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metal-organic compounds
Bis[μ-3-(hydroxyimino)butan-2-one benzoylhydrazonato]bis[pyridinecopper(II)] methanol solvate
In the title complex, [Cu2(C11H11N3O2)2(C5H5N)2]·CH4O, the two CuII atoms are bridged by two oxime O atoms of diacetyl monoxime benzoylhydrazone ligands, with a CuCu distance of 3.644 (2) Å. The center of the dimer corresponds to a crystallographic center of symmetry. Each CuII atom shows a square-pyramidal geometry defined by two N and two O atoms of hydrazone ligands and one pyridine N atom. The methanol solvent molecules lie on special positions with twofold rotation symmetry and form intramolecular O—HO hydrogen bonds.
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536804024523/sj6009sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536804024523/sj6009Isup2.hkl |
CCDC reference: 255418
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.006 Å
- Disorder in solvent or counterion
- R factor = 0.051
- wR factor = 0.122
- Data-to-parameter ratio = 16.8
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.50 Ratio PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 50.00 Perc.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion
Computing details top
Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.
Bis[µ-3-(hydroxyimino)butan-2-one benzoylhydrazonato]bis[pyridinecopper(II)]
methanol solvate top
Crystal data top
C32H32Cu2N8O4·CH4O | F(000) = 1552 |
Mr = 751.78 | Dx = 1.477 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 7270 reflections |
a = 17.617 (4) Å | θ = 3.2–27.5° |
b = 8.363 (3) Å | µ = 1.31 mm−1 |
c = 23.099 (4) Å | T = 293 K |
β = 96.695 (11)° | Prism, dark blue |
V = 3380.0 (16) Å3 | 0.28 × 0.22 × 0.12 mm |
Z = 4 |
Data collection top
Rigaku R-AXIS RAPID diffractometer | 3865 independent reflections |
Radiation source: fine-focus sealed tube | 2569 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.068 |
Detector resolution: 10 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ω scans | h = −20→22 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −10→10 |
Tmin = 0.710, Tmax = 0.859 | l = −29→29 |
16098 measured reflections |
Refinement top
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)] = 0.051 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.122 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0629P)2 + 1.2139P] where P = (Fo2 + 2Fc2)/3 |
