Diaqua­bis­(N,N-diethyl­pyridine-3-carboxamide-κN1)bis­{4-[2-(2,4-dioxopentan-3-yl­idene)hydrazin-1-yl]benzoato-κO}copper(II)

Alieva, R.A.; Mardanova, V.I.; Chyraqov, F.M.; Gurbanov, A.V.; Ng, S.W.

doi:10.1107/S1600536811056200

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 2| February 2012| Page m127

doi:10.1107/S1600536811056200

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Diaquabis(N,N-diethylpyridine-3-carboxamide-κN¹)bis{4-[2-(2,4-dioxopentan-3-ylidene)hydrazin-1-yl]benzoato-κO}copper(II)

Rafiqa A. Alieva,^a Vusala I. Mardanova,^a Famil M. Chyraqov,^a Atash V. Gurbanov ^a and Seik Weng Ng ^b,^c ^*

^aDepartment of Organic Chemistry, Baku State University, Baku, Azerbaijan, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cChemistry Department, Faculty of Science, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 25 December 2011; accepted 29 December 2011; online 11 January 2012)

In the title compound, [Cu(C₁₂H₁₁N₂O₄)₂(C₁₀H₁₄N₂O)₂(H₂O)₂], the Cu^II atom lies on a center of inversion and is coordinated by carboxylate O atoms, pyridine N atoms and two water molecules in an elongated octahedral geometry. The pyridine ring is oriented at a dihedral angle of 74.83 (12)° with respect to the benzene ring. Intramolecular O—H⋯O and N—H⋯O hydrogen bonding is observed. The water molecule is a hydrogen-bond donor to the carbonyl O atom of an adjacent carboxylate group, generating a chain running along the a axis. One of the ethyl groups is disordered over two sets of sites in a 0.787 (5):0.213 ratio.

Related literature

For a related structure, see: Maharramov et al. (2011 ).

Experimental

Crystal data

[Cu(C₁₂H₁₁N₂O₄)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]
M_r = 950.49
Triclinic, $[P \overline 1]$
a = 7.7429 (4) Å
b = 8.7029 (4) Å
c = 19.0069 (9) Å
α = 85.695 (1)°
β = 83.218 (1)°
γ = 64.882 (1)°
V = 1151.12 (10) Å³
Z = 1
Mo Kα radiation
μ = 0.54 mm⁻¹
T = 296 K
0.30 × 0.30 × 0.20 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.854, T_max = 0.899
13589 measured reflections
5775 independent reflections
4780 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.134
S = 1.04
5775 reflections
305 parameters
38 restraints
H-atom parameters constrained
Δρ_max = 0.87 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—O1	1.9661 (15)
Cu1—N3	2.0151 (17)
Cu1—O1W	2.531 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3	0.88	1.88	2.558 (3)	132
O1w—H11⋯O2	0.84	2.06	2.712 (3)	135
O1w—H12⋯O5ⁱ	0.84	2.12	2.955 (3)	172
Symmetry code: (i) x+1, y, z.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811056200/xu5431sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811056200/xu5431Isup2.hkl

checkCIF report

Comment top

We have been investigating the adducts of 3-diethylpridine-3-carboxamide with copper(II) salts; a previous study reported the copper bis(thienoylacetonate) adduct (Maharramov et al., 2011). The reaction of the N-heterocycle with copper bis(4-[(2,4-dioxopentan-3-yl)diazenyl]benzoate yielded the title diaqua bis-adduct (Scheme I). The Cu^II atom in Cu(H₂O)₂(C₁₀H₁₄N₂O)₂(C₁₂H₁₁N₂O₄)₂ lies on a center-of-inversion, and is coordinated to the O atom of the carboxylate ion, the N atom of the N-heterocycle and a water molecule in an all-trans octahedral geometry (Fig.1). The water molecule is hydrogen-bond donor to the the double-bond carbonyl O atom of adjacent carboxylate and N-heterocycle to generate a linear chain running along the a-axis of the triclinic unit cell (Table 1).

Related literature top

For a related structure, see: Maharramov et al. (2011).

