Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827011204276X/sk3453sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827011204276X/sk3453Isup2.hkl |
CCDC reference: 914645
Crystals of (I) were prepared at room temperature by the reaction of [Cu(sal-L-glu)(H2O)2].H2O [where sal-L-glu is N-salicylidene-L-glutamate(2-)], with imidazole in ethanol solution in a 1:2 molar ratio. Crystals were obtained after a few days by slow evaporation of the solvent at room temperature. The crystals were filtered off and washed with a small amount of cooled ethanol and ether and were finally air dried.
Aromatic, primary and secondary H atoms were refined isotropically, with Uiso(H) = 1.2Ueq(C), and their positions were constrained to an ideal geometry using an appropriate riding model (C—H = 0.95 Å for aromatic, 1.00 Å for primary and 0.99 Å for secondary H atoms). For methyl groups, the C—C—H angles were kept fixed (109.5°), while the torsion angles were allowed to refine with the starting positions based on the circular Fourier synthesis averaged using the local threefold axis, with Uiso(H) = 1.5Ueq(C) and the C—H distances constrained to 0.98 Å. For the hydroxy group, the C—O—H angle was kept fixed (109.5°), while the torsion angle was allowed to refine with the starting positions based on the circular Fourier synthesis, with Uiso(H) = 1.5Ueq(O) and the O—H distance constrained to 0.84 Å.
Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003) and SADABS (Sheldrick, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
[Cu(C3H4N2)4(C2H6O)2][Cu2(C15H14N3O5)2] | Z = 1 |
Mr = 1187.67 | F(000) = 613 |
Triclinic, P1 | Dx = 1.494 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.0275 (1) Å | Cell parameters from 8192 reflections |
b = 9.9401 (1) Å | θ = 2.1–30.5° |
c = 16.8444 (1) Å | µ = 1.27 mm−1 |
α = 96.607 (1)° | T = 173 K |
β = 95.134 (1)° | Needle, blue |
γ = 96.394 (1)° | 0.60 × 0.12 × 0.09 mm |
V = 1319.71 (2) Å3 |
Siemens SMART CCD area-detector diffractometer | 7695 independent reflections |
Radiation source: fine-focus sealed tube | 6910 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ω scans | θmax = 30.5°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −11→11 |
Tmin = 0.516, Tmax = 0.894 | k = −14→13 |
19560 measured reflections | l = −23→23 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0487P)2 + 0.7014P] where P = (Fo2 + 2Fc2)/3 |
7695 reflections | (Δ/σ)max = 0.001 |
342 parameters | Δρmax = 0.65 e Å−3 |
0 restraints | Δρmin = −0.51 e Å−3 |
[Cu(C3H4N2)4(C2H6O)2][Cu2(C15H14N3O5)2] | γ = 96.394 (1)° |
Mr = 1187.67 | V = 1319.71 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.0275 (1) Å | Mo Kα radiation |
b = 9.9401 (1) Å | µ = 1.27 mm−1 |
c = 16.8444 (1) Å | T = 173 K |
α = 96.607 (1)° | 0.60 × 0.12 × 0.09 mm |
β = 95.134 (1)° |
Siemens SMART CCD area-detector diffractometer | 7695 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 6910 reflections with I > 2σ(I) |
Tmin = 0.516, Tmax = 0.894 | Rint = 0.026 |
19560 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.65 e Å−3 |
7695 reflections | Δρmin = −0.51 e Å−3 |
342 parameters |
