catena-Poly[[[{1-[(E)-phenyl(pyridin-2-yl-κN)methylidene]semicarbazidato-κ2N1,O}copper(II)]-μ-dicyanamido-κ2N1:N5] monohydrate]

Kunnath, R.J.; Prathapachandra Kurup, M.R.; Ng, S.W.

doi:10.1107/S1600536812035283

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page m1176

doi:10.1107/S1600536812035283

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catena-Poly[[[{1-[(E)-phenyl(pyridin-2-yl-κN)methylidene]semicarbazidato-κ²N¹,O}copper(II)]-μ-dicyanamido-κ²N¹:N⁵] monohydrate]

Roji J. Kunnath,^a M.R. Prathapachandra Kurup ^a and Seik Weng Ng ^b,^c ^*

^aDepartment of Applied Chemistry, Cochin University of Science and Technology, Kochi 682 022, India, ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia, and ^cChemistry Department, King Abdulaziz University, PO Box 80203 Jeddah, Saudi Arabia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 30 July 2012; accepted 9 August 2012; online 15 August 2012)

The Cu^II atoms in the title coordination polymer, {[Cu(C₁₃H₁₁N₄O)(C₂N₃)]·H₂O}_n, are N,N′,O-chelated by the deprotonated Schiff base ligands, and adjacent metal atoms are bridged by the dicyanamide ions, generating a polymeric chain that propagates along the b axis. The two independent metal atoms show a square-pyramidal N₄O coordination. The two independent water molecules are disordered over two positions; each water molecule is a hydrogen-bond donor to a carbonyl O atom. Weak N—H⋯N hydrogen bonding is also observed.

Related literature

For the synthesis of the Schiff base ligand, see: de Lima et al. (2008 ). For a related copper(II) derivative, see: Peŕez-Rebolledo et al. (2006 ).

Experimental

Crystal data

[Cu(C₁₃H₁₁N₄O)(C₂N₃)]·H₂O
M_r = 386.86
Orthorhombic, P b c a
a = 12.3996 (2) Å
b = 21.0115 (4) Å
c = 26.7059 (5) Å
V = 6957.8 (2) Å³
Z = 16
Mo Kα radiation
μ = 1.28 mm⁻¹
T = 293 K
0.40 × 0.30 × 0.20 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.629, T_max = 0.784
110924 measured reflections
7982 independent reflections
5027 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.166
S = 1.12
7982 reflections
457 parameters
12 restraints
H-atom parameters constrained
Δρ_max = 0.80 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H42⋯N7ⁱ	0.88	2.13	3.006 (5)	176
N8—H82⋯N3ⁱⁱ	0.88	2.15	3.025 (5)	179
O1w—H1w1⋯O1	0.84	2.05	2.88 (2)	169
O2w—H2w1⋯O2	0.84	2.34	3.151 (19)	161
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2010 ); cell refinement: SAINT (Bruker, 2010); 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/S1600536812035283/xu5601sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812035283/xu5601Isup2.hkl

checkCIF report

Comment top

2-Benzoylpyridine semicarbazone (de Lima et al., 2008) is a Schiff base that is capable of N,N',O-chelation to transition metal ions. This feature has been documented a copper(II) dichloride adduct; in this, the Schiff base exists as a neutral molecule (Peŕez-Rebolledo et al., 2006). However, the Cu^II atom in the coordination polymer, [Cu(C₂N₃)(C₁₃H₁₁N₄O)^.H₂O]_n (I), is N,N',O-chelated instead by the deprotonated Schiff base (Fig. 1). Adjacent metal atoms are bridged by the dicyanamide ion to generate a chain that propagates along the b axis of the orthorhombic unit cell (Fig. 2). The two independent metal atoms show square pyramidal coordination. The two independent water molecules are disordered over two positions; each water molecule is a hydrogen-bond donor to a carbonyl O atom.

Related literature top

For the synthesis of the Schiff base ligand, see: de Lima et al. (2008). For a related copper(II) derivative, see: Peŕez-Rebolledo et al. (2006).

Experimental top

A methanol solution (20 ml) of 2-benzoylpyridine semicarbazone (0.240 g,1 mmol) (de Lima et al., 2008), copper acetate monohydrate (0.199 g, 1 mmol) and sodium dicyanamide (0.089 g, 1 mmol) was heated for 5 h. The dark green solid was collected and recrystallized from methanol.

