Methanol[1-(meth­oxy­methanimido­yl)-2-(pyridin-2-ylmeth­yl)guanidine]bis(perchlorato)copper(II)

The title complex, [Cu(ClO₄)₂(C₉H₁₃N₅O)(CH₃OH)], was synthesized from a methanolysis reaction of N-(methyl­pyri­din-2-yl)cyano­guanidine (L³) and copper(II) perchlorate hexa­hydrate in a 1:1 molar ratio. The Cu^II ion is six-coordinated by an N₃O₃ donor set which confers a highly distorted and asymmetric octa­hedral geometry. Three N-donor atoms from the chelating 1-(meth­oxy­methanimido­yl)-2-(pyri­din-2-ylmeth­yl)guanidine (L^3m) ligand and one O atom from the methanol mol­ecule define the equatorial plane, with two perchlorate O atoms in the apical sites, one of which has a long Cu—O bond of 2.9074 (19) Å. The dihedral angle between the five- and six-membered chelate rings is 8.21 (8)°. Two molecules are associated into a dimeric unit by inter­molecular N—H...O(perchlorate) hydrogen bonds. Additionally, the weakly coordinated perchlorate anions also link adjacent [Cu(ClO₄)₂(L^3m)(CH₃OH)] dimers by hydrogen-bonding inter­actions, resulting in a two-dimensional layer in the (100) plane. Further C—H...O hydrogen bonds link the two-dimensional layers along [100] to generate a three-dimensional network.

S1. Comment

Amidino-O-alkylureas (aOau) are a series of guanidine derivatives which have important roles in supramolecular architectures and bioinorganic systems because of their versatile hydrogen-bonding potential (Hubberstey et al., 2000). Several copper(II) complexes containing N-donor aOau ligands with various extended structures have been reported. For example, Suksangpanya and co-workers have reported the synthesis of two-dimensional rhombic (4,4) grids using copper(II) halides of two bidentate (N-alkylamidino-O-alkylurea) ligands (Suksangpanya et al., 2003). Also, copper(II) halide complexes containing tridentate (Suksangpanya et al., 2004) and tetradentate (Suksangpanya et al., 2002) aOau derivatives have been intensively investigated by single-crystal X-ray diffraction. Crystallographic data indicate that their different extended hydrogen-bonding interactions depend partially on the substituents on the aOau ligand defining the hydrogen-bond donors and acceptors. Recently, Chaveerach and co-workers have investigated the DNA binding and nuclease behaviors (Chaveerach et al., 2010) and the interactions with cytosine nucleobase (Meenongwa et al., 2011) of copper(II) complexes containing amidino-O-methylurea (L^1m) and N-(methylphenyl)-amidino-O-methylurea (L^2m). Herein, we present the structure of the title compound, (I), a copper(II) bis(perchlorate) complex of N-(methylpyridin-2-yl)-amidino-O-methylurea (L^3m) (Scheme 1), which was prepared using a procedure similar to that previously reported (Suksangpanya et al., 2004) but using copper(II) perchlorate hexahydrate instead of a copper(II) halide.

The initial product was obtained as a purple solid (Scheme 2) with a d–d transition at λ_max = 583.0 nm. The elemental analysis was in agreement with the formula [Cu(L^3m)(ClO₄)](ClO₄). In the presence of methanol, the product solution turned greenish-blue in color and displayed an electronic absorption at λ_max = 621.4 nm. This result could mirror the change in the coordination geometry at the Cu^II center between solid and solution phases of this complex. Suitable single crystals of the title complex, (I), were obtained by slow evaporation of a methanol solution of the initial product.