Experimental top

4-[(2,4-Dioxopentan-3-yl)diazenyl]benzoic acid and N,N-diethylpyridine-3-carboxamide were purchased from a chemical supplier. The carboxylic acid (0.0248 g, 0.01 mol) in water (50 ml) and an excess of cardioamine (5 ml) were added to a solution of copper acetate hydrate (0.0156 g, 0.01 mol) in water (50 ml). The green solution was filtered and then set aside for the growth of crystals within a week; yield 70%.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of Cu(H₂O)₂(C₁₀H₁₄N₂O)₂(C₁₂H₁₁N₂O₄)₂ at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The disorder is not shown.

Diaquabis(N,N-diethylpyridine-3-carboxamide-κN¹)bis{4- [2-(2,4-dioxopentan-3-ylidene)hydrazin-1-yl]benzoato-κO}copper(II) top

Crystal data top

[Cu(C₁₂H₁₁N₂O₄)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]	Z = 1
M_r = 950.49	F(000) = 499
Triclinic, P1	D_x = 1.371 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7429 (4) Å	Cell parameters from 4939 reflections
b = 8.7029 (4) Å	θ = 2.6–28.4°
c = 19.0069 (9) Å	µ = 0.54 mm⁻¹
α = 85.695 (1)°	T = 296 K
β = 83.218 (1)°	Prism, blue
γ = 64.882 (1)°	0.30 × 0.30 × 0.20 mm
V = 1151.12 (10) Å³

Data collection top

Bruker SMART APEX diffractometer	5775 independent reflections
Radiation source: fine-focus sealed tube	4780 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 28.4°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.854, T_max = 0.899	k = −11→11
13589 measured reflections	l = −25→25

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0788P)² + 0.3231P] where P = (F_o² + 2F_c²)/3
5775 reflections	(Δ/σ)_max = 0.001
305 parameters	Δρ_max = 0.87 e Å⁻³
38 restraints	Δρ_min = −0.60 e Å⁻³

Crystal data top

[Cu(C₁₂H₁₁N₂O₄)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]	γ = 64.882 (1)°
M_r = 950.49	V = 1151.12 (10) Å³
Triclinic, P1	Z = 1
a = 7.7429 (4) Å	Mo Kα radiation
b = 8.7029 (4) Å	µ = 0.54 mm⁻¹
c = 19.0069 (9) Å	T = 296 K
α = 85.695 (1)°	0.30 × 0.30 × 0.20 mm
β = 83.218 (1)°