Computing details top

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); 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 a portion of the chain structure of [Cu(C₂N₃)(C₁₃H₁₁N₄O)^.H₂O]_n at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius. The disorder in the water molecules is not shown.
	Fig. 2. Dicyanamide-bridged chain structure. Water molecules are not shown.

catena-Poly[[[{1-[(E)-phenyl(pyridin-2-yl-κN)methylidene]semicarbazidato-κ²N¹,O}copper(II)]-µ-dicyanamido-κ²N¹:N⁵] monohydrate] top

Crystal data top

[Cu(C₁₃H₁₁N₄O)(C₂N₃)]·H₂O	F(000) = 3152
M_r = 386.86	D_x = 1.477 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9967 reflections
a = 12.3996 (2) Å	θ = 2.7–26.5°
b = 21.0115 (4) Å	µ = 1.28 mm⁻¹
c = 26.7059 (5) Å	T = 293 K
V = 6957.8 (2) Å³	Prim, green
Z = 16	0.40 × 0.30 × 0.20 mm

Data collection top

Bruker Kappa APEXII diffractometer	7982 independent reflections
Radiation source: fine-focus sealed tube	5027 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
ω scans	θ_max = 27.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −16→14
T_min = 0.629, T_max = 0.784	k = −27→27
110924 measured reflections	l = −34→34

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.166	H-atom parameters constrained
S = 1.12	w = 1/[σ²(F_o²) + (0.0668P)² + 9.8211P] where P = (F_o² + 2F_c²)/3
7982 reflections	(Δ/σ)_max = 0.001
457 parameters	Δρ_max = 0.80 e Å⁻³
12 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

[Cu(C₁₃H₁₁N₄O)(C₂N₃)]·H₂O	V = 6957.8 (2) Å³
M_r = 386.86	Z = 16
Orthorhombic, Pbca	Mo Kα radiation
a = 12.3996 (2) Å	µ = 1.28 mm⁻¹
b = 21.0115 (4) Å	T = 293 K
c = 26.7059 (5) Å	0.40 × 0.30 × 0.20 mm

Data collection top

Bruker Kappa APEXII diffractometer	7982 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	5027 reflections with I > 2σ(I)
T_min = 0.629, T_max = 0.784	R_int = 0.054
110924 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	12 restraints
wR(F²) = 0.166	H-atom parameters constrained
S = 1.12	Δρ_max = 0.80 e Å⁻³
7982 reflections	Δρ_min = −0.46 e Å⁻³
457 parameters