The molecular structure of (I) is shown in Fig. 1. This complex crystallizes in the triclinic space group P1 with one molecule of [Cu(L^3m)(CH₃OH)(ClO₄)₂] in the asymmetric unit. The Cu^II cation is coordinated by three N donor atoms (N1, N2 and N3) from the chelating L^3m ligand and by atom O2 from the methanol molecule (as a result of crystal growth from that solvent) lying in the equatorial plane, and atoms O3 and O9 from mutually trans perchlorate anions located at the two apical sites. The Cu—N bond distances range from 1.9315 (17) to 1.9711 (17) Å and the Cu1—O2 bond distance is 2.0132 (16) Å, while perchlorate atom O3 lies at a distance of 2.4935 (17) Å from the Cu^II center. The remaining axial site at Cu1 is occupied by atom O9 from another perchlorate anion. Although the Cu1—O9 distance of 2.9074 (19) Å is quite long (Dobrzyńska et al., 2010; Husain et al., 2011) compared with the average Cu—O(perchlorate) bond of 2.495 Å calculated from 91 examples of a perchlorate ion terminally coordinated to copper (Orpen et al., 1989), the role of O9 in completing the coordination around the Cu^II center results in the overall geometry being a distorted octahedron. The N1—Cu1—N3 and N2—Cu1—O2 angles are approximately linear (Table 1). Atom Cu1 is displaced by 0.0531 (2) Å from the mean plane through the equatorial donor atoms in the direction of the O3 axial donor, with a dihedral angle of 8.21 (8)° between the least-squares mean planes of the five-membered CuN₂C₂ and six-membered CuN₃C₂ chelate rings.

Two [Cu(L^3m)(CH₃OH)(ClO₄)₂] molecules form a dimeric unit (Fig. 2) via N—H···O hydrogen bonds (Table 2, entries 3, 4 and 5). The weakly coordinated perchlorate anion plays a major role in constructing an extensive network via N—H···O (Table 2, entries 1 and 2) and C—H···O (Table 2, entries 8 and 9) hydrogen bonds to form a two-dimensional layer in the (100) plane (Fig. 3). Further O—H···O and C—H···O hydrogen bonds (Table 2, entries 6 and 7) perpendicular to (010) link the two-dimensional layers to generate a three-dimensional network (Fig. 4). Although the title complex contains aromatic moieties, these are not observed to participate in π–π stacking interactions.

A comparison between (I) and the previously reported copper(II) complex containing the same L^3m ligand but with halide anions instead of perchlorate anions, [Cu(L^3m)X₂] (X = Cl or Br; Suksangpanya et al., 2004) is also possible: both complexes show differences in geometry and chromophore. The [Cu(L^3m)X₂] complex displays a slightly distorted square-pyramidal geometry with a CuN₃X₂ chromophore, while a CuN₃O₃ chromophore with a highly-distorted octahedral geometry is observed in (I). This difference may arise from the fact that perchlorate anions are more sterically demanding than halide anions, but the fact that perchlorate is a poorly coordinating ligand may also be significant. As a result, the remaining free basal position is coordinated by a methanol molecule from the recrystallization solvent.

In summary, we have determined the crystal structure of [Cu(L^3m)(CH₃OH)(ClO₄)₂], (I). This is controlled not only by the high potential for hydrogen-bond formation exhibited by the L^3m ligand, resulting in a three-dimensional packing motif, but also by the size, geometry and weak coordination of the perchlorate anion.

Related literature

For related literature, see: Chaveerach et al. (2010); Dobrzyńska et al. (2010); Hubberstey et al. (2000); Husain et al. (2011); Meenongwa et al. (2011); Orpen et al. (1989); Rose & Swain (1956); Shapiro et al. (1961); Suksangpanya et al. (2002, 2003, 2004).

S2. Experimental

The N-(methylpyridin-2-yl)cyanoguanidine precursor (L³) was prepared as described previously (Rose & Swain, 1956; Shapiro et al., 1961). The copper(II) complex was prepared by mixing a 1:1 molar ratio of the N-(methylpyridin-2-yl)cyanoguanidine precursor (0.1760 g, 1 mmol) and copper(II) perchlorate hexahydrate (0.3705 g,1 mmol, Sigma–Aldrich, 98%) in methanol (50 ml). The reaction was refluxed for 24 h. The resulting greenish-blue mixture was then cooled to ambient temperature and filtered to remove excess solids. The solvent was removed in vacuo to give a deep-purple solid (yield 0.4448 g, 94.8%; m.p. 492.5–495 K). Selected IR data (KBr pellet, ν, cm^-1): 3390 (m, N—H), 1686 (s, C═N), 1571 (m, NH₂), 1547 (m, C═C), 1346 (m, C—O), 1144 (s, ClO₄), 1088 (s, ClO₄). Diffuse reflectance (λ_max, nm): 583.0. Visible (2 mM in MeOH, λ_max, nm): 621.4. Analysis, calculated for [Cu(L^3m)(ClO₄)](ClO₄), (C₉H₁₃N₅O₉Cl₂Cu) (MW = 469.5): C 23.00, H 2.77, N 14.91%; found: C 23.13, H 2.76, N 15.04%. ESI+ MS (m/z): 371 [Cu(L^3m)(ClO₄)+H]²⁺, 271 [Cu(L^3m)]²⁺.

