Synthesis, structure and bioactivity of Ni²⁺ and Cu²⁺ acyl­hydrazone complexes

Two acyl­hydrazone complexes, bis{6-methyl-N′-[1-(pyrazin-2-yl-κN¹)ethyl­idene]nicotinohydrazidato-κ²N′,O}nickel(II), [Ni(C₁₃H₁₂N₅O)₂], (I), and di-μ-azido-κ⁴N¹:N¹-bis­({6-methyl-N′-[1-(pyrazin-2-yl-κN¹)ethyl­idene]nicotinohydrazidato-κ²N′,O}nickel(II)), [Cu₂(C₁₃H₁₂N₅O)₂(N₃)₂], (II), derived from 6-methyl-N′-[1-(pyrazin-2-yl)ethyl­idene]nicotinohydrazide (HL) and azide salts, have been synthesized. HL acts as an N,N′,O-tridentate ligand in both complexes. Complex (I) crystallizes in the ortho­rhom­bic space group Pbcn and has a mononuclear structure, the azide co-ligand is not involved in crystallization and the Ni²⁺ centre lies in a distorted {N₄O₂} octa­hedral coordination environment. Complex (II) crystallizes in the triclinic space group P and is a centrosymmetric binuclear complex with a crystallographically independent Cu²⁺ centre coordinating to three donor atoms from the deprotonated L⁻ ligand and to two N atoms belonging to two bridging azide anions. The two- and one-dimensional supra­molecular structures are constructed by hydrogen-bonding inter­actions in (I) and (II), respectively. The in vitro urease inhibitory evaluation revealed that complex (II) showed a better inhibitory activity, with the IC₅₀ value being 1.32±0.4 µM. Both complexes can effectively bind to bovine serum albumin (BSA) by 1:1 binding, which was assessed via tryptophan emission–quenching measurements. The bioactivities of the two complexes towards jack bean urease were also studied by mol­ecular docking. The effects of the metal ions and the coordination environments in the two complexes on in vitro urease inhibitory activity are preliminarily discussed.

Computing details

For both structures, data collection: CrysAlis PRO (Agilent, 2014); cell refinement: CrysAlis PRO (Agilent, 2014); data reduction: CrysAlis PRO (Agilent, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Bis{6-methyl-N'-[1-(pyrazin-2-yl-κN¹)ethylidene]nicotinohydrazidato-κ²N',O}nickel(II) (I)

Crystal data

[Ni(C13H12N5O)2]	Dx = 1.439 Mg m^−3
Mr = 567.26	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbcn	Cell parameters from 8956 reflections
a = 11.9385 (6) Å	θ = 2.5–26.2°
b = 9.7023 (4) Å	µ = 0.79 mm^−1
c = 22.5975 (10) Å	T = 273 K
V = 2617.5 (2) Å^3	Block, green
Z = 4	0.24 × 0.15 × 0.13 mm
F(000) = 1176

Data collection

CCD area detector diffractometer	2307 independent reflections
Radiation source: fine-focus sealed tube	1720 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.047
phi and ω scans	θmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −14→14
Tmin = 0.834, Tmax = 0.905	k = −11→9
23203 measured reflections	l = −26→26

