Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111004641/gg3247sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111004641/gg3247Isup2.hkl |
CCDC reference: 824029
A round-bottomed flask was charged with Cu(CF3SO3)2 (1 equivalent, 0.28 mmol, 101 mg) and bromophenylterpyridine (1 equivalent, 0.28 mmol, 109 mg) in acetonitrile (10 ml) with a stirring bar. To increase the solubility of the organic ligand, chloroform (5 ml) was added to the reaction mixture. The reaction was heated at 358 K for 3 h and then slowly cooled to room temperature under magnetic stirring. A deep-green [Blue given in CIF - please clarify] crystalline solid was formed. The crystals were filtered off and characterized as the title compound (yield 80 mg; 45%). HRMS (ESI): m/z = 486.93614 (C21H14BrClCuN3 requires 487.25896).
Although the reaction procedure does not involve the Cl- anion, it seems that the presence of copper and air photocatalysed the decomposition of the chloroform solvent to form the chloride anion, which was then available to coordinate to the metal centre so as to give rise to the title compound.
The H atoms were generated geometrically, with C—H = 0.95 Å, and were included in the refinement in the riding-model approximation, with Uiso(H) = 1.2Ueq(C).
Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: UdMX (Maris, 2004) and XPREP (Bruker, 2008).
[Cu(CF3O3S)Cl(C21H14BrN3)] | F(000) = 1260 |
Mr = 636.32 | Dx = 1.829 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54178 Å |
Hall symbol: -P 2yn | Cell parameters from 28837 reflections |
a = 7.7841 (2) Å | θ = 3.6–69.4° |
b = 16.3043 (4) Å | µ = 5.78 mm−1 |
c = 18.2533 (4) Å | T = 150 K |
β = 93.884 (1)° | Block, blue |
V = 2311.28 (10) Å3 | 0.10 × 0.06 × 0.06 mm |
Z = 4 |
Bruker Microstar diffractometer | 4344 independent reflections |
Radiation source: rotating anode | 4016 reflections with I > 2σ(I) |
Helios optics monochromator | Rint = 0.039 |
Detector resolution: 8.3 pixels mm-1 | θmax = 69.6°, θmin = 3.6° |
ω scans | h = −8→9 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −19→19 |
Tmin = 0.452, Tmax = 0.707 | l = −22→22 |
47414 measured reflections |
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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0486P)2 + 0.8516P] where P = (Fo2 + 2Fc2)/3 |
4344 reflections | (Δ/σ)max = 0.002 |
316 parameters | Δρmax = 0.71 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
[Cu(CF3O3S)Cl(C21H14BrN3)] | V = 2311.28 (10) Å3 |
Mr = 636.32 | Z = 4 |
Monoclinic, P21/n | Cu Kα radiation |
a = 7.7841 (2) Å | µ = 5.78 mm−1 |
b = 16.3043 (4) Å | T = 150 K |
c = 18.2533 (4) Å | 0.10 × 0.06 × 0.06 mm |
β = 93.884 (1)° |
Bruker Microstar diffractometer | 4344 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4016 reflections with I > 2σ(I) |
