The title compound, [Cu
2Cl
4(C
10H
8N
2)
2], represents the first example of a simple dimeric coordination complex of Cu
II 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
CCDC reference: 296573
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (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
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%).
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).
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.
Di-µ-chloro-bis[(2,2-bipyridine)chlorocopper(II)]
top
Crystal data top
[Cu2Cl4(C10H8Cl2N2)2] | Z = 1 |
Mr = 581.24 | F(000) = 290 |
Triclinic, P1 | Dx = 1.897 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.1923 (7) Å | Cell parameters from 6682 reflections |
b = 8.9872 (8) Å | θ = 2.6–24.7° |
c = 9.4241 (9) Å | µ = 2.63 mm−1 |
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 tube | 1142 reflections with I > 2σ(I) |
Horizontally mounted graphite crystal monochromator | Rint = 0.103 |
Detector resolution: 9 pixels mm-1 | θmax = 24.7°, θmin = 2.6° |
ϕ scans and ω scans with κ offsets | h = −8→8 |
Absorption correction: multi-scan (XPREP in SHELXTL; Sheldrick, 2005) | k = −10→10 |
Tmin = 0.600, Tmax = 0.944 | l = −10→11 |
6682 measured reflections | |
Refinement top
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)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.180 | H-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 parameters | Δρmax = 1.09 e Å−3 |
0 restraints | Δρmin = −0.84 e Å−3 |
Crystal data top
[Cu2Cl4(C10H8Cl2N2)2] | γ = 95.617 (4)° |
Mr = 581.24 | V = 508.91 (8) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.1923 (7) Å | Mo Kα radiation |
b = 8.9872 (8) Å | µ = 2.63 mm−1 |
c = 9.4241 (9) Å | T = 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 = 0.944 | Rint = 0.103 |
6682 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
wR(F2) = 0.180 | H-atom parameters constrained |
S = 1.17 | Δρmax = 1.09 e Å−3 |
1701 reflections | Δρmin = −0.84 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
Cu1 | 0.76745 (18) | 0.07115 (14) | 0.50096 (14) | 0.0254 (4) | |
Cl1 | 0.5435 (4) | −0.1882 (3) | 0.3299 (3) | 0.0289 (6) | |
Cl2 | 0.9535 (4) | −0.0203 (3) | 0.6743 (3) | 0.0285 (6) | |
N1 | 0.9259 (11) | 0.3189 (9) | 0.6568 (9) | 0.0206 (18) | |
N2 | 0.6256 (11) | 0.1749 (9) | 0.3606 (9) | 0.0191 (17) | |
C1 | 1.0731 (14) | 0.3821 (13) | 0.8066 (12) | 0.029 (2) | |
H1 | 1.1265 | 0.3056 | 0.8420 | 0.035* | |
C2 | 1.1529 (15) | 0.5565 (12) | 0.9147 (12) | 0.031 (3) | |
H2 | 1.2581 | 0.5984 | 1.0218 | 0.037* | |
C3 | 1.0750 (15) | 0.6662 (12) | 0.8617 (12) | 0.030 (2) | |
H3 | 1.1240 | 0.7857 | 0.9334 | 0.036* | |
