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Acta Cryst. (2007). E63, m2104-m2105    [ doi:10.1107/S1600536807032849 ]

Tetra-[mu]-acetato-bis{[N-(4-methylphenyl)pyridine-3-carboxamide]copper(II)} ethanol disolvate

C.-Y. Shi, C.-H. Ge, X.-M. Song and Q.-T. Liu

Abstract top

The title compound, [Cu2(C2H3O2)4(C13H12N2O)2]·2C2H5OH, contains a centrosymmetric dinuclear copper(II) unit bridged by four acetate groups with two pyridine amide ligands occupying the axial positions. Each Cu atom is in a square-pyramidal coordination environment, and is displaced from the basal plane of the O atoms by 0.2071 (3) Å towards the pyridine nitrogen. The Cu...Cu separation is 2.6442 (5) Å. The amide groups of the ligands participate in the formation of intermolecular hydrogen bonds. Hydrogen bonds and [pi]-[pi] interactions between the pyridyl and benzene rings of neighbouring molecules [centroid-to-centroid distance 3.640 (4) Å] generate a two-dimensional supramolecular network.

Comment top

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).

Related literature top

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).

Experimental top

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.

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of title compound, with displacement ellipsoids drawn at the 30% probability level. H atoms and ethanol molecules have been omitted for clarity. Unlabelled atoms or labelled with the suffix A are generated by the symmetry operation (-x, -y, -z).
[Figure 2] Fig. 2. Packing diagram of the title compound viewed along the b axis, with H atoms are omitted for clarity. Hydrogen bonds are indicated as dashed lines, π-π interactions are shown as double arrows.
Tetra-µ-acetato-bis{[N-(4-methylphenyl)pyridine-3-\ carboxamide]copper(II)} ethanol disolvate top
Crystal data top
[Cu2(C2H3O2)4(C13H12N2O)2]·2C2H6OZ = 1
Mr = 879.88F(000) = 458
Triclinic, P1Dx = 1.455 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.3874 (6) ÅCell parameters from 857 reflections
b = 8.9727 (7) Åθ = 2.7–22.7°
c = 13.4394 (10) ŵ = 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
Data collection top
Bruker SMART CCD area-detector
diffractometer		3863 independent reflections
Radiation source: fine-focus sealed tube3592 reflections with I > 2σ(I)
graphiteRint = 0.012
φ and ω scansθmax = 26.0°, θmin = 1.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→7
Tmin = 0.764, Tmax = 0.817k = −11→11
5652 measured reflectionsl = −13→16
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.089H 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 parametersΔρmax = 0.80 e Å−3
1 restraintΔρmin = −0.37 e Å−3
Crystal data top
