Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032849/rz2147sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032849/rz2147Isup2.hkl |
CCDC reference: 657555
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.003 Å
- R factor = 0.032
- wR factor = 0.089
- Data-to-parameter ratio = 14.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.17 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for C18 PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor .... 2.01
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.12 PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 1 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 2 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
N-(4-methylphenyl)-3-pyridinecarboxamide was prepared by reaction of nicotinoyl chloride hydrochloride and 4-methylaniline in the presence of triethylamine, similarly to the literature method (Noveron et al., 2002). An ethanolic solution of the organic ligand (0.5 mmol in 20 ml e thanol) was added dropwise to Cu(OAc)2 (0.5 mmol in 5 ml e thanol) with stirring. Single crystals suitable for X-ray analysis were obtained by slow evaporation of the solvent at room temperature.
The H atom bound to the N atom was located in a difference Fourier map and refined with a distance restraint of 0.87 (2) Å. All other H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93–0.97 Å, O—H = 0.84 Å and with Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(C, O) for methyl and hydroxy groups.
Recently, there has been growing interest in the rational design and construction of supramolecular architectures based on metal-organic frameworks with weak non-covalent interactions, such as hydrogen bonding and π-π stacking interactions (Kitagawa et al., 2004; Whitesides & Grzybowski, 2002; James, 2003; Evans & Lin, 2002). The amide group can be either hydrogen bonding donor or acceptor to form intra- or intermolecular hydrogen bonds. It can be further used to construct supramolecular coordination networks. During the past decade, various types of pyridine amide ligands and their compounds with transition metals have been synthesized (see, for example, Clement et al., 1998; Noveron et al., 2002; Belda & Moberg, 2005). As far as we know, among the studies on transition metal-pyridinecarboxamide coordination compounds, most ligands are chelating bidentate 2-pyridinecarboxamide derivatives but few are concerned with non-chelation-controlled 3- or 4-pyridinecarboxamide groups (see, for example, Ge et al., 2005). In this paper, the crystal structure of the title copper(II) dinuclear complex is reported.
The title compound consists of centrosymmetric [Cu2(µ-CH3COO)4] units with a geometry similar to that of other copper acetate derivatives. Coordination around the metal centre includes four oxygen atoms (O2, O3, O4 and O5) from four different acetate groups in a basal plane, while the axial site is occupied by a pyridine amide ligand coordinated through the pyridine nitrogen atom (Fig.1). As a result, each CuII atom presents a distorted square pyramidal geometry. The average value of the Cu—O bond distances is 1.976 (2) Å. The copper atom is displaced from the basal plane to the apical N atom by 0.2071 (3) Å. The Cu···Cu seperation is 2.6442 (5) Å. The amide groups of the ligands and the hydroxy groups of the solvate molecules are involved in the formation of intermolecular hydrogen bonds (Table 1) to give one-dimensional chains. The chains are further stacked through face-to-face π–π interactions occurring between the pyridyl and phenyl rings of centrosymmetrically related molecules (Cg1···Cg2i = 3.640 (4) Å; Cg1 and Cg2 are the centroids of the pyridyl and benzene rings, respectively; symmetry code: (i) 1 - x, -y, 1 - z) to generate a two-dimensional network (Fig.2).
For general background, see: Kitagawa et al. (2004); Whitesides & Grzybowski (2002); James (2003); Evans & Lin (2002). For related structures, see: Clement et al. (1998); Noveron et al. (2002); Belda & Moberg (2005); Ge et al. (2005).
Data collection: XSCANS (Bruker, 1997); cell refinement: XSCANS; data reduction: SHELXTL (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXL97.
