Bis{2-[bis­(3,5-dimethyl-1H-pyrazol-1-yl-κN2)meth­yl]pyridine-κN}copper(II) dinitrate

Liu, J.-C.; Guo, G.-Z.; Xiao, C.-H.; Song, X.-Y.; Li, M.

doi:10.1107/S1600536811045636

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 12| December 2011| Page m1691

https://doi.org/10.1107/S1600536811045636

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Bis{2-[bis(3,5-dimethyl-1H-pyrazol-1-yl-κN²)methyl]pyridine-κN}copper(II) dinitrate

Jia-Cheng Liu,^a ^* Guo-Zhe Guo,^a Chao-Hu Xiao,^a Xue-Yan Song ^a and Meng Li ^a

^aKey Laboratory of Polymer Materials of Gansu Province, Key Laboratory of Bioelectrochemistry & Environmental Analysis of Gansu College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, People's Republic of China
^*Correspondence e-mail: jcliu8@nwnu.edu.cn

(Received 19 October 2011; accepted 31 October 2011; online 5 November 2011)

In the mononuclear title complex, [Cu(C₁₆H₁₉N₅)₂](NO₃)₂, the Cu^II ion is located on a twofold rotation axis and is six-coordinated by six N atoms from two 2-[bis(3,5-dimethyl-1H-pyrazol-1-yl)methyl]pyridine ligands, forming a distorted octahedral geometry. In the crystal, molecules are linked by weak C—H⋯O interactions.

Related literature

For background to complexes based on rigid ligands containing pyrazole, see: Zhang et al. (2009 ); Otten et al. (2009 ); Arroyo et al. (2000 ); Morin et al. (2011 ). For the bioinorganic chemistry of cooper complexes, see: Turski & Thiele (2009 ); Finney et al. (2009 ); Tardito & Marchiò (2009 ).

Experimental

Crystal data

[Cu(C₁₆H₁₉N₅)₂](NO₃)₂
M_r = 750.28
Monoclinic, C 2/c
a = 24.819 (6) Å
b = 10.918 (3) Å
c = 17.592 (4) Å
β = 132.348 (2)°
V = 3523.0 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.68 mm⁻¹
T = 296 K
0.23 × 0.22 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.859, T_max = 0.899
12411 measured reflections
3266 independent reflections
2601 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.104
S = 1.07
3266 reflections
235 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O3ⁱ	0.93	2.39	3.245 (4)	153
C8—H8⋯O2ⁱⁱ	0.93	2.46	3.338 (4)	158
C15—H15c⋯O2ⁱⁱⁱ	0.96	2.29	3.202 (6)	159
Symmetry codes: (i) $[-x+1, y-1, -z+{\script{3\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); 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: https://doi.org/10.1107/S1600536811045636/ff2036sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811045636/ff2036Isup2.hkl

checkCIF report

Comment top

The rigid ligand with pyrazole is one of the most desirable ligand to biologists and bioinorganic chemists for specific performance, such as catalysis and fluxional behaviour (Zhang et al., 2009; Otten et al., 2009; Arroyo et al., 2000), and also in electrochemistry (Morin et al. (2011)). Especially, the research field dealing with copper complexes embrace wide range of topics, such as metastasis development (Turski et al., 2009; Finney et al., 2009), anticancer activity (Tardito et al., 2009), and other aspects of bioinorganic chemistry. In the present work, we report the synthesis and the structure of the title complex [Cu(bpz*mpy)₂](NO₃)_2.

An X-ray diffraction study performed on title complex [Cu(bpz*mpy)₂](NO₃)₂ (Fig. 1) reveals that it crystallizes in the monoclinic system with space group C2/c. The central copper ion is six-coordinated by six nitrogen atoms from two ligands. N(1), N(1A), N(5) and N(5A) atoms form the equatorial plane with distance of Cu—N being in the range of 2.030 (2)–2.045 (2) Å, N(2) and N(2 A) atoms are in apical position with distance of Cu—N being 2.339 (2) Å [symmetry codes: (A) = 1 - x, y, 3/2 - z]. Consequently, the central copper ion coordination geometry can be described as a distorted octahedral coordination environment.

In the crystal, molecules are linked by weak intermolecular C—H···O interactions (Fig. 2).

Related literature top

For background to complexes based on rigid ligands containing pyrazole, see: Zhang et al. (2009); Otten et al. (2009); Arroyo et al. (2000); Morin et al. (2011). For the bioinorganic chemistry of cooper complexes, see: Turski et al. (2009); Finney et al. (2009); Tardito et al. (2009).