[Cu2(C2H3O2)4(C13H12N2O)2]·2C2H6Oγ = 87.8028 (11)°
Mr = 879.88V = 1004.38 (13) Å3
Triclinic, P1Z = 1
a = 8.3874 (6) ÅMo Kα radiation
b = 8.9727 (7) ŵ = 1.13 mm−1
c = 13.4394 (10) ÅT = 295 K
α = 87.5385 (10)°0.24 × 0.22 × 0.18 mm
β = 84.0111 (11)°
Data collection top
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 = 0.817Rint = 0.012
5652 measured reflectionsθmax = 26.0°
Refinement top
R[F2 > 2σ(F2)] = 0.032H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.089Δρmax = 0.80 e Å−3
S = 1.08Δρmin = −0.37 e Å−3
3863 reflectionsAbsolute structure: ?
262 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.04088 (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)
N10.0854 (2)−0.05405 (19)0.24740 (12)0.0276 (4)
O5−0.1308 (2)−0.18505 (19)−0.07058 (12)0.0401 (4)
C70.4107 (2)0.1781 (2)0.59872 (15)0.0271 (4)
N20.3303 (2)0.0881 (2)0.53644 (13)0.0277 (4)
C20.2010 (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)
C30.1349 (3)−0.1172 (2)0.44608 (15)0.0309 (4)
H30.1512−0.13880.51260.037*
C100.5679 (3)0.3390 (2)0.73204 (17)0.0334 (5)
O10.3362 (3)0.2339 (2)0.39399 (14)0.0663 (7)
C40.0438 (3)−0.2090 (2)0.39560 (16)0.0347 (5)
H4−0.0014−0.29340.42780.042*
C10.1730 (3)0.0336 (2)0.29597 (15)0.0296 (4)
H10.21770.11660.26160.036*
C15−0.2020 (3)−0.4033 (3)0.0268 (2)0.0462 (6)
H14A−0.1494−0.46380.07510.069*
H14B−0.1923−0.4522−0.03580.069*
H14C−0.3133−0.38900.05030.069*
C50.0213 (3)−0.1737 (2)0.29731 (15)0.0315 (4)
H5−0.0409−0.23510.26420.038*
C80.4870 (3)0.3079 (3)0.56612 (18)0.0389 (5)
H80.48690.34250.49990.047*
C120.4136 (3)0.1294 (3)0.69781 (16)0.0394 (5)
H120.36250.04240.72080.047*
C90.5641 (3)0.3865 (3)0.63337 (19)0.0420 (6)
H90.61460.47400.61090.050*
C17−0.4343 (3)0.1845 (3)0.09855 (19)0.0461 (6)
H17A−0.44580.18330.17040.069*
H17B−0.51720.12760.07590.069*
H17C−0.44280.28560.07270.069*
C60.2965 (3)0.1202 (2)0.44166 (16)0.0338 (5)
C130.6533 (3)0.4252 (3)0.8036 (2)0.0449 (6)
H13A0.70170.51030.76870.067*
H13B0.73490.36200.83020.067*
H13C0.57750.45800.85740.067*
C110.4920 (3)0.2090 (3)0.76295 (17)0.0412 (6)
H110.49330.17400.82900.049*
O60.2147 (2)0.81818 (18)0.67434 (12)0.0449 (4)
H200.19360.84980.73070.067*
C180.2257 (4)0.6616 (3)0.6802 (3)0.0630 (8)
H18A0.29690.62970.73000.076*
H18B0.27200.62560.61620.076*
C190.0700 (7)0.5953 (5)0.7065 (4)0.1196 (19)
H19A0.02830.62290.77260.179*
H19B0.08220.48860.70460.179*
H19C−0.00280.63080.65950.179*
H20.302 (3)0.007 (2)0.5640 (17)0.029 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.02822 (15)0.03793 (16)0.01920 (14)−0.00463 (10)−0.00729 (10)−0.00319 (10)
O30.0315 (8)0.0495 (9)0.0241 (7)0.0022 (7)−0.0038 (6)−0.0010 (6)
O20.0326 (8)0.0676 (11)0.0282 (8)0.0085 (8)−0.0078 (6)−0.0057 (7)