Data collection top

Bruker SMART APEX diffractometer	5775 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4780 reflections with I > 2σ(I)
T_min = 0.854, T_max = 0.899	R_int = 0.021
13589 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	38 restraints
wR(F²) = 0.134	H-atom parameters constrained
S = 1.04	Δρ_max = 0.87 e Å⁻³
5775 reflections	Δρ_min = −0.60 e Å⁻³
305 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.5000	0.5000	0.5000	0.03554 (14)
O1	0.3598 (2)	0.6157 (2)	0.41786 (8)	0.0404 (4)
O2	0.5907 (3)	0.6225 (3)	0.33710 (10)	0.0507 (4)
O3	−0.3219 (4)	0.6427 (5)	0.09450 (14)	0.1056 (11)
O4	−0.1745 (8)	0.8431 (10)	−0.0897 (2)	0.227 (3)
O5	0.1024 (3)	0.1348 (3)	0.40938 (10)	0.0572 (5)
O1W	0.8200 (3)	0.4833 (3)	0.44344 (11)	0.0595 (5)
H11	0.8057	0.5337	0.4036	0.089*
H12	0.8971	0.3811	0.4384	0.089*
N1	−0.0399 (3)	0.6766 (3)	0.13788 (11)	0.0530 (6)
H1	−0.1407	0.6544	0.1492	0.064*
N2	−0.0036 (4)	0.7205 (4)	0.07303 (12)	0.0596 (6)
N3	0.5343 (3)	0.2781 (2)	0.46170 (9)	0.0332 (4)
N4	0.2425 (3)	0.1170 (3)	0.29832 (12)	0.0548 (6)
C1	0.4304 (3)	0.6252 (3)	0.35487 (12)	0.0349 (4)
C2	0.3041 (3)	0.6390 (3)	0.29785 (11)	0.0344 (4)
C3	0.1242 (3)	0.6404 (3)	0.31392 (11)	0.0374 (5)
H3	0.0787	0.6335	0.3610	0.045*
C4	0.0114 (3)	0.6519 (3)	0.26069 (12)	0.0415 (5)
H4	−0.1087	0.6515	0.2718	0.050*
C5	0.0797 (4)	0.6640 (3)	0.19063 (12)	0.0430 (5)
C6	0.2596 (4)	0.6615 (4)	0.17352 (13)	0.0491 (6)
H6	0.3050	0.6687	0.1264	0.059*
C7	0.3706 (4)	0.6480 (4)	0.22731 (12)	0.0441 (5)
H7	0.4922	0.6450	0.2161	0.053*
C8	−0.4004 (7)	0.7049 (9)	−0.0225 (3)	0.129 (2)
H8A	−0.4899	0.6572	−0.0064	0.193*
H8B	−0.3189	0.6437	−0.0625	0.193*
H8C	−0.4689	0.8220	−0.0361	0.193*
C9	−0.2808 (5)	0.6920 (6)	0.03616 (17)	0.0761 (10)
C10	−0.1170 (4)	0.7337 (5)	0.02394 (15)	0.0648 (8)
C11	−0.0650 (7)	0.7972 (8)	−0.0451 (2)	0.1111 (18)
C12	0.1209 (7)	0.8104 (8)	−0.0604 (2)	0.1074 (16)
H12A	0.1154	0.8841	−0.1012	0.161*
H12B	0.2216	0.6998	−0.0697	0.161*
H12C	0.1460	0.8560	−0.0203	0.161*
C13	0.6999 (3)	0.1395 (3)	0.46307 (12)	0.0377 (5)
H13	0.7986	0.1436	0.4853	0.045*
C14	0.7286 (4)	−0.0088 (3)	0.43248 (14)	0.0449 (5)
H14	0.8446	−0.1038	0.4347	0.054*
C15	0.5843 (4)	−0.0161 (3)	0.39847 (13)	0.0432 (5)
H15	0.6025	−0.1147	0.3767	0.052*
C16	0.4116 (3)	0.1270 (3)	0.39742 (11)	0.0345 (4)
C17	0.3914 (3)	0.2698 (3)	0.43054 (11)	0.0342 (4)
H17	0.2743	0.3644	0.4314	0.041*
C18	0.2401 (3)	0.1260 (3)	0.36835 (12)	0.0372 (5)
C19	0.3737 (6)	0.1654 (6)	0.24655 (19)	0.0557 (10)	0.787 (5)
H19A	0.4367	0.2170	0.2716	0.067*	0.787 (5)
H19B	0.2989	0.2488	0.2126	0.067*	0.787 (5)
C19'	0.4245 (16)	0.0383 (16)	0.2512 (7)	0.056*	0.213 (5)
H19C	0.4122	−0.0242	0.2134	0.067*	0.213 (5)
H19D	0.5315	−0.0346	0.2774	0.067*	0.213 (5)
C20	0.5230 (6)	0.0140 (7)	0.2076 (2)	0.0766 (14)	0.787 (5)
H20A	0.6053	0.0494	0.1754	0.115*	0.787 (5)
H20B	0.4611	−0.0353	0.1816	0.115*	0.787 (5)
H20C	0.5977	−0.0686	0.2411	0.115*	0.787 (5)