Tmin = 0.452, Tmax = 0.707 | Rint = 0.039 |
47414 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.073 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.71 e Å−3 |
4344 reflections | Δρmin = −0.33 e Å−3 |
316 parameters |
Experimental. X-ray crystallographic data for (I) were collected from a single-crystal sample, which was mounted on a loop fiber. Data were collected using a Bruker Microstar diffractometer equipped with a Platinum 135 CCD detector, Helios optics and a Kappa goniometer. The crystal-to-detector distance was 4.0 cm, and the data collection was carried out in 512 × 512 pixel mode. The initial unit-cell parameters were determined by a least-squares fit of the angular setting of strong reflections, collected by a 3.0 degree scan in 33 frames over three different parts of the reciprocal space (99 frames total). |
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 | 0.40934 (3) | 0.905424 (16) | 0.454742 (14) | 0.02276 (9) | |
Cl1 | 0.23317 (6) | 1.00983 (3) | 0.43312 (3) | 0.03348 (12) | |
Br1 | 1.37255 (3) | 0.442745 (14) | 0.598587 (12) | 0.03687 (9) | |
N1 | 0.57990 (19) | 0.92948 (9) | 0.37810 (8) | 0.0231 (3) | |
N2 | 0.58819 (18) | 0.82762 (9) | 0.48463 (8) | 0.0209 (3) | |
N3 | 0.31217 (19) | 0.85826 (10) | 0.54644 (8) | 0.0236 (3) | |
C1 | 0.5655 (3) | 0.98667 (12) | 0.32572 (10) | 0.0285 (4) | |
H1 | 0.4641 | 1.0192 | 0.3208 | 0.034* | |
C2 | 0.6944 (3) | 0.99998 (13) | 0.27832 (11) | 0.0327 (4) | |
H2 | 0.6810 | 1.0409 | 0.2413 | 0.039* | |
C3 | 0.8423 (3) | 0.95322 (13) | 0.28537 (11) | 0.0340 (4) | |
H3 | 0.9325 | 0.9620 | 0.2537 | 0.041* | |
C4 | 0.8578 (2) | 0.89316 (13) | 0.33935 (11) | 0.0287 (4) | |
H4 | 0.9583 | 0.8601 | 0.3451 | 0.034* | |
C5 | 0.7237 (2) | 0.88245 (11) | 0.38458 (10) | 0.0228 (4) | |
C6 | 0.7257 (2) | 0.82202 (11) | 0.44488 (9) | 0.0215 (4) | |
C7 | 0.8529 (2) | 0.76442 (11) | 0.46223 (10) | 0.0224 (4) | |
H7 | 0.9488 | 0.7595 | 0.4330 | 0.027* | |
C8 | 0.8381 (2) | 0.71359 (11) | 0.52336 (10) | 0.0219 (4) | |
C9 | 0.6976 (2) | 0.72503 (11) | 0.56646 (10) | 0.0226 (4) | |
H9 | 0.6879 | 0.6939 | 0.6100 | 0.027* | |
C10 | 0.5732 (2) | 0.78236 (11) | 0.54474 (9) | 0.0217 (4) | |
C11 | 0.4136 (2) | 0.80105 (11) | 0.58155 (10) | 0.0227 (4) | |
C12 | 0.3674 (2) | 0.76315 (12) | 0.64508 (10) | 0.0273 (4) | |
H12 | 0.4416 | 0.7242 | 0.6696 | 0.033* | |
C13 | 0.2098 (3) | 0.78326 (13) | 0.67239 (11) | 0.0320 (4) | |
H13 | 0.1745 | 0.7578 | 0.7157 | 0.038* | |
C14 | 0.1061 (2) | 0.84039 (14) | 0.63582 (11) | 0.0331 (4) | |
H14 | −0.0023 | 0.8543 | 0.6534 | 0.040* | |
C15 | 0.1608 (2) | 0.87752 (13) | 0.57309 (11) | 0.0290 (4) | |
H15 | 0.0894 | 0.9175 | 0.5484 | 0.035* | |
C16 | 0.9671 (2) | 0.64860 (11) | 0.54150 (10) | 0.0232 (4) | |
C17 | 1.1343 (2) | 0.65440 (12) | 0.51783 (10) | 0.0256 (4) | |