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0569P)^2 + 2.7448P] where P = (Fo^2 + 2Fc^2)/3
2307 reflections	(Δ/σ)max < 0.001
179 parameters	Δρmax = 0.40 e Å^−3
0 restraints	Δρmin = −0.18 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq
Ni1	0.0000	0.24251 (5)	0.7500	0.0356 (2)
C1	0.0214 (3)	0.4757 (4)	0.84393 (15)	0.0533 (9)
H1	−0.0558	0.4708	0.8493	0.064*
C2	0.0821 (4)	0.5697 (4)	0.87618 (16)	0.0664 (10)
H2	0.0449	0.6257	0.9032	0.080*
C3	0.2404 (3)	0.4995 (3)	0.83124 (15)	0.0529 (8)
H3	0.3174	0.5062	0.8258	0.063*
C4	0.1818 (2)	0.4031 (3)	0.79856 (13)	0.0402 (7)
C5	0.2322 (2)	0.3108 (3)	0.75412 (12)	0.0379 (7)
C6	0.3558 (3)	0.3024 (4)	0.74455 (16)	0.0560 (9)
H6A	0.3894	0.2507	0.7762	0.084*
H6B	0.3869	0.3936	0.7438	0.084*
H6C	0.3706	0.2573	0.7076	0.084*
C7	0.0996 (3)	0.0900 (3)	0.66016 (13)	0.0434 (7)
C8	0.1161 (3)	−0.0018 (3)	0.60861 (14)	0.0550 (9)
C9	0.2162 (4)	−0.0139 (5)	0.57894 (19)	0.0853 (13)
H9	0.2780	0.0384	0.5902	0.102*
C10	0.2234 (5)	−0.1051 (6)	0.5322 (2)	0.1057 (18)
H10	0.2910	−0.1157	0.5122	0.127*
C11	0.1331 (6)	−0.1789 (4)	0.51517 (19)	0.1000 (19)
C12	0.0303 (5)	−0.0817 (5)	0.5879 (2)	0.0993 (17)
H12	−0.0385	−0.0749	0.6070	0.119*
C13	0.1392 (7)	−0.2780 (5)	0.4635 (2)	0.146 (3)
H13A	0.0840	−0.3491	0.4684	0.220*
H13B	0.2124	−0.3187	0.4619	0.220*
H13C	0.1250	−0.2290	0.4273	0.220*
N1	0.06958 (19)	0.3924 (2)	0.80568 (10)	0.0404 (6)
N2	0.1916 (3)	0.5830 (3)	0.87003 (14)	0.0675 (9)
N3	0.1596 (2)	0.2387 (2)	0.72554 (12)	0.0385 (6)
N4	0.1912 (2)	0.1529 (3)	0.68041 (11)	0.0444 (6)
N5	0.0378 (5)	−0.1688 (5)	0.54224 (18)	0.1206 (18)
O1	0.00128 (16)	0.1004 (2)	0.68171 (10)	0.0454 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0229 (3)	0.0408 (3)	0.0432 (3)	0.000	0.0000 (2)	0.000
C1	0.053 (2)	0.054 (2)	0.053 (2)	0.0030 (16)	0.0068 (16)	−0.0048 (17)
C2	0.086 (3)	0.056 (2)	0.057 (2)	0.003 (2)	0.003 (2)	−0.0080 (18)
C3	0.0490 (19)	0.054 (2)	0.0556 (19)	−0.0142 (17)	−0.0106 (17)	0.0053 (17)
C4	0.0344 (16)	0.0405 (16)	0.0455 (17)	−0.0057 (13)	−0.0083 (13)	0.0077 (14)
C5	0.0243 (15)	0.0412 (16)	0.0483 (17)	−0.0013 (12)	−0.0008 (13)	0.0108 (14)
C6	0.0275 (16)	0.063 (2)	0.078 (3)	−0.0055 (16)	0.0029 (15)	0.0105 (18)
C7	0.0477 (19)	0.0404 (16)	0.0419 (17)	−0.0001 (14)	0.0055 (14)	0.0021 (14)
C8	0.074 (2)	0.0470 (18)	0.0439 (18)	−0.0052 (18)	0.0120 (17)	0.0008 (15)
C9	0.085 (3)	0.097 (3)	0.074 (3)	0.008 (3)	0.017 (2)	−0.022 (2)
C10	0.135 (5)	0.103 (4)	0.079 (3)	0.013 (4)	0.045 (3)	−0.028 (3)
C11	0.191 (6)	0.051 (2)	0.058 (3)	−0.025 (3)	0.044 (3)	−0.005 (2)
C12	0.121 (4)	0.100 (4)	0.077 (3)	−0.053 (3)	0.042 (3)	−0.038 (3)
C13	0.284 (10)	0.077 (3)	0.079 (3)	−0.040 (5)	0.069 (5)	−0.028 (3)
N1	0.0341 (14)	0.0423 (14)	0.0448 (14)	−0.0016 (11)	−0.0021 (11)	−0.0011 (12)
N2	0.084 (2)	0.0570 (19)	0.0613 (19)	−0.0162 (18)	−0.0083 (17)	−0.0069 (16)
N3	0.0279 (13)	0.0415 (14)	0.0459 (13)	−0.0002 (10)	0.0022 (11)	0.0015 (11)
N4	0.0383 (14)	0.0470 (15)	0.0480 (14)	0.0015 (12)	0.0099 (12)	−0.0030 (12)
N5	0.183 (5)	0.101 (3)	0.079 (3)	−0.074 (3)	0.053 (3)	−0.042 (2)
O1	0.0351 (12)	0.0517 (12)	0.0495 (12)	−0.0071 (10)	0.0019 (9)	−0.0078 (10)

