Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805028631/om6259sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805028631/om6259Isup2.hkl |
CCDC reference: 287690
Synthesis of the ligand L was accomplished by minor variation of the published literature procedure, using 4-pyridine carboxaldehyde rather than 3-pyridine carboxaldehyde (Dong et al., 2000b). Cu(tta)2 was prepared in bulk as follows: thenoyltrifluoroacetone (Htta, 10 mmol) and NaOH (10 mmol) were added to ethanol (50 ml) to deprotonate the tta ligand (tta−). Then CuCl2·2H2O (5 mmol) was added to the tta− solution to produce Cu(tta)2 as a light-green precipitate. The precipitate was harvested by vacuum filtration and washed with cold ethanol for use in the next step. The title compound was obtained by slow diffusion of a solution containing L (0.1 mmol) dissolved in ethanol (8 ml) into a solution of Cu(tta)2 (0.1 mmol) dissolved in methylene chloride (8 ml). Initially, the two solutions were carefully layered, and emerald-green crystals appeared at the interface of the two solutions after several weeks.
Non-hydrogen atoms were refined with anisotropic displacement parameters. Hydrogen atoms were placed in geometrically idealized positions and included as riding atoms with C—H distances fixed at 0.93 Å.
Solution of the structure of 1 was routine with one notable exception. The thiophene ring of the tta ligand is disordered; and the disorder is modeled as a two-component rotational disorder about the ipso carbon bond (C10 - C11). Both disorder components lie essentially in the same plane. The geometry of the minor component (C7B - C10B, S1B) was restrained to be similar to that of the major component (C7A - C10A, S1A). The pivot atom C10(A/B) is common to both components, and atoms less than 0.5 Å from their disorder counterparts were assigned equal displacement parameters. The total occupancy was restrained to sum to unity. The final refined occupancies are A/B = 0.773 (3)/0.227 (3).
Data collection: SMART (Bruker, 2001 or? 1998); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL V6.1 (Sheldrick, 2000); software used to prepare material for publication: SHELXTL V6.1.
[Cu(C8H4F3O2S)2(C12H10N4)] | Z = 1 |
Mr = 716.12 | F(000) = 361 |
Triclinic, P1 | Dx = 1.603 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.6890 (11) Å | Cell parameters from 4033 reflections |
b = 9.7518 (13) Å | θ = 2.3–25.1° |
c = 10.2035 (13) Å | µ = 0.96 mm−1 |
α = 116.398 (2)° | T = 294 K |
β = 99.417 (2)° | Prism, green |
γ = 97.919 (2)° | 0.30 × 0.24 × 0.20 mm |
V = 741.99 (17) Å3 |
Bruker SMART APEX CCD diffractometer | 2577 independent reflections |
Radiation source: fine-focus sealed tube | 2495 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
