Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807047009/hg2298sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807047009/hg2298Isup2.hkl |
CCDC reference: 667102
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.003 Å
- R factor = 0.031
- wR factor = 0.086
- Data-to-parameter ratio = 13.0
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X) Cu1 - O2 .. 11.82 su
Alert level C PLAT154_ALERT_1_C The su's on the Cell Angles are Equal (x 10000) 300 Deg. PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for Cl2 PLAT432_ALERT_2_C Short Inter X...Y Contact O4 .. C10 .. 2.97 Ang. PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.12 Ratio
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1 (3) 2.93
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 4 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 2 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
2, 6-Diformyl-4-fluorophenol was prepared according to the literature method of Taniguchi (1984). To a solution of 2, 6-diformyl-4-fluorophenol (0.6 mmol, 0.101 g) in absolute methanol (10 ml) was added methanol solution (10 ml) of Cu(OAc)2H2O (0.3 mmol, 0.06 g). The solution was stirred vigorously while a methanol solution (10 ml) containing ethylenediamine (0.6 mmol, 0.036 g) was added dropwise over a period of 2 h. The mixture was still stirred for 12 h at room temperature. Then, the Cu(ClO4)26H2O (0.3 mmol, 0.111 g) was added to the solution and stirred for 6 h at room temperature. The dark-green block-shaped crystals suitable for X-ray diffraction were obtained by slow diffusion of ethyl acetate into the mother solution over a period of three weeks.
All H atoms for C—H distances were placed in calculated positions in the range 0.93–0.97 Å, and included in the refinement in the riding-model approximation, with U(H) set to 1.2–1.5Ueq(C). The methanol H atom was located in a difference Fourier map, and was refined with an O–H distance restraint of 0.808 Å; its temperature factor was set to 1.5Ueq(O).
Since the Robson-style homodinuclear macrocyclic complexes were synthesized via template condensation, there has been an increasing interest in the research of these complexes (Pilkington & Robson, 1970; Aono et al., 1997). In the past, most of these complexes were synthesized by cyclocondensation between 2,6-diformyl-4-R-phenol (R = CH3, Cl, Br, CH3O, n-butyl) and alkylenediamine by stepwise template reaction (Gou & Fenton, 1994; Adams et al., 1995). But only a few crystal structures of the complexes with fluorophenyl substituents have been published (Chen et al., 2005; Chen et al., 2007). In this paper, we report the synthesis and crystal structure of the title complex with fluorophenyl substituents.
The crystal structure of the title complex is shown in Fig. 1. Selected bond distances and angles relevant to the coordination geometries of copper atoms are listed in Table 1. Each copper atom is coordinated by two endogenous phenolic O atoms, two azomethine nitrogen atoms and one oxygen atom from methanol molecule. The coordination polyhedron of each CuII can be described as distorted tetragonal pyramid. The deviation of Cu1 and Cu1* from the mean plane of atoms N1, N2, O1, O1* [mean deviation = 0.0182 (3) Å] and N1*, N2*, O1, O1* [mean deviation = 0.0182 (3) Å] are 0.1713 (3)Å and -0.1714 (3) Å, respectively. The two atom groups O1, O1*, Cu1, Cu1* and N1, N2, N1*, N2* are almost coplanar with the dihedral angle of the two planes 7.0 (3)°. The parallelogram formed by atoms N1, N2, N1*, N2* approximates a rectangle with the angle of N1—N2—N1* 89.7 (3)°. The Cu···Cu distance is 2.8998 (7) Å. The Cu—N bond lengths are 1.886 (2) and 1.885 (2) Å. the Cu—O bondlengths to the methanol molecule are both 2.364 (2) Å, which is much longer than those for the phenolic O atoms [1.8905 (17)Å and 1.9021 (17) Å]. The crystal structure of is stabilized by intramolecular and intermolecular hydrogen bonds of types O—H···O and C—H···O, where O atoms belong to methanol molecules or perchlorate ions.