3865 reflections | (Δ/σ)max < 0.001 |
230 parameters | Δρmax = 0.40 e Å−3 |
1 restraint | Δρmin = −0.25 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cu1 | 0.92540 (2) | 0.03169 (5) | 0.547199 (17) | 0.04586 (15) | |
O1 | 0.97494 (13) | −0.1215 (3) | 0.43731 (10) | 0.0536 (6) | |
O2 | 0.88797 (13) | 0.1480 (3) | 0.61548 (10) | 0.0541 (6) | |
O3 | 1.0134 (5) | 0.1661 (10) | 0.7117 (3) | 0.099 (2) | 0.50 |
N1 | 0.91798 (15) | −0.0623 (3) | 0.46478 (12) | 0.0459 (6) | |
N2 | 0.81645 (15) | 0.0191 (3) | 0.52814 (12) | 0.0466 (6) | |
N3 | 0.76989 (16) | 0.0861 (3) | 0.56525 (12) | 0.0492 (7) | |
N4 | 0.95372 (17) | −0.2046 (3) | 0.59067 (13) | 0.0549 (7) | |
C1 | 0.8294 (2) | −0.1947 (5) | 0.38962 (15) | 0.0595 (9) | |
C2 | 0.84838 (19) | −0.0989 (4) | 0.44363 (14) | 0.0447 (7) | |
C3 | 0.78946 (19) | −0.0388 (4) | 0.47834 (15) | 0.0466 (7) | |
C4 | 0.7065 (2) | −0.0457 (5) | 0.45723 (18) | 0.0633 (10) | |
C5 | 0.81457 (19) | 0.1495 (4) | 0.60965 (15) | 0.0473 (8) | |
C6 | 0.7745 (2) | 0.2320 (4) | 0.65464 (15) | 0.0484 (8) | |
C7 | 0.6960 (2) | 0.2433 (5) | 0.64894 (19) | 0.0682 (11) | |
C8 | 0.6590 (3) | 0.3214 (6) | 0.6899 (2) | 0.0841 (14) | |
C9 | 0.7010 (3) | 0.3900 (5) | 0.7375 (2) | 0.0768 (13) | |
C10 | 0.7788 (3) | 0.3818 (5) | 0.74363 (18) | 0.0707 (11) | |
C11 | 0.8159 (2) | 0.3030 (4) | 0.70246 (16) | 0.0597 (9) | |
C12 | 0.9927 (2) | −0.3192 (5) | 0.5671 (2) | 0.0696 (11) | |
C13 | 1.0094 (3) | −0.4633 (5) | 0.5933 (3) | 0.0909 (15) | |
C14 | 0.9858 (4) | −0.4922 (6) | 0.6458 (3) | 0.1033 (19) | |
C15 | 0.9462 (3) | −0.3770 (6) | 0.6712 (2) | 0.0919 (15) | |
C16 | 0.9309 (2) | −0.2351 (5) | 0.64225 (17) | 0.0673 (11) | |
C17 | 0.9940 (17) | 0.0717 (11) | 0.7604 (6) | 0.074 (4) | 0.50 |
H1A | 0.8729 | −0.1982 | 0.3682 | 0.089* | |
H1B | 0.7871 | −0.1462 | 0.3660 | 0.089* | |
H1C | 0.8159 | −0.3014 | 0.3998 | 0.089* | |
H4A | 0.6782 | 0.0101 | 0.4841 | 0.095* | |
H4B | 0.6902 | −0.1553 | 0.4545 | 0.095* | |
H4C | 0.6974 | 0.0036 | 0.4195 | 0.095* | |
H7 | 0.6675 | 0.1973 | 0.6168 | 0.082* | |
H8 | 0.6059 | 0.3278 | 0.6856 | 0.101* | |
H9 | 0.6763 | 0.4420 | 0.7656 | 0.092* | |
H10 | 0.8070 | 0.4293 | 0.7756 | 0.085* | |
H11 | 0.8690 | 0.2977 | 0.7069 | 0.072* | |
H12 | 1.0094 | −0.3002 | 0.5310 | 0.083* | |
H13 | 1.0367 | −0.5402 | 0.5753 | 0.109* | |
H14 | 0.9963 | −0.5898 | 0.6643 | 0.124* | |
