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The Cu atom in the title complex, [Cu(C6Cl2O4)(C10H8N2)], has a square-planar CuN2O2 environment. The structure is built of monomeric neutral, essentially planar, mol­ecules stacked along the b axis, with the stacks held together by means of weak π–π, π...Cl, and π...Cu inter­actions. The mol­ecules of neighbouring stacks are linked via C—H...O hydrogen bonds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805027649/ya6258sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805027649/ya6258Isup2.hkl
Contains datablock I

CCDC reference: 287766

Key indicators

  • Single-crystal X-ray study
  • T = 295 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.035
  • wR factor = 0.065
  • Data-to-parameter ratio = 19.9

checkCIF/PLATON results

No syntax errors found



Alert level C GOODF01_ALERT_2_C The least squares goodness of fit parameter lies outside the range 0.80 <> 2.00 Goodness of fit given = 0.740 PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low .... 47 Perc. PLAT333_ALERT_2_C Large Average Benzene C-C Dist. C13 -C18 1.45 Ang. PLAT335_ALERT_2_C Large Benzene C-C Range C13 -C18 0.20 Ang. PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C17 - C18 ... 1.56 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 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 4 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

To date, there is only one structurally characterized CuII complex in the literature with both 2,2-bipyridine (bpy) and the chloranilate dianion (chl) as ligands, namely the dimeric cation of [{Cu(C10H8N2)(CH3OH)}2(chl)](PF6)2 (Fujii et al., 1994). The title monomeric neutral complex, (I), was obtained in an attempt to prepare a hybrid inorganic–metal-organic material based on the auto-assembly of the above-mentioned dimer and Keggin-type polyoxometallates.

The Cu atom in the title compound is coordinated by both the neutral bpy and the dianionic chl ligands in a chelating bidentate fashion, leading to a square-planar CuN2O2 coordination environment (Fig. 1).

The crystal structure shows infinite ladder-like columns of monomeric complexes stacked along the b axis (Fig. 2). In addition to intermolecular Cu1···O2i contacts [3.210 (2) Å], the stacks are held together by means of an alternating sequence of π(C7—N12)···π(chl)i, π(N1—C6)···Cl2i and π(chl)···Cu1ii interactions [symmetry codes: (i) −x, −y, −z; (ii) −x, 1 − y, −z], the centroid–centroid or centroid–atom distances being 3.416 (2), 3.558 (1) and 3.451 (1) Å, respectively. The stacks are connected to each other through an extended network of C—H···O hydrogen bonds (Table 2), involving those O atoms which are not coordinated to the Cu atom. These C—H···O interactions give rise to layers parallel to the ab plane.

Experimental top

Upon addition of a solution containing Cu(NO3)2·2H2O (96 mg), 2,2'-bipyridine (62 mg) and chloranilic acid (42 mg) in methanol (40 ml) to a solution of K4SiW12O40 (667 mg) in water (50 ml), a green precipitate was formed. The title compound was obtained as prismatic dark-red crystals by recrystallization of the precipitate in a 1:2 mixture of water and dimethyformamide. Elemental analysis, found: C 44.92, H 1.97, N 6.51%; calculated for C16CuCl2H8N2O4: C 45.04, H 1.89, N 6.57%. Spectroscopic analysis: IR (Medium?, ν, cm−1): 1643, 1533, 1368, 845, 774, 604, 565. Axial electron paramagnetic resonance signal: gparallel = 2.205, gperpendicular = 2.052.