ω scans | θmax = 25.1°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −10→10 |
Tmin = 0.658, Tmax = 0.830 | k = −11→11 |
4780 measured reflections | l = −12→12 |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0508P)2 + 0.2977P] where P = (Fo2 + 2Fc2)/3 |
2577 reflections | (Δ/σ)max < 0.001 |
218 parameters | Δρmax = 0.31 e Å−3 |
10 restraints | Δρmin = −0.36 e Å−3 |
[Cu(C8H4F3O2S)2(C12H10N4)] | γ = 97.919 (2)° |
Mr = 716.12 | V = 741.99 (17) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.6890 (11) Å | Mo Kα radiation |
b = 9.7518 (13) Å | µ = 0.96 mm−1 |
c = 10.2035 (13) Å | T = 294 K |
α = 116.398 (2)° | 0.30 × 0.24 × 0.20 mm |
β = 99.417 (2)° |
Bruker SMART APEX CCD diffractometer | 2577 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2495 reflections with I > 2σ(I) |
Tmin = 0.658, Tmax = 0.830 | Rint = 0.027 |
4780 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | 10 restraints |
wR(F2) = 0.095 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.31 e Å−3 |
2577 reflections | Δρmin = −0.36 e Å−3 |
218 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 | Occ. (<1) | |
Cu1 | 0.5000 | 0.5000 | 0.0000 | 0.03727 (14) | |
C1 | 0.2040 (3) | 0.5213 (3) | 0.1210 (3) | 0.0537 (6) | |
H1 | 0.1703 | 0.4159 | 0.0473 | 0.064* | |
C2 | 0.0957 (3) | 0.5909 (3) | 0.1978 (3) | 0.0548 (6) | |
H2 | −0.0079 | 0.5327 | 0.1764 | 0.066* | |
C3 | 0.1425 (3) | 0.7480 (3) | 0.3069 (3) | 0.0481 (5) | |
C4 | 0.3022 (3) | 0.8251 (3) | 0.3399 (3) | 0.0531 (6) | |
H4 | 0.3406 | 0.9290 | 0.4163 | 0.064* | |
C5 | 0.4024 (3) | 0.7470 (3) | 0.2590 (3) | 0.0531 (6) | |
H5 | 0.5088 | 0.8002 | 0.2829 | 0.064* | |
C6 | 0.0248 (3) | 0.8277 (3) | 0.3776 (3) | 0.0526 (6) | |
H6 | −0.0810 | 0.7717 | 0.3509 | 0.063* | |
S1A | 0.18025 (19) | −0.01533 (17) | −0.17703 (13) | 0.0749 (4) | 0.773 (3) |
C7A | 0.0985 (12) | −0.1689 (9) | −0.1537 (10) | 0.078 (2) | 0.773 (3) |
H7A | 0.0196 | −0.2560 | −0.2283 | 0.093* | 0.773 (3) |
C8A | 0.1589 (10) | −0.1515 (13) | −0.0182 (12) | 0.076 (2) | 0.773 (3) |
H8A | 0.1310 | −0.2255 | 0.0132 | 0.092* | 0.773 (3) |
C9A | 0.2734 (16) | −0.0027 (14) | 0.0739 (12) | 0.0702 (14) | 0.773 (3) |
H9A | 0.3246 | 0.0324 | 0.1745 | 0.084* | 0.773 (3) |
C10A | 0.2998 (3) | 0.0806 (3) | 0.0023 (3) | 0.0486 (5) | 0.773 (3) |
S1B | 0.2897 (14) | −0.0111 (12) | 0.1091 (10) | 0.0702 (14) | 0.227 (3) |
C7B | 0.125 (4) | −0.151 (5) | −0.020 (4) | 0.076 (2) | 0.227 (3) |
H7B | 0.0665 | −0.2268 | −0.0045 | 0.092* | 0.227 (3) |
C8B | 0.089 (5) | −0.140 (4) | −0.146 (3) | 0.078 (2) | 0.227 (3) |
H8B | 0.0079 | −0.2100 | −0.2309 | 0.093* | 0.227 (3) |
C9B | 0.194 (3) | −0.003 (2) | −0.1318 (15) | 0.0749 (4) | 0.227 (3) |
H9B | 0.1883 | 0.0233 | −0.2090 | 0.090* | 0.227 (3) |
C10B | 0.2998 (3) | 0.0806 (3) | 0.0023 (3) | 0.0486 (5) | 0.227 (3) |
