Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807029674/zl2041sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807029674/zl2041Isup2.hkl |
CCDC reference: 654801
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.003 Å
- R factor = 0.023
- wR factor = 0.067
- Data-to-parameter ratio = 17.7
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.65 Ratio PLAT230_ALERT_2_C Hirshfeld Test Diff for O5 - C5 .. 5.91 su PLAT230_ALERT_2_C Hirshfeld Test Diff for N1 - C6 .. 5.03 su PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for N1
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.06
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 1 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 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
A mixture of chloroacetic acid (1 mmol) and CuCO3.Cu(OH)2.H2O (0.5 mmol) in a mixture of water (50 ml) and DMF (25 ml) was heated to boiling. The solution was filtered and allowed to cool to room temperature. Turquoise prismatic crystals of (I) were obtained after a few days.
All H atoms were initially located in a difference Fourier synthesis, but were positioned with idealized geometry, with C–H = 0.93, 0.96 and 0.97 Å, and refined using a riding model. The methyl H atoms were allowed to rotate to best fit the experimental electron density (AFIX 137). The isotropic displacement parameters of all H atoms were refined freely.
The structure determination of the title compound, (I), was undertaken as a continuation of earlier studies of copper(II) complexes with monochloroacetic acid (Sieroń, 2007).
The title compound (I) contains a dimeric copper(II) complex, [Cu2(CH2ClCOO)4(DMF)2], composed of two CuII centres, four chloroacetate and two DMF ligands (Fig. 1).
The CuII atom has a regular five-coordinate square-pyramidal environment, with the basal plane defined by the O atoms of four bridging bidentate carboxylate groups of monochloroacetate ligands. The CuII atom deviates out of the mean plane formed by the four basal O atoms towards the apical O5 atom of the DMF ligand by 0.2104 (7) Å. The O–C distances in the chloroacetate groups are approximately equal and range from 1.247 (2) to 1.262 (2) Å, indicating the distinct delocalization of their π electrons (Borthwick, 1980). The planes of the two independent bridging chloroacetate groups are perpendicular within experimental error. The apical DMF ligand is twisted by a dihedral angle of 33.8 (1)° with respect to the C1/O1/O3i mean plane. Selected bond distances and bond angles are listed in Table 1. Complex molecules are linked by two Csp3–H···O hydrogen bonds (Table 2), forming eight-membered rings described by the R22(8) graph-set motif (Etter et al., 1990) as shown in Fig. 2. The Cu···Cu distance of 2.6614 (4) Å is comparable to those found in other dimeric copper(II) monochloroacetates (Shi et al., 1999, 2001; Calderazzo et al., 2003).
For related literature, see: Borthwick (1980); Calderazzo et al. (2003); Etter et al. (1990); Shi et al. (1999, 2001), Sieroń (2007).
Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2003).
[Cu2(C2H2ClO2)4(C3H7NO)2] | Z = 1 |
Mr = 647.24 | F(000) = 326 |
Triclinic, P1 | Dx = 1.745 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.9969 (6) Å | Cell parameters from 3751 reflections |
