Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807030073/dn2202sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807030073/dn2202Isup2.hkl |
CCDC reference: 654808
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.005 Å
- Disorder in solvent or counterion
- R factor = 0.043
- wR factor = 0.084
- Data-to-parameter ratio = 10.0
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT088_ALERT_3_C Poor Data / Parameter Ratio .................... 9.98 PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.57 PLAT244_ALERT_4_C Low 'Solvent' Ueq as Compared to Neighbors for B1 PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 31.00 Perc. PLAT369_ALERT_2_C Long C(sp2)-C(sp2) Bond C1 - C2 ... 1.54 Ang.
Alert level G PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 251
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 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 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The 4'-Phenyl-2,2':6',2''-terpyridine was synthesized according to a published procedure (Constable et al., 1990). The 4'-phenyl-2,2':6',2''-terpyridine (15.4 mg, 0.05 mmol) was dissolved on warm ethanol (10 ml), solid copper(II) tetrafluoroborate hydrate (11.9 mg, 0.05 mmol) was added and then a warm aqueous solution (5 ml) of 2,3-pyridinedicarboxylic acid (8.36 mg, 0.05 mmol) was added to form a blue solution. Blue crystals suitable for X-ray structure determination were obtained by slow evaporation after three days at room temperature.
C-bound H atoms were placed in geometrically idealized positions and refined using a riding model with C–H = 0.93 Å, and Uiso(H) = 1.2Ueq(C). The O-bound H atom was located in a difference map and refined isotropically.The fluorine atoms of the tetrafluoroborate were refined with statistical disorder over three positions, with site occupancies of 0.54 (1) (for F1, F2 and F3), 0.25 (1) (for F1B, F2B and F3B) and 0.22 (1) (for F1C, F2C and F3C).
Compounds with the 3-carboxylpyridine-2-carboxylato as ligand have been reported with the carboxyl group forming intermolecular (Turner et al., 2007), (Patrick et al., 2003), (Goher et al., 1993) or intramolecular (Xiang et al., 2006), (Sengupta et al., 2001), (Okabe et al., 1996), (Goher et al., 1993), (Drew et al., 1971), hydrogen bonds. In an attempt to use the carboxyl group in this ligand as an intermolecular H-bond site to organize the molecules in the crystal, the title compound, (I), was synthesized. Unfortunately, only an intramolecular O–H···O is observed.
In compound (I), the metal center has a square pyramidal geometry with the 4'-phenyl-2,2':6',2''-terpyridine coordinated as tridentate in equatorial position and the 3-carboxylpyridine-2-carboxylato coordinated as bidentate with the pyridine N atom in equatorial and the O atom of the carboxylate in axial position (Fig. 1). The 4-phenyl ring in the trpy (C26 - C31) forms an angle of 40.0 (2) Å with the central ring of the trpy (N14/C15—C19). The phenyl ring of the 3-carboxylpyridine-2-carboxylato is almost perpendicular to the trpy, the angle between the mean planes of N14/C15—C19 and N1/C2—C6 is 81.6 (2) Å.
The molecules intercalate with π - π stacking between N14/C15—C19 and N20/C21—C25 of a molecule generated by the symmetry code (1/2 + x,1/2 - y,1/2 + z), the rings are almost parallel (2.05 °) and have a centroid-centroid distance of 3.770 (2)Å an interplanar distance of 3.55 Å, and an offset angle of 19.7°.
For related structures see: Turner et al. (2007); Xiang et al. (2006); Patrick et al. (2003); Sengupta et al. (2001); Okabe et al. (1996); Goher et al. (1993); Drew et al. (1971). For related literature, see: Constable et al. (1990).
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: publCIF (Westrip, 2007) and enCIFer (Allen et al., 2004).