[Cu2(C2H3O2)4(C13H12N2O)2]·2C2H6O | Z = 1 |
Mr = 879.88 | F(000) = 458 |
Triclinic, P1 | Dx = 1.455 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.3874 (6) Å | Cell parameters from 857 reflections |
b = 8.9727 (7) Å | θ = 2.7–22.7° |
c = 13.4394 (10) Å | µ = 1.13 mm−1 |
α = 87.5385 (10)° | T = 295 K |
β = 84.0111 (11)° | Block, green |
γ = 87.8028 (11)° | 0.24 × 0.22 × 0.18 mm |
V = 1004.38 (13) Å3 |
Bruker SMART CCD area-detector diffractometer | 3863 independent reflections |
Radiation source: fine-focus sealed tube | 3592 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.012 |
φ and ω scans | θmax = 26.0°, θmin = 1.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→7 |
Tmin = 0.764, Tmax = 0.817 | k = −11→11 |
5652 measured reflections | l = −13→16 |
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) = 0.089 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0455P)2 + 0.6567P] where P = (Fo2 + 2Fc2)/3 |
3863 reflections | (Δ/σ)max = 0.002 |
262 parameters | Δρmax = 0.80 e Å−3 |
1 restraint | Δρmin = −0.37 e Å−3 |
[Cu2(C2H3O2)4(C13H12N2O)2]·2C2H6O | γ = 87.8028 (11)° |
Mr = 879.88 | V = 1004.38 (13) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.3874 (6) Å | Mo Kα radiation |
b = 8.9727 (7) Å | µ = 1.13 mm−1 |
c = 13.4394 (10) Å | T = 295 K |
α = 87.5385 (10)° | 0.24 × 0.22 × 0.18 mm |
β = 84.0111 (11)° |
Bruker SMART CCD area-detector diffractometer | 3863 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3592 reflections with I > 2σ(I) |
Tmin = 0.764, Tmax = 0.817 | Rint = 0.012 |
5652 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 1 restraint |
wR(F2) = 0.089 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.80 e Å−3 |
3863 reflections | Δρmin = −0.37 e Å−3 |
262 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 | ||
Cu1 | 0.04088 (3) | −0.01389 (3) | 0.092416 (17) | 0.02796 (10) | |
O3 | −0.17511 (18) | 0.08329 (18) | 0.12550 (11) | 0.0351 (3) | |
O2 | −0.24597 (19) | 0.0984 (2) | −0.03016 (12) | 0.0426 (4) | |
O4 | −0.0597 (2) | −0.20760 (18) | 0.08519 (12) | 0.0405 (4) | |
N1 | 0.0854 (2) | −0.05405 (19) | 0.24740 (12) | 0.0276 (4) | |
O5 | −0.1308 (2) | −0.18505 (19) | −0.07058 (12) | 0.0401 (4) | |
C7 | 0.4107 (2) | 0.1781 (2) | 0.59872 (15) | 0.0271 (4) | |
N2 | 0.3303 (2) | 0.0881 (2) | 0.53644 (13) | 0.0277 (4) | |
C2 | 0.2010 (2) | 0.0074 (2) | 0.39562 (14) | 0.0274 (4) | |
C16 | −0.2730 (3) | 0.1171 (2) | 0.06194 (15) | 0.0310 (4) | |
C14 | −0.1247 (3) | −0.2537 (2) | 0.01231 (16) | 0.0324 (5) | |
C3 | 0.1349 (3) | −0.1172 (2) | 0.44608 (15) | 0.0309 (4) | |
H3 | 0.1512 | −0.1388 | 0.5126 | 0.037* | |
C10 | 0.5679 (3) | 0.3390 (2) | 0.73204 (17) | 0.0334 (5) | |
O1 | 0.3362 (3) | 0.2339 (2) | 0.39399 (14) | 0.0663 (7) | |
C4 | 0.0438 (3) | −0.2090 (2) | 0.39560 (16) | 0.0347 (5) | |
H4 | −0.0014 | −0.2934 | 0.4278 | 0.042* | |
C1 | 0.1730 (3) | 0.0336 (2) | 0.29597 (15) | 0.0296 (4) | |
H1 | 0.2177 | 0.1166 | 0.2616 | 0.036* | |
