The salicylaldehyde semicarbazonate anion O,N,O-chelates to the Cu atom in the title compound, bis[μ-2-(semicarbazonomethyl)phenolato]-1κ3O3,N1,O:2κO;1κO:2κ3O3,N1,O-bis[(formato-κO)copper(II)] [Cu2(C8H8N3O2)2(CHO2)2], the N and O atoms occupying three sites of the square-planar environment around it. The fourth site is occupied by the negatively charged O atom of the formate anion. Two molecules are bridged through the phenoxy O atom across a center of symmetry to give a dinuclear compound, so that the Cu atom exists in a square-pyramidal geometry [Cu←Ophenoxy = 2.546 (1) Å in the apical position]. Hydrogen bonds link the dinuclear molecules into a three-dimensional network architecture.
Supporting information
CCDC reference: 284012
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.003 Å
- R factor = 0.033
- wR factor = 0.090
- Data-to-parameter ratio = 23.1
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT411_ALERT_2_B Short Inter H...H Contact H4 .. H4 .. 2.03 Ang.
Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Cu1 - O1_a .. 5.15 su
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 2
0 ALERT level A = In general: serious problem
1 ALERT level B = Potentially serious problem
2 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
2 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
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; 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-2-(semicarbazonomethyl)phenolato]-
1
κ3O3,
N1,
O:2
κO;1
κO:2
κ3O3,
N1,
O-bis[(formato-
κO)copper(II)]
top
Crystal data top
[Cu2(C8H8N3O2)2(CHO2)2] | F(000) = 580 |
Mr = 573.46 | Dx = 1.835 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 1754 reflections |
a = 7.7562 (5) Å | θ = 2.6–32.0° |
b = 14.1641 (8) Å | µ = 2.11 mm−1 |
c = 9.6837 (6) Å | T = 173 K |
β = 102.743 (1)° | Prism, green |
V = 1037.6 (1) Å3 | 0.33 × 0.11 × 0.07 mm |
Z = 2 | |
Data collection top
Bruker SMART 1000 area-detector diffractometer | 3551 independent reflections |
Radiation source: fine-focus sealed tube | 2997 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
Detector resolution: 8.33 pixels mm-1 | θmax = 32.0°, θmin = 2.6° |
φ and ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −21→20 |
Tmin = 0.675, Tmax = 0.866 | l = −14→14 |
13226 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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0459P)2 + 0.5822P] where P = (Fo2 + 2Fc2)/3 |
3551 reflections | (Δ/σ)max = 0.001 |
154 parameters | Δρmax = 0.59 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
Cu1 | 0.34785 (3) | 0.50742 (1) | 0.35372 (2) | 0.01738 (7) | |
O1 | 0.3408 (2) | 0.4413 (1) | 0.5253 (1) | 0.0213 (2) | |
O2 | 0.3463 (2) | 0.5854 (1) | 0.1843 (1) | 0.0203 (2) | |
O3 | 0.4146 (2) | 0.3927 (1) | 0.2734 (1) | 0.0214 (3) | |