[Cu(C7H4NO4)(C21H15N3)]BF4 | F(000) = 1268.3 |
Mr = 625.82 | Dx = 1.611 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 5948 reflections |
a = 9.7975 (5) Å | θ = 2.3–30.9° |
b = 25.102 (1) Å | µ = 0.92 mm−1 |
c = 11.0414 (6) Å | T = 298 K |
β = 108.183 (1)° | Prism, blue |
V = 2579.9 (2) Å3 | 0.24 × 0.16 × 0.06 mm |
Z = 4 |
Bruker SMART APEX CCD diffractometer | 4561 independent reflections |
Radiation source: fine-focus sealed tube | 3122 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.058 |
Detector resolution: 0.661 pixels mm-1 | θmax = 25.0°, θmin = 2.1° |
ω scans | h = −11→11 |
Absorption correction: analytical (Sheldrick, 2000) | k = −29→29 |
Tmin = 0.797, Tmax = 0.946 | l = −13→13 |
21071 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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.88 | w = 1/[σ2(Fo2) + (0.036P)2] where P = (Fo2 + 2Fc2)/3 |
4561 reflections | (Δ/σ)max = 0.001 |
457 parameters | Δρmax = 0.63 e Å−3 |
251 restraints | Δρmin = −0.25 e Å−3 |
[Cu(C7H4NO4)(C21H15N3)]BF4 | V = 2579.9 (2) Å3 |
Mr = 625.82 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.7975 (5) Å | µ = 0.92 mm−1 |
b = 25.102 (1) Å | T = 298 K |
c = 11.0414 (6) Å | 0.24 × 0.16 × 0.06 mm |
β = 108.183 (1)° |
Bruker SMART APEX CCD diffractometer | 4561 independent reflections |
Absorption correction: analytical (Sheldrick, 2000) | 3122 reflections with I > 2σ(I) |
Tmin = 0.797, Tmax = 0.946 | Rint = 0.058 |
21071 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | 251 restraints |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.88 | Δρmax = 0.63 e Å−3 |
4561 reflections | Δρmin = −0.25 e Å−3 |
457 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 | 0.93735 (4) | 0.164025 (14) | 0.23849 (4) | 0.03900 (14) | |
O1 | 0.8720 (2) | 0.14954 (8) | 0.4057 (2) | 0.0472 (6) | |
O2 | 0.7696 (3) | 0.08826 (9) | 0.4917 (2) | 0.0698 (8) | |
O3 | 0.7734 (3) | −0.00739 (10) | 0.5131 (3) | 0.0752 (8) | |
H3 | 0.754 (4) | 0.0275 (5) | 0.501 (3) | 0.090* | |
O4 | 0.8507 (3) | −0.07591 (9) | 0.4332 (2) | 0.0640 (7) | |
C1 | 0.8353 (3) | 0.10311 (13) | 0.4160 (3) | 0.0433 (8) | |
N1 | 0.8989 (3) | 0.08547 (9) | 0.2279 (2) | 0.0369 (6) | |
C2 | 0.8651 (3) | 0.06176 (11) | 0.3245 (3) | 0.0345 (8) | |
C3 | 0.8586 (3) | 0.00616 (12) | 0.3314 (3) | 0.0371 (8) | |
C4 | 0.8873 (3) | −0.02276 (12) | 0.2352 (3) | 0.0469 (9) | |
H4 | 0.8897 | −0.0598 | 0.2397 | 0.056* | |
C5 | 0.9120 (4) | 0.00184 (13) | 0.1340 (4) | 0.0549 (10) | |
