Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104020566/sk1754sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104020566/sk1754Isup2.hkl |
CCDC reference: 254912
Squaric acid (H2Sq; 0.57 g, 5 mmol) dissolved in water (25 ml) was neutralized with NaOH (0.40 g, 10 mmol) and added to a hot solution of copper(II) chloride dihydrate (0.853 g, 5 mmol) dissolved in water (50 ml). The mixture was stirred at 353 K for 12 h and then cooled to room temperature. The green crystals which formed were filtered off and washed with water, and dried in vacuo. A solution of 1,10-phenanthroline (0.72 g, 4 mmol) in ethanol (20 ml) was added dropwise with stirring to a suspension of CuSq·2H2O (0.42 g, 2 mmol) in water (50 ml). The mixture was then stirred at 323 K for 12 h and cooled to room temperature. After a few days, well formed crystals of (I) were selected for X-ray studies.
H atoms on C atoms were placed in calculated positions (C—H = 0.93 Å) and were allowed to ride on their parent atom [Uiso(H) = 1.2Ueq(C)]. The remaining H atoms were located in a difference map and refined isotropically. Δρmax and Δρmin of 0.2 and −0.39 Å3, respectively, were found at distances of 0.73 and 0.86 Å from atoms O1 and Cu1, respectively.
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Cu(C4O4)(C12H8N2)2]·3H2O | F(000) = 1212 |
Mr = 590.05 | Dx = 1.529 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 16767 reflections |
a = 12.5563 (9) Å | θ = 1.6–28.0° |
b = 16.291 (1) Å | µ = 0.91 mm−1 |
c = 12.6208 (9) Å | T = 293 K |
β = 96.896 (6)° | Prism, black |
V = 2563.0 (3) Å3 | 0.42 × 0.28 × 0.17 mm |
Z = 4 |
Stoe IPDS 2 diffractometer | 5051 independent reflections |
Radiation source: fine-focus sealed tube | 3155 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.105 |
Detector resolution: 6.67 pixels mm-1 | θmax = 26.0°, θmin = 2.1° |
ω scans | h = −15→15 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −20→20 |
Tmin = 0.736, Tmax = 0.89 | l = −15→15 |
36262 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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.068 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.82 | w = 1/[σ2(Fo2) + (0.0295P)2] where P = (Fo2 + 2Fc2)/3 |
5051 reflections | (Δ/σ)max = 0.001 |
385 parameters | Δρmax = 0.20 e Å−3 |
0 restraints | Δρmin = −0.39 e Å−3 |
[Cu(C4O4)(C12H8N2)2]·3H2O | V = 2563.0 (3) Å3 |
Mr = 590.05 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.5563 (9) Å | µ = 0.91 mm−1 |
b = 16.291 (1) Å | T = 293 K |
c = 12.6208 (9) Å | 0.42 × 0.28 × 0.17 mm |
β = 96.896 (6)° |
Stoe IPDS 2 diffractometer | 5051 independent reflections |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 3155 reflections with I > 2σ(I) |
Tmin = 0.736, Tmax = 0.89 | Rint = 0.105 |
36262 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.068 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.82 | Δρmax = 0.20 e Å−3 |
5051 reflections | Δρmin = −0.39 e Å−3 |
385 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 | ||
C1 | 0.1749 (2) | 0.12453 (14) | 0.56760 (18) | 0.0501 (6) | |
