Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102018097/gg1141sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102018097/gg1141Isup2.hkl | |
Portable Document Format (PDF) file https://doi.org/10.1107/S0108270102018097/gg1141sup3.pdf |
CCDC reference: 199407
The ligand 2,6-bis(pyrazol-1-yl)pyridine was synthesized by heating to reflux for 72 h the mixture formed by adding 2,6-dichloropyridine (4.12 g, 27.8 mmol) to a solution of sodium pyrazolate previously prepared in tetrahydrofuran (100 ml) by reaction of pyrazole (3.80 g, 55.8 mmol) with excess NaH (60% dispersion in mineral oil (2.80 g, 70 mmol). After cooling, the mixture was poured into iced water and the resultant precipitate recovered by filtration (yield: 5.10 g, 23.7 mmol, 85%). For the preapration of the title compound, (I), isonicotinamide (0.040 g, 0.33 mmol) was added to a mixture of 2,6-bis(pyrazol-1-yl)pyridine (0.068 g, 0.32 mmol) and hydrated {CuII(BF4)}- (0.100 g, 0.32 mmol) in acetonitrile (25 ml). After stirring at ambient temperature for 24 h, the resulting green solution afforded a small crop of green plate-like crystals.
The anions are affected by disorder which was modelled by allowing alternative positions for each F atom, with extensive restraints applied to B—F distances and F—B—F angles. Around B1, the major and minor orientations refined to 0.57 (2) and 0.43 (2), respectively, while the corresponding occupancies around B2 converged to 0.60 (1) and 0.40 (1). Aromatic and amide H atoms, after location from ΔF syntheses, were placed geometrically and refined with a riding model, for which the C—H and N—H distances were constrained to be 0.95 and 0.88 Å, respectively, and Uiso(H) = 1.2Ueq(C, N). Methyl H atoms were located and treated similarly, with C—H distances constrained to be 0.98 Å and Uiso(H) = 1.5Ueq(C)
Data collection: IPDS (Stoe & Cie, 1995); cell refinement: IPDS; data reduction: IPDS; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2002).
[Cu(C2H3N)(C11H9N5)(C6H6N2O)](BF4)2·2C2H3N | F(000) = 2808 |
Mr = 693.68 | Dx = 1.560 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac2ab | Cell parameters from 12955 reflections |
a = 8.1790 (16) Å | θ = 2.5–25.5° |
b = 22.747 (5) Å | µ = 0.83 mm−1 |
c = 31.752 (6) Å | T = 193 K |
V = 5907 (2) Å3 | Plate, green |
Z = 8 | 0.32 × 0.08 × 0.02 mm |
Stoe IPDS diffractometer | 6613 independent reflections |
Radiation source: fine-focus sealed tube | 4385 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
area detector scans | θmax = 28.1°, θmin = 3.1° |
Absorption correction: multi-scan (IPDS; Stoe & Cie, 1995) | h = −9→9 |
Tmin = 0.84, Tmax = 0.95 | k = −30→25 |
19461 measured reflections | l = −42→29 |