C15 | −0.2020 (3) | −0.4033 (3) | 0.0268 (2) | 0.0462 (6) | |
H14A | −0.1494 | −0.4638 | 0.0751 | 0.069* | |
H14B | −0.1923 | −0.4522 | −0.0358 | 0.069* | |
H14C | −0.3133 | −0.3890 | 0.0503 | 0.069* | |
C5 | 0.0213 (3) | −0.1737 (2) | 0.29731 (15) | 0.0315 (4) | |
H5 | −0.0409 | −0.2351 | 0.2642 | 0.038* | |
C8 | 0.4870 (3) | 0.3079 (3) | 0.56612 (18) | 0.0389 (5) | |
H8 | 0.4869 | 0.3425 | 0.4999 | 0.047* | |
C12 | 0.4136 (3) | 0.1294 (3) | 0.69781 (16) | 0.0394 (5) | |
H12 | 0.3625 | 0.0424 | 0.7208 | 0.047* | |
C9 | 0.5641 (3) | 0.3865 (3) | 0.63337 (19) | 0.0420 (6) | |
H9 | 0.6146 | 0.4740 | 0.6109 | 0.050* | |
C17 | −0.4343 (3) | 0.1845 (3) | 0.09855 (19) | 0.0461 (6) | |
H17A | −0.4458 | 0.1833 | 0.1704 | 0.069* | |
H17B | −0.5172 | 0.1276 | 0.0759 | 0.069* | |
H17C | −0.4428 | 0.2856 | 0.0727 | 0.069* | |
C6 | 0.2965 (3) | 0.1202 (2) | 0.44166 (16) | 0.0338 (5) | |
C13 | 0.6533 (3) | 0.4252 (3) | 0.8036 (2) | 0.0449 (6) | |
H13A | 0.7017 | 0.5103 | 0.7687 | 0.067* | |
H13B | 0.7349 | 0.3620 | 0.8302 | 0.067* | |
H13C | 0.5775 | 0.4580 | 0.8574 | 0.067* | |
C11 | 0.4920 (3) | 0.2090 (3) | 0.76295 (17) | 0.0412 (6) | |
H11 | 0.4933 | 0.1740 | 0.8290 | 0.049* | |
O6 | 0.2147 (2) | 0.81818 (18) | 0.67434 (12) | 0.0449 (4) | |
H20 | 0.1936 | 0.8498 | 0.7307 | 0.067* | |
C18 | 0.2257 (4) | 0.6616 (3) | 0.6802 (3) | 0.0630 (8) | |
H18A | 0.2969 | 0.6297 | 0.7300 | 0.076* | |
H18B | 0.2720 | 0.6256 | 0.6162 | 0.076* | |
C19 | 0.0700 (7) | 0.5953 (5) | 0.7065 (4) | 0.1196 (19) | |
H19A | 0.0283 | 0.6229 | 0.7726 | 0.179* | |
H19B | 0.0822 | 0.4886 | 0.7046 | 0.179* | |
H19C | −0.0028 | 0.6308 | 0.6595 | 0.179* | |
H2 | 0.302 (3) | 0.007 (2) | 0.5640 (17) | 0.029 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.02822 (15) | 0.03793 (16) | 0.01920 (14) | −0.00463 (10) | −0.00729 (10) | −0.00319 (10) |
O3 | 0.0315 (8) | 0.0495 (9) | 0.0241 (7) | 0.0022 (7) | −0.0038 (6) | −0.0010 (6) |
O2 | 0.0326 (8) | 0.0676 (11) | 0.0282 (8) | 0.0085 (8) | −0.0078 (6) | −0.0057 (7) |
O4 | 0.0546 (10) | 0.0393 (9) | 0.0312 (8) | −0.0126 (7) | −0.0162 (7) | −0.0030 (7) |
N1 | 0.0277 (9) | 0.0334 (9) | 0.0227 (8) | −0.0031 (7) | −0.0061 (7) | −0.0018 (7) |
O5 | 0.0461 (9) | 0.0471 (9) | 0.0303 (8) | −0.0173 (7) | −0.0123 (7) | −0.0035 (7) |
C7 | 0.0265 (10) | 0.0318 (10) | 0.0246 (10) | −0.0020 (8) | −0.0078 (8) | −0.0059 (8) |
N2 | 0.0330 (9) | 0.0289 (9) | 0.0229 (8) | −0.0083 (7) | −0.0089 (7) | −0.0003 (7) |
C2 | 0.0284 (10) | 0.0331 (10) | 0.0217 (9) | −0.0020 (8) | −0.0067 (8) | −0.0033 (8) |
C16 | 0.0302 (11) | 0.0357 (11) | 0.0276 (10) | −0.0034 (9) | −0.0045 (8) | −0.0002 (8) |
C14 | 0.0296 (11) | 0.0377 (11) | 0.0313 (11) | −0.0053 (9) | −0.0063 (8) | −0.0072 (9) |
C3 | 0.0389 (12) | 0.0341 (11) | 0.0215 (9) | −0.0035 (9) | −0.0103 (8) | −0.0005 (8) |
C10 | 0.0303 (11) | 0.0356 (11) | 0.0366 (12) | −0.0002 (9) | −0.0103 (9) | −0.0110 (9) |
O1 | 0.1108 (18) | 0.0575 (12) | 0.0392 (10) | −0.0492 (12) | −0.0395 (11) | 0.0178 (9) |