Experimental top

Cu(NO₃)₂.3H₂O (0.1 mmol, 24.2 mg), bpz*mpy (0.2 mmol, 56.3 mg) were dissolved in MeOH. The resulting green solution was stirred for 1 h at the ambient temperature. Blue and block crystal was obtained by evaporation after one week, and washed with methol. Yield: 47 wt%.

Structure description top

In the crystal, molecules are linked by weak intermolecular C—H···O interactions (Fig. 2).

For background to complexes based on rigid ligands containing pyrazole, see: Zhang et al. (2009); Otten et al. (2009); Arroyo et al. (2000); Morin et al. (2011). For the bioinorganic chemistry of cooper complexes, see: Turski et al. (2009); Finney et al. (2009); Tardito et al. (2009).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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 structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms have been omitted for clarity. Symmetry code: (A)= 1 - x, y, 3/2 - z.
	Fig. 2. The crystal packing of the title compound, viewed along the a axis. Weak interaction among the molecules are shown as dashed lines.

Bis{2-[bis(3,5-dimethyl-1H-pyrazol-1-yl-κN²)methyl]pyridine- κN}copper(II) dinitrate top

Crystal data top

[Cu(C₁₆H₁₉N₅)₂](NO₃)₂	F(000) = 1564
M_r = 750.28	D_x = 1.415 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4634 reflections
a = 24.819 (6) Å	θ = 2.2–25.8°
b = 10.918 (3) Å	µ = 0.68 mm⁻¹
c = 17.592 (4) Å	T = 296 K
β = 132.348 (2)°	Block, blue
V = 3523.0 (14) Å³	0.23 × 0.22 × 0.16 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	3266 independent reflections
Radiation source: fine-focus sealed tube	2601 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
φ and ω scans	θ_max = 25.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −30→29
T_min = 0.859, T_max = 0.899	k = −13→13
12411 measured reflections	l = −20→21

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.104	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0412P)² + 5.0393P] where P = (F_o² + 2F_c²)/3
3266 reflections	(Δ/σ)_max < 0.001
235 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

[Cu(C₁₆H₁₉N₅)₂](NO₃)₂	V = 3523.0 (14) Å³
M_r = 750.28	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 24.819 (6) Å	µ = 0.68 mm⁻¹
b = 10.918 (3) Å	T = 296 K
c = 17.592 (4) Å	0.23 × 0.22 × 0.16 mm
β = 132.348 (2)°

