(2,9-Dimethyl-1,10-phenanthroline-κ2N,N′)(4-hydroxy­benzoato-κ2O,O′)(nitrato-κO)copper(II)

Zhai, C.-P.; Yan, F.-M.; Zhao, P.-Z.

doi:10.1107/S1600536808034788

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page m1479

doi:10.1107/S1600536808034788

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(2,9-Dimethyl-1,10-phenanthroline-κ²N,N′)(4-hydroxybenzoato-κ²O,O′)(nitrato-κO)copper(II)

Cui-Ping Zhai,^a Feng-Mei Yan ^b and Pei-Zheng Zhao ^c ^*

^aCollege of Chemistry and Chemical Engineering, Henan University, Kaifeng 475001, People's Republic of China, ^bDepartment of Chemistry and Chemical Engineering, Huanghuai University, Zhumadian 463000, People's Republic of China, and ^cCollege of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007, People's Republic of China
^*Correspondence e-mail: pz_zhao@hotmail.com

(Received 19 October 2008; accepted 24 October 2008; online 31 October 2008)

In the title compound, [Cu(C₇H₅O₃)(NO₃)(C₁₄H₁₂N₂)], the Cu^II ion is five-coordinated in a slightly distorted square-pyramidal geometry by one O atom of a nitrate anion, two O atoms of a 4-hydroxybenzoate anion, and two N atoms from a bidentate 2,9-dimethyl-1,10-phenanthroline (dmphen) ligand. In the crystal structure, inversion-related molecules are linked into dimers by O—H⋯O hydrogen bonds. The packing is further stabilized by π–π interactions involving the benzene rings of the dmphen and hydroxybenzoate units, with centroid–centroid distances of 3.4930 (14) or 3.5727 (14) Å.

Related literature

For related structures, see: Xuan et al. (2007 ); Zhao et al. (2007 ); Okabe et al. (2007 ). For general background, see: Selvakumar et al. (2006 ).

Experimental

Crystal data

[Cu(C₇H₅O₃)(NO₃)(C₁₄H₁₂N₂)]
M_r = 470.92
Triclinic, $[P \overline 1]$
a = 9.594 (1) Å
b = 9.802 (1) Å
c = 12.347 (1) Å
α = 78.687 (14)°
β = 70.409 (13)°
γ = 63.740 (12)°
V = 979.4 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.16 mm⁻¹
T = 291 (2) K
0.37 × 0.30 × 0.17 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.673, T_max = 0.830
7393 measured reflections
3613 independent reflections
3129 reflections with I > 2σ(I)
R_int = 0.016

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.082
S = 1.02
3613 reflections
283 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O1	2.004 (3)
Cu1—N1	2.007 (3)
Cu1—N2	2.008 (3)
Cu1—O2	2.026 (2)
Cu1—O4	2.292 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3⋯O4ⁱ	0.82	1.97	2.767 (4)	164
Symmetry code: (i) -x, -y+1, -z+1.

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808034788/ci2692sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808034788/ci2692Isup2.hkl

checkCIF report

Comment top

The construction of novel Cu^II complexes are important for the development of new therapeutic drug design because of their antitumor activity (Selvakumar et al., 2006). A number of Cu^II complexes have been synthesized and their crystal structures have been reported (Okabe et al., 2007; Xuan et al.,2007; Zhao et al., 2007). The title compound was recently obtained from the reaction of copper nitrate, sodium 4-hydroxybenzoate and dmphen in an ethanol-water mixture, and its crystal structure is reported here (Fig.1).

The Cu^II atom lies in a slightly distorted square-pyramidal coordination environment with one nitrate anion coordinated in the apical position. A bidentate 4-hydroxybenzoate anion binds to the Cu^II atom as a chelate through two oxygen atoms of the carboxylate group, together with two N atoms of the dmphen, constitute the base of the pyramid. The corresponding bond lengths are listed in Table 1.

In the crystal structure, inversion related molecules are linked into a dimer by O—H···O hydrogen bonds (Fig. 2). The packing is further stabilized by π-π interactions involving the benzene rings of the dmphen (C5-C8/C13/C14; centroid Cg1) and hydroxybenzoate (C16-C21; centroid Cg2) ligands (Fig. 2). The Cg1···Cg1ⁱⁱ and Cg1···Cg2ⁱⁱⁱ distances are 3.4930 (14) Å and 3.5727 (14) Å, respectively [symmetry codes: (ii) 1 - x,-y,1 - z; (iii) 2-x, -y, -z]. This combination of hydrogen bonds and stacking interactions builds a three-dimensional network architecture.