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	0.74889 (4)	0.32160 (2)	0.591725 (16)	0.03950 (15)
Cu2	0.51236 (4)	0.06952 (2)	0.406562 (15)	0.03717 (15)
O1	0.6417 (2)	0.38125 (13)	0.61888 (10)	0.0541 (8)
O2	0.6166 (2)	0.13248 (12)	0.38040 (10)	0.0489 (7)
O1W	0.4729 (16)	0.4332 (10)	0.5571 (8)	0.269 (7)	0.50
H1W1	0.5266	0.4228	0.5745	0.404*
H1W2	0.4808	0.4710	0.5475	0.404*
O2W	0.8427 (16)	0.1463 (9)	0.4332 (7)	0.234 (6)	0.50
H2W1	0.7879	0.1336	0.4177	0.280*
H2W2	0.8367	0.1858	0.4373	0.280*
O1W'	0.4691 (17)	0.5292 (11)	0.5296 (8)	0.269 (7)	0.50
O2W'	0.7929 (19)	0.1888 (10)	0.4402 (8)	0.234 (6)	0.50
N1	0.8834 (3)	0.26882 (16)	0.58984 (12)	0.0469 (8)
N2	0.7736 (3)	0.31179 (14)	0.66329 (11)	0.0362 (7)
N3	0.7020 (3)	0.33965 (15)	0.69487 (11)	0.0419 (7)
N4	0.5629 (3)	0.41008 (19)	0.69133 (14)	0.0644 (11)
H41	0.5184	0.4351	0.6749	0.077*
H42	0.5586	0.4073	0.7241	0.077*
N5	0.3807 (3)	0.01320 (15)	0.40768 (10)	0.0396 (7)
N6	0.4882 (2)	0.06112 (14)	0.33509 (11)	0.0358 (7)
N7	0.5555 (3)	0.09307 (15)	0.30382 (11)	0.0394 (7)
N8	0.6909 (3)	0.16608 (17)	0.30793 (13)	0.0555 (9)
H81	0.7353	0.1909	0.3246	0.067*
H82	0.6936	0.1649	0.2750	0.067*
N9	0.6399 (4)	0.2399 (2)	0.58076 (14)	0.0683 (12)
N10	0.5250 (4)	0.1525 (2)	0.55530 (14)	0.0735 (13)
N11	0.5158 (3)	0.09809 (17)	0.47568 (12)	0.0497 (8)
N12	0.7496 (3)	0.35269 (18)	0.52272 (13)	0.0509 (9)
N13	0.7622 (4)	0.3993 (2)	0.43995 (14)	0.0799 (15)
N14	0.8717 (3)	0.48903 (18)	0.41363 (13)	0.0539 (9)
C1	0.9380 (4)	0.2496 (2)	0.54957 (17)	0.0673 (14)
H1	0.9131	0.2611	0.5180	0.081*
C2	1.0297 (5)	0.2132 (3)	0.5532 (2)	0.0814 (18)
H2	1.0658	0.1998	0.5246	0.098*
C3	1.0669 (5)	0.1972 (2)	0.6000 (2)	0.0747 (16)
H3	1.1305	0.1741	0.6035	0.090*
C4	1.0095 (4)	0.2154 (2)	0.64189 (17)	0.0546 (11)
H4	1.0326	0.2039	0.6737	0.066*
C5	0.9172 (3)	0.25110 (17)	0.63568 (14)	0.0419 (9)
C6	0.8486 (3)	0.27313 (16)	0.67749 (13)	0.0360 (8)
C7	0.8605 (3)	0.24717 (17)	0.72905 (13)	0.0384 (8)
C8	0.7886 (4)	0.2016 (2)	0.74534 (17)	0.0546 (11)
H8	0.7321	0.1890	0.7247	0.066*
C9	0.8002 (5)	0.1745 (2)	0.7924 (2)	0.0696 (14)
H9	0.7519	0.1436	0.8032	0.084*
C10	0.8835 (5)	0.1935 (3)	0.82286 (19)	0.0758 (16)
H10	0.8909	0.1758	0.8546	0.091*
C11	0.9552 (5)	0.2379 (3)	0.80682 (19)	0.0831 (17)
H11	1.0119	0.2504	0.8275	0.100*
C12	0.9440 (4)	0.2645 (2)	0.76020 (17)	0.0653 (13)
H12	0.9937	0.2947	0.7494	0.078*
C13	0.6370 (3)	0.37643 (18)	0.66655 (14)	0.0427 (9)
C14	0.3281 (4)	−0.0096 (2)	0.44722 (15)	0.0527 (11)
