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In the title polymeric complex, [Cu(C8H4NO2)2(C10H8N2)]n, the CuII center is located on an inversion center and surrounded by two N-donor mol­ecules and two 4-cyano­benzoato ligands, which impose a square-planar environment on the metal. The spacer linker, 4,4′-bi­pyridine, is located on an inversion center and links adjacent metal atoms into a one-dimensional chain with a Cu...Cu separation of 11.218 (2) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803000989/ob6207sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803000989/ob6207Isup2.hkl
Contains datablock I

CCDC reference: 204695

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.005 Å
  • R factor = 0.051
  • wR factor = 0.096
  • Data-to-parameter ratio = 13.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 28.25 From the CIF: _reflns_number_total 2504 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 2778 Completeness (_total/calc) 90.14% Alert C: < 95% complete PLAT_213 Alert C Atom N2 has ADP max/min Ratio ........... 3.60 oblate PLAT_213 Alert C Atom C8 has ADP max/min Ratio ........... 3.10 prolate PLAT_213 Alert C Atom C9 has ADP max/min Ratio ........... 3.80 prolate PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(10) - C(13) = 1.44 Ang. PLAT_731 Alert C Bond Calc 0.89(4), Rep 0.891(19) .... 2.11 su-Ratio C8 -H5 1.555 1.555
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
6 Alert Level C = Please check

Comment top

In recent years, much attention has been paid to in the field of coordination polymers and especially focused on the ligands of 4,4'-bipyridne, terethphate and their derivatives due to their potential applications in gas adsorption, ion exchange and heterogeneous catalysis (Eddaoudi et al., 2002; Moulton & Zaworotko, 2001; Seo et al., 2000). Complexes with 4-cyanobenzoic acid were sparse and recent one suggests that this kind of complexes has strong blue fluorescent emission (Yuan et al., 2001). Moreover complex with the combination of 4-cyanobenzoic acid and 4,4'-bipyridine has not been reported so far. Here, we present the crystal structure of the CuII one-dimensional complex, the title compound, (I).

Compound (I) consists of one-dimensional CuII complex in which the geometry around the CuII ion, located on an inversion center, is best described as a square planar, as can be seen in Fig. 1. The geometry of Cu atom is completed by two O atoms from two 4-cyanobenzoato ligands and two N atoms from two 4,4'-bipyridine. Two benzoate groups and two pyridine rings of 4,4'-bipyridine ligands are respectively located on the opposite sides to minimize repulsion between the ligands. The Cu—O1 bond length [1.9176 (18) Å] is shorter than those of the compounds such as [Cu(py)2(H2O)(C6H5COO)2] (Yang et al., 2001) and [Cu(C6H5COO)2(2,2'-bipy)] (Yang et al., 1994). The 4-cyanobenzoate is monodentately coordinated to copper center and the distance of Cu—O2 [2.861 (3) Å] is longer and is considered as non-bonding. This coordination mode of 4-cyanobenzoato ligand results in the four-coordinated copper geometry. The Cu—N1 bond length [2.051 (2) Å] is similar to those of [Cu(py)2(H2O)(C6H5COO)2] (Yang et al., 2001) and [Cu(C6H5COO)2(2,2'-bipy)] (Yang et al., 1994) or those of CuII complexes with 4,4'-bipyridine bridging linker (Xu et al., 2002; Zhu et al., 2002). The spacer ligand, 4,4'-bipyridine, located on an inversion center, links adjacent Cu atoms and extends the complex into one-dimensional chain along [110] (Fig. 2). The Cu···Cu separation of the network is 11.218 (2) Å, which is normal distance found in related to copper/4,4'-bipyridine complexes. As expected, all other bond distances and angles are within normal range, and in good agreement with those of other 4,4'-bipyridine and carboxyl-containing complexes.