For related literature, see: Adams et al. (1995); Aono et al. (1997); Bruker (2000); Chen et al. (2005, 2007); Gou & Fenton (1994); Pilkington & Robson (1970); Taniguchi (1984).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL (Bruker, 2000); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL (Bruker, 2000).
[Cu2(C20H16F2N4O2)(CH4O)2](ClO4)2 | Z = 1 |
Mr = 772.43 | F(000) = 390 |
Triclinic, P1 | Dx = 1.889 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.8124 (13) Å | Cell parameters from 1982 reflections |
b = 8.4132 (15) Å | θ = 2.5–29.0° |
c = 10.8144 (18) Å | µ = 1.85 mm−1 |
α = 103.127 (3)° | T = 296 K |
β = 96.272 (3)° | Block, blue |
γ = 97.569 (3)° | 0.20 × 0.20 × 0.10 mm |
V = 679.0 (2) Å3 |
Bruker SMART CCD area-detector diffractometer | 2633 independent reflections |
Radiation source: fine-focus sealed tube | 2268 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.011 |
φ and ω scans | θmax = 26.0°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −9→9 |
Tmin = 0.709, Tmax = 0.837 | k = −10→9 |
3953 measured reflections | l = −13→11 |
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)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.086 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0487P)2 + 0.1892P] where P = (Fo2 + 2Fc2)/3 |
2633 reflections | (Δ/σ)max < 0.001 |
203 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
[Cu2(C20H16F2N4O2)(CH4O)2](ClO4)2 | γ = 97.569 (3)° |
Mr = 772.43 | V = 679.0 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.8124 (13) Å | Mo Kα radiation |
b = 8.4132 (15) Å | µ = 1.85 mm−1 |
c = 10.8144 (18) Å | T = 296 K |
α = 103.127 (3)° | 0.20 × 0.20 × 0.10 mm |
β = 96.272 (3)° |
Bruker SMART CCD area-detector diffractometer | 2633 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2268 reflections with I > 2σ(I) |
Tmin = 0.709, Tmax = 0.837 | Rint = 0.011 |
3953 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.086 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.31 e Å−3 |
2633 reflections | Δρmin = −0.24 e Å−3 |
203 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 | 0.01488 (4) | −0.09325 (4) | 0.37234 (3) | 0.04503 (13) | |
C1 | 0.2955 (3) | 0.1735 (3) | 0.5123 (2) | 0.0370 (5) | |
C2 | 0.3570 (3) | 0.3063 (3) | 0.6204 (2) | 0.0354 (5) | |
C3 | 0.5275 (3) | 0.3910 (3) | 0.6307 (2) | 0.0420 (6) | |