O40.0546 (10)0.0393 (9)0.0312 (8)−0.0126 (7)−0.0162 (7)−0.0030 (7)
N10.0277 (9)0.0334 (9)0.0227 (8)−0.0031 (7)−0.0061 (7)−0.0018 (7)
O50.0461 (9)0.0471 (9)0.0303 (8)−0.0173 (7)−0.0123 (7)−0.0035 (7)
C70.0265 (10)0.0318 (10)0.0246 (10)−0.0020 (8)−0.0078 (8)−0.0059 (8)
N20.0330 (9)0.0289 (9)0.0229 (8)−0.0083 (7)−0.0089 (7)−0.0003 (7)
C20.0284 (10)0.0331 (10)0.0217 (9)−0.0020 (8)−0.0067 (8)−0.0033 (8)
C160.0302 (11)0.0357 (11)0.0276 (10)−0.0034 (9)−0.0045 (8)−0.0002 (8)
C140.0296 (11)0.0377 (11)0.0313 (11)−0.0053 (9)−0.0063 (8)−0.0072 (9)
C30.0389 (12)0.0341 (11)0.0215 (9)−0.0035 (9)−0.0103 (8)−0.0005 (8)
C100.0303 (11)0.0356 (11)0.0366 (12)−0.0002 (9)−0.0103 (9)−0.0110 (9)
O10.1108 (18)0.0575 (12)0.0392 (10)−0.0492 (12)−0.0395 (11)0.0178 (9)
C40.0456 (13)0.0314 (11)0.0288 (11)−0.0099 (9)−0.0093 (9)0.0023 (9)
C10.0324 (11)0.0347 (11)0.0225 (10)−0.0053 (9)−0.0059 (8)0.0021 (8)
C150.0516 (15)0.0421 (13)0.0480 (14)−0.0145 (11)−0.0136 (12)−0.0043 (11)
C50.0351 (11)0.0337 (11)0.0280 (10)−0.0049 (9)−0.0101 (9)−0.0053 (8)
C80.0464 (13)0.0398 (12)0.0339 (12)−0.0128 (10)−0.0186 (10)0.0056 (9)
C120.0518 (14)0.0428 (12)0.0262 (11)−0.0213 (11)−0.0094 (10)0.0013 (9)
C90.0473 (14)0.0354 (12)0.0471 (14)−0.0126 (10)−0.0207 (11)0.0046 (10)
C170.0365 (13)0.0604 (16)0.0405 (13)0.0082 (11)−0.0035 (10)−0.0022 (11)
C60.0408 (12)0.0364 (11)0.0262 (10)−0.0103 (9)−0.0105 (9)0.0004 (9)
C130.0452 (14)0.0455 (14)0.0482 (14)−0.0065 (11)−0.0165 (11)−0.0178 (11)
C110.0514 (14)0.0501 (14)0.0246 (11)−0.0151 (11)−0.0103 (10)−0.0034 (10)
O60.0689 (12)0.0384 (9)0.0287 (8)−0.0104 (8)−0.0081 (8)−0.0019 (7)
C180.084 (2)0.0405 (15)0.0635 (19)0.0048 (14)−0.0047 (16)−0.0034 (13)
C190.168 (5)0.070 (3)0.128 (4)−0.062 (3)−0.034 (4)0.013 (3)
Geometric parameters (Å, °) top
Cu1—O5i1.9629 (16)O1—C61.219 (3)
Cu1—O41.9712 (16)C4—C51.376 (3)
Cu1—O2i1.9717 (16)C4—H40.9300
Cu1—O31.9960 (15)C1—H10.9300
Cu1—N12.1669 (17)C15—H14A0.9600
Cu1—Cu1i2.6442 (5)C15—H14B0.9600
O3—C161.265 (3)C15—H14C0.9600
O2—C161.252 (3)C5—H50.9300
O2—Cu1i1.9717 (16)C8—C91.394 (3)
O4—C141.261 (3)C8—H80.9300
N1—C11.331 (3)C12—C111.385 (3)
N1—C51.341 (3)C12—H120.9300
O5—C141.254 (3)C9—H90.9300
O5—Cu1i1.9629 (16)C17—H17A0.9600
C7—C81.383 (3)C17—H17B0.9600
C7—C121.386 (3)C17—H17C0.9600
C7—N21.423 (2)C13—H13A0.9600
N2—C61.350 (3)C13—H13B0.9600
N2—H20.831 (16)C13—H13C0.9600
C2—C31.386 (3)C11—H110.9300
C2—C11.392 (3)O6—C181.404 (3)
C2—C61.506 (3)O6—H200.8200
C16—C171.504 (3)C18—C191.459 (6)
C14—C151.509 (3)C18—H18A0.9700
C3—C41.388 (3)C18—H18B0.9700
C3—H30.9300C19—H19A0.9600
C10—C111.378 (3)C19—H19B0.9600
C10—C91.379 (3)C19—H19C0.9600
C10—C131.512 (3)
O5i—Cu1—O4168.04 (6)C14—C15—H14A109.5