Experimental top

The title complex, (I), was synthesized by three layered-solution approach in a tube of ca 0.8 cm diameter with a 20 cm length. The top layer was 10 ml of methanol solution of 4,4'-bipyridine (0.2 mol l−1) and 4-cyanobenzoic acid (0.05 mol l−1). The middle layer was 3 ml of mixed solvents of methanol and water with volume ratio 1:1. The bottom layer was 5 ml of water solution of Cu(NO3)2·3H2O (0.5 mol l−1). After 3 d, crystals of (I) were obtained and filtered out.

Refinement top

The completeness was relatively low (90.1%) although all parameters were set according to the suggestions of SMART. The H atoms were refined isotropically. C—H bond lengths are 0.89 (4)–0.92 (2) Å. Atom displacement parameters of N2, C8 and C9 are abnormal. Their displacement ellipsoids are much elongated, suggesting some disorder.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SHELXTL (Bruker, 1997); 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: SHELXTL.

Figures top
[Figure 1] Fig. 1. ORTEP diagram of (I) showing atom labeling scheme. Displacement ellipsoids represent 50% probability.
[Figure 2] Fig. 2. The packing view of the title complex (I).
(I) top
Crystal data top
[Cu(C8H4NO2)2(C10H8N2)]Z = 1
Mr = 511.97F(000) = 261
Triclinic, P1Dx = 1.507 Mg m3
a = 5.3279 (10) ÅMo Kα radiation, λ = 0.71073 Å
b = 8.9739 (17) ÅCell parameters from 978 reflections
c = 12.195 (2) Åθ = 5.3–48.0°
α = 99.734 (3)°µ = 1.01 mm1
β = 92.495 (4)°T = 293 K
γ = 100.190 (4)°Plate, blue
V = 563.99 (18) Å30.31 × 0.11 × 0.04 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
2504 independent reflections
Radiation source: fine-focus sealed tube2053 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
ϕ and ω scansθmax = 28.3°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 76
Tmin = 0.820, Tmax = 0.965k = 118
3490 measured reflectionsl = 1515
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)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096All H-atom parameters refined
S = 0.95 w = 1/[σ2(Fo2) + (0.0303P)2]
where P = (Fo2 + 2Fc2)/3
2504 reflections(Δ/σ)max = 0.042
192 parametersΔρmax = 0.43 e Å3
4 restraintsΔρmin = 0.36 e Å3
Crystal data top
[Cu(C8H4NO2)2(C10H8N2)]γ = 100.190 (4)°
Mr = 511.97V = 563.99 (18) Å3
Triclinic, P1Z = 1
a = 5.3279 (10) ÅMo Kα radiation
b = 8.9739 (17) ŵ = 1.01 mm1
c = 12.195 (2) ÅT = 293 K
α = 99.734 (3)°0.31 × 0.11 × 0.04 mm
β = 92.495 (4)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
2504 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
2053 reflections with I > 2σ(I)