Geometric parameters (Å, º)

Ni1—N1	2.095 (2)	C6—H6B	0.9600
Ni1—N1^i	2.095 (2)	C6—H6C	0.9600
Ni1—N3	1.984 (2)	C7—C8	1.480 (4)
Ni1—N3^i	1.984 (2)	C7—N4	1.333 (4)
Ni1—O1^i	2.069 (2)	C7—O1	1.275 (3)
Ni1—O1	2.069 (2)	C8—C9	1.376 (5)
C1—H1	0.9300	C8—C12	1.367 (6)
C1—C2	1.374 (5)	C9—H9	0.9300
C1—N1	1.316 (4)	C9—C10	1.381 (6)
C2—H2	0.9300	C10—H10	0.9300
C2—N2	1.322 (5)	C10—C11	1.350 (7)
C3—H3	0.9300	C11—C13	1.515 (6)
C3—C4	1.382 (4)	C11—N5	1.295 (7)
C3—N2	1.328 (4)	C12—H12	0.9300
C4—C5	1.474 (4)	C12—N5	1.336 (5)
C4—N1	1.354 (4)	C13—H13A	0.9600
C5—C6	1.493 (4)	C13—H13B	0.9600
C5—N3	1.288 (4)	C13—H13C	0.9600
C6—H6A	0.9600	N3—N4	1.370 (3)
N1—Ni1—N1^i	92.07 (13)	H6B—C6—H6C	109.5
N3^i—Ni1—N1	103.09 (10)	N4—C7—C8	115.9 (3)
N3—Ni1—N1	78.43 (10)	O1—C7—C8	118.1 (3)
N3—Ni1—N1^i	103.09 (10)	O1—C7—N4	126.0 (3)
N3^i—Ni1—N1^i	78.43 (10)	C9—C8—C7	123.4 (3)
N3^i—Ni1—N3	177.86 (13)	C12—C8—C7	120.8 (3)
N3^i—Ni1—O1^i	76.86 (9)	C12—C8—C9	115.8 (4)
N3—Ni1—O1^i	101.68 (9)	C8—C9—H9	120.6
N3^i—Ni1—O1	101.68 (9)	C8—C9—C10	118.8 (5)
N3—Ni1—O1	76.86 (9)	C10—C9—H9	120.6
O1—Ni1—N1^i	91.00 (9)	C9—C10—H10	119.7
O1^i—Ni1—N1^i	155.16 (8)	C11—C10—C9	120.5 (5)
O1—Ni1—N1	155.16 (8)	C11—C10—H10	119.7
O1^i—Ni1—N1	91.00 (9)	C10—C11—C13	121.2 (5)
O1^i—Ni1—O1	96.45 (13)	N5—C11—C10	121.8 (4)
C2—C1—H1	119.2	N5—C11—C13	117.0 (6)
N1—C1—H1	119.2	C8—C12—H12	117.5
N1—C1—C2	121.7 (3)	N5—C12—C8	124.9 (5)
C1—C2—H2	119.0	N5—C12—H12	117.5
N2—C2—C1	122.1 (4)	C11—C13—H13A	109.5
N2—C2—H2	119.0	C11—C13—H13B	109.5
C4—C3—H3	118.5	C11—C13—H13C	109.5
N2—C3—H3	118.5	H13A—C13—H13B	109.5
N2—C3—C4	122.9 (3)	H13A—C13—H13C	109.5
C3—C4—C5	124.7 (3)	H13B—C13—H13C	109.5
N1—C4—C3	119.3 (3)	C1—N1—Ni1	130.3 (2)
N1—C4—C5	116.0 (3)	C1—N1—C4	117.6 (3)
C4—C5—C6	122.4 (3)	C4—N1—Ni1	112.00 (19)
