A novel binuclear copper complex incorporating a nalidixic acid derivative displaying a one-dimensional coordination polymeric structure

The identification of the anti­bacterial action of nalidixic acid (nx) was central to the development of the quinolone anti­bacterial compounds. The ability of the nx naphthyridyl ring to inter­act with and inhibit some proteins has encouraged the investigation of similar structures in the search for more active compounds with less adverse effects. The possibility of structural modification by attachment of other biologically active moieties to the naphthyridyl ring of nx allowed the development of new active anti­microbial mol­ecules. Hydrazone derivatives of nx can be synthesized easily based on the condensation of the hydrazide derivative of nx with the desired aldehyde or ketone. Only a few complexes with nx hydrazone derivatives have been described but for none were the crystal structures elucidated. The synthesis of a new one-dimensional Cu^II coordination polymer, namely catena-poly[[copper(II)-di-μ-chlorido-cop­per(II)-{μ-1-ethyl-N′-[(1H-imidazol-4-yl)methyl­idene]-7-methyl-4-oxo-1,4-di­hydro-1,8-naphthyridine-3-carbohydrazidato}-[di­methano­lcopper(II)]-{μ-1-ethyl-N′-[(1H-imidazol-3-yl)methyl­idene]-7-methyl-4-oxo-1,4-di­hydro-1,8-naphthyridine-3-carbohydrazidato}] dichloride methanol tetra­solvate], {[Cu₃(C₁₆H₁₅N₆O₂)₂Cl₂(CH₃OH)₂]Cl₂·4CH₃OH}_n, with the (1H-imidazol-4-yl)methyl­idene carbohydrazide derivative of nalidixic acid (denoted h4imi), is presented and its structure is compared to the density functional theory (DFT) optimized structure of free h4imi. The title structure presents an octa­hedral Cu^II ion on an inversion centre alternating along a polymer chain with a square-pyramidal Cu^II ion, with the two Cu^II centres bridged by two chloride ligands. Hydrogen bonds involving chloride counter-ions and methanol solvent mol­ecules mediate the three-dimensional packing of the polymer. Comparison of the geometrical results from the structure analysis with those derived from a DFT study of the free ligand reveal the differences that arise upon coordination.

Computing details

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

catena-Poly[[copper(II)-di-µ-chlorido-copper(II)-{µ-1-ethyl-N'-[(1H-imidazol-3-yl)methylidene]-7-methyl-4-oxo-1,4-dihydro-1,8-naphthyridine-3-carbohydrazidato}-[dimethanolcopper(II)]-{µ-1-ethyl-N'-[(1H-imidazol-3-yl)methylidene]-7-methyl-4-oxo-1,4-dihydro-1,8-naphthyridine-3-carbohydrazidato}] dichloride methanol tetrasolvate]

Crystal data

[Cu3(C16H15N6O2)2Cl2(CH4O)2]Cl2·4CH4O	F(000) = 2260
Mr = 1107.26	Dx = 1.671 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 18.5958 (11) Å	Cell parameters from 9900 reflections
b = 16.6608 (10) Å	θ = 2.8–28.2°
c = 14.2394 (9) Å	µ = 1.74 mm^−1
β = 93.692 (2)°	T = 150 K
V = 4402.5 (5) Å^3	Block, green
Z = 4	0.26 × 0.17 × 0.13 mm

Data collection

Bruker APEXII CCD diffractometer	4751 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.029
Absorption correction: multi-scan (SADABS; Bruker, 2014)	θmax = 28.3°, θmin = 1.6°
Tmin = 0.691, Tmax = 0.746	h = −24→23
34794 measured reflections	k = −22→21
5471 independent reflections	l = −18→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.027	H-atom parameters constrained
wR(F^2) = 0.074	w = 1/[σ^2(Fo^2) + (0.0356P)^2 + 7.5985P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
5471 reflections	Δρmax = 0.54 e Å^−3
294 parameters	Δρmin = −0.51 e Å^−3
25 restraints

Special details

Experimental. SADABS-2014/5 (Bruker,2014) was used for absorption correction. wR2(int) was 0.0498 before and 0.0405 after correction. The Ratio of minimum to maximum transmission is 0.9269. The λ/2 correction factor is 0.00150.

