Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032321/ng2274sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032321/ng2274Isup2.hkl |
CCDC reference: 657543
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.006 Å
- R factor = 0.041
- wR factor = 0.101
- Data-to-parameter ratio = 15.1
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.98 PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 300 Deg. PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.16 Ratio
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (2) 2.11
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 1 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 0 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
For the acetate group as a bridging ligand in multinuclear complexes, see: Panagiotopoulos et al. (1995); Taft et al. (1993); Tangoulis, Raptopolou, Paschalidou et al. 1997; Tangoulis, Raptopolou, Terzis et al., 1997; Tong et al. (2000). For other dinuclear copper compounds, see: Moreland & Doedens (1978).
Cu(OOCCH3)2.H2O (0.133 g, 0.664 mmol) and ethanolamine (0.041 g, 0.676 mmol) were dissoved in 8 ml of water; the solution was added into an 8 ml me thanol solution containing 2-chloromethylpyridine (0.170 g, 1.33 mmol). Green crystals were obtained after allowing the mixed solution to stand at room temperature for one week.
The H atoms were placed in calculated positions and refined as riding, with C—H = 0.93 Å, Uiso(H) = 1.2Ueq(C) for pyridine ring; C—H = 0.96 Å, Uiso(H) = 1.5Ueq(C) for methyl group, and C—H = 0.97 Å, Uiso(H) = 1.2Ueq(C) for the chloromethyl group.
The acetate anion is an useful ligand and a large number of multi-atom bridge complexes have been synthesized with it as a bridging ligand (Panagiotopoulos et al. 1995; Taft et al. 1993; Tangoulis, Raptopolou, Paschalidou et al. 1997; Tangoulis, Raptopolou, Terzis et al., 1997; Tong, et al. 2000). We had intended to synthesize a multi-nuclear CuII complex by using acetate and 2-chloromethylpyridine as ligands, but the title dinuclear complex was obtained.
Two copper atoms are briged by four acetate groups; the copper atoms are also coordinated by the heterocycle so that the geometry at copper is a square pyramid. The bond dimensions are similar to those in other binculear copper systems (Moreland & Doedens, 1978)..
For the acetate group as a bridging ligand in multinuclear complexes, see: Panagiotopoulos et al. (1995); Taft et al. (1993); Tangoulis, Raptopolou, Paschalidou et al. 1997; Tangoulis, Raptopolou, Terzis et al., 1997; Tong et al. (2000). For other dinuclear copper compounds, see: Moreland & Doedens (1978).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. Molecular structure showing the atom numbering scheme with thermal ellipsoids drawn at the 30% probability level; hydrogen bonds (line of dashes). [Symmetry codes: (i) 1 - x, 1 - y, 1 - z] |
[Cu2(C2H3O2)4(C6H6ClN)2] | Z = 1 |
Mr = 618.39 | F(000) = 314 |
Triclinic, P1 | Dx = 1.678 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.8592 (19) Å | Cell parameters from 1146 reflections |
b = 7.959 (2) Å | θ = 2.6–24.9° |
c = 10.734 (3) Å | µ = 2.00 mm−1 |