C20'	0.439 (3)	0.200 (2)	0.2245 (11)	0.077*	0.213 (5)
H20D	0.5386	0.2116	0.2463	0.115*	0.213 (5)
H20E	0.3193	0.2951	0.2361	0.115*	0.213 (5)
H20F	0.4691	0.1967	0.1740	0.115*	0.213 (5)
C21	0.0848 (4)	0.0938 (4)	0.27090 (17)	0.0589 (7)
H21A	0.0448	0.0222	0.3041	0.071*
H21B	0.1313	0.0360	0.2263	0.071*
C22	−0.0839 (5)	0.2577 (5)	0.2597 (2)	0.0864 (12)
H22A	−0.1821	0.2360	0.2419	0.130*
H22B	−0.0458	0.3283	0.2261	0.130*
H22C	−0.1323	0.3145	0.3039	0.130*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0516 (3)	0.0368 (2)	0.0268 (2)	−0.02437 (18)	−0.01424 (16)	0.00124 (14)
O1	0.0516 (9)	0.0441 (9)	0.0290 (8)	−0.0215 (8)	−0.0134 (7)	0.0016 (6)
O2	0.0466 (10)	0.0675 (12)	0.0454 (10)	−0.0294 (9)	−0.0143 (8)	0.0039 (8)
O3	0.0876 (18)	0.210 (4)	0.0570 (15)	−0.099 (2)	−0.0132 (13)	0.0126 (18)
O4	0.184 (4)	0.498 (9)	0.082 (2)	−0.224 (5)	−0.083 (3)	0.115 (4)
O5	0.0441 (10)	0.0895 (15)	0.0458 (10)	−0.0355 (10)	−0.0040 (8)	−0.0016 (10)
O1W	0.0570 (12)	0.0683 (13)	0.0441 (10)	−0.0167 (10)	−0.0075 (9)	−0.0026 (9)
N1	0.0507 (12)	0.0858 (17)	0.0326 (10)	−0.0375 (12)	−0.0123 (9)	0.0053 (10)
N2	0.0576 (14)	0.0968 (19)	0.0350 (11)	−0.0416 (14)	−0.0148 (10)	0.0078 (11)
N3	0.0383 (9)	0.0379 (9)	0.0295 (9)	−0.0203 (8)	−0.0083 (7)	−0.0015 (7)
N4	0.0488 (12)	0.0846 (17)	0.0400 (11)	−0.0339 (12)	−0.0082 (9)	−0.0130 (11)
C1	0.0445 (12)	0.0303 (10)	0.0326 (10)	−0.0164 (9)	−0.0117 (9)	0.0010 (8)
C2	0.0416 (11)	0.0357 (10)	0.0283 (10)	−0.0175 (9)	−0.0088 (9)	0.0011 (8)
C3	0.0415 (12)	0.0445 (12)	0.0265 (10)	−0.0183 (10)	−0.0045 (9)	0.0014 (8)
C4	0.0389 (12)	0.0551 (14)	0.0337 (11)	−0.0228 (11)	−0.0056 (9)	0.0023 (10)
C5	0.0456 (13)	0.0589 (14)	0.0300 (11)	−0.0259 (11)	−0.0113 (9)	0.0023 (10)
C6	0.0511 (14)	0.0775 (18)	0.0263 (11)	−0.0347 (14)	−0.0050 (10)	0.0025 (11)
C7	0.0432 (13)	0.0639 (15)	0.0329 (11)	−0.0303 (12)	−0.0062 (10)	0.0045 (10)
C8	0.106 (3)	0.240 (6)	0.085 (3)	−0.110 (4)	−0.048 (3)	0.023 (4)
C9	0.0617 (19)	0.131 (3)	0.0475 (17)	−0.050 (2)	−0.0140 (14)	−0.0019 (18)
C10	0.0590 (17)	0.110 (3)	0.0374 (14)	−0.0452 (18)	−0.0163 (12)	0.0070 (15)
C11	0.101 (3)	0.215 (6)	0.051 (2)	−0.098 (4)	−0.033 (2)	0.035 (3)
C12	0.105 (3)	0.186 (5)	0.061 (2)	−0.092 (3)	−0.014 (2)	0.023 (3)
C13	0.0352 (11)	0.0465 (12)	0.0352 (11)	−0.0197 (10)	−0.0072 (9)	−0.0019 (9)
C14	0.0363 (12)	0.0443 (12)	0.0493 (14)	−0.0105 (10)	−0.0062 (10)	−0.0089 (10)
C15	0.0452 (13)	0.0408 (12)	0.0454 (13)	−0.0180 (10)	−0.0036 (10)	−0.0129 (10)
C16	0.0381 (11)	0.0408 (11)	0.0306 (10)	−0.0216 (9)	−0.0051 (8)	−0.0030 (8)
C17	0.0357 (11)	0.0363 (10)	0.0336 (10)	−0.0169 (9)	−0.0080 (9)	−0.0007 (8)
C18	0.0394 (12)	0.0387 (11)	0.0377 (11)	−0.0189 (9)	−0.0076 (9)	−0.0045 (9)
C19	0.063 (2)	0.076 (3)	0.0377 (17)	−0.038 (2)	−0.0095 (16)	0.0061 (16)
C20	0.066 (3)	0.101 (4)	0.051 (2)	−0.026 (2)	0.004 (2)	−0.001 (2)
C21	0.0562 (16)	0.0630 (17)	0.0628 (18)	−0.0236 (14)	−0.0216 (14)	−0.0170 (14)
C22	0.078 (2)	0.076 (2)	0.100 (3)	−0.0175 (19)	−0.039 (2)	−0.017 (2)