N3—C5—C4	113.4 (3)	C2—N2—C3	116.3 (3)
N3—C5—C6	124.2 (3)	C5—N3—Ni1	119.8 (2)
C5—C6—H6A	109.5	C5—N3—N4	121.2 (3)
C5—C6—H6B	109.5	N4—N3—Ni1	118.93 (19)
C5—C6—H6C	109.5	C7—N4—N3	107.9 (2)
H6A—C6—H6B	109.5	C11—N5—C12	118.1 (5)
H6A—C6—H6C	109.5	C7—O1—Ni1	110.16 (18)
Ni1—N3—N4—C7	2.4 (3)	N1^i—Ni1—N3—N4	−88.3 (2)
C1—C2—N2—C3	−0.6 (6)	N1—Ni1—N3—N4	−177.7 (2)
C2—C1—N1—Ni1	−179.0 (3)	N1^i—Ni1—O1—C7	101.3 (2)
C2—C1—N1—C4	−0.6 (5)	N1—Ni1—O1—C7	4.2 (3)
C3—C4—C5—C6	6.7 (5)	N1—C1—C2—N2	0.9 (6)
C3—C4—C5—N3	−174.0 (3)	N1—C4—C5—C6	−175.0 (3)
C3—C4—N1—Ni1	178.7 (2)	N1—C4—C5—N3	4.3 (4)
C3—C4—N1—C1	0.0 (4)	N2—C3—C4—C5	178.5 (3)
C4—C3—N2—C2	0.0 (5)	N2—C3—C4—N1	0.3 (5)
C4—C5—N3—Ni1	−7.2 (3)	N3—Ni1—N1—C1	175.5 (3)
C4—C5—N3—N4	176.5 (2)	N3^i—Ni1—N1—C1	−6.1 (3)
C5—C4—N1—Ni1	0.3 (3)	N3—Ni1—N1—C4	−2.99 (19)
C5—C4—N1—C1	−178.3 (3)	N3^i—Ni1—N1—C4	175.47 (19)
C5—N3—N4—C7	178.7 (3)	N3^i—Ni1—N3—C5	−129.6 (2)
C6—C5—N3—Ni1	172.0 (2)	N3^i—Ni1—N3—N4	46.8 (2)
C6—C5—N3—N4	−4.3 (4)	N3^i—Ni1—O1—C7	179.7 (2)
C7—C8—C9—C10	178.5 (4)	N3—Ni1—O1—C7	−1.9 (2)
C7—C8—C12—N5	−179.1 (5)	N4—C7—C8—C9	−6.0 (5)
C8—C7—N4—N3	176.7 (2)	N4—C7—C8—C12	173.5 (4)
C8—C7—O1—Ni1	−176.9 (2)	N4—C7—O1—Ni1	4.4 (4)
C8—C9—C10—C11	1.4 (8)	O1—Ni1—N1—C1	169.4 (3)
C8—C12—N5—C11	−0.2 (9)	O1^i—Ni1—N1—C1	−82.8 (3)
C9—C8—C12—N5	0.5 (8)	O1—Ni1—N1—C4	−9.0 (3)
C9—C10—C11—C13	179.2 (5)	O1^i—Ni1—N1—C4	98.7 (2)
C9—C10—C11—N5	−1.1 (9)	O1^i—Ni1—N3—C5	−82.7 (2)
C10—C11—N5—C12	0.5 (9)	O1—Ni1—N3—C5	−176.7 (2)
C12—C8—C9—C10	−1.0 (7)	O1—Ni1—N3—N4	−0.36 (19)
C13—C11—N5—C12	−179.8 (5)	O1^i—Ni1—N3—N4	93.6 (2)
N1^i—Ni1—N1—C1	72.5 (3)	O1^i—Ni1—O1—C7	−102.4 (2)
N1^i—Ni1—N1—C4	−105.9 (2)	O1—C7—C8—C9	175.2 (4)
N1^i—Ni1—N3—C5	95.3 (2)	O1—C7—C8—C12	−5.3 (5)
N1—Ni1—N3—C5	5.9 (2)	O1—C7—N4—N3	−4.6 (4)