H14	0.3484	0.0040	0.4790	0.063*
C15	0.2455 (4)	−0.0522 (3)	0.44297 (19)	0.0741 (16)
H15	0.2098	−0.0671	0.4713	0.089*
C16	0.2161 (5)	−0.0725 (3)	0.3959 (2)	0.0832 (18)
H16	0.1602	−0.1016	0.3920	0.100*
C17	0.2703 (4)	−0.0494 (2)	0.35449 (17)	0.0626 (13)
H17	0.2513	−0.0627	0.3225	0.075*
C18	0.3520 (3)	−0.00673 (18)	0.36126 (13)	0.0403 (8)
C19	0.4168 (3)	0.02092 (17)	0.32052 (13)	0.0368 (8)
C20	0.4045 (3)	−0.00038 (17)	0.26745 (13)	0.0369 (8)
C21	0.3209 (4)	0.0214 (2)	0.23788 (15)	0.0562 (11)
H21	0.2697	0.0492	0.2508	0.067*
C22	0.3144 (4)	0.0011 (3)	0.18867 (17)	0.0664 (13)
H22	0.2580	0.0154	0.1687	0.080*
C23	0.3888 (4)	−0.0392 (2)	0.16898 (16)	0.0644 (14)
H23	0.3844	−0.0514	0.1356	0.077*
C24	0.4709 (4)	−0.0618 (2)	0.19901 (19)	0.0647 (14)
H24	0.5207	−0.0906	0.1862	0.078*
C25	0.4789 (4)	−0.0417 (2)	0.24776 (17)	0.0521 (10)
H25	0.5354	−0.0562	0.2676	0.062*
C26	0.6197 (3)	0.13029 (17)	0.33247 (14)	0.0409 (9)
C27	0.5897 (4)	0.1987 (2)	0.56680 (14)	0.0471 (10)
C28	0.5253 (3)	0.12554 (19)	0.51235 (14)	0.0447 (9)
C29	0.7585 (3)	0.3768 (2)	0.48527 (16)	0.0483 (10)
C30	0.8225 (3)	0.4478 (2)	0.42797 (13)	0.0455 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0501 (3)	0.0411 (3)	0.0272 (2)	−0.00041 (19)	0.00001 (19)	−0.00053 (18)
Cu2	0.0476 (3)	0.0394 (3)	0.0245 (2)	−0.0023 (2)	−0.00390 (18)	−0.00204 (17)
O1	0.070 (2)	0.0597 (18)	0.0327 (14)	0.0195 (15)	−0.0050 (13)	0.0012 (12)
O2	0.0662 (19)	0.0471 (16)	0.0334 (14)	−0.0157 (14)	−0.0080 (13)	−0.0001 (11)
O1W	0.220 (9)	0.323 (11)	0.266 (10)	0.038 (8)	−0.025 (8)	−0.002 (8)
O2W	0.247 (10)	0.253 (11)	0.201 (8)	0.037 (8)	−0.069 (8)	−0.052 (8)
O1W'	0.220 (9)	0.323 (11)	0.266 (10)	0.038 (8)	−0.025 (8)	−0.002 (8)
O2W'	0.247 (10)	0.253 (11)	0.201 (8)	0.037 (8)	−0.069 (8)	−0.052 (8)
N1	0.059 (2)	0.0457 (18)	0.0354 (17)	0.0038 (16)	0.0107 (15)	0.0022 (14)
N2	0.0452 (18)	0.0354 (16)	0.0281 (14)	0.0019 (14)	−0.0007 (13)	−0.0020 (12)
N3	0.046 (2)	0.0472 (18)	0.0323 (16)	0.0081 (15)	−0.0028 (14)	−0.0045 (14)
N4	0.075 (3)	0.078 (3)	0.0401 (19)	0.036 (2)	0.0021 (18)	0.0022 (18)
N5	0.0458 (19)	0.0448 (17)	0.0282 (15)	−0.0011 (14)	0.0010 (13)	0.0004 (13)
N6	0.0418 (18)	0.0395 (17)	0.0261 (14)	−0.0010 (13)	−0.0031 (12)	−0.0002 (12)
N7	0.0487 (19)	0.0429 (17)	0.0266 (14)	−0.0060 (15)	−0.0046 (13)	0.0028 (13)
N8	0.070 (3)	0.054 (2)	0.0427 (19)	−0.0245 (19)	−0.0014 (17)	0.0026 (16)
N9	0.090 (3)	0.063 (2)	0.052 (2)	−0.027 (2)	0.001 (2)	−0.0150 (19)