Geometric parameters (Å, º) top

Cu1—O1	1.9661 (15)	C8—H8B	0.9600
Cu1—O1ⁱ	1.9661 (15)	C8—H8C	0.9600
Cu1—N3	2.0151 (17)	C9—C10	1.450 (5)
Cu1—N3ⁱ	2.0151 (17)	C10—C11	1.466 (5)
Cu1—O1W	2.531 (2)	C11—C12	1.485 (6)
O1—C1	1.268 (3)	C12—H12A	0.9600
O2—C1	1.239 (3)	C12—H12B	0.9600
O3—C9	1.215 (4)	C12—H12C	0.9600
O4—C11	1.195 (5)	C13—C14	1.376 (3)
O5—C18	1.222 (3)	C13—H13	0.9300
O1W—H11	0.8400	C14—C15	1.380 (3)
O1W—H12	0.8400	C14—H14	0.9300
N1—N2	1.297 (3)	C15—C16	1.389 (3)
N1—C5	1.411 (3)	C15—H15	0.9300
N1—H1	0.8800	C16—C17	1.377 (3)
N2—C10	1.322 (3)	C16—C18	1.500 (3)
N3—C13	1.338 (3)	C17—H17	0.9300
N3—C17	1.345 (3)	C19—C20	1.507 (6)
N4—C18	1.337 (3)	C19—H19A	0.9700
N4—C21	1.476 (3)	C19—H19B	0.9700
N4—C19'	1.493 (10)	C19'—C20'	1.506 (11)
N4—C19	1.497 (4)	C19'—H19C	0.9700
C1—C2	1.509 (3)	C19'—H19D	0.9700
C2—C3	1.386 (3)	C20—H20A	0.9600
C2—C7	1.387 (3)	C20—H20B	0.9600
C3—C4	1.384 (3)	C20—H20C	0.9600
C3—H3	0.9300	C20'—H20D	0.9600
C4—C5	1.387 (3)	C20'—H20E	0.9600
C4—H4	0.9300	C20'—H20F	0.9600
C5—C6	1.384 (4)	C21—C22	1.491 (4)
C6—C7	1.379 (3)	C21—H21A	0.9700
C6—H6	0.9300	C21—H21B	0.9700
C7—H7	0.9300	C22—H22A	0.9600
C8—C9	1.500 (5)	C22—H22B	0.9600
C8—H8A	0.9600	C22—H22C	0.9600