b = 8.0326 (5) Å | θ = 2.6–31.2° |
c = 10.2420 (7) Å | µ = 2.21 mm−1 |
α = 87.824 (5)° | T = 294 K |
β = 71.974 (6)° | Prism, blue-green |
γ = 80.015 (6)° | 0.45 × 0.25 × 0.20 mm |
V = 616.05 (8) Å3 |
Kuma KM-4 CCD diffractometer | 2814 independent reflections |
Radiation source: CX-Mo12x0.4-S Seifert Mo tube | 2660 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.009 |
Detector resolution: 8.2356 pixels mm-1 | θmax = 27.5°, θmin = 2.6° |
ω scans | h = −10→10 |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | k = −10→8 |
Tmin = 0.511, Tmax = 0.639 | l = −11→13 |
6079 measured reflections |
Refinement on F2 | Hydrogen site location: difference Fourier map |
Least-squares matrix: full | Only H-atom displacement parameters refined |
R[F2 > 2σ(F2)] = 0.023 | w = 1/[σ2(Fo2) + (0.0379P)2 + 0.2335P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.067 | (Δ/σ)max = 0.001 |
S = 1.07 | Δρmax = 0.60 e Å−3 |
2814 reflections | Δρmin = −0.35 e Å−3 |
159 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0116 (18) |
Primary atom site location: structure-invariant direct methods |
[Cu2(C2H2ClO2)4(C3H7NO)2] | γ = 80.015 (6)° |
Mr = 647.24 | V = 616.05 (8) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.9969 (6) Å | Mo Kα radiation |
b = 8.0326 (5) Å | µ = 2.21 mm−1 |
c = 10.2420 (7) Å | T = 294 K |
α = 87.824 (5)° | 0.45 × 0.25 × 0.20 mm |
β = 71.974 (6)° |
Kuma KM-4 CCD diffractometer | 2814 independent reflections |
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006) | 2660 reflections with I > 2σ(I) |
Tmin = 0.511, Tmax = 0.639 | Rint = 0.009 |
6079 measured reflections |
R[F2 > 2σ(F2)] = 0.023 | 0 restraints |
wR(F2) = 0.067 | Only H-atom displacement parameters refined |
S = 1.07 | Δρmax = 0.60 e Å−3 |
2814 reflections | Δρmin = −0.35 e Å−3 |
159 parameters |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.10233 (3) | 0.56685 (2) | −0.11043 (2) | 0.0311 (1) | |
Cl1 | 0.09850 (10) | 0.09076 (8) | −0.39180 (6) | 0.0685 (2) | |
Cl2 | 0.41733 (10) | 0.10139 (9) | 0.20517 (8) | 0.0734 (3) | |
O1 | 0.0899 (2) | 0.35412 (17) | −0.19692 (14) | 0.0464 (4) | |
O2 | 0.30126 (17) | 0.44111 (18) | −0.05042 (14) | 0.0444 (4) | |
O3 | −0.08262 (19) | 0.24157 (16) | −0.01133 (13) | 0.0440 (4) | |
O4 | 0.12946 (18) | 0.32648 (19) | 0.13481 (15) | 0.0469 (4) | |
O5 | 0.26071 (19) | 0.66002 (18) | −0.29703 (13) | 0.0454 (4) | |
N1 | 0.3366 (2) | 0.6631 (2) | −0.52957 (16) | 0.0482 (5) | |
C1 | 0.0121 (2) | 0.2386 (2) | −0.13520 (17) | 0.0348 (5) | |
C2 | 0.0355 (3) | 0.0721 (3) | −0.2111 (2) | 0.0499 (6) | |
C3 | 0.2762 (2) | 0.3470 (2) | 0.05293 (18) | 0.0348 (5) | |
C4 | 0.4480 (3) | 0.2523 (3) | 0.0732 (2) | 0.0496 (6) | |
C5 | 0.2393 (3) | 0.6247 (3) | −0.4080 (2) | 0.0485 (6) | |
C6 | 0.3121 (5) | 0.6134 (6) | −0.6568 (3) | 0.0921 (13) | |
C7 | 0.4803 (4) | 0.7616 (3) | −0.5441 (3) | 0.0669 (8) | |
H1 | 0.12560 | −0.00930 | −0.18720 | 0.100 (11)* | |
H2 | −0.07580 | 0.02850 | −0.18020 | 0.080 (9)* | |
H3 | 0.52120 | 0.19530 | −0.01230 | 0.068 (8)* | |
H4 | 0.51300 | 0.33380 | 0.09390 | 0.084 (9)* | |
H5 | 0.14680 | 0.56640 | −0.40360 | 0.069 (8)* | |
H61 | 0.22190 | 0.54310 | −0.63630 | 0.18 (2)* | |
H62 | 0.42240 | 0.55170 | −0.71460 | 0.138 (16)* | |
H63 | 0.27580 | 0.71250 | −0.70330 | 0.16 (2)* | |