H3 | 0.5719 | 0.4799 | 0.7003 | 0.050* | |
C4 | 0.6272 (3) | 0.3414 (3) | 0.5374 (3) | 0.0442 (6) | |
C5 | 0.5696 (3) | 0.2153 (3) | 0.4317 (2) | 0.0417 (6) | |
H5 | 0.6421 | 0.1883 | 0.3700 | 0.050* | |
C6 | 0.4006 (3) | 0.1256 (3) | 0.4157 (2) | 0.0358 (5) | |
C7 | 0.3459 (3) | −0.0089 (3) | 0.2995 (2) | 0.0390 (5) | |
H7 | 0.4248 | −0.0265 | 0.2412 | 0.047* | |
C8 | 0.1400 (4) | −0.2311 (3) | 0.1512 (2) | 0.0459 (6) | |
H8A | 0.2396 | −0.2760 | 0.1197 | 0.055* | |
H8B | 0.0860 | −0.1823 | 0.0869 | 0.055* | |
C9 | 0.0077 (3) | −0.3705 (3) | 0.1745 (2) | 0.0432 (6) | |
H9A | −0.0661 | −0.4279 | 0.0946 | 0.052* | |
H9B | 0.0694 | −0.4498 | 0.2056 | 0.052* | |
C10 | −0.2534 (3) | −0.3680 (3) | 0.2794 (2) | 0.0386 (5) | |
H10 | −0.3024 | −0.4645 | 0.2179 | 0.046* | |
C11 | −0.0536 (4) | 0.2138 (4) | 0.2389 (4) | 0.0703 (9) | |
H11A | −0.0062 | 0.2864 | 0.3210 | 0.105* | |
H11B | −0.1355 | 0.2649 | 0.1947 | 0.105* | |
H11C | 0.0391 | 0.1924 | 0.1891 | 0.105* | |
Cl2 | 0.37721 (9) | 0.23525 (8) | 0.03502 (6) | 0.04801 (18) | |
F1 | 0.7932 (2) | 0.4251 (2) | 0.54902 (17) | 0.0679 (5) | |
N1 | 0.1980 (3) | −0.1037 (2) | 0.27212 (19) | 0.0394 (5) | |
N2 | −0.1008 (3) | −0.2997 (2) | 0.27003 (18) | 0.0368 (4) | |
O1 | 0.1343 (2) | 0.0926 (2) | 0.49992 (17) | 0.0534 (5) | |
O2 | −0.1394 (3) | 0.0628 (2) | 0.25626 (19) | 0.0533 (5) | |
O3 | 0.2525 (4) | 0.0916 (3) | 0.0236 (3) | 0.0959 (9) | |
O4 | 0.4365 (3) | 0.2247 (4) | −0.0854 (2) | 0.0825 (7) | |
O5 | 0.2965 (4) | 0.3775 (3) | 0.0673 (3) | 0.0877 (8) | |
O6 | 0.5174 (3) | 0.2428 (3) | 0.1313 (2) | 0.0847 (8) | |
H2 | −0.178 (6) | 0.007 (5) | 0.185 (2) | 0.127* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0476 (2) | 0.0403 (2) | 0.03627 (19) | −0.00728 (14) | 0.01882 (14) | −0.01080 (13) |
C1 | 0.0417 (13) | 0.0348 (12) | 0.0315 (12) | 0.0000 (10) | 0.0084 (10) | 0.0038 (10) |
C2 | 0.0400 (12) | 0.0314 (12) | 0.0326 (12) | 0.0025 (10) | 0.0041 (10) | 0.0056 (9) |
C3 | 0.0412 (13) | 0.0396 (13) | 0.0391 (13) | 0.0004 (11) | 0.0001 (11) | 0.0036 (11) |
C4 | 0.0329 (12) | 0.0492 (15) | 0.0474 (15) | −0.0003 (11) | 0.0016 (11) | 0.0111 (12) |
C5 | 0.0363 (12) | 0.0491 (15) | 0.0408 (14) | 0.0062 (11) | 0.0098 (10) | 0.0119 (11) |
C6 | 0.0395 (12) | 0.0365 (12) | 0.0322 (12) | 0.0049 (10) | 0.0085 (10) | 0.0089 (10) |