Data collection top

Bruker APEXII CCD diffractometer	3266 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2601 reflections with I > 2σ(I)
T_min = 0.859, T_max = 0.899	R_int = 0.022
12411 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.104	H-atom parameters constrained
S = 1.07	Δρ_max = 0.37 e Å⁻³
3266 reflections	Δρ_min = −0.32 e Å⁻³
235 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	0.5000	−0.01320 (4)	0.7500	0.03860 (15)
C1	0.48707 (15)	−0.2377 (2)	0.8338 (2)	0.0508 (7)
H1	0.5351	−0.2502	0.8646	0.061*
C2	0.45590 (17)	−0.3194 (3)	0.8536 (2)	0.0595 (8)
H2	0.4828	−0.3849	0.8980	0.071*
C3	0.38457 (16)	−0.3035 (3)	0.8069 (2)	0.0598 (8)
H3	0.3621	−0.3586	0.8183	0.072*
C4	0.34694 (15)	−0.2046 (2)	0.7430 (2)	0.0492 (6)
H4	0.2985	−0.1920	0.7102	0.059*
C5	0.38190 (13)	−0.1246 (2)	0.72802 (18)	0.0368 (5)
C6	0.34211 (13)	−0.0120 (2)	0.66153 (19)	0.0389 (5)
H6	0.2941	−0.0109	0.6403	0.047*
C7	0.26736 (15)	−0.0142 (3)	0.4692 (2)	0.0554 (7)
C8	0.28709 (17)	−0.0194 (3)	0.4136 (2)	0.0611 (8)
H8	0.2559	−0.0196	0.3423	0.073*
C9	0.36269 (16)	−0.0244 (2)	0.4835 (2)	0.0498 (7)
C10	0.4118 (2)	−0.0301 (4)	0.4627 (3)	0.0755 (10)
H10A	0.4604	−0.0078	0.5237	0.113*
H10B	0.3947	0.0257	0.4082	0.113*
H10C	0.4119	−0.1119	0.4427	0.113*
C11	0.19391 (19)	−0.0068 (5)	0.4360 (3)	0.1009 (15)
H11A	0.1859	−0.0785	0.4588	0.151*
H11B	0.1570	−0.0018	0.3623	0.151*
H11C	0.1916	0.0647	0.4655	0.151*
C12	0.35339 (18)	0.1970 (3)	0.7337 (2)	0.0553 (7)
C13	0.4112 (2)	0.2737 (3)	0.7987 (3)	0.0666 (9)
H13	0.4104	0.3487	0.8230	0.080*
C14	0.47163 (17)	0.2200 (2)	0.8223 (2)	0.0540 (7)
C15	0.2759 (2)	0.2089 (3)	0.6840 (4)	0.0882 (12)
H15A	0.2455	0.2171	0.6110	0.132*
H15B	0.2705	0.2800	0.7105	0.132*
H15C	0.2617	0.1373	0.6985	0.132*
C16	0.54737 (19)	0.2688 (3)	0.8906 (3)	0.0773 (10)
H16A	0.5811	0.2021	0.9172	0.116*
H16B	0.5580	0.3130	0.9465	0.116*
H16C	0.5518	0.3228	0.8520	0.116*
N1	0.45132 (11)	−0.14066 (18)	0.77218 (15)	0.0392 (5)
N2	0.38955 (12)	−0.0231 (2)	0.57884 (16)	0.0463 (5)
N3	0.33024 (11)	−0.01645 (19)	0.56902 (16)	0.0416 (5)
N4	0.37949 (12)	0.09956 (18)	0.71912 (16)	0.0420 (5)
N5	0.45224 (12)	0.11305 (19)	0.77316 (17)	0.0448 (5)
N6	0.35109 (14)	0.5779 (2)	0.41294 (19)	0.0512 (6)
O1	0.35080 (16)	0.6715 (3)	0.4505 (2)	0.1132 (11)
O2	0.29475 (13)	0.5446 (3)	0.3289 (2)	0.0896 (8)
O3	0.40686 (15)	0.5216 (2)	0.4542 (2)	0.1047 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0389 (3)	0.0372 (2)	0.0438 (3)	0.000	0.0295 (2)	0.000
C1	0.0402 (15)	0.0482 (15)	0.0480 (16)	0.0088 (12)	0.0232 (14)	0.0131 (12)
C2	0.0570 (19)	0.0490 (16)	0.0591 (19)	0.0058 (13)	0.0337 (16)	0.0185 (14)
C3	0.0576 (19)	0.0546 (17)	0.0637 (19)	−0.0056 (14)	0.0394 (17)	0.0134 (14)
C4	0.0440 (15)	0.0497 (15)	0.0526 (16)	−0.0009 (12)	0.0320 (14)	0.0070 (13)
C5	0.0368 (13)	0.0370 (12)	0.0341 (13)	0.0017 (10)	0.0229 (12)	0.0016 (10)
C6	0.0371 (13)	0.0431 (13)	0.0409 (13)	0.0054 (11)	0.0280 (12)	0.0068 (11)
C7	0.0431 (16)	0.0669 (18)	0.0400 (15)	0.0112 (14)	0.0215 (14)	0.0093 (13)
C8	0.0593 (19)	0.075 (2)	0.0334 (14)	0.0083 (16)	0.0248 (15)	0.0067 (14)
C9	0.0621 (18)	0.0511 (15)	0.0426 (15)	0.0026 (13)	0.0378 (15)	0.0022 (12)
C10	0.085 (2)	0.103 (3)	0.061 (2)	0.004 (2)	0.059 (2)	0.0016 (19)
C11	0.0434 (19)	0.176 (5)	0.057 (2)	0.017 (2)	0.0226 (18)	0.004 (2)
C12	0.078 (2)	0.0428 (15)	0.078 (2)	0.0118 (14)	0.0658 (19)	0.0078 (14)
C13	0.108 (3)	0.0402 (15)	0.096 (3)	−0.0011 (17)	0.086 (2)	−0.0072 (16)
C14	0.076 (2)	0.0427 (15)	0.0636 (19)	−0.0079 (14)	0.0553 (18)	−0.0085 (13)
C15	0.093 (3)	0.062 (2)	0.147 (4)	0.0158 (19)	0.096 (3)	0.001 (2)
C16	0.088 (3)	0.062 (2)	0.090 (3)	−0.0267 (18)	0.063 (2)	−0.0329 (18)
N1	0.0345 (11)	0.0405 (11)	0.0383 (12)	0.0020 (9)	0.0227 (10)	0.0039 (9)
N2	0.0425 (12)	0.0615 (14)	0.0384 (12)	0.0045 (10)	0.0286 (11)	0.0039 (10)
N3	0.0368 (11)	0.0503 (12)	0.0366 (11)	0.0080 (9)	0.0243 (10)	0.0077 (9)
N4	0.0501 (13)	0.0391 (11)	0.0494 (13)	0.0049 (9)	0.0386 (12)	0.0045 (9)
N5	0.0505 (13)	0.0415 (12)	0.0508 (13)	−0.0030 (10)	0.0374 (12)	−0.0043 (10)
N6	0.0515 (15)	0.0467 (13)	0.0554 (15)	−0.0091 (11)	0.0361 (14)	−0.0065 (11)
O1	0.103 (2)	0.098 (2)	0.116 (2)	−0.0088 (17)	0.065 (2)	−0.0504 (18)
O2	0.0583 (15)	0.0995 (19)	0.0702 (16)	−0.0095 (14)	0.0268 (14)	−0.0291 (14)
O3	0.0630 (16)	0.0806 (18)	0.098 (2)	0.0121 (14)	0.0247 (16)	−0.0141 (15)