Tmin = 0.820, Tmax = 0.965Rint = 0.035
3490 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0514 restraints
wR(F2) = 0.096All H-atom parameters refined
S = 0.95Δρmax = 0.43 e Å3
2504 reflectionsΔρmin = 0.36 e Å3
192 parameters
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
Cu0.50001.00000.50000.03066 (19)
O10.3001 (4)0.8941 (2)0.36588 (17)0.0399 (6)
O20.5852 (5)1.0203 (3)0.2725 (2)0.0742 (9)
N10.6939 (4)0.8213 (3)0.49639 (18)0.0308 (6)
N20.3402 (9)0.5813 (6)0.2040 (3)0.146 (2)
C10.8993 (6)0.8275 (4)0.5667 (2)0.0352 (8)
C21.0204 (5)0.7063 (3)0.5704 (2)0.0346 (7)
C30.9394 (5)0.5677 (3)0.4988 (2)0.0283 (6)
C40.7315 (6)0.5622 (4)0.4239 (3)0.0364 (8)
C50.6167 (6)0.6875 (3)0.4257 (2)0.0362 (8)
C60.3881 (6)0.9305 (4)0.2763 (3)0.0414 (8)
C70.2254 (6)0.8525 (4)0.1706 (3)0.0417 (8)
C80.2956 (10)0.8816 (7)0.0725 (4)0.120 (2)
C90.1526 (11)0.8136 (8)0.0273 (4)0.136 (3)
C100.0661 (8)0.7126 (5)0.0238 (3)0.0664 (12)
C110.1403 (8)0.6822 (5)0.0747 (4)0.0822 (15)
C120.0071 (8)0.7531 (5)0.1726 (3)0.0686 (13)
C130.2206 (9)0.6389 (6)0.1251 (3)0.0930 (16)
H10.958 (5)0.922 (3)0.608 (2)0.031 (8)*
H21.152 (4)0.717 (3)0.621 (2)0.046 (9)*
H30.664 (5)0.478 (3)0.375 (2)0.026 (7)*
H40.475 (5)0.687 (3)0.381 (2)0.032 (8)*
H50.445 (5)0.936 (5)0.060 (4)0.107 (16)*
H60.212 (8)0.833 (5)0.094 (2)0.122 (18)*
H70.299 (5)0.621 (4)0.075 (3)0.116 (17)*
H80.056 (7)0.727 (4)0.235 (3)0.080 (14)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu0.0388 (3)0.0289 (3)0.0229 (3)0.0133 (2)0.0112 (2)0.0031 (2)
O10.0500 (13)0.0380 (13)0.0294 (11)0.0175 (10)0.0156 (10)0.0053 (10)
O20.0598 (17)0.088 (2)0.0538 (17)0.0191 (16)0.0205 (14)0.0063 (15)
N10.0327 (13)0.0277 (13)0.0305 (13)0.0094 (11)0.0072 (11)0.0002 (11)
N20.152 (4)0.176 (5)0.065 (3)0.041 (4)0.064 (3)0.016 (3)
C10.0375 (17)0.0291 (17)0.0340 (17)0.0070 (14)0.0132 (14)0.0055 (14)
C20.0308 (16)0.0315 (17)0.0376 (17)0.0081 (14)0.0160 (14)0.0023 (14)
C30.0291 (15)0.0265 (16)0.0286 (14)0.0075 (12)0.0028 (12)0.0021 (12)
C40.0422 (18)0.0257 (17)0.0358 (17)0.0067 (14)0.0165 (15)0.0056 (14)
C50.0376 (18)0.0315 (17)0.0366 (17)0.0112 (14)0.0162 (15)0.0020 (14)
C60.044 (2)0.038 (2)0.0362 (19)0.0100 (16)0.0149 (16)0.0063 (15)
C70.0432 (19)0.044 (2)0.0306 (17)0.0002 (16)0.0118 (15)0.0006 (15)
C80.104 (4)0.171 (6)0.043 (3)0.086 (4)0.024 (3)0.023 (3)
C90.130 (5)0.204 (7)0.027 (2)0.085 (4)0.022 (3)0.020 (3)
C100.069 (3)0.080 (3)0.033 (2)0.007 (2)0.022 (2)0.006 (2)
C110.073 (3)0.101 (4)0.045 (2)0.041 (3)0.017 (2)0.002 (2)
C120.069 (3)0.089 (3)0.032 (2)0.018 (2)0.011 (2)0.006 (2)
C130.099 (3)0.109 (4)0.047 (3)0.021 (3)0.029 (2)0.002 (3)