C7 | 0.0430 (13) | 0.0401 (13) | 0.0355 (13) | 0.0083 (11) | 0.0170 (10) | 0.0065 (10) |
C8 | 0.0538 (15) | 0.0460 (14) | 0.0324 (13) | 0.0045 (12) | 0.0163 (11) | −0.0045 (11) |
C9 | 0.0511 (14) | 0.0359 (13) | 0.0363 (13) | 0.0047 (11) | 0.0125 (11) | −0.0056 (10) |
C10 | 0.0480 (14) | 0.0310 (12) | 0.0316 (12) | 0.0035 (10) | 0.0026 (10) | 0.0001 (9) |
C11 | 0.0641 (19) | 0.063 (2) | 0.089 (3) | 0.0053 (16) | 0.0208 (18) | 0.0283 (19) |
Cl2 | 0.0509 (4) | 0.0473 (4) | 0.0397 (4) | 0.0023 (3) | 0.0051 (3) | 0.0021 (3) |
F1 | 0.0386 (8) | 0.0844 (13) | 0.0654 (11) | −0.0136 (8) | 0.0076 (8) | 0.0003 (9) |
N1 | 0.0470 (11) | 0.0349 (11) | 0.0326 (10) | 0.0030 (9) | 0.0131 (9) | −0.0008 (8) |
N2 | 0.0432 (11) | 0.0340 (10) | 0.0295 (10) | 0.0037 (9) | 0.0090 (8) | −0.0002 (8) |
O1 | 0.0478 (10) | 0.0536 (11) | 0.0412 (10) | −0.0181 (9) | 0.0211 (8) | −0.0163 (8) |
O2 | 0.0550 (11) | 0.0431 (11) | 0.0543 (12) | 0.0014 (9) | 0.0079 (9) | 0.0001 (9) |
O3 | 0.0901 (18) | 0.0763 (18) | 0.103 (2) | −0.0284 (14) | 0.0149 (16) | 0.0088 (15) |
O4 | 0.0919 (18) | 0.113 (2) | 0.0528 (13) | 0.0309 (16) | 0.0281 (13) | 0.0240 (14) |
O5 | 0.0994 (18) | 0.0747 (17) | 0.0813 (17) | 0.0365 (15) | 0.0077 (15) | −0.0065 (13) |
O6 | 0.0933 (18) | 0.0789 (17) | 0.0677 (16) | 0.0063 (14) | −0.0271 (14) | 0.0115 (13) |
Cu1—N2 | 1.885 (2) | C8—N1 | 1.473 (3) |
Cu1—N1 | 1.886 (2) | C8—C9 | 1.543 (4) |
Cu1—O1 | 1.8905 (17) | C8—H8A | 0.9700 |
Cu1—O1i | 1.9021 (17) | C8—H8B | 0.9700 |
Cu1—O2 | 2.364 (2) | C9—N2 | 1.479 (3) |
Cu1—Cu1i | 2.8998 (7) | C9—H9A | 0.9700 |
C1—O1 | 1.327 (3) | C9—H9B | 0.9700 |
C1—C2 | 1.409 (3) | C10—N2 | 1.278 (3) |
C1—C6 | 1.418 (3) | C10—C2i | 1.465 (3) |
C2—C3 | 1.406 (3) | C10—H10 | 0.9300 |
C2—C10i | 1.465 (3) | C11—O2 | 1.418 (4) |
C3—C4 | 1.366 (4) | C11—H11A | 0.9600 |
C3—H3 | 0.9300 | C11—H11B | 0.9600 |
C4—C5 | 1.359 (4) | C11—H11C | 0.9600 |
C4—F1 | 1.370 (3) | Cl2—O6 | 1.411 (2) |
C5—C6 | 1.404 (3) | Cl2—O4 | 1.417 (2) |
C5—H5 | 0.9300 | Cl2—O5 | 1.417 (2) |
C6—C7 | 1.467 (3) | Cl2—O3 | 1.421 (3) |
C7—N1 | 1.279 (3) | O1—Cu1i | 1.9022 (17) |
C7—H7 | 0.9300 | O2—H2 | 0.810 (10) |
N2—Cu1—N1 | 90.13 (8) | C9—C8—H8A | 109.8 |
N2—Cu1—O1 | 169.19 (9) | N1—C8—H8B | 109.8 |
N1—Cu1—O1 | 94.42 (8) | C9—C8—H8B | 109.8 |
N2—Cu1—O1i | 93.32 (8) | H8A—C8—H8B | 108.2 |