H1 | 0.1378 | 0.0761 | 0.5762 | 0.060* | |
C2 | 0.1852 (2) | 0.15123 (15) | 0.46545 (19) | 0.0526 (7) | |
H2 | 0.1547 | 0.1212 | 0.4069 | 0.063* | |
C3 | 0.2403 (2) | 0.22193 (15) | 0.45041 (19) | 0.0503 (6) | |
H3 | 0.2472 | 0.2402 | 0.3818 | 0.060* | |
C4 | 0.28630 (19) | 0.26662 (13) | 0.53953 (17) | 0.0403 (6) | |
C5 | 0.3460 (2) | 0.34057 (13) | 0.53399 (19) | 0.0470 (6) | |
H4 | 0.3575 | 0.3614 | 0.4677 | 0.056* | |
C6 | 0.3862 (2) | 0.38084 (13) | 0.62313 (19) | 0.0460 (6) | |
H5 | 0.4245 | 0.4291 | 0.6170 | 0.055* | |
C7 | 0.37136 (18) | 0.35101 (12) | 0.72739 (17) | 0.0396 (5) | |
C8 | 0.4104 (2) | 0.38954 (14) | 0.8226 (2) | 0.0511 (7) | |
H6 | 0.4496 | 0.4379 | 0.8217 | 0.061* | |
C9 | 0.3906 (2) | 0.35583 (15) | 0.9172 (2) | 0.0596 (7) | |
H7 | 0.4151 | 0.3817 | 0.9811 | 0.071* | |
C10 | 0.3339 (2) | 0.28286 (15) | 0.9178 (2) | 0.0536 (7) | |
H8 | 0.3215 | 0.2606 | 0.9831 | 0.064* | |
C11 | 0.31432 (18) | 0.27777 (12) | 0.73458 (17) | 0.0366 (5) | |
C12 | 0.27173 (18) | 0.23571 (12) | 0.64017 (17) | 0.0365 (5) | |
C13 | 0.3688 (2) | −0.00929 (17) | 0.7422 (2) | 0.0618 (7) | |
H9 | 0.3605 | 0.0106 | 0.6726 | 0.074* | |
C14 | 0.4287 (3) | −0.08130 (18) | 0.7649 (3) | 0.0766 (9) | |
H10 | 0.4576 | −0.1095 | 0.7109 | 0.092* | |
C15 | 0.4439 (2) | −0.10912 (17) | 0.8671 (3) | 0.0754 (9) | |
H11 | 0.4842 | −0.1563 | 0.8834 | 0.090* | |
C16 | 0.3997 (2) | −0.06770 (15) | 0.9471 (2) | 0.0578 (7) | |
C17 | 0.4119 (3) | −0.09206 (17) | 1.0578 (3) | 0.0722 (9) | |
H12 | 0.4548 | −0.1371 | 1.0791 | 0.087* | |
C18 | 0.3634 (3) | −0.05170 (19) | 1.1301 (3) | 0.0729 (9) | |
H13 | 0.3736 | −0.0690 | 1.2008 | 0.087* | |
C19 | 0.2965 (2) | 0.01712 (16) | 1.1019 (2) | 0.0551 (7) | |
C20 | 0.2391 (3) | 0.05921 (19) | 1.1724 (2) | 0.0677 (8) | |
H14 | 0.2460 | 0.0439 | 1.2439 | 0.081* | |
C21 | 0.1734 (3) | 0.12224 (17) | 1.1384 (2) | 0.0649 (8) | |
H15 | 0.1344 | 0.1497 | 1.1856 | 0.078* | |
C22 | 0.1653 (2) | 0.14522 (15) | 1.0318 (2) | 0.0548 (6) | |
H16 | 0.1196 | 0.1882 | 1.0085 | 0.066* | |
C23 | 0.2845 (2) | 0.04386 (14) | 0.99515 (19) | 0.0437 (6) | |
C24 | 0.33839 (19) | 0.00196 (13) | 0.9173 (2) | 0.0452 (6) | |
C25 | −0.00589 (19) | 0.10904 (12) | 0.75297 (17) | 0.0376 (5) | |
C26 | −0.10638 (19) | 0.09052 (13) | 0.69038 (17) | 0.0393 (5) | |
C27 | −0.1484 (2) | 0.17085 (15) | 0.72044 (19) | 0.0502 (6) | |
C28 | −0.0443 (2) | 0.18846 (13) | 0.78328 (18) | 0.0433 (6) | |
N1 | 0.21616 (15) | 0.16550 (11) | 0.65441 (14) | 0.0417 (5) | |
N2 | 0.29648 (16) | 0.24345 (10) | 0.82892 (14) | 0.0409 (5) | |
N3 | 0.32373 (16) | 0.03127 (11) | 0.81575 (16) | 0.0461 (5) | |
N4 | 0.22013 (16) | 0.10835 (11) | 0.96170 (15) | 0.0435 (5) | |
O1 | 0.08312 (13) | 0.07068 (9) | 0.77176 (13) | 0.0474 (4) | |
O2 | −0.14186 (14) | 0.03201 (9) | 0.63277 (13) | 0.0525 (4) | |
O3 | −0.23398 (17) | 0.20783 (13) | 0.69983 (18) | 0.0880 (7) | |
O4 | −0.00259 (16) | 0.24558 (10) | 0.83919 (14) | 0.0633 (5) | |
O5 | 0.0410 (3) | 0.30172 (18) | 0.1968 (2) | 0.0928 (8) | |
O6 | 0.1494 (3) | 0.48992 (15) | 0.0398 (2) | 0.0897 (9) | |