Experimental. Data were collected at 173 K using a Siemens SMART CCD diffractometer equipped with LT-2 A cooling device. A full sphere of reciprocal space was scanned by 0.3° steps in ω with a crystal–to–detector distance of 3.97 cm, 30 s per frame. Preliminary orientation matrix was obtained from the first 100 frames using SMART (Bruker, 2003). The collected frames were integrated using the preliminary orientation matrix which was updated every 100 frames. Final cell parameters were obtained by refinement on the position of 8192 reflections with I>10σ(I) after integration of all the frames data using SAINT (Bruker, 2003). |
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 | 0.13452 (2) | 0.630052 (16) | 0.479545 (10) | 0.01747 (5) | |
Cu2 | 1.0000 | 0.0000 | 0.0000 | 0.01931 (6) | |
O1 | 0.40911 (19) | 0.57001 (14) | 0.15490 (9) | 0.0419 (3) | |
O2 | 0.40280 (18) | 0.34096 (14) | 0.13837 (10) | 0.0425 (3) | |
O3 | 0.16929 (14) | 0.47814 (10) | 0.54060 (6) | 0.0206 (2) | |
O5 | 0.10670 (14) | 0.78228 (10) | 0.41445 (6) | 0.0221 (2) | |
O6 | 0.17486 (17) | 0.86298 (11) | 0.30070 (7) | 0.0297 (3) | |
N1 | 0.23993 (16) | 0.55297 (12) | 0.38624 (7) | 0.0178 (2) | |
N2 | 0.08240 (16) | 0.74564 (12) | 0.57708 (7) | 0.0192 (2) | |
N3 | −0.01714 (18) | 0.91090 (13) | 0.65249 (8) | 0.0235 (3) | |
H3 | −0.0641 | 0.9849 | 0.6662 | 0.028* | |
C1 | 0.34089 (18) | 0.45884 (14) | 0.38862 (9) | 0.0190 (3) | |
H1 | 0.4084 | 0.4462 | 0.3455 | 0.023* | |
C2 | 0.35872 (17) | 0.37114 (13) | 0.45233 (9) | 0.0182 (2) | |
C3 | 0.46818 (19) | 0.26835 (14) | 0.44106 (10) | 0.0224 (3) | |
H3A | 0.5250 | 0.2611 | 0.3939 | 0.027* | |
C4 | 0.4940 (2) | 0.17786 (15) | 0.49765 (11) | 0.0258 (3) | |
H4 | 0.5674 | 0.1101 | 0.4892 | 0.031* | |
C5 | 0.4085 (2) | 0.18953 (15) | 0.56764 (10) | 0.0261 (3) | |
H5 | 0.4232 | 0.1278 | 0.6060 | 0.031* | |
C6 | 0.3025 (2) | 0.29101 (15) | 0.58099 (9) | 0.0233 (3) | |
H6 | 0.2484 | 0.2978 | 0.6290 | 0.028* | |
C7 | 0.27345 (17) | 0.38493 (13) | 0.52395 (9) | 0.0182 (2) | |
C8 | 0.23665 (19) | 0.63546 (14) | 0.31764 (8) | 0.0191 (3) | |
H8 | 0.3537 | 0.6555 | 0.3025 | 0.023* | |
C9 | 0.11962 (19) | 0.56409 (15) | 0.24275 (9) | 0.0223 (3) | |
H9A | 0.0057 | 0.5408 | 0.2592 | 0.027* | |
H9B | 0.1103 | 0.6298 | 0.2032 | 0.027* | |
C10 | 0.17714 (19) | 0.43306 (15) | 0.20089 (9) | 0.0217 (3) | |
H10A | 0.0869 | 0.3904 | 0.1587 | 0.026* | |
H10B | 0.1889 | 0.3684 | 0.2410 | 0.026* | |
C11 | 0.34439 (19) | 0.45190 (15) | 0.16194 (9) | 0.0221 (3) | |
C12 | 0.1081 (2) | 0.72372 (15) | 0.65720 (9) | 0.0236 (3) | |
H12 | 0.1598 | 0.6505 | 0.6762 | 0.028* | |
C13 | 0.0463 (2) | 0.82577 (16) | 0.70441 (9) | 0.0270 (3) | |
H13 | 0.0471 | 0.8358 | 0.7612 | 0.032* | |
C14 | 0.0062 (2) | 0.85949 (15) | 0.57691 (9) | 0.0221 (3) | |
H14 | −0.0269 | 0.8986 | 0.5300 | 0.027* | |
C15 | 0.16902 (19) | 0.77178 (14) | 0.34626 (8) | 0.0189 (3) | |
N1A | 0.85635 (16) | −0.10789 (13) | 0.07061 (7) | 0.0205 (2) | |
N3A | 0.66783 (19) | −0.25775 (15) | 0.11300 (9) | 0.0304 (3) | |
H3A1 | 0.5775 | −0.3166 | 0.1132 | 0.036* | |
C2A | 0.7109 (2) | −0.19082 (17) | 0.05029 (10) | 0.0262 (3) | |
H2A | 0.6470 | −0.2013 | −0.0008 | 0.031* | |