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cu1	0.47615 (2)	0.68901 (2)	0.36649 (2)	0.01472 (6)
Cl1	0.64032 (3)	0.05663 (3)	0.32933 (5)	0.04294 (16)
Cu2	0.2500	0.7500	0.5000	0.01651 (8)
Cl2	0.41153 (2)	0.67586 (3)	0.19402 (3)	0.01953 (10)
O2	0.28293 (7)	0.64150 (7)	0.49541 (9)	0.0181 (3)
C18	0.22719 (13)	0.73844 (17)	0.26149 (16)	0.0379 (6)
H18A	0.1956	0.7328	0.2040	0.057*
H18B	0.2632	0.6954	0.2642	0.057*
H18C	0.2516	0.7905	0.2612	0.057*
C5	0.34270 (9)	0.63378 (10)	0.45766 (12)	0.0142 (3)
C10	0.32155 (10)	0.49200 (11)	0.47609 (13)	0.0191 (4)
H10	0.2781	0.5089	0.5016	0.023*
N6	0.40462 (9)	0.30580 (9)	0.42752 (11)	0.0200 (3)
C7	0.43359 (9)	0.52754 (11)	0.41004 (12)	0.0143 (3)
O1	0.48136 (7)	0.57491 (8)	0.38402 (9)	0.0199 (3)
N2	0.48830 (8)	0.80569 (9)	0.37265 (11)	0.0169 (3)
C2	0.54366 (10)	0.85055 (12)	0.35118 (13)	0.0210 (4)
H2	0.5879	0.8299	0.3317	0.025*
N1	0.52919 (9)	0.92866 (10)	0.36055 (13)	0.0254 (4)
H1	0.5587	0.9685	0.3500	0.030*
C1	0.46128 (11)	0.93587 (12)	0.38905 (15)	0.0239 (4)
H1A	0.4364	0.9843	0.4010	0.029*
C3	0.43578 (10)	0.85916 (11)	0.39719 (13)	0.0184 (4)
C4	0.36732 (10)	0.83710 (11)	0.42980 (13)	0.0185 (4)
H4	0.3357	0.8803	0.4412	0.022*
N3	0.34300 (8)	0.76657 (9)	0.44565 (11)	0.0158 (3)
C6	0.36748 (9)	0.55065 (10)	0.44654 (12)	0.0145 (3)
N5	0.33399 (8)	0.41321 (9)	0.47135 (12)	0.0206 (3)
C9	0.39648 (10)	0.38588 (11)	0.43381 (12)	0.0170 (3)
C13	0.46479 (11)	0.27836 (12)	0.39315 (13)	0.0214 (4)
C12	0.51965 (11)	0.32959 (12)	0.36530 (13)	0.0218 (4)
H12	0.5629	0.3080	0.3437	0.026*
C11	0.51000 (10)	0.41102 (12)	0.36973 (12)	0.0187 (4)
H11	0.5460	0.4464	0.3497	0.022*
C8	0.44637 (9)	0.44187 (11)	0.40417 (12)	0.0155 (3)
C14	0.47078 (13)	0.18882 (12)	0.38232 (15)	0.0287 (5)
H14A	0.4522	0.1623	0.4372	0.043*
H14B	0.5214	0.1741	0.3775	0.043*