Related literature top

For related structures, see: Xuan et al. (2007); Zhao et al. (2007); Okabe et al. (2007). For general background, see: Selvakumar et al. (2006).

Experimental top

4-Hydroxybenzoic acid (0.1389 g, 1 mmol) and NaOH (0.0380 g, 1 mmol) were dissolved in distilled water (10 ml) and 10 ml of Cu(NO₃)₂.3H₂O (0.1220 g, 1 mmol) was added. This solution was added to a solution of 2,9-dimethyl-1,10-phenanthroline hemihydrate (C₁₄H₁₂N₂^.0.5H₂O, 0.1088 g, 0.5 mmol) in ethanol (10 ml). The mixture was stirred at 323 K and then refluxed for 5 h, cooled to room temperature and filtered. Green single crystals of the title compound appeared over a period of two weeks by slow evaporation at room temperature.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title complex, with atom labels and 30% probability displacement ellipsoids.
	Fig. 2. The hydrogen-bonding motifs, and π-π interactions between the aromatic rings of neighboring molecules in the crystal structure of the title compound. Dashed lines indicate the hydrogen bonds.

(2,9-Dimethyl-1,10-phenanthroline-κ²N,N')(4-hydroxybenzoato- κ²O,O')(nitrato-κO)copper(II) top

Crystal data top

[Cu(C₇H₅O₃)(NO₃)(C₁₄H₁₂N₂)]	Z = 2
M_r = 470.92	F(000) = 482
Triclinic, P1	D_x = 1.597 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.594 (1) Å	Cell parameters from 3492 reflections
b = 9.802 (1) Å	θ = 2.5–26.8°
c = 12.347 (1) Å	µ = 1.16 mm⁻¹
α = 78.687 (14)°	T = 291 K
β = 70.409 (13)°	Block, green
γ = 63.740 (12)°	0.37 × 0.30 × 0.17 mm
V = 979.4 (2) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	3613 independent reflections
Radiation source: fine-focus sealed tube	3129 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.016
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −11→11
T_min = 0.673, T_max = 0.830	k = −11→11
7393 measured reflections	l = −14→14

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0426P)² + 0.3425P] where P = (F_o² + 2F_c²)/3
3613 reflections	(Δ/σ)_max = 0.001
283 parameters	Δρ_max = 0.29 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