N10	0.097 (3)	0.082 (3)	0.041 (2)	−0.045 (3)	0.021 (2)	−0.029 (2)
N11	0.062 (2)	0.055 (2)	0.0321 (17)	−0.0067 (17)	−0.0025 (15)	−0.0054 (15)
N12	0.058 (2)	0.056 (2)	0.0389 (19)	−0.0099 (17)	0.0001 (16)	0.0063 (16)
N13	0.100 (3)	0.096 (3)	0.043 (2)	−0.056 (3)	−0.028 (2)	0.030 (2)
N14	0.061 (2)	0.058 (2)	0.0425 (19)	−0.0145 (19)	−0.0045 (17)	0.0155 (16)
C1	0.089 (4)	0.068 (3)	0.044 (2)	0.022 (3)	0.027 (2)	0.007 (2)
C2	0.101 (4)	0.084 (4)	0.060 (3)	0.041 (3)	0.036 (3)	0.007 (3)
C3	0.079 (4)	0.069 (3)	0.076 (4)	0.035 (3)	0.031 (3)	0.011 (3)
C4	0.062 (3)	0.051 (2)	0.051 (3)	0.012 (2)	0.007 (2)	0.009 (2)
C5	0.050 (2)	0.0348 (19)	0.041 (2)	0.0007 (17)	0.0088 (17)	0.0028 (15)
C6	0.043 (2)	0.0308 (17)	0.0345 (18)	−0.0025 (16)	0.0010 (15)	0.0002 (14)
C7	0.043 (2)	0.0394 (19)	0.0326 (18)	0.0044 (16)	0.0035 (16)	0.0042 (15)
C8	0.062 (3)	0.047 (2)	0.056 (3)	−0.007 (2)	0.004 (2)	0.005 (2)
C9	0.079 (4)	0.056 (3)	0.074 (3)	−0.002 (3)	0.023 (3)	0.020 (3)
C10	0.088 (4)	0.089 (4)	0.051 (3)	0.012 (3)	0.002 (3)	0.034 (3)
C11	0.081 (4)	0.121 (5)	0.048 (3)	−0.013 (4)	−0.019 (3)	0.025 (3)
C12	0.064 (3)	0.085 (3)	0.047 (2)	−0.025 (3)	−0.011 (2)	0.016 (2)
C13	0.051 (2)	0.042 (2)	0.035 (2)	0.0092 (18)	−0.0012 (17)	−0.0034 (16)
C14	0.059 (3)	0.065 (3)	0.033 (2)	−0.002 (2)	0.0065 (19)	0.0007 (18)
C15	0.066 (3)	0.106 (4)	0.051 (3)	−0.023 (3)	0.011 (2)	0.014 (3)
C16	0.071 (4)	0.118 (5)	0.061 (3)	−0.043 (3)	−0.003 (3)	0.013 (3)
C17	0.064 (3)	0.082 (3)	0.042 (2)	−0.032 (3)	−0.006 (2)	0.003 (2)
C18	0.042 (2)	0.048 (2)	0.0305 (18)	−0.0046 (17)	−0.0027 (15)	−0.0003 (15)
C19	0.042 (2)	0.0369 (19)	0.0314 (18)	−0.0001 (16)	−0.0041 (15)	0.0008 (14)
C20	0.042 (2)	0.0375 (19)	0.0307 (18)	−0.0070 (16)	−0.0029 (15)	−0.0030 (14)
C21	0.059 (3)	0.071 (3)	0.038 (2)	0.011 (2)	−0.011 (2)	−0.008 (2)
C22	0.076 (3)	0.084 (3)	0.039 (2)	−0.002 (3)	−0.023 (2)	−0.008 (2)
C23	0.086 (4)	0.074 (3)	0.034 (2)	−0.028 (3)	0.004 (2)	−0.019 (2)
C24	0.071 (3)	0.055 (3)	0.069 (3)	−0.007 (2)	0.020 (3)	−0.032 (2)
C25	0.053 (3)	0.054 (3)	0.049 (2)	−0.001 (2)	−0.003 (2)	−0.007 (2)
C26	0.050 (2)	0.037 (2)	0.0356 (19)	0.0002 (17)	−0.0006 (17)	0.0036 (16)
C27	0.060 (3)	0.053 (2)	0.0280 (18)	−0.007 (2)	0.0055 (18)	−0.0048 (17)
C28	0.052 (2)	0.049 (2)	0.033 (2)	−0.0117 (19)	0.0037 (17)	−0.0062 (17)
C29	0.047 (2)	0.054 (2)	0.043 (2)	−0.0148 (19)	−0.0113 (18)	0.0046 (19)
C30	0.050 (2)	0.062 (3)	0.0252 (18)	−0.008 (2)	−0.0133 (17)	0.0066 (17)

