Bis[1-cyclo­propyl-6-fluoro-4-oxo-7-(1-piperazin-4-ium-1-yl)-1,4-dihydro­quinoline-3-carboxyl­ate-κ2O3,O4]bis­(nitrato-κO)copper(II)

Yang, J.; Yan, S.-W.; Ye, Z.-L.; Xin, G.-H.; Chang, S.-C.

doi:10.1107/S1600536812007830

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 3| March 2012| Pages m341-m342

doi:10.1107/S1600536812007830

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Bis[1-cyclopropyl-6-fluoro-4-oxo-7-(1-piperazin-4-ium-1-yl)-1,4-dihydroquinoline-3-carboxylate-κ²O³,O⁴]bis(nitrato-κO)copper(II)

Juan Yang,^a ^* Shi-Wei Yan,^a Zhong-Li Ye,^a Guang-Hua Xin ^a and Suo-Cheng Chang ^a

^aCollege of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, People's Republic of China
^*Correspondence e-mail: yangjuanai2008@126.com

(Received 19 February 2012; accepted 21 February 2012; online 29 February 2012)

In the title complex, [Cu(NO₃)₂(C₁₇H₁₈FN₃O₃)₂], the Cu^II ion is located on an inversion center. It exhibits a distorted octahedral geometry, being coordinated by six O atoms, four from two ciprofloxacin ligand molecules (L), which act as bidentate ligands, and two from two nitrate anions. In the ligand, the piperazine ring has a chair conformation and the quinoline system is essentially planar [maximum deviation = 0.097 (2) Å]. One of the nitrate O atoms is disordered over two positions [occupancy ratio = 0.51 (6):0.49 (6)]. There is a C—H⋯F interaction in the complex. In the crystal, molecules are linked via N—H⋯O hydrogen bonds generating a two-dimensional network lying parallel to (111). The presence of C—H⋯O interactions leads to the formation of a three-dimensional structure. The title complex was prepared by hydrothermal synthesis, and the hexahydrate form of this complex, synthesized by conventional methods, has been reported previously [Hernandez-Gil et al. (2009 ). Polyhedron, 28, 138–144].

Related literature

For general background on the use of quinolones in the treatment of infections, see: Barbas et al. (2006 ); Basavoju et al. (2006 ); Xiao et al. (2005 ). For the synthesis and crystal structure of the hexahydrate form of this complex, see: Hernandez-Gil et al. (2009).

Experimental

Crystal data

[Cu(NO₃)₂(C₁₇H₁₈FN₃O₃)₂]
M_r = 850.25
Triclinic, $[P \overline 1]$
a = 8.8921 (18) Å
b = 9.863 (2) Å
c = 11.186 (2) Å
α = 77.62 (3)°
β = 81.95 (3)°
γ = 64.15 (3)°
V = 861.1 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.73 mm⁻¹
T = 293 K
0.50 × 0.48 × 0.35 mm

Data collection

Bruker APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.713, T_max = 0.785
4702 measured reflections
2935 independent reflections
2766 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.136
S = 1.00
2935 reflections
269 parameters
H-atom parameters constrained
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O2ⁱ	0.90	1.86	2.749 (3)	170
N3—H3B⋯O4ⁱⁱ	0.90	2.00	2.838 (19)	155
N3—H3B⋯O6ⁱⁱ	0.90	2.21	2.995 (3)	146
C13—H13A⋯O4ⁱⁱⁱ	0.97	2.40	3.25 (3)	147
C13—H13B⋯O5ⁱ	0.97	2.58	3.382 (3)	140
C15—H15A⋯O3^iv	0.97	2.57	3.514 (3)	165
C17—H17A⋯F1	0.97	2.18	2.857 (3)	125
Symmetry codes: (i) -x, -y-1, -z+1; (ii) x-1, y, z+1; (iii) x-1, y, z; (iv) -x-1, -y, -z+1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812007830/su2380sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812007830/su2380Isup2.hkl

checkCIF report

Comment top

Ciprofloxacin is member of a class of quinolones used to treat infections (Barbas et al., 2006; Basavoju et al., 2006; Xiao et al. 2005). The title copper(II) complex was prepared by mixing Ciprofloxacin [cyclopropyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-pip -erazinyl)-3-quinolinecarboxylic acid, L] with Cu(NO₃)₂ under hydrothermal conditions. The synthesis and crystal structure of the hexahydrate form of this complex have been described by (Hernandez-Gil et al., 2009). Herein, we report on the crystal structure of the title complex.