H5 | 0.9243 | −0.0179 | 0.0669 | 0.066* | |
C6 | 0.9182 (4) | 0.05619 (13) | 0.1337 (3) | 0.0507 (9) | |
H6 | 0.9365 | 0.0733 | 0.0657 | 0.061* | |
C7 | 0.8259 (4) | −0.02882 (14) | 0.4319 (3) | 0.0480 (9) | |
N8 | 1.1567 (3) | 0.16328 (10) | 0.3086 (2) | 0.0370 (6) | |
C9 | 1.2439 (4) | 0.12160 (13) | 0.3443 (3) | 0.0454 (9) | |
H9 | 1.2034 | 0.0878 | 0.3380 | 0.055* | |
C10 | 1.3912 (4) | 0.12612 (14) | 0.3902 (3) | 0.0518 (9) | |
H10 | 1.4483 | 0.0960 | 0.4160 | 0.062* | |
C11 | 1.4525 (4) | 0.17548 (14) | 0.3974 (3) | 0.0537 (10) | |
H11 | 1.5518 | 0.1794 | 0.4259 | 0.064* | |
C12 | 1.3637 (3) | 0.21937 (13) | 0.3616 (3) | 0.0478 (9) | |
H12 | 1.4027 | 0.2534 | 0.3668 | 0.057* | |
C13 | 1.2169 (3) | 0.21217 (12) | 0.3179 (3) | 0.0363 (8) | |
N14 | 0.9758 (2) | 0.23913 (9) | 0.2358 (2) | 0.0340 (6) | |
C15 | 1.1114 (3) | 0.25650 (11) | 0.2800 (3) | 0.0352 (8) | |
C16 | 1.1407 (3) | 0.31016 (11) | 0.2911 (3) | 0.0388 (8) | |
H16 | 1.2352 | 0.3220 | 0.3212 | 0.047* | |
C17 | 1.0275 (3) | 0.34679 (11) | 0.2569 (3) | 0.0365 (8) | |
C18 | 0.8878 (3) | 0.32764 (11) | 0.2081 (3) | 0.0379 (8) | |
H18 | 0.8107 | 0.3511 | 0.1827 | 0.045* | |
C19 | 0.8651 (3) | 0.27295 (11) | 0.1976 (3) | 0.0343 (7) | |
N20 | 0.7350 (3) | 0.19182 (10) | 0.1475 (2) | 0.0381 (6) | |
C21 | 0.7243 (3) | 0.24570 (12) | 0.1464 (3) | 0.0348 (7) | |
C22 | 0.5939 (3) | 0.27147 (13) | 0.1016 (3) | 0.0432 (8) | |
H22 | 0.5892 | 0.3085 | 0.1008 | 0.052* | |
C23 | 0.4704 (3) | 0.24127 (14) | 0.0578 (3) | 0.0514 (9) | |
H23 | 0.3813 | 0.2578 | 0.0269 | 0.062* | |
C24 | 0.4804 (4) | 0.18665 (14) | 0.0600 (3) | 0.0524 (10) | |
H24 | 0.3983 | 0.1657 | 0.0316 | 0.063* | |
C25 | 0.6140 (3) | 0.16369 (13) | 0.1053 (3) | 0.0490 (9) | |
H25 | 0.6204 | 0.1267 | 0.1065 | 0.059* | |
C26 | 1.0554 (3) | 0.40427 (12) | 0.2780 (3) | 0.0384 (8) | |
C27 | 1.1720 (4) | 0.42823 (13) | 0.2552 (3) | 0.0536 (10) | |
H27 | 1.2338 | 0.4080 | 0.2246 | 0.064* | |
C28 | 1.1973 (4) | 0.48222 (14) | 0.2775 (4) | 0.0648 (11) | |
H28 | 1.2756 | 0.4979 | 0.2611 | 0.078* | |
C29 | 1.1096 (4) | 0.51244 (14) | 0.3230 (3) | 0.0614 (11) | |
H29 | 1.1283 | 0.5485 | 0.3385 | 0.074* | |
C30 | 0.9930 (4) | 0.48949 (13) | 0.3459 (3) | 0.0565 (10) | |
H30 | 0.9318 | 0.5101 | 0.3762 | 0.068* | |
C31 | 0.9662 (4) | 0.43578 (12) | 0.3240 (3) | 0.0483 (9) | |
H31 | 0.8873 | 0.4205 | 0.3403 | 0.058* | |
B1 | 1.0843 (4) | 0.15628 (14) | −0.0468 (4) | 0.0564 (12) | |
F1 | 0.9637 (6) | 0.1576 (3) | −0.0024 (8) | 0.048 (2) | 0.537 (14) |