C11 | 0.4094 (3) | 0.2333 (3) | 0.0550 (3) | 0.0432 (5) | |
C12 | 0.5098 (3) | 0.3102 (3) | 0.2010 (3) | 0.0528 (6) | |
H12 | 0.4956 | 0.2665 | 0.2640 | 0.063* | |
C13 | 0.6291 (3) | 0.4468 (3) | 0.2592 (3) | 0.0507 (5) | |
C14 | 0.7235 (4) | 0.5171 (4) | 0.4238 (4) | 0.0777 (9) | |
F1 | 0.6929 (4) | 0.4315 (3) | 0.4883 (3) | 0.1459 (13) | |
F2 | 0.6961 (3) | 0.6568 (3) | 0.5064 (2) | 0.1215 (9) | |
F3 | 0.8803 (2) | 0.5471 (3) | 0.4360 (3) | 0.1191 (8) | |
N1 | 0.3544 (2) | 0.5974 (2) | 0.1469 (2) | 0.0461 (4) | |
N2 | 0.0653 (3) | 0.9717 (3) | 0.4746 (3) | 0.0586 (5) | |
O1 | 0.4021 (2) | 0.28584 (18) | −0.03896 (18) | 0.0471 (4) | |
O2 | 0.6728 (2) | 0.5257 (2) | 0.1969 (2) | 0.0544 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0385 (2) | 0.0342 (2) | 0.0402 (2) | 0.00695 (15) | 0.01063 (15) | 0.01903 (16) |
C1 | 0.0480 (13) | 0.0381 (12) | 0.0639 (15) | 0.0050 (10) | 0.0066 (11) | 0.0190 (11) |
C2 | 0.0432 (12) | 0.0442 (14) | 0.0679 (15) | 0.0033 (10) | 0.0087 (11) | 0.0229 (12) |
C3 | 0.0486 (12) | 0.0441 (13) | 0.0490 (12) | 0.0064 (10) | 0.0076 (10) | 0.0229 (11) |
C4 | 0.0530 (13) | 0.0442 (13) | 0.0484 (12) | 0.0027 (11) | 0.0088 (10) | 0.0143 (11) |
C5 | 0.0448 (12) | 0.0497 (14) | 0.0526 (13) | 0.0011 (10) | 0.0054 (10) | 0.0191 (11) |
C6 | 0.0475 (13) | 0.0500 (15) | 0.0565 (14) | 0.0065 (10) | 0.0110 (11) | 0.0244 (12) |
S1A | 0.0853 (7) | 0.0645 (7) | 0.0608 (7) | −0.0038 (5) | −0.0058 (6) | 0.0322 (7) |
C7A | 0.073 (2) | 0.047 (4) | 0.086 (2) | −0.003 (3) | −0.003 (2) | 0.022 (3) |
C8A | 0.073 (5) | 0.0621 (19) | 0.092 (2) | −0.007 (3) | 0.008 (3) | 0.0455 (18) |
C9A | 0.087 (2) | 0.0563 (15) | 0.077 (4) | −0.0044 (14) | 0.010 (3) | 0.049 (2) |
C10A | 0.0486 (12) | 0.0464 (13) | 0.0533 (13) | 0.0116 (10) | 0.0130 (10) | 0.0260 (11) |
S1B | 0.087 (2) | 0.0563 (15) | 0.077 (4) | −0.0044 (14) | 0.010 (3) | 0.049 (2) |
C7B | 0.073 (5) | 0.0621 (19) | 0.092 (2) | −0.007 (3) | 0.008 (3) | 0.0455 (18) |
C8B | 0.073 (2) | 0.047 (4) | 0.086 (2) | −0.003 (3) | −0.003 (2) | 0.022 (3) |
C9B | 0.0853 (7) | 0.0645 (7) | 0.0608 (7) | −0.0038 (5) | −0.0058 (6) | 0.0322 (7) |
C10B | 0.0486 (12) | 0.0464 (13) | 0.0533 (13) | 0.0116 (10) | 0.0130 (10) | 0.0260 (11) |
C11 | 0.0433 (11) | 0.0423 (12) | 0.0526 (12) | 0.0143 (9) | 0.0187 (10) | 0.0266 (10) |
C12 | 0.0536 (13) | 0.0546 (15) | 0.0569 (14) | 0.0055 (11) | 0.0096 (11) | 0.0358 (12) |
C13 | 0.0443 (12) | 0.0549 (14) | 0.0573 (13) | 0.0116 (11) | 0.0115 (10) | 0.0311 (12) |
C14 | 0.0652 (18) | 0.083 (2) | 0.0727 (19) | −0.0088 (16) | −0.0084 (15) | 0.0429 (18) |
F1 | 0.160 (2) | 0.156 (2) | 0.0983 (16) | −0.0595 (19) | −0.0478 (16) | 0.0957 (17) |
F2 | 0.141 (2) | 0.1082 (18) | 0.0659 (12) | 0.0149 (16) | 0.0045 (13) | 0.0114 (12) |