C4A | 0.7912 (2) | −0.21658 (19) | 0.17611 (11) | 0.0318 (4) | |
H4A | 0.7950 | −0.2465 | 0.2277 | 0.038* | |
C5A | 0.9082 (2) | −0.12371 (17) | 0.14998 (9) | 0.0250 (3) | |
H5A | 1.0075 | −0.0781 | 0.1808 | 0.030* | |
N1B | 0.88269 (16) | 0.17106 (13) | 0.02825 (8) | 0.0209 (2) | |
N3B | 0.69987 (18) | 0.30377 (15) | 0.07838 (9) | 0.0290 (3) | |
H3B | 0.6203 | 0.3313 | 0.1068 | 0.035* | |
C2B | 0.7615 (2) | 0.18189 (17) | 0.07787 (10) | 0.0263 (3) | |
H2B | 0.7236 | 0.1127 | 0.1089 | 0.032* | |
C4B | 0.7850 (2) | 0.37652 (18) | 0.02618 (11) | 0.0327 (4) | |
H4B | 0.7687 | 0.4653 | 0.0137 | 0.039* | |
C5B | 0.8982 (2) | 0.29490 (17) | −0.00431 (11) | 0.0300 (3) | |
H5B | 0.9750 | 0.3189 | −0.0416 | 0.036* | |
O3C | 0.77625 (16) | −0.07884 (13) | −0.12461 (8) | 0.0313 (3) | |
H3C | 0.7379 | −0.1620 | −0.1321 | 0.047* | |
C1C | 0.5324 (3) | −0.0495 (3) | −0.22109 (13) | 0.0452 (5) | |
H1C1 | 0.6021 | −0.0452 | −0.2658 | 0.068* | |
H1C2 | 0.4411 | 0.0072 | −0.2282 | 0.068* | |
H1C3 | 0.4843 | −0.1442 | −0.2199 | 0.068* | |
C2C | 0.6408 (2) | 0.0028 (2) | −0.14211 (12) | 0.0348 (4) | |
H2C1 | 0.6904 | 0.0979 | −0.1442 | 0.042* | |
H2C2 | 0.5679 | 0.0039 | −0.0977 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.02400 (9) | 0.01273 (8) | 0.01862 (9) | 0.00762 (6) | 0.00815 (6) | 0.00463 (6) |
Cu2 | 0.02176 (12) | 0.01692 (11) | 0.02207 (12) | 0.00350 (9) | 0.01122 (9) | 0.00634 (9) |
O1 | 0.0463 (8) | 0.0278 (6) | 0.0554 (9) | −0.0020 (6) | 0.0281 (7) | 0.0097 (6) |
O2 | 0.0348 (7) | 0.0274 (6) | 0.0667 (10) | 0.0042 (5) | 0.0272 (7) | −0.0052 (6) |
O3 | 0.0262 (5) | 0.0160 (4) | 0.0231 (5) | 0.0089 (4) | 0.0081 (4) | 0.0064 (4) |
O5 | 0.0315 (6) | 0.0166 (5) | 0.0225 (5) | 0.0110 (4) | 0.0115 (4) | 0.0072 (4) |
O6 | 0.0518 (7) | 0.0194 (5) | 0.0239 (5) | 0.0158 (5) | 0.0147 (5) | 0.0091 (4) |
N1 | 0.0236 (6) | 0.0130 (5) | 0.0182 (5) | 0.0055 (4) | 0.0055 (4) | 0.0026 (4) |
N2 | 0.0243 (6) | 0.0150 (5) | 0.0202 (5) | 0.0054 (4) | 0.0070 (4) | 0.0040 (4) |
N3 | 0.0328 (7) | 0.0162 (5) | 0.0234 (6) | 0.0076 (5) | 0.0089 (5) | 0.0007 (4) |
C1 | 0.0223 (6) | 0.0153 (6) | 0.0208 (6) | 0.0059 (5) | 0.0063 (5) | 0.0017 (5) |
C2 | 0.0192 (6) | 0.0123 (5) | 0.0238 (6) | 0.0038 (5) | 0.0025 (5) | 0.0030 (5) |
C3 | 0.0224 (7) | 0.0149 (6) | 0.0311 (7) | 0.0065 (5) | 0.0049 (6) | 0.0026 (5) |
C4 | 0.0240 (7) | 0.0139 (6) | 0.0408 (9) | 0.0076 (5) | 0.0020 (6) | 0.0051 (6) |
C5 | 0.0267 (7) | 0.0173 (6) | 0.0356 (8) | 0.0050 (5) | −0.0010 (6) | 0.0102 (6) |
C6 | 0.0261 (7) | 0.0200 (6) | 0.0259 (7) | 0.0057 (5) | 0.0029 (5) | 0.0087 (5) |
C7 | 0.0189 (6) | 0.0127 (5) | 0.0240 (6) | 0.0035 (5) | 0.0024 (5) | 0.0048 (5) |
C8 | 0.0261 (7) | 0.0154 (6) | 0.0178 (6) | 0.0073 (5) | 0.0056 (5) | 0.0033 (5) |
C9 | 0.0228 (7) | 0.0226 (7) | 0.0225 (7) | 0.0067 (5) | 0.0044 (5) | 0.0018 (5) |
C10 | 0.0228 (7) | 0.0199 (6) | 0.0223 (6) | 0.0022 (5) | 0.0061 (5) | −0.0008 (5) |
C11 | 0.0239 (7) | 0.0211 (6) | 0.0211 (6) | 0.0004 (5) | 0.0049 (5) | 0.0024 (5) |
C12 | 0.0319 (8) | 0.0181 (6) | 0.0223 (7) | 0.0062 (6) | 0.0037 (6) | 0.0051 (5) |
C13 | 0.0414 (9) | 0.0204 (7) | 0.0201 (7) | 0.0049 (6) | 0.0071 (6) | 0.0026 (5) |