F2 | 1.1713 (14) | 0.1141 (4) | 0.0048 (14) | 0.087 (4) | 0.537 (14) |
F3 | 1.1512 (9) | 0.2052 (2) | −0.0138 (14) | 0.071 (4) | 0.537 (14) |
F4 | 1.0292 (13) | 0.1520 (4) | −0.1777 (5) | 0.097 (3) | 0.537 (14) |
F1B | 0.9442 (8) | 0.1429 (7) | −0.0690 (19) | 0.092 (5) | 0.250 (8) |
F2B | 1.159 (3) | 0.1154 (10) | 0.031 (3) | 0.068 (5) | 0.250 (8) |
F3B | 1.127 (2) | 0.2018 (6) | 0.0264 (18) | 0.067 (5) | 0.250 (8) |
F4B | 1.1384 (18) | 0.1567 (6) | −0.1481 (11) | 0.093 (4) | 0.250 (8) |
F1C | 1.007 (2) | 0.1714 (9) | 0.0328 (17) | 0.070 (5) | 0.215 (12) |
F2C | 1.186 (3) | 0.1190 (12) | 0.013 (4) | 0.080 (7) | 0.215 (12) |
F3C | 1.1472 (17) | 0.1973 (7) | −0.093 (2) | 0.080 (4) | 0.215 (12) |
F4C | 0.9825 (19) | 0.1355 (9) | −0.1543 (17) | 0.084 (5) | 0.215 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0377 (2) | 0.0258 (2) | 0.0521 (3) | −0.00247 (19) | 0.01201 (19) | 0.0014 (2) |
O1 | 0.0622 (16) | 0.0309 (13) | 0.0509 (15) | −0.0032 (11) | 0.0214 (12) | −0.0050 (11) |
O2 | 0.105 (2) | 0.0463 (15) | 0.083 (2) | −0.0069 (14) | 0.0654 (18) | −0.0038 (14) |
O3 | 0.119 (2) | 0.0430 (16) | 0.080 (2) | −0.0027 (17) | 0.0537 (19) | 0.0127 (15) |
O4 | 0.087 (2) | 0.0342 (14) | 0.0670 (18) | −0.0035 (13) | 0.0185 (15) | 0.0097 (13) |
C1 | 0.046 (2) | 0.039 (2) | 0.044 (2) | −0.0005 (17) | 0.0123 (18) | −0.0020 (17) |
N1 | 0.0406 (16) | 0.0258 (14) | 0.0457 (17) | −0.0039 (12) | 0.0156 (14) | −0.0030 (13) |
C2 | 0.0277 (17) | 0.0314 (18) | 0.042 (2) | −0.0031 (14) | 0.0075 (15) | 0.0001 (15) |
C3 | 0.0304 (18) | 0.0299 (18) | 0.047 (2) | −0.0034 (14) | 0.0062 (16) | 0.0011 (16) |
C4 | 0.046 (2) | 0.0252 (18) | 0.070 (3) | −0.0041 (16) | 0.0203 (19) | −0.0049 (18) |
C5 | 0.071 (3) | 0.034 (2) | 0.072 (3) | −0.0080 (18) | 0.041 (2) | −0.0120 (19) |
C6 | 0.064 (2) | 0.038 (2) | 0.059 (3) | −0.0078 (18) | 0.033 (2) | −0.0015 (18) |
C7 | 0.051 (2) | 0.041 (2) | 0.049 (2) | −0.0081 (18) | 0.0099 (19) | 0.0021 (19) |
N8 | 0.0393 (15) | 0.0281 (14) | 0.0433 (16) | 0.0033 (13) | 0.0123 (13) | 0.0023 (13) |
C9 | 0.049 (2) | 0.036 (2) | 0.052 (2) | 0.0038 (18) | 0.0171 (18) | 0.0042 (17) |
C10 | 0.048 (2) | 0.044 (2) | 0.062 (3) | 0.0175 (19) | 0.0144 (19) | 0.0061 (18) |
C11 | 0.037 (2) | 0.055 (2) | 0.065 (3) | 0.0059 (19) | 0.0096 (18) | −0.005 (2) |
C12 | 0.037 (2) | 0.037 (2) | 0.066 (3) | −0.0050 (17) | 0.0115 (18) | −0.0077 (17) |
C13 | 0.0365 (19) | 0.0322 (19) | 0.040 (2) | −0.0007 (15) | 0.0117 (16) | −0.0020 (15) |
