Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802021591/cm6025sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802021591/cm6025Isup2.hkl |
CCDC reference: 202306
Key indicators
- Single-crystal X-ray study
- T = 300 K
- Mean (C-C) = 0.004 Å
- R factor = 0.036
- wR factor = 0.098
- Data-to-parameter ratio = 15.8
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
The title compound was obtained by mixing 1 mmol of Cu(NO3)2·2.5H2O (0.233 g) with 1 mmol of 1,10-phenanthroline (0.180 g) in 20 ml of MeOH and adding 1 mmol of lithium lactate (0.096 g) previously dissolved in the minimal amount of water. This solution was left standing and air-stable crystals were collected the following day.
H atoms for water molecule (H1A and H1B) and hydroxyl group (H18) were found in difference maps. The remaining H atoms, bonded to sp2– and sp3-hybridized C atoms, were placed at idealized positions. In the final cycles, all H atoms were constrained to ride on their parent atoms, with Uiso(H) = xUeq(parent), where x = 1.5 for Csp3—H and x = 1.2 for for Csp2—H groups. Constrained distances: methine C—H = 0.98 Å, methyl C—H = 0.96 Å and aryl C—H = 0.93 Å.
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 1998); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1998); software used to prepare material for publication: SHELXL97.
[Cu(C3H5O3)(C12H8N2)(H2O)]NO3 | F(000) = 844 |
Mr = 412.84 | Dx = 1.695 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 68 reflections |
a = 8.5646 (13) Å | θ = 4.8–12.5° |
b = 19.985 (3) Å | µ = 1.40 mm−1 |
c = 9.7854 (13) Å | T = 300 K |
β = 104.960 (11)° | Regular prism, blue |
V = 1618.2 (4) Å3 | 0.62 × 0.26 × 0.22 mm |
Z = 4 |
Bruker P4 diffractometer | 3156 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.023 |
Graphite monochromator | θmax = 27.5°, θmin = 2.0° |
ω scans | h = −1→11 |
Absorption correction: gaussian (XSCANS; Siemens, 1996) | k = −25→1 |
Tmin = 0.599, Tmax = 0.782 | l = −12→12 |
4687 measured reflections | 3 standard reflections every 97 reflections |
3706 independent reflections | intensity decay: 1.5% |
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)] = 0.037 | Hydrogen site location: See text |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0487P)2 + 0.9828P] where P = (Fo2 + 2Fc2)/3 |
3706 reflections | (Δ/σ)max = 0.001 |
235 parameters | Δρmax = 0.47 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
[Cu(C3H5O3)(C12H8N2)(H2O)]NO3 | V = 1618.2 (4) Å3 |
Mr = 412.84 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.5646 (13) Å | µ = 1.40 mm−1 |
b = 19.985 (3) Å | T = 300 K |
c = 9.7854 (13) Å | 0.62 × 0.26 × 0.22 mm |
β = 104.960 (11)° |
Bruker P4 diffractometer | 3156 reflections with I > 2σ(I) |
Absorption correction: gaussian (XSCANS; Siemens, 1996) | Rint = 0.023 |