H14C	0.4426	0.1718	0.3253	0.043*
N4	0.38150 (8)	0.69624 (9)	0.42930 (10)	0.0137 (3)
O3	0.18547 (8)	0.73350 (9)	0.34110 (11)	0.0269 (3)
H3	0.1699	0.6865	0.3462	0.040*
O4	0.72490 (11)	−0.01627 (17)	0.16711 (16)	0.0682 (7)
H4A	0.6959	−0.0077	0.2089	0.102*
C17	0.79330 (15)	−0.03305 (19)	0.20971 (18)	0.0463 (6)
H17A	0.7883	−0.0541	0.2732	0.069*
H17B	0.8221	0.0163	0.2135	0.069*
H17C	0.8174	−0.0730	0.1722	0.069*
C15A	0.2775 (4)	0.3515 (7)	0.4911 (7)	0.0275 (5)	0.326 (4)
H15A	0.2700	0.3163	0.4353	0.033*	0.326 (4)
H15B	0.2962	0.3176	0.5443	0.033*	0.326 (4)
C16A	0.2070 (3)	0.3846 (4)	0.5139 (5)	0.0275 (5)	0.326 (4)
H16A	0.1871	0.4170	0.4610	0.041*	0.326 (4)
H16B	0.2133	0.4183	0.5703	0.041*	0.326 (4)
H16C	0.1739	0.3405	0.5257	0.041*	0.326 (4)
C15B	0.2817 (2)	0.3587 (3)	0.5150 (3)	0.0275 (5)	0.674 (4)
H15C	0.2727	0.3778	0.5790	0.033*	0.674 (4)
H15D	0.3019	0.3038	0.5203	0.033*	0.674 (4)
C16B	0.21244 (16)	0.35759 (19)	0.4550 (2)	0.0275 (5)	0.674 (4)
H16D	0.2212	0.3362	0.3927	0.041*	0.674 (4)
H16E	0.1935	0.4123	0.4486	0.041*	0.674 (4)
H16F	0.1774	0.3235	0.4846	0.041*	0.674 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.01062 (11)	0.01627 (11)	0.01774 (11)	−0.00031 (8)	0.00466 (7)	0.00048 (8)
Cl1	0.0347 (3)	0.0247 (3)	0.0716 (4)	−0.0144 (2)	0.0205 (3)	−0.0068 (3)
Cu2	0.01243 (15)	0.01206 (15)	0.02623 (16)	0.00088 (11)	0.01043 (12)	0.00055 (11)
Cl2	0.01096 (19)	0.0261 (2)	0.0220 (2)	−0.00067 (16)	0.00461 (15)	−0.00184 (17)
O2	0.0140 (6)	0.0136 (6)	0.0279 (7)	0.0008 (5)	0.0116 (5)	0.0008 (5)
C18	0.0325 (12)	0.0531 (16)	0.0286 (11)	−0.0070 (11)	0.0046 (9)	0.0044 (10)
C5	0.0114 (8)	0.0159 (8)	0.0156 (7)	0.0004 (6)	0.0021 (6)	−0.0007 (6)
C10	0.0147 (8)	0.0155 (8)	0.0277 (9)	0.0023 (7)	0.0065 (7)	0.0005 (7)
N6	0.0205 (8)	0.0155 (8)	0.0238 (8)	0.0039 (6)	−0.0001 (6)	−0.0011 (6)