[Cu(C₇H₅O₃)(NO₃)(C₁₄H₁₂N₂)]	γ = 63.740 (12)°
M_r = 470.92	V = 979.4 (2) Å³
Triclinic, P1	Z = 2
a = 9.594 (1) Å	Mo Kα radiation
b = 9.802 (1) Å	µ = 1.16 mm⁻¹
c = 12.347 (1) Å	T = 291 K
α = 78.687 (14)°	0.37 × 0.30 × 0.17 mm
β = 70.409 (13)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3613 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	3129 reflections with I > 2σ(I)
T_min = 0.673, T_max = 0.830	R_int = 0.016
7393 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.082	H-atom parameters constrained
S = 1.03	Δρ_max = 0.29 e Å⁻³
3613 reflections	Δρ_min = −0.28 e Å⁻³
283 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
Cu1	0.56944 (3)	0.10556 (3)	0.31286 (2)	0.04415 (11)
O1	0.3621 (2)	0.0772 (2)	0.38002 (17)	0.0671 (5)
O2	0.4119 (2)	0.2318 (2)	0.44919 (15)	0.0621 (5)
O3	−0.33023 (19)	0.4060 (2)	0.72945 (16)	0.0582 (4)
H3	−0.3541	0.4863	0.7561	0.087*
O4	0.4677 (2)	0.3057 (2)	0.18943 (16)	0.0622 (5)
O5	0.4474 (2)	0.1655 (2)	0.08484 (18)	0.0701 (5)
O6	0.3103 (3)	0.4068 (3)	0.0818 (2)	0.1043 (9)
N1	0.7212 (2)	−0.0741 (2)	0.21653 (16)	0.0421 (4)
N2	0.7676 (2)	0.1464 (2)	0.28006 (16)	0.0422 (4)
N3	0.4092 (2)	0.2916 (2)	0.11642 (18)	0.0504 (5)
C1	0.5285 (3)	−0.1813 (3)	0.2297 (3)	0.0715 (8)
H1A	0.5038	−0.2040	0.3114	0.107*
H1B	0.5249	−0.2569	0.1929	0.107*
H1C	0.4503	−0.0827	0.2133	0.107*
C2	0.6932 (3)	−0.1819 (3)	0.1857 (2)	0.0510 (6)
C3	0.8195 (4)	−0.2957 (3)	0.1132 (2)	0.0641 (7)
H3A	0.7983	−0.3690	0.0920	0.077*
C4	0.9713 (3)	−0.3004 (3)	0.0738 (2)	0.0625 (7)
H4	1.0537	−0.3774	0.0270	0.075*
C5	1.0041 (3)	−0.1884 (3)	0.10370 (19)	0.0496 (6)
C6	1.1587 (3)	−0.1807 (3)	0.0638 (2)	0.0602 (7)
H6	1.2452	−0.2542	0.0160	0.072*
C7	1.1814 (3)	−0.0682 (3)	0.0943 (2)	0.0598 (7)
H7	1.2828	−0.0648	0.0666	0.072*
C8	1.0515 (3)	0.0449 (3)	0.1683 (2)	0.0498 (6)
C9	1.0668 (3)	0.1644 (4)	0.2035 (2)	0.0643 (7)
H9	1.1659	0.1724	0.1787	0.077*
C10	0.9371 (3)	0.2677 (4)	0.2736 (3)	0.0665 (7)
H10	0.9485	0.3463	0.2964	0.080*
C11	0.7859 (3)	0.2593 (3)	0.3126 (2)	0.0522 (6)
C12	0.6441 (3)	0.3759 (3)	0.3901 (3)	0.0737 (8)
H12A	0.5606	0.4308	0.3523	0.111*
H12B	0.6781	0.4456	0.4075	0.111*
H12C	0.6030	0.3258	0.4602	0.111*
C13	0.8981 (2)	0.0411 (3)	0.20915 (18)	0.0406 (5)
C14	0.8733 (3)	−0.0774 (2)	0.17599 (18)	0.0410 (5)
C15	0.3136 (3)	0.1778 (3)	0.4508 (2)	0.0473 (5)
C16	0.1466 (3)	0.2347 (3)	0.52814 (18)	0.0417 (5)
C17	0.0886 (3)	0.3593 (3)	0.59319 (19)	0.0470 (5)
H17	0.1576	0.4037	0.5909	0.056*
C18	−0.0697 (3)	0.4184 (3)	0.6611 (2)	0.0468 (5)
H18	−0.1069	0.5020	0.7041	0.056*
C19	−0.1735 (3)	0.3527 (3)	0.66513 (19)	0.0431 (5)