H17 | 1.1651 | 0.7006 | 0.4898 | 0.031* | |
C18 | 1.2551 (2) | 0.59374 (12) | 0.53468 (11) | 0.0288 (4) | |
H18 | 1.3687 | 0.5985 | 0.5192 | 0.035* | |
C19 | 1.2083 (2) | 0.52629 (12) | 0.57431 (10) | 0.0274 (4) | |
C20 | 1.0431 (3) | 0.51764 (13) | 0.59721 (11) | 0.0308 (4) | |
H20 | 1.0121 | 0.4703 | 0.6236 | 0.037* | |
C21 | 0.9241 (2) | 0.57916 (13) | 0.58098 (10) | 0.0280 (4) | |
H21 | 0.8110 | 0.5740 | 0.5970 | 0.034* | |
F1 | 0.02448 (14) | 0.67842 (8) | 0.30605 (7) | 0.0362 (3) | |
F2 | 0.21350 (18) | 0.64436 (8) | 0.23121 (7) | 0.0474 (3) | |
F3 | 0.25878 (18) | 0.62114 (8) | 0.34733 (8) | 0.0482 (3) | |
O1 | 0.25040 (16) | 0.79914 (9) | 0.38212 (7) | 0.0283 (3) | |
O2 | 0.47382 (19) | 0.75758 (12) | 0.30338 (10) | 0.0505 (5) | |
O3 | 0.2102 (2) | 0.82285 (10) | 0.25089 (8) | 0.0436 (4) | |
S3 | 0.29491 (6) | 0.77536 (3) | 0.30915 (2) | 0.02805 (12) | |
C22 | 0.1937 (2) | 0.67463 (13) | 0.29795 (11) | 0.0302 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.01972 (14) | 0.02611 (16) | 0.02256 (15) | 0.00442 (10) | 0.00220 (10) | −0.00067 (10) |
Cl1 | 0.0314 (2) | 0.0307 (2) | 0.0384 (3) | 0.01190 (18) | 0.00304 (19) | −0.00048 (19) |
Br1 | 0.03649 (14) | 0.04247 (15) | 0.03127 (13) | 0.02009 (9) | −0.00053 (9) | −0.00149 (9) |
N1 | 0.0211 (7) | 0.0266 (8) | 0.0214 (7) | 0.0012 (6) | −0.0001 (6) | −0.0001 (6) |
N2 | 0.0172 (7) | 0.0260 (8) | 0.0195 (7) | −0.0003 (6) | 0.0013 (5) | −0.0015 (6) |
N3 | 0.0192 (7) | 0.0299 (8) | 0.0216 (7) | 0.0017 (6) | 0.0018 (6) | −0.0049 (6) |
C1 | 0.0296 (9) | 0.0301 (10) | 0.0252 (9) | 0.0030 (8) | −0.0031 (7) | 0.0017 (7) |
C2 | 0.0404 (11) | 0.0328 (10) | 0.0245 (10) | 0.0000 (9) | 0.0000 (8) | 0.0064 (8) |
C3 | 0.0350 (11) | 0.0402 (11) | 0.0276 (10) | −0.0014 (9) | 0.0072 (8) | 0.0062 (9) |
C4 | 0.0241 (9) | 0.0362 (10) | 0.0262 (9) | 0.0024 (8) | 0.0052 (7) | 0.0046 (8) |
C5 | 0.0214 (8) | 0.0265 (9) | 0.0203 (8) | −0.0001 (7) | −0.0004 (7) | −0.0004 (7) |
C6 | 0.0177 (8) | 0.0273 (9) | 0.0195 (8) | −0.0025 (7) | 0.0014 (6) | −0.0024 (7) |
C7 | 0.0186 (8) | 0.0280 (9) | 0.0208 (8) | 0.0009 (7) | 0.0033 (6) | −0.0001 (7) |
C8 | 0.0186 (8) | 0.0265 (9) | 0.0205 (8) | −0.0004 (7) | −0.0002 (6) | −0.0020 (7) |
C9 | 0.0217 (8) | 0.0277 (9) | 0.0184 (8) | −0.0007 (7) | 0.0016 (7) | 0.0006 (7) |
C10 | 0.0180 (8) | 0.0287 (9) | 0.0184 (8) | −0.0022 (7) | 0.0015 (6) | −0.0025 (7) |
C11 | 0.0182 (8) | 0.0294 (9) | 0.0208 (8) | −0.0010 (7) | 0.0024 (7) | −0.0058 (7) |
C12 | 0.0233 (9) | 0.0365 (10) | 0.0222 (9) | −0.0007 (8) | 0.0026 (7) | −0.0005 (8) |
C13 | 0.0273 (10) | 0.0457 (12) | 0.0240 (10) | −0.0046 (8) | 0.0094 (8) | −0.0036 (8) |
C14 | 0.0217 (9) | 0.0460 (12) | 0.0324 (10) | 0.0005 (8) | 0.0079 (8) | −0.0097 (9) |