Suitable single crystals of (I) were obtained as blue columns from a methanol solution of the initial product by slow evaporation at 283 K over one week.

S3. Refinement

H atoms bonded to C and N were positioned geometrically and refined using a riding model, with N—H = 0.88 Å and C—H = 0.98, 0.99 or 0.95 Å for methyl, methylene and aromatic H, and with U_iso(H) = 1.2U_eq(C,N). The H atom bonded to the methanol O atom was located in a difference Fourier map and refined with an O—H distance restraint of 0.75 (3) Å.

Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000) and SHELXTL (Sheldrick, 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: publCIF (Westrip, 2010).

Figures

	Fig. 1. The molecular structure of complex (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view of dimer formation in (I), showing the N—H···O hydrogen bonds (dashed lines). Weakly coordinated perchlorate aions have been omitted for clarity. [Symmetry code: (iii) -x + 1, -y + 1, -z + 2.] [All atoms must have unique labels. Please send revised plot]
	Fig. 3. A view of the crystal packing of (I) in the (100) plane, showing how the hydrogen bonds (dashed lines) involving perchlorate counter-ions form a two-dimensional layer. All H atoms not involved in the depicted interactions and hydrogen bonds within the dimer and the two-dimensional layer have been omitted for clarity. [Symmetry codes: (i) -x+1, -y+2, -z+1; (ii) -x+1, -y+1, -z+1; (v) -x, -y+1, -z+1; (vi) x-1, y, z.]

Methanol[1-(methoxymethanimidoyl)-2-(pyridin-2- ylmethyl)guanidine]bis(perchlorato)copper(II)

Crystal data

[Cu(ClO4)2(C9H13N5O)(CH4O)]	Z = 2
Mr = 501.73	F(000) = 510
Triclinic, P1	Dx = 1.839 Mg m^−3
Hall symbol: -P 1	Melting point: 495.0 K
a = 8.034 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.804 (3) Å	Cell parameters from 5357 reflections
c = 12.093 (3) Å	θ = 2.4–27.6°
α = 74.720 (4)°	µ = 1.56 mm^−1
β = 80.455 (4)°	T = 150 K
γ = 86.176 (4)°	Column, blue
V = 905.9 (4) Å^3	0.30 × 0.15 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	4119 independent reflections
Radiation source: sealed tube	3857 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.014
ω scans	θmax = 27.6°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.656, Tmax = 0.746	k = −12→12
8026 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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0401P)^2 + 0.7806P] where P = (Fo^2 + 2Fc^2)/3
4119 reflections	(Δ/σ)max = 0.001
259 parameters	Δρmax = 0.47 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

