Crystal structure of bis­{μ2-3-(pyridin-2-yl)-5-[(1,2,4-triazol-1-yl)meth­yl]-1,2,4-triazolato}bis­[aqua­nitrato­copper(II)] dihydrate

Doroschuk, R.

doi:10.1107/S2056989016003479

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Volume 72| Part 4| April 2016| Pages 486-488

https://doi.org/10.1107/S2056989016003479

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Crystal structure of bis{μ₂-3-(pyridin-2-yl)-5-[(1,2,4-triazol-1-yl)methyl]-1,2,4-triazolato}bis[aquanitratocopper(II)] dihydrate

Roman Doroschuk ^a ^*

^aDepartment of Inorganic Chemistry, Taras Shevchenko National University of Kyiv, 64, Volodymyrska Str., 01033, Kyiv, Ukraine
^*Correspondence e-mail: rdoroschuk@ukr.net

Edited by C. Rizzoli, Universita degli Studi di Parma, Italy (Received 10 February 2016; accepted 29 February 2016; online 11 March 2016)

The structure of the dinuclear title complex, [Cu₂(C₁₀H₈N₇)₂(NO₃)₂(H₂O)₂]·2H₂O, consists of centrosymmetric dimeric units with a copper–copper separation of 4.0408 (3) Å. The Cu^II ions in the dimer display a distorted octahedral coordination geometry and are bridged by two triazole rings, forming an approximately planar Cu₂N₄ core (r.m.s. deviation = 0.049 Å). In the crystal, O—H⋯O, O—H⋯N and C—H⋯O hydrogen bonds and π–π interactions link the molecules into a three-dimensional network.

Keywords: crystal structure; 1,2,4-triazole; dinuclear copper complex; hydrogen bonds.

CCDC reference: 1456451

1. Chemical context

The presence in the triazole ring, three donor atoms and the possibility of introducing in the heterocycle substituents of a different nature creates the conditions for target synthesis of complexes with interesting structures and properties. The study of this type of coordination compound is promising since, as a result, a compound can be obtained with useful physical properties such as optical, magnetic or catalytic (Soghomonian et al., 1993 ; Blake et al., 1999 ). Another interesting aspect of these compounds is the possibility of their use as functional models of enzymes such as catechol oxidase (Moliner et al., 2001 ; Klingele et al., 2009 ; Selmeczi et al., 2003 ).

2. Structural commentary

The structure of the title complex molecule (Fig. 1) has a crystallographically imposed centre of symmetry, and contains two copper(II) metal atoms doubly bridged by the triazole rings of two deprotonated ligands. Each copper(II) ion is coordinated in a distorted elongated octahedral geometry by one pyridine and three triazole nitrogen atoms forming the equatorial plane, and by the O atoms of a water molecule and a monodentate nitrate anion at the apices. The Cu—N bond lengths involving the bridging triazole ring [mean value 1.9722 (15) Å] are slightly, but significantly, shorter than those involving the pyridine and peripheral triazole rings [Cu1—N4 = 2.0386 (16) and Cu1—N7 = 2.0409 (17) Å]. The inner Cu₂N₄ core is approximately planar [r.m.s. deviation = 0.049 Å; maximum displacement 0.062 (2) Å for atom N2], with a Cu⋯Cu separation of 4.0408 (3) Å, in good agreement with the values usually observed in μ-triazolyl-bridged complexes (Haasnoot, 2000 ). The central triazole ring makes dihedral angles of 7.78 (8) and 49.30 (8)°, respectively, with the pyridine and peripheral triazole rings. The six-membered chelate ring Cu1/N5/C7/C8/N6/N7 assumes a boat conformation [puckering parameters: Q_T = 0.619 (2) Å; θ2 = 88.62 (16)°], while the five-membered Cu1/N2/C1/C2/N4 chelate ring adopts a flattened envelope conformation with the Cu atom as flap [puckering parameters: Q = 0.127 (2) Å; φ = −156.8 (8)°].

Figure 1
The molecular structure of the title compound with displacement ellipsoids drawn at the 40% probability level. Dashed lines indicate hydrogen bonds. Unlabelled atoms are related to labelled atoms by (−x, 1 − y, −z).