C15 | 0.0205 (9) | 0.0368 (10) | 0.0300 (10) | 0.0037 (8) | 0.0024 (7) | −0.0076 (8) |
C16 | 0.0213 (8) | 0.0293 (9) | 0.0188 (8) | 0.0024 (7) | 0.0007 (7) | −0.0005 (7) |
C17 | 0.0221 (9) | 0.0279 (9) | 0.0270 (9) | 0.0005 (7) | 0.0023 (7) | −0.0018 (7) |
C18 | 0.0210 (9) | 0.0360 (11) | 0.0296 (10) | 0.0022 (7) | 0.0033 (7) | −0.0048 (8) |
C19 | 0.0262 (9) | 0.0324 (10) | 0.0232 (9) | 0.0098 (8) | −0.0018 (7) | −0.0035 (7) |
C20 | 0.0323 (10) | 0.0334 (10) | 0.0265 (10) | 0.0038 (8) | 0.0006 (8) | 0.0064 (8) |
C21 | 0.0220 (9) | 0.0363 (10) | 0.0260 (10) | 0.0040 (8) | 0.0035 (7) | 0.0060 (8) |
F1 | 0.0244 (6) | 0.0415 (7) | 0.0428 (7) | −0.0069 (5) | 0.0021 (5) | 0.0005 (5) |
F2 | 0.0514 (8) | 0.0493 (8) | 0.0426 (7) | −0.0129 (6) | 0.0124 (6) | −0.0241 (6) |
F3 | 0.0442 (7) | 0.0413 (7) | 0.0578 (9) | 0.0095 (6) | −0.0045 (6) | 0.0075 (6) |
O1 | 0.0230 (6) | 0.0386 (7) | 0.0237 (7) | −0.0012 (5) | 0.0037 (5) | −0.0085 (5) |
O2 | 0.0244 (7) | 0.0729 (12) | 0.0563 (10) | −0.0121 (7) | 0.0174 (7) | −0.0336 (9) |
O3 | 0.0623 (10) | 0.0418 (9) | 0.0266 (8) | −0.0140 (8) | 0.0024 (7) | 0.0012 (6) |
S3 | 0.0239 (2) | 0.0375 (3) | 0.0235 (2) | −0.00757 (18) | 0.00693 (17) | −0.00897 (18) |
C22 | 0.0251 (9) | 0.0362 (11) | 0.0294 (10) | −0.0006 (8) | 0.0026 (8) | −0.0047 (8) |
Cu1—N1 | 2.0311 (16) | C9—H9 | 0.9500 |
Cu1—N2 | 1.9345 (15) | C10—C11 | 1.483 (2) |
Cu1—N3 | 2.0338 (16) | C11—C12 | 1.383 (3) |
Cu1—Cl1 | 2.2048 (5) | C12—C13 | 1.394 (3) |
Cu1—O1 | 2.4635 (14) | C12—H12 | 0.9500 |
Br1—C19 | 1.8998 (18) | C13—C14 | 1.376 (3) |
N1—C1 | 1.335 (2) | C13—H13 | 0.9500 |
N1—C5 | 1.355 (2) | C14—C15 | 1.387 (3) |
N2—C10 | 1.334 (2) | C14—H14 | 0.9500 |
N2—C6 | 1.336 (2) | C15—H15 | 0.9500 |
N3—C15 | 1.342 (2) | C16—C21 | 1.395 (3) |
N3—C11 | 1.355 (2) | C16—C17 | 1.402 (3) |
C1—C2 | 1.385 (3) | C17—C18 | 1.385 (3) |
C1—H1 | 0.9500 | C17—H17 | 0.9500 |
C2—C3 | 1.380 (3) | C18—C19 | 1.379 (3) |
C2—H2 | 0.9500 | C18—H18 | 0.9500 |
C3—C4 | 1.389 (3) | C19—C20 | 1.386 (3) |
C3—H3 | 0.9500 | C20—C21 | 1.384 (3) |
C4—C5 | 1.385 (3) | C20—H20 | 0.9500 |
C4—H4 | 0.9500 | C21—H21 | 0.9500 |
C5—C6 | 1.476 (2) | F1—C22 | 1.337 (2) |
C6—C7 | 1.386 (3) | F2—C22 | 1.333 (2) |
C7—C8 | 1.401 (3) | F3—C22 | 1.329 (3) |
C7—H7 | 0.9500 | O1—S3 | 1.4515 (13) |
C8—C9 | 1.403 (2) | O2—S3 | 1.4334 (16) |
C8—C16 | 1.482 (3) | O3—S3 | 1.4387 (17) |
C9—C10 | 1.385 (3) | S3—C22 | 1.827 (2) |
N1—Cu1—Cl1 | 98.93 (5) | N2—C10—C11 | 112.44 (15) |
N2—Cu1—Cl1 | 169.69 (5) | C9—C10—C11 | 126.87 (16) |
N3—Cu1—Cl1 | 100.24 (5) | N3—C11—C12 | 121.89 (16) |
N1—Cu1—O1 | 95.34 (5) | N3—C11—C10 | 113.96 (16) |
N1—Cu1—N2 | 80.18 (6) | C12—C11—C10 | 124.14 (17) |
N1—Cu1—N3 | 159.51 (6) | C11—C12—C13 | 118.67 (18) |
N2—Cu1—O1 | 90.92 (5) | C11—C12—H12 | 120.7 |
N2—Cu1—N3 | 79.67 (6) | C13—C12—H12 | 120.7 |
