Crystal structure of {6,6′-dihy­droxy-2,2′-[imino­bis­(propane-1,3-diyl­nitrilo­methanylyl­idene)]diphenolato-κ5O1,N,N′,N′′,O1′}copper(II)

Noor, S.; Kumar, S.; Sabir, S.; Seidel, R.W.; Goddard, R.

doi:10.1107/S2056989015019684

metal-organic compounds

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ISSN: 2056-9890

Volume 71| Part 11| November 2015| Pages m203-m204

https://doi.org/10.1107/S2056989015019684

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Crystal structure of {6,6′-dihydroxy-2,2′-[iminobis(propane-1,3-diylnitrilomethanylylidene)]diphenolato-κ⁵O¹,N,N′,N′′,O^1′}copper(II)

Shabana Noor,^a ^* Sarvendra Kumar,^b ^* Suhail Sabir,^a Rüdiger W. Seidel ^c and Richard Goddard ^c

^aDepartment of Chemistry, Aligarh Muslim University, Aligarh 202 002, India, ^bFaculty of Pharmaceutical Science, Tokyo University of Science, Noda, Japan, and ^cMax-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz-1, 45470 Mülheim an der Ruhr, Germany
^*Correspondence e-mail: shabanachem0711@gmail.com, s.kumar@msn.com

Edited by H. Ishida, Okayama University, Japan (Received 4 October 2015; accepted 17 October 2015; online 24 October 2015)

The title compound, [Cu(C₂₀H₂₃N₃O₄)], crystallizes in the space group Cc with two independent molecules in the asymmetric unit. The Cu^II atoms are each coordinated by the pentadentate Schiff base ligand in a distorted trigonal bipyramidal N₃O₂ geometry. The equatorial plane is formed by the two phenolic O atoms and the amine N atom, while the axial positions are occupied by the two imine N atoms. In the crystal, the two independent molecules are each connected into a column along the b axis through intermolecular O—H⋯O hydrogen bonds. The two independent columns are further linked through an N—H⋯O hydrogen bond, forming a double-column structure.

Keywords: crystal structure; Cu^II complex; Schiff bases; distorted trigonal bipyramidal coordination geometry; hydrogen bond.

CCDC reference: 1404639

1. Related literature

For characteristic properties of Schiff bases and their metal complexes, see: Averseng et al. (2001 ); Sanmartin et al. (2000 ); Brown & Wardeska (1982 ); Lan et al. (2009 ).

2. Experimental

2.1. Crystal data

[Cu(C₂₀H₂₃N₃O₄)]
M_r = 432.95
Monoclinic C c
a = 28.4747 (8) Å
b = 6.186 (5) Å
c = 22.925 (12) Å
β = 114.792 (11)°
V = 3666 (3) Å³
Z = 8
Mo Kα radiation
μ = 1.23 mm⁻¹
T = 100 K
0.07 × 0.06 × 0.02 mm

2.2. Data collection

Enraf–Nonius KappaCCD diffractometer
Absorption correction: Gaussian (SADABS; Bruker, 2006 ) T_min = 0.904, T_max = 0.974
26717 measured reflections
12062 independent reflections
11048 reflections with I > 2σ(I)
R_int = 0.050

2.3. Refinement

R[F² > 2σ(F²)] = 0.070
wR(F²) = 0.182
S = 1.25
12062 reflections
510 parameters
8 restraints
H-atom parameters constrained
Δρ_max = 1.82 e Å⁻³
Δρ_min = −1.65 e Å⁻³
Absolute structure: Parsons & Flack (2004 ), 5103 Friedel pairs
Absolute structure parameter: 0.10 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3ⁱ	0.84	1.95	2.699 (8)	147
O4—H4A⋯O1ⁱⁱ	0.84	1.90	2.686 (8)	156
O6—H6⋯O7ⁱ	0.84	2.08	2.758 (8)	137
O6—H6⋯O8ⁱ	0.84	2.40	3.101 (8)	142
O8—H8⋯O5ⁱⁱ	0.84	2.05	2.806 (7)	149
N2—H2A⋯O6	1.00	2.36	3.163 (8)	137
Symmetry codes: (i) x, y+1, z; (ii) x, y-1, z.