α = 100.458 (3)° | T = 298 K |
β = 110.406 (3)° | Prism, green |
γ = 94.199 (3)° | 0.28 × 0.20 × 0.18 mm |
V = 612.0 (3) Å3 |
Bruker SMART APEX diffractometer | 2359 independent reflections |
Radiation source: fine-focus sealed tube | 2033 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
φ and ω scans | θmax = 26.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→9 |
Tmin = 0.604, Tmax = 0.714 | k = −9→8 |
3405 measured reflections | l = −9→13 |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0544P)2] where P = (Fo2 + 2Fc2)/3 |
2359 reflections | (Δ/σ)max = 0.001 |
156 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.30 e Å−3 |
[Cu2(C2H3O2)4(C6H6ClN)2] | γ = 94.199 (3)° |
Mr = 618.39 | V = 612.0 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.8592 (19) Å | Mo Kα radiation |
b = 7.959 (2) Å | µ = 2.00 mm−1 |
c = 10.734 (3) Å | T = 298 K |
α = 100.458 (3)° | 0.28 × 0.20 × 0.18 mm |
β = 110.406 (3)° |
Bruker SMART APEX diffractometer | 2359 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2033 reflections with I > 2σ(I) |
Tmin = 0.604, Tmax = 0.714 | Rint = 0.019 |
3405 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.102 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.41 e Å−3 |
2359 reflections | Δρmin = −0.30 e Å−3 |
156 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Cu1 | 0.53281 (5) | 0.54185 (5) | 0.39664 (4) | 0.03081 (16) | |
N1 | 0.6345 (3) | 0.6340 (3) | 0.2462 (3) | 0.0307 (6) | |
C1 | 0.8136 (4) | 0.6281 (5) | 0.2745 (4) | 0.0394 (8) | |
H1 | 0.8788 | 0.5878 | 0.3509 | 0.047* | |
C2 | 0.9059 (5) | 0.6781 (5) | 0.1972 (4) | 0.0518 (10) | |
H2 | 1.0306 | 0.6720 | 0.2213 | 0.062* | |
C3 | 0.8126 (6) | 0.7373 (6) | 0.0839 (4) | 0.0562 (11) | |
H3 | 0.8720 | 0.7725 | 0.0297 | 0.067* | |
C4 | 0.6293 (6) | 0.7429 (5) | 0.0532 (4) | 0.0519 (10) | |
H4 | 0.5619 | 0.7809 | −0.0239 | 0.062* | |
C5 | 0.5439 (5) | 0.6927 (4) | 0.1357 (3) | 0.0352 (8) | |
C6 | 0.3446 (5) | 0.7041 (5) | 0.1064 (4) | 0.0485 (10) | |
H6A | 0.3019 | 0.6401 | 0.1613 | 0.058* | |
H6B | 0.2739 | 0.6522 | 0.0112 | 0.058* | |
C7 | 0.8014 (4) | 0.6730 (4) | 0.6705 (3) | 0.0343 (7) | |
C8 | 0.9816 (4) | 0.7811 (5) | 0.7643 (3) | 0.0457 (9) | |
H8A | 1.0788 | 0.7415 | 0.7375 | 0.068* | |
H8B | 1.0041 | 0.7707 | 0.8562 | 0.068* | |
H8C | 0.9766 | 0.8998 | 0.7589 | 0.068* | |
C9 | 0.6582 (4) | 0.2378 (4) | 0.4730 (4) | 0.0365 (8) | |
C10 | 0.7477 (5) | 0.0791 (5) | 0.4577 (4) | 0.0502 (10) | |
H10A | 0.8771 | 0.1072 | 0.5097 | 0.075* | |
H10B | 0.7279 | 0.0370 | 0.3633 | 0.075* | |
H10C | 0.6954 | −0.0083 | 0.4902 | 0.075* | |
O1 | 0.6491 (3) | 0.3325 (3) | 0.3890 (3) | 0.0450 (6) | |
O2 | 0.5984 (3) | 0.2664 (3) | 0.5675 (3) | 0.0442 (6) | |
O3 | 0.7596 (3) | 0.6660 (3) | 0.5456 (2) | 0.0411 (6) | |
O4 | 0.7053 (3) | 0.5988 (3) | 0.7225 (2) | 0.0427 (6) | |
Cl1 | 0.30915 (15) | 0.92261 (15) | 0.14306 (12) | 0.0668 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0349 (2) | 0.0329 (3) | 0.0310 (2) | 0.00724 (17) | 0.01565 (17) | 0.01476 (17) |
N1 | 0.0333 (14) | 0.0323 (15) | 0.0305 (14) | 0.0048 (12) | 0.0140 (11) | 0.0119 (11) |
C1 | 0.0367 (18) | 0.048 (2) | 0.041 (2) | 0.0113 (16) | 0.0184 (16) | 0.0170 (16) |