O4 | 0.5353 (2) | 0.3125 (1) | 0.1236 (2) | 0.0260 (3) | |
N1 | 0.2300 (2) | 0.6166 (1) | 0.4066 (2) | 0.0184 (3) | |
N2 | 0.2159 (2) | 0.6886 (1) | 0.3089 (2) | 0.0216 (3) | |
N3 | 0.2503 (2) | 0.7260 (1) | 0.0843 (2) | 0.0240 (3) | |
C1 | 0.2459 (2) | 0.4659 (1) | 0.6179 (2) | 0.0189 (3) | |
C2 | 0.2351 (2) | 0.4016 (1) | 0.7273 (2) | 0.0237 (3) | |
C3 | 0.1459 (3) | 0.4247 (2) | 0.8319 (2) | 0.0287 (4) | |
C4 | 0.0599 (3) | 0.5114 (2) | 0.8307 (2) | 0.0309 (4) | |
C5 | 0.0667 (2) | 0.5746 (2) | 0.7239 (2) | 0.0254 (4) | |
C6 | 0.1584 (2) | 0.5540 (1) | 0.6172 (2) | 0.0194 (3) | |
C7 | 0.1561 (2) | 0.6265 (1) | 0.5128 (2) | 0.0204 (3) | |
C8 | 0.2728 (2) | 0.6644 (1) | 0.1901 (2) | 0.0181 (3) | |
C9 | 0.4956 (2) | 0.3882 (1) | 0.1718 (2) | 0.0193 (3) | |
H2n | 0.1741 | 0.7449 | 0.3219 | 0.026* | |
H3n1 | 0.2871 | 0.7123 | 0.0069 | 0.029* | |
H3n2 | 0.1986 | 0.7805 | 0.0915 | 0.029* | |
H2 | 0.2901 | 0.3416 | 0.7292 | 0.028* | |
H3 | 0.1431 | 0.3808 | 0.9055 | 0.034* | |
H4 | −0.0019 | 0.5265 | 0.9023 | 0.037* | |
H5 | 0.0079 | 0.6335 | 0.7222 | 0.030* | |
H7 | 0.0976 | 0.6842 | 0.5225 | 0.025* | |
H9 | 0.5263 | 0.4453 | 0.1319 | 0.023* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0206 (1) | 0.0153 (1) | 0.0185 (1) | 0.0030 (1) | 0.0090 (1) | 0.0020 (1) |
O1 | 0.024 (1) | 0.021 (1) | 0.023 (1) | 0.004 (1) | 0.011 (1) | 0.005 (1) |
O2 | 0.024 (1) | 0.018 (1) | 0.022 (1) | 0.005 (1) | 0.011 (1) | 0.002 (1) |
O3 | 0.026 (1) | 0.016 (1) | 0.025 (1) | 0.000 (1) | 0.013 (1) | −0.001 (1) |
O4 | 0.035 (1) | 0.018 (1) | 0.031 (1) | −0.003 (1) | 0.018 (1) | −0.005 (1) |
N1 | 0.022 (1) | 0.017 (1) | 0.018 (1) | 0.002 (1) | 0.008 (1) | 0.003 (1) |
N2 | 0.031 (1) | 0.016 (1) | 0.022 (1) | 0.007 (1) | 0.014 (1) | 0.005 (1) |
N3 | 0.034 (1) | 0.018 (1) | 0.024 (1) | 0.006 (1) | 0.014 (1) | 0.005 (1) |
C1 | 0.016 (1) | 0.023 (1) | 0.018 (1) | −0.002 (1) | 0.004 (1) | 0.003 (1) |
C2 | 0.021 (1) | 0.027 (1) | 0.023 (1) | −0.003 (1) | 0.005 (1) | 0.006 (1) |
C3 | 0.028 (1) | 0.039 (1) | 0.021 (1) | −0.004 (1) | 0.008 (1) | 0.009 (1) |
C4 | 0.031 (1) | 0.045 (1) | 0.021 (1) | 0.002 (1) | 0.013 (1) | 0.005 (1) |
C5 | 0.025 (1) | 0.035 (1) | 0.019 (1) | 0.004 (1) | 0.010 (1) | 0.001 (1) |
C6 | 0.017 (1) | 0.026 (1) | 0.016 (1) | 0.001 (1) | 0.006 (1) | 0.002 (1) |
C7 | 0.022 (1) | 0.022 (1) | 0.019 (1) | 0.004 (1) | 0.008 (1) | 0.000 (1) |
C8 | 0.019 (1) | 0.018 (1) | 0.020 (1) | 0.000 (1) | 0.008 (1) | 0.001 (1) |
C9 | 0.022 (1) | 0.016 (1) | 0.021 (8) | −0.002 (1) | 0.007 (1) | 0.000 (1) |
Geometric parameters (Å, º) top
Cu1—O1 | 1.918 (1) | C2—C3 | 1.386 (3) |
Cu1—O1i | 2.546 (1) | C3—C4 | 1.396 (3) |
Cu1—O2 | 1.976 (1) | C4—C5 | 1.378 (3) |
Cu1—O3 | 1.922 (1) | C5—C6 | 1.408 (2) |
Cu1—N1 | 1.923 (1) | C6—C7 | 1.439 (2) |
O1—C1 | 1.326 (2) | N2—H2n | 0.88 |
O2—C8 | 1.262 (2) | N3—H3n1 | 0.88 |