Geometric parameters (Å, º) top

Cu1—N2	1.946 (3)	C1—H1	0.9300
Cu1—N12	1.955 (3)	C2—C3	1.376 (7)
Cu1—O1	1.966 (3)	C2—H2	0.9300
Cu1—N1	2.004 (4)	C3—C4	1.380 (6)
Cu1—N9	2.205 (4)	C3—H3	0.9300
Cu2—N6	1.940 (3)	C4—C5	1.377 (6)
Cu2—N11	1.941 (3)	C4—H4	0.9300
Cu2—O2	1.977 (3)	C5—C6	1.479 (5)
Cu2—N5	2.016 (3)	C6—C7	1.488 (5)
Cu2—N14ⁱ	2.228 (4)	C7—C8	1.378 (6)
O1—C13	1.278 (4)	C7—C12	1.378 (6)
O2—C26	1.281 (4)	C8—C9	1.387 (7)
O1W—H1W1	0.8401	C8—H8	0.9300
O1W—H1W2	0.8401	C9—C10	1.375 (8)
O2W—H2W1	0.8400	C9—H9	0.9300
O2W—H2W2	0.8400	C10—C11	1.359 (8)
N1—C1	1.333 (5)	C10—H10	0.9300
N1—C5	1.346 (5)	C11—C12	1.371 (6)
N2—C6	1.292 (5)	C11—H11	0.9300
N2—N3	1.358 (4)	C12—H12	0.9300
N3—C13	1.349 (5)	C14—C15	1.364 (7)
N4—C13	1.334 (5)	C14—H14	0.9300
N4—H41	0.8800	C15—C16	1.377 (7)
N4—H42	0.8800	C15—H15	0.9300
N5—C14	1.331 (5)	C16—C17	1.383 (7)
N5—C18	1.356 (4)	C16—H16	0.9300
N6—C19	1.284 (5)	C17—C18	1.365 (6)
N6—N7	1.358 (4)	C17—H17	0.9300
N7—C26	1.353 (5)	C18—C19	1.472 (5)
N8—C26	1.332 (5)	C19—C20	1.494 (5)
N8—H81	0.8800	C20—C25	1.372 (6)
N8—H82	0.8800	C20—C21	1.381 (6)
N9—C27	1.129 (5)	C21—C22	1.384 (6)
N10—C28	1.280 (5)	C21—H21	0.9300
N10—C27	1.296 (6)	C22—C23	1.358 (7)
N11—C28	1.143 (5)	C22—H22	0.9300
N12—C29	1.127 (5)	C23—C24	1.381 (7)
N13—C29	1.300 (5)	C23—H23	0.9300
N13—C30	1.303 (6)	C24—C25	1.372 (6)
N14—C30	1.127 (5)	C24—H24	0.9300
N14—Cu2ⁱⁱ	2.228 (4)	C25—H25	0.9300
C1—C2	1.372 (7)