The asymmetric unit of the title compound is compossed of one Cu^II ion, that is located on an inversion center, one L ligand and one NO₃^- anion (Fig. 1). The Cu^II ion is coordinated by six O atoms, four from two L ligand molecules and two from two NO₃^- anions, in a distorted octahedral geometry. There is a C—H···F interaction in the complex. In the ligand the piperazine ring (N2,N3,C14—C17) has a chair conformation and the quinoline moiety (N1,C2—C10) is essentially planer [max. devsion = 0.097 (2) Å].

In the crystal, molecules are linked via N—H···O hydrogen bonds generating a two-dimensional network lieing parallel to (1 1 1). The presence of C—H···O interactions leads to the formation of a three-dimensional structure.

The geometrical parameters of the title compound are very similar to those of the hexhydrate form of this complex (Hernandez-Gil et al., 2009).

Related literature top

For general background on the use of quinolones in the treatment of infections, see: Barbas et al. (2006); Basavoju et al. (2006); Xiao et al. (2005). For the synthesis and crystal structure of the hexahydrate form of this complex, see: Hernandez-Gil et al. (2009).

Experimental top

A mixture of Cu(NO₃)₂^.3H₂O (0.121 g, 0.5 mmol), cyclopropyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-pip -erazinyl)-3-quinolinecarboxylic acid (HL; 0.192 g, 0.5 mmol) in distilled water (7 ml), was stirred for 20 min in air. The mixture was then transferred to a 23 ml Teflon-lined hydrothermal bomb. The bomb was kept at 383 K for 72 h under autogenous pressure. Upon cooling, blue block-like crystals of the title compound were obtained from the reaction mixture.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound, with the atom numbering and displacement ellipsoids drawn at the 30% probability level. H atoms have been omitted for clarity [Symmetry code: (i) -x, -y, -z].

Bis[1-cyclopropyl-6-fluoro-4-oxo-7-(1-piperazin-4-ium-1-yl)-1,4- dihydroquinoline-3-carboxylate-κ²O³,O⁴]bis(nitrato- κO)copper(II) top

Crystal data top

[Cu(NO₃)₂(C₁₇H₁₈FN₃O₃)₂]	Z = 1
M_r = 850.25	F(000) = 439
Triclinic, P1	D_x = 1.640 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.8921 (18) Å	Cell parameters from 4702 reflections
b = 9.863 (2) Å	θ = 1.9–25.0°
c = 11.186 (2) Å	µ = 0.73 mm⁻¹
α = 77.62 (3)°	T = 293 K
β = 81.95 (3)°	Block, blue
γ = 64.15 (3)°	0.50 × 0.48 × 0.35 mm
V = 861.1 (3) Å³

Data collection top

Bruker APEX CCD area-detector diffractometer	2935 independent reflections
Radiation source: fine-focus sealed tube	2766 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
phi and ω scans	θ_max = 25.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.713, T_max = 0.785	k = −11→11
4702 measured reflections	l = −13→13

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.136	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.124P)²] where P = (F_o² + 2F_c²)/3
2935 reflections	(Δ/σ)_max = 0.010
269 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Cu(NO₃)₂(C₁₇H₁₈FN₃O₃)₂]	γ = 64.15 (3)°
M_r = 850.25	V = 861.1 (3) Å³
Triclinic, P1	Z = 1
a = 8.8921 (18) Å	Mo Kα radiation
b = 9.863 (2) Å	µ = 0.73 mm⁻¹
c = 11.186 (2) Å	T = 293 K
α = 77.62 (3)°	0.50 × 0.48 × 0.35 mm
β = 81.95 (3)°

Data collection top

Bruker APEX CCD area-detector diffractometer	2935 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2766 reflections with I > 2σ(I)
T_min = 0.713, T_max = 0.785	R_int = 0.026
4702 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.136	H-atom parameters constrained
S = 1.00	Δρ_max = 0.43 e Å⁻³
2935 reflections	Δρ_min = −0.34 e Å⁻³
269 parameters

Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

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	0.00000	0.00000	0.00000	0.0353 (2)
F1	−0.35238 (18)	0.05781 (15)	0.56641 (12)	0.0421 (4)
O1	0.0564 (2)	−0.19893 (19)	−0.03746 (15)	0.0468 (5)
O2	0.13735 (19)	−0.44723 (18)	0.00732 (14)	0.0393 (5)
O3	−0.12571 (19)	−0.03396 (17)	0.14953 (13)	0.0363 (5)
O4	0.471 (2)	−0.314 (4)	0.2079 (17)	0.121 (5)	0.51 (6)
O5	0.2223 (3)	−0.2423 (4)	0.2922 (2)	0.1016 (12)
O6	0.2794 (3)	−0.1278 (3)	0.1173 (2)	0.0720 (8)
N1	−0.14125 (19)	−0.43566 (19)	0.32933 (15)	0.0255 (5)
N2	−0.3720 (2)	−0.2050 (2)	0.69774 (16)	0.0292 (5)
N3	−0.4207 (3)	−0.2834 (2)	0.95656 (17)	0.0443 (6)
N4	0.3188 (3)	−0.2350 (3)	0.20525 (19)	0.0497 (8)
C1	0.0559 (2)	−0.3170 (2)	0.03294 (18)	0.0302 (6)
C2	−0.0471 (2)	−0.3005 (2)	0.15213 (18)	0.0267 (6)
C3	−0.1197 (2)	−0.1630 (2)	0.20359 (18)	0.0276 (6)
C4	−0.1884 (2)	−0.1755 (2)	0.32806 (17)	0.0264 (6)
C5	−0.2417 (3)	−0.0520 (2)	0.39143 (19)	0.0315 (6)
C6	−0.2984 (3)	−0.0651 (2)	0.51032 (19)	0.0304 (6)
C7	−0.3090 (2)	−0.2001 (2)	0.57654 (18)	0.0271 (6)
C8	−0.2596 (2)	−0.3220 (2)	0.51328 (17)	0.0267 (5)
C9	−0.1994 (2)	−0.3108 (2)	0.39076 (17)	0.0237 (5)
C10	−0.0668 (2)	−0.4268 (2)	0.21705 (17)	0.0271 (6)
C11	−0.1454 (2)	−0.5794 (2)	0.39316 (18)	0.0283 (6)
C12	−0.1739 (3)	−0.6783 (3)	0.3222 (2)	0.0432 (8)
C13	−0.3071 (3)	−0.5953 (3)	0.4123 (2)	0.0376 (7)
C14	−0.4089 (3)	−0.3377 (3)	0.75118 (19)	0.0328 (7)
C15	−0.5121 (3)	−0.3117 (3)	0.8697 (2)	0.0410 (7)
C16	−0.3878 (3)	−0.1462 (3)	0.9029 (2)	0.0420 (7)
C17	−0.2872 (3)	−0.1690 (3)	0.78328 (19)	0.0347 (6)
O4A	0.449 (3)	−0.3490 (11)	0.1929 (13)	0.089 (5)	0.49 (6)
H3B	−0.48200	−0.26860	1.02760	0.0530*
H5A	−0.23800	0.03950	0.35130	0.0380*
H3A	−0.32310	−0.36560	0.97240	0.0530*
H10A	−0.02510	−0.51320	0.18030	0.0330*
H11A	−0.06810	−0.63430	0.45940	0.0340*
H12A	−0.11320	−0.78830	0.34430	0.0520*
H12B	−0.19280	−0.64120	0.23560	0.0520*
H13A	−0.40620	−0.50830	0.37990	0.0450*
H13B	−0.32660	−0.65540	0.48860	0.0450*
H14A	−0.30510	−0.42850	0.76610	0.0390*
H14B	−0.46950	−0.35400	0.69400	0.0390*
H15A	−0.61880	−0.22440	0.85430	0.0490*
H15B	−0.53360	−0.40080	0.90530	0.0490*
H16A	−0.32700	−0.12930	0.95960	0.0500*
H16B	−0.49310	−0.05670	0.88960	0.0500*
H17A	−0.27240	−0.07680	0.74670	0.0420*
H17B	−0.17730	−0.25190	0.79800	0.0420*