3. Supramolecular features

In the crystal, the complex molecules and water molecules of crystallization are linked through O—H⋯O, O—H⋯N and C—H⋯O hydrogen bonds (Table 1), forming a three-dimensional network (Fig. 2). The crystal structure is further stabilized by π–π stacking interactions with centroid–centroid separations Cg1⋯Cg2ⁱⁱ = 3.8296 (13) Å and Cg3⋯Cg3ⁱⁱⁱ = 3.5372 (10), and perpendicular interplanar distances Cg1⋯Cg2ⁱⁱ = 3.5584 (9) and Cg3⋯Cg3^{iii =} 3.3234 (10) Å [Cg1, Cg2 and Cg3 are the centroids of the N1/C2/N3/C7ⁱ/N5ⁱ, N4/C2–C6 and N6/N7/C9/N8/C10 rings, respectively; symmetry codes: (i) −x, 1 − y, −z; (ii) −x, −y, −z; (iii) 1 − x, −y, 1 − z].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H41O⋯O5ⁱ	0.71 (3)	2.03 (3)	2.735 (2)	172 (3)
O4—H42O⋯O5ⁱⁱ	0.79 (3)	1.96 (3)	2.735 (2)	168 (3)
O5—H51O⋯O2ⁱⁱⁱ	0.78 (3)	2.02 (3)	2.773 (2)	163 (3)
O5—H52O⋯N3^iv	0.76 (3)	2.08 (3)	2.836 (2)	177 (3)
C5—H5⋯O1ⁱ	0.95	2.43	3.360 (3)	166
C8—H8A⋯O4	0.99	2.56	3.160 (3)	119
C8—H8B⋯O2ⁱⁱⁱ	0.99	2.36	3.319 (3)	162
C9—H9⋯O3^v	0.95	2.44	3.205 (3)	137
Symmetry codes: (i) x, y-1, z; (ii) -x+1, -y+1, -z; (iii) x+1, y, z; (iv) -x, -y+1, -z; (v) -x, -y, -z+1.

Figure 2
Packing diagram of the title compound, viewed along the b axis. Intermolecular hydrogen bonds are shown as blue dotted lines.

4. Database survey

The Cambridge Structural Database (CSD Version 5.36 with three updates; Groom & Allen, 2014 ), returned 45 entries with the triazole bridging fragment Cu–(N–N)₂–Cu. The most similar are: diaquabis(μ-3,5-bis(2-pyridyl)-1,2,4-triazolato-N′,N¹,N²,N′′)bis(trifluoromethanesulfonato-O)dicopper(II) (Prins et al., 1985 ), bis[μ-5-(pyridin-2-yl)-3-(1H-1,2,4-triazol-3-yl)-1,2,4-triazolato]diaquadicopper diperchlorate (Zhou et al., 2014 ), bis[μ₃-(pyridin-2-yl)-5-([5-(pyridin-2-yl)-1,2,4-triazol-1-id-3-yl]methyl)-1,2,4-triazol-1-ide]triaquatricopper diperchlorate dihydrate (Gusev et al., 2014 ) and bis(μ-5-(2-ethoxy-2-oxoethyl)-3-(pyridin-2-yl)-1H-1,2,4-triazolyl)bis(acetonitrile)bis(perchlorato-O)dicopper (Khomenko et al., 2012 ). Only 10 compounds containing a pyridyl and a methylene moiety, as substituents in the 3- and 5-positions of 1,2,4-triazole, were found (Lin et al., 2013 ; Gusev et al., 2014 and references therein).

5. Synthesis and crystallization

A water solution of Cu(NO₃)₂·3H₂O (0.25 mmol, 0.0605 g) was added to a hot solution of 2-[5-(1,2,4,)-triazol-1-yl-methyl-1H-(1,2,4)-triazol-3yl]pyridine (0.25 mmol, 0.059 g) in water (7 ml). The transparent blue solution was left to evaporate slowly in the air and after few hours, blue single crystals suitable for X-ray analysis were obtained (yield: 67%).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. H atoms of water molecules were located from a difference Fourier map and refined freely. All other H atoms were constrained to ride on their parent atoms, with C—H = 0.95–0.99 Å and with U_iso(H) = 1.2U_eq(C).