Refinement top

The positions of all H atoms were calculated geometrically and refined as riding, with C—H = 0.93 Å and with Uiso(H) = 1.2Ueq(C). The low goodness-of-fit value (0.74) is most probably the result of a rather poorly diffracting crystal.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis RED (Oxford Diffraction, 2003); data reduction: CrysAlis RED; program(s) used to solve structure: DIRDIF99.2 (Beurskens et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX publication routines (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. A plot of (I), with 50% probability displacement ellipsoids. H atoms have been omitted for clarity.
[Figure 2] Fig. 2. (a) The ladder-like column, highlighting the intermolecular Cu—O, ππ, π···Cl and π···Cu interactions. (b) A projection of a layer on the ab plane, together with a detail of the C—H···O network.
(2,2'-Bipyridyl-κ2N,N')(chloranilato-κ2O,O')copper(II) top
Crystal data top
[Cu(C6Cl2O4)(C10H8N2)]F(000) = 1704
Mr = 426.68Dx = 1.831 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 6500 reflections
a = 24.987 (3) Åθ = 3.5–25°
b = 7.438 (1) ŵ = 1.78 mm1
c = 17.215 (2) ÅT = 295 K
β = 104.57 (1)°Prism, dark red
V = 3096.6 (7) Å30.14 × 0.11 × 0.06 mm
Z = 8
Data collection top
Oxford Diffraction Xcalibur
diffractometer
4506 independent reflections
Radiation source: fine-focus sealed tube2120 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.045
Detector resolution: 1024 × 1024 with blocks 2 × 2 pixels mm-1θmax = 30.0°, θmin = 3.3°
ω scansh = 3335
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2003)
k = 810
Tmin = 0.802, Tmax = 0.903l = 2423
14006 measured reflections
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.035 w = 1/[σ2(Fo2) + (0.0227P)2]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.065(Δ/σ)max < 0.001
S = 0.74Δρmax = 0.57 e Å3
4506 reflectionsΔρmin = 0.31 e Å3
226 parameters
Crystal data top
[Cu(C6Cl2O4)(C10H8N2)]V = 3096.6 (7) Å3
Mr = 426.68Z = 8
Monoclinic, C2/cMo Kα radiation
a = 24.987 (3) ŵ = 1.78 mm1
b = 7.438 (1) ÅT = 295 K
c = 17.215 (2) Å0.14 × 0.11 × 0.06 mm
β = 104.57 (1)°
Data collection top
Oxford Diffraction Xcalibur
diffractometer
4506 independent reflections
Absorption correction: analytical
(CrysAlis RED; Oxford Diffraction, 2003)
2120 reflections with I > 2σ(I)
Tmin = 0.802, Tmax = 0.903Rint = 0.045
14006 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0350 restraints
wR(F2) = 0.065H-atom parameters constrained
S = 0.74Δρmax = 0.57 e Å3
4506 reflectionsΔρmin = 0.31 e Å3
226 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.050506 (13)0.21793 (4)0.02153 (2)0.03594 (11)
Cl20.12598 (3)0.18923 (10)0.18043 (4)0.0448 (2)
Cl10.06659 (3)0.51922 (10)0.17048 (4)0.0479 (2)
O20.01831 (6)0.1861 (2)0.05719 (10)0.0399 (5)
O40.20367 (7)0.3575 (3)0.09432 (12)0.0504 (6)
O10.00710 (7)0.3375 (2)0.08286 (10)0.0402 (5)
O30.17809 (7)0.4977 (3)0.05564 (12)0.0516 (6)
N120.09663 (8)0.1055 (3)0.04055 (12)0.0294 (5)
C140.04423 (10)0.3515 (3)0.04461 (15)0.0297 (6)