O3—C9 | 1.280 (2) | N3—H3n2 | 0.88 |
O4—C9 | 1.234 (2) | C2—H2 | 0.95 |
N1—C7 | 1.290 (2) | C3—H3 | 0.95 |
N1—N2 | 1.380 (2) | C4—H4 | 0.95 |
N2—C8 | 1.364 (2) | C5—H5 | 0.95 |
N3—C8 | 1.328 (2) | C7—H7 | 0.95 |
C1—C2 | 1.413 (2) | C9—H9 | 0.95 |
C1—C6 | 1.419 (3) | | |
| | | |
O1—Cu1—O1i | 86.90 (5) | C5—C6—C7 | 116.0 (2) |
O1—Cu1—O2 | 174.84 (5) | C1—C6—C7 | 124.2 (2) |
O1—Cu1—O3 | 89.97 (5) | N1—C7—C6 | 122.9 (2) |
O1—Cu1—N1 | 93.19 (6) | O2—C8—N3 | 122.1 (2) |
O1i—Cu1—O2 | 93.10 (5) | O2—C8—N2 | 119.6 (2) |
O1i—Cu1—O3 | 96.57 (5) | N3—C8—N2 | 118.3 (2) |
O1i—Cu1—N1 | 96.11 (5) | O4—C9—O3 | 122.7 (2) |
O2—Cu1—O3 | 95.16 (5) | C8—N2—H2n | 123.2 |
O2—Cu1—N1 | 81.67 (5) | N1—N2—H2n | 123.2 |
O3—Cu1—N1 | 167.07 (6) | C8—N3—H3n1 | 120.0 |
C1—O1—Cu1 | 125.7 (1) | C8—N3—H3n2 | 120.0 |
C8—O2—Cu1 | 112.3 (1) | H3n1—N3—H3n2 | 120.0 |
C9—O3—Cu1 | 125.1 (1) | C3—C2—H2 | 119.4 |
C7—N1—N2 | 119.0 (1) | C1—C2—H2 | 119.4 |
C7—N1—Cu1 | 128.3 (1) | C2—C3—H3 | 119.5 |
N2—N1—Cu1 | 112.5 (1) | C4—C3—H3 | 119.5 |
C8—N2—N1 | 113.7 (1) | C5—C4—H4 | 120.6 |
O1—C1—C2 | 118.1 (2) | C3—C4—H4 | 120.6 |
O1—C1—C6 | 124.3 (2) | C4—C5—H5 | 119.2 |
C2—C1—C6 | 117.5 (2) | C6—C5—H5 | 119.2 |
C3—C2—C1 | 121.2 (2) | N1—C7—H7 | 118.5 |
C2—C3—C4 | 121.1 (2) | C6—C7—H7 | 118.5 |
C5—C4—C3 | 118.7 (2) | O4—C9—H9 | 118.7 |
C4—C5—C6 | 121.7 (2) | O3—C9—H9 | 118.7 |
C5—C6—C1 | 119.8 (2) | | |
| | | |
O3—Cu1—O1—C1 | −154.9 (1) | Cu1—O1—C1—C6 | −11.6 (2) |
N1—Cu1—O1—C1 | 12.6 (2) | O1—C1—C2—C3 | 176.6 (2) |
O1i—Cu1—O1—C1 | 108.5 (2) | C6—C1—C2—C3 | −1.4 (3) |
O3—Cu1—O2—C8 | 167.0 (1) | C1—C2—C3—C4 | 1.5 (3) |
N1—Cu1—O2—C8 | −0.4 (1) | C2—C3—C4—C5 | −0.6 (3) |
O1i—Cu1—O2—C8 | −96.1 (1) | C3—C4—C5—C6 | −0.4 (3) |
O1—Cu1—O3—C9 | −157.2 (2) | C4—C5—C6—C1 | 0.4 (3) |
N1—Cu1—O3—C9 | 98.5 (3) | C4—C5—C6—C7 | −179.5 (2) |
O2—Cu1—O3—C9 | 23.4 (2) | O1—C1—C6—C5 | −177.5 (2) |
O1i—Cu1—O3—C9 | −70.3 (2) | C2—C1—C6—C5 | 0.5 (3) |
O1—Cu1—N1—C7 | −8.6 (2) | O1—C1—C6—C7 | 2.4 (3) |
O3—Cu1—N1—C7 | 95.3 (3) | C2—C1—C6—C7 | −179.6 (2) |
O2—Cu1—N1—C7 | 171.9 (2) | N2—N1—C7—C6 | 177.7 (2) |
O1i—Cu1—N1—C7 | −95.8 (2) | Cu1—N1—C7—C6 | 3.1 (3) |
O1—Cu1—N1—N2 | 176.5 (1) | C5—C6—C7—N1 | −177.9 (2) |
O3—Cu1—N1—N2 | −79.6 (3) | C1—C6—C7—N1 | 2.2 (3) |
O2—Cu1—N1—N2 | −3.0 (1) | Cu1—O2—C8—N3 | −176.9 (2) |
O1i—Cu1—N1—N2 | 89.2 (1) | Cu1—O2—C8—N2 | 3.9 (2) |
C7—N1—N2—C8 | −169.7 (2) | N1—N2—C8—O2 | −6.6 (2) |
Cu1—N1—N2—C8 | 5.8 (2) | N1—N2—C8—N3 | 174.2 (2) |
Cu1—O1—C1—C2 | 170.5 (1) | Cu1—O3—C9—O4 | −179.8 (2) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2n···O4ii | 0.88 | 2.05 | 2.804 (2) | 143 |
N3—H3n1···O4iii | 0.88 | 2.09 | 2.931 (2) | 159 |
N3—H3n2···O1ii | 0.88 | 2.53 | 3.256 (2) | 140 |
N3—H3n2···O3ii | 0.88 | 2.35 | 3.144 (2) | 151 |
Symmetry codes: (ii) −x+1/2, y+1/2, −z+1/2; (iii) −x+1, −y+1, −z. |