H15 | 0.9299 | −0.3941 | 0.7076 | 0.110* | |
H16 | 0.9033 | −0.1572 | 0.6595 | 0.081* | |
H17A | 1.0340 | 0.0808 | 0.7923 | 0.111* | 0.50 |
H17B | 0.9883 | −0.0383 | 0.7489 | 0.111* | 0.50 |
H17C | 0.9469 | 0.1099 | 0.7725 | 0.111* | 0.50 |
H18 | 0.9791 | 0.1588 | 0.6846 | 0.149* | 0.50 |
Atomic displacement parameters (Å2) top
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0390 (2) | 0.0538 (2) | 0.0440 (2) | −0.00290 (19) | 0.00185 (16) | −0.00842 (19) |
O1 | 0.0426 (13) | 0.0663 (15) | 0.0522 (14) | −0.0098 (11) | 0.0071 (11) | −0.0166 (12) |
O2 | 0.0412 (13) | 0.0644 (14) | 0.0559 (14) | 0.0022 (11) | 0.0028 (11) | −0.0128 (11) |
O3 | 0.090 (5) | 0.108 (5) | 0.091 (5) | −0.028 (5) | −0.023 (4) | 0.039 (4) |
N1 | 0.0424 (15) | 0.0471 (15) | 0.0477 (15) | −0.0055 (12) | 0.0033 (12) | −0.0049 (12) |
N2 | 0.0393 (14) | 0.0546 (15) | 0.0452 (15) | −0.0042 (12) | 0.0025 (12) | −0.0029 (13) |
N3 | 0.0408 (15) | 0.0574 (15) | 0.0497 (17) | −0.0004 (12) | 0.0067 (13) | −0.0018 (13) |
N4 | 0.0525 (18) | 0.0552 (17) | 0.0549 (18) | −0.0064 (14) | −0.0034 (14) | −0.0021 (14) |
C1 | 0.057 (2) | 0.071 (2) | 0.049 (2) | −0.0130 (18) | −0.0030 (17) | −0.0119 (18) |
C2 | 0.0439 (18) | 0.0486 (17) | 0.0400 (17) | −0.0068 (14) | −0.0023 (14) | −0.0003 (14) |
C3 | 0.0428 (17) | 0.0465 (17) | 0.0493 (19) | −0.0049 (15) | 0.0006 (14) | 0.0049 (15) |
C4 | 0.044 (2) | 0.082 (3) | 0.062 (2) | −0.0034 (19) | −0.0017 (17) | −0.001 (2) |
C5 | 0.0485 (19) | 0.0442 (17) | 0.0499 (19) | −0.0010 (15) | 0.0089 (16) | 0.0027 (14) |
C6 | 0.051 (2) | 0.0460 (17) | 0.050 (2) | −0.0007 (15) | 0.0147 (16) | 0.0043 (15) |
C7 | 0.057 (2) | 0.072 (2) | 0.078 (3) | −0.0052 (19) | 0.017 (2) | −0.016 (2) |
C8 | 0.058 (3) | 0.098 (3) | 0.102 (4) | −0.004 (2) | 0.032 (3) | −0.028 (3) |
C9 | 0.086 (3) | 0.076 (3) | 0.076 (3) | 0.001 (2) | 0.039 (3) | −0.011 (2) |
C10 | 0.090 (3) | 0.069 (3) | 0.055 (2) | −0.002 (2) | 0.018 (2) | −0.013 (2) |
C11 | 0.063 (2) | 0.061 (2) | 0.056 (2) | 0.0011 (19) | 0.0104 (19) | −0.0048 (18) |
C12 | 0.062 (3) | 0.068 (3) | 0.076 (3) | 0.009 (2) | 0.001 (2) | 0.004 (2) |
C13 | 0.087 (4) | 0.062 (3) | 0.121 (5) | 0.009 (2) | −0.002 (3) | 0.004 (3) |
C14 | 0.109 (4) | 0.069 (3) | 0.124 (5) | −0.001 (3) | −0.017 (4) | 0.034 (3) |
C15 | 0.110 (4) | 0.091 (4) | 0.073 (3) | −0.024 (3) | 0.004 (3) | 0.024 (3) |
C16 | 0.078 (3) | 0.066 (2) | 0.057 (2) | −0.015 (2) | 0.005 (2) | −0.001 (2) |