C20	−0.1163 (3)	0.2265 (3)	0.6021 (2)	0.0496 (6)
H20	−0.1845	0.1806	0.6060	0.060*
C21	0.0425 (3)	0.1690 (3)	0.5334 (2)	0.0481 (5)
H21	0.0798	0.0855	0.4903	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.03013 (15)	0.04953 (18)	0.05171 (18)	−0.01577 (12)	−0.00692 (11)	−0.00997 (12)
O1	0.0446 (9)	0.0701 (12)	0.0827 (13)	−0.0273 (9)	0.0080 (9)	−0.0326 (10)
O2	0.0428 (9)	0.0921 (14)	0.0585 (10)	−0.0370 (9)	0.0016 (8)	−0.0242 (9)
O3	0.0380 (9)	0.0583 (11)	0.0737 (12)	−0.0203 (8)	−0.0022 (8)	−0.0164 (9)
O4	0.0612 (11)	0.0592 (11)	0.0719 (12)	−0.0204 (9)	−0.0303 (10)	−0.0054 (9)
O5	0.0574 (11)	0.0630 (12)	0.0845 (14)	−0.0193 (9)	−0.0084 (10)	−0.0260 (10)
O6	0.1100 (19)	0.0705 (14)	0.129 (2)	0.0055 (13)	−0.0824 (17)	−0.0155 (14)
N1	0.0362 (9)	0.0428 (10)	0.0467 (10)	−0.0140 (8)	−0.0142 (8)	−0.0023 (8)
N2	0.0334 (9)	0.0479 (10)	0.0472 (10)	−0.0164 (8)	−0.0136 (8)	−0.0037 (8)
N3	0.0319 (10)	0.0550 (13)	0.0567 (12)	−0.0123 (9)	−0.0060 (9)	−0.0118 (10)
C1	0.0650 (17)	0.0609 (17)	0.105 (2)	−0.0342 (14)	−0.0248 (16)	−0.0169 (16)
C2	0.0521 (14)	0.0424 (13)	0.0617 (15)	−0.0162 (11)	−0.0243 (12)	−0.0028 (11)
C3	0.0733 (19)	0.0473 (14)	0.0741 (18)	−0.0150 (13)	−0.0308 (15)	−0.0147 (13)
C4	0.0585 (16)	0.0519 (15)	0.0574 (16)	0.0012 (12)	−0.0186 (13)	−0.0148 (12)
C5	0.0440 (13)	0.0516 (14)	0.0397 (12)	−0.0069 (10)	−0.0137 (10)	−0.0015 (10)
C6	0.0371 (13)	0.0738 (18)	0.0433 (14)	−0.0045 (12)	−0.0047 (10)	−0.0027 (12)
C7	0.0319 (12)	0.0829 (19)	0.0499 (14)	−0.0182 (12)	−0.0061 (10)	0.0056 (13)
C8	0.0356 (12)	0.0675 (16)	0.0433 (13)	−0.0215 (11)	−0.0122 (10)	0.0063 (11)
C9	0.0444 (14)	0.091 (2)	0.0704 (18)	−0.0419 (14)	−0.0157 (13)	0.0026 (15)
C10	0.0567 (16)	0.0772 (19)	0.084 (2)	−0.0401 (15)	−0.0211 (15)	−0.0098 (16)
C11	0.0445 (13)	0.0579 (15)	0.0634 (15)	−0.0236 (11)	−0.0204 (11)	−0.0074 (12)
C12	0.0550 (16)	0.0690 (18)	0.106 (2)	−0.0223 (14)	−0.0214 (16)	−0.0340 (17)
C13	0.0326 (11)	0.0506 (13)	0.0363 (11)	−0.0159 (9)	−0.0120 (9)	0.0038 (9)
C14	0.0344 (11)	0.0448 (12)	0.0385 (11)	−0.0107 (9)	−0.0139 (9)	0.0021 (9)
C15	0.0407 (12)	0.0554 (14)	0.0438 (13)	−0.0203 (11)	−0.0092 (10)	−0.0012 (11)
C16	0.0388 (11)	0.0499 (13)	0.0374 (11)	−0.0214 (10)	−0.0092 (9)	0.0005 (10)
C17	0.0432 (12)	0.0598 (14)	0.0459 (13)	−0.0306 (11)	−0.0088 (10)	−0.0033 (11)
C18	0.0475 (13)	0.0489 (13)	0.0458 (13)	−0.0230 (11)	−0.0068 (10)	−0.0093 (10)
C19	0.0355 (11)	0.0477 (12)	0.0433 (12)	−0.0172 (10)	−0.0091 (9)	0.0003 (10)
C20	0.0418 (12)	0.0523 (14)	0.0610 (15)	−0.0259 (11)	−0.0104 (11)	−0.0073 (11)
C21	0.0455 (13)	0.0465 (13)	0.0517 (14)	−0.0198 (10)	−0.0073 (10)	−0.0105 (10)