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)] = 0.059 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.175 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.115P)2] where P = (Fo2 + 2Fc2)/3 |
6613 reflections | (Δ/σ)max = 0.002 |
401 parameters | Δρmax = 0.88 e Å−3 |
40 restraints | Δρmin = −0.74 e Å−3 |
[Cu(C2H3N)(C11H9N5)(C6H6N2O)](BF4)2·2C2H3N | V = 5907 (2) Å3 |
Mr = 693.68 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 8.1790 (16) Å | µ = 0.83 mm−1 |
b = 22.747 (5) Å | T = 193 K |
c = 31.752 (6) Å | 0.32 × 0.08 × 0.02 mm |
Stoe IPDS diffractometer | 6613 independent reflections |
Absorption correction: multi-scan (IPDS; Stoe & Cie, 1995) | 4385 reflections with I > 2σ(I) |
Tmin = 0.84, Tmax = 0.95 | Rint = 0.052 |
19461 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 40 restraints |
wR(F2) = 0.175 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.88 e Å−3 |
6613 reflections | Δρmin = −0.74 e Å−3 |
401 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 | 0.52637 (6) | 0.308975 (16) | 0.103332 (14) | 0.02755 (15) | |
N1 | 0.4945 (4) | 0.39363 (12) | 0.10617 (9) | 0.0261 (6) | |
C2 | 0.6115 (5) | 0.42767 (14) | 0.12180 (11) | 0.0285 (7) | |
C3 | 0.5956 (5) | 0.48748 (15) | 0.12475 (12) | 0.0351 (8) | |
H3 | 0.6795 | 0.5113 | 0.1364 | 0.042* | |
C4 | 0.4513 (5) | 0.51138 (15) | 0.10985 (14) | 0.0383 (9) | |
H4 | 0.4363 | 0.5527 | 0.1113 | 0.046* | |
C5 | 0.3278 (5) | 0.47697 (15) | 0.09290 (13) | 0.0370 (9) | |
H5 | 0.2285 | 0.4934 | 0.0828 | 0.044* | |
C6 | 0.3583 (5) | 0.41722 (13) | 0.09158 (11) | 0.0261 (7) | |
N61 | 0.2532 (4) | 0.37461 (11) | 0.07436 (9) | 0.0270 (6) | |
N62 | 0.3070 (4) | 0.31766 (11) | 0.07441 (10) | 0.0304 (7) | |
C63 | 0.1926 (5) | 0.28783 (15) | 0.05390 (13) | 0.0345 (8) | |
H63 | 0.1958 | 0.2467 | 0.0489 | 0.041* | |
C64 | 0.0666 (5) | 0.32513 (16) | 0.04063 (13) | 0.0358 (8) | |
H64 | −0.0287 | 0.3144 | 0.0254 | 0.043* | |
C65 | 0.1085 (5) | 0.37984 (15) | 0.05404 (12) | 0.0316 (7) | |
H65 | 0.0479 | 0.4150 | 0.0499 | 0.038* | |
N21 | 0.7485 (4) | 0.39461 (11) | 0.13394 (9) | 0.0294 (6) | |
N22 | 0.7431 (4) | 0.33528 (12) | 0.12769 (9) | 0.0299 (6) | |
C23 | 0.8842 (5) | 0.31541 (15) | 0.14199 (12) | 0.0353 (8) | |
H23 | 0.9161 | 0.2753 | 0.1417 | 0.042* | |
C24 | 0.9804 (6) | 0.36112 (18) | 0.15765 (14) | 0.0406 (9) | |
H24 | 1.0862 | 0.3580 | 0.1698 | 0.049* | |
C25 | 0.8912 (6) | 0.41119 (16) | 0.15190 (13) | 0.0380 (9) | |
H25 | 0.9231 | 0.4501 | 0.1591 | 0.046* | |
N11 | 0.5693 (4) | 0.22559 (11) | 0.09176 (10) | 0.0285 (6) | |
C12 | 0.7079 (5) | 0.20804 (13) | 0.07385 (12) | 0.0311 (8) | |
H12 | 0.7908 | 0.2365 | 0.0688 | 0.037* | |
C13 | 0.7373 (5) | 0.15040 (14) | 0.06217 (12) | 0.0329 (8) | |