O1—Cu1—O1ⁱ	180.00 (5)	C10—C11—C12	121.0 (3)
O1—Cu1—N3	88.22 (7)	C11—C12—H12A	109.5
O1ⁱ—Cu1—N3	91.78 (7)	C11—C12—H12B	109.5
O1—Cu1—N3ⁱ	91.78 (7)	H12A—C12—H12B	109.5
O1ⁱ—Cu1—N3ⁱ	88.22 (7)	C11—C12—H12C	109.5
N3—Cu1—N3ⁱ	180.00 (9)	H12A—C12—H12C	109.5
O1—Cu1—O1W	94.78 (7)	H12B—C12—H12C	109.5
O1ⁱ—Cu1—O1W	85.22 (7)	N3—C13—C14	121.9 (2)
N3—Cu1—O1W	94.61 (7)	N3—C13—H13	119.1
N3ⁱ—Cu1—O1W	85.39 (7)	C14—C13—H13	119.1
C1—O1—Cu1	127.21 (15)	C13—C14—C15	119.7 (2)
Cu1—O1W—H11	109.5	C13—C14—H14	120.2
Cu1—O1W—H12	109.5	C15—C14—H14	120.2
H11—O1W—H12	109.5	C14—C15—C16	118.6 (2)
N2—N1—C5	121.0 (2)	C14—C15—H15	120.7
N2—N1—H1	119.5	C16—C15—H15	120.7
C5—N1—H1	119.5	C17—C16—C15	118.5 (2)
N1—N2—C10	120.8 (3)	C17—C16—C18	118.7 (2)
C13—N3—C17	118.55 (18)	C15—C16—C18	122.47 (19)
C13—N3—Cu1	121.68 (14)	N3—C17—C16	122.6 (2)
C17—N3—Cu1	119.68 (15)	N3—C17—H17	118.7
C18—N4—C21	118.4 (2)	C16—C17—H17	118.7
C18—N4—C19'	122.4 (6)	O5—C18—N4	122.2 (2)
C21—N4—C19'	111.2 (6)	O5—C18—C16	119.0 (2)
C18—N4—C19	122.2 (2)	N4—C18—C16	118.8 (2)
C21—N4—C19	118.0 (2)	N4—C19—C20	111.8 (4)
O2—C1—O1	125.9 (2)	N4—C19—H19A	109.3
O2—C1—C2	118.8 (2)	C20—C19—H19A	109.3
O1—C1—C2	115.3 (2)	N4—C19—H19B	109.3
C3—C2—C7	118.9 (2)	C20—C19—H19B	109.3
C3—C2—C1	121.8 (2)	H19A—C19—H19B	107.9
C7—C2—C1	119.3 (2)	N4—C19'—C20'	97.5 (11)
C4—C3—C2	120.8 (2)	N4—C19'—H19C	112.3
C4—C3—H3	119.6	C20'—C19'—H19C	112.3
C2—C3—H3	119.6	N4—C19'—H19D	112.3
C3—C4—C5	119.2 (2)	C20'—C19'—H19D	112.3
C3—C4—H4	120.4	H19C—C19'—H19D	109.9
C5—C4—H4	120.4	C19—C20—H20A	109.5
C6—C5—C4	120.9 (2)	C19—C20—H20B	109.5
C6—C5—N1	121.6 (2)	H20A—C20—H20B	109.5
C4—C5—N1	117.5 (2)	C19—C20—H20C	109.5
C7—C6—C5	119.0 (2)	H20A—C20—H20C	109.5
C7—C6—H6	120.5	H20B—C20—H20C	109.5
C5—C6—H6	120.5	C19'—C20'—H20D	109.5
C6—C7—C2	121.2 (2)	C19'—C20'—H20E	109.5
C6—C7—H7	119.4	H20D—C20'—H20E	109.5
C2—C7—H7	119.4	C19'—C20'—H20F	109.5
C9—C8—H8A	109.5	H20D—C20'—H20F	109.5
C9—C8—H8B	109.5	H20E—C20'—H20F	109.5
H8A—C8—H8B	109.5	N4—C21—C22	112.7 (3)
C9—C8—H8C	109.5	N4—C21—H21A	109.1
H8A—C8—H8C	109.5	C22—C21—H21A	109.1
H8B—C8—H8C	109.5	N4—C21—H21B	109.1
O3—C9—C10	120.1 (3)	C22—C21—H21B	109.1
O3—C9—C8	118.5 (4)	H21A—C21—H21B	107.8
C10—C9—C8	121.3 (3)	C21—C22—H22A	109.5
N2—C10—C9	124.0 (3)	C21—C22—H22B	109.5
N2—C10—C11	114.1 (3)	H22A—C22—H22B	109.5
C9—C10—C11	121.9 (3)	C21—C22—H22C	109.5
O4—C11—C10	120.1 (4)	H22A—C22—H22C	109.5
O4—C11—C12	118.8 (4)	H22B—C22—H22C	109.5

