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The title compound, [Cu2Cl4(C10H8N2)2], represents the first example of a simple dimeric coordination complex of CuII and 2,2′-bipyridine (bpy). The metal is in a five-coordinate distorted square-pyramidal environment, bonded to a 2,2′- bipyridine mol­ecule, two bridging chlorides and one terminal chloride. There is a centre of symmetry at the mid-point of the Cu...Cu vector.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805040754/hg6279sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805040754/hg6279Isup2.hkl
Contains datablock I

CCDC reference: 296573

Key indicators

  • Single-crystal X-ray study
  • T = 120 K
  • Mean [sigma](C-C) = 0.015 Å
  • R factor = 0.063
  • wR factor = 0.180
  • Data-to-parameter ratio = 12.5

checkCIF/PLATON results

No syntax errors found



Alert level A PLAT027_ALERT_3_A _diffrn_reflns_theta_full (too) Low ............ 24.68 Deg.
Author Response: The measured crystal was small and therefore diffracted rather weakly. This reduced the upper diffraction limit. \Q range for unit cell determination was 1.00-25.03 \%. For the data collection the final range was 2.5-24.68 deg. The data collection was repeated by using larger crystal, which met the criteria of \Q=25\% (upper \Q limit was 26.50 \%). However, larger crystals were twinned. With the best twinned crystal use of twin model (twin law -1.000 0.000 0.000 0.197 0.982 -0.035 -0.098 -0.991 -0.982, BASF=0.45), led to the same solution than the weak unique data but with poorer R-values and poorer esd's for bond lengths and angles. Therefore, the unique data set was chosen as the final data set.

Alert level C RINTA01_ALERT_3_C The value of Rint is greater than 0.10 Rint given 0.103 THETM01_ALERT_3_C The value of sine(theta_max)/wavelength is less than 0.590 Calculated sin(theta_max)/wavelength = 0.5875 PLAT020_ALERT_3_C The value of Rint is greater than 0.10 ......... 0.10 PLAT023_ALERT_3_C Resolution (too) Low [sin(th)/Lambda < 0.6]..... 24.68 Deg. PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 2.00 Ratio PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ? PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ... 15
1 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 9 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 6 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

Copper compounds display a variety of coordination geometries and coordination numbers that vary from three to six. Jahn–Teller distortion leads to the absence of regular octahedral structures in CuII chemistry. Complexes of the general formula Cu(NN)X2 (X = CI and Br, and NN = a dinitrogen chelate) are known to have different geometries with the coordination number of the copper atom varying from four to six. Particular attention has been devoted to polymeric CuII complexes with chlorides and substituted bipyridines as ligands (Garland et al., 1988; Hernandez-Molina et al., 1999; Wang et al., 2004).

The title compound, (I), represents the first example of a binuclear complex of CuII chloride and 2,2'-bipyridine and is the most distorted when compared with the other two dimeric complexes containing copper and (a substituted) bipyridine (Gonzalez et al., 1993; Tynan et al., 2005), since the distance of the bridging chloride to a vicinal Cu atom is 2.909?(3) Å. The CuII atom is five-coordinate and the geometry about the Cu atom is square pyramidal. The coordination sphere is occupied by two N atoms provided by the chelate 2,2'-bipyridine, as well as two asymmetrically bridging and one terminal chlorides.

Interaction of Cu1—Cl1ii, in order to form a chain structure, is very weak since the distance is 3.130 (3) Å (Wang et al., 2004) [symmetry code: (ii) 1 − x, −y, 1 − z]. Although there are no stacking interactions in the crystal, the structure is stabilized by a series of intra- and inter-chain C—H···Cl contacts (Table 2 and Fig. 2). The H1—Cl2 and H10—Cl1 interactions constitute the intrachain contacts, and the H4—Cl2iii and H7—Cl1iii interactions are very weak inter-chain contacts [symmetry code: (iii) x, 1 + y, z].