H13 | 0.8380 | 0.1394 | 0.0495 | 0.040* | |
C14 | 0.6156 (5) | 0.10920 (13) | 0.06944 (11) | 0.0276 (7) | |
C15 | 0.4735 (5) | 0.12711 (14) | 0.08878 (12) | 0.0312 (7) | |
H15 | 0.3896 | 0.0994 | 0.0947 | 0.037* | |
C16 | 0.4535 (5) | 0.18550 (14) | 0.09951 (12) | 0.0308 (7) | |
H16 | 0.3549 | 0.1975 | 0.1127 | 0.037* | |
C17 | 0.6301 (5) | 0.04512 (13) | 0.05692 (12) | 0.0311 (8) | |
O17 | 0.5367 (4) | 0.00906 (11) | 0.07204 (10) | 0.0437 (7) | |
N17 | 0.7451 (5) | 0.03136 (12) | 0.02906 (11) | 0.0390 (8) | |
H17A | 0.7566 | −0.0053 | 0.0207 | 0.047* | |
H17B | 0.8098 | 0.0589 | 0.0190 | 0.047* | |
B1 | 0.1475 (5) | 0.12611 (15) | −0.00064 (12) | 0.0314 (8) | |
F11A | 0.0250 (6) | 0.0869 (2) | −0.01047 (14) | 0.0361 (12)* | 0.57 |
F12A | 0.2924 (5) | 0.09134 (17) | 0.00153 (16) | 0.0362 (10)* | 0.57 |
F13A | 0.1517 (7) | 0.1775 (2) | −0.02314 (18) | 0.0438 (14)* | 0.57 |
F14A | 0.1375 (7) | 0.1399 (2) | 0.04272 (15) | 0.0439 (14)* | 0.57 |
F11B | −0.0059 (7) | 0.1004 (3) | −0.01074 (18) | 0.0333 (15)* | 0.43 |
F12B | 0.2772 (9) | 0.0931 (3) | −0.0126 (3) | 0.055 (2)* | 0.43 |
F13B | 0.1690 (9) | 0.1678 (3) | −0.0328 (2) | 0.0413 (18)* | 0.43 |
F14B | 0.1282 (9) | 0.1545 (3) | 0.03640 (18) | 0.0418 (17)* | 0.43 |
B2 | 1.0488 (6) | 0.16208 (18) | 0.17207 (15) | 0.0475 (12) | |
F21A | 0.9755 (8) | 0.2040 (2) | 0.19773 (15) | 0.0488 (13)* | 0.60 |
F22A | 1.0674 (8) | 0.1894 (2) | 0.13152 (15) | 0.0616 (13)* | 0.60 |
F23A | 1.2059 (7) | 0.1514 (3) | 0.1869 (2) | 0.0726 (16)* | 0.60 |
F24A | 0.9480 (8) | 0.1165 (3) | 0.1674 (2) | 0.0853 (19)* | 0.60 |
F21B | 1.0372 (13) | 0.2085 (3) | 0.1977 (2) | 0.059 (2)* | 0.40 |
F22B | 0.9892 (17) | 0.1684 (6) | 0.1329 (3) | 0.118 (4)* | 0.40 |
F23B | 1.1988 (10) | 0.1355 (4) | 0.1695 (3) | 0.080 (3)* | 0.40 |
F24B | 0.9687 (11) | 0.1112 (3) | 0.1900 (3) | 0.069 (2)* | 0.40 |
N2 | 0.4097 (5) | 0.29291 (14) | 0.16880 (11) | 0.0400 (8) | |
C21 | 0.3516 (5) | 0.29218 (15) | 0.20130 (13) | 0.0369 (8) | |
C22 | 0.2758 (7) | 0.2915 (2) | 0.24242 (13) | 0.0510 (11) | |
H22A | 0.2420 | 0.3314 | 0.2500 | 0.076* | |
H22B | 0.3542 | 0.2768 | 0.2633 | 0.076* | |
H22C | 0.1798 | 0.2657 | 0.2418 | 0.076* | |
N3 | 0.5626 (8) | 0.0452 (2) | 0.18208 (18) | 0.0770 (16) | |
C31 | 0.5720 (7) | 0.0925 (2) | 0.19272 (15) | 0.0504 (11) | |
C32 | 0.5849 (8) | 0.1528 (2) | 0.20617 (19) | 0.0633 (14) | |
H32A | 0.7005 | 0.1639 | 0.2080 | 0.095* | |
H32B | 0.5337 | 0.1572 | 0.2339 | 0.095* | |
H32C | 0.5293 | 0.1783 | 0.1858 | 0.095* | |
N4 | 0.5251 (9) | 0.4160 (3) | 0.2284 (2) | 0.0872 (18) | |
C41 | 0.4310 (9) | 0.4523 (3) | 0.22369 (18) | 0.0673 (17) | |
C42 | 0.3117 (10) | 0.4987 (3) | 0.2179 (2) | 0.083 (2) | |
H42A | 0.2559 | 0.5063 | 0.2447 | 0.125* | |