Data collection: DATCOL (Bruker, 2006); cell refinement: EVALCCD (Duisenberg et al., 2003 ); data reduction: EVALCCD; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ); molecular graphics: DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: enCIFer (Allen et al., 2004 ).

Supporting information

CCDC reference: 1404639

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989015019684/is5426sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015019684/is5426Isup2.hkl

checkCIF report

Comment top

Schiff bases and their coordination compounds play an important role in metal coordination chemistry. A large number of Schiff bases and their metal complexes have been synthesized and extensively studied because they have some characteristic properties such as manifestations of novel structures, thermal stability, relevant biological properties, high synthesis flexibility and medicinal utility (Brown & Wardeska, 1982; Averseng et al., 2001; Sanmartin et al., 2000; Lan et al., 2009).

The title compound crystallizes in the non-centrosymmetric monoclinic space group Cc with two molecules in the asymmetric unit. Since the two independent molecules have a similar geometry, we restrict the following discussion to one molecule. The Schiff ligand coordinates the metal ions as a pentadentate [ONNNO] chelating ligand through the phenolic O atoms (O1 and O2) and one aminic (N2) and two iminic N atoms (N1 and N3). The equatorial plane of the trigonal bipyramidal geometry is formed by atoms N2, O1 and O3. The Cu1—N2 [2.226 (6) Å] bond is significantly longer than the other two Cu1—O1 [2.074 (5) Å] and Cu1—O3 [2.049 (5) Å]. The two axial bond lengths are almost equal [Cu1—N1 = 1.939 (6) and Cu1—N3 = 1.942 (6) Å]. Deviation from regular trigonal bipyramid is evident from the bond angles of N2—Cu1—O1 = 113.3 (2)°, N2—Cu1—O3 = 125.3 (2)° and O1—Cu1—O3 = 121.1 (2)°. The terminal OH groups of the ligands are uncoordinated.

Related literature top

For characteristic properties of Schiff bases and their metal complexes, see: Averseng et al. (2001); Sanmartin et al. (2000); Brown & Wardeska (1982); Lan et al. (2009).

Experimental top

To a stirred solution of the Schiff base H₄L (0.4 mmol, 0.148 mg) dissolved in (20 ml EtOH and 20 ml CH₃CN) were added Cu(OAc)_2.H₂O (0.4 mmol, 0.08 g) followed by Et₃N (0.12 mmol, 0.16 ml). The resulting mixture was refluxed for 5–6 h. The reaction mixture was filtered. Dark colored crystals were obtained after 2–5 days by slow diffusion of diethyl ether into the solution.

Structure description top

For characteristic properties of Schiff bases and their metal complexes, see: Averseng et al. (2001); Sanmartin et al. (2000); Brown & Wardeska (1982); Lan et al. (2009).

Computing details top

Data collection: DATCOL (Bruker, 2006); cell refinement: EVALCCD (Duisenberg et al., 2003); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: enCIFer (Allen et al., 2004).

Figures top

	Fig. 1. Asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by small spheres of arbitrary radii. Carbon-bound H atoms are omitted for clarity. The intermolecular N—H···O hydrogen bond is illustrated by a dashed line.
	Fig. 2. Intermolecular O—H···O hydrogen bonds between symmetry-related molecules along the crystallographic b axis.