C7	0.0118 (8)	0.0170 (8)	0.0140 (7)	0.0021 (6)	0.0010 (6)	0.0011 (6)
O1	0.0144 (6)	0.0190 (6)	0.0272 (7)	0.0018 (5)	0.0087 (5)	0.0044 (5)
N2	0.0124 (7)	0.0199 (8)	0.0188 (7)	−0.0031 (6)	0.0035 (5)	−0.0015 (6)
C2	0.0152 (8)	0.0246 (10)	0.0234 (9)	−0.0053 (7)	0.0037 (7)	−0.0028 (7)
N1	0.0199 (8)	0.0218 (8)	0.0351 (9)	−0.0096 (7)	0.0068 (7)	−0.0010 (7)
C1	0.0194 (9)	0.0189 (9)	0.0343 (11)	−0.0051 (8)	0.0080 (8)	−0.0013 (8)
C3	0.0160 (8)	0.0177 (9)	0.0219 (9)	−0.0021 (7)	0.0041 (7)	−0.0002 (7)
C4	0.0162 (9)	0.0149 (8)	0.0249 (9)	0.0018 (7)	0.0060 (7)	0.0000 (7)
N3	0.0137 (7)	0.0142 (7)	0.0203 (7)	0.0001 (6)	0.0061 (5)	0.0005 (6)
C6	0.0126 (8)	0.0140 (8)	0.0172 (8)	−0.0004 (6)	0.0036 (6)	−0.0005 (6)
N5	0.0145 (7)	0.0139 (7)	0.0340 (9)	0.0008 (6)	0.0066 (6)	0.0034 (6)
C9	0.0149 (8)	0.0159 (8)	0.0198 (8)	0.0032 (7)	−0.0005 (6)	0.0001 (7)
C13	0.0249 (10)	0.0197 (9)	0.0190 (8)	0.0087 (8)	−0.0022 (7)	−0.0014 (7)
C12	0.0201 (9)	0.0259 (10)	0.0196 (8)	0.0095 (8)	0.0016 (7)	−0.0024 (7)
C11	0.0158 (9)	0.0235 (9)	0.0168 (8)	0.0045 (7)	0.0019 (6)	0.0006 (7)
C8	0.0136 (8)	0.0187 (9)	0.0141 (8)	0.0042 (7)	0.0004 (6)	−0.0005 (6)
C14	0.0352 (12)	0.0199 (10)	0.0311 (11)	0.0097 (9)	0.0029 (9)	−0.0032 (8)
N4	0.0123 (7)	0.0134 (7)	0.0159 (7)	0.0014 (5)	0.0041 (5)	0.0005 (5)
O3	0.0258 (7)	0.0222 (7)	0.0336 (8)	−0.0020 (6)	0.0088 (6)	−0.0022 (6)
O4	0.0375 (11)	0.108 (2)	0.0586 (13)	0.0008 (12)	0.0000 (9)	−0.0433 (13)
C17	0.0439 (15)	0.0617 (18)	0.0333 (13)	−0.0011 (13)	0.0017 (11)	−0.0019 (12)
C15A	0.0185 (8)	0.0213 (11)	0.0430 (16)	−0.0039 (7)	0.0045 (10)	0.0080 (11)
C16A	0.0185 (8)	0.0213 (11)	0.0430 (16)	−0.0039 (7)	0.0045 (10)	0.0080 (11)
C15B	0.0185 (8)	0.0213 (11)	0.0430 (16)	−0.0039 (7)	0.0045 (10)	0.0080 (11)
C16B	0.0185 (8)	0.0213 (11)	0.0430 (16)	−0.0039 (7)	0.0045 (10)	0.0080 (11)