C4 | 0.9258 (14) | 0.6019 (12) | 0.7044 (12) | 0.026 (2) | |
H4 | 0.8741 | 0.6761 | 0.6646 | 0.031* | |
C5 | 0.8532 (14) | 0.4290 (11) | 0.6061 (11) | 0.021 (2) | |
C6 | 0.6930 (14) | 0.3470 (12) | 0.4354 (12) | 0.023 (2) | |
C7 | 0.6122 (15) | 0.4373 (13) | 0.3544 (12) | 0.027 (2) | |
H7 | 0.6584 | 0.5578 | 0.4084 | 0.033* | |
C8 | 0.4652 (15) | 0.3501 (13) | 0.1956 (13) | 0.029 (2) | |
H8 | 0.4112 | 0.4101 | 0.1378 | 0.035* | |
C9 | 0.3944 (16) | 0.1735 (14) | 0.1184 (13) | 0.034 (3) | |
H9 | 0.2904 | 0.1115 | 0.0094 | 0.041* | |
C10 | 0.4813 (14) | 0.0922 (12) | 0.2067 (11) | 0.025 (2) | |
H10 | 0.4360 | −0.0281 | 0.1552 | 0.030* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cu1 | 0.0292 (8) | 0.0161 (7) | 0.0182 (7) | −0.0002 (5) | −0.0038 (5) | 0.0069 (5) |
Cl1 | 0.0297 (15) | 0.0199 (13) | 0.0253 (14) | −0.0003 (11) | 0.0004 (11) | 0.0086 (11) |
Cl2 | 0.0314 (15) | 0.0216 (13) | 0.0248 (14) | 0.0022 (11) | 0.0005 (11) | 0.0118 (11) |
N1 | 0.025 (5) | 0.015 (4) | 0.014 (4) | 0.001 (3) | 0.003 (4) | 0.003 (3) |
N2 | 0.022 (4) | 0.016 (4) | 0.018 (4) | 0.006 (3) | 0.006 (4) | 0.009 (3) |
C1 | 0.025 (6) | 0.035 (6) | 0.023 (6) | 0.002 (5) | 0.004 (5) | 0.014 (5) |
C2 | 0.030 (6) | 0.023 (5) | 0.016 (5) | −0.007 (5) | −0.006 (5) | 0.000 (4) |
C3 | 0.033 (6) | 0.018 (5) | 0.028 (6) | −0.005 (5) | 0.006 (5) | 0.007 (5) |
C4 | 0.027 (6) | 0.016 (5) | 0.028 (6) | 0.005 (4) | 0.003 (5) | 0.011 (4) |
C5 | 0.024 (5) | 0.020 (5) | 0.022 (5) | 0.007 (4) | 0.012 (4) | 0.010 (4) |
C6 | 0.020 (5) | 0.018 (5) | 0.030 (6) | 0.002 (4) | 0.012 (5) | 0.011 (4) |
C7 | 0.033 (6) | 0.029 (6) | 0.029 (6) | 0.014 (5) | 0.009 (5) | 0.021 (5) |
C8 | 0.031 (6) | 0.038 (6) | 0.035 (6) | 0.018 (5) | 0.011 (5) | 0.030 (5) |
C9 | 0.042 (7) | 0.041 (7) | 0.024 (6) | 0.017 (5) | 0.008 (5) | 0.021 (5) |
C10 | 0.032 (6) | 0.019 (5) | 0.014 (5) | 0.003 (4) | −0.001 (4) | 0.005 (4) |
Geometric parameters (Å, º) top
Cu1—N2 | 2.024 (7) | C3—C4 | 1.376 (13) |
Cu1—N1 | 2.037 (7) | C3—H3 | 0.9500 |
Cu1—Cl1 | 2.272 (3) | C4—C5 | 1.370 (12) |
Cu1—Cl2 | 2.280 (3) | C4—H4 | 0.9500 |
Cu1—Cl2i | 2.909 (3) | C5—C6 | 1.479 (13) |
Cl1—Cu1ii | 3.130 (3) | C6—C7 | 1.392 (13) |
N1—C1 | 1.324 (12) | C7—C8 | 1.370 (14) |
N1—C5 | 1.355 (11) | C7—H7 | 0.9500 |
N2—C10 | 1.333 (11) | C8—C9 | 1.397 (14) |
N2—C6 | 1.359 (11) | C8—H8 | 0.9500 |
C1—C2 | 1.394 (13) | C9—C10 | 1.383 (13) |
C1—H1 | 0.9500 | C9—H9 | 0.9500 |
C2—C3 | 1.377 (14) | C10—H10 | 0.9500 |
C2—H2 | 0.9500 | | |
| | | |
N2—Cu1—N1 | 81.0 (3) | C4—C3—H3 | 120.2 |
N2—Cu1—Cl1 | 93.4 (2) | C2—C3—H3 | 120.2 |
N1—Cu1—Cl1 | 170.2 (2) | C5—C4—C3 | 118.9 (9) |
N2—Cu1—Cl2 | 174.0 (2) | C5—C4—H4 | 120.6 |