Tmin = 0.599, Tmax = 0.782 | 3 standard reflections every 97 reflections |
4687 measured reflections | intensity decay: 1.5% |
3706 independent reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.099 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.47 e Å−3 |
3706 reflections | Δρmin = −0.54 e Å−3 |
235 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. H atoms for water molecule (H1A, H1B) and hydroxyl group (H18) were found on difference maps and refined as remaining H's (Riding) |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.32933 (3) | 0.138442 (13) | 0.96197 (3) | 0.03422 (11) | |
O1 | 0.1751 (2) | 0.19093 (9) | 1.0800 (2) | 0.0476 (4) | |
H1A | 0.1317 | 0.2210 | 1.0371 | 0.071* | |
H1B | 0.2400 | 0.2014 | 1.1624 | 0.071* | |
N1 | 0.1930 (2) | 0.05822 (10) | 0.8921 (2) | 0.0359 (4) | |
C2 | 0.0723 (3) | 0.05154 (13) | 0.7765 (3) | 0.0431 (6) | |
H2A | 0.0440 | 0.0879 | 0.7157 | 0.052* | |
C3 | −0.0140 (3) | −0.00842 (14) | 0.7428 (3) | 0.0473 (6) | |
H3A | −0.0970 | −0.0116 | 0.6603 | 0.057* | |
C4 | 0.0240 (3) | −0.06221 (13) | 0.8314 (3) | 0.0445 (6) | |
H4A | −0.0335 | −0.1020 | 0.8102 | 0.053* | |
C5 | 0.1512 (3) | −0.05677 (12) | 0.9551 (3) | 0.0389 (5) | |
C6 | 0.2008 (3) | −0.10980 (13) | 1.0562 (3) | 0.0458 (6) | |
H6A | 0.1478 | −0.1508 | 1.0413 | 0.055* | |
C7 | 0.3247 (3) | −0.10032 (12) | 1.1734 (3) | 0.0463 (6) | |
H7A | 0.3557 | −0.1354 | 1.2372 | 0.056* | |
C8 | 0.4089 (3) | −0.03772 (12) | 1.2014 (3) | 0.0391 (5) | |
C9 | 0.5363 (3) | −0.02492 (14) | 1.3217 (3) | 0.0464 (6) | |
H9A | 0.5723 | −0.0580 | 1.3894 | 0.056* | |
C10 | 0.6064 (3) | 0.03711 (14) | 1.3372 (3) | 0.0482 (6) | |
H10A | 0.6906 | 0.0463 | 1.4163 | 0.058* | |
C11 | 0.5528 (3) | 0.08664 (13) | 1.2354 (3) | 0.0430 (6) | |
H11A | 0.6022 | 0.1284 | 1.2485 | 0.052* | |
N12 | 0.4331 (2) | 0.07592 (10) | 1.1202 (2) | 0.0350 (4) | |
C13 | 0.3617 (3) | 0.01466 (11) | 1.1040 (2) | 0.0336 (5) | |
C14 | 0.2321 (3) | 0.00490 (11) | 0.9803 (2) | 0.0336 (5) | |
O15 | 0.2472 (2) | 0.18721 (8) | 0.78856 (17) | 0.0414 (4) | |
C16 | 0.3121 (3) | 0.24350 (11) | 0.7801 (2) | 0.0331 (5) | |
C17 | 0.4617 (3) | 0.26269 (11) | 0.8967 (2) | 0.0354 (5) | |
H17A | 0.5533 | 0.2686 | 0.8550 | 0.043* | |
O18 | 0.4950 (2) | 0.20790 (8) | 0.99464 (19) | 0.0441 (4) | |
H18 | 0.5871 | 0.2140 | 1.0563 | 0.066* | |
O19 | 0.2643 (2) | 0.28460 (9) | 0.68378 (18) | 0.0430 (4) | |
C20 | 0.4369 (4) | 0.32612 (13) | 0.9706 (3) | 0.0513 (7) | |
H20A | 0.5333 | 0.3364 | 1.0428 | 0.077* | |
H20B | 0.3483 | 0.3204 | 1.0129 | 0.077* | |
H20C | 0.4132 | 0.3621 | 0.9034 | 0.077* | |
N21 | 0.3937 (3) | 0.18194 (11) | 0.4271 (2) | 0.0469 (5) | |
O22 | 0.5171 (3) | 0.18147 (13) | 0.5268 (3) | 0.0796 (8) | |