C14 | 0.0313 (7) | 0.0166 (6) | 0.0205 (6) | 0.0078 (5) | 0.0062 (5) | 0.0032 (5) |
C15 | 0.0249 (7) | 0.0139 (6) | 0.0192 (6) | 0.0063 (5) | 0.0043 (5) | 0.0022 (5) |
N1A | 0.0222 (6) | 0.0194 (5) | 0.0218 (6) | 0.0023 (4) | 0.0089 (4) | 0.0061 (4) |
N3A | 0.0298 (7) | 0.0246 (6) | 0.0388 (8) | −0.0027 (5) | 0.0148 (6) | 0.0098 (6) |
C2A | 0.0245 (7) | 0.0263 (7) | 0.0284 (7) | −0.0010 (6) | 0.0082 (6) | 0.0061 (6) |
C4A | 0.0382 (9) | 0.0341 (9) | 0.0285 (8) | 0.0072 (7) | 0.0151 (7) | 0.0148 (7) |
C5A | 0.0279 (7) | 0.0266 (7) | 0.0222 (7) | 0.0046 (6) | 0.0080 (6) | 0.0053 (5) |
N1B | 0.0224 (6) | 0.0200 (6) | 0.0216 (6) | 0.0029 (4) | 0.0071 (4) | 0.0035 (4) |
N3B | 0.0256 (6) | 0.0272 (7) | 0.0356 (7) | 0.0085 (5) | 0.0101 (5) | −0.0006 (6) |
C2B | 0.0241 (7) | 0.0251 (7) | 0.0322 (8) | 0.0052 (6) | 0.0117 (6) | 0.0044 (6) |
C4B | 0.0416 (10) | 0.0242 (7) | 0.0358 (9) | 0.0123 (7) | 0.0108 (7) | 0.0051 (6) |
C5B | 0.0412 (9) | 0.0222 (7) | 0.0307 (8) | 0.0087 (6) | 0.0149 (7) | 0.0077 (6) |
O3C | 0.0282 (6) | 0.0246 (6) | 0.0413 (7) | 0.0017 (5) | 0.0059 (5) | 0.0051 (5) |
C1C | 0.0386 (10) | 0.0560 (13) | 0.0396 (10) | −0.0023 (9) | −0.0003 (8) | 0.0113 (9) |
C2C | 0.0288 (8) | 0.0340 (9) | 0.0420 (10) | 0.0044 (7) | 0.0058 (7) | 0.0044 (7) |
Cu1—O3 | 1.9533 (10) | C9—H9A | 0.9900 |
Cu1—N1 | 1.9694 (12) | C9—H9B | 0.9900 |
Cu1—O5 | 1.9887 (10) | C10—C11 | 1.549 (2) |
Cu1—N2 | 1.9974 (12) | C10—H10A | 0.9900 |
Cu2—N1A | 2.0391 (12) | C10—H10B | 0.9900 |
Cu2—N1Ai | 2.0391 (12) | C12—C13 | 1.380 (2) |
Cu2—N1Bi | 2.0628 (13) | C12—H12 | 0.9500 |
Cu2—N1B | 2.0628 (13) | C13—H13 | 0.9500 |
O1—C11 | 1.2528 (19) | C14—H14 | 0.9500 |
O2—C11 | 1.281 (2) | N1A—C2A | 1.345 (2) |
O3—C7 | 1.3383 (16) | N1A—C5A | 1.396 (2) |
O5—C15 | 1.2911 (17) | N3A—C2A | 1.362 (2) |
O6—C15 | 1.2531 (17) | N3A—C4A | 1.378 (2) |
N1—C1 | 1.3061 (18) | N3A—H3A1 | 0.8800 |
N1—C8 | 1.4918 (17) | C2A—H2A | 0.9500 |
N2—C14 | 1.3452 (18) | C4A—C5A | 1.379 (2) |
N2—C12 | 1.3926 (19) | C4A—H4A | 0.9500 |
N3—C14 | 1.3533 (19) | C5A—H5A | 0.9500 |
N3—C13 | 1.388 (2) | N1B—C2B | 1.3432 (19) |
N3—H3 | 0.8800 | N1B—C5B | 1.402 (2) |
C1—C2 | 1.4653 (19) | N3B—C2B | 1.358 (2) |
C1—H1 | 0.9500 | N3B—C4B | 1.381 (2) |
C2—C3 | 1.4274 (19) | N3B—H3B | 0.8800 |
C2—C7 | 1.440 (2) | C2B—H2B | 0.9500 |
C3—C4 | 1.401 (2) | C4B—C5B | 1.379 (2) |
C3—H3A | 0.9500 | C4B—H4B | 0.9500 |
C4—C5 | 1.416 (2) | C5B—H5B | 0.9500 |
C4—H4 | 0.9500 | O3C—C2C | 1.456 (2) |
C5—C6 | 1.402 (2) | O3C—H3C | 0.8400 |
C5—H5 | 0.9500 | C1C—C2C | 1.527 (3) |
C6—C7 | 1.4366 (19) | C1C—H1C1 | 0.9800 |
C6—H6 | 0.9500 | C1C—H1C2 | 0.9800 |
C8—C9 | 1.553 (2) | C1C—H1C3 | 0.9800 |
C8—C15 | 1.5569 (19) | C2C—H2C1 | 0.9900 |
C8—H8 | 1.0000 | C2C—H2C2 | 0.9900 |
C9—C10 | 1.545 (2) | ||
O3—Cu1—N1 | 94.15 (5) | C11—C10—H10B | 108.3 |
O3—Cu1—O5 | 177.53 (4) | H10A—C10—H10B | 107.4 |
N1—Cu1—O5 | 83.52 (4) | O1—C11—O2 | 125.82 (15) |
O3—Cu1—N2 | 91.78 (5) | O1—C11—C10 | 119.14 (14) |
N1—Cu1—N2 | 164.51 (5) | O2—C11—C10 | 115.03 (13) |
O5—Cu1—N2 | 90.28 (5) | C13—C12—N2 | 108.89 (13) |
N1A—Cu2—N1Ai | 180.0 | C13—C12—H12 | 125.6 |