N3—Cu1—O1—C1	−77.11 (18)	N2—C10—C11—O4	−166.7 (7)
N3ⁱ—Cu1—O1—C1	102.89 (18)	C9—C10—C11—O4	12.6 (10)
O1W—Cu1—O1—C1	17.37 (18)	N2—C10—C11—C12	11.7 (7)
C5—N1—N2—C10	−179.4 (3)	C9—C10—C11—C12	−169.1 (5)
O1—Cu1—N3—C13	138.76 (18)	C17—N3—C13—C14	1.2 (3)
O1ⁱ—Cu1—N3—C13	−41.24 (18)	Cu1—N3—C13—C14	−175.28 (18)
O1W—Cu1—N3—C13	44.11 (18)	N3—C13—C14—C15	0.8 (4)
O1—Cu1—N3—C17	−37.72 (17)	C13—C14—C15—C16	−1.3 (4)
O1ⁱ—Cu1—N3—C17	142.28 (17)	C14—C15—C16—C17	−0.2 (4)
O1W—Cu1—N3—C17	−132.37 (16)	C14—C15—C16—C18	−173.6 (2)
Cu1—O1—C1—O2	−28.8 (3)	C13—N3—C17—C16	−2.8 (3)
Cu1—O1—C1—C2	150.44 (15)	Cu1—N3—C17—C16	173.76 (16)
O2—C1—C2—C3	179.1 (2)	C15—C16—C17—N3	2.3 (3)
O1—C1—C2—C3	−0.2 (3)	C18—C16—C17—N3	176.0 (2)
O2—C1—C2—C7	0.1 (3)	C21—N4—C18—O5	−8.4 (4)
O1—C1—C2—C7	−179.2 (2)	C19'—N4—C18—O5	−154.6 (7)
C7—C2—C3—C4	−0.5 (4)	C19—N4—C18—O5	158.5 (3)
C1—C2—C3—C4	−179.5 (2)	C21—N4—C18—C16	172.2 (2)
C2—C3—C4—C5	−0.7 (4)	C19'—N4—C18—C16	26.0 (7)
C3—C4—C5—C6	1.2 (4)	C19—N4—C18—C16	−20.9 (4)
C3—C4—C5—N1	−179.6 (2)	C17—C16—C18—O5	−64.4 (3)
N2—N1—C5—C6	−14.1 (4)	C15—C16—C18—O5	109.1 (3)
N2—N1—C5—C4	166.8 (3)	C17—C16—C18—N4	115.1 (3)
C4—C5—C6—C7	−0.5 (4)	C15—C16—C18—N4	−71.5 (3)
N1—C5—C6—C7	−179.7 (3)	C18—N4—C19—C20	112.8 (4)
C5—C6—C7—C2	−0.7 (4)	C21—N4—C19—C20	−80.2 (4)
C3—C2—C7—C6	1.2 (4)	C19'—N4—C19—C20	9.6 (9)
C1—C2—C7—C6	−179.7 (2)	C18—N4—C19'—C20'	−99.5 (11)
N1—N2—C10—C9	−3.8 (6)	C21—N4—C19'—C20'	112.1 (10)
N1—N2—C10—C11	175.4 (4)	C19—N4—C19'—C20'	3.3 (9)
O3—C9—C10—N2	0.6 (7)	C18—N4—C21—C22	86.4 (4)
C8—C9—C10—N2	−178.2 (4)	C19'—N4—C21—C22	−123.8 (6)
O3—C9—C10—C11	−178.6 (5)	C19—N4—C21—C22	−81.0 (4)
C8—C9—C10—C11	2.7 (7)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3	0.88	1.88	2.558 (3)	132
O1w—H11···O2	0.84	2.06	2.712 (3)	135
O1w—H12···O5ⁱⁱ	0.84	2.12	2.955 (3)	172

Symmetry code: (ii) x+1, y, z.

Experimental details

Crystal data
Chemical formula	[Cu(C₁₂H₁₁N₂O₄)₂(C₁₀H₁₄N₂O)₂(H₂O)₂]
M_r	950.49
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	7.7429 (4), 8.7029 (4), 19.0069 (9)
α, β, γ (°)	85.695 (1), 83.218 (1), 64.882 (1)
V (Å³)	1151.12 (10)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.54
Crystal size (mm)	0.30 × 0.30 × 0.20

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.854, 0.899
No. of measured, independent and observed [I > 2σ(I)] reflections	13589, 5775, 4780
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.669

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.134, 1.04
No. of reflections	5775
No. of parameters	305
No. of restraints	38
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.87, −0.60

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

Cu1—O1	1.9661 (15)	Cu1—O1W	2.531 (2)
Cu1—N3	2.0151 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3	0.88	1.88	2.558 (3)	132
O1w—H11···O2	0.84	2.06	2.712 (3)	135
O1w—H12···O5ⁱ	0.84	2.12	2.955 (3)	172

Symmetry code: (i) x+1, y, z.

Acknowledgements

We thank Baku State University and the University of Malaya for supporting this study.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Maharramov, A. M., Mardanova, V. I., Chyraqov, F., Gurbanov, A. V. & Ng, S. W. (2011). Acta Cryst. E67, m708–m709. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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