Geometric parameters (Å, º) top

Cu1—O1	2.004 (3)	C5—C6	1.429 (4)
Cu1—N1	2.007 (3)	C6—C7	1.356 (4)
Cu1—N2	2.008 (3)	C6—H6	0.93
Cu1—O2	2.026 (2)	C7—C8	1.425 (4)
Cu1—O4	2.292 (3)	C7—H7	0.93
Cu1—C15	2.357 (3)	C8—C13	1.402 (4)
O1—C15	1.269 (3)	C8—C9	1.406 (4)
O2—C15	1.264 (3)	C9—C10	1.352 (4)
O3—C19	1.353 (3)	C9—H9	0.93
O3—H3	0.82	C10—C11	1.402 (4)
O4—N3	1.266 (3)	C10—H10	0.93
O5—N3	1.228 (3)	C11—C12	1.501 (4)
O6—N3	1.221 (3)	C12—H12A	0.96
N1—C2	1.346 (3)	C12—H12B	0.96
N1—C14	1.363 (3)	C12—H12C	0.96
N2—C11	1.345 (3)	C13—C14	1.438 (3)
N2—C13	1.370 (3)	C15—C16	1.478 (3)
C1—C2	1.486 (4)	C16—C21	1.387 (3)
C1—H1A	0.96	C16—C17	1.390 (3)
C1—H1B	0.96	C17—C18	1.380 (3)
C1—H1C	0.96	C17—H17	0.93
C2—C3	1.408 (4)	C18—C19	1.390 (3)
C3—C4	1.354 (4)	C18—H18	0.93
C3—H3A	0.93	C19—C20	1.388 (4)
C4—C5	1.409 (4)	C20—C21	1.386 (3)
C4—H4	0.93	C20—H20	0.93
C5—C14	1.406 (3)	C21—H21	0.93

O1—Cu1—N1	105.07 (10)	C6—C7—H7	119.7
O1—Cu1—N2	167.57 (8)	C8—C7—H7	119.7
N1—Cu1—N2	84.14 (10)	C13—C8—C9	116.6 (2)
O1—Cu1—O2	64.92 (9)	C13—C8—C7	119.8 (2)
N1—Cu1—O2	161.37 (8)	C9—C8—C7	123.6 (2)
N2—Cu1—O2	103.84 (9)	C10—C9—C8	119.9 (2)
O1—Cu1—O4	94.09 (10)	C10—C9—H9	120.1
N1—Cu1—O4	106.75 (12)	C8—C9—H9	120.1
N2—Cu1—O4	91.11 (10)	C9—C10—C11	121.6 (3)
O2—Cu1—O4	90.11 (12)	C9—C10—H10	119.2
O1—Cu1—C15	32.57 (9)	C11—C10—H10	119.2
N1—Cu1—C15	136.29 (9)	N2—C11—C10	119.8 (2)
N2—Cu1—C15	136.17 (10)	N2—C11—C12	119.8 (2)
O2—Cu1—C15	32.40 (8)	C10—C11—C12	120.3 (2)
O4—Cu1—C15	91.14 (10)	C11—C12—H12A	109.5
C15—O1—Cu1	89.23 (15)	C11—C12—H12B	109.5
C15—O2—Cu1	88.38 (16)	H12A—C12—H12B	109.5
C19—O3—H3	109.5	C11—C12—H12C	109.5
N3—O4—Cu1	121.09 (17)	H12A—C12—H12C	109.5
C2—N1—C14	118.7 (2)	H12B—C12—H12C	109.5
C2—N1—Cu1	130.40 (18)	N2—C13—C8	123.0 (2)
C14—N1—Cu1	110.83 (15)	N2—C13—C14	117.3 (2)
C11—N2—C13	119.1 (2)	C8—C13—C14	119.7 (2)
C11—N2—Cu1	130.43 (16)	N1—C14—C5	123.5 (2)
C13—N2—Cu1	110.44 (16)	N1—C14—C13	117.20 (19)
O6—N3—O5	121.6 (2)	C5—C14—C13	119.3 (2)
O6—N3—O4	117.7 (2)	O2—C15—O1	117.3 (2)
O5—N3—O4	120.7 (2)	O2—C15—C16	121.2 (2)
C2—C1—H1A	109.5	O1—C15—C16	121.4 (2)
C2—C1—H1B	109.5	O2—C15—Cu1	59.23 (14)
H1A—C1—H1B	109.5	O1—C15—Cu1	58.19 (13)
C2—C1—H1C	109.5	C16—C15—Cu1	174.09 (17)
H1A—C1—H1C	109.5	C21—C16—C17	118.8 (2)
H1B—C1—H1C	109.5	C21—C16—C15	120.6 (2)
N1—C2—C3	120.2 (2)	C17—C16—C15	120.5 (2)
N1—C2—C1	119.6 (2)	C18—C17—C16	121.1 (2)
C3—C2—C1	120.1 (2)	C18—C17—H17	119.5
C4—C3—C2	121.3 (3)	C16—C17—H17	119.5
C4—C3—H3A	119.4	C17—C18—C19	119.8 (2)
C2—C3—H3A	119.4	C17—C18—H18	120.1
C3—C4—C5	119.8 (2)	C19—C18—H18	120.1
C3—C4—H4	120.1	O3—C19—C20	117.7 (2)
C5—C4—H4	120.1	O3—C19—C18	122.6 (2)
C14—C5—C4	116.5 (2)	C20—C19—C18	119.7 (2)
C14—C5—C6	119.4 (2)	C21—C20—C19	120.0 (2)
C4—C5—C6	124.1 (2)	C21—C20—H20	120.0
C7—C6—C5	121.1 (2)	C19—C20—H20	120.0
C7—C6—H6	119.4	C20—C21—C16	120.7 (2)
C5—C6—H6	119.4	C20—C21—H21	119.7
C6—C7—C8	120.6 (2)	C16—C21—H21	119.7