Geometric parameters (Å, º) top
Cu—O11.9176 (18)C4—C51.369 (4)
Cu—O1i1.9176 (18)C4—H30.89 (2)
Cu—N1i2.051 (2)C5—H40.92 (2)
Cu—N12.051 (2)C6—C71.511 (4)
O1—C61.277 (4)C7—C81.323 (6)
O2—C61.214 (4)C7—C121.339 (5)
N1—C51.341 (3)C8—C91.392 (6)
N1—C11.347 (3)C8—H50.891 (19)
N2—C131.123 (4)C9—C101.350 (6)
C1—C21.365 (4)C9—H60.911 (19)
C1—H10.90 (3)C10—C111.337 (6)
C2—C31.380 (4)C10—C131.443 (4)
C2—H20.895 (16)C11—C121.390 (5)
C3—C41.393 (3)C11—H70.922 (19)
C3—C3ii1.478 (5)C12—H80.89 (4)
O1—Cu—O1i180.000 (1)C4—C5—H4123.5 (17)
O1—Cu—N1i89.83 (8)O2—C6—O1124.6 (3)
O1i—Cu—N1i90.17 (8)O2—C6—C7120.6 (3)
O1—Cu—N190.17 (8)O1—C6—C7114.8 (3)
O1i—Cu—N189.83 (8)C8—C7—C12117.8 (3)
N1i—Cu—N1180.000 (1)C8—C7—C6120.4 (3)
C6—O1—Cu114.5 (2)C12—C7—C6121.8 (3)
C5—N1—C1115.6 (2)C7—C8—C9122.8 (5)
C5—N1—Cu121.49 (17)C7—C8—H5126 (3)
C1—N1—Cu122.85 (19)C9—C8—H5111 (3)
N1—C1—C2123.6 (3)C10—C9—C8118.6 (5)
N1—C1—H1113.5 (16)C10—C9—H6121 (3)
C2—C1—H1122.7 (16)C8—C9—H6120 (3)
C1—C2—C3120.9 (2)C11—C10—C9119.4 (4)
C1—C2—H2118.8 (19)C11—C10—C13120.0 (4)
C3—C2—H2120.3 (19)C9—C10—C13120.6 (4)
C2—C3—C4115.6 (3)C10—C11—C12120.3 (4)
C2—C3—C3ii122.9 (3)C10—C11—H7117 (3)
C4—C3—C3ii121.4 (3)C12—C11—H7122 (3)
C5—C4—C3120.4 (3)C7—C12—C11121.1 (4)
C5—C4—H3117.3 (16)C7—C12—H8124 (2)
C3—C4—H3122.2 (16)C11—C12—H8115 (2)
N1—C5—C4123.8 (2)N2—C13—C10179.7 (6)
N1—C5—H4112.7 (16)
Symmetry codes: (i) x+1, y+2, z+1; (ii) x+2, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Cu(C8H4NO2)2(C10H8N2)]
Mr511.97
Crystal system, space groupTriclinic, P1
Temperature (K)293
a, b, c (Å)5.3279 (10), 8.9739 (17), 12.195 (2)
α, β, γ (°)99.734 (3), 92.495 (4), 100.190 (4)
V3)563.99 (18)
Z1
Radiation typeMo Kα
µ (mm1)1.01
Crystal size (mm)0.31 × 0.11 × 0.04
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.820, 0.965
No. of measured, independent and
observed [I > 2σ(I)] reflections
3490, 2504, 2053
Rint0.035
(sin θ/λ)max1)0.666
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.051, 0.096, 0.95
No. of reflections2504
No. of parameters192
No. of restraints4
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.43, 0.36

Computer programs: SMART (Bruker, 1997), SMART, SHELXTL (Bruker, 1997), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL.

Selected geometric parameters (Å, º) top
Cu—O11.9176 (18)C1—C21.365 (4)
Cu—N12.051 (2)C2—C31.380 (4)
O1—C61.277 (4)C3—C41.393 (3)
O2—C61.214 (4)C3—C3i1.478 (5)
N1—C51.341 (3)C4—C51.369 (4)
N1—C11.347 (3)
O1—Cu—N190.17 (8)O2—C6—O1124.6 (3)
C6—O1—Cu114.5 (2)
Symmetry code: (i) x+2, y+1, z+1.
 

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