N1—Cu1—O1i | 167.69 (9) | N2—C9—C8 | 109.70 (19) |
O1—Cu1—O1i | 80.26 (8) | N2—C9—H9A | 109.7 |
N2—Cu1—O2 | 94.58 (8) | C8—C9—H9A | 109.7 |
N1—Cu1—O2 | 95.01 (8) | N2—C9—H9B | 109.7 |
O1—Cu1—O2 | 94.78 (8) | C8—C9—H9B | 109.7 |
O1i—Cu1—O2 | 96.48 (8) | H9A—C9—H9B | 108.2 |
N2—Cu1—Cu1i | 132.72 (6) | N2—C10—C2i | 125.1 (2) |
N1—Cu1—Cu1i | 133.72 (6) | N2—C10—H10 | 117.5 |
O1—Cu1—Cu1i | 40.28 (5) | C2i—C10—H10 | 117.5 |
O1i—Cu1—Cu1i | 39.98 (5) | O2—C11—H11A | 109.5 |
O2—Cu1—Cu1i | 97.38 (5) | O2—C11—H11B | 109.5 |
O1—C1—C2 | 119.1 (2) | H11A—C11—H11B | 109.5 |
O1—C1—C6 | 119.2 (2) | O2—C11—H11C | 109.5 |
C2—C1—C6 | 121.7 (2) | H11A—C11—H11C | 109.5 |
C3—C2—C1 | 118.1 (2) | H11B—C11—H11C | 109.5 |
C3—C2—C10i | 117.1 (2) | O6—Cl2—O4 | 110.58 (16) |
C1—C2—C10i | 124.8 (2) | O6—Cl2—O5 | 109.79 (16) |
C4—C3—C2 | 119.3 (2) | O4—Cl2—O5 | 109.75 (16) |
C4—C3—H3 | 120.4 | O6—Cl2—O3 | 109.72 (18) |
C2—C3—H3 | 120.4 | O4—Cl2—O3 | 107.74 (18) |
C5—C4—C3 | 123.6 (2) | O5—Cl2—O3 | 109.22 (18) |
C5—C4—F1 | 117.9 (2) | C7—N1—C8 | 124.5 (2) |
C3—C4—F1 | 118.5 (2) | C7—N1—Cu1 | 126.02 (17) |
C4—C5—C6 | 120.0 (2) | C8—N1—Cu1 | 109.37 (15) |
C4—C5—H5 | 120.0 | C10—N2—C9 | 124.4 (2) |
C6—C5—H5 | 120.0 | C10—N2—Cu1 | 125.07 (17) |
C5—C6—C1 | 117.4 (2) | C9—N2—Cu1 | 110.53 (15) |
C5—C6—C7 | 117.4 (2) | C1—O1—Cu1 | 130.12 (15) |
C1—C6—C7 | 125.2 (2) | C1—O1—Cu1i | 128.21 (16) |
N1—C7—C6 | 125.0 (2) | Cu1—O1—Cu1i | 99.74 (8) |
N1—C7—H7 | 117.5 | C11—O2—Cu1 | 119.82 (19) |
C6—C7—H7 | 117.5 | C11—O2—H2 | 105 (4) |
N1—C8—C9 | 109.45 (19) | Cu1—O2—H2 | 110 (4) |
N1—C8—H8A | 109.8 | ||
O1—C1—C2—C3 | −179.4 (2) | C2i—C10—N2—C9 | 174.9 (2) |
C6—C1—C2—C3 | −0.2 (4) | C2i—C10—N2—Cu1 | −6.7 (3) |
O1—C1—C2—C10i | −2.3 (4) | C8—C9—N2—C10 | 155.9 (2) |
C6—C1—C2—C10i | 176.8 (2) | C8—C9—N2—Cu1 | −22.7 (2) |
C1—C2—C3—C4 | −0.6 (4) | N1—Cu1—N2—C10 | −174.2 (2) |
C10i—C2—C3—C4 | −177.9 (2) | O1—Cu1—N2—C10 | 70.8 (5) |
C2—C3—C4—C5 | 1.6 (4) | O1i—Cu1—N2—C10 | 17.6 (2) |
C2—C3—C4—F1 | −179.9 (2) | O2—Cu1—N2—C10 | −79.2 (2) |
C3—C4—C5—C6 | −1.6 (4) | Cu1i—Cu1—N2—C10 | 25.3 (2) |
F1—C4—C5—C6 | 179.9 (2) | N1—Cu1—N2—C9 | 4.38 (17) |
C4—C5—C6—C1 | 0.7 (4) | O1—Cu1—N2—C9 | −110.6 (4) |
C4—C5—C6—C7 | 179.9 (2) | O1i—Cu1—N2—C9 | −163.80 (16) |
O1—C1—C6—C5 | 179.4 (2) | O2—Cu1—N2—C9 | 99.42 (16) |
C2—C1—C6—C5 | 0.2 (3) | Cu1i—Cu1—N2—C9 | −156.14 (13) |