C17 | 0.091 (11) | 0.079 (5) | 0.051 (12) | −0.017 (8) | 0.001 (10) | 0.007 (5) |
Geometric parameters (Å, º) top
Cu1—O1i | 1.905 (2) | C5—C6 | 1.492 (4) |
Cu1—O2 | 2.028 (2) | C6—C7 | 1.377 (5) |
Cu1—N1 | 2.050 (3) | C6—C11 | 1.385 (5) |
Cu1—N2 | 1.922 (3) | C7—C8 | 1.376 (5) |
Cu1—N4 | 2.246 (3) | C7—H7 | 0.9300 |
O2—C5 | 1.285 (4) | C8—C9 | 1.377 (6) |
N3—C5 | 1.328 (4) | C8—H8 | 0.9300 |
N2—N3 | 1.373 (4) | C9—C10 | 1.363 (6) |
N2—C3 | 1.287 (4) | C9—H9 | 0.9300 |
C2—C3 | 1.472 (5) | C10—C11 | 1.382 (5) |
C2—N1 | 1.303 (4) | C10—H10 | 0.9300 |
O1—N1 | 1.343 (3) | C11—H11 | 0.9300 |
O1—Cu1i | 1.905 (2) | C12—C13 | 1.365 (6) |
O3—C17 | 1.448 (8) | C12—H12 | 0.9300 |
O3—H18 | 0.8200 | C13—C14 | 1.347 (8) |
N4—C16 | 1.326 (5) | C13—H13 | 0.9300 |
N4—C12 | 1.332 (5) | C14—C15 | 1.363 (8) |
C1—C2 | 1.487 (4) | C14—H14 | 0.9300 |
C1—H1A | 0.9600 | C15—C16 | 1.374 (6) |
C1—H1B | 0.9600 | C15—H15 | 0.9300 |
C1—H1C | 0.9600 | C16—H16 | 0.9300 |
C3—C4 | 1.488 (5) | C17—H17A | 0.9600 |
C4—H4A | 0.9600 | C17—H17B | 0.9600 |
C4—H4B | 0.9600 | C17—H17C | 0.9600 |
C4—H4C | 0.9600 | ||
O1i—Cu1—N2 | 159.9 (1) | C6—C7—H7 | 119.4 |
O1i—Cu1—O2 | 92.35 (9) | C6—C11—H11 | 119.8 |
O1i—Cu1—N1 | 106.5 (1) | C7—C8—C9 | 119.5 (4) |
O1i—Cu1—N4 | 96.4 (1) | C7—C8—H8 | 120.2 |
O2—Cu1—N1 | 156.2 (1) | C7—C6—C11 | 118.5 (3) |
O2—Cu1—N4 | 98.6 (1) | C7—C6—C5 | 121.1 (3) |
N2—Cu1—O2 | 78.3 (1) | C8—C7—C6 | 121.2 (4) |
N2—Cu1—N1 | 79.2 (1) | C8—C7—H7 | 119.4 |
N2—Cu1—N4 | 102.6 (1) | C8—C9—H9 | 119.9 |
N1—Cu1—N4 | 93.7 (1) | C9—C10—C11 | 120.2 (4) |
O1—N1—Cu1 | 127.6 (2) | C9—C10—H10 | 119.9 |
N1—O1—Cu1i | 119.3 (2) | C9—C8—H8 | 120.2 |
O2—C5—N3 | 125.2 (3) | C10—C9—C8 | 120.2 (4) |
O2—C5—C6 | 118.9 (3) | C10—C9—H9 | 119.9 |
N1—C2—C3 | 114.1 (3) | C10—C11—C6 | 120.4 (4) |
N1—C2—C1 | 123.5 (3) | C10—C11—H11 | 119.8 |
N2—C3—C2 | 113.9 (3) | C11—C6—C5 | 120.4 (3) |
N2—C3—C4 | 123.6 (3) | C11—C10—H10 | 119.9 |
N3—N2—Cu1 | 119.2 (2) | C12—N4—Cu1 | 123.3 (3) |
N3—C5—C6 | 115.9 (3) | C12—C13—H13 | 120.5 |
N4—C12—C13 | 123.3 (5) | C13—C14—C15 | 119.2 (5) |
N4—C12—H12 | 118.4 | C13—C14—H14 | 120.4 |
N4—C16—C15 | 122.8 (4) | C13—C12—H12 | 118.4 |
N4—C16—H16 | 118.6 | C14—C13—C12 | 119.0 (5) |
C2—N1—O1 | 117.3 (3) | C14—C13—H13 | 120.5 |
C2—N1—Cu1 | 113.2 (2) | C14—C15—C16 | 118.8 (5) |
C2—C1—H1A | 109.5 | C14—C15—H15 | 120.6 |