O7 | 0.4802 (2) | 0.12802 (17) | 0.48944 (19) | 0.0734 (6) | |
Cu1 | 0.21389 (2) | 0.135933 (16) | 0.80737 (2) | 0.04113 (9) | |
H17 | 0.482 (3) | 0.165 (2) | 0.448 (3) | 0.118 (16)* | |
H18 | 0.436 (3) | 0.095 (2) | 0.476 (3) | 0.105 (16)* | |
H19 | 0.019 (4) | 0.330 (3) | 0.135 (4) | 0.15 (2)* | |
H20 | 0.103 (4) | 0.305 (3) | 0.186 (3) | 0.124 (19)* | |
H21 | 0.117 (3) | 0.452 (2) | 0.031 (3) | 0.098 (15)* | |
H22 | 0.210 (3) | 0.476 (2) | 0.064 (3) | 0.101 (14)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0593 (17) | 0.0432 (14) | 0.0452 (15) | −0.0074 (12) | −0.0046 (12) | −0.0054 (11) |
C2 | 0.0633 (18) | 0.0531 (16) | 0.0383 (14) | 0.0030 (13) | −0.0069 (12) | −0.0090 (12) |
C3 | 0.0615 (18) | 0.0541 (15) | 0.0345 (14) | 0.0106 (13) | 0.0025 (12) | 0.0032 (11) |
C4 | 0.0476 (15) | 0.0377 (12) | 0.0355 (13) | 0.0082 (11) | 0.0046 (11) | 0.0003 (10) |
C5 | 0.0583 (17) | 0.0409 (13) | 0.0433 (14) | 0.0071 (11) | 0.0126 (12) | 0.0089 (10) |
C6 | 0.0532 (16) | 0.0341 (13) | 0.0523 (15) | −0.0016 (11) | 0.0127 (12) | 0.0032 (11) |
C7 | 0.0442 (14) | 0.0331 (12) | 0.0420 (13) | 0.0019 (10) | 0.0075 (10) | −0.0010 (10) |
C8 | 0.0611 (18) | 0.0386 (13) | 0.0536 (16) | −0.0100 (12) | 0.0066 (13) | −0.0043 (11) |
C9 | 0.082 (2) | 0.0552 (15) | 0.0408 (14) | −0.0206 (15) | 0.0028 (13) | −0.0115 (13) |
C10 | 0.0682 (19) | 0.0561 (15) | 0.0363 (15) | −0.0116 (14) | 0.0053 (13) | −0.0025 (12) |
C11 | 0.0373 (14) | 0.0346 (11) | 0.0375 (13) | 0.0040 (10) | 0.0029 (10) | −0.0008 (10) |
C12 | 0.0379 (14) | 0.0348 (12) | 0.0362 (12) | 0.0058 (10) | 0.0020 (10) | −0.0012 (10) |
C13 | 0.0590 (19) | 0.0677 (18) | 0.0600 (18) | 0.0007 (15) | 0.0121 (15) | −0.0071 (14) |
C14 | 0.071 (2) | 0.0618 (19) | 0.100 (3) | 0.0083 (16) | 0.0234 (19) | −0.0209 (18) |
C15 | 0.055 (2) | 0.0499 (17) | 0.120 (3) | 0.0068 (14) | 0.004 (2) | 0.0029 (18) |
C16 | 0.0442 (17) | 0.0447 (14) | 0.082 (2) | −0.0034 (12) | −0.0020 (15) | 0.0075 (14) |
C17 | 0.061 (2) | 0.0502 (17) | 0.099 (3) | −0.0084 (15) | −0.0198 (18) | 0.0302 (17) |
C18 | 0.076 (2) | 0.070 (2) | 0.068 (2) | −0.0196 (17) | −0.0141 (18) | 0.0304 (17) |
C19 | 0.0593 (18) | 0.0535 (15) | 0.0499 (17) | −0.0164 (13) | −0.0036 (14) | 0.0165 (13) |
C20 | 0.085 (2) | 0.078 (2) | 0.0416 (17) | −0.0286 (17) | 0.0113 (16) | 0.0098 (15) |
C21 | 0.078 (2) | 0.0708 (19) | 0.0502 (16) | −0.0183 (17) | 0.0251 (15) | −0.0023 (14) |
C22 | 0.0602 (17) | 0.0542 (15) | 0.0524 (16) | −0.0053 (13) | 0.0164 (13) | 0.0000 (13) |
C23 | 0.0426 (15) | 0.0426 (13) | 0.0449 (14) | −0.0122 (11) | 0.0010 (11) | 0.0059 (11) |
C24 | 0.0385 (15) | 0.0398 (13) | 0.0559 (16) | −0.0081 (11) | −0.0003 (12) | 0.0079 (11) |
C25 | 0.0434 (15) | 0.0353 (11) | 0.0350 (13) | −0.0044 (10) | 0.0076 (11) | 0.0048 (9) |
C26 | 0.0426 (15) | 0.0447 (13) | 0.0311 (13) | −0.0038 (11) | 0.0063 (11) | 0.0020 (10) |
C27 | 0.0518 (18) | 0.0556 (14) | 0.0423 (15) | 0.0100 (13) | 0.0018 (13) | 0.0002 (12) |
C28 | 0.0549 (17) | 0.0364 (12) | 0.0393 (14) | −0.0006 (11) | 0.0090 (12) | 0.0021 (10) |
N1 | 0.0453 (12) | 0.0391 (10) | 0.0387 (11) | −0.0033 (9) | −0.0034 (9) | −0.0017 (8) |