O23 | 0.3678 (3) | 0.23108 (11) | 0.3466 (3) | 0.0720 (7) | |
O24 | 0.2997 (3) | 0.13421 (11) | 0.4069 (3) | 0.0681 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.03555 (16) | 0.02848 (15) | 0.03075 (16) | −0.00216 (10) | −0.00566 (11) | 0.00270 (10) |
O1 | 0.0472 (10) | 0.0450 (10) | 0.0461 (10) | 0.0064 (8) | 0.0042 (8) | 0.0018 (8) |
N1 | 0.0383 (10) | 0.0311 (9) | 0.0331 (10) | −0.0010 (8) | −0.0002 (8) | 0.0003 (7) |
C2 | 0.0434 (13) | 0.0411 (13) | 0.0369 (12) | −0.0040 (10) | −0.0042 (10) | 0.0010 (10) |
C3 | 0.0459 (14) | 0.0475 (14) | 0.0404 (13) | −0.0090 (11) | −0.0034 (11) | −0.0056 (11) |
C4 | 0.0473 (14) | 0.0378 (12) | 0.0466 (14) | −0.0091 (10) | 0.0088 (11) | −0.0122 (11) |
C5 | 0.0444 (13) | 0.0296 (11) | 0.0420 (13) | 0.0005 (9) | 0.0101 (10) | −0.0052 (9) |
C6 | 0.0528 (15) | 0.0327 (12) | 0.0518 (15) | 0.0011 (11) | 0.0137 (12) | −0.0006 (11) |
C7 | 0.0574 (15) | 0.0283 (11) | 0.0522 (15) | 0.0076 (10) | 0.0123 (12) | 0.0083 (10) |
C8 | 0.0412 (12) | 0.0338 (11) | 0.0412 (12) | 0.0077 (9) | 0.0084 (10) | 0.0042 (10) |
C9 | 0.0474 (14) | 0.0438 (13) | 0.0427 (13) | 0.0073 (11) | 0.0020 (11) | 0.0120 (11) |
C10 | 0.0439 (14) | 0.0523 (15) | 0.0390 (13) | 0.0011 (11) | −0.0062 (10) | 0.0070 (11) |
C11 | 0.0411 (13) | 0.0406 (12) | 0.0391 (12) | −0.0023 (10) | −0.0045 (10) | 0.0033 (10) |
N12 | 0.0347 (10) | 0.0323 (9) | 0.0328 (9) | 0.0007 (8) | −0.0007 (8) | 0.0021 (7) |
C13 | 0.0349 (11) | 0.0290 (10) | 0.0346 (11) | 0.0030 (9) | 0.0049 (9) | 0.0002 (9) |
C14 | 0.0362 (11) | 0.0287 (10) | 0.0344 (11) | 0.0009 (8) | 0.0063 (9) | −0.0026 (8) |
O15 | 0.0421 (9) | 0.0368 (9) | 0.0338 (8) | −0.0096 (7) | −0.0108 (7) | 0.0046 (7) |
C16 | 0.0286 (10) | 0.0343 (11) | 0.0293 (10) | −0.0008 (8) | −0.0052 (8) | 0.0005 (8) |
C17 | 0.0295 (10) | 0.0346 (11) | 0.0343 (11) | −0.0033 (8) | −0.0061 (8) | 0.0062 (9) |
O18 | 0.0348 (8) | 0.0367 (8) | 0.0451 (9) | −0.0040 (7) | −0.0180 (7) | 0.0106 (7) |
O19 | 0.0407 (9) | 0.0386 (9) | 0.0376 (9) | −0.0048 (7) | −0.0120 (7) | 0.0098 (7) |
C20 | 0.0577 (16) | 0.0385 (13) | 0.0449 (14) | 0.0007 (12) | −0.0098 (12) | −0.0045 (11) |
N21 | 0.0469 (12) | 0.0429 (12) | 0.0456 (12) | 0.0025 (10) | 0.0025 (10) | −0.0019 (9) |
O22 | 0.0641 (14) | 0.0782 (17) | 0.0734 (16) | −0.0074 (12) | −0.0240 (12) | 0.0075 (13) |
O23 | 0.0983 (18) | 0.0507 (12) | 0.0569 (13) | −0.0050 (12) | 0.0017 (12) | 0.0095 (10) |
O24 | 0.0598 (13) | 0.0535 (13) | 0.0791 (16) | −0.0131 (10) | −0.0036 (11) | 0.0039 (11) |
Cu1—O15 | 1.9256 (16) | C8—C9 | 1.407 (4) |
Cu1—O18 | 1.9516 (17) | C9—C10 | 1.369 (4) |
Cu1—N1 | 1.9970 (19) | C9—H9A | 0.9300 |
Cu1—N12 | 2.0096 (19) | C10—C11 | 1.395 (4) |
Cu1—O1 | 2.2283 (19) | C10—H10A | 0.9300 |
Cu1—Cu1i | 6.2127 (8) | C11—N12 | 1.331 (3) |
O1—H1A | 0.7711 | C11—H11A | 0.9300 |