N1—Cu1—Cl2 | 93.3 (2) | C3—C4—H4 | 120.6 |
Cl1—Cu1—Cl2 | 92.52 (9) | N1—C5—C4 | 122.3 (9) |
N2—Cu1—Cl2i | 88.4 (2) | N1—C5—C6 | 114.5 (8) |
N1—Cu1—Cl2i | 90.1 (2) | C4—C5—C6 | 123.2 (8) |
Cl1—Cu1—Cl2i | 97.79 (9) | N2—C6—C7 | 121.0 (9) |
Cl2—Cu1—Cl2i | 89.91 (8) | N2—C6—C5 | 115.8 (8) |
C1—N1—C5 | 118.2 (8) | C7—C6—C5 | 123.2 (8) |
C1—N1—Cu1 | 127.1 (7) | C8—C7—C6 | 119.1 (9) |
C5—N1—Cu1 | 114.2 (6) | C8—C7—H7 | 120.5 |
C10—N2—C6 | 119.2 (8) | C6—C7—H7 | 120.5 |
C10—N2—Cu1 | 126.9 (6) | C7—C8—C9 | 120.2 (9) |
C6—N2—Cu1 | 114.0 (6) | C7—C8—H8 | 119.9 |
N1—C1—C2 | 122.7 (9) | C9—C8—H8 | 119.9 |
N1—C1—H1 | 118.6 | C10—C9—C8 | 117.5 (9) |
C2—C1—H1 | 118.6 | C10—C9—H9 | 121.3 |
C3—C2—C1 | 118.1 (9) | C8—C9—H9 | 121.3 |
C3—C2—H2 | 120.9 | N2—C10—C9 | 123.0 (9) |
C1—C2—H2 | 120.9 | N2—C10—H10 | 118.5 |
C4—C3—C2 | 119.6 (9) | C9—C10—H10 | 118.5 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···Cl2 | 0.95 | 2.61 | 3.209 (11) | 121 |
C10—H10···Cl1 | 0.95 | 2.62 | 3.209 (9) | 121 |
C7—H7···Cl1iii | 0.95 | 2.81 | 3.542 (10) | 135 |
C4—H4···Cl2iii | 0.95 | 2.69 | 3.517 (10) | 146 |
Symmetry code: (iii) x, y+1, z. |
Experimental details
Crystal data |
Chemical formula | [Cu2Cl4(C10H8Cl2N2)2] |
Mr | 581.24 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 508.91 (8) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 2.63 |
Crystal size (mm) | 0.22 × 0.06 × 0.02 |
|
Data collection |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (XPREP in SHELXTL; Sheldrick, 2005) |
Tmin, Tmax | 0.600, 0.944 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6682, 1701, 1142 |
Rint | 0.103 |
(sin θ/λ)max (Å−1) | 0.587 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.180, 1.17 |
No. of reflections | 1701 |
No. of parameters | 136 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.09, −0.84 |
Selected geometric parameters (Å, º) topCu1—N2 | 2.024 (7) | Cu1—Cl2 | 2.280 (3) |
Cu1—N1 | 2.037 (7) | Cu1—Cl2i | 2.909 (3) |
Cu1—Cl1 | 2.272 (3) | Cl1—Cu1ii | 3.130 (3) |
| | | |
N2—Cu1—N1 | 81.0 (3) | Cl1—Cu1—Cl2 | 92.52 (9) |
N2—Cu1—Cl1 | 93.4 (2) | N2—Cu1—Cl2i | 88.4 (2) |
N1—Cu1—Cl1 | 170.2 (2) | N1—Cu1—Cl2i | 90.1 (2) |
N2—Cu1—Cl2 | 174.0 (2) | Cl1—Cu1—Cl2i | 97.79 (9) |
N1—Cu1—Cl2 | 93.3 (2) | Cl2—Cu1—Cl2i | 89.91 (8) |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) −x+1, −y, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···Cl2 | 0.95 | 2.61 | 3.209 (11) | 121 |
C10—H10···Cl1 | 0.95 | 2.62 | 3.209 (9) | 121 |
C7—H7···Cl1iii | 0.95 | 2.81 | 3.542 (10) | 135 |
C4—H4···Cl2iii | 0.95 | 2.69 | 3.517 (10) | 146 |
Symmetry code: (iii) x, y+1, z. |
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].