H42B | 0.2313 | 0.4866 | 0.1968 | 0.125* | |
H42C | 0.3671 | 0.5345 | 0.2085 | 0.125* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0260 (3) | 0.0204 (2) | 0.0363 (2) | 0.00328 (14) | −0.00215 (17) | −0.00143 (14) |
N1 | 0.0221 (18) | 0.0233 (12) | 0.0328 (14) | 0.0018 (10) | −0.0026 (11) | −0.0020 (10) |
C2 | 0.026 (2) | 0.0270 (14) | 0.0321 (17) | −0.0006 (12) | −0.0015 (14) | −0.0005 (12) |
C3 | 0.033 (2) | 0.0277 (15) | 0.044 (2) | 0.0008 (14) | −0.0046 (16) | −0.0042 (14) |
C4 | 0.038 (3) | 0.0236 (15) | 0.054 (2) | 0.0038 (14) | −0.0081 (17) | −0.0062 (14) |
C5 | 0.030 (3) | 0.0287 (16) | 0.052 (2) | 0.0051 (14) | −0.0053 (16) | −0.0030 (15) |
C6 | 0.021 (2) | 0.0254 (14) | 0.0317 (16) | 0.0040 (12) | −0.0001 (12) | −0.0022 (11) |
N61 | 0.0245 (18) | 0.0229 (12) | 0.0337 (14) | 0.0038 (10) | −0.0028 (12) | −0.0024 (10) |
N62 | 0.0293 (19) | 0.0210 (12) | 0.0411 (16) | 0.0036 (10) | −0.0014 (12) | −0.0028 (11) |
C63 | 0.030 (2) | 0.0284 (15) | 0.045 (2) | 0.0012 (13) | −0.0029 (16) | −0.0023 (14) |
C64 | 0.028 (2) | 0.0351 (17) | 0.044 (2) | −0.0018 (14) | −0.0077 (15) | −0.0016 (14) |
C65 | 0.024 (2) | 0.0316 (15) | 0.0390 (19) | 0.0051 (13) | −0.0010 (14) | 0.0016 (13) |
N21 | 0.0271 (19) | 0.0262 (13) | 0.0348 (15) | 0.0011 (11) | −0.0052 (12) | −0.0009 (11) |
N22 | 0.0303 (19) | 0.0251 (12) | 0.0343 (15) | 0.0037 (11) | −0.0033 (12) | 0.0017 (10) |
C23 | 0.035 (3) | 0.0344 (16) | 0.0366 (18) | 0.0082 (14) | −0.0044 (15) | 0.0035 (14) |
C24 | 0.031 (3) | 0.044 (2) | 0.047 (2) | 0.0036 (16) | −0.0115 (17) | 0.0000 (16) |
C25 | 0.032 (3) | 0.0395 (18) | 0.042 (2) | −0.0011 (15) | −0.0093 (16) | −0.0010 (15) |
N11 | 0.028 (2) | 0.0207 (12) | 0.0365 (15) | 0.0011 (10) | 0.0006 (12) | 0.0008 (10) |
C12 | 0.026 (2) | 0.0202 (13) | 0.047 (2) | −0.0010 (12) | 0.0063 (15) | −0.0007 (13) |
C13 | 0.027 (2) | 0.0242 (14) | 0.048 (2) | −0.0001 (13) | 0.0068 (15) | −0.0011 (13) |
C14 | 0.029 (2) | 0.0217 (13) | 0.0318 (17) | 0.0018 (12) | 0.0017 (13) | 0.0010 (11) |
C15 | 0.027 (2) | 0.0261 (15) | 0.0403 (18) | −0.0033 (13) | 0.0044 (15) | −0.0012 (13) |
C16 | 0.027 (2) | 0.0250 (15) | 0.0400 (18) | 0.0005 (12) | 0.0056 (14) | −0.0012 (13) |
C17 | 0.029 (2) | 0.0218 (14) | 0.043 (2) | −0.0007 (12) | 0.0022 (15) | −0.0024 (12) |
O17 | 0.0410 (19) | 0.0244 (11) | 0.0657 (19) | −0.0079 (11) | 0.0194 (14) | −0.0041 (11) |
N17 | 0.047 (2) | 0.0202 (12) | 0.0501 (19) | −0.0025 (12) | 0.0166 (16) | −0.0041 (12) |
B1 | 0.028 (2) | 0.0288 (16) | 0.038 (2) | −0.0047 (14) | 0.0027 (16) | −0.0054 (14) |
B2 | 0.044 (4) | 0.042 (2) | 0.057 (3) | 0.009 (2) | −0.001 (2) | −0.007 (2) |
N2 | 0.044 (2) | 0.0364 (15) | 0.0399 (18) | 0.0021 (14) | 0.0070 (15) | −0.0002 (13) |