C2 | 0.042 (2) | 0.063 (3) | 0.062 (3) | 0.0084 (19) | 0.0298 (19) | 0.021 (2) |
C3 | 0.062 (3) | 0.070 (3) | 0.058 (3) | 0.007 (2) | 0.042 (2) | 0.027 (2) |
C4 | 0.067 (3) | 0.058 (3) | 0.041 (2) | 0.009 (2) | 0.0240 (19) | 0.0271 (19) |
C5 | 0.0428 (19) | 0.0328 (19) | 0.0318 (17) | 0.0038 (15) | 0.0141 (15) | 0.0117 (14) |
C6 | 0.041 (2) | 0.053 (2) | 0.051 (2) | 0.0050 (18) | 0.0078 (17) | 0.0285 (19) |
C7 | 0.0365 (18) | 0.0324 (19) | 0.0352 (18) | 0.0106 (15) | 0.0132 (15) | 0.0085 (14) |
C8 | 0.0361 (18) | 0.058 (3) | 0.037 (2) | 0.0024 (17) | 0.0081 (15) | 0.0076 (17) |
C9 | 0.0309 (17) | 0.0303 (19) | 0.045 (2) | 0.0040 (14) | 0.0107 (15) | 0.0082 (15) |
C10 | 0.056 (2) | 0.037 (2) | 0.066 (3) | 0.0205 (19) | 0.028 (2) | 0.0183 (19) |
O1 | 0.0557 (15) | 0.0406 (15) | 0.0547 (15) | 0.0177 (12) | 0.0322 (13) | 0.0219 (12) |
O2 | 0.0543 (15) | 0.0415 (15) | 0.0499 (15) | 0.0209 (12) | 0.0265 (12) | 0.0219 (12) |
O3 | 0.0413 (13) | 0.0536 (16) | 0.0285 (12) | 0.0018 (12) | 0.0113 (10) | 0.0144 (11) |
O4 | 0.0432 (13) | 0.0543 (16) | 0.0305 (12) | −0.0031 (12) | 0.0124 (10) | 0.0157 (11) |
Cl1 | 0.0626 (7) | 0.0657 (8) | 0.0815 (8) | 0.0271 (6) | 0.0277 (6) | 0.0299 (6) |
Cu1—O2i | 1.958 (2) | C6—Cl1 | 1.776 (4) |
Cu1—O1 | 1.960 (2) | C6—H6A | 0.9700 |
Cu1—O3 | 1.973 (2) | C6—H6B | 0.9700 |
Cu1—O4i | 1.974 (2) | C7—O3 | 1.254 (4) |
Cu1—N1 | 2.243 (3) | C7—O4 | 1.256 (4) |
Cu1—Cu1i | 2.6302 (9) | C7—C8 | 1.507 (4) |
N1—C1 | 1.339 (4) | C8—H8A | 0.9600 |
N1—C5 | 1.339 (4) | C8—H8B | 0.9600 |
C1—C2 | 1.368 (5) | C8—H8C | 0.9600 |
C1—H1 | 0.9300 | C9—O2 | 1.252 (4) |
C2—C3 | 1.369 (5) | C9—O1 | 1.263 (4) |
C2—H2 | 0.9300 | C9—C10 | 1.501 (5) |
C3—C4 | 1.367 (5) | C10—H10A | 0.9600 |
C3—H3 | 0.9300 | C10—H10B | 0.9600 |
C4—C5 | 1.378 (5) | C10—H10C | 0.9600 |
C4—H4 | 0.9300 | O2—Cu1i | 1.958 (2) |
C5—C6 | 1.499 (5) | O4—Cu1i | 1.974 (2) |
O2i—Cu1—O1 | 168.18 (10) | N1—C5—C6 | 116.9 (3) |
O2i—Cu1—O3 | 90.24 (11) | C4—C5—C6 | 121.1 (3) |
O1—Cu1—O3 | 89.38 (11) | C5—C6—Cl1 | 110.9 (3) |
O2i—Cu1—O4i | 88.84 (11) | C5—C6—H6A | 109.5 |
O1—Cu1—O4i | 89.14 (11) | Cl1—C6—H6A | 109.5 |
O3—Cu1—O4i | 168.32 (9) | C5—C6—H6B | 109.5 |
O2i—Cu1—N1 | 98.54 (10) | Cl1—C6—H6B | 109.5 |
O1—Cu1—N1 | 93.27 (10) | H6A—C6—H6B | 108.1 |
O3—Cu1—N1 | 89.37 (9) | O3—C7—O4 | 125.4 (3) |
O4i—Cu1—N1 | 102.29 (9) | O3—C7—C8 | 116.3 (3) |
O2i—Cu1—Cu1i | 82.46 (7) | O4—C7—C8 | 118.3 (3) |
O1—Cu1—Cu1i | 85.80 (7) | C7—C8—H8A | 109.5 |
O3—Cu1—Cu1i | 81.15 (7) | C7—C8—H8B | 109.5 |
O4i—Cu1—Cu1i | 87.19 (7) | H8A—C8—H8B | 109.5 |
N1—Cu1—Cu1i | 170.47 (7) | C7—C8—H8C | 109.5 |
C1—N1—C5 | 117.0 (3) | H8A—C8—H8C | 109.5 |
C1—N1—Cu1 | 113.2 (2) | H8B—C8—H8C | 109.5 |
C5—N1—Cu1 | 129.8 (2) | O2—C9—O1 | 125.0 (3) |
N1—C1—C2 | 123.6 (3) | O2—C9—C10 | 117.8 (3) |
N1—C1—H1 | 118.2 | O1—C9—C10 | 117.2 (3) |
C2—C1—H1 | 118.2 | C9—C10—H10A | 109.5 |
C1—C2—C3 | 119.3 (3) | C9—C10—H10B | 109.5 |
C1—C2—H2 | 120.4 | H10A—C10—H10B | 109.5 |
C3—C2—H2 | 120.4 | C9—C10—H10C | 109.5 |
C4—C3—C2 | 117.8 (3) | H10A—C10—H10C | 109.5 |
C4—C3—H3 | 121.1 | H10B—C10—H10C | 109.5 |
C2—C3—H3 | 121.1 | C9—O1—Cu1 | 121.2 (2) |