Symmetry code: (i) −x, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···N5^ii	0.93	2.54	3.448 (6)	164
C3—H3···O1^iii	0.93	2.38	3.278 (4)	161

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

Di-µ-azido-κ⁴N¹:N¹-bis({6-methyl-N'-[1-(pyrazin-2-yl-κN¹)ethylidene]nicotinohydrazidato-κ²N',O}nickel(II)) (II)

Crystal data

[Cu2(C13H12N5O)2(N3)2]	Z = 1
Mr = 719.71	F(000) = 366
Triclinic, P1	Dx = 1.638 Mg m^−3
a = 7.8491 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.8762 (6) Å	Cell parameters from 3711 reflections
c = 12.3391 (8) Å	θ = 2.7–26.4°
α = 100.236 (2)°	µ = 1.51 mm^−1
β = 94.225 (2)°	T = 293 K
γ = 101.865 (2)°	Block, blue
V = 729.81 (9) Å^3	0.24 × 0.2 × 0.17 mm

Data collection

CCD area detector diffractometer	3163 independent reflections
Radiation source: fine-focus sealed tube	2438 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
phi and ω scans	θmax = 27.1°, θmin = 2.7°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014)	h = −10→8
Tmin = 0.713, Tmax = 0.783	k = −10→10
7758 measured reflections	l = −15→15