O1—H1B | 0.8785 | N12—C13 | 1.360 (3) |
N1—C2 | 1.328 (3) | C13—C14 | 1.429 (3) |
N1—C14 | 1.357 (3) | O15—C16 | 1.267 (3) |
C2—C3 | 1.402 (4) | C16—O19 | 1.238 (3) |
C2—H2A | 0.9300 | C16—C17 | 1.528 (3) |
C3—C4 | 1.367 (4) | C17—O18 | 1.435 (3) |
C3—H3A | 0.9300 | C17—C20 | 1.502 (4) |
C4—C5 | 1.409 (4) | C17—H17A | 0.9800 |
C4—H4A | 0.9300 | O18—H18 | 0.8690 |
C5—C14 | 1.404 (3) | C20—H20A | 0.9600 |
C5—C6 | 1.437 (4) | C20—H20B | 0.9600 |
C6—C7 | 1.360 (4) | C20—H20C | 0.9600 |
C6—H6A | 0.9300 | N21—O24 | 1.231 (3) |
C7—C8 | 1.435 (4) | N21—O22 | 1.239 (3) |
C7—H7A | 0.9300 | N21—O23 | 1.243 (3) |
C8—C13 | 1.403 (3) | ||
O15—Cu1—O18 | 82.49 (7) | C9—C8—C7 | 124.2 (2) |
O15—Cu1—N1 | 93.24 (7) | C10—C9—C8 | 118.7 (2) |
O18—Cu1—N1 | 164.40 (9) | C10—C9—H9A | 120.6 |
O15—Cu1—N12 | 169.12 (8) | C8—C9—H9A | 120.6 |
O18—Cu1—N12 | 99.07 (7) | C9—C10—C11 | 120.6 (2) |
N1—Cu1—N12 | 82.40 (8) | C9—C10—H10A | 119.7 |
O15—Cu1—O1 | 95.03 (8) | C11—C10—H10A | 119.7 |
O18—Cu1—O1 | 94.78 (8) | N12—C11—C10 | 122.0 (2) |
N1—Cu1—O1 | 100.55 (8) | N12—C11—H11A | 119.0 |
N12—Cu1—O1 | 95.57 (8) | C10—C11—H11A | 119.0 |
O15—Cu1—Cu1i | 127.59 (6) | C11—N12—C13 | 118.0 (2) |
O18—Cu1—Cu1i | 108.31 (5) | C11—N12—Cu1 | 130.06 (17) |
N1—Cu1—Cu1i | 62.70 (6) | C13—N12—Cu1 | 111.93 (14) |
N12—Cu1—Cu1i | 41.66 (6) | N12—C13—C8 | 123.4 (2) |
O1—Cu1—Cu1i | 132.90 (5) | N12—C13—C14 | 116.73 (19) |
Cu1—O1—H1A | 110.6 | C8—C13—C14 | 119.9 (2) |
Cu1—O1—H1B | 105.6 | N1—C14—C5 | 123.3 (2) |
H1A—O1—H1B | 114.6 | N1—C14—C13 | 116.18 (19) |
C2—N1—C14 | 118.2 (2) | C5—C14—C13 | 120.6 (2) |
C2—N1—Cu1 | 129.05 (17) | C16—O15—Cu1 | 116.12 (14) |
C14—N1—Cu1 | 112.74 (15) | O19—C16—O15 | 125.1 (2) |
N1—C2—C3 | 122.2 (2) | O19—C16—C17 | 116.8 (2) |
N1—C2—H2A | 118.9 | O15—C16—C17 | 118.15 (19) |
C3—C2—H2A | 118.9 | O18—C17—C20 | 110.5 (2) |
C4—C3—C2 | 119.9 (2) | O18—C17—C16 | 106.91 (17) |
C4—C3—H3A | 120.0 | C20—C17—C16 | 112.1 (2) |
C2—C3—H3A | 120.0 | O18—C17—H17A | 109.1 |
C3—C4—C5 | 119.3 (2) | C20—C17—H17A | 109.1 |
C3—C4—H4A | 120.3 | C16—C17—H17A | 109.1 |
C5—C4—H4A | 120.3 | C17—O18—Cu1 | 115.01 (12) |
C14—C5—C4 | 117.1 (2) | C17—O18—H18 | 110.2 |
C14—C5—C6 | 118.8 (2) | Cu1—O18—H18 | 134.8 |
C4—C5—C6 | 124.1 (2) | C17—C20—H20A | 109.5 |
C7—C6—C5 | 120.3 (2) | C17—C20—H20B | 109.5 |
C7—C6—H6A | 119.8 | H20A—C20—H20B | 109.5 |
C5—C6—H6A | 119.8 | C17—C20—H20C | 109.5 |
C6—C7—C8 | 121.8 (2) | H20A—C20—H20C | 109.5 |
C6—C7—H7A | 119.1 | H20B—C20—H20C | 109.5 |
C8—C7—H7A | 119.1 | O24—N21—O22 | 120.7 (3) |
C13—C8—C9 | 117.3 (2) | O24—N21—O23 | 120.5 (2) |
C13—C8—C7 | 118.6 (2) | O22—N21—O23 | 118.8 (3) |
O15—Cu1—N1—C2 | −10.4 (2) | Cu1—N12—C13—C8 | −178.60 (19) |
O18—Cu1—N1—C2 | −83.8 (4) | C11—N12—C13—C14 | 179.1 (2) |