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

	x	y	z	Uiso*/Ueq
Cu1	0.28810 (3)	0.78462 (2)	0.71615 (2)	0.0218 (1)
Cl1	0.12760 (6)	0.73533 (5)	1.01644 (4)	0.0274 (1)
Cl2	0.38940 (6)	0.80286 (5)	0.40055 (4)	0.0249 (1)
O1	0.68822 (19)	0.76408 (15)	0.89641 (14)	0.0285 (4)
O2	0.23440 (19)	0.99142 (15)	0.65346 (14)	0.0263 (4)
O3	0.0930 (2)	0.78386 (19)	0.89958 (14)	0.0367 (5)
O4	0.1728 (3)	0.58684 (19)	1.0403 (2)	0.0527 (7)
O5	0.2676 (2)	0.8100 (2)	1.03095 (16)	0.0437 (6)
O6	−0.0189 (2)	0.7585 (2)	1.09430 (15)	0.0469 (6)
O7	0.3912 (3)	0.65291 (19)	0.44288 (17)	0.0570 (7)
O8	0.2231 (2)	0.8571 (3)	0.39177 (17)	0.0602 (8)
O9	0.4607 (2)	0.8636 (2)	0.47813 (15)	0.0410 (5)
O10	0.4936 (2)	0.84241 (16)	0.28729 (14)	0.0324 (5)
N1	0.4771 (2)	0.82838 (17)	0.77985 (15)	0.0232 (5)
N2	0.3498 (2)	0.58576 (17)	0.74996 (15)	0.0234 (5)
N3	0.0938 (2)	0.72402 (18)	0.66206 (14)	0.0231 (5)
N4	0.5002 (2)	0.38271 (18)	0.83200 (16)	0.0305 (5)
N5	0.5686 (2)	0.59538 (18)	0.85322 (15)	0.0248 (5)
C1	0.7007 (3)	0.9073 (2)	0.9044 (2)	0.0324 (7)
C2	0.5720 (2)	0.7379 (2)	0.83952 (17)	0.0224 (5)
C3	0.4673 (3)	0.5222 (2)	0.80801 (17)	0.0235 (5)
C4	0.2400 (3)	0.4978 (2)	0.71433 (19)	0.0275 (6)
C5	0.0916 (3)	0.5849 (2)	0.67133 (17)	0.0250 (5)
C6	−0.0419 (3)	0.5241 (2)	0.64272 (19)	0.0308 (6)
C7	−0.1750 (3)	0.6098 (3)	0.60346 (19)	0.0333 (7)
C8	−0.1720 (3)	0.7538 (3)	0.59397 (19)	0.0301 (6)
C9	−0.0365 (3)	0.8075 (2)	0.62329 (18)	0.0276 (6)
C10	0.1438 (3)	1.0781 (2)	0.7250 (2)	0.0344 (7)
H1	0.50000	0.91830	0.76680	0.0280*
H1A	0.73550	0.96880	0.82670	0.0490*
H1B	0.78440	0.91020	0.95410	0.0490*
H1C	0.59060	0.94020	0.93770	0.0490*
H4A	0.44020	0.32760	0.80790	0.0370*
H4B	0.58190	0.34610	0.87190	0.0370*
H4C	0.19990	0.41800	0.78090	0.0330*
H4D	0.30390	0.45840	0.65200	0.0330*
H5	0.63980	0.54370	0.89620	0.0300*
H6	−0.04150	0.42520	0.65010	0.0370*
H7	−0.26710	0.57070	0.58330	0.0400*
H8	−0.26240	0.81450	0.56760	0.0360*
H9	−0.03420	0.90630	0.61610	0.0330*
H10A	0.02770	1.04570	0.75130	0.0520*
H10B	0.14230	1.17700	0.67960	0.0520*
H10C	0.20010	1.07050	0.79240	0.0520*