N3—Cu1—O1 | 88.61 (5) | C14—C13—C12 | 119.17 (19) |
Cl1—Cu1—O1 | 99.39 (4) | C14—C13—H13 | 120.4 |
C1—N1—C5 | 119.10 (16) | C12—C13—H13 | 120.4 |
C1—N1—Cu1 | 126.97 (13) | C13—C14—C15 | 119.55 (18) |
C5—N1—Cu1 | 113.90 (12) | C13—C14—H14 | 120.2 |
C10—N2—C6 | 121.81 (15) | C15—C14—H14 | 120.2 |
C10—N2—Cu1 | 119.55 (12) | N3—C15—C14 | 121.53 (18) |
C6—N2—Cu1 | 118.63 (12) | N3—C15—H15 | 119.2 |
C15—N3—C11 | 119.17 (16) | C14—C15—H15 | 119.2 |
C15—N3—Cu1 | 126.47 (13) | C21—C16—C17 | 118.32 (17) |
C11—N3—Cu1 | 114.35 (12) | C21—C16—C8 | 120.87 (16) |
N1—C1—C2 | 121.86 (18) | C17—C16—C8 | 120.79 (17) |
N1—C1—H1 | 119.1 | C18—C17—C16 | 120.93 (18) |
C2—C1—H1 | 119.1 | C18—C17—H17 | 119.5 |
C3—C2—C1 | 119.35 (19) | C16—C17—H17 | 119.5 |
C3—C2—H2 | 120.3 | C19—C18—C17 | 119.11 (17) |
C1—C2—H2 | 120.3 | C19—C18—H18 | 120.4 |
C2—C3—C4 | 119.16 (19) | C17—C18—H18 | 120.4 |
C2—C3—H3 | 120.4 | C18—C19—C20 | 121.53 (18) |
C4—C3—H3 | 120.4 | C18—C19—Br1 | 119.78 (14) |
C5—C4—C3 | 118.65 (19) | C20—C19—Br1 | 118.69 (15) |
C5—C4—H4 | 120.7 | C21—C20—C19 | 118.90 (19) |
C3—C4—H4 | 120.7 | C21—C20—H20 | 120.5 |
N1—C5—C4 | 121.86 (17) | C19—C20—H20 | 120.5 |
N1—C5—C6 | 114.17 (15) | C20—C21—C16 | 121.19 (18) |
C4—C5—C6 | 123.93 (17) | C20—C21—H21 | 119.4 |
N2—C6—C7 | 120.55 (16) | C16—C21—H21 | 119.4 |
N2—C6—C5 | 113.02 (15) | O2—S3—O3 | 116.96 (11) |
C7—C6—C5 | 126.43 (16) | O2—S3—O1 | 114.51 (9) |
C6—C7—C8 | 119.16 (16) | O3—S3—O1 | 114.12 (9) |
C6—C7—H7 | 120.4 | O2—S3—C22 | 102.91 (10) |
C8—C7—H7 | 120.4 | O3—S3—C22 | 103.22 (9) |
C7—C8—C9 | 118.50 (16) | O1—S3—C22 | 102.41 (9) |
C7—C8—C16 | 120.69 (16) | F3—C22—F2 | 108.33 (17) |
C9—C8—C16 | 120.80 (16) | F3—C22—F1 | 106.75 (16) |
C10—C9—C8 | 119.09 (16) | F2—C22—F1 | 107.08 (16) |
C10—C9—H9 | 120.5 | F3—C22—S3 | 111.87 (14) |
C8—C9—H9 | 120.5 | F2—C22—S3 | 111.08 (14) |
N2—C10—C9 | 120.68 (16) | F1—C22—S3 | 111.51 (14) |
N2—Cu1—N1—C1 | −177.44 (17) | Cu1—N2—C10—C9 | 178.65 (13) |
N3—Cu1—N1—C1 | −167.07 (16) | C6—N2—C10—C11 | 177.79 (15) |
Cl1—Cu1—N1—C1 | −7.86 (16) | Cu1—N2—C10—C11 | −0.9 (2) |
N2—Cu1—N1—C5 | 0.45 (13) | C8—C9—C10—N2 | −1.6 (3) |
N3—Cu1—N1—C5 | 10.8 (3) | C8—C9—C10—C11 | 177.87 (17) |
Cl1—Cu1—N1—C5 | 170.04 (12) | C15—N3—C11—C12 | −1.5 (3) |
N1—Cu1—N2—C10 | 176.27 (14) | Cu1—N3—C11—C12 | 179.57 (14) |
N3—Cu1—N2—C10 | −0.06 (13) | C15—N3—C11—C10 | 177.20 (16) |
Cl1—Cu1—N2—C10 | 90.4 (3) | Cu1—N3—C11—C10 | −1.77 (19) |
N1—Cu1—N2—C6 | −2.41 (13) | N2—C10—C11—N3 | 1.7 (2) |
N3—Cu1—N2—C6 | −178.74 (14) | C9—C10—C11—N3 | −177.75 (17) |
Cl1—Cu1—N2—C6 | −88.3 (3) | N2—C10—C11—C12 | −179.66 (17) |
N2—Cu1—N3—C15 | −177.83 (16) | C9—C10—C11—C12 | 0.9 (3) |
N1—Cu1—N3—C15 | 171.78 (17) | N3—C11—C12—C13 | 1.6 (3) |
Cl1—Cu1—N3—C15 | 12.65 (16) | C10—C11—C12—C13 | −176.90 (17) |