Experimental top

Compound (I) was produced unexpectedly. A solution of of 2,2'-bipyridine (15.6 mg, 0.1 mmol) in methanol (1 ml) was added to an aqueous solution (9 ml) of CuCl2 (13.3 mg, 0.1 mmol) containing an equivalent amount of trans-aconitic acid (11.6 mg, 0.066 mmol). A clear green solution was obtained. Green needles of (I) precipitated after slow evaporation of the solution (yield 10 mg, 35%).

Refinement top

The H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(parent atom).

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Crystal Impact, 2005); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 40% probability displacement ellipsoids.
[Figure 2] Fig. 2. A representation of intra- and inter-chain C—H···Cl contacts (dashed lines), resulting in the formation of a one-dimensional chain.
Di-µ-chloro-bis[(2,2-bipyridine)chlorocopper(II)] top
Crystal data top
[Cu2Cl4(C10H8Cl2N2)2]Z = 1
Mr = 581.24F(000) = 290
Triclinic, P1Dx = 1.897 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.1923 (7) ÅCell parameters from 6682 reflections
b = 8.9872 (8) Åθ = 2.6–24.7°
c = 9.4241 (9) ŵ = 2.63 mm1
α = 115.136 (6)°T = 120 K
β = 107.201 (5)°Needle, green
γ = 95.617 (4)°0.22 × 0.06 × 0.02 mm
V = 508.91 (8) Å3
Data collection top
Nonius KappaCCD
diffractometer
1701 independent reflections
Radiation source: fine-focus sealed tube1142 reflections with I > 2σ(I)
Horizontally mounted graphite crystal monochromatorRint = 0.103
Detector resolution: 9 pixels mm-1θmax = 24.7°, θmin = 2.6°
ϕ scans and ω scans with κ offsetsh = 88
Absorption correction: multi-scan
(XPREP in SHELXTL; Sheldrick, 2005)
k = 1010
Tmin = 0.600, Tmax = 0.944l = 1011
6682 measured reflections
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)] = 0.063Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.180H-atom parameters constrained
S = 1.17 w = 1/[σ2(Fo2) + (0.066P)2 + 2.6959P]
where P = (Fo2 + 2Fc2)/3
1701 reflections(Δ/σ)max < 0.001
136 parametersΔρmax = 1.09 e Å3
0 restraintsΔρmin = 0.84 e Å3
Crystal data top
[Cu2Cl4(C10H8Cl2N2)2]γ = 95.617 (4)°
Mr = 581.24V = 508.91 (8) Å3
Triclinic, P1Z = 1
a = 7.1923 (7) ÅMo Kα radiation
b = 8.9872 (8) ŵ = 2.63 mm1
c = 9.4241 (9) ÅT = 120 K
α = 115.136 (6)°0.22 × 0.06 × 0.02 mm
β = 107.201 (5)°
Data collection top
Nonius KappaCCD
diffractometer
1701 independent reflections
Absorption correction: multi-scan
(XPREP in SHELXTL; Sheldrick, 2005)
1142 reflections with I > 2σ(I)
Tmin = 0.600, Tmax = 0.944Rint = 0.103
6682 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0630 restraints
wR(F2) = 0.180H-atom parameters constrained
S = 1.17Δρmax = 1.09 e Å3
1701 reflectionsΔρmin = 0.84 e Å3
136 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
Cu10.76745 (18)0.07115 (14)0.50096 (14)0.0254 (4)
Cl10.5435 (4)0.1882 (3)0.3299 (3)0.0289 (6)
Cl20.9535 (4)0.0203 (3)0.6743 (3)0.0285 (6)
N10.9259 (11)0.3189 (9)0.6568 (9)0.0206 (18)
N20.6256 (11)0.1749 (9)0.3606 (9)0.0191 (17)
C11.0731 (14)0.3821 (13)0.8066 (12)0.029 (2)
H11.12650.30560.84200.035*