N2 | 0.0485 (13) | 0.0426 (10) | 0.0313 (11) | −0.0031 (9) | 0.0037 (9) | −0.0011 (9) |
N3 | 0.0415 (13) | 0.0482 (11) | 0.0486 (13) | −0.0027 (9) | 0.0059 (10) | −0.0020 (10) |
N4 | 0.0464 (13) | 0.0424 (11) | 0.0422 (12) | −0.0059 (9) | 0.0073 (10) | 0.0009 (9) |
O1 | 0.0432 (11) | 0.0349 (8) | 0.0627 (11) | 0.0004 (7) | 0.0010 (8) | −0.0010 (7) |
O2 | 0.0587 (12) | 0.0506 (10) | 0.0458 (10) | −0.0110 (8) | −0.0035 (8) | −0.0069 (8) |
O3 | 0.0687 (16) | 0.0900 (14) | 0.0985 (17) | 0.0356 (12) | −0.0176 (13) | −0.0169 (12) |
O4 | 0.0823 (15) | 0.0410 (9) | 0.0648 (12) | −0.0062 (9) | 0.0010 (10) | −0.0146 (9) |
O5 | 0.085 (2) | 0.0981 (19) | 0.095 (2) | −0.0230 (16) | 0.0103 (17) | −0.0108 (16) |
O6 | 0.0650 (18) | 0.0620 (15) | 0.133 (2) | −0.0037 (14) | −0.0244 (16) | 0.0027 (14) |
O7 | 0.0691 (16) | 0.0648 (14) | 0.0828 (16) | −0.0002 (13) | −0.0052 (12) | 0.0149 (13) |
Cu1 | 0.04469 (17) | 0.04051 (15) | 0.03731 (15) | −0.00568 (15) | 0.00138 (11) | 0.00260 (14) |
C1—N1 | 1.333 (3) | C17—H12 | 0.9300 |
C1—C2 | 1.381 (3) | C18—C19 | 1.420 (4) |
C1—H1 | 0.9300 | C18—H13 | 0.9300 |
C2—C3 | 1.368 (3) | C19—C20 | 1.392 (4) |
C2—H2 | 0.9300 | C19—C23 | 1.406 (3) |
C3—C4 | 1.405 (3) | C20—C21 | 1.354 (4) |
C3—H3 | 0.9300 | C20—H14 | 0.9300 |
C4—C12 | 1.399 (3) | C21—C22 | 1.388 (4) |
C4—C5 | 1.425 (3) | C21—H15 | 0.9300 |
C5—C6 | 1.347 (3) | C22—N4 | 1.328 (3) |
C5—H4 | 0.9300 | C22—H16 | 0.9300 |
C6—C7 | 1.436 (3) | C23—N4 | 1.362 (3) |
C6—H5 | 0.9300 | C23—C24 | 1.431 (3) |
C7—C8 | 1.391 (3) | C24—N3 | 1.360 (3) |
C7—C11 | 1.400 (3) | C25—O1 | 1.278 (3) |
C8—C9 | 1.364 (3) | C25—C26 | 1.438 (3) |
C8—H6 | 0.9300 | C25—C28 | 1.448 (3) |
C9—C10 | 1.386 (3) | C26—O2 | 1.248 (3) |
C9—H7 | 0.9300 | C26—C27 | 1.478 (3) |
C10—N2 | 1.329 (3) | C27—O3 | 1.232 (3) |
C10—H8 | 0.9300 | C27—C28 | 1.474 (3) |
C11—N2 | 1.358 (3) | C28—O4 | 1.245 (3) |
C11—C12 | 1.422 (3) | N1—Cu1 | 1.9931 (18) |
C12—N1 | 1.363 (3) | N2—Cu1 | 2.0371 (18) |
C13—N3 | 1.321 (3) | N3—Cu1 | 2.188 (2) |
C13—C14 | 1.405 (4) | N4—Cu1 | 1.9913 (19) |
C13—H9 | 0.9300 | O1—Cu1 | 1.9623 (16) |
C14—C15 | 1.359 (4) | O5—H19 | 0.92 (5) |
C14—H10 | 0.9300 | O5—H20 | 0.81 (4) |
C15—C16 | 1.385 (4) | O6—H21 | 0.74 (4) |
C15—H11 | 0.9300 | O6—H22 | 0.82 (4) |
C16—C24 | 1.397 (3) | O7—H17 | 0.80 (4) |
C16—C17 | 1.442 (4) | O7—H18 | 0.78 (4) |
C17—C18 | 1.330 (4) | ||
N1—C1—C2 | 122.6 (2) | C20—C19—C18 | 124.4 (3) |
N1—C1—H1 | 118.7 | C23—C19—C18 | 118.5 (3) |
C2—C1—H1 | 118.7 | C21—C20—C19 | 120.9 (3) |
C3—C2—C1 | 120.0 (2) | C21—C20—H14 | 119.6 |
C3—C2—H2 | 120.0 | C19—C20—H14 | 119.6 |
C1—C2—H2 | 120.0 | C20—C21—C22 | 118.9 (3) |
C2—C3—C4 | 119.4 (2) | C20—C21—H15 | 120.6 |
C2—C3—H3 | 120.3 | C22—C21—H15 | 120.6 |
C4—C3—H3 | 120.3 | N4—C22—C21 | 122.7 (3) |
C12—C4—C3 | 117.0 (2) | N4—C22—H16 | 118.7 |
C12—C4—C5 | 118.4 (2) | C21—C22—H16 | 118.7 |
C3—C4—C5 | 124.5 (2) | N4—C23—C19 | 121.8 (2) |
C6—C5—C4 | 121.1 (2) | N4—C23—C24 | 117.9 (2) |
C6—C5—H4 | 119.4 | C19—C23—C24 | 120.3 (2) |
C4—C5—H4 | 119.4 | N3—C24—C16 | 123.2 (2) |