N2—Cu1—N3—C11 | 1.06 (12) | C11—C12—C13—C14 | −0.5 (3) |
N1—Cu1—N3—C11 | −9.3 (3) | C12—C13—C14—C15 | −0.7 (3) |
Cl1—Cu1—N3—C11 | −168.46 (12) | C11—N3—C15—C14 | 0.2 (3) |
C5—N1—C1—C2 | −0.8 (3) | Cu1—N3—C15—C14 | 179.02 (14) |
Cu1—N1—C1—C2 | 177.03 (15) | C13—C14—C15—N3 | 0.9 (3) |
N1—C1—C2—C3 | −0.3 (3) | C7—C8—C16—C21 | −154.31 (18) |
C1—C2—C3—C4 | 0.8 (3) | C9—C8—C16—C21 | 25.0 (3) |
C2—C3—C4—C5 | −0.2 (3) | C7—C8—C16—C17 | 24.1 (3) |
C1—N1—C5—C4 | 1.3 (3) | C9—C8—C16—C17 | −156.65 (17) |
Cu1—N1—C5—C4 | −176.73 (15) | C21—C16—C17—C18 | −1.6 (3) |
C1—N1—C5—C6 | 179.39 (16) | C8—C16—C17—C18 | −179.98 (17) |
Cu1—N1—C5—C6 | 1.31 (19) | C16—C17—C18—C19 | 1.1 (3) |
C3—C4—C5—N1 | −0.9 (3) | C17—C18—C19—C20 | 0.4 (3) |
C3—C4—C5—C6 | −178.70 (18) | C17—C18—C19—Br1 | −179.57 (14) |
C10—N2—C6—C7 | 4.4 (3) | C18—C19—C20—C21 | −1.3 (3) |
Cu1—N2—C6—C7 | −176.90 (13) | Br1—C19—C20—C21 | 178.66 (15) |
C10—N2—C6—C5 | −174.92 (15) | C19—C20—C21—C16 | 0.8 (3) |
Cu1—N2—C6—C5 | 3.7 (2) | C17—C16—C21—C20 | 0.6 (3) |
N1—C5—C6—N2 | −3.2 (2) | C8—C16—C21—C20 | 179.05 (18) |
C4—C5—C6—N2 | 174.81 (18) | O2—S3—C22—F3 | 56.95 (16) |
N1—C5—C6—C7 | 177.48 (17) | O3—S3—C22—F3 | 179.07 (14) |
C4—C5—C6—C7 | −4.5 (3) | O1—S3—C22—F3 | −62.15 (15) |
N2—C6—C7—C8 | −1.9 (3) | O2—S3—C22—F2 | −64.24 (16) |
C5—C6—C7—C8 | 177.43 (17) | O3—S3—C22—F2 | 57.88 (16) |
C6—C7—C8—C9 | −2.3 (3) | O1—S3—C22—F2 | 176.66 (13) |
C6—C7—C8—C16 | 177.01 (16) | O2—S3—C22—F1 | 176.41 (14) |
C7—C8—C9—C10 | 3.9 (3) | O3—S3—C22—F1 | −61.47 (16) |
C16—C8—C9—C10 | −175.35 (16) | O1—S3—C22—F1 | 57.31 (15) |
C6—N2—C10—C9 | −2.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···O1i | 0.95 | 2.53 | 3.461 (2) | 166 |
C7—H7···O1i | 0.95 | 2.66 | 3.556 (2) | 157 |
C9—H9···O3ii | 0.95 | 2.58 | 3.451 (2) | 152 |
C12—H12···O3ii | 0.95 | 2.60 | 3.481 (2) | 155 |
C13—H13···O2iii | 0.95 | 2.32 | 3.183 (2) | 150 |
C15—H15···Cl1iv | 0.95 | 2.82 | 3.5696 (19) | 137 |
C17—H17···O1i | 0.95 | 2.66 | 3.581 (2) | 164 |
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+3/2, z+1/2; (iii) x−1/2, −y+3/2, z+1/2; (iv) −x, −y+2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Cu(CF3O3S)Cl(C21H14BrN3)] |
Mr | 636.32 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 150 |
a, b, c (Å) | 7.7841 (2), 16.3043 (4), 18.2533 (4) |
β (°) | 93.884 (1) |
V (Å3) | 2311.28 (10) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 5.78 |
Crystal size (mm) | 0.10 × 0.06 × 0.06 |
Data collection | |
Diffractometer | Bruker Microstar diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.452, 0.707 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 47414, 4344, 4016 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.608 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.073, 1.07 |
No. of reflections | 4344 |