C4 | 0.0456 (13) | 0.0314 (11) | 0.0288 (11) | −0.0099 (9) | −0.0093 (9) | 0.0023 (9) |
C1 | 0.0324 (11) | 0.0347 (11) | 0.0225 (10) | −0.0053 (9) | −0.0059 (8) | 0.0021 (8) |
C15 | 0.0516 (15) | 0.0421 (13) | 0.0480 (14) | −0.0145 (11) | −0.0136 (12) | −0.0043 (11) |
C5 | 0.0351 (11) | 0.0337 (11) | 0.0280 (10) | −0.0049 (9) | −0.0101 (9) | −0.0053 (8) |
C8 | 0.0464 (13) | 0.0398 (12) | 0.0339 (12) | −0.0128 (10) | −0.0186 (10) | 0.0056 (9) |
C12 | 0.0518 (14) | 0.0428 (12) | 0.0262 (11) | −0.0213 (11) | −0.0094 (10) | 0.0013 (9) |
C9 | 0.0473 (14) | 0.0354 (12) | 0.0471 (14) | −0.0126 (10) | −0.0207 (11) | 0.0046 (10) |
C17 | 0.0365 (13) | 0.0604 (16) | 0.0405 (13) | 0.0082 (11) | −0.0035 (10) | −0.0022 (11) |
C6 | 0.0408 (12) | 0.0364 (11) | 0.0262 (10) | −0.0103 (9) | −0.0105 (9) | 0.0004 (9) |
C13 | 0.0452 (14) | 0.0455 (14) | 0.0482 (14) | −0.0065 (11) | −0.0165 (11) | −0.0178 (11) |
C11 | 0.0514 (14) | 0.0501 (14) | 0.0246 (11) | −0.0151 (11) | −0.0103 (10) | −0.0034 (10) |
O6 | 0.0689 (12) | 0.0384 (9) | 0.0287 (8) | −0.0104 (8) | −0.0081 (8) | −0.0019 (7) |
C18 | 0.084 (2) | 0.0405 (15) | 0.0635 (19) | 0.0048 (14) | −0.0047 (16) | −0.0034 (13) |
C19 | 0.168 (5) | 0.070 (3) | 0.128 (4) | −0.062 (3) | −0.034 (4) | 0.013 (3) |
Cu1—O5i | 1.9629 (16) | O1—C6 | 1.219 (3) |
Cu1—O4 | 1.9712 (16) | C4—C5 | 1.376 (3) |
Cu1—O2i | 1.9717 (16) | C4—H4 | 0.9300 |
Cu1—O3 | 1.9960 (15) | C1—H1 | 0.9300 |
Cu1—N1 | 2.1669 (17) | C15—H14A | 0.9600 |
Cu1—Cu1i | 2.6442 (5) | C15—H14B | 0.9600 |
O3—C16 | 1.265 (3) | C15—H14C | 0.9600 |
O2—C16 | 1.252 (3) | C5—H5 | 0.9300 |
O2—Cu1i | 1.9717 (16) | C8—C9 | 1.394 (3) |
O4—C14 | 1.261 (3) | C8—H8 | 0.9300 |
N1—C1 | 1.331 (3) | C12—C11 | 1.385 (3) |
N1—C5 | 1.341 (3) | C12—H12 | 0.9300 |
O5—C14 | 1.254 (3) | C9—H9 | 0.9300 |
O5—Cu1i | 1.9629 (16) | C17—H17A | 0.9600 |
C7—C8 | 1.383 (3) | C17—H17B | 0.9600 |
C7—C12 | 1.386 (3) | C17—H17C | 0.9600 |
C7—N2 | 1.423 (2) | C13—H13A | 0.9600 |
N2—C6 | 1.350 (3) | C13—H13B | 0.9600 |
N2—H2 | 0.831 (16) | C13—H13C | 0.9600 |
C2—C3 | 1.386 (3) | C11—H11 | 0.9300 |
C2—C1 | 1.392 (3) | O6—C18 | 1.404 (3) |
C2—C6 | 1.506 (3) | O6—H20 | 0.8200 |
C16—C17 | 1.504 (3) | C18—C19 | 1.459 (6) |
C14—C15 | 1.509 (3) | C18—H18A | 0.9700 |
C3—C4 | 1.388 (3) | C18—H18B | 0.9700 |
C3—H3 | 0.9300 | C19—H19A | 0.9600 |
C10—C11 | 1.378 (3) | C19—H19B | 0.9600 |
C10—C9 | 1.379 (3) | C19—H19C | 0.9600 |
C10—C13 | 1.512 (3) | ||
O5i—Cu1—O4 | 168.04 (6) | C14—C15—H14A | 109.5 |
O5i—Cu1—O2i | 88.33 (8) | C14—C15—H14B | 109.5 |
O4—Cu1—O2i | 90.30 (8) | H14A—C15—H14B | 109.5 |
O5i—Cu1—O3 | 88.91 (7) | C14—C15—H14C | 109.5 |
O4—Cu1—O3 | 89.94 (7) | H14A—C15—H14C | 109.5 |
O2i—Cu1—O3 | 167.81 (6) | H14B—C15—H14C | 109.5 |
O5i—Cu1—N1 | 98.67 (6) | N1—C5—C4 | 122.55 (19) |
O4—Cu1—N1 | 93.29 (6) | N1—C5—H5 | 118.7 |
O2i—Cu1—N1 | 97.74 (6) | C4—C5—H5 | 118.7 |
O3—Cu1—N1 | 94.41 (6) | C7—C8—C9 | 119.5 (2) |
