(3-Carboxy­pyridine-2-carboxyl­ato-κ2N,O)(4′-phenyl-2,2′:6′,2′′-terpyridine-κ3N,N′,N′′)copper(II) tetra­fluoridoborate

Martínez-Vargas, S.; Toscano, R.A.; Valdés-Martínez, J.

doi:10.1107/S1600536807030073

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(3-Carboxypyridine-2-carboxylato-κ²N,O)(4′-phenyl-2,2′:6′,2′′-terpyridine-κ³N,N′,N′′)copper(II) tetrafluoridoborate

S. Martínez-Vargas, R. A. Toscano and J. Valdés-Martínez

The title compound, [Cu(C₇H₄NO₄)(C₂₁H₁₅N₃)]BF₄, was obtained from an attempt to use 3-carboxypyridine-2-carboxylate as an N,O-bidentate ligand with the carboxyl group as an intermolecular hydrogen-bond site to organize the molecules in the crystal structure. Unfortunately, instead of an intermolecular hydrogen bond, an intramolecular O—H

O hydrogen bond was observed, and the molecules are organized by van der Waals and π–π stacking interactions [3.770 (2) Å]. The metal center has a square-pyramidal geometry, with the 4′-phenyl-2,2′:6′,2′′-terpyridine coordinated in a tridentate manner in basal positions and the 3-carboxypyridine-2-carboxylate ligand coordinated as a bidentate ligand with the pyridine N atom basal and the O atom of the carboxylate group apical. The F atoms are disordered over three sites with occupancies of approximately 2:1:1.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807030073/dn2202sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807030073/dn2202Isup2.hkl Contains datablock I

CCDC reference: 654808

checkCIF report

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

Comment top

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 19.7Â°.

Related literature top

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).

Experimental top

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.

Structure description top

Computing details top

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).

Figures top

Fig. 1. The molecular structure of the complex cation in (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radius.

(3-Carboxypyridine-2-carboxylato-κ²N,O)(4'-phenyl-2,2':6',2''-terpyridine- κ³N,N',N'')copper(II) tetrafluoridoborate top

Crystal data top

[Cu(C₇H₄NO₄)(C₂₁H₁₅N₃)]BF₄	F(000) = 1268.3
M_r = 625.82	D_x = 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

Data collection top

Bruker SMART APEX CCD diffractometer	4561 independent reflections
Radiation source: fine-focus sealed tube	3122 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
Detector resolution: 0.661 pixels mm^-1	θ_max = 25.0°, θ_min = 2.1°
ω scans	h = −11→11
Absorption correction: analytical (Sheldrick, 2000)	k = −29→29
T_min = 0.797, T_max = 0.946	l = −13→13
21071 measured reflections

Refinement top

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(F_o²) + (0.036P)²] where P = (F_o² + 2F_c²)/3
4561 reflections	(Δ/σ)_max = 0.001
457 parameters	Δρ_max = 0.63 e Å⁻³
251 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

[Cu(C₇H₄NO₄)(C₂₁H₁₅N₃)]BF₄	V = 2579.9 (2) Å³
M_r = 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)°

Data collection top

Bruker SMART APEX CCD diffractometer	4561 independent reflections
Absorption correction: analytical (Sheldrick, 2000)	3122 reflections with I > 2σ(I)
T_min = 0.797, T_max = 0.946	R_int = 0.058
21071 measured reflections

Refinement top

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	Δρ_max = 0.63 e Å⁻³
4561 reflections	Δρ_min = −0.25 e Å⁻³
457 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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
M_r	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)
T_min, T_max	0.797, 0.946
No. of measured, independent and observed [I > 2σ(I)] reflections	21071, 4561, 3122
R_int	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
Δρ_max, Δρ_min (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).

Hydrogen-bond geometry (Å, º) top

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)

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