{6,6'-Dihydroxy-2,2'-[iminobis(propane-1,3-diylnitrilomethanylylidene)]diphenolato-κ⁵O¹,N,N',N'',O^1'}copper(II) top

Crystal data top

[Cu(C₂₀H₂₃N₃O₄)]	F(000) = 1800
M_r = 432.95	D_x = 1.569 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 28.4747 (8) Å	Cell parameters from 32601 reflections
b = 6.186 (5) Å	θ = 2.9–33.1°
c = 22.925 (12) Å	µ = 1.23 mm⁻¹
β = 114.792 (11)°	T = 100 K
V = 3666 (3) Å³	Prism, grey
Z = 8	0.07 × 0.06 × 0.02 mm

Data collection top

Enraf–Nonius KappaCCD diffractometer	12062 independent reflections
Radiation source: 0.2 x 2mm² focus rotating anode	11048 reflections with I > 2σ(I)
Incoatec Helios focusing multilayer optics monochromator	R_int = 0.050
Detector resolution: 18.02 pixels mm^-1	θ_max = 33.1°, θ_min = 2.9°
φ and ω scans	h = −43→43
Absorption correction: gaussian (SADABS; Bruker, 2006)	k = −9→9
T_min = 0.904, T_max = 0.974	l = −35→34
26717 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.070	H-atom parameters constrained
wR(F²) = 0.182	w = 1/[σ²(F_o²) + 45.2966P] where P = (F_o² + 2F_c²)/3
S = 1.25	(Δ/σ)_max < 0.001
12062 reflections	Δρ_max = 1.82 e Å⁻³
510 parameters	Δρ_min = −1.65 e Å⁻³
8 restraints	Absolute structure: Parsons & Flack (2004), 5103 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.10 (2)

Crystal data top

[Cu(C₂₀H₂₃N₃O₄)]	V = 3666 (3) Å³
M_r = 432.95	Z = 8
Monoclinic, Cc	Mo Kα radiation
a = 28.4747 (8) Å	µ = 1.23 mm⁻¹
b = 6.186 (5) Å	T = 100 K
c = 22.925 (12) Å	0.07 × 0.06 × 0.02 mm
β = 114.792 (11)°

Data collection top

Enraf–Nonius KappaCCD diffractometer	12062 independent reflections
Absorption correction: gaussian (SADABS; Bruker, 2006)	11048 reflections with I > 2σ(I)
T_min = 0.904, T_max = 0.974	R_int = 0.050
26717 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.070	H-atom parameters constrained
wR(F²) = 0.182	w = 1/[σ²(F_o²) + 45.2966P] where P = (F_o² + 2F_c²)/3
S = 1.25	Δρ_max = 1.82 e Å⁻³
12062 reflections	Δρ_min = −1.65 e Å⁻³
510 parameters	Absolute structure: Parsons & Flack (2004), 5103 Friedel pairs
8 restraints	Absolute structure parameter: 0.10 (2)

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refined as a 2-component inversion twin.