Geometric parameters (Å, º)

Cu1—Cl2^i	2.3206 (5)	C4—N3	1.284 (2)
Cu1—Cl2	2.6727 (5)	N3—N4	1.400 (2)
Cu1—O1	1.9190 (13)	N5—C9	1.387 (2)
Cu1—N4	2.0285 (14)	N5—C15A	1.509 (11)
Cu2—O2	1.9110 (12)	N5—C15B	1.495 (5)
Cu2—O2^ii	1.9110 (12)	C9—C8	1.400 (3)
Cu2—N3^ii	1.9593 (15)	C13—C12	1.407 (3)
Cl2—Cu1^i	2.3206 (5)	C13—C14	1.505 (3)
O2—C5	1.272 (2)	C12—H12	0.9500
C18—H18A	0.9800	C12—C11	1.371 (3)
C18—H18B	0.9800	C11—H11	0.9500
C18—H18C	0.9800	C11—C8	1.407 (2)
C18—O3	1.417 (3)	C14—H14A	0.9800
C5—C6	1.472 (2)	C14—H14B	0.9800
C5—N4	1.343 (2)	C14—H14C	0.9800
C10—H10	0.9500	O3—H3	0.8400
C10—C6	1.381 (2)	O4—H4A	0.8400
C10—N5	1.335 (2)	O4—C17	1.402 (3)
N6—C9	1.346 (2)	C17—H17A	0.9800
N6—C13	1.331 (2)	C17—H17B	0.9800
C7—O1	1.262 (2)	C17—H17C	0.9800
C7—C6	1.418 (2)	C15A—H15A	0.9900
C7—C8	1.450 (2)	C15A—H15B	0.9900
N2—C2	1.324 (2)	C15A—C16A	1.478 (8)
N2—C3	1.383 (2)	C16A—H16A	0.9800
C2—H2	0.9500	C16A—H16B	0.9800
C2—N1	1.337 (3)	C16A—H16C	0.9800
N1—H1	0.8800	C15B—H15C	0.9900
N1—C1	1.356 (3)	C15B—H15D	0.9900
C1—H1A	0.9500	C15B—C16B	1.499 (4)
C1—C3	1.371 (3)	C16B—H16D	0.9800
C3—C4	1.431 (2)	C16B—H16E	0.9800
C4—H4	0.9500	C16B—H16F	0.9800
Cl2^i—Cu1—Cl2	90.757 (16)	N5—C9—C8	119.05 (16)
O1—Cu1—Cl2^i	85.16 (4)	N6—C13—C12	122.51 (18)
O1—Cu1—Cl2	93.11 (4)	N6—C13—C14	116.60 (19)
O1—Cu1—N4	92.27 (6)	C12—C13—C14	120.87 (18)
N4—Cu1—Cl2	93.35 (4)	C13—C12—H12	120.4
N4—Cu1—Cl2^i	175.27 (4)	C11—C12—C13	119.22 (17)
O2^ii—Cu2—O2	180.0	C11—C12—H12	120.4
O2—Cu2—N3^ii	99.97 (6)	C12—C11—H11	120.2
O2^ii—Cu2—N3^ii	80.03 (6)	C12—C11—C8	119.56 (18)
Cu1^i—Cl2—Cu1	88.356 (16)	C8—C11—H11	120.2
C5—O2—Cu2	113.63 (11)	C9—C8—C7	121.61 (16)
H18A—C18—H18B	109.5	C9—C8—C11	116.76 (17)
H18A—C18—H18C	109.5	C11—C8—C7	121.62 (17)
H18B—C18—H18C	109.5	C13—C14—H14A	109.5
O3—C18—H18A	109.5	C13—C14—H14B	109.5
O3—C18—H18B	109.5	C13—C14—H14C	109.5
O3—C18—H18C	109.5	H14A—C14—H14B	109.5
O2—C5—C6	115.40 (15)	H14A—C14—H14C	109.5
O2—C5—N4	123.35 (16)	H14B—C14—H14C	109.5
N4—C5—C6	121.25 (15)	C5—N4—Cu1	125.78 (12)
C6—C10—H10	117.7	C5—N4—N3	107.93 (14)
N5—C10—H10	117.7	N3—N4—Cu1	126.19 (11)
N5—C10—C6	124.58 (17)	C18—O3—H3	109.5
C13—N6—C9	117.76 (17)	C17—O4—H4A	109.5
O1—C7—C6	125.53 (16)	O4—C17—H17A	109.5
O1—C7—C8	118.53 (15)	O4—C17—H17B	109.5
C6—C7—C8	115.93 (15)	O4—C17—H17C	109.5
C7—O1—Cu1	128.84 (12)	H17A—C17—H17B	109.5
C2—N2—C3	105.49 (16)	H17A—C17—H17C	109.5
N2—C2—H2	124.4	H17B—C17—H17C	109.5
N2—C2—N1	111.22 (17)	N5—C15A—H15A	108.5
N1—C2—H2	124.4	N5—C15A—H15B	108.5
C2—N1—H1	125.9	H15A—C15A—H15B	107.5