Table 2
Experimental details

Crystal data
Chemical formula	[Cu₂(C₁₀H₈N₇)₂(NO₃)₂(H₂O)₂]·2H₂O
M_r	775.63
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	173
a, b, c (Å)	8.8421 (2), 8.8636 (2), 10.5686 (2)
α, β, γ (°)	70.114 (1), 88.6311 (10), 66.765 (1)
V (Å³)	709.87 (3)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	1.58
Crystal size (mm)	0.50 × 0.50 × 0.45

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2003 )
T_min, T_max	0.505, 0.536
No. of measured, independent and observed [I > 2σ(I)] reflections	8672, 2945, 2711
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.629

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.073, 1.07
No. of reflections	2945
No. of parameters	233
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.57
Computer programs: APEX2 and SAINT (Bruker, 2003), SHELXS97 and SHELXTL (Sheldrick, 2008 ) and SHELXL2014 (Sheldrick, 2015 ).

Supporting information

CCDC reference: 1456451

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989016003479/rz5185sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989016003479/rz5185Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Bis{µ₂-3-(pyridin-2-yl)-5-[(1,2,4-triazol-1-yl)methyl]-1,2,4-triazolato}bis[aquanitratocopper(II)] dihydrate top

Crystal data top

[Cu₂(C₁₀H₈N₇)₂(NO₃)₂(H₂O)₂]·2H₂O	Z = 1
M_r = 775.63	F(000) = 394
Triclinic, P1	D_x = 1.814 Mg m⁻³
a = 8.8421 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.8636 (2) Å	Cell parameters from 6116 reflections
c = 10.5686 (2) Å	θ = 2.5–26.5°
α = 70.114 (1)°	µ = 1.58 mm⁻¹
β = 88.6311 (10)°	T = 173 K
γ = 66.765 (1)°	Prism, blue
V = 709.87 (3) Å³	0.50 × 0.50 × 0.45 mm

Data collection top

Bruker APEXII CCD diffractometer	2711 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.025
Absorption correction: multi-scan (SADABS; Bruker, 2003)	θ_max = 26.6°, θ_min = 2.5°
T_min = 0.505, T_max = 0.536	h = −8→11
8672 measured reflections	k = −11→11
2945 independent reflections	l = −13→13

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.027	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.073	w = 1/[σ²(F_o²) + (0.0387P)² + 0.4452P] where P = (F_o² + 2F_c²)/3
S = 1.07	(Δ/σ)_max < 0.001
2945 reflections	Δρ_max = 0.26 e Å⁻³
233 parameters	Δρ_min = −0.57 e Å⁻³