No. of parameters | 316 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.71, −0.33 |
Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), UdMX (Maris, 2004) and XPREP (Bruker, 2008).
Cu1—N1 | 2.0311 (16) | Cu1—Cl1 | 2.2048 (5) |
Cu1—N2 | 1.9345 (15) | Cu1—O1 | 2.4635 (14) |
Cu1—N3 | 2.0338 (16) | ||
N1—Cu1—Cl1 | 98.93 (5) | N1—Cu1—N3 | 159.51 (6) |
N2—Cu1—Cl1 | 169.69 (5) | N2—Cu1—O1 | 90.92 (5) |
N3—Cu1—Cl1 | 100.24 (5) | N2—Cu1—N3 | 79.67 (6) |
N1—Cu1—O1 | 95.34 (5) | N3—Cu1—O1 | 88.61 (5) |
N1—Cu1—N2 | 80.18 (6) | Cl1—Cu1—O1 | 99.39 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···O1i | 0.95 | 2.53 | 3.461 (2) | 166.1 |
C7—H7···O1i | 0.95 | 2.66 | 3.556 (2) | 157 |
C9—H9···O3ii | 0.95 | 2.58 | 3.451 (2) | 152.3 |
C12—H12···O3ii | 0.95 | 2.60 | 3.481 (2) | 155.1 |
C13—H13···O2iii | 0.95 | 2.32 | 3.183 (2) | 150.0 |
C15—H15···Cl1iv | 0.95 | 2.82 | 3.5696 (19) | 136.8 |
C17—H17···O1i | 0.95 | 2.66 | 3.581 (2) | 164 |
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+3/2, z+1/2; (iii) x−1/2, −y+3/2, z+1/2; (iv) −x, −y+2, −z+1. |
Polypyridine ligands, e.g. 2,2':6',2''-terpyridine (tpy), have been the focus of much attention due to their incorporation into devices with many potential applications, such as electrochromic materials, anion-recognition devices and solar photovoltaic cells (Han et al., 2008; Bhaumik et al., 2010). In particular, several ruthenium(II) complexes based on polypyridine ligands have been prepared and structurally characterized. Heteroleptic complexes are designed to increase the excited-state lifetime of ruthenium(II) bis(tpy) complexes for use in such devices (Rajeshwar et al., 2008). In the literature there are, however, fewer examples of CuII complexes of substituted tpy ligands and their derivatives (Chen et al., 2010; McMurtrie & Dance, 2009; Uma et al., 2005; Medlycott et al., 2008; Wang et al., 2009). Previous work by our group has described the synthesis of new homoleptic tridentate complexes containing one central triazine ring that may be applied to the development of new redox mediators (Medlycott et al., 2007, 2008). As an extension of this study, we are currently investigating the supramolecular reactivity of the tridentate pyridyl-substituted ligand tpy to form copper complexes. Against this background, we present here the structure of the title copper–tpy complex, (I).
The CuII centre in (I) is coordinated in a slightly distorted square-pyramidal environment by three N donors from the tridentate ligand. The Cl atom occupies the fourth coordination site of the basal plane. The three N atoms and Cl atom of the basal plane are nearly coplanar, with the largest deviation from the least-squares plane being 0.0524 (8) Å for atom N2. The Cu atom is displaced by 0.1420 (7) Å out of the basal plane.