N14 | 0.0296 (15) | 0.0266 (14) | 0.0431 (16) | −0.0004 (12) | 0.0074 (13) | 0.0011 (12) |
C15 | 0.0361 (19) | 0.0285 (18) | 0.041 (2) | −0.0026 (15) | 0.0128 (16) | 0.0004 (15) |
C16 | 0.0324 (18) | 0.0340 (18) | 0.047 (2) | −0.0033 (15) | 0.0081 (16) | −0.0012 (15) |
C17 | 0.038 (2) | 0.0319 (18) | 0.0393 (19) | −0.0027 (15) | 0.0122 (16) | −0.0002 (15) |
C18 | 0.0367 (18) | 0.0282 (18) | 0.046 (2) | 0.0024 (15) | 0.0084 (15) | 0.0032 (15) |
C19 | 0.0338 (18) | 0.0306 (17) | 0.038 (2) | 0.0002 (15) | 0.0101 (15) | 0.0013 (15) |
N20 | 0.0351 (16) | 0.0297 (15) | 0.0472 (17) | −0.0035 (12) | 0.0095 (13) | −0.0002 (12) |
C21 | 0.0331 (18) | 0.0354 (19) | 0.0360 (19) | −0.0003 (15) | 0.0108 (15) | 0.0009 (15) |
C22 | 0.040 (2) | 0.0361 (19) | 0.051 (2) | 0.0006 (16) | 0.0101 (17) | 0.0036 (17) |
C23 | 0.033 (2) | 0.055 (2) | 0.061 (3) | 0.0025 (18) | 0.0076 (18) | 0.0060 (19) |
C24 | 0.032 (2) | 0.052 (2) | 0.067 (3) | −0.0107 (18) | 0.0065 (18) | 0.0030 (19) |
C25 | 0.043 (2) | 0.038 (2) | 0.063 (2) | −0.0076 (18) | 0.0122 (18) | −0.0006 (18) |
C26 | 0.0376 (19) | 0.0323 (18) | 0.042 (2) | −0.0031 (16) | 0.0080 (16) | 0.0003 (16) |
C27 | 0.061 (2) | 0.039 (2) | 0.065 (3) | −0.0039 (19) | 0.027 (2) | 0.0024 (19) |
C28 | 0.069 (3) | 0.042 (2) | 0.085 (3) | −0.020 (2) | 0.027 (2) | 0.003 (2) |
C29 | 0.077 (3) | 0.031 (2) | 0.067 (3) | −0.010 (2) | 0.008 (2) | −0.0044 (19) |
C30 | 0.056 (2) | 0.039 (2) | 0.068 (3) | 0.0030 (19) | 0.010 (2) | −0.0080 (19) |
C31 | 0.045 (2) | 0.034 (2) | 0.061 (2) | −0.0051 (17) | 0.0107 (18) | −0.0014 (17) |
B1 | 0.047 (3) | 0.046 (3) | 0.075 (4) | −0.006 (2) | 0.016 (3) | 0.008 (3) |
F1 | 0.034 (3) | 0.053 (4) | 0.044 (5) | −0.013 (3) | −0.008 (3) | −0.005 (3) |
F2 | 0.057 (7) | 0.043 (5) | 0.146 (8) | 0.011 (5) | 0.012 (6) | 0.000 (5) |
F3 | 0.040 (3) | 0.042 (3) | 0.137 (10) | −0.006 (2) | 0.036 (5) | 0.004 (4) |
F4 | 0.121 (7) | 0.118 (6) | 0.064 (4) | 0.007 (5) | 0.045 (4) | 0.012 (3) |
F1B | 0.049 (6) | 0.096 (8) | 0.092 (10) | −0.024 (6) | −0.032 (7) | 0.024 (8) |
F2B | 0.059 (9) | 0.058 (9) | 0.100 (9) | 0.019 (8) | 0.041 (7) | 0.035 (7) |
F3B | 0.059 (9) | 0.068 (7) | 0.083 (8) | −0.005 (6) | 0.035 (6) | −0.019 (6) |
F4B | 0.111 (9) | 0.109 (8) | 0.067 (7) | −0.029 (8) | 0.036 (7) | −0.006 (6) |
F1C | 0.078 (10) | 0.072 (10) | 0.052 (8) | 0.011 (8) | 0.009 (8) | −0.020 (6) |
F2C | 0.046 (10) | 0.063 (11) | 0.132 (13) | 0.005 (9) | 0.028 (11) | 0.028 (11) |
F3C | 0.078 (7) | 0.084 (8) | 0.085 (9) | 0.001 (7) | 0.035 (7) | 0.027 (7) |