N1A—Cu2—N1Bi | 88.77 (5) | N2—C12—H12 | 125.6 |
N1Ai—Cu2—N1Bi | 91.23 (5) | N3—C13—C12 | 106.43 (13) |
N1A—Cu2—N1B | 91.23 (5) | N3—C13—H13 | 126.8 |
N1Ai—Cu2—N1B | 88.77 (5) | C12—C13—H13 | 126.8 |
N1Bi—Cu2—N1B | 180.0 | N2—C14—N3 | 110.98 (13) |
C7—O3—Cu1 | 125.14 (9) | N2—C14—H14 | 124.5 |
C15—O5—Cu1 | 115.76 (9) | N3—C14—H14 | 124.5 |
C1—N1—C8 | 119.38 (12) | O6—C15—O5 | 124.23 (13) |
C1—N1—Cu1 | 124.10 (10) | O6—C15—C8 | 117.82 (12) |
C8—N1—Cu1 | 114.46 (8) | O5—C15—C8 | 117.92 (12) |
C14—N2—C12 | 106.09 (12) | C2A—N1A—C5A | 106.18 (13) |
C14—N2—Cu1 | 125.46 (10) | C2A—N1A—Cu2 | 129.31 (11) |
C12—N2—Cu1 | 128.38 (10) | C5A—N1A—Cu2 | 123.92 (10) |
C14—N3—C13 | 107.60 (12) | C2A—N3A—C4A | 107.62 (14) |
C14—N3—H3 | 126.2 | C2A—N3A—H3A1 | 126.2 |
C13—N3—H3 | 126.2 | C4A—N3A—H3A1 | 126.2 |
N1—C1—C2 | 125.43 (13) | N1A—C2A—N3A | 110.66 (15) |
N1—C1—H1 | 117.3 | N1A—C2A—H2A | 124.7 |
C2—C1—H1 | 117.3 | N3A—C2A—H2A | 124.7 |
C3—C2—C7 | 119.86 (13) | C5A—C4A—N3A | 106.91 (14) |
C3—C2—C1 | 116.69 (13) | C5A—C4A—H4A | 126.5 |
C7—C2—C1 | 123.44 (12) | N3A—C4A—H4A | 126.5 |
C4—C3—C2 | 121.76 (14) | C4A—C5A—N1A | 108.63 (15) |
C4—C3—H3A | 119.1 | C4A—C5A—H5A | 125.7 |
C2—C3—H3A | 119.1 | N1A—C5A—H5A | 125.7 |
C3—C4—C5 | 118.65 (13) | C2B—N1B—C5B | 104.89 (13) |
C3—C4—H4 | 120.7 | C2B—N1B—Cu2 | 126.15 (11) |
C5—C4—H4 | 120.7 | C5B—N1B—Cu2 | 128.71 (10) |
C6—C5—C4 | 120.85 (14) | C2B—N3B—C4B | 107.39 (14) |
C6—C5—H5 | 119.6 | C2B—N3B—H3B | 126.3 |
C4—C5—H5 | 119.6 | C4B—N3B—H3B | 126.3 |
C5—C6—C7 | 121.67 (14) | N1B—C2B—N3B | 111.79 (14) |
C5—C6—H6 | 119.2 | N1B—C2B—H2B | 124.1 |
C7—C6—H6 | 119.2 | N3B—C2B—H2B | 124.1 |
O3—C7—C6 | 118.17 (13) | C5B—C4B—N3B | 106.42 (15) |
O3—C7—C2 | 124.64 (12) | C5B—C4B—H4B | 126.8 |
C6—C7—C2 | 117.19 (12) | N3B—C4B—H4B | 126.8 |
N1—C8—C9 | 113.10 (12) | C4B—C5B—N1B | 109.50 (15) |
N1—C8—C15 | 107.57 (11) | C4B—C5B—H5B | 125.3 |
C9—C8—C15 | 107.96 (11) | N1B—C5B—H5B | 125.3 |
N1—C8—H8 | 109.4 | C2C—O3C—H3C | 109.5 |
C9—C8—H8 | 109.4 | C2C—C1C—H1C1 | 109.5 |
C15—C8—H8 | 109.4 | C2C—C1C—H1C2 | 109.5 |
C10—C9—C8 | 115.32 (12) | H1C1—C1C—H1C2 | 109.5 |
C10—C9—H9A | 108.4 | C2C—C1C—H1C3 | 109.5 |
C8—C9—H9A | 108.4 | H1C1—C1C—H1C3 | 109.5 |
C10—C9—H9B | 108.4 | H1C2—C1C—H1C3 | 109.5 |
C8—C9—H9B | 108.4 | O3C—C2C—C1C | 113.49 (17) |
H9A—C9—H9B | 107.5 | O3C—C2C—H2C1 | 108.9 |
C9—C10—C11 | 116.10 (12) | C1C—C2C—H2C1 | 108.9 |
C9—C10—H10A | 108.3 | O3C—C2C—H2C2 | 108.9 |
C11—C10—H10A | 108.3 | C1C—C2C—H2C2 | 108.9 |
C9—C10—H10B | 108.3 | H2C1—C2C—H2C2 | 107.7 |
N1—Cu1—O3—C7 | 15.35 (12) | C8—C9—C10—C11 | −65.05 (17) |
N2—Cu1—O3—C7 | −150.33 (12) | C9—C10—C11—O1 | −11.1 (2) |
N1—Cu1—O5—C15 | −2.52 (11) | C9—C10—C11—O2 | 169.94 (15) |
N2—Cu1—O5—C15 | 163.26 (11) | C14—N2—C12—C13 | 0.00 (18) |
O3—Cu1—N1—C1 | −19.06 (12) | Cu1—N2—C12—C13 | −177.12 (11) |
O5—Cu1—N1—C1 | 160.14 (12) | C14—N3—C13—C12 | 0.30 (19) |
N2—Cu1—N1—C1 | 93.2 (2) | N2—C12—C13—N3 | −0.18 (19) |
O3—Cu1—N1—C8 | 177.42 (10) | C12—N2—C14—N3 | 0.20 (18) |
O5—Cu1—N1—C8 | −3.39 (10) | Cu1—N2—C14—N3 | 177.42 (10) |
N2—Cu1—N1—C8 | −70.4 (2) | C13—N3—C14—N2 | −0.31 (19) |
O3—Cu1—N2—C14 | −163.51 (13) | Cu1—O5—C15—O6 | −174.04 (12) |