C21.1529 (15)0.5565 (12)0.9147 (12)0.031 (3)
H21.25810.59841.02180.037*
C31.0750 (15)0.6662 (12)0.8617 (12)0.030 (2)
H31.12400.78570.93340.036*
C40.9258 (14)0.6019 (12)0.7044 (12)0.026 (2)
H40.87410.67610.66460.031*
C50.8532 (14)0.4290 (11)0.6061 (11)0.021 (2)
C60.6930 (14)0.3470 (12)0.4354 (12)0.023 (2)
C70.6122 (15)0.4373 (13)0.3544 (12)0.027 (2)
H70.65840.55780.40840.033*
C80.4652 (15)0.3501 (13)0.1956 (13)0.029 (2)
H80.41120.41010.13780.035*
C90.3944 (16)0.1735 (14)0.1184 (13)0.034 (3)
H90.29040.11150.00940.041*
C100.4813 (14)0.0922 (12)0.2067 (11)0.025 (2)
H100.43600.02810.15520.030*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0292 (8)0.0161 (7)0.0182 (7)0.0002 (5)0.0038 (5)0.0069 (5)
Cl10.0297 (15)0.0199 (13)0.0253 (14)0.0003 (11)0.0004 (11)0.0086 (11)
Cl20.0314 (15)0.0216 (13)0.0248 (14)0.0022 (11)0.0005 (11)0.0118 (11)
N10.025 (5)0.015 (4)0.014 (4)0.001 (3)0.003 (4)0.003 (3)
N20.022 (4)0.016 (4)0.018 (4)0.006 (3)0.006 (4)0.009 (3)
C10.025 (6)0.035 (6)0.023 (6)0.002 (5)0.004 (5)0.014 (5)
C20.030 (6)0.023 (5)0.016 (5)0.007 (5)0.006 (5)0.000 (4)
C30.033 (6)0.018 (5)0.028 (6)0.005 (5)0.006 (5)0.007 (5)
C40.027 (6)0.016 (5)0.028 (6)0.005 (4)0.003 (5)0.011 (4)
C50.024 (5)0.020 (5)0.022 (5)0.007 (4)0.012 (4)0.010 (4)
C60.020 (5)0.018 (5)0.030 (6)0.002 (4)0.012 (5)0.011 (4)
C70.033 (6)0.029 (6)0.029 (6)0.014 (5)0.009 (5)0.021 (5)
C80.031 (6)0.038 (6)0.035 (6)0.018 (5)0.011 (5)0.030 (5)
C90.042 (7)0.041 (7)0.024 (6)0.017 (5)0.008 (5)0.021 (5)
C100.032 (6)0.019 (5)0.014 (5)0.003 (4)0.001 (4)0.005 (4)
Geometric parameters (Å, º) top
Cu1—N22.024 (7)C3—C41.376 (13)
Cu1—N12.037 (7)C3—H30.9500
Cu1—Cl12.272 (3)C4—C51.370 (12)
Cu1—Cl22.280 (3)C4—H40.9500
Cu1—Cl2i2.909 (3)C5—C61.479 (13)
Cl1—Cu1ii3.130 (3)C6—C71.392 (13)
N1—C11.324 (12)C7—C81.370 (14)
N1—C51.355 (11)C7—H70.9500
N2—C101.333 (11)C8—C91.397 (14)
N2—C61.359 (11)C8—H80.9500
C1—C21.394 (13)C9—C101.383 (13)
C1—H10.9500C9—H90.9500
C2—C31.377 (14)C10—H100.9500
C2—H20.9500
N2—Cu1—N181.0 (3)C4—C3—H3120.2
N2—Cu1—Cl193.4 (2)C2—C3—H3120.2
N1—Cu1—Cl1170.2 (2)C5—C4—C3118.9 (9)
N2—Cu1—Cl2174.0 (2)C5—C4—H4120.6
N1—Cu1—Cl293.3 (2)C3—C4—H4120.6
Cl1—Cu1—Cl292.52 (9)N1—C5—C4122.3 (9)
N2—Cu1—Cl2i88.4 (2)N1—C5—C6114.5 (8)
N1—Cu1—Cl2i90.1 (2)C4—C5—C6123.2 (8)
Cl1—Cu1—Cl2i97.79 (9)N2—C6—C7121.0 (9)
Cl2—Cu1—Cl2i89.91 (8)N2—C6—C5115.8 (8)
C1—N1—C5118.2 (8)C7—C6—C5123.2 (8)
C1—N1—Cu1127.1 (7)C8—C7—C6119.1 (9)
C5—N1—Cu1114.2 (6)C8—C7—H7120.5
C10—N2—C6119.2 (8)C6—C7—H7120.5
C10—N2—Cu1126.9 (6)C7—C8—C9120.2 (9)
C6—N2—Cu1114.0 (6)C7—C8—H8119.9
N1—C1—C2122.7 (9)C9—C8—H8119.9
N1—C1—H1118.6C10—C9—C8117.5 (9)
C2—C1—H1118.6C10—C9—H9121.3
C3—C2—C1118.1 (9)C8—C9—H9121.3
C3—C2—H2120.9N2—C10—C9123.0 (9)
C1—C2—H2120.9N2—C10—H10118.5
C4—C3—C2119.6 (9)C9—C10—H10118.5
Symmetry codes: (i) x+2, y, z+1; (ii) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···Cl20.952.613.209 (11)121
C10—H10···Cl10.952.623.209 (9)121
C7—H7···Cl1iii0.952.813.542 (10)135
C4—H4···Cl2iii0.952.693.517 (10)146
Symmetry code: (iii) x, y+1, z.