N10.12136 (8)0.2463 (3)0.10076 (12)0.0299 (5)
C110.07935 (10)0.0408 (3)0.11404 (16)0.0345 (7)
H110.04180.04570.13930.041*
C130.08389 (10)0.4339 (3)0.07398 (15)0.0295 (6)
C40.22449 (11)0.2563 (4)0.20481 (18)0.0486 (8)
H40.25930.2570.24060.058*
C50.21735 (11)0.1806 (4)0.13017 (17)0.0411 (8)
H50.24740.1330.11450.049*
C90.17024 (12)0.0388 (4)0.11707 (18)0.0460 (8)
H90.19510.08710.14350.055*
C20.12891 (11)0.3214 (3)0.17286 (16)0.0364 (7)
H20.09850.36920.18760.044*
C60.16529 (10)0.1756 (3)0.07862 (16)0.0309 (6)
C70.15100 (10)0.0987 (3)0.00320 (16)0.0292 (6)
C170.15539 (10)0.3535 (3)0.05616 (16)0.0318 (7)
C180.14057 (11)0.4355 (3)0.03006 (17)0.0337 (7)
C100.11473 (12)0.0332 (4)0.15452 (18)0.0416 (7)
H100.10150.07870.20610.05*
C160.11130 (10)0.2769 (3)0.08430 (15)0.0302 (6)
C80.18877 (11)0.0272 (4)0.04072 (17)0.0390 (7)
H80.22620.02380.01470.047*
C30.17999 (12)0.3311 (4)0.22641 (17)0.0430 (8)
H30.18430.38690.2760.052*
C150.05865 (10)0.2665 (3)0.03730 (15)0.0296 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.02128 (16)0.0516 (2)0.03440 (19)0.01046 (17)0.00610 (14)0.00087 (19)
Cl20.0357 (4)0.0540 (5)0.0399 (4)0.0033 (3)0.0008 (3)0.0046 (4)
Cl10.0517 (5)0.0584 (5)0.0374 (4)0.0070 (4)0.0183 (4)0.0028 (4)
O20.0229 (10)0.0592 (13)0.0368 (11)0.0125 (9)0.0061 (8)0.0099 (10)
O40.0215 (10)0.0682 (15)0.0592 (14)0.0086 (10)0.0058 (10)0.0048 (11)
O10.0203 (10)0.0626 (14)0.0356 (11)0.0096 (9)0.0030 (8)0.0060 (10)
O30.0313 (11)0.0638 (14)0.0655 (14)0.0152 (10)0.0230 (10)0.0007 (12)
N120.0231 (12)0.0357 (13)0.0303 (13)0.0058 (10)0.0084 (10)0.0050 (11)
C140.0255 (14)0.0323 (16)0.0325 (16)0.0050 (12)0.0095 (12)0.0080 (13)
N10.0241 (11)0.0380 (15)0.0282 (12)0.0055 (10)0.0077 (9)0.0032 (11)
C110.0264 (15)0.0382 (18)0.0389 (17)0.0063 (13)0.0080 (13)0.0047 (15)
C130.0294 (15)0.0337 (16)0.0284 (15)0.0052 (12)0.0129 (12)0.0028 (13)
C40.0275 (15)0.063 (2)0.0475 (19)0.0043 (15)0.0051 (14)0.0070 (18)
C50.0222 (15)0.052 (2)0.0482 (19)0.0055 (13)0.0073 (14)0.0095 (16)
C90.0410 (19)0.052 (2)0.053 (2)0.0091 (15)0.0264 (16)0.0021 (17)
C20.0346 (16)0.0415 (19)0.0356 (17)0.0043 (13)0.0137 (14)0.0061 (14)
C60.0229 (14)0.0348 (17)0.0352 (16)0.0045 (12)0.0078 (12)0.0097 (13)
C70.0243 (14)0.0279 (15)0.0372 (17)0.0058 (11)0.0112 (13)0.0078 (13)
C170.0217 (14)0.0324 (16)0.0419 (18)0.0035 (12)0.0091 (13)0.0114 (14)
C180.0271 (15)0.0308 (17)0.0465 (18)0.0069 (12)0.0154 (14)0.0128 (14)
C100.0434 (19)0.0447 (19)0.0399 (17)0.0024 (15)0.0165 (15)0.0027 (15)
C160.0253 (14)0.0306 (16)0.0334 (15)0.0035 (12)0.0050 (12)0.0022 (14)
C80.0246 (15)0.0438 (19)0.051 (2)0.0079 (13)0.0134 (14)0.0044 (16)
C30.0416 (18)0.052 (2)0.0314 (16)0.0069 (15)0.0022 (15)0.0048 (15)
C150.0223 (14)0.0329 (16)0.0351 (16)0.0047 (12)0.0098 (12)0.0042 (14)
Geometric parameters (Å, º) top
Cu1—O11.9128 (17)C4—C51.373 (4)
Cu1—O21.9176 (17)C4—C31.376 (4)
Cu1—N11.956 (2)C4—H40.93
Cu1—N121.947 (2)C5—C61.378 (3)
Cl2—C161.730 (3)C5—H50.93
Cl1—C131.728 (3)C9—C81.370 (4)
O2—C151.290 (3)C9—C101.375 (3)
O4—C171.220 (3)C9—H90.93
O1—C141.290 (3)C2—C31.376 (3)