N1—Cu1—N2—C14 | 84.0 (2) | Cu1—O5—C15—C8 | 7.78 (17) |
O5—Cu1—N2—C14 | 17.84 (13) | N1—C8—C15—O6 | 171.77 (13) |
O3—Cu1—N2—C12 | 13.09 (13) | C9—C8—C15—O6 | −65.87 (17) |
N1—Cu1—N2—C12 | −99.4 (2) | N1—C8—C15—O5 | −9.93 (18) |
O5—Cu1—N2—C12 | −165.56 (13) | C9—C8—C15—O5 | 112.43 (14) |
C8—N1—C1—C2 | 179.41 (13) | N1Bi—Cu2—N1A—C2A | −85.74 (14) |
Cu1—N1—C1—C2 | 16.6 (2) | N1B—Cu2—N1A—C2A | 94.27 (14) |
N1—C1—C2—C3 | 176.04 (14) | N1Bi—Cu2—N1A—C5A | 84.19 (12) |
N1—C1—C2—C7 | −4.4 (2) | N1B—Cu2—N1A—C5A | −95.81 (12) |
C7—C2—C3—C4 | 0.9 (2) | C5A—N1A—C2A—N3A | 0.30 (18) |
C1—C2—C3—C4 | −179.50 (14) | Cu2—N1A—C2A—N3A | 171.61 (11) |
C2—C3—C4—C5 | 0.1 (2) | C4A—N3A—C2A—N1A | −0.3 (2) |
C3—C4—C5—C6 | −1.2 (2) | C2A—N3A—C4A—C5A | 0.2 (2) |
C4—C5—C6—C7 | 1.3 (2) | N3A—C4A—C5A—N1A | 0.01 (19) |
Cu1—O3—C7—C6 | 171.46 (10) | C2A—N1A—C5A—C4A | −0.19 (18) |
Cu1—O3—C7—C2 | −8.9 (2) | Cu2—N1A—C5A—C4A | −172.09 (11) |
C5—C6—C7—O3 | 179.37 (14) | N1A—Cu2—N1B—C2B | 1.01 (14) |
C5—C6—C7—C2 | −0.3 (2) | N1Ai—Cu2—N1B—C2B | −178.99 (14) |
C3—C2—C7—O3 | 179.57 (13) | N1A—Cu2—N1B—C5B | −172.51 (14) |
C1—C2—C7—O3 | 0.0 (2) | N1Ai—Cu2—N1B—C5B | 7.49 (14) |
C3—C2—C7—C6 | −0.8 (2) | C5B—N1B—C2B—N3B | 0.21 (19) |
C1—C2—C7—C6 | 179.67 (13) | Cu2—N1B—C2B—N3B | −174.57 (11) |
C1—N1—C8—C9 | 83.97 (16) | C4B—N3B—C2B—N1B | 0.1 (2) |
Cu1—N1—C8—C9 | −111.66 (11) | C2B—N3B—C4B—C5B | −0.4 (2) |
C1—N1—C8—C15 | −156.90 (13) | N3B—C4B—C5B—N1B | 0.5 (2) |
Cu1—N1—C8—C15 | 7.47 (14) | C2B—N1B—C5B—C4B | −0.5 (2) |
N1—C8—C9—C10 | −66.68 (16) | Cu2—N1B—C5B—C4B | 174.13 (12) |
C15—C8—C9—C10 | 174.41 (12) |
Symmetry code: (i) −x+2, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O3C—H3C···O2ii | 0.84 | 1.99 | 2.8064 (18) | 166 |
N3B—H3B···O2 | 0.88 | 1.88 | 2.7178 (19) | 158 |
N3—H3···O6iii | 0.88 | 1.89 | 2.7716 (16) | 176 |
N3A—H3A1···O1iv | 0.88 | 1.90 | 2.7370 (19) | 159 |
C2A—H2A···O2ii | 0.95 | 2.54 | 3.353 (2) | 144 |
C2B—H2B···N1A | 0.95 | 2.58 | 3.052 (2) | 111 |
C5A—H5A···O3Ci | 0.95 | 2.53 | 3.148 (2) | 123 |
C5A—H5A···O6v | 0.95 | 2.49 | 3.196 (2) | 131 |
C1C—H1C1···O6vi | 0.98 | 2.56 | 3.306 (3) | 133 |
C14—H14···O5 | 0.95 | 2.53 | 2.9629 (18) | 108 |
Symmetry codes: (i) −x+2, −y, −z; (ii) −x+1, −y, −z; (iii) −x, −y+2, −z+1; (iv) x, y−1, z; (v) x+1, y−1, z; (vi) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C3H4N2)4(C2H6O)2][Cu2(C15H14N3O5)2] |
Mr | 1187.67 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 173 |
a, b, c (Å) | 8.0275 (1), 9.9401 (1), 16.8444 (1) |
α, β, γ (°) | 96.607 (1), 95.134 (1), 96.394 (1) |
V (Å3) | 1319.71 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.27 |
Crystal size (mm) | 0.60 × 0.12 × 0.09 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.516, 0.894 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19560, 7695, 6910 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.714 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.087, 1.00 |
No. of reflections | 7695 |
No. of parameters | 342 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.65, −0.51 |
Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003) and SADABS (Sheldrick, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2010), SHELXTL (Sheldrick, 2008).