C2—C1—H1B | 109.5 | C15—C14—H14 | 120.4 |
C2—C1—H1C | 109.5 | C15—C16—H16 | 118.6 |
C2—C3—C4 | 122.5 (3) | C16—N4—C12 | 117.0 (3) |
C3—C4—H4A | 109.5 | C16—N4—Cu1 | 119.8 (3) |
C3—C4—H4B | 109.5 | C16—C15—H15 | 120.6 |
C3—N2—N3 | 121.8 (3) | H1A—C1—H1B | 109.5 |
C3—N2—Cu1 | 118.7 (2) | H1A—C1—H1C | 109.5 |
C3—C2—C1 | 122.5 (3) | H1B—C1—H1C | 109.5 |
C3—C4—H4C | 109.5 | H4A—C4—H4B | 109.5 |
C5—O2—Cu1 | 109.7 (2) | H4A—C4—H4C | 109.5 |
C5—N3—N2 | 107.6 (3) | H4B—C4—H4C | 109.5 |
Cu1i—O1—N1—C2 | 164.2 (2) | N1—C2—C3—C4 | 170.4 (3) |
Cu1i—O1—N1—Cu1 | −32.7 (3) | N2—N3—C5—O2 | 0.6 (5) |
Cu1—N2—N3—C5 | −0.1 (3) | N2—N3—C5—C6 | 178.8 (3) |
Cu1—N1—C2—C3 | 10.6 (3) | N2—Cu1—O2—C5 | 0.5 (2) |
Cu1—N1—C2—C1 | −168.7 (3) | N2—Cu1—N4—C16 | −68.3 (3) |
Cu1—N2—C3—C2 | 4.0 (4) | N2—Cu1—N1—C2 | −6.8 (2) |
Cu1—O2—C5—N3 | −0.8 (4) | N2—Cu1—N1—O1 | −170.5 (3) |
Cu1—O2—C5—C6 | −178.9 (2) | N2—Cu1—N4—C12 | 111.3 (3) |
Cu1—N4—C12—C13 | −179.5 (4) | N3—N2—C3—C2 | 177.4 (3) |
Cu1—N4—C16—C15 | 180.0 (3) | N3—N2—C3—C4 | −2.7 (5) |
O1—N1—C2—C1 | −3.3 (5) | N3—C5—C6—C7 | −1.3 (5) |
Cu1—N2—C3—C4 | −176.2 (3) | N3—C5—C6—C11 | −179.5 (3) |
O1i—Cu1—O2—C5 | 162.5 (2) | N4—Cu1—N1—O1 | −68.3 (3) |
O1i—Cu1—N1—C2 | −166.9 (2) | N4—Cu1—O2—C5 | −100.7 (2) |
O1i—Cu1—N1—O1 | 29.4 (3) | N4—Cu1—N1—C2 | 95.3 (2) |
O1i—Cu1—N2—C3 | 109.7 (3) | N4—Cu1—N2—C3 | −90.2 (3) |
O1i—Cu1—N2—N3 | −64.0 (4) | N4—Cu1—N2—N3 | 96.1 (2) |
O1i—Cu1—N4—C16 | 104.9 (3) | N4—C12—C13—C14 | −0.2 (8) |
O1i—Cu1—N4—C12 | −75.5 (3) | C1—C2—C3—N2 | 169.5 (3) |
O1—N1—C2—C3 | 176.0 (3) | C1—C2—C3—C4 | −10.3 (5) |
O2—Cu1—N4—C12 | −168.8 (3) | C3—N2—N3—C5 | −173.6 (3) |
O2—Cu1—N2—N3 | −0.2 (2) | C5—C6—C7—C8 | −179.0 (4) |
O2—Cu1—N4—C16 | 11.5 (3) | C5—C6—C11—C10 | 178.9 (3) |
O2—Cu1—N2—C3 | 173.4 (3) | C6—C7—C8—C9 | 0.2 (7) |
O2—C5—C6—C7 | 176.9 (3) | C7—C8—C9—C10 | 0.6 (7) |
O2—Cu1—N1—C2 | −26.0 (4) | C7—C6—C11—C10 | 0.7 (5) |
O2—Cu1—N1—O1 | 170.3 (2) | C8—C9—C10—C11 | −0.7 (7) |
O2—C5—C6—C11 | −1.3 (5) | C9—C10—C11—C6 | 0.1 (6) |
N1—C2—C3—N2 | −9.8 (4) | C11—C6—C7—C8 | −0.8 (6) |
N1—Cu1—O2—C5 | 19.7 (4) | C12—C13—C14—C15 | −0.3 (9) |
N1—Cu1—N2—N3 | −172.4 (2) | C13—C14—C15—C16 | 0.7 (9) |
N1—Cu1—N2—C3 | 1.2 (2) | C12—N4—C16—C15 | 0.3 (6) |
N1—Cu1—N4—C16 | −148.1 (3) | C14—C15—C16—N4 | −0.8 (8) |
N1—Cu1—N4—C12 | 31.6 (3) | C16—N4—C12—C13 | 0.2 (6) |
Symmetry code: (i) −x+2, −y, −z+1. |
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