O3—C181.223 (3)C2—H20.93
N12—C111.320 (3)C6—C71.478 (3)
N12—C71.350 (3)C7—C81.378 (3)
C14—C131.366 (3)C17—C161.429 (3)
C14—C151.504 (3)C17—C181.561 (4)
N1—C21.331 (3)C10—H100.93
N1—C61.355 (3)C16—C151.362 (3)
C11—C101.371 (3)C8—H80.93
C11—H110.93C3—H30.93
C13—C181.428 (3)
O1—Cu1—O285.14 (7)C10—C9—H9120.1
O1—Cu1—N12177.54 (8)N1—C2—C3122.5 (2)
O2—Cu1—N1296.23 (8)N1—C2—H2118.8
O1—Cu1—N196.00 (8)C3—C2—H2118.8
O2—Cu1—N1178.79 (8)N1—C6—C5120.5 (2)
N12—Cu1—N182.65 (9)N1—C6—C7113.5 (2)
C15—O2—Cu1112.13 (15)C5—C6—C7125.9 (2)
C14—O1—Cu1112.63 (15)N12—C7—C8121.1 (2)
C11—N12—C7119.4 (2)N12—C7—C6114.4 (2)
C11—N12—Cu1125.90 (17)C8—C7—C6124.5 (2)
C7—N12—Cu1114.74 (17)O4—C17—C16124.7 (3)
O1—C14—C13124.6 (2)O4—C17—C18117.9 (2)
O1—C14—C15114.7 (2)C16—C17—C18117.4 (2)
C13—C14—C15120.7 (2)O3—C18—C13124.1 (3)
C2—N1—C6119.4 (2)O3—C18—C17118.1 (2)
C2—N1—Cu1125.93 (17)C13—C18—C17117.8 (2)
C6—N1—Cu1114.66 (17)C11—C10—C9118.5 (3)
N12—C11—C10122.4 (3)C11—C10—H10120.8
N12—C11—H11118.8C9—C10—H10120.8
C10—C11—H11118.8C15—C16—C17122.2 (2)
C14—C13—C18121.5 (2)C15—C16—Cl2119.18 (19)
C14—C13—Cl1119.4 (2)C17—C16—Cl2118.59 (19)
C18—C13—Cl1118.73 (19)C9—C8—C7118.8 (3)
C5—C4—C3119.7 (3)C9—C8—H8120.6
C5—C4—H4120.2C7—C8—H8120.6
C3—C4—H4120.2C2—C3—C4118.3 (3)
C4—C5—C6119.5 (3)C2—C3—H3120.8
C4—C5—H5120.2C4—C3—H3120.8
C6—C5—H5120.2O2—C15—C16124.8 (2)
C8—C9—C10119.8 (3)O2—C15—C14115.1 (2)
C8—C9—H9120.1C16—C15—C14120.1 (2)
O1—Cu1—O2—C154.97 (17)N1—C6—C7—N122.5 (3)
N12—Cu1—O2—C15172.98 (17)C5—C6—C7—N12178.0 (2)
O2—Cu1—O1—C143.75 (17)N1—C6—C7—C8176.7 (2)
N1—Cu1—O1—C14176.66 (17)C5—C6—C7—C82.8 (4)
O2—Cu1—N12—C112.1 (2)C14—C13—C18—O3175.4 (3)
N1—Cu1—N12—C11178.4 (2)Cl1—C13—C18—O31.8 (4)
O2—Cu1—N12—C7179.08 (17)C14—C13—C18—C174.9 (4)
N1—Cu1—N12—C70.47 (17)Cl1—C13—C18—C17178.53 (18)
Cu1—O1—C14—C13178.7 (2)O4—C17—C18—O30.9 (4)
Cu1—O1—C14—C152.0 (3)C16—C17—C18—O3178.3 (2)
O1—Cu1—N1—C22.5 (2)O4—C17—C18—C13178.8 (2)
N12—Cu1—N1—C2179.6 (2)C16—C17—C18—C132.0 (3)
O1—Cu1—N1—C6179.83 (17)N12—C11—C10—C90.5 (4)
N12—Cu1—N1—C61.90 (17)C8—C9—C10—C110.7 (4)
C7—N12—C11—C100.2 (4)O4—C17—C16—C15176.0 (2)
Cu1—N12—C11—C10178.6 (2)C18—C17—C16—C153.1 (4)
O1—C14—C13—C18176.4 (2)O4—C17—C16—Cl22.3 (4)
C15—C14—C13—C182.9 (4)C18—C17—C16—Cl2178.59 (17)
O1—C14—C13—Cl12.8 (4)C10—C9—C8—C70.3 (4)
C15—C14—C13—Cl1176.45 (18)N12—C7—C8—C90.4 (4)
C3—C4—C5—C62.0 (4)C6—C7—C8—C9179.5 (3)
C6—N1—C2—C30.2 (4)N1—C2—C3—C41.5 (4)
Cu1—N1—C2—C3177.82 (19)C5—C4—C3—C22.4 (4)
C2—N1—C6—C50.2 (4)Cu1—O2—C15—C16175.3 (2)
Cu1—N1—C6—C5177.64 (19)Cu1—O2—C15—C145.1 (3)
C2—N1—C6—C7179.3 (2)C17—C16—C15—O2174.1 (2)
Cu1—N1—C6—C72.8 (3)Cl2—C16—C15—O24.1 (4)
C4—C5—C6—N10.7 (4)C17—C16—C15—C145.4 (4)
C4—C5—C6—C7179.9 (3)Cl2—C16—C15—C14176.36 (18)
C11—N12—C7—C80.7 (4)O1—C14—C15—O22.2 (3)
Cu1—N12—C7—C8178.3 (2)C13—C14—C15—O2177.2 (2)
C11—N12—C7—C6179.8 (2)O1—C14—C15—C16178.2 (2)
Cu1—N12—C7—C60.9 (3)C13—C14—C15—C162.4 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···O3i0.932.543.465 (3)173
C8—H8···O3i0.932.403.330 (3)177
C9—H9···O4i0.932.493.171 (4)130
Symmetry code: (i) x+1/2, y1/2, z.