Experimental details

Crystal data
Chemical formula[Cu2Cl4(C10H8Cl2N2)2]
Mr581.24
Crystal system, space groupTriclinic, P1
Temperature (K)120
a, b, c (Å)7.1923 (7), 8.9872 (8), 9.4241 (9)
α, β, γ (°)115.136 (6), 107.201 (5), 95.617 (4)
V3)508.91 (8)
Z1
Radiation typeMo Kα
µ (mm1)2.63
Crystal size (mm)0.22 × 0.06 × 0.02
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(XPREP in SHELXTL; Sheldrick, 2005)
Tmin, Tmax0.600, 0.944
No. of measured, independent and
observed [I > 2σ(I)] reflections
6682, 1701, 1142
Rint0.103
(sin θ/λ)max1)0.587
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.063, 0.180, 1.17
No. of reflections1701
No. of parameters136
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.09, 0.84

Computer programs: COLLECT (Nonius, 2000), DENZO/SCALEPACK (Otwinowski & Minor, 1997), DENZO/SCALEPACK, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Crystal Impact, 2005), SHELXL97.

Selected geometric parameters (Å, º) top
Cu1—N22.024 (7)Cu1—Cl22.280 (3)
Cu1—N12.037 (7)Cu1—Cl2i2.909 (3)
Cu1—Cl12.272 (3)Cl1—Cu1ii3.130 (3)
N2—Cu1—N181.0 (3)Cl1—Cu1—Cl292.52 (9)
N2—Cu1—Cl193.4 (2)N2—Cu1—Cl2i88.4 (2)
N1—Cu1—Cl1170.2 (2)N1—Cu1—Cl2i90.1 (2)
N2—Cu1—Cl2174.0 (2)Cl1—Cu1—Cl2i97.79 (9)
N1—Cu1—Cl293.3 (2)Cl2—Cu1—Cl2i89.91 (8)
Symmetry codes: (i) x+2, y, z+1; (ii) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···Cl20.952.613.209 (11)121
C10—H10···Cl10.952.623.209 (9)121
C7—H7···Cl1iii0.952.813.542 (10)135
C4—H4···Cl2iii0.952.693.517 (10)146
Symmetry code: (iii) x, y+1, z.
 

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