F4C | 0.070 (9) | 0.112 (10) | 0.072 (9) | −0.006 (7) | 0.023 (8) | −0.020 (8) |
Cu1—N14 | 1.925 (2) | C17—C18 | 1.390 (4) |
Cu1—N1 | 2.004 (2) | C17—C26 | 1.474 (4) |
Cu1—N8 | 2.045 (2) | C18—C19 | 1.390 (4) |
Cu1—N20 | 2.045 (2) | C18—H18 | 0.9300 |
Cu1—O1 | 2.165 (2) | C19—C21 | 1.485 (4) |
Cu1—F1 | 2.756 (7) | N20—C25 | 1.333 (4) |
O1—C1 | 1.236 (3) | N20—C21 | 1.356 (3) |
O2—C1 | 1.260 (4) | C21—C22 | 1.378 (4) |
O3—C7 | 1.283 (4) | C22—C23 | 1.381 (4) |
O3—H3 | 0.897 (11) | C22—H22 | 0.9300 |
O4—C7 | 1.206 (4) | C23—C24 | 1.374 (4) |
C1—C2 | 1.539 (4) | C23—H23 | 0.9300 |
N1—C6 | 1.334 (4) | C24—C25 | 1.374 (4) |
N1—C2 | 1.350 (3) | C24—H24 | 0.9300 |
C2—C3 | 1.400 (4) | C25—H25 | 0.9300 |
C3—C4 | 1.386 (4) | C26—C27 | 1.382 (4) |
C3—C7 | 1.526 (4) | C26—C31 | 1.387 (4) |
C4—C5 | 1.362 (4) | C27—C28 | 1.386 (4) |
C4—H4 | 0.9300 | C27—H27 | 0.9300 |
C5—C6 | 1.366 (4) | C28—C29 | 1.354 (5) |
C5—H5 | 0.9300 | C28—H28 | 0.9300 |
C6—H6 | 0.9300 | C29—C30 | 1.372 (5) |
N8—C9 | 1.330 (4) | C29—H29 | 0.9300 |
N8—C13 | 1.351 (3) | C30—C31 | 1.380 (4) |
C9—C10 | 1.377 (4) | C30—H30 | 0.9300 |
C9—H9 | 0.9300 | C31—H31 | 0.9300 |
C10—C11 | 1.368 (4) | B1—F1B | 1.360 (6) |
C10—H10 | 0.9300 | B1—F2 | 1.366 (6) |
C11—C12 | 1.383 (4) | B1—F3C | 1.376 (7) |
C11—H11 | 0.9300 | B1—F2C | 1.379 (7) |
C12—C13 | 1.379 (4) | B1—F4B | 1.379 (6) |
C12—H12 | 0.9300 | B1—F4 | 1.380 (5) |
C13—C15 | 1.487 (4) | B1—F1C | 1.382 (7) |
N14—C15 | 1.337 (3) | B1—F3 | 1.385 (5) |
N14—C19 | 1.338 (3) | B1—F3B | 1.385 (7) |
C15—C16 | 1.375 (4) | B1—F2B | 1.390 (7) |
C16—C17 | 1.399 (4) | B1—F4C | 1.392 (7) |
C16—H16 | 0.9300 | B1—F1 | 1.414 (5) |
N14—Cu1—N1 | 175.58 (10) | C15—C16—H16 | 120.2 |
N14—Cu1—N8 | 80.04 (10) | C17—C16—H16 | 120.2 |
N1—Cu1—N8 | 99.75 (10) | C18—C17—C16 | 118.6 (3) |
N14—Cu1—N20 | 79.78 (10) | C18—C17—C26 | 120.8 (3) |
N1—Cu1—N20 | 99.86 (10) | C16—C17—C26 | 120.5 (3) |
N8—Cu1—N20 | 158.79 (10) | C19—C18—C17 | 119.1 (3) |
N14—Cu1—O1 | 106.81 (9) | C19—C18—H18 | 120.4 |
N1—Cu1—O1 | 77.56 (9) | C17—C18—H18 | 120.4 |
N8—Cu1—O1 | 103.36 (9) | N14—C19—C18 | 120.5 (3) |
N20—Cu1—O1 | 88.70 (9) | N14—C19—C21 | 113.2 (3) |
N14—Cu1—F1 | 87.96 (17) | C18—C19—C21 | 126.3 (3) |
N1—Cu1—F1 | 87.62 (17) | C25—N20—C21 | 117.8 (3) |
N8—Cu1—F1 | 87.76 (15) | C25—N20—Cu1 | 127.7 (2) |
N20—Cu1—F1 | 85.07 (14) | C21—N20—Cu1 | 113.92 (19) |
O1—Cu1—F1 | 162.70 (17) | N20—C21—C22 | 122.1 (3) |
C1—O1—Cu1 | 114.2 (2) | N20—C21—C19 | 113.3 (3) |