C21 | 0.034 (2) | 0.0343 (17) | 0.042 (2) | 0.0042 (14) | −0.0036 (17) | 0.0027 (15) |
C22 | 0.055 (3) | 0.064 (3) | 0.034 (2) | 0.003 (2) | 0.0069 (19) | 0.0048 (18) |
N3 | 0.100 (5) | 0.050 (2) | 0.081 (4) | 0.005 (2) | 0.022 (3) | −0.012 (2) |
C31 | 0.052 (3) | 0.049 (2) | 0.050 (3) | 0.011 (2) | 0.008 (2) | −0.0031 (19) |
C32 | 0.070 (4) | 0.054 (3) | 0.065 (3) | 0.008 (2) | −0.003 (3) | −0.016 (2) |
N4 | 0.100 (5) | 0.065 (3) | 0.097 (4) | −0.002 (3) | −0.002 (4) | 0.000 (3) |
C41 | 0.089 (5) | 0.056 (3) | 0.058 (3) | −0.023 (3) | 0.002 (3) | 0.004 (2) |
C42 | 0.091 (6) | 0.083 (4) | 0.074 (4) | 0.001 (4) | 0.003 (4) | 0.015 (3) |
Cu1—N1 | 1.945 (3) | C14—C17 | 1.516 (4) |
Cu1—N2 | 2.316 (3) | C15—C16 | 1.381 (5) |
Cu1—N11 | 1.964 (3) | C15—H15 | 0.9500 |
Cu1—N22 | 2.024 (3) | C16—H16 | 0.9500 |
Cu1—N62 | 2.026 (3) | C17—O17 | 1.220 (4) |
N1—C6 | 1.320 (5) | C17—N17 | 1.328 (5) |
N1—C2 | 1.327 (4) | N17—H17A | 0.8800 |
C2—C3 | 1.370 (5) | N17—H17B | 0.8800 |
C2—N21 | 1.404 (5) | B1—F11A | 1.378 (5) |
C3—C4 | 1.383 (6) | B1—F12A | 1.426 (5) |
C3—H3 | 0.9500 | B1—F13A | 1.371 (5) |
C4—C5 | 1.387 (6) | B1—F14A | 1.414 (6) |
C4—H4 | 0.9500 | B1—F11B | 1.421 (6) |
C5—C6 | 1.382 (4) | B1—F12B | 1.354 (7) |
C5—H5 | 0.9500 | B1—F13B | 1.405 (6) |
C6—N61 | 1.406 (4) | B1—F14B | 1.351 (6) |
N61—C65 | 1.353 (5) | B2—F21A | 1.391 (6) |
N61—N62 | 1.368 (3) | B2—F22A | 1.437 (6) |
N62—C63 | 1.326 (5) | B2—F23A | 1.390 (7) |
C63—C64 | 1.400 (5) | B2—F24A | 1.333 (7) |
C63—H63 | 0.9500 | B2—F21B | 1.337 (7) |
C64—C65 | 1.359 (5) | B2—F22B | 1.345 (8) |
C64—H64 | 0.9500 | B2—F23B | 1.371 (7) |
C65—H65 | 0.9500 | B2—F24B | 1.447 (7) |
N21—C25 | 1.353 (5) | N2—C21 | 1.136 (5) |
N21—N22 | 1.365 (4) | C21—C22 | 1.446 (6) |
N22—C23 | 1.320 (5) | C22—H22A | 0.9800 |
C23—C24 | 1.396 (6) | C22—H22B | 0.9800 |
C23—H23 | 0.9500 | C22—H22C | 0.9800 |
C24—C25 | 1.365 (6) | N3—C31 | 1.129 (6) |
C24—H24 | 0.9500 | C31—C32 | 1.440 (6) |
C25—H25 | 0.9500 | C32—H32A | 0.9800 |
N11—C12 | 1.329 (5) | C32—H32B | 0.9800 |
N11—C16 | 1.338 (5) | C32—H32C | 0.9800 |
C12—C13 | 1.384 (4) | N4—C41 | 1.139 (9) |
C12—H12 | 0.9500 | C41—C42 | 1.449 (10) |
C13—C14 | 1.387 (5) | C42—H42A | 0.9800 |
C13—H13 | 0.9500 | C42—H42B | 0.9800 |
C14—C15 | 1.376 (5) | C42—H42C | 0.9800 |
N1—Cu1—N2 | 93.41 (12) | N11—C12—H12 | 118.4 |
N1—Cu1—N11 | 171.42 (13) | C13—C12—H12 | 118.4 |
N1—Cu1—N22 | 78.87 (12) | C12—C13—C14 | 118.1 (3) |
N1—Cu1—N62 | 78.80 (11) | C12—C13—H13 | 120.9 |
N2—Cu1—N11 | 95.12 (12) | C14—C13—H13 | 120.9 |
N2—Cu1—N22 | 93.70 (14) | C15—C14—C13 | 118.7 (3) |
N2—Cu1—N62 | 93.29 (14) | C15—C14—C17 | 117.9 (3) |
N11—Cu1—N22 | 101.55 (12) | C13—C14—C17 | 123.4 (3) |