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0317P)^2 + 0.4086P] where P = (Fo^2 + 2Fc^2)/3
3163 reflections	(Δ/σ)max < 0.001
210 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.32 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.48975 (4)	0.69878 (4)	0.00180 (3)	0.03177 (13)
C1	0.4083 (4)	0.5429 (4)	−0.2461 (2)	0.0435 (7)
H1	0.3211	0.4542	−0.2304	0.052*
C2	0.4464 (5)	0.5393 (4)	−0.3541 (2)	0.0538 (9)
H2	0.3855	0.4453	−0.4091	0.065*
C3	0.6506 (4)	0.7945 (4)	−0.3010 (2)	0.0444 (7)
H3	0.7336	0.8856	−0.3181	0.053*
C4	0.6197 (3)	0.8001 (3)	−0.1912 (2)	0.0323 (6)
C5	0.7154 (3)	0.9364 (3)	−0.0967 (2)	0.0302 (6)
C6	0.8551 (4)	1.0884 (4)	−0.1088 (2)	0.0411 (7)
H6A	0.8903	1.1675	−0.0384	0.062*
H6B	0.8112	1.1500	−0.1613	0.062*
H6C	0.9540	1.0459	−0.1346	0.062*
C7	0.6608 (3)	0.9474 (3)	0.1760 (2)	0.0306 (6)
C8	0.7331 (3)	1.0384 (3)	0.2907 (2)	0.0316 (6)
C9	0.8744 (4)	1.1820 (4)	0.3129 (2)	0.0398 (7)
H9	0.9230	1.2282	0.2550	0.048*
C10	0.9423 (4)	1.2556 (4)	0.4195 (2)	0.0428 (7)
H10	1.0378	1.3516	0.4346	0.051*
C11	0.8694 (4)	1.1875 (4)	0.5048 (2)	0.0452 (8)
C12	0.6652 (4)	0.9781 (4)	0.3811 (2)	0.0442 (7)
H12	0.5691	0.8828	0.3680	0.053*
C13	0.9416 (5)	1.2654 (5)	0.6235 (3)	0.0721 (12)
H13A	0.8499	1.2987	0.6641	0.108*
H13B	1.0337	1.3679	0.6266	0.108*
H13C	0.9873	1.1792	0.6557	0.108*
N1	0.4956 (3)	0.6724 (3)	−0.16489 (17)	0.0331 (5)
N2	0.5656 (4)	0.6634 (4)	−0.3827 (2)	0.0540 (7)
N3	0.6642 (3)	0.9067 (3)	−0.00367 (17)	0.0286 (5)
N4	0.7384 (3)	1.0147 (3)	0.09616 (17)	0.0319 (5)
N5	0.7310 (4)	1.0502 (4)	0.4864 (2)	0.0530 (7)
N6	0.6952 (3)	0.5074 (3)	0.00231 (19)	0.0349 (5)
N7	0.7937 (3)	0.5260 (3)	−0.0673 (2)	0.0373 (6)
N8	0.8893 (4)	0.5527 (4)	−0.1304 (3)	0.0647 (8)
O1	0.5340 (2)	0.8106 (2)	0.16055 (14)	0.0360 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0343 (2)	0.0281 (2)	0.0298 (2)	0.00161 (13)	0.00432 (14)	0.00316 (13)
C1	0.0509 (18)	0.0366 (17)	0.0368 (17)	0.0012 (14)	−0.0028 (14)	0.0043 (13)
C2	0.075 (2)	0.0443 (19)	0.0319 (17)	0.0039 (17)	−0.0035 (16)	−0.0028 (14)
C3	0.0541 (19)	0.0433 (18)	0.0345 (16)	0.0070 (15)	0.0100 (14)	0.0068 (14)
C4	0.0353 (15)	0.0323 (15)	0.0317 (15)	0.0120 (12)	0.0039 (12)	0.0077 (12)
C5	0.0315 (14)	0.0292 (14)	0.0321 (15)	0.0096 (12)	0.0056 (12)	0.0076 (11)
C6	0.0409 (17)	0.0422 (17)	0.0373 (16)	0.0014 (14)	0.0080 (13)	0.0078 (13)
C7	0.0287 (14)	0.0290 (14)	0.0334 (15)	0.0089 (12)	0.0037 (12)	0.0015 (12)
C8	0.0348 (15)	0.0304 (14)	0.0294 (14)	0.0078 (12)	0.0052 (12)	0.0041 (11)
C9	0.0448 (17)	0.0396 (17)	0.0330 (16)	0.0028 (14)	0.0075 (13)	0.0079 (13)
C10	0.0446 (17)	0.0394 (17)	0.0342 (16)	−0.0079 (13)	−0.0018 (14)	0.0032 (13)
C11	0.0533 (19)	0.0441 (18)	0.0343 (16)	0.0047 (15)	−0.0003 (14)	0.0068 (14)
C12	0.0480 (18)	0.0410 (17)	0.0393 (17)	0.0000 (14)	0.0060 (14)	0.0081 (14)
C13	0.094 (3)	0.071 (3)	0.0342 (18)	−0.011 (2)	−0.0101 (19)	0.0060 (17)
N1	0.0375 (13)	0.0313 (12)	0.0290 (12)	0.0070 (10)	−0.0014 (10)	0.0048 (10)
N2	0.0734 (19)	0.0508 (17)	0.0317 (14)	0.0052 (15)	0.0070 (13)	0.0014 (12)
N3	0.0323 (12)	0.0262 (11)	0.0262 (11)	0.0063 (9)	0.0038 (10)	0.0020 (9)
N4	0.0338 (12)	0.0320 (12)	0.0277 (12)	0.0041 (10)	0.0048 (10)	0.0030 (10)
N5	0.0651 (18)	0.0545 (17)	0.0343 (15)	0.0002 (14)	0.0059 (13)	0.0105 (13)
N6	0.0328 (13)	0.0313 (13)	0.0384 (13)	0.0020 (10)	0.0054 (11)	0.0064 (10)
N7	0.0323 (13)	0.0303 (13)	0.0465 (15)	0.0032 (10)	0.0026 (12)	0.0059 (11)
N8	0.0599 (19)	0.064 (2)	0.075 (2)	0.0091 (15)	0.0360 (17)	0.0213 (16)
O1	0.0375 (11)	0.0334 (10)	0.0321 (10)	−0.0017 (8)	0.0063 (9)	0.0036 (8)

Geometric parameters (Å, º)