Cu1—O3 | 1.9533 (10) | Cu1—N2 | 1.9974 (12) |
Cu1—N1 | 1.9694 (12) | Cu2—N1A | 2.0391 (12) |
Cu1—O5 | 1.9887 (10) | Cu2—N1B | 2.0628 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3C—H3C···O2i | 0.84 | 1.99 | 2.8064 (18) | 166 |
N3B—H3B···O2 | 0.88 | 1.88 | 2.7178 (19) | 158 |
N3—H3···O6ii | 0.88 | 1.89 | 2.7716 (16) | 176 |
N3A—H3A1···O1iii | 0.88 | 1.90 | 2.7370 (19) | 159 |
C2A—H2A···O2i | 0.95 | 2.54 | 3.353 (2) | 144 |
C2B—H2B···N1A | 0.95 | 2.58 | 3.052 (2) | 111 |
C5A—H5A···O3Civ | 0.95 | 2.53 | 3.148 (2) | 123 |
C5A—H5A···O6v | 0.95 | 2.49 | 3.196 (2) | 131 |
C1C—H1C1···O6vi | 0.98 | 2.56 | 3.306 (3) | 133 |
C14—H14···O5 | 0.95 | 2.53 | 2.9629 (18) | 108 |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y+2, −z+1; (iii) x, y−1, z; (iv) −x+2, −y, −z; (v) x+1, y−1, z; (vi) −x+1, −y+1, −z. |
Recently, considerable attention has been devoted to copper(II) complexes containing Schiff bases derived from salicylaldehyde and various amino acids, and N- or O-donor neutral ligands; this is due to the interest from many fields of bioinorganic chemistry. Copper(II) complexes of tridentate Schiff bases derived from salicylaldehyde and glutamic acid containing water or diazoles as additional ligands have proved to be superoxide dismutase mimetics, the most efficient scavenger of O2-. radicals, [and to?] exhibit antimicrobial, anti-inflammatory and antipyretic activities. In our previous work (Andrezálová et al., 1998; Kohútová et al., 2000), the synthesis and properties of copper(II) complexes containing Schiff bases derived from salicylaldehyde and glutamic acid were described. The neutral ligands pyridine, pyrazole, imidazole and their derivatives were used. As stated earlier, based on IR spectra and then confirmed by single-crystal X-ray analysis (Krätsmár-Šmogrovič et al., 1991; Kožíšek et al., 1991; Sivý et al., 1994), one of the two carboxylic acid groups of glutamic acid remained uncoordinated even after complexation. From this group of substances the structures of (1-methylimidazole)(N-salicylidene-rac-glutamato)copper(II) (Langer et al., 2003), (2-methylimidazole)(N-salicylidene-rac-glutamato)copper(II) (Langer, Scholtzová et al., 2004), aqua(N-salicylidene-L-glutamato methyl ester)copper(II) monohydrate (Langer, Gyepesová et al., 2004) and dimeric (isoquinoline)(N-salicylidene-D,L-glutamato)copper(II) ethanol solvate (Langer et al., 2009) have been determined. In a continuation of these studies, a new complex trans-bis(ethanol)tetrakis(1H-imidazole)copper(II) bis[µ-N-(2-oxidobenzylidene)-D,L-glutamato]bis[(1H-imidazole)cuprate(II)], (I), is presented herein. In the structure of (I), both ions are located on centres of inversion (Fig. 1). This complex has quite spectacular structural features. The cation is mononuclear, while the anion is binuclear and compound (I) is a racemic complex. Racemic complexes are often observed even though optically active amino acids have been employed (for examples, see Kettmann et al., 1993; Sivý et al., 1994; Langer et al., 2003; Langer, Scholtzová et al., 2004).