Geometric parameters (Å, º) top

Cu1—N5ⁱ	2.030 (2)	C9—C10	1.491 (4)
Cu1—N5	2.030 (2)	C10—H10A	0.9600
Cu1—N1	2.045 (2)	C10—H10B	0.9600
Cu1—N1ⁱ	2.045 (2)	C10—H10C	0.9600
Cu1—N2ⁱ	2.339 (2)	C11—H11A	0.9600
Cu1—N2	2.339 (2)	C11—H11B	0.9600
C1—N1	1.337 (3)	C11—H11C	0.9600
C1—C2	1.370 (4)	C12—N4	1.358 (3)
C1—H1	0.9300	C12—C13	1.363 (4)
C2—C3	1.371 (4)	C12—C15	1.488 (4)
C2—H2	0.9300	C13—C14	1.388 (4)
C3—C4	1.374 (4)	C13—H13	0.9300
C3—H3	0.9300	C14—N5	1.334 (3)
C4—C5	1.376 (3)	C14—C16	1.490 (4)
C4—H4	0.9300	C15—H15A	0.9600
C5—N1	1.341 (3)	C15—H15B	0.9600
C5—C6	1.516 (3)	C15—H15C	0.9600
C6—N3	1.446 (3)	C16—H16A	0.9600
C6—N4	1.451 (3)	C16—H16B	0.9600
C6—H6	0.9800	C16—H16C	0.9600
C7—N3	1.352 (3)	N2—N3	1.363 (3)
C7—C8	1.359 (4)	N4—N5	1.369 (3)
C7—C11	1.495 (5)	N6—O3	1.211 (3)
C8—C9	1.388 (4)	N6—O2	1.219 (3)
C8—H8	0.9300	N6—O1	1.220 (3)
C9—N2	1.324 (3)