C3—C4—C5 | 120.4 (3) | C9—O2—Cu1i | 125.5 (2) |
C3—C4—H4 | 119.8 | C7—O3—Cu1 | 126.7 (2) |
C5—C4—H4 | 119.8 | C7—O4—Cu1i | 119.5 (2) |
N1—C5—C4 | 121.9 (3) | ||
O2i—Cu1—N1—C1 | 131.3 (2) | C4—C5—C6—Cl1 | −71.9 (4) |
O1—Cu1—N1—C1 | −48.1 (2) | O2—C9—O1—Cu1 | −0.8 (5) |
O3—Cu1—N1—C1 | 41.2 (2) | C10—C9—O1—Cu1 | 179.3 (2) |
O4i—Cu1—N1—C1 | −138.0 (2) | O2i—Cu1—O1—C9 | −7.9 (7) |
O2i—Cu1—N1—C5 | −48.5 (3) | O3—Cu1—O1—C9 | 80.3 (3) |
O1—Cu1—N1—C5 | 132.0 (3) | O4i—Cu1—O1—C9 | −88.1 (3) |
O3—Cu1—N1—C5 | −138.6 (3) | N1—Cu1—O1—C9 | 169.6 (3) |
O4i—Cu1—N1—C5 | 42.2 (3) | Cu1i—Cu1—O1—C9 | −0.9 (3) |
C5—N1—C1—C2 | −0.1 (5) | O1—C9—O2—Cu1i | 2.9 (5) |
Cu1—N1—C1—C2 | −179.9 (3) | C10—C9—O2—Cu1i | −177.1 (2) |
N1—C1—C2—C3 | −0.2 (6) | O4—C7—O3—Cu1 | 1.1 (5) |
C1—C2—C3—C4 | −0.2 (6) | C8—C7—O3—Cu1 | −178.4 (2) |
C2—C3—C4—C5 | 1.0 (6) | O2i—Cu1—O3—C7 | 81.3 (3) |
C1—N1—C5—C4 | 0.8 (5) | O1—Cu1—O3—C7 | −86.9 (3) |
Cu1—N1—C5—C4 | −179.4 (3) | O4i—Cu1—O3—C7 | −4.2 (6) |
C1—N1—C5—C6 | −178.3 (3) | N1—Cu1—O3—C7 | 179.8 (3) |
Cu1—N1—C5—C6 | 1.6 (4) | Cu1i—Cu1—O3—C7 | −1.1 (3) |
C3—C4—C5—N1 | −1.3 (6) | O3—C7—O4—Cu1i | −0.2 (5) |
C3—C4—C5—C6 | 177.7 (4) | C8—C7—O4—Cu1i | 179.3 (2) |
N1—C5—C6—Cl1 | 107.1 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C2H3O2)4(C6H6ClN)2] |
Mr | 618.39 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 7.8592 (19), 7.959 (2), 10.734 (3) |
α, β, γ (°) | 100.458 (3), 110.406 (3), 94.199 (3) |
V (Å3) | 612.0 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 2.00 |
Crystal size (mm) | 0.28 × 0.20 × 0.18 |
Data collection | |
Diffractometer | Bruker SMART APEX |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.604, 0.714 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3405, 2359, 2033 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.102, 1.04 |
No. of reflections | 2359 |
No. of parameters | 156 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.30 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXTL (Bruker, 2001), SHELXTL.
Cu1—O2i | 1.958 (2) | Cu1—O4i | 1.974 (2) |
Cu1—O1 | 1.960 (2) | Cu1—N1 | 2.243 (3) |
Cu1—O3 | 1.973 (2) | ||
O2i—Cu1—O1 | 168.18 (10) | O2i—Cu1—N1 | 98.54 (10) |
O2i—Cu1—O3 | 90.24 (11) | O1—Cu1—N1 | 93.27 (10) |
O1—Cu1—O3 | 89.38 (11) | O3—Cu1—N1 | 89.37 (9) |
O1—Cu1—O4i | 89.14 (11) | O4i—Cu1—N1 | 102.29 (9) |
O3—Cu1—O4i | 168.32 (9) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
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The acetate anion is an useful ligand and a large number of multi-atom bridge complexes have been synthesized with it as a bridging ligand (Panagiotopoulos et al. 1995; Taft et al. 1993; Tangoulis, Raptopolou, Paschalidou et al. 1997; Tangoulis, Raptopolou, Terzis et al., 1997; Tong, et al. 2000). We had intended to synthesize a multi-nuclear CuII complex by using acetate and 2-chloromethylpyridine as ligands, but the title dinuclear complex was obtained.
Two copper atoms are briged by four acetate groups; the copper atoms are also coordinated by the heterocycle so that the geometry at copper is a square pyramid. The bond dimensions are similar to those in other binculear copper systems (Moreland & Doedens, 1978)..