The two CuII ions are located in different coordination polyhedra, as shown in Fig. 2. The mononuclear unit of the cation is formed by four imidazole ligands [Cu2—N distances = 2.0391 (12)–2.0628 (13) Å] and by two O atoms of ethanol molecules [Cu2—O = 2.6228 (13) Å]. The anion has square-pyramidal CuII coordination defined by a tridentate N-salicylidene-rac-glutamate Schiff base dianion and a neutral monodentate imidazole ligand bound in the basal plane. The axial position is occupied by a phenolic O atom from an adjacent glutamate ligand [Cu1—O3(-x, -y+1, -z+1) = 2.5305 (11) Å], forming a centrosymmetric dimer. The molecules are arranged in dimeric units in good agreement with the result found for other dimeric compounds of this type, e.g. dimeric (imidazole-κN3)(N-salicylidene-rac-alaninato-κ3O,N,O')copper(II), with a Cu—Oapical distance of 2.500 (3) Å (Warda, 1998) and dimeric (pyrazole-κN2)(N-salicylidene-2,2-dimethylglycinato-κ3O, N,O')copper(II) pyrazole solvate (Hill & Warda,1999), in which the apex of the pyramids are [is] occupied by the phenolate O atom from an adjacent chelate molecule at a distance of 2.605 (2) Å, thus building a centrosymmetric dimer. All equatorial distances involving CuII in (I) are in normal ranges, the most variable copper distance in this class of compounds being the apical one. A rich variety of axial distortions ranging from square-planar to square-pyramidal has been found. It may be one of the reasons for the diversity of interactions of these CuII complexes with biological systems, e.g. the structure of (1-methylimidazole)(N-salicylidene-rac-glutamato)copper(II) (Langer et al., 2003) adopts a square-planar copper coordination mode. Atoms N1A and N1B, together with their respective centrosymmetrically related partners [N1Ai and N1Bi; symmetry code: (i) -x + 2, -y, -z], coordinate in a plane around the Cu2 atom, which lies on a centre of symmetry. The Cu2—N1A and Cu2—N1B bond lengths in (I) (Table 1) are slightly longer than the Cu1—N2 bond length in the anion, which indicates different bond strengths. Both ethanol O atoms (O3C and O3Ci) interact weakly in axial positions with the Cu2 atom, at a distance of 2.6228 (13) Å. The cation displays a slightly distorted octahedral coordination. The ions are associated via hydrogen bonding (Table 2), thus forming a complicated three-dimensional network.
In order to understand some interesting features of the electronic structure of the title compound, the electronic structures for two chemically relevant models A and B were calculated at the B3LYP/6–31G* level using the GAUSSIAN98 (Frisch et al., 1998) and PC GAMESS (Granovsky, 2003) programs. Model A represents the bidental anion with both CH2–COO- groups removed and dangling bonds capped with H atoms. All H atoms were re-optimized at the B3LYP/6–31G* level. The purpose of this model is twofold: (i) to estimate the bonding energy of both Cu—O bonds and (ii) to understand the spin state of both subunits and the electronic configuration of the central Cu atom. The most stable spin state is a triplet, but energetically very close is an open-shell singlet (S2 = 1.005). The interaction energy of two identical doublet subunits is approximatelly 4 kcal mol-1 (BSSE corrected). From the NBO analysis (Glendening et al., 1993) it follows that the electronic configuration of both Cu atoms in the anion (both in triplet or open-shell singlet coupling) is 4 s0.373 d9.15. Model B consists of the cation with two CH2–COO- groups (representing two different anions) as hydrogen-bond acceptors for ethanol molecules. As in the previous case, all H atoms were re-optimized. The electronic configuration of the central Cu atom from NBO analysis is 4 s0.333 d9.14, i.e. only slightly different from that of the Cu atoms in the anion. The interaction energy of ethanol in this model (i.e. 1/2 of energy for removing both ethanol molecules) is approximatelly 23 kcal mol-1 (BSSE corrected). The calculated Cu2—O3C energy is 11 kcal mol-1; the HB energy for the EtOH–CH3COO- interaction is 18 kcal mol-1. This relatively large HB energy is due to the fact that the O2 atom possesses a large negative charge (the Mulliken charge is -0.62). Thus, ethanol serves as a bridge, which binds the cation and anion by a relatively strong hydrogen bond in addition to the ionic interaction. This implies that the presence of ethanol is important for building the crystal structure.