N12—Cu1—N1—C2 | 179.7 (2) | Cu1—N12—C13—C14 | 1.3 (3) |
O1—Cu1—N1—C2 | 85.4 (2) | C9—C8—C13—N12 | 0.4 (4) |
Cu1i—Cu1—N1—C2 | −141.5 (2) | C7—C8—C13—N12 | 180.0 (2) |
O15—Cu1—N1—C14 | 171.03 (17) | C9—C8—C13—C14 | −179.5 (2) |
O18—Cu1—N1—C14 | 97.6 (3) | C7—C8—C13—C14 | 0.1 (4) |
N12—Cu1—N1—C14 | 1.04 (17) | C2—N1—C14—C5 | 0.0 (4) |
O1—Cu1—N1—C14 | −93.24 (17) | Cu1—N1—C14—C5 | 178.78 (19) |
Cu1i—Cu1—N1—C14 | 39.85 (14) | C2—N1—C14—C13 | −179.4 (2) |
C14—N1—C2—C3 | −0.5 (4) | Cu1—N1—C14—C13 | −0.6 (3) |
Cu1—N1—C2—C3 | −179.0 (2) | C4—C5—C14—N1 | 0.1 (4) |
N1—C2—C3—C4 | 0.9 (4) | C6—C5—C14—N1 | −179.2 (2) |
C2—C3—C4—C5 | −0.7 (4) | C4—C5—C14—C13 | 179.5 (2) |
C3—C4—C5—C14 | 0.2 (4) | C6—C5—C14—C13 | 0.2 (4) |
C3—C4—C5—C6 | 179.5 (3) | N12—C13—C14—N1 | −0.5 (3) |
C14—C5—C6—C7 | −0.5 (4) | C8—C13—C14—N1 | 179.4 (2) |
C4—C5—C6—C7 | −179.8 (3) | N12—C13—C14—C5 | −179.9 (2) |
C5—C6—C7—C8 | 0.6 (4) | C8—C13—C14—C5 | 0.0 (4) |
C6—C7—C8—C13 | −0.4 (4) | O18—Cu1—O15—C16 | −10.20 (18) |
C6—C7—C8—C9 | 179.1 (3) | N1—Cu1—O15—C16 | −175.13 (18) |
C13—C8—C9—C10 | 0.1 (4) | N12—Cu1—O15—C16 | −109.2 (4) |
C7—C8—C9—C10 | −179.5 (3) | O1—Cu1—O15—C16 | 83.98 (18) |
C8—C9—C10—C11 | −0.2 (4) | Cu1i—Cu1—O15—C16 | −117.56 (17) |
C9—C10—C11—N12 | −0.2 (5) | Cu1—O15—C16—O19 | −172.1 (2) |
C10—C11—N12—C13 | 0.6 (4) | Cu1—O15—C16—C17 | 8.2 (3) |
C10—C11—N12—Cu1 | 178.0 (2) | O19—C16—C17—O18 | −179.5 (2) |
O15—Cu1—N12—C11 | 114.3 (4) | O15—C16—C17—O18 | 0.2 (3) |
O18—Cu1—N12—C11 | 16.9 (2) | O19—C16—C17—C20 | 59.3 (3) |
N1—Cu1—N12—C11 | −178.8 (2) | O15—C16—C17—C20 | −121.1 (3) |
O1—Cu1—N12—C11 | −78.8 (2) | C20—C17—O18—Cu1 | 113.9 (2) |
Cu1i—Cu1—N12—C11 | 124.3 (3) | C16—C17—O18—Cu1 | −8.3 (2) |
O15—Cu1—N12—C13 | −68.2 (4) | O15—Cu1—O18—C17 | 10.21 (17) |
O18—Cu1—N12—C13 | −165.58 (16) | N1—Cu1—O18—C17 | 85.1 (3) |
N1—Cu1—N12—C13 | −1.27 (16) | N12—Cu1—O18—C17 | 179.33 (17) |
O1—Cu1—N12—C13 | 98.66 (16) | O1—Cu1—O18—C17 | −84.25 (17) |
Cu1i—Cu1—N12—C13 | −58.17 (14) | Cu1i—Cu1—O18—C17 | 137.40 (16) |
C11—N12—C13—C8 | −0.8 (4) |
Symmetry code: (i) −x+1, −y, −z+2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O18—H18···O19ii | 0.87 | 1.70 | 2.562 (2) | 172 |
O1—H1B···O23iii | 0.88 | 1.94 | 2.819 (3) | 174 |
O1—H1A···O22iv | 0.77 | 2.17 | 2.871 (3) | 151 |
O1—H1B···N21iii | 0.88 | 2.61 | 3.434 (3) | 156 |
Symmetry codes: (ii) x+1/2, −y+1/2, z+1/2; (iii) x, y, z+1; (iv) x−1/2, −y+1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C3H5O3)(C12H8N2)(H2O)]NO3 |
Mr | 412.84 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 300 |
a, b, c (Å) | 8.5646 (13), 19.985 (3), 9.7854 (13) |
β (°) | 104.960 (11) |
V (Å3) | 1618.2 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.40 |
Crystal size (mm) | 0.62 × 0.26 × 0.22 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | Gaussian (XSCANS; Siemens, 1996) |