N11—Cu1—N62 | 99.67 (12) | C14—C15—C16 | 119.6 (3) |
N22—Cu1—N62 | 156.94 (11) | C14—C15—H15 | 120.2 |
C6—N1—C2 | 120.1 (3) | C16—C15—H15 | 120.2 |
C6—N1—Cu1 | 119.9 (2) | N11—C16—C15 | 121.8 (3) |
C2—N1—Cu1 | 119.9 (2) | N11—C16—H16 | 119.1 |
C21—N2—Cu1 | 171.8 (3) | C15—C16—H16 | 119.1 |
N2—C21—C22 | 179.3 (5) | O17—C17—N17 | 123.2 (3) |
N1—C2—C3 | 122.5 (3) | O17—C17—C14 | 119.6 (3) |
N1—C2—N21 | 111.5 (3) | N17—C17—C14 | 117.2 (3) |
C3—C2—N21 | 126.1 (3) | C17—N17—H17A | 120.0 |
C2—C3—C4 | 116.6 (3) | C17—N17—H17B | 120.0 |
C2—C3—H3 | 121.7 | H17A—N17—H17B | 120.0 |
C4—C3—H3 | 121.7 | F11A—B1—F12A | 104.8 (4) |
C3—C4—C5 | 122.2 (3) | F11A—B1—F13A | 116.9 (4) |
C3—C4—H4 | 118.9 | F11A—B1—F14A | 108.8 (4) |
C5—C4—H4 | 118.9 | F12A—B1—F13A | 118.5 (4) |
C6—C5—C4 | 115.8 (4) | F12A—B1—F14A | 97.1 (4) |
C6—C5—H5 | 122.1 | F13A—B1—F14A | 108.6 (4) |
C4—C5—H5 | 122.1 | F11B—B1—F12B | 113.6 (5) |
N1—C6—C5 | 122.8 (3) | F11B—B1—F13B | 103.0 (5) |
N1—C6—N61 | 111.8 (3) | F11B—B1—F14B | 106.8 (5) |
C5—C6—N61 | 125.4 (3) | F12B—B1—F13B | 94.1 (5) |
C65—N61—N62 | 111.4 (3) | F12B—B1—F14B | 127.0 (5) |
C65—N61—C6 | 131.3 (3) | F13B—B1—F14B | 108.9 (5) |
N62—N61—C6 | 117.1 (3) | F21A—B2—F22A | 105.9 (4) |
C63—N62—N61 | 104.9 (3) | F21A—B2—F23A | 108.6 (5) |
C63—N62—Cu1 | 142.9 (2) | F21A—B2—F24A | 109.4 (5) |
N61—N62—Cu1 | 112.2 (2) | F22A—B2—F23A | 106.3 (5) |
N62—C63—C64 | 110.9 (3) | F22A—B2—F24A | 107.5 (5) |
N62—C63—H63 | 124.5 | F23A—B2—F24A | 118.3 (5) |
C64—C63—H63 | 124.5 | F21B—B2—F22B | 117.0 (7) |
C65—C64—C63 | 106.0 (3) | F21B—B2—F23B | 116.7 (7) |
C65—C64—H64 | 127.0 | F21B—B2—F24B | 111.1 (6) |
C63—C64—H64 | 127.0 | F22B—B2—F23B | 108.4 (8) |
N61—C65—C64 | 106.8 (3) | F22B—B2—F24B | 106.6 (8) |
N61—C65—H65 | 126.6 | F23B—B2—F24B | 94.3 (6) |
C64—C65—H65 | 126.6 | C21—C22—H22A | 109.5 |
C25—N21—N22 | 111.4 (3) | C21—C22—H22B | 109.5 |
C25—N21—C2 | 131.0 (3) | H22A—C22—H22B | 109.5 |
N22—N21—C2 | 117.6 (3) | C21—C22—H22C | 109.5 |
C23—N22—N21 | 105.1 (3) | H22A—C22—H22C | 109.5 |
C23—N22—Cu1 | 142.7 (2) | H22B—C22—H22C | 109.5 |
N21—N22—Cu1 | 112.1 (2) | N3—C31—C32 | 179.6 (7) |
N22—C23—C24 | 111.1 (3) | C31—C32—H32A | 109.5 |
N22—C23—H23 | 124.4 | C31—C32—H32B | 109.5 |
C24—C23—H23 | 124.4 | H32A—C32—H32B | 109.5 |
C25—C24—C23 | 105.8 (4) | C31—C32—H32C | 109.5 |
C25—C24—H24 | 127.1 | H32A—C32—H32C | 109.5 |
C23—C24—H24 | 127.1 | H32B—C32—H32C | 109.5 |
N21—C25—C24 | 106.6 (3) | N4—C41—C42 | 179.6 (8) |
N21—C25—H25 | 126.7 | C41—C42—H42A | 109.5 |
C24—C25—H25 | 126.7 | C41—C42—H42B | 109.5 |
C12—N11—C16 | 118.5 (3) | H42A—C42—H42B | 109.5 |
C12—N11—Cu1 | 121.5 (2) | C41—C42—H42C | 109.5 |
C16—N11—Cu1 | 119.8 (3) | H42A—C42—H42C | 109.5 |
N11—C12—C13 | 123.2 (3) | H42B—C42—H42C | 109.5 |