F3 | 0.0629 (12) | 0.152 (2) | 0.1292 (18) | −0.0043 (13) | −0.0233 (12) | 0.0805 (17) |
N1 | 0.0440 (10) | 0.0388 (10) | 0.0509 (10) | 0.0070 (8) | 0.0064 (8) | 0.0202 (9) |
N2 | 0.0519 (12) | 0.0529 (13) | 0.0609 (12) | 0.0102 (10) | 0.0158 (10) | 0.0187 (11) |
O1 | 0.0559 (9) | 0.0414 (8) | 0.0475 (8) | 0.0096 (7) | 0.0150 (7) | 0.0242 (7) |
O2 | 0.0497 (9) | 0.0517 (10) | 0.0631 (10) | 0.0041 (7) | 0.0135 (8) | 0.0310 (9) |
Cu1—O1i | 1.9759 (15) | C7A—H7A | 0.9300 |
Cu1—O1 | 1.9759 (15) | C8A—C9A | 1.436 (11) |
Cu1—N1i | 2.1062 (19) | C8A—H8A | 0.9300 |
Cu1—N1 | 2.1062 (19) | C9A—C10A | 1.333 (7) |
Cu1—O2i | 2.1950 (18) | C9A—H9A | 0.9300 |
Cu1—O2 | 2.1950 (18) | C10A—C11 | 1.464 (3) |
C1—N1 | 1.331 (3) | S1B—C7B | 1.700 (8) |
C1—C2 | 1.380 (3) | C7B—C8B | 1.322 (6) |
C1—H1 | 0.9300 | C7B—H7B | 0.9300 |
C2—C3 | 1.384 (3) | C8B—C9B | 1.438 (12) |
C2—H2 | 0.9300 | C8B—H8B | 0.9300 |
C3—C4 | 1.393 (3) | C9B—H9B | 0.9300 |
C3—C6 | 1.460 (3) | C11—O1 | 1.270 (3) |
C4—C5 | 1.370 (4) | C11—C12 | 1.394 (3) |
C4—H4 | 0.9300 | C12—C13 | 1.384 (3) |
C5—N1 | 1.343 (3) | C12—H12 | 0.9300 |
C5—H5 | 0.9300 | C13—O2 | 1.254 (3) |
C6—N2 | 1.261 (3) | C13—C14 | 1.527 (4) |
C6—H6 | 0.9300 | C14—F1 | 1.299 (4) |
S1A—C7A | 1.698 (6) | C14—F2 | 1.326 (4) |
S1A—C10A | 1.700 (2) | C14—F3 | 1.327 (4) |
C7A—C8A | 1.320 (5) | N2—N2ii | 1.404 (4) |
O1i—Cu1—O1 | 180.0 | C7A—C8A—C9A | 110.7 (6) |
O1i—Cu1—N1i | 90.97 (7) | C7A—C8A—H8A | 124.6 |
O1—Cu1—N1i | 89.03 (7) | C9A—C8A—H8A | 124.6 |
O1i—Cu1—N1 | 89.03 (7) | C10A—C9A—C8A | 114.0 (6) |
O1—Cu1—N1 | 90.97 (7) | C10A—C9A—H9A | 123.0 |
N1i—Cu1—N1 | 180.0 | C8A—C9A—H9A | 123.0 |
O1i—Cu1—O2i | 88.01 (6) | C9A—C10A—C11 | 130.4 (5) |
O1—Cu1—O2i | 91.99 (6) | C9A—C10A—S1A | 110.3 (5) |
N1i—Cu1—O2i | 87.16 (7) | C11—C10A—S1A | 119.30 (17) |
N1—Cu1—O2i | 92.84 (7) | C8B—C7B—S1B | 112.8 (7) |
O1i—Cu1—O2 | 91.99 (6) | C8B—C7B—H7B | 123.6 |
O1—Cu1—O2 | 88.01 (6) | S1B—C7B—H7B | 123.6 |
N1i—Cu1—O2 | 92.84 (7) | C7B—C8B—C9B | 110.7 (9) |
N1—Cu1—O2 | 87.16 (7) | C7B—C8B—H8B | 124.6 |
O2i—Cu1—O2 | 180.00 (8) | C9B—C8B—H8B | 124.6 |
N1—C1—C2 | 123.3 (2) | C8B—C9B—H9B | 123.3 |
N1—C1—H1 | 118.3 | O1—C11—C12 | 125.2 (2) |
C2—C1—H1 | 118.3 | O1—C11—C10A | 115.5 (2) |
C1—C2—C3 | 119.5 (2) | C12—C11—C10A | 119.25 (19) |
C1—C2—H2 | 120.3 | C13—C12—C11 | 124.9 (2) |
C3—C2—H2 | 120.3 | C13—C12—H12 | 117.6 |
C2—C3—C4 | 117.1 (2) | C11—C12—H12 | 117.6 |
C2—C3—C6 | 120.1 (2) | O2—C13—C12 | 129.5 (2) |
C4—C3—C6 | 122.7 (2) | O2—C13—C14 | 113.1 (2) |
C5—C4—C3 | 119.6 (2) | C12—C13—C14 | 117.4 (2) |
C5—C4—H4 | 120.2 | F1—C14—F2 | 107.6 (3) |
C3—C4—H4 | 120.2 | F1—C14—F3 | 108.1 (3) |
N1—C5—C4 | 123.2 (2) | F2—C14—F3 | 104.3 (3) |
N1—C5—H5 | 118.4 | F1—C14—C13 | 115.2 (3) |
C4—C5—H5 | 118.4 | F2—C14—C13 | 110.2 (3) |
N2—C6—C3 | 120.6 (2) | F3—C14—C13 | 110.8 (3) |