Tmin, Tmax | 0.599, 0.782 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4687, 3706, 3156 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.099, 1.04 |
No. of reflections | 3706 |
No. of parameters | 235 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.47, −0.54 |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXTL-Plus (Sheldrick, 1998), SHELXL97 (Sheldrick, 1997), SHELXL97.
Cu1—O15 | 1.9256 (16) | C8—C9 | 1.407 (4) |
Cu1—O18 | 1.9516 (17) | C9—C10 | 1.369 (4) |
Cu1—N1 | 1.9970 (19) | C10—C11 | 1.395 (4) |
Cu1—N12 | 2.0096 (19) | C11—N12 | 1.331 (3) |
Cu1—O1 | 2.2283 (19) | N12—C13 | 1.360 (3) |
N1—C2 | 1.328 (3) | C13—C14 | 1.429 (3) |
N1—C14 | 1.357 (3) | O15—C16 | 1.267 (3) |
C2—C3 | 1.402 (4) | C16—O19 | 1.238 (3) |
C3—C4 | 1.367 (4) | C16—C17 | 1.528 (3) |
C4—C5 | 1.409 (4) | C17—O18 | 1.435 (3) |
C5—C14 | 1.404 (3) | C17—C20 | 1.502 (4) |
C5—C6 | 1.437 (4) | N21—O24 | 1.231 (3) |
C6—C7 | 1.360 (4) | N21—O22 | 1.239 (3) |
C7—C8 | 1.435 (4) | N21—O23 | 1.243 (3) |
C8—C13 | 1.403 (3) | ||
O15—Cu1—O18 | 82.49 (7) | C10—C9—C8 | 118.7 (2) |
O15—Cu1—N1 | 93.24 (7) | C9—C10—C11 | 120.6 (2) |
O18—Cu1—N1 | 164.40 (9) | N12—C11—C10 | 122.0 (2) |
O15—Cu1—N12 | 169.12 (8) | C11—N12—C13 | 118.0 (2) |
O18—Cu1—N12 | 99.07 (7) | C11—N12—Cu1 | 130.06 (17) |
N1—Cu1—N12 | 82.40 (8) | C13—N12—Cu1 | 111.93 (14) |
O15—Cu1—O1 | 95.03 (8) | N12—C13—C8 | 123.4 (2) |
O18—Cu1—O1 | 94.78 (8) | N12—C13—C14 | 116.73 (19) |
N1—Cu1—O1 | 100.55 (8) | C8—C13—C14 | 119.9 (2) |
N12—Cu1—O1 | 95.57 (8) | N1—C14—C5 | 123.3 (2) |
C2—N1—C14 | 118.2 (2) | N1—C14—C13 | 116.18 (19) |
C2—N1—Cu1 | 129.05 (17) | C5—C14—C13 | 120.6 (2) |
C14—N1—Cu1 | 112.74 (15) | C16—O15—Cu1 | 116.12 (14) |
N1—C2—C3 | 122.2 (2) | O19—C16—O15 | 125.1 (2) |
C4—C3—C2 | 119.9 (2) | O19—C16—C17 | 116.8 (2) |
C3—C4—C5 | 119.3 (2) | O15—C16—C17 | 118.15 (19) |
C14—C5—C4 | 117.1 (2) | O18—C17—C20 | 110.5 (2) |
C14—C5—C6 | 118.8 (2) | O18—C17—C16 | 106.91 (17) |
C4—C5—C6 | 124.1 (2) | C20—C17—C16 | 112.1 (2) |
C7—C6—C5 | 120.3 (2) | C17—O18—Cu1 | 115.01 (12) |
C6—C7—C8 | 121.8 (2) | O24—N21—O22 | 120.7 (3) |
C13—C8—C9 | 117.3 (2) | O24—N21—O23 | 120.5 (2) |
C13—C8—C7 | 118.6 (2) | O22—N21—O23 | 118.8 (3) |
C9—C8—C7 | 124.2 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
O18—H18···O19i | 0.87 | 1.70 | 2.562 (2) | 172 |
O1—H1B···O23ii | 0.88 | 1.94 | 2.819 (3) | 174 |
O1—H1A···O22iii | 0.77 | 2.17 | 2.871 (3) | 151 |
Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) x, y, z+1; (iii) x−1/2, −y+1/2, z+1/2. |