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Cu1	0.11824 (3)	0.26915 (3)	0.15525 (2)	0.01617 (9)
N1	−0.2107 (2)	0.3725 (2)	0.34951 (17)	0.0208 (4)
N2	−0.0714 (2)	0.3636 (2)	0.01433 (17)	0.0166 (3)
N3	−0.3010 (2)	0.3463 (2)	−0.04965 (17)	0.0185 (3)
N4	0.0614 (2)	0.0562 (2)	0.20396 (16)	0.0169 (3)
N5	0.1657 (2)	0.4800 (2)	0.08348 (17)	0.0169 (3)
N6	0.3708 (2)	0.2657 (2)	0.34195 (17)	0.0184 (3)
N7	0.2554 (2)	0.2013 (2)	0.33410 (17)	0.0185 (3)
N8	0.3280 (2)	0.1530 (3)	0.55105 (19)	0.0291 (4)
O1	−0.1224 (2)	0.4373 (2)	0.27750 (19)	0.0352 (4)
O2	−0.34096 (19)	0.4721 (2)	0.38151 (16)	0.0281 (3)
O3	−0.1751 (2)	0.2133 (2)	0.38786 (18)	0.0361 (4)
O4	0.3491 (2)	0.1266 (2)	0.07991 (19)	0.0289 (4)
H41O	0.388 (3)	0.033 (4)	0.104 (3)	0.029 (8)*
H42O	0.376 (3)	0.168 (4)	0.010 (3)	0.032 (8)*
O5	0.5124 (2)	0.7700 (2)	0.15015 (19)	0.0254 (3)
H51O	0.563 (4)	0.698 (4)	0.219 (3)	0.042 (9)*
H52O	0.458 (4)	0.736 (4)	0.125 (3)	0.041 (9)*
C1	−0.1560 (2)	0.2649 (2)	0.03218 (19)	0.0165 (4)
C2	−0.0792 (2)	0.0862 (2)	0.13281 (19)	0.0172 (4)
C3	0.1479 (3)	−0.1054 (3)	0.2939 (2)	0.0207 (4)
H3	0.2474	−0.1283	0.3438	0.025*
C4	0.0969 (3)	−0.2412 (3)	0.3170 (2)	0.0237 (4)
H4	0.1614	−0.3551	0.3810	0.028*
C5	−0.0481 (3)	−0.2088 (3)	0.2461 (2)	0.0239 (4)
H5	−0.0858	−0.2994	0.2614	0.029*
C6	−0.1384 (3)	−0.0411 (3)	0.1517 (2)	0.0221 (4)
H6	−0.2389	−0.0149	0.1013	0.027*
C7	0.3006 (2)	0.4957 (2)	0.1186 (2)	0.0173 (4)
C8	0.4370 (2)	0.3469 (3)	0.2234 (2)	0.0204 (4)
H8A	0.5019	0.2577	0.1842	0.025*
H8B	0.5126	0.3913	0.2508	0.025*
C9	0.2342 (3)	0.1361 (3)	0.4624 (2)	0.0227 (4)
H9	0.1591	0.0820	0.4898	0.027*
C10	0.4109 (3)	0.2351 (3)	0.4713 (2)	0.0249 (4)
H10	0.4888	0.2679	0.5026	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01744 (14)	0.01210 (13)	0.01794 (14)	−0.00721 (9)	−0.00253 (9)	−0.00253 (10)
N1	0.0217 (9)	0.0206 (8)	0.0188 (8)	−0.0079 (7)	−0.0028 (7)	−0.0063 (7)
N2	0.0175 (8)	0.0123 (7)	0.0186 (8)	−0.0065 (6)	−0.0017 (6)	−0.0031 (6)
N3	0.0192 (8)	0.0183 (8)	0.0192 (8)	−0.0098 (7)	0.0007 (7)	−0.0052 (7)
N4	0.0192 (8)	0.0149 (7)	0.0165 (8)	−0.0071 (6)	0.0009 (6)	−0.0054 (6)
N5	0.0165 (8)	0.0132 (7)	0.0183 (8)	−0.0058 (6)	−0.0029 (6)	−0.0027 (6)
N6	0.0178 (8)	0.0149 (7)	0.0209 (9)	−0.0071 (6)	−0.0037 (6)	−0.0038 (7)
N7	0.0168 (8)	0.0169 (8)	0.0211 (9)	−0.0079 (6)	−0.0007 (6)	−0.0047 (7)
N8	0.0331 (10)	0.0328 (10)	0.0214 (9)	−0.0139 (8)	0.0005 (8)	−0.0090 (8)
O1	0.0337 (9)	0.0291 (8)	0.0463 (11)	−0.0184 (7)	0.0147 (8)	−0.0121 (8)
O2	0.0240 (8)	0.0294 (8)	0.0283 (8)	−0.0063 (6)	0.0038 (6)	−0.0128 (7)
O3	0.0486 (11)	0.0177 (8)	0.0398 (10)	−0.0139 (7)	0.0086 (8)	−0.0074 (7)
O4	0.0316 (9)	0.0164 (8)	0.0332 (10)	−0.0058 (7)	0.0129 (7)	−0.0079 (7)
O5	0.0245 (8)	0.0180 (7)	0.0312 (9)	−0.0098 (7)	−0.0023 (7)	−0.0045 (7)
C1	0.0187 (9)	0.0154 (9)	0.0170 (9)	−0.0089 (7)	0.0013 (7)	−0.0053 (7)
C2	0.0197 (9)	0.0165 (9)	0.0164 (9)	−0.0077 (7)	0.0031 (7)	−0.0067 (8)
C3	0.0219 (10)	0.0172 (9)	0.0195 (10)	−0.0059 (8)	0.0000 (8)	−0.0049 (8)
C4	0.0341 (12)	0.0143 (9)	0.0185 (10)	−0.0087 (8)	0.0023 (8)	−0.0025 (8)
C5	0.0361 (12)	0.0179 (9)	0.0226 (11)	−0.0162 (9)	0.0069 (9)	−0.0073 (8)
C6	0.0265 (11)	0.0212 (10)	0.0221 (10)	−0.0140 (8)	0.0015 (8)	−0.0069 (8)
C7	0.0167 (9)	0.0177 (9)	0.0179 (10)	−0.0082 (7)	0.0007 (7)	−0.0056 (8)
C8	0.0168 (9)	0.0196 (9)	0.0225 (10)	−0.0090 (8)	−0.0020 (8)	−0.0027 (8)
C9	0.0244 (10)	0.0204 (10)	0.0214 (10)	−0.0087 (8)	0.0019 (8)	−0.0058 (8)
C10	0.0281 (11)	0.0234 (10)	0.0226 (11)	−0.0101 (9)	−0.0038 (8)	−0.0079 (9)