N1—Cu1—O1—C15	165.73 (15)	C13—N2—C11—C10	0.2 (4)
N2—Cu1—O1—C15	28.8 (4)	Cu1—N2—C11—C10	−176.80 (19)
O2—Cu1—O1—C15	2.50 (14)	C13—N2—C11—C12	179.9 (2)
O4—Cu1—O1—C15	−85.71 (18)	Cu1—N2—C11—C12	3.0 (4)
O1—Cu1—O2—C15	−2.51 (14)	C9—C10—C11—N2	−0.1 (4)
N1—Cu1—O2—C15	−63.2 (3)	C9—C10—C11—C12	−179.9 (3)
N2—Cu1—O2—C15	−176.87 (14)	C11—N2—C13—C8	0.0 (3)
O4—Cu1—O2—C15	91.96 (17)	Cu1—N2—C13—C8	177.49 (17)
O1—Cu1—O4—N3	−57.54 (18)	C11—N2—C13—C14	−179.8 (2)
N1—Cu1—O4—N3	49.54 (19)	Cu1—N2—C13—C14	−2.2 (2)
N2—Cu1—O4—N3	133.76 (17)	C9—C8—C13—N2	−0.1 (3)
O2—Cu1—O4—N3	−122.40 (18)	C7—C8—C13—N2	−179.7 (2)
C15—Cu1—O4—N3	−90.02 (19)	C9—C8—C13—C14	179.6 (2)
O1—Cu1—N1—C2	9.1 (2)	C7—C8—C13—C14	0.0 (3)
N2—Cu1—N1—C2	−179.4 (2)	C2—N1—C14—C5	−0.4 (3)
O2—Cu1—N1—C2	64.0 (3)	Cu1—N1—C14—C5	−178.41 (17)
O4—Cu1—N1—C2	−90.0 (2)	C2—N1—C14—C13	178.98 (19)
C15—Cu1—N1—C2	20.2 (3)	Cu1—N1—C14—C13	1.0 (2)
O1—Cu1—N1—C14	−173.18 (14)	C4—C5—C14—N1	−0.2 (3)
N2—Cu1—N1—C14	−1.68 (14)	C6—C5—C14—N1	178.8 (2)
O2—Cu1—N1—C14	−118.3 (2)	C4—C5—C14—C13	−179.5 (2)
O4—Cu1—N1—C14	87.72 (16)	C6—C5—C14—C13	−0.5 (3)
C15—Cu1—N1—C14	−162.11 (14)	N2—C13—C14—N1	0.9 (3)
O1—Cu1—N2—C11	−42.2 (5)	C8—C13—C14—N1	−178.84 (19)
N1—Cu1—N2—C11	179.3 (2)	N2—C13—C14—C5	−179.72 (19)
O2—Cu1—N2—C11	−17.8 (2)	C8—C13—C14—C5	0.6 (3)
O4—Cu1—N2—C11	72.6 (2)	Cu1—O2—C15—O1	4.0 (2)
C15—Cu1—N2—C11	−20.2 (3)	Cu1—O2—C15—C16	−173.1 (2)
O1—Cu1—N2—C13	140.6 (3)	Cu1—O1—C15—O2	−4.1 (2)
N1—Cu1—N2—C13	2.12 (14)	Cu1—O1—C15—C16	173.1 (2)
O2—Cu1—N2—C13	165.01 (14)	O1—Cu1—C15—O2	175.8 (2)
O4—Cu1—N2—C13	−104.60 (17)	N1—Cu1—C15—O2	155.62 (14)
C15—Cu1—N2—C13	162.59 (14)	N2—Cu1—C15—O2	4.4 (2)
Cu1—O4—N3—O6	155.5 (2)	O4—Cu1—C15—O2	−88.41 (18)
Cu1—O4—N3—O5	−22.2 (3)	N1—Cu1—C15—O1	−20.2 (2)
C14—N1—C2—C3	0.2 (3)	N2—Cu1—C15—O1	−171.39 (14)
Cu1—N1—C2—C3	177.79 (18)	O2—Cu1—C15—O1	−175.8 (2)
C14—N1—C2—C1	179.5 (2)	O4—Cu1—C15—O1	95.81 (18)
Cu1—N1—C2—C1	−3.0 (3)	O2—C15—C16—C21	−176.7 (2)
N1—C2—C3—C4	0.5 (4)	O1—C15—C16—C21	6.3 (4)
C1—C2—C3—C4	−178.7 (3)	O2—C15—C16—C17	6.2 (3)
C2—C3—C4—C5	−1.1 (4)	O1—C15—C16—C17	−170.8 (2)
C3—C4—C5—C14	0.9 (4)	C21—C16—C17—C18	−0.6 (3)
C3—C4—C5—C6	−178.0 (2)	C15—C16—C17—C18	176.6 (2)
C14—C5—C6—C7	−0.1 (4)	C16—C17—C18—C19	0.1 (4)
C4—C5—C6—C7	178.8 (2)	C17—C18—C19—O3	−179.5 (2)
C5—C6—C7—C8	0.7 (4)	C17—C18—C19—C20	1.0 (3)
C6—C7—C8—C13	−0.6 (4)	O3—C19—C20—C21	178.9 (2)
C6—C7—C8—C9	179.8 (2)	C18—C19—C20—C21	−1.6 (4)
C13—C8—C9—C10	0.1 (4)	C19—C20—C21—C16	1.1 (4)
C7—C8—C9—C10	179.7 (3)	C17—C16—C21—C20	0.0 (4)
C8—C9—C10—C11	0.0 (4)	C15—C16—C21—C20	−177.2 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O4ⁱ	0.82	1.97	2.767 (4)	164