O1—C1—C6—C7 | 0.2 (4) | C2—C1—O1—Cu1 | −177.49 (18) |
C2—C1—C6—C7 | −178.9 (2) | C6—C1—O1—Cu1 | 3.3 (4) |
C5—C6—C7—N1 | 178.6 (2) | C2—C1—O1—Cu1i | −16.6 (3) |
C1—C6—C7—N1 | −2.3 (4) | C6—C1—O1—Cu1i | 164.21 (18) |
N1—C8—C9—N2 | 35.4 (3) | N2—Cu1—O1—C1 | 110.7 (4) |
C6—C7—N1—C8 | 175.7 (2) | N1—Cu1—O1—C1 | −4.0 (2) |
C6—C7—N1—Cu1 | 0.6 (4) | O1i—Cu1—O1—C1 | 164.9 (3) |
C9—C8—N1—C7 | 152.6 (2) | O2—Cu1—O1—C1 | −99.4 (2) |
C9—C8—N1—Cu1 | −31.5 (2) | Cu1i—Cu1—O1—C1 | 164.9 (3) |
N2—Cu1—N1—C7 | −168.4 (2) | N2—Cu1—O1—Cu1i | −54.2 (4) |
O1—Cu1—N1—C7 | 1.8 (2) | N1—Cu1—O1—Cu1i | −168.81 (10) |
O1i—Cu1—N1—C7 | −62.0 (5) | O1i—Cu1—O1—Cu1i | 0.0 |
O2—Cu1—N1—C7 | 97.0 (2) | O2—Cu1—O1—Cu1i | 95.78 (9) |
Cu1i—Cu1—N1—C7 | −8.2 (3) | N2—Cu1—O2—C11 | −144.7 (2) |
N2—Cu1—N1—C8 | 15.90 (17) | N1—Cu1—O2—C11 | −54.2 (2) |
O1—Cu1—N1—C8 | −173.91 (17) | O1—Cu1—O2—C11 | 40.7 (2) |
O1i—Cu1—N1—C8 | 122.3 (4) | O1i—Cu1—O2—C11 | 121.4 (2) |
O2—Cu1—N1—C8 | −78.71 (17) | Cu1i—Cu1—O2—C11 | 81.1 (2) |
Cu1i—Cu1—N1—C8 | 176.09 (13) |
Symmetry code: (i) −x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10···O6ii | 0.93 | 2.58 | 3.456 (4) | 156 |
C7—H7···O4iii | 0.93 | 2.53 | 3.364 (3) | 150 |
C5—H5···O2iv | 0.93 | 2.43 | 3.319 (3) | 161 |
C3—H3···O5v | 0.93 | 2.56 | 3.431 (4) | 156 |
C9—H9A···O5vi | 0.97 | 2.52 | 3.321 (4) | 140 |
O2—H2···O4vi | 0.81 (1) | 2.57 (4) | 3.195 (3) | 135 (4) |
O2—H2···O3vi | 0.81 (1) | 2.20 (2) | 2.993 (4) | 166 (5) |
Symmetry codes: (ii) x−1, y−1, z; (iii) −x+1, −y, −z; (iv) x+1, y, z; (v) −x+1, −y+1, −z+1; (vi) −x, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C20H16F2N4O2)(CH4O)2](ClO4)2 |
Mr | 772.43 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 7.8124 (13), 8.4132 (15), 10.8144 (18) |
α, β, γ (°) | 103.127 (3), 96.272 (3), 97.569 (3) |
V (Å3) | 679.0 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 1.85 |
Crystal size (mm) | 0.20 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.709, 0.837 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3953, 2633, 2268 |
Rint | 0.011 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.086, 1.07 |
No. of reflections | 2633 |
No. of parameters | 203 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.31, −0.24 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXTL (Bruker, 2000).