Geometric parameters (Å, º) top

Cu1—N5	1.9709 (15)	N8—C9	1.349 (3)
Cu1—N2	1.9732 (16)	O4—H41O	0.71 (3)
Cu1—N4	2.0386 (16)	O4—H42O	0.79 (3)
Cu1—N7	2.0409 (17)	O5—H51O	0.78 (3)
Cu1—O4	2.2293 (16)	O5—H52O	0.76 (3)
N1—O3	1.234 (2)	C1—C2	1.463 (3)
N1—O1	1.244 (2)	C2—C6	1.376 (3)
N1—O2	1.266 (2)	C3—C4	1.391 (3)
N2—C1	1.326 (2)	C3—H3	0.9500
N2—N5ⁱ	1.356 (2)	C4—C5	1.377 (3)
N3—C7ⁱ	1.342 (2)	C4—H4	0.9500
N3—C1	1.346 (3)	C5—C6	1.391 (3)
N4—C3	1.335 (3)	C5—H5	0.9500
N4—C2	1.352 (3)	C6—H6	0.9500
N5—C7	1.329 (2)	C7—N3ⁱ	1.342 (2)
N5—N2ⁱ	1.356 (2)	C7—C8	1.496 (3)
N6—C10	1.328 (3)	C8—H8A	0.9900
N6—N7	1.368 (2)	C8—H8B	0.9900
N6—C8	1.455 (3)	C9—H9	0.9500
N7—C9	1.321 (3)	C10—H10	0.9500
N8—C10	1.323 (3)

N5—Cu1—N2	93.75 (6)	N2—C1—N3	113.40 (17)
N5—Cu1—N4	172.58 (6)	N2—C1—C2	116.86 (17)
N2—Cu1—N4	80.29 (6)	N3—C1—C2	129.72 (17)
N5—Cu1—N7	88.59 (6)	N4—C2—C6	122.81 (18)
N2—Cu1—N7	161.96 (7)	N4—C2—C1	112.59 (16)
N4—Cu1—N7	98.45 (6)	C6—C2—C1	124.57 (18)
N5—Cu1—O4	87.79 (7)	N4—C3—C4	122.16 (19)
N2—Cu1—O4	108.72 (7)	N4—C3—H3	118.9
N4—Cu1—O4	89.95 (6)	C4—C3—H3	118.9
N7—Cu1—O4	89.23 (7)	C5—C4—C3	119.35 (19)
O3—N1—O1	120.96 (18)	C5—C4—H4	120.3
O3—N1—O2	119.57 (17)	C3—C4—H4	120.3
O1—N1—O2	119.45 (17)	C4—C5—C6	118.81 (18)
C1—N2—N5ⁱ	105.92 (15)	C4—C5—H5	120.6
C1—N2—Cu1	114.60 (13)	C6—C5—H5	120.6
N5ⁱ—N2—Cu1	137.73 (12)	C2—C6—C5	118.65 (19)
C7ⁱ—N3—C1	101.45 (15)	C2—C6—H6	120.7
C3—N4—C2	118.20 (16)	C5—C6—H6	120.7
C3—N4—Cu1	127.56 (14)	N5—C7—N3ⁱ	113.47 (17)
C2—N4—Cu1	114.23 (13)	N5—C7—C8	121.54 (17)
C7—N5—N2ⁱ	105.75 (15)	N3ⁱ—C7—C8	124.98 (17)
C7—N5—Cu1	126.66 (13)	N6—C8—C7	111.03 (16)
N2ⁱ—N5—Cu1	127.56 (12)	N6—C8—H8A	109.4
C10—N6—N7	108.72 (16)	C7—C8—H8A	109.4
C10—N6—C8	128.56 (17)	N6—C8—H8B	109.4
N7—N6—C8	122.68 (16)	C7—C8—H8B	109.4
C9—N7—N6	102.89 (16)	H8A—C8—H8B	108.0
C9—N7—Cu1	132.81 (14)	N7—C9—N8	114.40 (19)
N6—N7—Cu1	122.03 (12)	N7—C9—H9	122.8
C10—N8—C9	102.87 (18)	N8—C9—H9	122.8
Cu1—O4—H41O	121 (2)	N8—C10—N6	111.12 (18)
Cu1—O4—H42O	123 (2)	N8—C10—H10	124.4
H41O—O4—H42O	112 (3)	N6—C10—H10	124.4
H51O—O5—H52O	107 (3)