Experimental details

Crystal data
Chemical formula[Cu(C6Cl2O4)(C10H8N2)]
Mr426.68
Crystal system, space groupMonoclinic, C2/c
Temperature (K)295
a, b, c (Å)24.987 (3), 7.438 (1), 17.215 (2)
β (°) 104.57 (1)
V3)3096.6 (7)
Z8
Radiation typeMo Kα
µ (mm1)1.78
Crystal size (mm)0.14 × 0.11 × 0.06
Data collection
DiffractometerOxford Diffraction Xcalibur
diffractometer
Absorption correctionAnalytical
(CrysAlis RED; Oxford Diffraction, 2003)
Tmin, Tmax0.802, 0.903
No. of measured, independent and
observed [I > 2σ(I)] reflections
14006, 4506, 2120
Rint0.045
(sin θ/λ)max1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.065, 0.74
No. of reflections4506
No. of parameters226
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.57, 0.31

Computer programs: CrysAlis CCD (Oxford Diffraction, 2003), CrysAlis RED (Oxford Diffraction, 2003), CrysAlis RED, DIRDIF99.2 (Beurskens et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX publication routines (Farrugia, 1999).

Selected geometric parameters (Å, º) top
Cu1—O11.9128 (17)Cu1—N11.956 (2)
Cu1—O21.9176 (17)Cu1—N121.947 (2)
O1—Cu1—O285.14 (7)O1—Cu1—N196.00 (8)
O1—Cu1—N12177.54 (8)O2—Cu1—N1178.79 (8)
O2—Cu1—N1296.23 (8)N12—Cu1—N182.65 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C5—H5···O3i0.932.543.465 (3)173
C8—H8···O3i0.932.403.330 (3)177
C9—H9···O4i0.932.493.171 (4)130
Symmetry code: (i) x+1/2, y1/2, z.
 

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