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

	x	y	z	U_iso*/U_eq
Cu1	0.60730 (3)	0.75260 (14)	0.60326 (4)	0.01256 (14)
Cu2	0.38464 (3)	−0.00703 (14)	0.28880 (4)	0.01287 (15)
C1	0.6659 (2)	1.0247 (11)	0.7213 (3)	0.0136 (11)
C2	0.6982 (3)	1.2023 (12)	0.7533 (4)	0.0185 (14)
C3	0.7240 (3)	1.2116 (14)	0.8196 (4)	0.0229 (16)
H3	0.7456	1.3318	0.8393	0.027*
C4	0.7188 (3)	1.0482 (14)	0.8576 (4)	0.0237 (16)
H4	0.7372	1.0550	0.9030	0.028*
C5	0.6867 (3)	0.8753 (14)	0.8294 (3)	0.0208 (14)
H5	0.6823	0.7651	0.8556	0.025*
C6	0.6601 (2)	0.8606 (12)	0.7615 (3)	0.0156 (12)
C7	0.6284 (3)	0.6718 (12)	0.7375 (3)	0.0157 (12)
H7	0.6249	0.5783	0.7684	0.019*
C8	0.5699 (3)	0.4285 (12)	0.6616 (4)	0.0178 (12)
H8A	0.5804	0.3304	0.6991	0.021*
H8B	0.5723	0.3483	0.6256	0.021*
C9	0.5138 (3)	0.5056 (13)	0.6422 (4)	0.0206 (13)
H9A	0.4899	0.4049	0.6097	0.025*
H9B	0.5059	0.4997	0.6804	0.025*
C10	0.5038 (3)	0.7342 (13)	0.6150 (4)	0.0185 (13)
H10A	0.4662	0.7642	0.5977	0.022*
H10B	0.5217	0.8379	0.6503	0.022*
C11	0.5012 (3)	0.9798 (13)	0.5322 (4)	0.0229 (15)
H11A	0.5136	1.0962	0.5648	0.027*
H11B	0.4630	0.9777	0.5142	0.027*
C12	0.5178 (3)	1.0307 (13)	0.4787 (4)	0.0233 (15)
H12A	0.4982	1.1583	0.4548	0.028*
H12B	0.5083	0.9072	0.4485	0.028*
C13	0.5753 (3)	1.0757 (12)	0.5011 (4)	0.0200 (14)
H13A	0.5815	1.1339	0.4647	0.024*
H13B	0.5862	1.1867	0.5354	0.024*
C14	0.6344 (3)	0.8169 (12)	0.4967 (3)	0.0185 (13)
H14	0.6335	0.9055	0.4624	0.022*
C15	0.6668 (3)	0.6281 (13)	0.5102 (3)	0.0164 (12)
C16	0.6939 (3)	0.5967 (16)	0.4708 (3)	0.0237 (16)
H16	0.6918	0.7040	0.4402	0.028*
C17	0.7225 (3)	0.4177 (17)	0.4763 (4)	0.0278 (19)
H17	0.7401	0.3996	0.4493	0.033*
C18	0.7265 (3)	0.2608 (15)	0.5208 (4)	0.0247 (16)
H18	0.7463	0.1346	0.5238	0.030*
C19	0.7018 (3)	0.2845 (12)	0.5615 (4)	0.0177 (13)
C20	0.6714 (2)	0.4730 (11)	0.5577 (3)	0.0138 (11)
C21	0.3889 (2)	0.2648 (11)	0.3996 (3)	0.0133 (11)
C22	0.4043 (3)	0.4517 (12)	0.4402 (3)	0.0166 (12)
C23	0.3904 (3)	0.4786 (14)	0.4908 (4)	0.0211 (14)
H23	0.4004	0.6064	0.5160	0.025*
C24	0.3619 (3)	0.3216 (15)	0.5052 (4)	0.0236 (15)
H24	0.3533	0.3407	0.5407	0.028*
C25	0.3462 (3)	0.1381 (13)	0.4678 (4)	0.0204 (14)
H25	0.3267	0.0306	0.4775	0.024*
C26	0.3591 (2)	0.1099 (12)	0.4149 (4)	0.0151 (12)
C27	0.3376 (3)	−0.0816 (12)	0.3766 (4)	0.0172 (12)
H27	0.3175	−0.1721	0.3907	0.021*
C28	0.3169 (2)	−0.3457 (12)	0.2958 (4)	0.0190 (13)