C6—N1—C2—C3 | 2.0 (5) | C3—C2—N21—C25 | 2.2 (6) |
C6—N1—C2—N21 | −177.5 (3) | N1—C2—N21—N22 | 0.9 (4) |
N1—C2—C3—C4 | −1.1 (6) | C3—C2—N21—N22 | −178.5 (4) |
N21—C2—C3—C4 | 178.3 (4) | C25—N21—N22—C23 | 0.0 (4) |
C2—C3—C4—C5 | 0.3 (6) | C2—N21—N22—C23 | −179.4 (3) |
C3—C4—C5—C6 | −0.4 (6) | N21—N22—C23—C24 | 0.4 (4) |
C2—N1—C6—C5 | −2.1 (5) | N22—C23—C24—C25 | −0.6 (5) |
C2—N1—C6—N61 | 176.8 (3) | N22—N21—C25—C24 | −0.3 (5) |
C4—C5—C6—N1 | 1.3 (6) | C2—N21—C25—C24 | 179.0 (4) |
C4—C5—C6—N61 | −177.5 (4) | C23—C24—C25—N21 | 0.5 (5) |
N1—C6—N61—C65 | −175.4 (4) | C16—N11—C12—C13 | 1.1 (6) |
C5—C6—N61—C65 | 3.5 (6) | N11—C12—C13—C14 | 0.3 (6) |
N1—C6—N61—N62 | −1.4 (4) | C12—C13—C14—C15 | −1.6 (5) |
C5—C6—N61—N62 | 177.5 (4) | C12—C13—C14—C17 | 178.0 (3) |
C65—N61—N62—C63 | −0.2 (4) | C13—C14—C15—C16 | 1.6 (5) |
C6—N61—N62—C63 | −175.4 (3) | C17—C14—C15—C16 | −178.0 (3) |
N61—N62—C63—C64 | 0.2 (4) | C12—N11—C16—C15 | −1.1 (6) |
N62—C63—C64—C65 | −0.1 (5) | C14—C15—C16—N11 | −0.3 (6) |
N62—N61—C65—C64 | 0.2 (4) | C15—C14—C17—O17 | −16.3 (6) |
C6—N61—C65—C64 | 174.4 (4) | C13—C14—C17—O17 | 164.1 (4) |
C63—C64—C65—N61 | 0.0 (4) | C15—C14—C17—N17 | 162.8 (4) |
N1—C2—N21—C25 | −178.4 (4) | C13—C14—C17—N17 | −16.8 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N17—H17A···F11Ai | 0.88 | 2.60 | 3.334 (6) | 142 |
N17—H17B···F11Aii | 0.88 | 2.09 | 2.900 (6) | 152 |
N17—H17B···F11Bii | 0.88 | 2.01 | 2.866 (7) | 163 |
N17—H17A···F12Ai | 0.88 | 2.12 | 2.971 (5) | 163 |
N17—H17A···F12Bi | 0.88 | 2.03 | 2.885 (7) | 163 |
C5—H5···O17iii | 0.95 | 2.22 | 3.140 (5) | 162 |
C65—H65···O17iii | 0.95 | 2.36 | 3.221 (4) | 151 |
Symmetry codes: (i) −x+1, −y, −z; (ii) x+1, y, z; (iii) −x+1/2, y+1/2, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu(C2H3N)(C11H9N5)(C6H6N2O)](BF4)2·2C2H3N |
Mr | 693.68 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 193 |
a, b, c (Å) | 8.1790 (16), 22.747 (5), 31.752 (6) |
V (Å3) | 5907 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.83 |
Crystal size (mm) | 0.32 × 0.08 × 0.02 |
Data collection | |
Diffractometer | Stoe IPDS diffractometer |
Absorption correction | Multi-scan (IPDS; Stoe & Cie, 1995) |
Tmin, Tmax | 0.84, 0.95 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 19461, 6613, 4385 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.662 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.175, 1.01 |
No. of reflections | 6613 |
No. of parameters | 401 |
No. of restraints | 40 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.88, −0.74 |
Computer programs: IPDS (Stoe & Cie, 1995), IPDS, SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), CAMERON (Watkin et al., 1996), SHELXL97 and PLATON (Spek, 2002).