H8A	−0.26680	−0.41200	0.55330	0.0320*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0494 (3)	0.0258 (3)	0.0272 (3)	−0.0183 (2)	0.0170 (2)	−0.0044 (2)
F1	0.0648 (8)	0.0285 (7)	0.0343 (7)	−0.0209 (6)	0.0109 (6)	−0.0136 (5)
O1	0.0742 (11)	0.0322 (9)	0.0315 (8)	−0.0263 (9)	0.0212 (8)	−0.0074 (7)
O2	0.0513 (9)	0.0299 (8)	0.0326 (8)	−0.0148 (7)	0.0116 (7)	−0.0113 (6)
O3	0.0487 (8)	0.0213 (8)	0.0304 (8)	−0.0131 (7)	0.0152 (6)	−0.0018 (6)
O4	0.064 (5)	0.163 (13)	0.055 (4)	0.015 (7)	0.000 (3)	0.005 (8)
O5	0.0879 (17)	0.178 (3)	0.0495 (13)	−0.0775 (19)	0.0127 (12)	−0.0038 (16)
O6	0.0717 (13)	0.0698 (15)	0.0623 (13)	−0.0261 (12)	0.0013 (11)	0.0021 (11)
N1	0.0326 (8)	0.0233 (9)	0.0226 (8)	−0.0148 (7)	0.0013 (6)	−0.0028 (6)
N2	0.0388 (9)	0.0288 (9)	0.0221 (8)	−0.0178 (8)	0.0051 (7)	−0.0053 (7)
N3	0.0597 (12)	0.0404 (11)	0.0237 (9)	−0.0153 (10)	0.0072 (8)	−0.0059 (8)
N4	0.0666 (14)	0.0604 (16)	0.0317 (11)	−0.0352 (13)	−0.0028 (10)	−0.0082 (10)
C1	0.0362 (10)	0.0317 (11)	0.0246 (10)	−0.0165 (9)	0.0020 (8)	−0.0059 (8)
C2	0.0314 (9)	0.0259 (10)	0.0228 (10)	−0.0133 (8)	0.0009 (7)	−0.0029 (7)
C3	0.0300 (9)	0.0243 (10)	0.0260 (10)	−0.0110 (8)	0.0014 (8)	−0.0018 (8)
C4	0.0304 (9)	0.0223 (10)	0.0250 (10)	−0.0116 (8)	0.0017 (8)	−0.0019 (8)
C5	0.0417 (10)	0.0237 (10)	0.0302 (10)	−0.0177 (9)	0.0027 (8)	−0.0008 (8)
C6	0.0389 (10)	0.0258 (11)	0.0279 (10)	−0.0148 (9)	0.0029 (8)	−0.0077 (8)
C7	0.0286 (9)	0.0301 (11)	0.0237 (10)	−0.0137 (9)	0.0020 (7)	−0.0059 (8)
C8	0.0327 (9)	0.0270 (10)	0.0220 (9)	−0.0160 (9)	−0.0004 (7)	−0.0004 (7)
C9	0.0268 (9)	0.0224 (10)	0.0228 (9)	−0.0119 (8)	−0.0009 (7)	−0.0028 (7)
C10	0.0311 (9)	0.0258 (10)	0.0247 (10)	−0.0123 (8)	0.0022 (8)	−0.0064 (8)
C11	0.0353 (10)	0.0239 (11)	0.0279 (10)	−0.0156 (9)	0.0010 (8)	−0.0038 (8)
C12	0.0637 (14)	0.0417 (13)	0.0394 (12)	−0.0367 (12)	0.0117 (11)	−0.0148 (10)
C13	0.0439 (12)	0.0423 (13)	0.0343 (11)	−0.0290 (11)	0.0060 (9)	−0.0033 (9)
C14	0.0410 (11)	0.0338 (12)	0.0267 (11)	−0.0208 (10)	0.0035 (8)	−0.0036 (9)
C15	0.0488 (12)	0.0411 (13)	0.0314 (11)	−0.0231 (11)	0.0090 (10)	−0.0006 (9)
C16	0.0591 (13)	0.0348 (12)	0.0294 (11)	−0.0160 (11)	0.0017 (10)	−0.0107 (9)
C17	0.0457 (11)	0.0331 (11)	0.0279 (10)	−0.0177 (10)	0.0016 (9)	−0.0101 (8)
O4A	0.132 (11)	0.040 (7)	0.050 (5)	−0.006 (4)	0.011 (5)	0.004 (3)