N5ⁱ—Cu1—N5	94.48 (12)	C9—C10—H10C	109.5
N5ⁱ—Cu1—N1	179.57 (9)	H10A—C10—H10C	109.5
N5—Cu1—N1	85.63 (8)	H10B—C10—H10C	109.5
N5ⁱ—Cu1—N1ⁱ	85.63 (8)	C7—C11—H11A	109.5
N5—Cu1—N1ⁱ	179.57 (9)	C7—C11—H11B	109.5
N1—Cu1—N1ⁱ	94.26 (12)	H11A—C11—H11B	109.5
N5ⁱ—Cu1—N2ⁱ	87.32 (8)	C7—C11—H11C	109.5
N5—Cu1—N2ⁱ	96.28 (8)	H11A—C11—H11C	109.5
N1—Cu1—N2ⁱ	93.08 (8)	H11B—C11—H11C	109.5
N1ⁱ—Cu1—N2ⁱ	83.31 (8)	N4—C12—C13	105.8 (3)
N5ⁱ—Cu1—N2	96.28 (8)	N4—C12—C15	123.3 (3)
N5—Cu1—N2	87.32 (8)	C13—C12—C15	130.8 (3)
N1—Cu1—N2	83.31 (8)	C12—C13—C14	107.9 (3)
N1ⁱ—Cu1—N2	93.08 (8)	C12—C13—H13	126.1
N2ⁱ—Cu1—N2	174.72 (11)	C14—C13—H13	126.1
N1—C1—C2	122.8 (3)	N5—C14—C13	109.3 (3)
N1—C1—H1	118.6	N5—C14—C16	123.0 (3)
C2—C1—H1	118.6	C13—C14—C16	127.7 (3)
C1—C2—C3	119.2 (3)	C12—C15—H15A	109.5
C1—C2—H2	120.4	C12—C15—H15B	109.5
C3—C2—H2	120.4	H15A—C15—H15B	109.5
C2—C3—C4	118.8 (3)	C12—C15—H15C	109.5
C2—C3—H3	120.6	H15A—C15—H15C	109.5
C4—C3—H3	120.6	H15B—C15—H15C	109.5
C3—C4—C5	119.2 (3)	C14—C16—H16A	109.5
C3—C4—H4	120.4	C14—C16—H16B	109.5
C5—C4—H4	120.4	H16A—C16—H16B	109.5
N1—C5—C4	122.4 (2)	C14—C16—H16C	109.5
N1—C5—C6	117.9 (2)	H16A—C16—H16C	109.5
C4—C5—C6	119.7 (2)	H16B—C16—H16C	109.5
N3—C6—N4	111.33 (19)	C1—N1—C5	117.7 (2)
N3—C6—C5	111.97 (19)	C1—N1—Cu1	122.61 (17)
N4—C6—C5	111.4 (2)	C5—N1—Cu1	119.60 (15)
N3—C6—H6	107.3	C9—N2—N3	105.1 (2)
N4—C6—H6	107.3	C9—N2—Cu1	141.70 (19)
C5—C6—H6	107.3	N3—N2—Cu1	112.94 (15)
N3—C7—C8	105.9 (3)	C7—N3—N2	111.6 (2)
N3—C7—C11	123.1 (3)	C7—N3—C6	130.0 (2)
C8—C7—C11	131.1 (3)	N2—N3—C6	118.4 (2)
C7—C8—C9	107.0 (3)	C12—N4—N5	111.0 (2)
C7—C8—H8	126.5	C12—N4—C6	128.9 (2)
C9—C8—H8	126.5	N5—N4—C6	119.95 (19)
N2—C9—C8	110.4 (2)	C14—N5—N4	106.0 (2)
N2—C9—C10	121.0 (3)	C14—N5—Cu1	136.0 (2)
C8—C9—C10	128.7 (3)	N4—N5—Cu1	117.58 (15)
C9—C10—H10A	109.5	O3—N6—O2	119.3 (3)
C9—C10—H10B	109.5	O3—N6—O1	121.5 (3)
H10A—C10—H10B	109.5	O2—N6—O1	119.1 (3)