H71 | 0.58380 | 0.71390 | −0.61730 | 0.099 (11)* | |
H72 | 0.50970 | 0.75850 | −0.45990 | 0.114 (13)* | |
H73 | 0.44110 | 0.87660 | −0.56460 | 0.160 (19)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0345 (1) | 0.0302 (1) | 0.0256 (1) | −0.0117 (1) | −0.0016 (1) | 0.0007 (1) |
Cl1 | 0.0935 (5) | 0.0635 (4) | 0.0471 (3) | −0.0030 (3) | −0.0226 (3) | −0.0226 (3) |
Cl2 | 0.0839 (4) | 0.0667 (4) | 0.0857 (5) | −0.0212 (3) | −0.0482 (4) | 0.0314 (3) |
O1 | 0.0620 (8) | 0.0387 (7) | 0.0344 (7) | −0.0211 (6) | −0.0014 (6) | −0.0072 (5) |
O2 | 0.0375 (6) | 0.0468 (7) | 0.0452 (7) | −0.0104 (5) | −0.0067 (5) | 0.0106 (6) |
O3 | 0.0575 (8) | 0.0348 (6) | 0.0368 (7) | −0.0173 (6) | −0.0046 (6) | −0.0034 (5) |
O4 | 0.0394 (7) | 0.0560 (8) | 0.0429 (7) | −0.0116 (6) | −0.0090 (6) | 0.0136 (6) |
O5 | 0.0524 (8) | 0.0470 (7) | 0.0303 (6) | −0.0182 (6) | 0.0015 (5) | 0.0043 (5) |
N1 | 0.0490 (9) | 0.0533 (10) | 0.0316 (8) | 0.0045 (7) | −0.0043 (7) | 0.0022 (7) |
C1 | 0.0404 (8) | 0.0298 (8) | 0.0351 (9) | −0.0075 (6) | −0.0114 (7) | −0.0042 (6) |
C2 | 0.0699 (13) | 0.0351 (9) | 0.0458 (11) | −0.0136 (9) | −0.0158 (10) | −0.0088 (8) |
C3 | 0.0381 (8) | 0.0302 (8) | 0.0370 (9) | −0.0099 (6) | −0.0101 (7) | −0.0026 (6) |
C4 | 0.0436 (10) | 0.0430 (10) | 0.0626 (13) | −0.0090 (8) | −0.0171 (9) | 0.0097 (9) |
C5 | 0.0437 (10) | 0.0527 (11) | 0.0426 (10) | −0.0095 (8) | −0.0036 (8) | 0.0021 (9) |
C6 | 0.080 (2) | 0.143 (3) | 0.0394 (13) | 0.012 (2) | −0.0140 (13) | −0.0079 (16) |
C7 | 0.0647 (14) | 0.0596 (14) | 0.0565 (14) | −0.0130 (11) | 0.0101 (12) | 0.0130 (11) |
Cu1—O1 | 1.9856 (14) | N1—C7 | 1.473 (4) |
Cu1—O2 | 1.9823 (15) | C1—C2 | 1.527 (3) |
Cu1—O3i | 1.9719 (13) | C3—C4 | 1.520 (3) |
Cu1—O4i | 1.9879 (16) | C2—H1 | 0.97 |
Cu1—O5 | 2.1304 (14) | C2—H2 | 0.97 |
Cl1—C2 | 1.769 (2) | C4—H3 | 0.97 |
Cl2—C4 | 1.769 (2) | C4—H4 | 0.97 |
O1—C1 | 1.249 (2) | C5—H5 | 0.93 |
O2—C3 | 1.262 (2) | C6—H61 | 0.96 |
O3—C1 | 1.259 (2) | C6—H62 | 0.96 |
O4—C3 | 1.247 (2) | C6—H63 | 0.96 |
O5—C5 | 1.250 (2) | C7—H71 | 0.96 |
N1—C5 | 1.306 (3) | C7—H72 | 0.96 |
N1—C6 | 1.456 (4) | C7—H73 | 0.96 |
Cu1···Cu1i | 2.6614 (4) | ||
O1—Cu1—O2 | 88.42 (6) | O5—C5—N1 | 125.1 (2) |
O1—Cu1—O5 | 93.93 (6) | Cl1—C2—H1 | 109 |
O1—Cu1—O3i | 167.75 (6) | Cl1—C2—H2 | 109 |
O1—Cu1—O4i | 90.31 (6) | C1—C2—H1 | 109 |
O2—Cu1—O5 | 97.35 (6) | C1—C2—H2 | 109 |
O2—Cu1—O3i | 90.21 (6) | H1—C2—H2 | 108 |
O2—Cu1—O4i | 167.87 (6) | Cl2—C4—H3 | 109 |
O3i—Cu1—O5 | 98.32 (5) | Cl2—C4—H4 | 109 |
O4i—Cu1—O5 | 94.78 (6) | C3—C4—H3 | 109 |
O3i—Cu1—O4i | 88.48 (6) | C3—C4—H4 | 109 |
Cu1—O1—C1 | 125.19 (12) | H3—C4—H4 | 108 |
Cu1—O2—C3 | 122.57 (12) | O5—C5—H5 | 117 |
Cu1i—O3—C1 | 120.41 (12) | N1—C5—H5 | 117 |
Cu1i—O4—C3 | 122.77 (13) | N1—C6—H61 | 109 |
Cu1—O5—C5 | 119.27 (15) | N1—C6—H62 | 109 |
C5—N1—C6 | 123.4 (2) | N1—C6—H63 | 109 |
C5—N1—C7 | 120.42 (19) | H61—C6—H62 | 109 |
C6—N1—C7 | 116.1 (2) | H61—C6—H63 | 109 |
O1—C1—O3 | 126.43 (16) | H62—C6—H63 | 110 |
O1—C1—C2 | 119.16 (16) | N1—C7—H71 | 109 |
O3—C1—C2 | 114.37 (15) | N1—C7—H72 | 109 |
Cl1—C2—C1 | 113.61 (15) | N1—C7—H73 | 109 |
O2—C3—O4 | 126.68 (17) | H71—C7—H72 | 109 |
O2—C3—C4 | 113.55 (16) | H71—C7—H73 | 109 |
O4—C3—C4 | 119.78 (16) | H72—C7—H73 | 109 |
Cl2—C4—C3 | 114.60 (15) |