H28A	0.3015	−0.4136	0.3228	0.023*
H28B	0.3429	−0.4468	0.2933	0.023*
C29	0.2746 (3)	−0.3076 (13)	0.2284 (5)	0.0253 (17)
H29A	0.2504	−0.1968	0.2309	0.030*
H29B	0.2548	−0.4433	0.2129	0.030*
C30	0.2949 (3)	−0.2340 (14)	0.1794 (4)	0.0264 (17)
H30A	0.3200	−0.3427	0.1781	0.032*
H30B	0.2657	−0.2303	0.1364	0.032*
C31	0.3389 (3)	0.0262 (13)	0.1427 (4)	0.0223 (15)
H31A	0.3102	0.0008	0.1000	0.027*
H31B	0.3669	−0.0770	0.1476	0.027*
C32	0.3589 (4)	0.2539 (14)	0.1445 (4)	0.0280 (17)
H32A	0.3293	0.3554	0.1305	0.034*
H32B	0.3746	0.2646	0.1133	0.034*
C33	0.3994 (3)	0.3251 (12)	0.2112 (4)	0.0178 (13)
H33A	0.4254	0.4203	0.2060	0.021*
H33B	0.3822	0.4078	0.2337	0.021*
C34	0.4716 (3)	0.0908 (11)	0.2587 (3)	0.0145 (11)
H34	0.4881	0.1910	0.2420	0.017*
C35	0.5015 (2)	−0.0938 (11)	0.2915 (3)	0.0125 (11)
C36	0.5534 (3)	−0.1017 (12)	0.2977 (3)	0.0161 (12)
H36	0.5660	0.0148	0.2814	0.019*
C37	0.5855 (3)	−0.2712 (13)	0.3264 (4)	0.0176 (13)
H37	0.6199	−0.2732	0.3300	0.021*
C38	0.5663 (3)	−0.4425 (12)	0.3503 (3)	0.0160 (12)
H38	0.5882	−0.5620	0.3701	0.019*
C39	0.5161 (2)	−0.4401 (10)	0.3453 (3)	0.0117 (10)
C40	0.4818 (2)	−0.2639 (10)	0.3173 (3)	0.0116 (10)
N1	0.6064 (2)	0.8803 (10)	0.5256 (3)	0.0152 (11)
N2	0.5213 (2)	0.7704 (10)	0.5638 (3)	0.0152 (10)
H2A	0.5066	0.6533	0.5311	0.018*
N3	0.6041 (2)	0.6173 (10)	0.6779 (3)	0.0140 (10)
N4	0.3424 (2)	−0.1445 (10)	0.3259 (3)	0.0147 (11)
N5	0.3203 (2)	−0.0198 (11)	0.1927 (3)	0.0196 (12)
H5A	0.2942	0.0922	0.1901	0.023*
N6	0.4254 (2)	0.1346 (10)	0.2496 (3)	0.0139 (10)
O1	0.64396 (19)	1.0198 (8)	0.6580 (2)	0.0154 (9)
O2	0.7072 (2)	1.3649 (9)	0.7190 (3)	0.0256 (13)
H2	0.6800	1.3917	0.6862	0.038*
O3	0.64872 (19)	0.4898 (8)	0.5970 (2)	0.0150 (9)
O4	0.7093 (2)	0.1270 (9)	0.6058 (3)	0.0232 (11)
H4A	0.6839	0.1226	0.6153	0.035*
O5	0.40226 (19)	0.2469 (8)	0.3519 (2)	0.0144 (8)
O6	0.4346 (2)	0.6078 (9)	0.4317 (3)	0.0203 (10)
H6	0.4406	0.5767	0.3998	0.030*
O7	0.43578 (18)	−0.2675 (8)	0.3168 (2)	0.0147 (9)
O8	0.5012 (2)	−0.6116 (9)	0.3707 (3)	0.0177 (10)
H8	0.4692	−0.6048	0.3601	0.027*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0175 (3)	0.0105 (3)	0.0090 (3)	−0.0002 (3)	0.0049 (2)	0.0018 (3)
Cu2	0.0123 (3)	0.0117 (3)	0.0148 (3)	−0.0012 (3)	0.0059 (2)	0.0003 (3)
C1	0.013 (2)	0.011 (3)	0.013 (3)	0.004 (2)	0.002 (2)	−0.002 (2)
C2	0.015 (3)	0.013 (3)	0.018 (3)	0.002 (2)	−0.003 (2)	−0.004 (2)