Cu1—N1 | 1.945 (3) | Cu1—N22 | 2.024 (3) |
Cu1—N2 | 2.316 (3) | Cu1—N62 | 2.026 (3) |
Cu1—N11 | 1.964 (3) | ||
N1—Cu1—N2 | 93.41 (12) | N2—Cu1—N22 | 93.70 (14) |
N1—Cu1—N11 | 171.42 (13) | N2—Cu1—N62 | 93.29 (14) |
N1—Cu1—N22 | 78.87 (12) | N11—Cu1—N22 | 101.55 (12) |
N1—Cu1—N62 | 78.80 (11) | N11—Cu1—N62 | 99.67 (12) |
N2—Cu1—N11 | 95.12 (12) | N22—Cu1—N62 | 156.94 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
N17—H17A···F11Ai | 0.88 | 2.60 | 3.334 (6) | 142 |
N17—H17B···F11Aii | 0.88 | 2.09 | 2.900 (6) | 152 |
N17—H17B···F11Bii | 0.88 | 2.01 | 2.866 (7) | 163 |
N17—H17A···F12Ai | 0.88 | 2.12 | 2.971 (5) | 163 |
N17—H17A···F12Bi | 0.88 | 2.03 | 2.885 (7) | 163 |
C5—H5···O17iii | 0.95 | 2.22 | 3.140 (5) | 162 |
C65—H65···O17iii | 0.95 | 2.36 | 3.221 (4) | 151 |
Symmetry codes: (i) −x+1, −y, −z; (ii) x+1, y, z; (iii) −x+1/2, y+1/2, z. |
The title compound, (I), comprises an acetonitrile[2,6-bis(pyrazol-1-yl)pyridine](isonicotinamide)copper(II) cation (Fig. 1), two tetrafluoroborate anions and two lattice acetonitrile molecules. All four F atoms of both tetrafluoroborate anions are disordered over two sites. The tridentate 2,6-bis(pyrazol-1-yl)pyridine ligand occupies three of the four basal positions of a distorted square-pyramidal CuN5 coordination sphere. The isonicotinamide ligand occupies the fourth basal position and the coordinated acetonitrile molecule the apical position. Of the three ligating N atoms of the tridentate ligand, the pyrazole N-donors atoms form much longer Cu···N contacts [2.024 (3) and 2.026 (3) Å] than the pyridine N-donor atom [1.946 (2) Å], which forms a similar Cu···N contact to the isonicotinamide N-donor atom [1.964 (2) Å]. Typical of square-pyramidal CuII centres, the apical acetonitrile N atom is somewhat more distant [2.316 (3) Å]. The magnitude of the distortion of the CuII coordination sphere (Fig. 1) can be quantified by the geometric parameter τ [i.e. (171.3 - 156.98)/60] of 0.24 (τ = 0.0 for C4v symmetry and τ = 1.0 for D3 h symmetry; Addison et al., 1984). The conformation of the pyridine ring of the isonicotinamide ligand is such that it makes a dihedral angle of 47.8(?)° with the pyridine ring of the tridentate ligand, which is effectively planar, with dihedral angles between the pyrazole and pyridine rings of 1.3 and 6.3°.
The cations form centrosymmetrically related pairs (Fig. 2) linked through two tetrafluoroborate anions by a R44(12) hydrogen-bonding motif (Etter, 1990; Bernstein et al., 1995). Pertinent structural parameters of the hydrogen-bonded contacts are collated in Table 2. The formation of this motif [Scheme 1(a)] was unexpected, the simpler R22(8) motif [Scheme 1(b)] based on the amide functionalities being anticipated by analogy with the well known carboxylic acid-based R22(8) supramolecular synthon [Scheme 1(c)] (Desiraju, 1995, 2000). Presumably, despite the greater strength of the N—H···O═C hydrogen bond compared with the N—H···F—BF3 hydrogen bond, the energy release associated with the formation of four of the latter is greater than that associated with the formation of two of the former. Two C—H···O hydrogen bonds, in the form of a R21(7) motif, link the dimers through the amide O atom, generating an undulating sheet structure parallel to the (001) plane (Table 2 and Fig. 3). The periodicity of the undulation (24.5 Å) is such that the two-dimensional network comprises three interpenetrating sheets analogous to those observed in {[Co2(µ-4,4'-azopyridine)3(NO3)4]}n (Withersby et al., 1999, 2000).