Symmetry code: (i) −x, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···O2ii | 0.97 | 2.48 | 3.394 (3) | 158 |
Symmetry code: (ii) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C2H2ClO2)4(C3H7NO)2] |
Mr | 647.24 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 294 |
a, b, c (Å) | 7.9969 (6), 8.0326 (5), 10.2420 (7) |
α, β, γ (°) | 87.824 (5), 71.974 (6), 80.015 (6) |
V (Å3) | 616.05 (8) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 2.21 |
Crystal size (mm) | 0.45 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Kuma KM-4 CCD |
Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2006) |
Tmin, Tmax | 0.511, 0.639 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6079, 2814, 2660 |
Rint | 0.009 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.023, 0.067, 1.07 |
No. of reflections | 2814 |
No. of parameters | 159 |
H-atom treatment | Only H-atom displacement parameters refined |
Δρmax, Δρmin (e Å−3) | 0.60, −0.35 |
Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), CrysAlis RED, SHELXTL (Sheldrick, 2001), SHELXTL and Mercury (Macrae et al., 2006), PLATON (Spek, 2003).
Cu1—O1 | 1.9856 (14) | O1—C1 | 1.249 (2) |
Cu1—O2 | 1.9823 (15) | O2—C3 | 1.262 (2) |
Cu1—O3i | 1.9719 (13) | O3—C1 | 1.259 (2) |
Cu1—O4i | 1.9879 (16) | O4—C3 | 1.247 (2) |
Cu1—O5 | 2.1304 (14) | O5—C5 | 1.250 (2) |
Cu1···Cu1i | 2.6614 (4) | ||
O1—Cu1—O2 | 88.42 (6) | O2—Cu1—O3i | 90.21 (6) |
O1—Cu1—O5 | 93.93 (6) | O2—Cu1—O4i | 167.87 (6) |
O1—Cu1—O3i | 167.75 (6) | O3i—Cu1—O5 | 98.32 (5) |
O1—Cu1—O4i | 90.31 (6) | O4i—Cu1—O5 | 94.78 (6) |
O2—Cu1—O5 | 97.35 (6) | O3i—Cu1—O4i | 88.48 (6) |
Symmetry code: (i) −x, −y+1, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···O2ii | 0.97 | 2.48 | 3.394 (3) | 158 |
Symmetry code: (ii) −x+1, −y+1, −z. |
The structure determination of the title compound, (I), was undertaken as a continuation of earlier studies of copper(II) complexes with monochloroacetic acid (Sieroń, 2007).
The title compound (I) contains a dimeric copper(II) complex, [Cu2(CH2ClCOO)4(DMF)2], composed of two CuII centres, four chloroacetate and two DMF ligands (Fig. 1).
The CuII atom has a regular five-coordinate square-pyramidal environment, with the basal plane defined by the O atoms of four bridging bidentate carboxylate groups of monochloroacetate ligands. The CuII atom deviates out of the mean plane formed by the four basal O atoms towards the apical O5 atom of the DMF ligand by 0.2104 (7) Å. The O–C distances in the chloroacetate groups are approximately equal and range from 1.247 (2) to 1.262 (2) Å, indicating the distinct delocalization of their π electrons (Borthwick, 1980). The planes of the two independent bridging chloroacetate groups are perpendicular within experimental error. The apical DMF ligand is twisted by a dihedral angle of 33.8 (1)° with respect to the C1/O1/O3i mean plane. Selected bond distances and bond angles are listed in Table 1. Complex molecules are linked by two Csp3–H···O hydrogen bonds (Table 2), forming eight-membered rings described by the R22(8) graph-set motif (Etter et al., 1990) as shown in Fig. 2. The Cu···Cu distance of 2.6614 (4) Å is comparable to those found in other dimeric copper(II) monochloroacetates (Shi et al., 1999, 2001; Calderazzo et al., 2003).