Cu1—Cu1^i	3.1610 (7)	C7—C8	1.481 (4)
Cu1—N1	2.035 (2)	C7—N4	1.328 (3)
Cu1—N3	1.921 (2)	C7—O1	1.283 (3)
Cu1—N6^i	1.933 (2)	C8—C9	1.383 (4)
Cu1—N6	2.423 (2)	C8—C12	1.388 (4)
Cu1—O1	1.9733 (18)	C9—H9	0.9300
C1—H1	0.9300	C9—C10	1.359 (4)
C1—C2	1.384 (4)	C10—H10	0.9300
C1—N1	1.328 (3)	C10—C11	1.373 (4)
C2—H2	0.9300	C11—C13	1.503 (4)
C2—N2	1.323 (4)	C11—N5	1.340 (4)
C3—H3	0.9300	C12—H12	0.9300
C3—C4	1.388 (4)	C12—N5	1.340 (4)
C3—N2	1.332 (4)	C13—H13A	0.9600
C4—C5	1.474 (4)	C13—H13B	0.9600
C4—N1	1.351 (3)	C13—H13C	0.9600
C5—C6	1.485 (4)	N3—N4	1.378 (3)
C5—N3	1.288 (3)	N6—Cu1^i	1.933 (2)
C6—H6A	0.9600	N6—N7	1.205 (3)
C6—H6B	0.9600	N7—N8	1.137 (3)
C6—H6C	0.9600
N1—Cu1—Cu1^i	92.99 (6)	O1—C7—C8	119.2 (2)
N1—Cu1—N6	88.24 (8)	O1—C7—N4	125.2 (2)
N3—Cu1—Cu1^i	132.40 (6)	C9—C8—C7	122.1 (2)
N3—Cu1—N1	79.57 (9)	C9—C8—C12	117.0 (3)
N3—Cu1—N6^i	175.77 (9)	C12—C8—C7	120.9 (2)
N3—Cu1—N6	94.82 (8)	C8—C9—H9	120.0
N3—Cu1—O1	79.90 (8)	C10—C9—C8	120.0 (3)
N6—Cu1—Cu1^i	37.67 (5)	C10—C9—H9	120.0
N6^i—Cu1—Cu1^i	49.99 (7)	C9—C10—H10	120.1
N6^i—Cu1—N1	97.11 (9)	C9—C10—C11	119.7 (3)
N6^i—Cu1—N6	87.66 (9)	C11—C10—H10	120.1
N6^i—Cu1—O1	103.19 (9)	C10—C11—C13	121.1 (3)
O1—Cu1—Cu1^i	104.09 (6)	N5—C11—C10	121.9 (3)
O1—Cu1—N1	159.01 (8)	N5—C11—C13	117.0 (3)
O1—Cu1—N6	97.79 (8)	C8—C12—H12	118.3
C2—C1—H1	119.9	N5—C12—C8	123.4 (3)
N1—C1—H1	119.9	N5—C12—H12	118.3
N1—C1—C2	120.3 (3)	C11—C13—H13A	109.5
C1—C2—H2	118.5	C11—C13—H13B	109.5
N2—C2—C1	123.0 (3)	C11—C13—H13C	109.5
N2—C2—H2	118.5	H13A—C13—H13B	109.5
C4—C3—H3	118.8	H13A—C13—H13C	109.5
N2—C3—H3	118.8	H13B—C13—H13C	109.5
N2—C3—C4	122.3 (3)	C1—N1—Cu1	129.3 (2)
C3—C4—C5	124.9 (3)	C1—N1—C4	118.1 (2)
N1—C4—C3	119.9 (2)	C4—N1—Cu1	112.23 (17)
N1—C4—C5	115.3 (2)	C2—N2—C3	116.4 (3)
C4—C5—C6	123.3 (2)	C5—N3—Cu1	120.73 (18)
N3—C5—C4	112.0 (2)	C5—N3—N4	122.2 (2)
N3—C5—C6	124.7 (2)	N4—N3—Cu1	117.00 (15)
C5—C6—H6A	109.5	C7—N4—N3	107.8 (2)
C5—C6—H6B	109.5	C11—N5—C12	118.0 (2)
C5—C6—H6C	109.5	Cu1^i—N6—Cu1	92.34 (9)
H6A—C6—H6B	109.5	N7—N6—Cu1^i	125.40 (19)