H11	0.312 (4)	1.026 (3)	0.618 (2)	0.034 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0201 (1)	0.0176 (1)	0.0280 (1)	0.0018 (1)	−0.0070 (1)	−0.0046 (1)
Cl1	0.0274 (2)	0.0271 (2)	0.0261 (2)	0.0042 (2)	−0.0050 (2)	−0.0045 (2)
Cl2	0.0231 (2)	0.0234 (2)	0.0283 (2)	−0.0026 (2)	−0.0028 (2)	−0.0071 (2)
O1	0.0274 (7)	0.0261 (7)	0.0349 (8)	0.0040 (6)	−0.0129 (6)	−0.0088 (6)
O2	0.0232 (7)	0.0206 (7)	0.0330 (8)	0.0013 (6)	−0.0051 (6)	−0.0031 (6)
O3	0.0282 (8)	0.0530 (10)	0.0262 (8)	0.0066 (7)	−0.0048 (6)	−0.0070 (7)
O4	0.0570 (12)	0.0307 (9)	0.0778 (14)	0.0154 (8)	−0.0388 (11)	−0.0132 (9)
O5	0.0440 (10)	0.0436 (10)	0.0453 (10)	−0.0075 (8)	−0.0152 (8)	−0.0079 (8)
O6	0.0404 (10)	0.0623 (12)	0.0310 (9)	0.0054 (9)	0.0064 (7)	−0.0087 (8)
O7	0.0949 (17)	0.0241 (9)	0.0460 (11)	−0.0154 (10)	0.0090 (11)	−0.0074 (8)
O8	0.0254 (9)	0.1061 (18)	0.0411 (11)	0.0139 (10)	−0.0066 (8)	−0.0080 (11)
O9	0.0406 (9)	0.0490 (10)	0.0394 (9)	−0.0115 (8)	−0.0054 (7)	−0.0198 (8)
O10	0.0348 (8)	0.0265 (8)	0.0344 (8)	−0.0061 (6)	0.0055 (7)	−0.0107 (6)
N1	0.0207 (8)	0.0183 (8)	0.0305 (9)	0.0008 (6)	−0.0049 (7)	−0.0056 (6)
N2	0.0245 (8)	0.0190 (8)	0.0268 (8)	0.0010 (6)	−0.0058 (7)	−0.0052 (6)
N3	0.0216 (8)	0.0243 (8)	0.0225 (8)	−0.0008 (6)	−0.0030 (6)	−0.0049 (6)
N4	0.0384 (10)	0.0202 (8)	0.0345 (10)	0.0061 (7)	−0.0139 (8)	−0.0065 (7)
N5	0.0252 (8)	0.0215 (8)	0.0271 (9)	0.0060 (6)	−0.0087 (7)	−0.0042 (6)
C1	0.0293 (10)	0.0281 (11)	0.0452 (13)	0.0010 (8)	−0.0123 (9)	−0.0153 (9)
C2	0.0197 (8)	0.0242 (9)	0.0227 (9)	0.0010 (7)	−0.0019 (7)	−0.0064 (7)
C3	0.0269 (9)	0.0207 (9)	0.0213 (9)	0.0012 (7)	−0.0011 (7)	−0.0045 (7)
C4	0.0303 (10)	0.0204 (9)	0.0327 (11)	−0.0011 (8)	−0.0070 (8)	−0.0068 (8)
C5	0.0253 (9)	0.0270 (10)	0.0217 (9)	−0.0030 (8)	−0.0021 (8)	−0.0050 (8)
C6	0.0312 (11)	0.0323 (11)	0.0301 (11)	−0.0071 (9)	−0.0024 (9)	−0.0100 (9)
C7	0.0271 (10)	0.0469 (13)	0.0275 (11)	−0.0102 (9)	−0.0033 (8)	−0.0108 (9)
C8	0.0225 (9)	0.0413 (12)	0.0253 (10)	0.0019 (9)	−0.0052 (8)	−0.0064 (9)
C9	0.0255 (10)	0.0300 (10)	0.0262 (10)	0.0012 (8)	−0.0040 (8)	−0.0060 (8)
C10	0.0301 (11)	0.0269 (11)	0.0460 (13)	0.0052 (9)	−0.0043 (10)	−0.0114 (10)