C2—N1—C1	108.25 (16)	C16A—C15A—N5	115.1 (8)
C1—N1—H1	125.9	C16A—C15A—H15A	108.5
N1—C1—H1A	127.0	C16A—C15A—H15B	108.5
N1—C1—C3	106.06 (17)	C15A—C16A—H16A	109.5
C3—C1—H1A	127.0	C15A—C16A—H16B	109.5
N2—C3—C4	125.04 (16)	C15A—C16A—H16C	109.5
C1—C3—N2	108.98 (16)	H16A—C16A—H16B	109.5
C1—C3—C4	125.93 (18)	H16A—C16A—H16C	109.5
C3—C4—H4	115.7	H16B—C16A—H16C	109.5
N3—C4—C3	128.51 (17)	N5—C15B—H15C	109.8
N3—C4—H4	115.7	N5—C15B—H15D	109.8
C4—N3—N4	123.15 (15)	N5—C15B—C16B	109.2 (3)
C10—C6—C5	115.40 (15)	H15C—C15B—H15D	108.3
C10—C6—C7	119.16 (16)	C16B—C15B—H15C	109.8
C7—C6—C5	125.43 (16)	C16B—C15B—H15D	109.8
C10—N5—C9	119.62 (16)	C15B—C16B—H16D	109.5
C10—N5—C15A	122.4 (4)	C15B—C16B—H16E	109.5
C10—N5—C15B	117.2 (2)	C15B—C16B—H16F	109.5
C9—N5—C15A	117.3 (4)	H16D—C16B—H16E	109.5
C9—N5—C15B	123.0 (2)	H16D—C16B—H16F	109.5
N6—C9—N5	116.84 (16)	H16E—C16B—H16F	109.5
N6—C9—C8	124.10 (17)
Cu2—O2—C5—C6	−175.80 (11)	C6—C5—N4—N3	177.71 (15)
Cu2—O2—C5—N4	4.2 (2)	C6—C10—N5—C9	−0.6 (3)
O2—C5—C6—C10	1.8 (2)	C6—C10—N5—C15A	−170.8 (4)
O2—C5—C6—C7	−177.27 (16)	C6—C10—N5—C15B	174.3 (2)
O2—C5—N4—Cu1	−178.81 (12)	C6—C7—O1—Cu1	−10.4 (3)
O2—C5—N4—N3	−2.3 (2)	C6—C7—C8—C9	−0.6 (2)
C10—N5—C9—N6	−177.46 (17)	C6—C7—C8—C11	−179.65 (16)
C10—N5—C9—C8	1.9 (3)	N5—C10—C6—C5	179.52 (18)
C10—N5—C15A—C16A	1.3 (9)	N5—C10—C6—C7	−1.4 (3)
C10—N5—C15B—C16B	72.4 (4)	N5—C9—C8—C7	−1.3 (3)
N6—C9—C8—C7	178.04 (17)	N5—C9—C8—C11	177.82 (16)
N6—C9—C8—C11	−2.9 (3)	C9—N6—C13—C12	1.1 (3)
N6—C13—C12—C11	−2.8 (3)	C9—N6—C13—C14	−176.99 (17)
O1—C7—C6—C5	1.8 (3)	C9—N5—C15A—C16A	−169.1 (5)
O1—C7—C6—C10	−177.20 (17)	C9—N5—C15B—C16B	−112.9 (3)
O1—C7—C8—C9	178.52 (16)	C13—N6—C9—N5	−178.89 (16)
O1—C7—C8—C11	−0.5 (3)	C13—N6—C9—C8	1.8 (3)
N2—C2—N1—C1	−0.3 (2)	C13—C12—C11—C8	1.6 (3)
N2—C3—C4—N3	2.8 (3)	C12—C11—C8—C7	−179.86 (17)
C2—N2—C3—C1	0.4 (2)	C12—C11—C8—C9	1.1 (3)
C2—N2—C3—C4	−177.00 (18)	C8—C7—O1—Cu1	170.57 (12)
C2—N1—C1—C3	0.5 (2)	C8—C7—C6—C5	−179.10 (16)
N1—C1—C3—N2	−0.5 (2)	C8—C7—C6—C10	1.9 (2)
N1—C1—C3—C4	176.82 (18)	C14—C13—C12—C11	175.23 (18)
C1—C3—C4—N3	−174.1 (2)	N4—C5—C6—C10	−178.20 (16)
C3—N2—C2—N1	−0.1 (2)	N4—C5—C6—C7	2.7 (3)
C3—C4—N3—N4	−2.3 (3)	C15A—N5—C9—N6	−6.8 (5)
C4—N3—N4—Cu1	−6.7 (2)	C15A—N5—C9—C8	172.5 (4)
C4—N3—N4—C5	176.81 (17)	C15B—N5—C9—N6	7.9 (3)
C6—C5—N4—Cu1	1.2 (2)	C15B—N5—C9—C8	−172.7 (2)

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

Hydrogen-bond geometry (Å)

D—H···A	D···A
O3—H3···Cl1^iii	3.066 (2)
N1—H1···Cl1^iv	3.022 (2)
O4—H4A···Cl1	3.123 (2)

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