O5i—Cu1—O2i88.33 (8)C14—C15—H14B109.5
O4—Cu1—O2i90.30 (8)H14A—C15—H14B109.5
O5i—Cu1—O388.91 (7)C14—C15—H14C109.5
O4—Cu1—O389.94 (7)H14A—C15—H14C109.5
O2i—Cu1—O3167.81 (6)H14B—C15—H14C109.5
O5i—Cu1—N198.67 (6)N1—C5—C4122.55 (19)
O4—Cu1—N193.29 (6)N1—C5—H5118.7
O2i—Cu1—N197.74 (6)C4—C5—H5118.7
O3—Cu1—N194.41 (6)C7—C8—C9119.5 (2)
O5i—Cu1—Cu1i87.25 (5)C7—C8—H8120.3
O4—Cu1—Cu1i80.79 (5)C9—C8—H8120.3
O2i—Cu1—Cu1i85.24 (5)C11—C12—C7120.6 (2)
O3—Cu1—Cu1i82.77 (4)C11—C12—H12119.7
N1—Cu1—Cu1i173.42 (5)C7—C12—H12119.7
C16—O3—Cu1124.23 (14)C10—C9—C8122.2 (2)
C16—O2—Cu1i122.86 (14)C10—C9—H9118.9
C14—O4—Cu1126.81 (15)C8—C9—H9118.9
C1—N1—C5118.08 (17)C16—C17—H17A109.5
C1—N1—Cu1123.62 (14)C16—C17—H17B109.5
C5—N1—Cu1118.30 (13)H17A—C17—H17B109.5
C14—O5—Cu1i119.77 (14)C16—C17—H17C109.5
C8—C7—C12118.82 (19)H17A—C17—H17C109.5
C8—C7—N2124.23 (18)H17B—C17—H17C109.5
C12—C7—N2116.95 (19)O1—C6—N2123.9 (2)
C6—N2—C7127.68 (18)O1—C6—C2119.83 (19)
C6—N2—H2118.9 (17)N2—C6—C2116.22 (18)
C7—N2—H2113.4 (17)C10—C13—H13A109.5
C3—C2—C1117.91 (19)C10—C13—H13B109.5
C3—C2—C6124.80 (18)H13A—C13—H13B109.5
C1—C2—C6117.26 (19)C10—C13—H13C109.5
O2—C16—O3124.8 (2)H13A—C13—H13C109.5
O2—C16—C17116.93 (19)H13B—C13—H13C109.5
O3—C16—C17118.28 (19)C10—C11—C12121.5 (2)
O5—C14—O4125.3 (2)C10—C11—H11119.3
O5—C14—C15117.69 (19)C12—C11—H11119.3
O4—C14—C15117.0 (2)C18—O6—H20109.5
C2—C3—C4118.87 (19)O6—C18—C19112.4 (3)
C2—C3—H3120.6O6—C18—H18A109.1
C4—C3—H3120.6C19—C18—H18A109.1
C11—C10—C9117.4 (2)O6—C18—H18B109.1
C11—C10—C13121.1 (2)C19—C18—H18B109.1
C9—C10—C13121.4 (2)H18A—C18—H18B107.8
C5—C4—C3119.2 (2)C18—C19—H19A109.5
C5—C4—H4120.4C18—C19—H19B109.5
C3—C4—H4120.4H19A—C19—H19B109.5
N1—C1—C2123.39 (19)C18—C19—H19C109.5
N1—C1—H1118.3H19A—C19—H19C109.5
C2—C1—H1118.3H19B—C19—H19C109.5
Symmetry codes: (i) −x, −y, −z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1—H1···O10.932.422.758 (3)101
C5—H5···O40.932.433.029 (3)122
C8—H8···O10.932.272.863 (3)121
C3—H3···O6ii0.932.313.231 (3)175
C12—H12···O6ii0.932.543.350 (3)146
O6—H20···O3iii0.822.042.850 (2)171
N2—H2···O6ii0.83 (2)2.29 (2)3.108 (2)166 (2)
Symmetry codes: (ii) x, y−1, z; (iii) −x, −y+1, −z+1.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C1—H1···O10.932.422.758 (3)101
C5—H5···O40.932.433.029 (3)122
C8—H8···O10.932.272.863 (3)121
C3—H3···O6i0.932.313.231 (3)175
C12—H12···O6i0.932.543.350 (3)146
O6—H20···O3ii0.822.042.850 (2)171
N2—H2···O6i0.83 (2)2.29 (2)3.108 (2)166 (2)
Symmetry codes: (i) x, y−1, z; (ii) −x, −y+1, −z+1.
Acknowledgements top

This project was supported by the Natural Science Foundation of the Education Bureau of Liaoning Province (05 L159).

references
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