Geometric parameters (Å, º) top

Cu1—O1	1.9267 (18)	C4—C5	1.408 (3)
Cu1—O3	1.9293 (16)	C4—C9	1.406 (3)
Cu1—O6	2.637 (3)	C5—C6	1.355 (3)
Cu1—O1ⁱ	1.9267 (18)	C6—C7	1.413 (3)
Cu1—O3ⁱ	1.9293 (16)	C7—C8	1.399 (3)
Cu1—O6ⁱ	2.637 (3)	C8—C9	1.399 (3)
F1—C6	1.352 (2)	C11—C13	1.495 (4)
O1—C1	1.260 (3)	C11—C12	1.500 (3)
O2—C1	1.243 (2)	C12—C13	1.504 (4)
O3—C3	1.268 (2)	C14—C15	1.505 (3)
O4—N4	1.23 (3)	C16—C17	1.503 (3)
O4A—N4	1.229 (17)	C5—H5A	0.9300
O5—N4	1.216 (4)	C8—H8A	0.9300
O6—N4	1.239 (3)	C10—H10A	0.9300
N1—C9	1.402 (3)	C11—H11A	0.9800
N1—C11	1.458 (3)	C12—H12A	0.9700
N1—C10	1.339 (3)	C12—H12B	0.9700
N2—C7	1.392 (3)	C13—H13A	0.9700
N2—C14	1.470 (3)	C13—H13B	0.9700
N2—C17	1.480 (3)	C14—H14A	0.9700
N3—C15	1.489 (4)	C14—H14B	0.9700
N3—C16	1.492 (3)	C15—H15A	0.9700
N3—H3A	0.9000	C15—H15B	0.9700
N3—H3B	0.9000	C16—H16A	0.9700
C1—C2	1.505 (3)	C16—H16B	0.9700
C2—C10	1.370 (3)	C17—H17A	0.9700
C2—C3	1.433 (3)	C17—H17B	0.9700
C3—C4	1.443 (3)