O5i—Cu1—Cu1i | 87.25 (5) | C7—C8—H8 | 120.3 |
O4—Cu1—Cu1i | 80.79 (5) | C9—C8—H8 | 120.3 |
O2i—Cu1—Cu1i | 85.24 (5) | C11—C12—C7 | 120.6 (2) |
O3—Cu1—Cu1i | 82.77 (4) | C11—C12—H12 | 119.7 |
N1—Cu1—Cu1i | 173.42 (5) | C7—C12—H12 | 119.7 |
C16—O3—Cu1 | 124.23 (14) | C10—C9—C8 | 122.2 (2) |
C16—O2—Cu1i | 122.86 (14) | C10—C9—H9 | 118.9 |
C14—O4—Cu1 | 126.81 (15) | C8—C9—H9 | 118.9 |
C1—N1—C5 | 118.08 (17) | C16—C17—H17A | 109.5 |
C1—N1—Cu1 | 123.62 (14) | C16—C17—H17B | 109.5 |
C5—N1—Cu1 | 118.30 (13) | H17A—C17—H17B | 109.5 |
C14—O5—Cu1i | 119.77 (14) | C16—C17—H17C | 109.5 |
C8—C7—C12 | 118.82 (19) | H17A—C17—H17C | 109.5 |
C8—C7—N2 | 124.23 (18) | H17B—C17—H17C | 109.5 |
C12—C7—N2 | 116.95 (19) | O1—C6—N2 | 123.9 (2) |
C6—N2—C7 | 127.68 (18) | O1—C6—C2 | 119.83 (19) |
C6—N2—H2 | 118.9 (17) | N2—C6—C2 | 116.22 (18) |
C7—N2—H2 | 113.4 (17) | C10—C13—H13A | 109.5 |
C3—C2—C1 | 117.91 (19) | C10—C13—H13B | 109.5 |
C3—C2—C6 | 124.80 (18) | H13A—C13—H13B | 109.5 |
C1—C2—C6 | 117.26 (19) | C10—C13—H13C | 109.5 |
O2—C16—O3 | 124.8 (2) | H13A—C13—H13C | 109.5 |
O2—C16—C17 | 116.93 (19) | H13B—C13—H13C | 109.5 |
O3—C16—C17 | 118.28 (19) | C10—C11—C12 | 121.5 (2) |
O5—C14—O4 | 125.3 (2) | C10—C11—H11 | 119.3 |
O5—C14—C15 | 117.69 (19) | C12—C11—H11 | 119.3 |
O4—C14—C15 | 117.0 (2) | C18—O6—H20 | 109.5 |
C2—C3—C4 | 118.87 (19) | O6—C18—C19 | 112.4 (3) |
C2—C3—H3 | 120.6 | O6—C18—H18A | 109.1 |
C4—C3—H3 | 120.6 | C19—C18—H18A | 109.1 |
C11—C10—C9 | 117.4 (2) | O6—C18—H18B | 109.1 |
C11—C10—C13 | 121.1 (2) | C19—C18—H18B | 109.1 |
C9—C10—C13 | 121.4 (2) | H18A—C18—H18B | 107.8 |
C5—C4—C3 | 119.2 (2) | C18—C19—H19A | 109.5 |
C5—C4—H4 | 120.4 | C18—C19—H19B | 109.5 |
C3—C4—H4 | 120.4 | H19A—C19—H19B | 109.5 |
N1—C1—C2 | 123.39 (19) | C18—C19—H19C | 109.5 |
N1—C1—H1 | 118.3 | H19A—C19—H19C | 109.5 |
C2—C1—H1 | 118.3 | H19B—C19—H19C | 109.5 |
Symmetry code: (i) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O1 | 0.93 | 2.42 | 2.758 (3) | 101 |
C5—H5···O4 | 0.93 | 2.43 | 3.029 (3) | 122 |
C8—H8···O1 | 0.93 | 2.27 | 2.863 (3) | 121 |
C3—H3···O6ii | 0.93 | 2.31 | 3.231 (3) | 175 |
C12—H12···O6ii | 0.93 | 2.54 | 3.350 (3) | 146 |
O6—H20···O3iii | 0.82 | 2.04 | 2.850 (2) | 171 |
N2—H2···O6ii | 0.83 (2) | 2.29 (2) | 3.108 (2) | 166 (2) |
Symmetry codes: (ii) x, y−1, z; (iii) −x, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C2H3O2)4(C13H12N2O)2]·2C2H6O |
Mr | 879.88 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 295 |
a, b, c (Å) | 8.3874 (6), 8.9727 (7), 13.4394 (10) |
α, β, γ (°) | 87.5385 (10), 84.0111 (11), 87.8028 (11) |
V (Å3) | 1004.38 (13) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.13 |
Crystal size (mm) | 0.24 × 0.22 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.764, 0.817 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5652, 3863, 3592 |
Rint | 0.012 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.089, 1.08 |
No. of reflections | 3863 |