N2—Cu1—N12	163.76 (14)	N2—C6—C7	125.0 (3)
N2—Cu1—O1	79.14 (12)	C5—C6—C7	121.8 (3)
N12—Cu1—O1	97.91 (14)	C8—C7—C12	118.6 (4)
N2—Cu1—N1	80.51 (13)	C8—C7—C6	118.8 (4)
N12—Cu1—N1	99.07 (14)	C12—C7—C6	122.4 (4)
O1—Cu1—N1	157.69 (13)	C7—C8—C9	120.3 (5)
N2—Cu1—N9	98.30 (14)	C7—C8—H8	119.9
N12—Cu1—N9	97.91 (15)	C9—C8—H8	119.9
O1—Cu1—N9	97.52 (15)	C10—C9—C8	119.6 (5)
N1—Cu1—N9	94.37 (16)	C10—C9—H9	120.2
N6—Cu2—N11	165.22 (14)	C8—C9—H9	120.2
N6—Cu2—O2	79.29 (12)	C11—C10—C9	120.3 (4)
N11—Cu2—O2	96.58 (13)	C11—C10—H10	119.8
N6—Cu2—N5	80.58 (12)	C9—C10—H10	119.8
N11—Cu2—N5	100.68 (13)	C10—C11—C12	120.0 (5)
O2—Cu2—N5	158.01 (11)	C10—C11—H11	120.0
N6—Cu2—N14ⁱ	96.54 (13)	C12—C11—H11	120.0
N11—Cu2—N14ⁱ	98.04 (14)	C11—C12—C7	121.1 (4)
O2—Cu2—N14ⁱ	96.66 (13)	C11—C12—H12	119.5
N5—Cu2—N14ⁱ	94.34 (14)	C7—C12—H12	119.5
C13—O1—Cu1	110.4 (2)	O1—C13—N4	118.9 (4)
C26—O2—Cu2	110.4 (2)	O1—C13—N3	125.2 (3)
H1W1—O1W—H1W2	108.7	N4—C13—N3	115.9 (3)
H2W1—O2W—H2W2	107.9	N5—C14—C15	122.6 (4)
C1—N1—C5	119.4 (4)	N5—C14—H14	118.7
C1—N1—Cu1	127.6 (3)	C15—C14—H14	118.7
C5—N1—Cu1	112.9 (3)	C14—C15—C16	118.6 (4)
C6—N2—N3	124.0 (3)	C14—C15—H15	120.7
C6—N2—Cu1	117.9 (2)	C16—C15—H15	120.7
N3—N2—Cu1	117.5 (2)	C15—C16—C17	119.5 (5)
C13—N3—N2	106.8 (3)	C15—C16—H16	120.3
C13—N4—H41	120.0	C17—C16—H16	120.3
C13—N4—H42	120.0	C18—C17—C16	119.1 (4)
H41—N4—H42	120.0	C18—C17—H17	120.5
C14—N5—C18	119.1 (4)	C16—C17—H17	120.5
C14—N5—Cu2	128.3 (3)	N5—C18—C17	121.2 (4)
C18—N5—Cu2	112.3 (2)	N5—C18—C19	114.2 (3)
C19—N6—N7	124.2 (3)	C17—C18—C19	124.5 (3)
C19—N6—Cu2	117.7 (2)	N6—C19—C18	114.3 (3)
N7—N6—Cu2	117.7 (2)	N6—C19—C20	123.7 (3)
C26—N7—N6	107.4 (3)	C18—C19—C20	121.8 (3)
C26—N8—H81	120.0	C25—C20—C21	119.7 (4)
C26—N8—H82	120.0	C25—C20—C19	119.0 (3)
H81—N8—H82	120.0	C21—C20—C19	121.4 (3)
C27—N9—Cu1	168.1 (4)	C20—C21—C22	119.0 (4)
C28—N10—C27	122.9 (4)	C20—C21—H21	120.5
C28—N11—Cu2	166.7 (3)	C22—C21—H21	120.5
C29—N12—Cu1	170.9 (4)	C23—C22—C21	121.4 (5)
C29—N13—C30	122.2 (4)	C23—C22—H22	119.3
C30—N14—Cu2ⁱⁱ	164.2 (3)	C21—C22—H22	119.3
N1—C1—C2	122.2 (5)	C22—C23—C24	119.4 (4)
N1—C1—H1	118.9	C22—C23—H23	120.3
C2—C1—H1	118.9	C24—C23—H23	120.3
C1—C2—C3	118.5 (4)	C25—C24—C23	119.9 (4)
C1—C2—H2	120.7	C25—C24—H24	120.1
C3—C2—H2	120.7	C23—C24—H24	120.1
C2—C3—C4	119.7 (5)	C20—C25—C24	120.7 (4)
C2—C3—H3	120.1	C20—C25—H25	119.7
C4—C3—H3	120.1	C24—C25—H25	119.7
C5—C4—C3	118.8 (4)	O2—C26—N8	119.4 (4)
C5—C4—H4	120.6	O2—C26—N7	124.6 (3)
C3—C4—H4	120.6	N8—C26—N7	116.0 (3)
N1—C5—C4	121.2 (4)	N9—C27—N10	173.3 (5)
N1—C5—C6	114.9 (3)	N11—C28—N10	172.7 (5)
C4—C5—C6	123.9 (4)	N12—C29—N13	173.4 (5)
N2—C6—C5	112.9 (3)	N14—C30—N13	174.2 (4)