Geometric parameters (Å, º)

Cu1—N1	1.9315 (17)	N5—C2	1.364 (3)
Cu1—N2	1.9319 (17)	N5—C3	1.381 (3)
Cu1—N3	1.9711 (17)	N5—H5	0.8800
Cu1—O2	2.0132 (16)	N4—C3	1.339 (3)
Cu1—O3	2.4935 (17)	N4—H4A	0.8800
Cu1—O9	2.9074 (19)	N4—H4B	0.8800
Cl1—O3	1.4350 (17)	C4—C5	1.503 (3)
Cl1—O4	1.4412 (18)	C4—H4C	0.9900
Cl1—O5	1.4403 (18)	C4—H4D	0.9900
Cl1—O6	1.4256 (18)	C9—C8	1.375 (3)
Cl2—O7	1.4235 (19)	C9—H9	0.9500
Cl2—O8	1.4150 (19)	C5—C6	1.394 (3)
Cl2—O9	1.4430 (17)	C6—C7	1.383 (3)
Cl2—O10	1.4527 (16)	C6—H6	0.9500
O2—C10	1.448 (3)	C8—C7	1.387 (3)
O2—H11	0.74 (3)	C8—H8	0.9500
N2—C3	1.297 (3)	C7—H7	0.9500
N2—C4	1.460 (3)	C1—H1A	0.9800
N1—C2	1.283 (3)	C1—H1B	0.9800
N1—H1	0.8800	C1—H1C	0.9800
N3—C5	1.340 (3)	C10—H10A	0.9800
N3—C9	1.353 (3)	C10—H10B	0.9800
O1—C2	1.323 (2)	C10—H10C	0.9800
O1—C1	1.444 (3)
N1—Cu1—N2	92.08 (7)	C3—N4—H4A	120.0
N1—Cu1—N3	174.89 (7)	C3—N4—H4B	120.0
N2—Cu1—N3	83.78 (7)	H4A—N4—H4B	120.0
N1—Cu1—O2	91.42 (7)	Cl2—O9—Cu1	113.57 (9)
N2—Cu1—O2	170.60 (7)	N1—C2—O1	127.18 (19)
N3—Cu1—O2	93.13 (7)	N1—C2—N5	124.15 (19)
N1—Cu1—O3	91.34 (7)	O1—C2—N5	108.67 (17)
N2—Cu1—O3	98.56 (7)	N2—C3—N4	124.49 (19)
N3—Cu1—O3	86.34 (6)	N2—C3—N5	121.65 (18)
O2—Cu1—O3	90.08 (6)	N4—C3—N5	113.85 (18)
N1—Cu1—O9	93.85 (6)	N2—C4—C5	109.72 (17)
N2—Cu1—O9	97.51 (6)	N2—C4—H4C	109.7
N3—Cu1—O9	89.66 (6)	C5—C4—H4C	109.7
O2—Cu1—O9	73.54 (6)	N2—C4—H4D	109.7
O3—Cu1—O9	162.91 (6)	C5—C4—H4D	109.7
O8—Cl2—O7	111.06 (15)	H4C—C4—H4D	108.2
O8—Cl2—O9	109.60 (13)	N3—C9—C8	122.0 (2)
O7—Cl2—O9	109.19 (13)	N3—C9—H9	119.0
O8—Cl2—O10	109.49 (11)	C8—C9—H9	119.0
O7—Cl2—O10	109.49 (11)	N3—C5—C6	121.63 (19)
O9—Cl2—O10	107.93 (10)	N3—C5—C4	116.66 (18)
O6—Cl1—O3	109.14 (11)	C6—C5—C4	121.71 (19)
O6—Cl1—O5	109.90 (12)	C7—C6—C5	119.0 (2)
O3—Cl1—O5	110.17 (11)	C7—C6—H6	120.5
O6—Cl1—O4	110.21 (13)	C5—C6—H6	120.5
O3—Cl1—O4	109.26 (12)	C9—C8—C7	119.1 (2)
O5—Cl1—O4	108.14 (12)	C9—C8—H8	120.4
C10—O2—Cu1	122.85 (14)	C7—C8—H8	120.4
C10—O2—H11	112 (2)	C6—C7—C8	119.1 (2)
Cu1—O2—H11	109 (2)	C6—C7—H7	120.5
C3—N2—C4	117.51 (17)	C8—C7—H7	120.5
C3—N2—Cu1	127.33 (14)	O1—C1—H1A	109.5
C4—N2—Cu1	114.90 (13)	O1—C1—H1B	109.5
C2—N1—Cu1	125.70 (14)	H1A—C1—H1B	109.5
C2—N1—H1	117.1	O1—C1—H1C	109.5
Cu1—N1—H1	117.1	H1A—C1—H1C	109.5
C5—N3—C9	119.11 (18)	H1B—C1—H1C	109.5
C5—N3—Cu1	114.56 (14)	O2—C10—H10A	109.5
C9—N3—Cu1	126.25 (15)	O2—C10—H10B	109.5
C2—O1—C1	118.04 (16)	H10A—C10—H10B	109.5
Cl1—O3—Cu1	128.06 (9)	O2—C10—H10C	109.5
C2—N5—C3	128.02 (17)	H10A—C10—H10C	109.5
C2—N5—H5	116.0	H10B—C10—H10C	109.5
C3—N5—H5	116.0

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O10^i	0.88	2.26	3.129 (3)	167
N4—H4A···O10^ii	0.88	2.25	2.932 (3)	134
N4—H4B···O4^iii	0.88	2.59	3.328 (3)	143
N4—H4B···O5^iii	0.88	2.11	2.950 (3)	159
N5—H5···O4^iii	0.88	2.03	2.889 (3)	167
O2—H11···O9^i	0.75 (3)	2.18 (3)	2.919 (3)	176
C4—H4C···O6^iv	0.99	2.37	3.316 (3)	159
C7—H7···O7^v	0.95	2.58	3.413 (4)	146
C8—H8···O9^vi	0.95	2.59	3.461 (3)	152

Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) −x+1, −y+1, −z+1; (iii) −x+1, −y+1, −z+2; (iv) −x, −y+1, −z+2; (v) −x, −y+1, −z+1; (vi) x−1, y, z.