N2—C6—H6 | 119.7 | C1—N1—C5 | 117.1 (2) |
C3—C6—H6 | 119.7 | C1—N1—Cu1 | 121.50 (16) |
C7A—S1A—C10A | 92.1 (2) | C5—N1—Cu1 | 120.86 (16) |
C8A—C7A—S1A | 112.8 (5) | C6—N2—N2ii | 112.2 (3) |
C8A—C7A—H7A | 123.6 | C11—O1—Cu1 | 127.61 (15) |
S1A—C7A—H7A | 123.6 | C13—O2—Cu1 | 117.51 (15) |
N1—C1—C2—C3 | 0.6 (4) | O2—C13—C14—F3 | −50.6 (4) |
C1—C2—C3—C4 | −4.0 (4) | C12—C13—C14—F3 | 130.0 (3) |
C1—C2—C3—C6 | 173.5 (2) | C2—C1—N1—C5 | 3.3 (4) |
C2—C3—C4—C5 | 3.6 (4) | C2—C1—N1—Cu1 | −168.2 (2) |
C6—C3—C4—C5 | −173.8 (2) | C4—C5—N1—C1 | −3.7 (4) |
C3—C4—C5—N1 | 0.3 (4) | C4—C5—N1—Cu1 | 167.8 (2) |
C2—C3—C6—N2 | −178.3 (3) | O1i—Cu1—N1—C1 | 144.57 (19) |
C4—C3—C6—N2 | −1.0 (4) | O1—Cu1—N1—C1 | −35.43 (19) |
C10A—S1A—C7A—C8A | −0.8 (10) | O2i—Cu1—N1—C1 | 56.60 (19) |
S1A—C7A—C8A—C9A | 2.3 (15) | O2—Cu1—N1—C1 | −123.40 (19) |
C7A—C8A—C9A—C10A | −3.2 (17) | O1i—Cu1—N1—C5 | −26.58 (19) |
C8A—C9A—C10A—C11 | −178.1 (8) | O1—Cu1—N1—C5 | 153.42 (19) |
C8A—C9A—C10A—S1A | 2.5 (13) | O2i—Cu1—N1—C5 | −114.54 (19) |
C7A—S1A—C10A—C9A | −1.0 (9) | O2—Cu1—N1—C5 | 65.46 (19) |
C7A—S1A—C10A—C11 | 179.5 (5) | C3—C6—N2—N2ii | 177.9 (3) |
C9A—C10A—C11—O1 | −177.0 (9) | C12—C11—O1—Cu1 | −10.6 (3) |
S1A—C10A—C11—O1 | 2.4 (3) | C10A—C11—O1—Cu1 | 168.33 (14) |
C9A—C10A—C11—C12 | 1.9 (9) | N1i—Cu1—O1—C11 | 115.73 (18) |
S1A—C10A—C11—C12 | −178.67 (19) | N1—Cu1—O1—C11 | −64.27 (18) |
O1—C11—C12—C13 | −7.7 (4) | O2i—Cu1—O1—C11 | −157.15 (18) |
C10A—C11—C12—C13 | 173.5 (2) | O2—Cu1—O1—C11 | 22.85 (18) |
C11—C12—C13—O2 | −1.3 (4) | C12—C13—O2—Cu1 | 22.3 (3) |
C11—C12—C13—C14 | 178.1 (3) | C14—C13—O2—Cu1 | −157.1 (2) |
O2—C13—C14—F1 | −173.7 (3) | O1i—Cu1—O2—C13 | 152.88 (18) |
C12—C13—C14—F1 | 6.9 (5) | O1—Cu1—O2—C13 | −27.12 (18) |
O2—C13—C14—F2 | 64.4 (3) | N1i—Cu1—O2—C13 | −116.06 (18) |
C12—C13—C14—F2 | −115.1 (3) | N1—Cu1—O2—C13 | 63.95 (18) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C8H4F3O2S)2(C12H10N4)] |
Mr | 716.12 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 294 |
a, b, c (Å) | 8.6890 (11), 9.7518 (13), 10.2035 (13) |
α, β, γ (°) | 116.398 (2), 99.417 (2), 97.919 (2) |
V (Å3) | 741.99 (17) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 0.96 |
Crystal size (mm) | 0.30 × 0.24 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.658, 0.830 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4780, 2577, 2495 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.095, 1.07 |
No. of reflections | 2577 |
No. of parameters | 218 |
No. of restraints | 10 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.36 |
Computer programs: SMART (Bruker, 2001 or? 1998), SAINT-Plus (Bruker, 2001), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL V6.1 (Sheldrick, 2000), SHELXTL V6.1.
Cu1—O1 | 1.9759 (15) | Cu1—O2 | 2.1950 (18) |
