., 1999), ESAFEJ (Cakir et al., 2003), PEPJOK (Valigura et al., 2006) and TIMXIX (Monfared et al., 2007)] showing the ligand in the role of a bridge, either in dimeric or polymeric compounds.