C5—C6—C7 | 121.6 (2) | N3—C24—C23 | 117.3 (2) |
C5—C6—H5 | 119.2 | C16—C24—C23 | 119.5 (2) |
C7—C6—H5 | 119.2 | O1—C25—C26 | 133.6 (2) |
C8—C7—C11 | 117.3 (2) | O1—C25—C28 | 134.4 (2) |
C8—C7—C6 | 124.6 (2) | C26—C25—C28 | 91.98 (19) |
C11—C7—C6 | 118.1 (2) | O2—C26—C25 | 135.1 (2) |
C9—C8—C7 | 119.5 (2) | O2—C26—C27 | 135.4 (2) |
C9—C8—H6 | 120.3 | C25—C26—C27 | 89.43 (18) |
C7—C8—H6 | 120.3 | O3—C27—C28 | 135.5 (2) |
C8—C9—C10 | 119.9 (2) | O3—C27—C26 | 135.1 (3) |
C8—C9—H7 | 120.1 | C28—C27—C26 | 89.40 (19) |
C10—C9—H7 | 120.1 | O4—C28—C25 | 133.4 (2) |
N2—C10—C9 | 122.6 (2) | O4—C28—C27 | 137.4 (2) |
N2—C10—H8 | 118.7 | C25—C28—C27 | 89.19 (19) |
C9—C10—H8 | 118.7 | C1—N1—C12 | 117.79 (19) |
N2—C11—C7 | 123.2 (2) | C1—N1—Cu1 | 128.73 (16) |
N2—C11—C12 | 116.82 (19) | C12—N1—Cu1 | 113.43 (14) |
C7—C11—C12 | 120.01 (19) | C10—N2—C11 | 117.6 (2) |
N1—C12—C4 | 123.1 (2) | C10—N2—Cu1 | 130.61 (16) |
N1—C12—C11 | 116.16 (19) | C11—N2—Cu1 | 111.83 (14) |
C4—C12—C11 | 120.7 (2) | C13—N3—C24 | 117.8 (2) |
N3—C13—C14 | 122.6 (3) | C13—N3—Cu1 | 132.57 (19) |
N3—C13—H9 | 118.7 | C24—N3—Cu1 | 109.42 (15) |
C14—C13—H9 | 118.7 | C22—N4—C23 | 118.6 (2) |
C15—C14—C13 | 118.9 (3) | C22—N4—Cu1 | 125.94 (17) |
C15—C14—H10 | 120.6 | C23—N4—Cu1 | 115.44 (15) |
C13—C14—H10 | 120.6 | C25—O1—Cu1 | 117.83 (13) |
C14—C15—C16 | 120.5 (3) | H19—O5—H20 | 91 (4) |
C14—C15—H11 | 119.8 | H21—O6—H22 | 107 (4) |
C16—C15—H11 | 119.8 | H17—O7—H18 | 117 (4) |
C15—C16—C24 | 117.1 (3) | O1—Cu1—N4 | 92.03 (7) |
C15—C16—C17 | 124.5 (3) | O1—Cu1—N1 | 91.03 (7) |
C24—C16—C17 | 118.4 (3) | N4—Cu1—N1 | 176.81 (8) |
C18—C17—C16 | 121.6 (3) | O1—Cu1—N2 | 153.50 (7) |
C18—C17—H12 | 119.2 | N4—Cu1—N2 | 95.96 (7) |
C16—C17—H12 | 119.2 | N1—Cu1—N2 | 81.68 (7) |
C17—C18—C19 | 121.6 (3) | O1—Cu1—N3 | 95.41 (7) |
C17—C18—H13 | 119.2 | N4—Cu1—N3 | 79.99 (8) |
C19—C18—H13 | 119.2 | N1—Cu1—N3 | 98.80 (7) |
C20—C19—C23 | 117.1 (3) | N2—Cu1—N3 | 110.84 (7) |
N1—C1—C2—C3 | 0.6 (4) | O3—C27—C28—O4 | 0.4 (5) |
C1—C2—C3—C4 | 0.2 (4) | C26—C27—C28—O4 | 179.3 (3) |
C2—C3—C4—C12 | −0.6 (4) | O3—C27—C28—C25 | −179.3 (3) |
C2—C3—C4—C5 | 179.5 (2) | C26—C27—C28—C25 | −0.41 (17) |
C12—C4—C5—C6 | −1.1 (3) | C2—C1—N1—C12 | −1.0 (4) |
C3—C4—C5—C6 | 178.8 (2) | C2—C1—N1—Cu1 | −178.04 (18) |
C4—C5—C6—C7 | 0.4 (4) | C4—C12—N1—C1 | 0.6 (3) |
C5—C6—C7—C8 | −179.9 (2) | C11—C12—N1—C1 | 179.9 (2) |
C5—C6—C7—C11 | 0.6 (3) | C4—C12—N1—Cu1 | 178.09 (17) |
C11—C7—C8—C9 | −0.9 (4) | C11—C12—N1—Cu1 | −2.6 (2) |
C6—C7—C8—C9 | 179.5 (2) | C9—C10—N2—C11 | −0.9 (4) |
C7—C8—C9—C10 | 1.3 (4) | C9—C10—N2—Cu1 | 178.9 (2) |
C8—C9—C10—N2 | −0.4 (4) | C7—C11—N2—C10 | 1.2 (3) |
C8—C7—C11—N2 | −0.3 (3) | C12—C11—N2—C10 | −178.7 (2) |
C6—C7—C11—N2 | 179.3 (2) | C7—C11—N2—Cu1 | −178.61 (17) |
C8—C7—C11—C12 | 179.6 (2) | C12—C11—N2—Cu1 | 1.5 (2) |
C6—C7—C11—C12 | −0.8 (3) | C14—C13—N3—C24 | 1.1 (4) |
C3—C4—C12—N1 | 0.2 (3) | C14—C13—N3—Cu1 | −172.9 (2) |
C5—C4—C12—N1 | −179.9 (2) | C16—C24—N3—C13 | 1.0 (4) |
C3—C4—C12—C11 | −179.1 (2) | C23—C24—N3—C13 | −176.7 (2) |
C5—C4—C12—C11 | 0.8 (3) | C16—C24—N3—Cu1 | 176.33 (19) |