D—H···A | D—H | H···A | D···A | D—H···A |
C10—H10···O6i | 0.93 | 2.58 | 3.456 (4) | 156 |
C7—H7···O4ii | 0.93 | 2.53 | 3.364 (3) | 150 |
C5—H5···O2iii | 0.93 | 2.43 | 3.319 (3) | 161 |
C3—H3···O5iv | 0.93 | 2.56 | 3.431 (4) | 156 |
C9—H9A···O5v | 0.97 | 2.52 | 3.321 (4) | 140 |
O2—H2···O4v | 0.810 (10) | 2.57 (4) | 3.195 (3) | 135 (4) |
O2—H2···O3v | 0.810 (10) | 2.199 (16) | 2.993 (4) | 166 (5) |
Symmetry codes: (i) x−1, y−1, z; (ii) −x+1, −y, −z; (iii) x+1, y, z; (iv) −x+1, −y+1, −z+1; (v) −x, −y, −z. |
Since the Robson-style homodinuclear macrocyclic complexes were synthesized via template condensation, there has been an increasing interest in the research of these complexes (Pilkington & Robson, 1970; Aono et al., 1997). In the past, most of these complexes were synthesized by cyclocondensation between 2,6-diformyl-4-R-phenol (R = CH3, Cl, Br, CH3O, n-butyl) and alkylenediamine by stepwise template reaction (Gou & Fenton, 1994; Adams et al., 1995). But only a few crystal structures of the complexes with fluorophenyl substituents have been published (Chen et al., 2005; Chen et al., 2007). In this paper, we report the synthesis and crystal structure of the title complex with fluorophenyl substituents.
The crystal structure of the title complex is shown in Fig. 1. Selected bond distances and angles relevant to the coordination geometries of copper atoms are listed in Table 1. Each copper atom is coordinated by two endogenous phenolic O atoms, two azomethine nitrogen atoms and one oxygen atom from methanol molecule. The coordination polyhedron of each CuII can be described as distorted tetragonal pyramid. The deviation of Cu1 and Cu1* from the mean plane of atoms N1, N2, O1, O1* [mean deviation = 0.0182 (3) Å] and N1*, N2*, O1, O1* [mean deviation = 0.0182 (3) Å] are 0.1713 (3)Å and -0.1714 (3) Å, respectively. The two atom groups O1, O1*, Cu1, Cu1* and N1, N2, N1*, N2* are almost coplanar with the dihedral angle of the two planes 7.0 (3)°. The parallelogram formed by atoms N1, N2, N1*, N2* approximates a rectangle with the angle of N1—N2—N1* 89.7 (3)°. The Cu···Cu distance is 2.8998 (7) Å. The Cu—N bond lengths are 1.886 (2) and 1.885 (2) Å. the Cu—O bondlengths to the methanol molecule are both 2.364 (2) Å, which is much longer than those for the phenolic O atoms [1.8905 (17)Å and 1.9021 (17) Å]. The crystal structure of is stabilized by intramolecular and intermolecular hydrogen bonds of types O—H···O and C—H···O, where O atoms belong to methanol molecules or perchlorate ions.