Symmetry code: (i) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu(C₇H₅O₃)(NO₃)(C₁₄H₁₂N₂)]
M_r	470.92
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	9.594 (1), 9.802 (1), 12.347 (1)
α, β, γ (°)	78.687 (14), 70.409 (13), 63.740 (12)
V (Å³)	979.4 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.16
Crystal size (mm)	0.37 × 0.30 × 0.17

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.673, 0.830
No. of measured, independent and observed [I > 2σ(I)] reflections	7393, 3613, 3129
R_int	0.016
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.082, 1.03
No. of reflections	3613
No. of parameters	283
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.28

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Cu1—O1	2.004 (3)	Cu1—O2	2.026 (2)
Cu1—N1	2.007 (3)	Cu1—O4	2.292 (3)
Cu1—N2	2.008 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3···O4ⁱ	0.82	1.97	2.767 (4)	164

Symmetry code: (i) −x, −y+1, −z+1.

Acknowledgements

Financial support from the Science Fund of Henan Province for Distinguished Young Scholars (grant No. 074100510005) is gratefully acknowledged.

References

Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Okabe, N., Tsuji, A. & Yodoshi, M. (2007). Acta Cryst. E63, m1756–m1757. Web of Science CSD CrossRef IUCr Journals Google Scholar
Selvakumar, B., Rajendiran, V., Maheswari, P. U., Stoeckli-Evans, H. & Palaniandavar, M. (2006). J. Inorg. Biochem. 100, 316–330. Web of Science CSD CrossRef PubMed CAS Google Scholar
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Xuan, X.-P., Zhao, P.-Z. & Zhang, S.-X. (2007). Acta Cryst. E63, m1817. Web of Science CSD CrossRef IUCr Journals Google Scholar
Zhao, P.-Z., Yan, F.-M., Xuan, X.-P. & Tang, Q.-H. (2007). Acta Cryst. E63, m2523. Web of Science CSD CrossRef IUCr Journals Google Scholar

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