N2—C11—C12—N1 | 0.7 (3) | C23—C24—N3—Cu1 | −1.4 (2) |
C7—C11—C12—N1 | −179.18 (19) | C21—C22—N4—C23 | 1.9 (4) |
N2—C11—C12—C4 | −180.0 (2) | C21—C22—N4—Cu1 | 179.65 (19) |
C7—C11—C12—C4 | 0.1 (3) | C19—C23—N4—C22 | −1.8 (3) |
N3—C13—C14—C15 | −2.1 (5) | C24—C23—N4—C22 | 176.6 (2) |
C13—C14—C15—C16 | 0.9 (5) | C19—C23—N4—Cu1 | −179.75 (17) |
C14—C15—C16—C24 | 1.1 (4) | C24—C23—N4—Cu1 | −1.3 (3) |
C14—C15—C16—C17 | −179.5 (3) | C26—C25—O1—Cu1 | 153.4 (2) |
C15—C16—C17—C18 | −177.0 (3) | C28—C25—O1—Cu1 | −24.5 (3) |
C24—C16—C17—C18 | 2.4 (4) | C25—O1—Cu1—N4 | 103.50 (16) |
C16—C17—C18—C19 | 0.4 (5) | C25—O1—Cu1—N1 | −77.43 (16) |
C17—C18—C19—C20 | 176.4 (3) | C25—O1—Cu1—N2 | −4.2 (3) |
C17—C18—C19—C23 | −1.8 (4) | C25—O1—Cu1—N3 | −176.36 (16) |
C23—C19—C20—C21 | 1.1 (4) | C22—N4—Cu1—O1 | −82.2 (2) |
C18—C19—C20—C21 | −177.2 (3) | C23—N4—Cu1—O1 | 95.55 (16) |
C19—C20—C21—C22 | −1.0 (4) | C22—N4—Cu1—N2 | 72.5 (2) |
C20—C21—C22—N4 | −0.6 (4) | C23—N4—Cu1—N2 | −109.76 (16) |
C20—C19—C23—N4 | 0.3 (4) | C22—N4—Cu1—N3 | −177.3 (2) |
C18—C19—C23—N4 | 178.7 (2) | C23—N4—Cu1—N3 | 0.41 (16) |
C20—C19—C23—C24 | −178.0 (2) | C1—N1—Cu1—O1 | −25.8 (2) |
C18—C19—C23—C24 | 0.3 (3) | C12—N1—Cu1—O1 | 157.05 (15) |
C15—C16—C24—N3 | −2.1 (4) | C1—N1—Cu1—N2 | 179.8 (2) |
C17—C16—C24—N3 | 178.5 (2) | C12—N1—Cu1—N2 | 2.63 (15) |
C15—C16—C24—C23 | 175.6 (2) | C1—N1—Cu1—N3 | 69.8 (2) |
C17—C16—C24—C23 | −3.8 (4) | C12—N1—Cu1—N3 | −107.32 (15) |
N4—C23—C24—N3 | 1.9 (3) | C10—N2—Cu1—O1 | 102.6 (3) |
C19—C23—C24—N3 | −179.7 (2) | C11—N2—Cu1—O1 | −77.6 (2) |
N4—C23—C24—C16 | −175.9 (2) | C10—N2—Cu1—N4 | −4.2 (2) |
C19—C23—C24—C16 | 2.5 (3) | C11—N2—Cu1—N4 | 175.61 (15) |
O1—C25—C26—O2 | −0.5 (4) | C10—N2—Cu1—N1 | 178.0 (2) |
C28—C25—C26—O2 | 178.0 (3) | C11—N2—Cu1—N1 | −2.23 (15) |
O1—C25—C26—C27 | −178.9 (2) | C10—N2—Cu1—N3 | −85.7 (2) |
C28—C25—C26—C27 | −0.42 (17) | C11—N2—Cu1—N3 | 94.07 (16) |
O2—C26—C27—O3 | 0.9 (5) | C13—N3—Cu1—O1 | 83.8 (2) |
C25—C26—C27—O3 | 179.3 (3) | C24—N3—Cu1—O1 | −90.56 (15) |
O2—C26—C27—C28 | −178.0 (3) | C13—N3—Cu1—N4 | 175.0 (2) |
C25—C26—C27—C28 | 0.42 (17) | C24—N3—Cu1—N4 | 0.55 (15) |
O1—C25—C28—O4 | −0.8 (4) | C13—N3—Cu1—N1 | −8.0 (2) |
C26—C25—C28—O4 | −179.3 (3) | C24—N3—Cu1—N1 | 177.56 (15) |
O1—C25—C28—C27 | 178.9 (2) | C13—N3—Cu1—N2 | −92.4 (2) |
C26—C25—C28—C27 | 0.42 (17) | C24—N3—Cu1—N2 | 93.17 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H17···O4i | 0.80 (4) | 2.03 (4) | 2.825 (3) | 175 (4) |
O7—H18···O6ii | 0.78 (4) | 2.01 (4) | 2.775 (4) | 165 (4) |
O5—H19···O7iii | 0.92 (5) | 1.96 (5) | 2.874 (4) | 169 (4) |
O5—H20···O3i | 0.81 (4) | 2.04 (5) | 2.825 (4) | 162 (4) |
O6—H21···O7iii | 0.74 (4) | 2.17 (4) | 2.878 (4) | 160 (4) |
O6—H22···O2i | 0.82 (4) | 1.96 (4) | 2.764 (3) | 167 (3) |
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) −x+1/2, y−1/2, −z+1/2; (iii) x−1/2, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C4O4)(C12H8N2)2]·3H2O |
Mr | 590.05 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 12.5563 (9), 16.291 (1), 12.6208 (9) |
β (°) | 96.896 (6) |