H6A—C6—H6C	109.5	N7—N6—Cu1	111.79 (17)
H6B—C6—H6C	109.5	N8—N7—N6	176.4 (3)
N4—C7—C8	115.6 (2)	C7—O1—Cu1	109.78 (16)
Cu1^i—Cu1—N1—C1	44.7 (2)	N1—Cu1—N6—Cu1^i	−97.19 (9)
Cu1^i—Cu1—N1—C4	−128.65 (17)	N1—Cu1—N6—N7	32.66 (19)
Cu1^i—Cu1—N3—C5	80.8 (2)	N1—Cu1—O1—C7	−17.7 (3)
Cu1^i—Cu1—N3—N4	−95.32 (17)	N1—C1—C2—N2	−1.7 (5)
Cu1^i—Cu1—N6—N7	129.8 (2)	N1—C4—C5—C6	−179.3 (2)
Cu1^i—Cu1—O1—C7	125.85 (16)	N1—C4—C5—N3	1.2 (3)
Cu1—N3—N4—C7	−2.6 (3)	N2—C3—C4—C5	176.8 (3)
Cu1^i—N6—N7—N8	167 (5)	N2—C3—C4—N1	−2.2 (4)
Cu1—N6—N7—N8	57 (5)	N3—Cu1—N1—C1	177.4 (3)
C1—C2—N2—C3	0.6 (5)	N3—Cu1—N1—C4	3.95 (17)
C2—C1—N1—Cu1	−172.2 (2)	N3—Cu1—N6—Cu1^i	−176.56 (9)
C2—C1—N1—C4	0.9 (4)	N3—Cu1—N6—N7	−46.72 (19)
C3—C4—C5—C6	1.6 (4)	N3—Cu1—O1—C7	−5.56 (17)
C3—C4—C5—N3	−177.9 (3)	N4—C7—C8—C9	−1.2 (4)
C3—C4—N1—Cu1	175.2 (2)	N4—C7—C8—C12	−178.7 (3)
C3—C4—N1—C1	1.0 (4)	N4—C7—O1—Cu1	6.6 (3)
C4—C3—N2—C2	1.4 (5)	N6—Cu1—N1—C1	82.1 (2)
C4—C5—N3—Cu1	2.5 (3)	N6^i—Cu1—N1—C1	−5.3 (3)
C4—C5—N3—N4	178.4 (2)	N6^i—Cu1—N1—C4	−178.70 (18)
C5—C4—N1—Cu1	−3.9 (3)	N6—Cu1—N1—C4	−91.27 (18)
C5—C4—N1—C1	−178.1 (2)	N6^i—Cu1—N3—C5	−42.1 (13)
C5—N3—N4—C7	−178.6 (2)	N6—Cu1—N3—C5	83.6 (2)
C6—C5—N3—Cu1	−177.0 (2)	N6^i—Cu1—N3—N4	141.8 (12)
C6—C5—N3—N4	−1.1 (4)	N6—Cu1—N3—N4	−92.47 (17)
C7—C8—C9—C10	−176.5 (3)	N6^i—Cu1—N6—Cu1^i	0.0
C7—C8—C12—N5	176.7 (3)	N6^i—Cu1—N6—N7	129.8 (2)
C8—C7—N4—N3	175.4 (2)	N6^i—Cu1—O1—C7	177.39 (17)
C8—C7—O1—Cu1	−171.71 (18)	N6—Cu1—O1—C7	87.98 (17)
C8—C9—C10—C11	−0.4 (5)	O1—Cu1—N1—C1	−170.5 (2)
C8—C12—N5—C11	0.0 (5)	O1—Cu1—N1—C4	16.1 (3)
C9—C8—C12—N5	−0.9 (5)	O1—Cu1—N3—C5	−179.3 (2)
C9—C10—C11—C13	179.8 (3)	O1—Cu1—N3—N4	4.60 (16)
C9—C10—C11—N5	−0.5 (5)	O1—Cu1—N6—Cu1^i	103.00 (9)
C10—C11—N5—C12	0.7 (5)	O1—Cu1—N6—N7	−127.16 (18)
C12—C8—C9—C10	1.1 (4)	O1—C7—C8—C9	177.2 (2)
C13—C11—N5—C12	−179.6 (3)	O1—C7—C8—C12	−0.3 (4)
N1—Cu1—N3—C5	−3.7 (2)	O1—C7—N4—N3	−2.9 (3)
N1—Cu1—N3—N4	−179.79 (18)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6C···N4^ii	0.96	2.58	3.450 (4)	150

Symmetry code: (ii) −x+2, −y+2, −z.