N2—Cu1—O1—C13	−7.3 (3)	C3—C4—C5—N1	−0.8 (7)
N12—Cu1—O1—C13	−171.1 (3)	C3—C4—C5—C6	179.6 (4)
N1—Cu1—O1—C13	−31.8 (5)	N3—N2—C6—C5	−178.4 (3)
N9—Cu1—O1—C13	89.8 (3)	Cu1—N2—C6—C5	10.5 (4)
N6—Cu2—O2—C26	−5.6 (3)	N3—N2—C6—C7	7.6 (6)
N11—Cu2—O2—C26	−171.2 (3)	Cu1—N2—C6—C7	−163.6 (3)
N5—Cu2—O2—C26	−29.6 (5)	N1—C5—C6—N2	−7.2 (5)
N14ⁱ—Cu2—O2—C26	89.9 (3)	C4—C5—C6—N2	172.5 (4)
N2—Cu1—N1—C1	−178.0 (4)	N1—C5—C6—C7	167.1 (3)
N12—Cu1—N1—C1	−14.5 (4)	C4—C5—C6—C7	−13.2 (6)
O1—Cu1—N1—C1	−153.6 (4)	N2—C6—C7—C8	72.8 (5)
N9—Cu1—N1—C1	84.3 (4)	C5—C6—C7—C8	−100.8 (5)
N2—Cu1—N1—C5	3.5 (3)	N2—C6—C7—C12	−110.7 (5)
N12—Cu1—N1—C5	167.1 (3)	C5—C6—C7—C12	75.7 (5)
O1—Cu1—N1—C5	28.0 (5)	C12—C7—C8—C9	0.6 (7)
N9—Cu1—N1—C5	−94.2 (3)	C6—C7—C8—C9	177.3 (4)
N12—Cu1—N2—C6	−98.0 (5)	C7—C8—C9—C10	0.3 (7)
O1—Cu1—N2—C6	−178.9 (3)	C8—C9—C10—C11	−0.9 (9)
N1—Cu1—N2—C6	−8.1 (3)	C9—C10—C11—C12	0.6 (9)
N9—Cu1—N2—C6	84.9 (3)	C10—C11—C12—C7	0.4 (9)
N12—Cu1—N2—N3	90.3 (6)	C8—C7—C12—C11	−1.0 (8)
O1—Cu1—N2—N3	9.4 (3)	C6—C7—C12—C11	−177.5 (5)
N1—Cu1—N2—N3	−179.8 (3)	Cu1—O1—C13—N4	−175.2 (3)
N9—Cu1—N2—N3	−86.8 (3)	Cu1—O1—C13—N3	5.1 (5)
C6—N2—N3—C13	180.0 (3)	N2—N3—C13—O1	2.2 (5)
Cu1—N2—N3—C13	−8.9 (4)	N2—N3—C13—N4	−177.5 (4)
N6—Cu2—N5—C14	−179.3 (4)	C18—N5—C14—C15	−0.4 (7)
N11—Cu2—N5—C14	−14.2 (4)	Cu2—N5—C14—C15	−173.8 (4)
O2—Cu2—N5—C14	−155.3 (3)	N5—C14—C15—C16	0.4 (9)
N14ⁱ—Cu2—N5—C14	84.8 (4)	C14—C15—C16—C17	−0.2 (10)
N6—Cu2—N5—C18	6.9 (3)	C15—C16—C17—C18	0.0 (9)
N11—Cu2—N5—C18	172.0 (3)	C14—N5—C18—C17	0.2 (6)
O2—Cu2—N5—C18	30.9 (5)	Cu2—N5—C18—C17	174.7 (4)
N14ⁱ—Cu2—N5—C18	−89.0 (3)	C14—N5—C18—C19	−179.1 (4)
N11—Cu2—N6—C19	−104.8 (6)	Cu2—N5—C18—C19	−4.7 (4)
O2—Cu2—N6—C19	−179.8 (3)	C16—C17—C18—N5	0.0 (8)
N5—Cu2—N6—C19	−8.7 (3)	C16—C17—C18—C19	179.2 (5)
N14ⁱ—Cu2—N6—C19	84.7 (3)	N7—N6—C19—C18	−178.9 (3)
N11—Cu2—N6—N7	82.0 (6)	Cu2—N6—C19—C18	8.4 (4)
O2—Cu2—N6—N7	7.0 (2)	N7—N6—C19—C20	5.5 (6)
N5—Cu2—N6—N7	178.1 (3)	Cu2—N6—C19—C20	−167.3 (3)
N14ⁱ—Cu2—N6—N7	−88.5 (3)	N5—C18—C19—N6	−2.1 (5)
C19—N6—N7—C26	−179.3 (3)	C17—C18—C19—N6	178.6 (4)
Cu2—N6—N7—C26	−6.6 (4)	N5—C18—C19—C20	173.7 (3)
N2—Cu1—N9—C27	−157 (2)	C17—C18—C19—C20	−5.7 (6)
N12—Cu1—N9—C27	24 (2)	N6—C19—C20—C25	74.0 (5)
O1—Cu1—N9—C27	123 (2)	C18—C19—C20—C25	−101.3 (4)
N1—Cu1—N9—C27	−76 (2)	N6—C19—C20—C21	−105.0 (5)
N6—Cu2—N11—C28	−52.0 (19)	C18—C19—C20—C21	79.7 (5)
O2—Cu2—N11—C28	20.8 (16)	C25—C20—C21—C22	−0.3 (7)
N5—Cu2—N11—C28	−145.5 (16)	C19—C20—C21—C22	178.7 (4)
N14ⁱ—Cu2—N11—C28	118.5 (16)	C20—C21—C22—C23	−0.5 (8)
C5—N1—C1—C2	−1.6 (8)	C21—C22—C23—C24	1.8 (8)
Cu1—N1—C1—C2	−179.9 (4)	C22—C23—C24—C25	−2.3 (7)
N1—C1—C2—C3	−1.0 (9)	C21—C20—C25—C24	−0.3 (6)
C1—C2—C3—C4	2.7 (9)	C19—C20—C25—C24	−179.3 (4)
C2—C3—C4—C5	−1.8 (8)	C23—C24—C25—C20	1.6 (7)
C1—N1—C5—C4	2.5 (6)	Cu2—O2—C26—N8	−175.3 (3)
Cu1—N1—C5—C4	−179.0 (3)	Cu2—O2—C26—N7	4.0 (5)
C1—N1—C5—C6	−177.8 (4)	N6—N7—C26—O2	1.5 (5)
Cu1—N1—C5—C6	0.7 (4)	N6—N7—C26—N8	−179.2 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H42···N7ⁱⁱⁱ	0.88	2.13	3.006 (5)	176
N8—H82···N3^iv	0.88	2.15	3.025 (5)	179
O1w—H1w1···O1	0.84	2.05	2.88 (2)	169
O2w—H2w1···O2	0.84	2.34	3.151 (19)	161

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

Experimental details

Crystal data
Chemical formula	[Cu(C₁₃H₁₁N₄O)(C₂N₃)]·H₂O
M_r	386.86
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	293
a, b, c (Å)	12.3996 (2), 21.0115 (4), 26.7059 (5)
V (Å³)	6957.8 (2)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	1.28
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.629, 0.784
No. of measured, independent and observed [I > 2σ(I)] reflections	110924, 7982, 5027
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.166, 1.12
No. of reflections	7982
No. of parameters	457
No. of restraints	12
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.80, −0.46

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H42···N7ⁱ	0.88	2.13	3.006 (5)	175.6
N8—H82···N3ⁱⁱ	0.88	2.15	3.025 (5)	178.9
O1w—H1w1···O1	0.84	2.05	2.88 (2)	168.9
O2w—H2w1···O2	0.84	2.34	3.151 (19)	161.0

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

Acknowledgements

RJK thanks the University Grants Commission (India) for a Junior Research Fellowship. We thank the Sophisticated Analytical Instruments Facility, Cochin University of S & T, for the diffraction measurements. We also thank the Ministry of Higher Education of Malaysia (grant No. UM.C/HIR/MOHE/SC/12) for supporting this study.

References

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