V (Å3) | 2563.0 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.91 |
Crystal size (mm) | 0.42 × 0.28 × 0.17 |
Data collection | |
Diffractometer | Stoe IPDS 2 diffractometer |
Absorption correction | Integration (X-RED32; Stoe & Cie, 2002) |
Tmin, Tmax | 0.736, 0.89 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 36262, 5051, 3155 |
Rint | 0.105 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.068, 0.82 |
No. of reflections | 5051 |
No. of parameters | 385 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.20, −0.39 |
Computer programs: X-AREA (Stoe & Cie, 2002), X-AREA, X-RED32 (Stoe & Cie, 2002), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), WinGX (Farrugia, 1999).
C25—O1 | 1.278 (3) | N2—Cu1 | 2.0371 (18) |
C26—O2 | 1.248 (3) | N3—Cu1 | 2.188 (2) |
C27—O3 | 1.232 (3) | N4—Cu1 | 1.9913 (19) |
C28—O4 | 1.245 (3) | O1—Cu1 | 1.9623 (16) |
N1—Cu1 | 1.9931 (18) | ||
O1—Cu1—N4 | 92.03 (7) | N1—Cu1—N2 | 81.68 (7) |
O1—Cu1—N1 | 91.03 (7) | O1—Cu1—N3 | 95.41 (7) |
N4—Cu1—N1 | 176.81 (8) | N4—Cu1—N3 | 79.99 (8) |
O1—Cu1—N2 | 153.50 (7) | N1—Cu1—N3 | 98.80 (7) |
N4—Cu1—N2 | 95.96 (7) | N2—Cu1—N3 | 110.84 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
O7—H17···O4i | 0.80 (4) | 2.03 (4) | 2.825 (3) | 175 (4) |
O7—H18···O6ii | 0.78 (4) | 2.01 (4) | 2.775 (4) | 165 (4) |
O5—H19···O7iii | 0.92 (5) | 1.96 (5) | 2.874 (4) | 169 (4) |
O5—H20···O3i | 0.81 (4) | 2.04 (5) | 2.825 (4) | 162 (4) |
O6—H21···O7iii | 0.74 (4) | 2.17 (4) | 2.878 (4) | 160 (4) |
O6—H22···O2i | 0.82 (4) | 1.96 (4) | 2.764 (3) | 167 (3) |
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) −x+1/2, y−1/2, −z+1/2; (iii) x−1/2, −y+1/2, z−1/2. |
Studies of the coordination chemistry of the squarate ligand have attracted increasing attention, because it gives rise to a wide variety of complexes and adopts mono- or polydentate coordination modes when acting as a ligand towards first row transition metal ions. The squarate dianion does not act like a chelating ligand but rather like a bridge between two or more metal atoms as a mono- or polydentate ligand (Bernardinelli et al., 1988; Solans et al., 1990; Castro et al., 1999; Crispini et al., 2000; Shu et al., 2000; Yang et al., 2003), or as a counter-ligand in some compounds (Castan et al., 1992; Uçar et al., 2004; Yeşilel et al., 2004). Therefore, very little has been published to date about the structure of mononuclear complexes of the squarate ligand (Solans at al., 1990; Grove et al., 2002; Kirchmaier et al., 2003). Additionally, mixed-ligand metal complexes of 1,10-phenanthroline and its substituted derivatives continue to attract attention because this moiety plays an important role in biological systems, such as binding of small molecules to DNA (Xu et al., 2002; Macias et al., 2003; Mudasir et al., 2003; Sastri et al., 2003; Maheswari & Palaniandavar, 2004). 1,10-Phenanthroline has also been extensively used as a ligand in both analytical and preparative coordination chemistry (Idriss et al., 1980; Templeton & Pollak, 1989; Koch & Ackermann, 1992; Lorenzo et al., 1998; Shabir & Forrow, 2003).