C10—N6—N7—C9	0.2 (2)	N4—C3—C4—C5	−0.6 (3)
C8—N6—N7—C9	178.21 (17)	C3—C4—C5—C6	0.9 (3)
C10—N6—N7—Cu1	165.14 (14)	N4—C2—C6—C5	−1.3 (3)
C8—N6—N7—Cu1	−16.9 (2)	C1—C2—C6—C5	176.53 (18)
N5ⁱ—N2—C1—N3	0.8 (2)	C4—C5—C6—C2	0.0 (3)
Cu1—N2—C1—N3	168.39 (13)	N2ⁱ—N5—C7—N3ⁱ	0.0 (2)
N5ⁱ—N2—C1—C2	179.30 (16)	Cu1—N5—C7—N3ⁱ	178.11 (12)
Cu1—N2—C1—C2	−13.1 (2)	N2ⁱ—N5—C7—C8	−178.85 (17)
C7ⁱ—N3—C1—N2	−0.8 (2)	Cu1—N5—C7—C8	−0.8 (3)
C7ⁱ—N3—C1—C2	−179.06 (19)	C10—N6—C8—C7	−127.1 (2)
C3—N4—C2—C6	1.6 (3)	N7—N6—C8—C7	55.3 (2)
Cu1—N4—C2—C6	−179.68 (15)	N5—C7—C8—N6	−46.0 (2)
C3—N4—C2—C1	−176.44 (16)	N3ⁱ—C7—C8—N6	135.26 (19)
Cu1—N4—C2—C1	2.2 (2)	N6—N7—C9—N8	−0.5 (2)
N2—C1—C2—N4	7.0 (2)	Cu1—N7—C9—N8	−162.96 (15)
N3—C1—C2—N4	−174.73 (18)	C10—N8—C9—N7	0.5 (2)
N2—C1—C2—C6	−171.04 (18)	C9—N8—C10—N6	−0.3 (2)
N3—C1—C2—C6	7.2 (3)	N7—N6—C10—N8	0.1 (2)
C2—N4—C3—C4	−0.7 (3)	C8—N6—C10—N8	−177.76 (18)
Cu1—N4—C3—C4	−179.13 (14)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O4—H41O···O5ⁱⁱ	0.71 (3)	2.03 (3)	2.735 (2)	172 (3)
O4—H42O···O5ⁱⁱⁱ	0.79 (3)	1.96 (3)	2.735 (2)	168 (3)
O5—H51O···O2^iv	0.78 (3)	2.02 (3)	2.773 (2)	163 (3)
O5—H52O···N3ⁱ	0.76 (3)	2.08 (3)	2.836 (2)	177 (3)
C5—H5···O1ⁱⁱ	0.95	2.43	3.360 (3)	166
C8—H8A···O4	0.99	2.56	3.160 (3)	119
C8—H8B···O2^iv	0.99	2.36	3.319 (3)	162
C9—H9···O3^v	0.95	2.44	3.205 (3)	137

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

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