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A large number of mixed copper chelates of the type [Cu(phen)(O–O)]n+ (n = 0 or 1, phen = different substituted 1,10 phenanthrolines and O–O = acetylacetonate, salycilaldehydate, oxalate or malonate) have been reported. We have studied their relative stability both via solution equilibrium studies, as well as from far IR spectroscopy in the solid state (Gasque, Medina et al., 1999). To validate the latter, isostructurality has first to be established by X-ray diffraction. In this context, most of the crystal structures for the compounds under study have been reported (Fabretti et al., 1985; Kwik et al., 1986; Solans et al., 1987; Su et al., 1995; Gasque, Moreno-Esparza et al., 1999).
Our current interest in relation with this topic is focused on mixed complexes where the O–O ligand is an α-hydroxy acid anion, such as glycolate (Medina et al., 2000) or lactate, of which an example, (I), is presented here.
The asymmetric unit of (I) (Fig. 1) contains one cation and one nitrate anion, both lying on general positions. The copper center is five-coordinated, in a common distorted square-pyramidal geometry, with a τ descriptor (Addison et al., 1984) very close to 0, τ = 0.08. The base of the pyramid is occupied by two O atoms of the racemic lactate ligand and two N atoms of the 1,10-phenanthroline ligand, with the expected coordination bond lengths (Table 1). The metal center is significantly displaced from this plane, the deviation from the calculated least-squares plane (N1, N12, O15 and O18) being 0.2206 (3) Å. This displacement is, for instance, 0.06 Å larger than that observed for the related complex including glycolate instead of lactate (Medina et al., 2000). This difference results from the ability for the nitrate ion to interact with the CuII in the glycolate-containing complex, giving a typical Jahn–Teller distorted octahedral coordination geometry, while in (I), an actual five-coordinated complex is obtained; the shortest separation between the anion and the metallic center is Cu1···O22 of 5.000 (3) Å. Finally, the apical coordination site in (I) is occupied by a water molecule, with a long bond length of 2.2283 (19) Å.
The functionality of the cation, together with the presence of nitrate as anion, greatly favors hydrogen bonding in the crystalline state (Table 2). Thus, the hydroxy group O18—H18 of the lactate ligand forms a remarkably strong hydrogen bond with the carboxylate atom O19 of a symmetry-related cation. Remaining significant O—H···O hydrogen bonds involve the coordinated water molecule. The resulting network is a one-dimensional supramolecular aggregate with [101] as base vector (Fig. 2), the steric hindrance of the 1,10-phenanthroline ligand avoiding inter-chain contacts. These features result in large metal–metal separations in the cell, the shortest Cu···Cu distance being Cu···Cui of 6.2127 (8) Å [symmetry code: (i) 1 − x, −y, 2 − z].