The Cu—N and Cu—Cl distances (Table 1) are comparable with those found in the Cambridge Structural Database (CSD, Version?; Allen, 2002) for 230 other Cu complexes having the same core as (I). In (I), the Cu—N bond lengths involving the peripheral pyridine rings are about 0.1 Å longer than that of the and central pyridine ring. These values compare well with those found in a copper complex containing 4'-p-tolyl-2,2':6',2''-terpyridine and two chloride ligands [Cu—N(peripheral) = 2.052 (3) and 2.035 (3) Å, Cu—N(central) = 1.940 (3) Å and Cu—Cl = 2.228 (1) Å, for the four atoms that form the base of the square-pyramidal coordination around the metal centre; Wang et al., 2009]. On the other hand, the CuN6 core of a homoleptic copper complex exhibits an even greater difference between the peripheral Cu—N and central Cu—N bond lengths [2.205 (4) versus 1.981 (5) Å; Uma et al., 2005]. The trans N2—Cu1—Cl1 angle in (I) deviates slightly from linearity, while the cis N1—Cu1—N2 and N2—Cu1—N3 angles have very similar values deviating by about 10° from 90° because of the bite constrictions of the ligand.
Fig. 1 shows the molecular structure of (I). The axial position of the square-pyramidal CuII coordination environment is occupied by one O atom of the triflate ligand, with an elongated Cu1—O1 distance of 2.4635 (14) Å. In addition, the triflate ligand extends almost perpendicular to the basal plane of the complex complex, as shown by the Cl1—Cu1—O1 and N2—Cu1—O1 angles (Table 1). Another interesting structural feature of (I) is the dihedral angle of 22.40 (7)° formed between the mean plane through the three pyridine rings and the plane of the bromophenyl group. A similar conformation was found in the two p-tolylterpyridine complexes mentioned above (Wang et al., 2009; Uma et al., 2005) [see Note 2]. The planes of the three pyridyl rings very slightly tilted with respect to each other to give dihedral angles between the pairs of rings containing atoms N1/N2, N2/N3 and N1/N3 of 6.4 (1), 3.7 (1) and 6.1 (1)°, respectively. The tilt between the planes of the central pyridyl and the bromophenyl ring is 24.62 (9)°.
As illustrated in Figs. 2–4, the crystal packing of (I) is effected by halogen–halogen interactions and weak hydrogen bonds. In Fig. 2, two molecules are paired by two halogen interactions to form a dimer about an inversion centre. The shortest intermolecular distance involving F and Br atoms is 3.148 (1) Å, while the predicted sum of the van der Waals radii for fluorine and bromine is 3.32 Å (Bondi, 1964). Thus, this interaction is rather weak. A survey of similar contacts in the CSD showed 171 reported cases, covering a range of 2.90–3.40 Å with a median (maximum occurrence) at 3.15 Å. Furthermore, the dimeric subunits of (I) are linked to each other across centres of inversion between the dimers by duplex C—H···Cl bonds (Table 2 and Fig. 3) involving the Cl atom and one of the pyridyl rings of the tpy ligand in an adjacent molecule (C15—H; Table 2 and Fig. 3). The C—H···Cl and Br···F interactions serve to link the molecules into extended chains which run parallel to the [120] direction.
Given that (I) has a nearly planar organic ligand, the crystal structure might have been expected to present several aromatic π–π interactions, particularly between the tpy ring systems. However, only one potential interaction is observed, maybe due the blocking caused by the presence of the triflate ligand. The bromophenyl rings from two centrosymmetrically-disposed molecules display a weak π–π interaction such that the centroids of the rings are separated by 3.7333 (11) Å, the perpendicular distance from the centroid of one ring to the plane of the other is 3.4034 (8) Å and the slippage of the centroids is 1.54 Å. Several weak C—H···O interactions (Table 2) appear to provide some support to the vertical alignment of the triflate ligand, and crosslink the above-mentioned chains to give a three-dimensional network. The planarity of the tpy ring system clearly facilitates the formation of these C—H···O interactions (Fig. 4).
In summary, the packing of the title copper complex shows that the presence of the trifluoromethanesulfonate anion plays an active role in the intermolecular interactions. The close Br···F contacts in (I) may be stabilizing interactions but they are apparently not structure-determining, since other weak C—H···Cl and C—H···O interactions contribute to the packing pattern.