Commonly, π–π stacking interactions have been observed in mixed-ligand phen complexes (Castillo et al., 2001; Zhou et al., 2001; Liang et al., 2002; Guo et al., 2004).π–π interactions in aromatic rings play vital roles in highly efficient and specific biological reactions, and control many molecular-recognition and self-assembly processes in solid-state and crystal engineering (Hunter, 1994; Desiraju, 1995; Claessens & Stoddart, 1997; Roesky & Andruh, 2003; Shi et al., 2004). In this context, the title mixed-ligand complex, (I), of copper squarate with phen has been prepared and its crystal structure is reported here. \sch
A view of the molecule of (I) and its atom-numbering scheme are shown in Fig. 1. Compound (I) has distorted square-pyramidal coordination geometry comprised of one carboxylate O atom from a monodentate squarate ligand and four N atoms from two chelating phen ligands. The coordinated squarate O atom [Cu1—O1 1.9623 (16) Å] and three phen N atoms [Cu1—N varying in the range 1.9913 (19)–2.03731 (18) Å] form the equatorial plane, whereas the fourth phen N atom is in the apical position [Cu1—N3 2.188 (2) Å]. The angles subtended at the Cu atom by the phen ligands are 81.68 (7) and 79.99 (8)°, which are in agreement with those previously reported for other phen-containing CuII complexes (Solans et al., 1990; Castro et al., 1999; Castillo et al., 2001). These `bite' angles are far from the ideal value of 90° because of the constrained geometry of the phen ring systems. There is also a significant tetragonal distortion of the equatorial plane [maximum atomic deviation 0.2739 (10) Å for atom N2], in which the Cu atom is 0.1639 (8) Å out of this mean plane.
The squarate ligand is essentially planar and the largest deviation from the mean plane is 0.0166 (13) Å for atom O2. The dihedral angle between the Cu basal equatorial plane and the squarate plane is 83.50 (5)°. The phen ligands are approximately planar, with r.m.s. deviations of 0.052 and 0.0127 Å for phen 1 (N1/N2/C1—C12) and phen 2 (N3/N4/C13—C24), respectively. Please check added definitions. The largest deviations from the mean planes are 0.024 (2) Å for atom C9 and 0.083 (3) Å for atom C14. The average C—C (1.40 Å) and C—N bonds (1.34 Å) and angles (120°) within the rings are in agreement with these previously reported for 1,10-phenenthroline-coordinated CuII complexes (Potocnak et al., 1996; Parker et al., 1996). The dihedral angles between the squarate plane and the phen mean planes are 82.80 (4) and 64.65 (4)°, while that between the phen mean planes is 70.00 (3)°.
In complex (I), the Cu1—O1 bond distance is nearly identical with that observed in [Cu(C4O4)(H2O)2(phen)]·2H2O (Solans et al., 1990), in which the Cu—O distance is 1.967 (2) Å, whereas it is 0.033 Å shorter than that in [Cu2(C4O4)(phen)4](ClO2)2·2H2O (Castro et al., 1999). This is clearly due to the fact that the squarate is coordinated to the Cu atom in a monodentate fashion and therefore most of the negative charge is located on the coordinated O atom. These C—O bond distances of the squarate ligand are found to be similar to those of related monodentate squarate complexes (Bernardinelli et al., 1988; Solans et al., 1990).
The crystal packing in (I) is formed by intermolecular hydrogen bonding (Fig. 2), and π–π and π–ring (Fig. 3) interactions. Each neutral complex unit is linked to a second unit via hydrogen-bonding interactions through the solvate water molecules and the O atoms of the squarate ligand. The uncoordinated O atoms of the squarate, which are linked to each other by means of two solvate molecules, also make a contribution to the crystal packing (Table 2).
The phen ligand belonging to a unit A at (x, y, z − 1) and that belonging to a crystallographically related unit B at (1 − x, −y, 1 − z) are stacked nearly parallel to each other, with a dihedral angle between their aromatic rings [ring 1 and ring 2 Please define] of 2.85° (Fig. 3). For the π–π stacking interaction, the interplanar separation of these aromatic rings is in the range 3.400–3.435 Å [Cg1···Cg2 3.7124 (15) Å; Cgx denotes the centroid of phen ring x] and the shortest interatomic contact is 3.444 Å. The third neighbouring phen ligand, belonging to unit C at (x + 1/2, 1/2 − y, z − 1/2), is stacked nearly parallel to units A and B. The dihedral angle between aromatic rings 1 and 3 Please define ring 3 (located in units B and C, respectively) is 9.59°, while this angle between aromatic rings 1 and 4 Please define ring 4 is 9.32°. For the π–π stacking interaction, the interplanar separation of these aromatic rings (1 and 3) is in the range 3.603–3.525 Å [Cg1···Cg3 3.6891 (15) Å] and the shortest interatomic contact is 3.429 Å, whereas the interplanar separation of the aromatic rings 1 and 4 is in the range 3.608–3.894 Å [Cg1···Cg4 4.1592 (15) Å] and the shortest interatomic contact is 3.814 Å.
In the structure of (I) there is also a weak C—H···π interaction between C5—H4 (of a phen ligand) and a phen ring (Fig. 3). The C—H···Cg contact distance between the centroid of a phen ring and the H atoms nearest that phen ring is 3.1993 Å. The perpendicular distance between atom H4 and the centre of the phen ring is 3.117 Å and the C—H···Cg angle is 88.33°.
These intermolecular interactions, namely an extensive network of hydrogen bonds, π–π stacking and π–ring interactions, are responsible for constructing an infinite three-dimensional lattice int he crystal of (I).