O1—Cu1—O3	93.27 (8)	C7—C8—C9	121.13 (17)
O1—Cu1—O6	86.89 (9)	N1—C9—C4	118.31 (17)
O1—Cu1—O1ⁱ	180.00	C4—C9—C8	120.46 (17)
O1—Cu1—O3ⁱ	86.74 (8)	N1—C9—C8	121.16 (17)
O1—Cu1—O6ⁱ	93.11 (9)	N1—C10—C2	125.14 (18)
O3—Cu1—O6	90.88 (8)	N1—C11—C13	119.88 (18)
O1ⁱ—Cu1—O3	86.74 (8)	N1—C11—C12	119.26 (17)
O3—Cu1—O3ⁱ	180.00	C12—C11—C13	60.31 (16)
O3—Cu1—O6ⁱ	89.12 (8)	C11—C12—C13	59.67 (17)
O1ⁱ—Cu1—O6	93.11 (9)	C11—C13—C12	60.02 (17)
O3ⁱ—Cu1—O6	89.12 (8)	N2—C14—C15	110.3 (2)
O6—Cu1—O6ⁱ	180.00	N3—C15—C14	109.6 (2)
O1ⁱ—Cu1—O3ⁱ	93.27 (8)	N3—C16—C17	110.1 (2)
O1ⁱ—Cu1—O6ⁱ	86.89 (9)	N2—C17—C16	110.8 (2)
O3ⁱ—Cu1—O6ⁱ	90.88 (8)	C4—C5—H5A	120.00
Cu1—O1—C1	129.10 (15)	C6—C5—H5A	120.00
Cu1—O3—C3	125.15 (14)	C7—C8—H8A	119.00
Cu1—O6—N4	127.7 (2)	C9—C8—H8A	119.00
C9—N1—C10	119.56 (17)	N1—C10—H10A	117.00
C9—N1—C11	119.69 (16)	C2—C10—H10A	117.00
C10—N1—C11	120.40 (16)	N1—C11—H11A	115.00
C7—N2—C14	115.73 (17)	C12—C11—H11A	115.00
C7—N2—C17	116.41 (19)	C13—C11—H11A	115.00
C14—N2—C17	112.28 (18)	C11—C12—H12A	118.00
C15—N3—C16	110.14 (18)	C11—C12—H12B	118.00
O4—N4—O5	122.7 (10)	C13—C12—H12A	118.00
O4—N4—O6	113.2 (11)	C13—C12—H12B	118.00
O5—N4—O6	122.6 (3)	H12A—C12—H12B	115.00
O4A—N4—O5	118.8 (8)	C11—C13—H13A	118.00
O4A—N4—O6	117.4 (7)	C11—C13—H13B	118.00
C15—N3—H3B	110.00	C12—C13—H13A	118.00
C16—N3—H3A	110.00	C12—C13—H13B	118.00
C15—N3—H3A	110.00	H13A—C13—H13B	115.00
H3A—N3—H3B	108.00	N2—C14—H14A	110.00
C16—N3—H3B	110.00	N2—C14—H14B	110.00
O1—C1—C2	119.11 (17)	C15—C14—H14A	110.00
O1—C1—O2	122.29 (19)	C15—C14—H14B	110.00
O2—C1—C2	118.60 (17)	H14A—C14—H14B	108.00
C3—C2—C10	118.39 (18)	N3—C15—H15A	110.00
C1—C2—C3	123.98 (17)	N3—C15—H15B	110.00
C1—C2—C10	117.58 (17)	C14—C15—H15A	110.00
C2—C3—C4	116.32 (17)	C14—C15—H15B	110.00
O3—C3—C2	125.45 (18)	H15A—C15—H15B	108.00
O3—C3—C4	118.23 (17)	N3—C16—H16A	110.00
C3—C4—C9	121.71 (17)	N3—C16—H16B	110.00
C3—C4—C5	120.11 (18)	C17—C16—H16A	110.00
C5—C4—C9	118.15 (18)	C17—C16—H16B	110.00
C4—C5—C6	120.65 (19)	H16A—C16—H16B	108.00
F1—C6—C5	118.54 (18)	N2—C17—H17A	110.00
C5—C6—C7	122.64 (18)	N2—C17—H17B	110.00
F1—C6—C7	118.78 (18)	C16—C17—H17A	109.00
N2—C7—C8	123.21 (18)	C16—C17—H17B	110.00
N2—C7—C6	119.81 (17)	H17A—C17—H17B	108.00
C6—C7—C8	116.94 (18)