No. of parameters | 262 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.80, −0.37 |
Computer programs: XSCANS (Bruker, 1997), XSCANS, SHELXTL (Siemens, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL, SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O1 | 0.93 | 2.42 | 2.758 (3) | 101.2 |
C5—H5···O4 | 0.93 | 2.43 | 3.029 (3) | 122.3 |
C8—H8···O1 | 0.93 | 2.27 | 2.863 (3) | 120.9 |
C3—H3···O6i | 0.93 | 2.31 | 3.231 (3) | 174.6 |
C12—H12···O6i | 0.93 | 2.54 | 3.350 (3) | 146.2 |
O6—H20···O3ii | 0.82 | 2.04 | 2.850 (2) | 171.3 |
N2—H2···O6i | 0.83 (2) | 2.29 (2) | 3.108 (2) | 165.9 (18) |
Symmetry codes: (i) x, y−1, z; (ii) −x, −y+1, −z+1. |
Recently, there has been growing interest in the rational design and construction of supramolecular architectures based on metal-organic frameworks with weak non-covalent interactions, such as hydrogen bonding and π-π stacking interactions (Kitagawa et al., 2004; Whitesides & Grzybowski, 2002; James, 2003; Evans & Lin, 2002). The amide group can be either hydrogen bonding donor or acceptor to form intra- or intermolecular hydrogen bonds. It can be further used to construct supramolecular coordination networks. During the past decade, various types of pyridine amide ligands and their compounds with transition metals have been synthesized (see, for example, Clement et al., 1998; Noveron et al., 2002; Belda & Moberg, 2005). As far as we know, among the studies on transition metal-pyridinecarboxamide coordination compounds, most ligands are chelating bidentate 2-pyridinecarboxamide derivatives but few are concerned with non-chelation-controlled 3- or 4-pyridinecarboxamide groups (see, for example, Ge et al., 2005). In this paper, the crystal structure of the title copper(II) dinuclear complex is reported.
The title compound consists of centrosymmetric [Cu2(µ-CH3COO)4] units with a geometry similar to that of other copper acetate derivatives. Coordination around the metal centre includes four oxygen atoms (O2, O3, O4 and O5) from four different acetate groups in a basal plane, while the axial site is occupied by a pyridine amide ligand coordinated through the pyridine nitrogen atom (Fig.1). As a result, each CuII atom presents a distorted square pyramidal geometry. The average value of the Cu—O bond distances is 1.976 (2) Å. The copper atom is displaced from the basal plane to the apical N atom by 0.2071 (3) Å. The Cu···Cu seperation is 2.6442 (5) Å. The amide groups of the ligands and the hydroxy groups of the solvate molecules are involved in the formation of intermolecular hydrogen bonds (Table 1) to give one-dimensional chains. The chains are further stacked through face-to-face π–π interactions occurring between the pyridyl and phenyl rings of centrosymmetrically related molecules (Cg1···Cg2i = 3.640 (4) Å; Cg1 and Cg2 are the centroids of the pyridyl and benzene rings, respectively; symmetry code: (i) 1 - x, -y, 1 - z) to generate a two-dimensional network (Fig.2).