C7—O3—H3 | 114 (2) | C22—C21—C19 | 124.6 (3) |
O1—C1—O2 | 124.3 (3) | C21—C22—C23 | 118.7 (3) |
O1—C1—C2 | 117.1 (3) | C21—C22—H22 | 120.6 |
O2—C1—C2 | 118.5 (3) | C23—C22—H22 | 120.6 |
C6—N1—C2 | 120.2 (3) | C24—C23—C22 | 119.5 (3) |
C6—N1—Cu1 | 121.2 (2) | C24—C23—H23 | 120.3 |
C2—N1—Cu1 | 118.4 (2) | C22—C23—H23 | 120.3 |
N1—C2—C3 | 120.6 (3) | C25—C24—C23 | 118.6 (3) |
N1—C2—C1 | 111.4 (3) | C25—C24—H24 | 120.7 |
C3—C2—C1 | 128.0 (3) | C23—C24—H24 | 120.7 |
C4—C3—C2 | 117.2 (3) | N20—C25—C24 | 123.2 (3) |
C4—C3—C7 | 113.3 (3) | N20—C25—H25 | 118.4 |
C2—C3—C7 | 129.5 (3) | C24—C25—H25 | 118.4 |
C5—C4—C3 | 121.4 (3) | C27—C26—C31 | 118.0 (3) |
C5—C4—H4 | 119.3 | C27—C26—C17 | 121.4 (3) |
C3—C4—H4 | 119.3 | C31—C26—C17 | 120.6 (3) |
C4—C5—C6 | 118.3 (3) | C26—C27—C28 | 120.3 (3) |
C4—C5—H5 | 120.8 | C26—C27—H27 | 119.8 |
C6—C5—H5 | 120.8 | C28—C27—H27 | 119.8 |
N1—C6—C5 | 122.1 (3) | C29—C28—C27 | 121.0 (3) |
N1—C6—H6 | 119.0 | C29—C28—H28 | 119.5 |
C5—C6—H6 | 119.0 | C27—C28—H28 | 119.5 |
O4—C7—O3 | 121.7 (3) | C28—C29—C30 | 119.6 (3) |
O4—C7—C3 | 119.0 (3) | C28—C29—H29 | 120.2 |
O3—C7—C3 | 119.2 (3) | C30—C29—H29 | 120.2 |
C9—N8—C13 | 117.9 (3) | C29—C30—C31 | 120.1 (3) |
C9—N8—Cu1 | 128.4 (2) | C29—C30—H30 | 119.9 |
C13—N8—Cu1 | 113.7 (2) | C31—C30—H30 | 119.9 |
N8—C9—C10 | 123.1 (3) | C30—C31—C26 | 120.9 (3) |
N8—C9—H9 | 118.4 | C30—C31—H31 | 119.5 |
C10—C9—H9 | 118.4 | C26—C31—H31 | 119.5 |
C11—C10—C9 | 119.1 (3) | F3C—B1—F2C | 110.2 (15) |
C11—C10—H10 | 120.4 | F1B—B1—F4B | 118.5 (9) |
C9—C10—H10 | 120.4 | F2—B1—F4 | 111.5 (7) |
C10—C11—C12 | 118.7 (3) | F3C—B1—F1C | 115.4 (11) |
C10—C11—H11 | 120.7 | F2C—B1—F1C | 109.8 (16) |
C12—C11—H11 | 120.7 | F2—B1—F3 | 113.2 (7) |
C13—C12—C11 | 119.3 (3) | F4—B1—F3 | 110.0 (5) |
C13—C12—H12 | 120.3 | F1B—B1—F3B | 114.3 (11) |
C11—C12—H12 | 120.3 | F4B—B1—F3B | 110.3 (9) |
N8—C13—C12 | 121.9 (3) | F1B—B1—F2B | 103.6 (14) |
N8—C13—C15 | 114.2 (3) | F4B—B1—F2B | 104.3 (13) |
C12—C13—C15 | 123.9 (3) | F3B—B1—F2B | 104.0 (15) |
C15—N14—C19 | 121.6 (2) | F3C—B1—F4C | 104.4 (10) |
C15—N14—Cu1 | 119.39 (19) | F2C—B1—F4C | 112.1 (17) |
C19—N14—Cu1 | 118.89 (19) | F1C—B1—F4C | 104.8 (10) |
N14—C15—C16 | 120.5 (3) | F2—B1—F1 | 110.7 (7) |
N14—C15—C13 | 112.5 (2) | F4—B1—F1 | 105.6 (5) |
C16—C15—C13 | 126.9 (3) | F3—B1—F1 | 105.4 (5) |
C15—C16—C17 | 119.6 (3) | B1—F1—Cu1 | 132.5 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 0.90 (1) | 1.54 (2) | 2.412 (3) | 163 (4) |
Experimental details