Cu1—N1 | 2.1062 (19) | N2—N2i | 1.404 (4) |
O1ii—Cu1—O1 | 180.0 | O1—Cu1—O2 | 88.01 (6) |
O1—Cu1—N1 | 90.97 (7) | N1—Cu1—O2 | 87.16 (7) |
N1ii—Cu1—N1 | 180.0 | O2ii—Cu1—O2 | 180.00 (8) |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) −x+1, −y+1, −z. |
The synthesis of new coordination polymers has interested chemists and materials scientists because of the potential applications of these materials in a variety of areas, including catalysis, optical applications and gas sorption (Atto et al., 1999; Wang et al., 1995; Chen et al., 1998). Our group has been interested in the synthesis of new N,N'-type organic ligands for the construction of new inorganic–organic coordination polymers. To this end, we have been successful in the synthesis of several Schiff base ligands, such as 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene (L), which have resulted in the generation of many new coordination compounds (Dong et al., 2000; Dong et al., 2000a). The title compound, catena-poly[Cu(L)2(tta)2] (tta is α-thenoyltrifluoroacetonato), (I), is a new example of a one-dimensional coordination polymer that uses an N,N'-type Schiff base ligand in its construction.
Compound (I) was prepared by the room temperature layering reaction of Cu(tta)2 in methylene chloride with the ligand (L) in ethanol. Emerald-green crystals formed upon diffusion of the two solutions into one another over the course of several weeks, and a suitable single-crystal was selected for the structure determination. In (I), Cu2+ centers are found in a distorted octahedral coordination environment and they are located on sites of crystallographic inversion symmetry. Consequently, each Cu2+ center is coordinated by pairs of symmetry-related ligands. A symmetry-related pair of tta ligands occupies the equatorial positions of Cu2+, with each tta ligand coordinated through its O atoms in a bidentate fashion. Two pyridyl N donor atoms, one from each of two different symmetry related L ligands, complete the octahedral coordination sphere by occupying the axial positions. The average Cu—O bond length is 2.085 Å, the Cu—N bond distance is 2.1062 (19) Å, and the intrachain distance between successive Cu centers is approximately 15.4 Å. The Cu—O and Cu—N distances are typical (Yang et al., 2001; Lingafelter & Braun, 1966), and the Cu···Cu distance provides an estimate of the length of L. The octahedrally coordinated Cu2+ centers are linked into one-dimensional chains by L, with each N-atom donor of a single L coordinated to two different Cu centers.
The packing arrangement of the one-dimensional chains is shown in Fig. 2, where it can be seen that the chains extend approximately along the body diagonal of the unit cell, in the crystallographic [111] direction.