N1—C1—C2—C3	1.4 (5)	N5—Cu1—N2—N3	−38.62 (17)
C1—C2—C3—C4	−1.0 (5)	N1—Cu1—N2—N3	47.29 (16)
C2—C3—C4—C5	−0.2 (4)	N1ⁱ—Cu1—N2—N3	141.22 (17)
C3—C4—C5—N1	1.3 (4)	C8—C7—N3—N2	0.0 (3)
C3—C4—C5—C6	−177.2 (3)	C11—C7—N3—N2	−179.8 (3)
N1—C5—C6—N3	67.1 (3)	C8—C7—N3—C6	179.4 (2)
C4—C5—C6—N3	−114.3 (3)	C11—C7—N3—C6	−0.4 (5)
N1—C5—C6—N4	−58.3 (3)	C9—N2—N3—C7	0.2 (3)
C4—C5—C6—N4	120.3 (2)	Cu1—N2—N3—C7	175.91 (18)
N3—C7—C8—C9	−0.2 (3)	C9—N2—N3—C6	−179.3 (2)
C11—C7—C8—C9	179.6 (4)	Cu1—N2—N3—C6	−3.6 (3)
C7—C8—C9—N2	0.3 (3)	N4—C6—N3—C7	−114.3 (3)
C7—C8—C9—C10	−179.5 (3)	C5—C6—N3—C7	120.3 (3)
N4—C12—C13—C14	−0.1 (3)	N4—C6—N3—N2	65.1 (3)
C15—C12—C13—C14	−179.6 (3)	C5—C6—N3—N2	−60.3 (3)
C12—C13—C14—N5	0.3 (3)	C13—C12—N4—N5	−0.1 (3)
C12—C13—C14—C16	−179.8 (3)	C15—C12—N4—N5	179.4 (3)
C2—C1—N1—C5	−0.4 (4)	C13—C12—N4—C6	176.1 (2)
C2—C1—N1—Cu1	176.1 (2)	C15—C12—N4—C6	−4.4 (4)
C4—C5—N1—C1	−1.0 (4)	N3—C6—N4—C12	110.1 (3)
C6—C5—N1—C1	177.6 (2)	C5—C6—N4—C12	−124.1 (3)
C4—C5—N1—Cu1	−177.61 (19)	N3—C6—N4—N5	−74.0 (3)
C6—C5—N1—Cu1	1.0 (3)	C5—C6—N4—N5	51.8 (3)
N5—Cu1—N1—C1	−133.1 (2)	C13—C14—N5—N4	−0.4 (3)
N1ⁱ—Cu1—N1—C1	46.47 (18)	C16—C14—N5—N4	179.8 (3)
N2ⁱ—Cu1—N1—C1	−37.0 (2)	C13—C14—N5—Cu1	171.5 (2)
N2—Cu1—N1—C1	139.1 (2)	C16—C14—N5—Cu1	−8.3 (5)
N5—Cu1—N1—C5	43.32 (18)	C12—N4—N5—C14	0.3 (3)
N1ⁱ—Cu1—N1—C5	−137.1 (2)	C6—N4—N5—C14	−176.3 (2)
N2ⁱ—Cu1—N1—C5	139.39 (18)	C12—N4—N5—Cu1	−173.37 (17)
N2—Cu1—N1—C5	−44.48 (18)	C6—N4—N5—Cu1	10.0 (3)
C8—C9—N2—N3	−0.4 (3)	N5ⁱ—Cu1—N5—C14	−40.8 (2)
C10—C9—N2—N3	179.5 (3)	N1—Cu1—N5—C14	139.7 (3)
C8—C9—N2—Cu1	−173.9 (2)	N2ⁱ—Cu1—N5—C14	47.0 (3)
C10—C9—N2—Cu1	5.9 (5)	N2—Cu1—N5—C14	−136.9 (3)
N5ⁱ—Cu1—N2—C9	40.4 (3)	N5ⁱ—Cu1—N5—N4	130.4 (2)
N5—Cu1—N2—C9	134.6 (3)	N1—Cu1—N5—N4	−49.17 (17)
N1—Cu1—N2—C9	−139.5 (3)	N2ⁱ—Cu1—N5—N4	−141.80 (17)
N1ⁱ—Cu1—N2—C9	−45.6 (3)	N2—Cu1—N5—N4	34.32 (17)
N5ⁱ—Cu1—N2—N3	−132.84 (17)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O3ⁱⁱ	0.93	2.39	3.245 (4)	153
C8—H8···O2ⁱⁱⁱ	0.93	2.46	3.338 (4)	158
C15—H15c···O2^iv	0.96	2.29	3.202 (6)	159

Symmetry codes: (ii) −x+1, y−1, −z+3/2; (iii) −x+1/2, y−1/2, −z+1/2; (iv) −x+1/2, −y+1/2, −z+1.

Experimental details

Crystal data
Chemical formula	[Cu(C₁₆H₁₉N₅)₂](NO₃)₂
M_r	750.28
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	296
a, b, c (Å)	24.819 (6), 10.918 (3), 17.592 (4)
β (°)	132.348 (2)
V (Å³)	3523.0 (14)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.68
Crystal size (mm)	0.23 × 0.22 × 0.16

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.859, 0.899
No. of measured, independent and observed [I > 2σ(I)] reflections	12411, 3266, 2601
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.104, 1.07
No. of reflections	3266
No. of parameters	235
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.32

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O3ⁱ	0.93	2.39	3.245 (4)	153
C8—H8···O2ⁱⁱ	0.93	2.46	3.338 (4)	158
C15—H15c···O2ⁱⁱⁱ	0.96	2.29	3.202 (6)	159

Symmetry codes: (i) −x+1, y−1, −z+3/2; (ii) −x+1/2, y−1/2, −z+1/2; (iii) −x+1/2, −y+1/2, −z+1.

Acknowledgements

This work was supported by the NSFC (No. 20871099) and the Natural Science Foundation of Gansu (No. 0710RJZA113).

References

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