Crystal data | |
Chemical formula | [Cu(C7H4NO4)(C21H15N3)]BF4 |
Mr | 625.82 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 9.7975 (5), 25.102 (1), 11.0414 (6) |
β (°) | 108.183 (1) |
V (Å3) | 2579.9 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.92 |
Crystal size (mm) | 0.24 × 0.16 × 0.06 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD |
Absorption correction | Analytical (Sheldrick, 2000) |
Tmin, Tmax | 0.797, 0.946 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21071, 4561, 3122 |
Rint | 0.058 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.085, 0.88 |
No. of reflections | 4561 |
No. of parameters | 457 |
No. of restraints | 251 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.63, −0.25 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXTL (Sheldrick, 2000), SHELXTL, publCIF (Westrip, 2007) and enCIFer (Allen et al., 2004).
D—H···A | D—H | H···A | D···A | D—H···A |
O3—H3···O2 | 0.897 (11) | 1.539 (15) | 2.412 (3) | 163 (4) |
Compounds with the 3-carboxylpyridine-2-carboxylato as ligand have been reported with the carboxyl group forming intermolecular (Turner et al., 2007), (Patrick et al., 2003), (Goher et al., 1993) or intramolecular (Xiang et al., 2006), (Sengupta et al., 2001), (Okabe et al., 1996), (Goher et al., 1993), (Drew et al., 1971), hydrogen bonds. In an attempt to use the carboxyl group in this ligand as an intermolecular H-bond site to organize the molecules in the crystal, the title compound, (I), was synthesized. Unfortunately, only an intramolecular O–H···O is observed.
In compound (I), the metal center has a square pyramidal geometry with the 4'-phenyl-2,2':6',2''-terpyridine coordinated as tridentate in equatorial position and the 3-carboxylpyridine-2-carboxylato coordinated as bidentate with the pyridine N atom in equatorial and the O atom of the carboxylate in axial position (Fig. 1). The 4-phenyl ring in the trpy (C26 - C31) forms an angle of 40.0 (2) Å with the central ring of the trpy (N14/C15—C19). The phenyl ring of the 3-carboxylpyridine-2-carboxylato is almost perpendicular to the trpy, the angle between the mean planes of N14/C15—C19 and N1/C2—C6 is 81.6 (2) Å.
The molecules intercalate with π - π stacking between N14/C15—C19 and N20/C21—C25 of a molecule generated by the symmetry code (1/2 + x,1/2 - y,1/2 + z), the rings are almost parallel (2.05 °) and have a centroid-centroid distance of 3.770 (2)Å an interplanar distance of 3.55 Å, and an offset angle of 19.7°.