O3—Cu1—O1—C1	−20.0 (2)	C16—N3—C15—C14	59.7 (3)
O6—Cu1—O1—C1	70.7 (2)	C15—N3—C16—C17	−58.6 (3)
O3ⁱ—Cu1—O1—C1	160.0 (2)	O1—C1—C2—C3	−12.9 (3)
O6ⁱ—Cu1—O1—C1	−109.3 (2)	O1—C1—C2—C10	169.7 (2)
O1—Cu1—O3—C3	15.06 (19)	O2—C1—C2—C3	167.3 (2)
O6—Cu1—O3—C3	−71.87 (18)	O2—C1—C2—C10	−10.1 (3)
O1ⁱ—Cu1—O3—C3	−164.94 (19)	C1—C2—C3—O3	9.7 (3)
O6ⁱ—Cu1—O3—C3	108.13 (18)	C1—C2—C3—C4	−169.18 (18)
O1—Cu1—O6—N4	−59.5 (2)	C10—C2—C3—O3	−172.9 (2)
O3—Cu1—O6—N4	33.7 (2)	C10—C2—C3—C4	8.3 (3)
O1ⁱ—Cu1—O6—N4	120.5 (2)	C1—C2—C10—N1	173.62 (19)
O3ⁱ—Cu1—O6—N4	−146.3 (2)	C3—C2—C10—N1	−4.0 (3)
Cu1—O1—C1—O2	−159.28 (17)	O3—C3—C4—C5	−7.5 (3)
Cu1—O1—C1—C2	20.9 (3)	O3—C3—C4—C9	174.55 (19)
Cu1—O3—C3—C2	−13.6 (3)	C2—C3—C4—C5	171.5 (2)
Cu1—O3—C3—C4	165.31 (14)	C2—C3—C4—C9	−6.5 (3)
Cu1—O6—N4—O4	149.8 (15)	C3—C4—C5—C6	−176.6 (2)
Cu1—O6—N4—O5	−44.3 (4)	C9—C4—C5—C6	1.4 (4)
C10—N1—C9—C4	4.7 (3)	C3—C4—C9—N1	0.1 (3)
C10—N1—C9—C8	−172.32 (19)	C3—C4—C9—C8	177.10 (19)
C11—N1—C9—C4	177.84 (18)	C5—C4—C9—N1	−177.9 (2)
C11—N1—C9—C8	0.9 (3)	C5—C4—C9—C8	−0.9 (3)
C9—N1—C10—C2	−2.8 (3)	C4—C5—C6—F1	−178.3 (2)
C11—N1—C10—C2	−175.92 (19)	C4—C5—C6—C7	−0.6 (4)
C9—N1—C11—C12	147.5 (2)	F1—C6—C7—N2	−0.9 (3)
C9—N1—C11—C13	76.9 (2)	F1—C6—C7—C8	176.9 (2)
C10—N1—C11—C12	−39.4 (3)	C5—C6—C7—N2	−178.5 (2)
C10—N1—C11—C13	−110.0 (2)	C5—C6—C7—C8	−0.7 (4)
C14—N2—C7—C6	168.5 (2)	N2—C7—C8—C9	178.99 (19)
C14—N2—C7—C8	−9.2 (3)	C6—C7—C8—C9	1.3 (3)
C17—N2—C7—C6	−56.3 (3)	C7—C8—C9—N1	176.45 (19)
C17—N2—C7—C8	126.0 (2)	C7—C8—C9—C4	−0.5 (3)
C7—N2—C14—C15	−166.8 (2)	N1—C11—C12—C13	−109.8 (2)
C17—N2—C14—C15	56.3 (3)	N1—C11—C13—C12	108.7 (2)
C7—N2—C17—C16	168.18 (19)	N2—C14—C15—N3	−58.1 (3)
C14—N2—C17—C16	−55.2 (3)	N3—C16—C17—N2	55.6 (3)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O2ⁱⁱ	0.90	1.86	2.749 (3)	170
N3—H3B···O4ⁱⁱⁱ	0.90	2.00	2.838 (19)	155
N3—H3B···O6ⁱⁱⁱ	0.90	2.21	2.995 (3)	146
C13—H13A···O4^iv	0.97	2.40	3.25 (3)	147
C13—H13B···O5ⁱⁱ	0.97	2.58	3.382 (3)	140
C15—H15A···O3^v	0.97	2.57	3.514 (3)	165
C17—H17A···F1	0.97	2.18	2.857 (3)	125

Symmetry codes: (ii) −x, −y−1, −z+1; (iii) x−1, y, z+1; (iv) x−1, y, z; (v) −x−1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu(NO₃)₂(C₁₇H₁₈FN₃O₃)₂]
M_r	850.25
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	8.8921 (18), 9.863 (2), 11.186 (2)
α, β, γ (°)	77.62 (3), 81.95 (3), 64.15 (3)
V (Å³)	861.1 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.73
Crystal size (mm)	0.50 × 0.48 × 0.35

Data collection
Diffractometer	Bruker APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.713, 0.785
No. of measured, independent and observed [I > 2σ(I)] reflections	4702, 2935, 2766
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.136, 1.00
No. of reflections	2935
No. of parameters	269
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.34

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL-Plus (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O2ⁱ	0.90	1.86	2.749 (3)	170
N3—H3B···O4ⁱⁱ	0.90	2.00	2.838 (19)	155
N3—H3B···O6ⁱⁱ	0.90	2.21	2.995 (3)	146
C13—H13A···O4ⁱⁱⁱ	0.97	2.40	3.25 (3)	147
C13—H13B···O5ⁱ	0.97	2.58	3.382 (3)	140
C15—H15A···O3^iv	0.97	2.57	3.514 (3)	165
C17—H17A···F1	0.97	2.18	2.857 (3)	125

Symmetry codes: (i) −x, −y−1, −z+1; (ii) x−1, y, z+1; (iii) x−1, y, z; (iv) −x−1, −y, −z+1.

Acknowledgements

This work was financially supported by the Science and Technology Foundation of Southwest University (grant No. SWUB2007035) and the Science and Technology Innovation Foundation for Students of Southwest University.

References

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