C3	0.016 (3)	0.025 (4)	0.021 (3)	0.006 (3)	0.001 (2)	−0.008 (3)
C4	0.024 (3)	0.031 (4)	0.011 (3)	0.008 (3)	0.002 (2)	−0.005 (3)
C5	0.019 (3)	0.029 (4)	0.011 (3)	0.008 (3)	0.003 (2)	0.001 (3)
C6	0.012 (3)	0.022 (3)	0.013 (3)	0.007 (2)	0.005 (2)	0.001 (2)
C7	0.017 (3)	0.019 (3)	0.014 (3)	0.004 (2)	0.010 (2)	0.004 (2)
C8	0.024 (3)	0.018 (3)	0.014 (3)	−0.002 (2)	0.010 (2)	0.001 (2)
C9	0.022 (3)	0.021 (3)	0.022 (3)	−0.006 (3)	0.012 (3)	−0.001 (3)
C10	0.017 (3)	0.018 (3)	0.021 (3)	−0.002 (2)	0.008 (2)	−0.004 (3)
C11	0.019 (3)	0.015 (3)	0.026 (4)	0.003 (3)	0.001 (3)	0.002 (3)
C12	0.023 (3)	0.019 (4)	0.016 (3)	0.000 (3)	−0.004 (2)	0.004 (3)
C13	0.023 (3)	0.015 (3)	0.018 (3)	−0.002 (2)	0.005 (3)	0.006 (3)
C14	0.023 (3)	0.017 (3)	0.009 (3)	−0.008 (2)	0.001 (2)	0.002 (2)
C15	0.014 (3)	0.026 (3)	0.008 (3)	−0.010 (2)	0.004 (2)	−0.003 (2)
C16	0.015 (3)	0.049 (5)	0.010 (3)	−0.009 (3)	0.007 (2)	−0.003 (3)
C17	0.015 (3)	0.052 (6)	0.016 (3)	−0.008 (3)	0.007 (2)	−0.014 (3)
C18	0.015 (3)	0.034 (4)	0.026 (4)	−0.006 (3)	0.008 (3)	−0.014 (3)
C19	0.013 (3)	0.017 (3)	0.023 (3)	−0.002 (2)	0.008 (2)	−0.006 (3)
C20	0.011 (2)	0.014 (3)	0.015 (3)	−0.003 (2)	0.005 (2)	−0.003 (2)
C21	0.012 (2)	0.013 (3)	0.014 (3)	0.002 (2)	0.004 (2)	0.001 (2)
C22	0.018 (3)	0.016 (3)	0.012 (3)	−0.004 (2)	0.003 (2)	0.000 (2)
C23	0.021 (3)	0.027 (4)	0.015 (3)	−0.007 (3)	0.007 (2)	−0.006 (3)
C24	0.020 (3)	0.036 (4)	0.016 (3)	−0.005 (3)	0.009 (3)	−0.003 (3)
C25	0.018 (3)	0.025 (4)	0.020 (3)	−0.004 (3)	0.010 (2)	0.002 (3)
C26	0.007 (2)	0.018 (3)	0.022 (3)	−0.001 (2)	0.008 (2)	0.002 (2)
C27	0.013 (3)	0.016 (3)	0.024 (3)	−0.003 (2)	0.009 (2)	0.000 (3)
C28	0.009 (2)	0.018 (3)	0.034 (4)	−0.005 (2)	0.013 (2)	−0.005 (3)
C29	0.010 (3)	0.021 (3)	0.042 (5)	−0.005 (2)	0.007 (3)	−0.013 (3)
C30	0.021 (3)	0.020 (4)	0.026 (4)	0.001 (3)	−0.002 (3)	−0.008 (3)
C31	0.028 (3)	0.021 (4)	0.012 (3)	0.007 (3)	0.002 (2)	−0.001 (3)
C32	0.041 (4)	0.023 (4)	0.016 (3)	0.011 (3)	0.007 (3)	0.006 (3)
C33	0.018 (3)	0.014 (3)	0.022 (3)	0.004 (2)	0.009 (3)	0.001 (2)
C34	0.016 (3)	0.013 (3)	0.017 (3)	0.000 (2)	0.008 (2)	0.002 (2)
C35	0.010 (2)	0.016 (3)	0.015 (3)	−0.004 (2)	0.008 (2)	−0.002 (2)
C36	0.015 (3)	0.019 (3)	0.017 (3)	−0.005 (2)	0.010 (2)	−0.005 (2)
C37	0.014 (3)	0.022 (3)	0.019 (3)	−0.001 (2)	0.008 (2)	−0.004 (3)
C38	0.015 (3)	0.017 (3)	0.015 (3)	0.003 (2)	0.004 (2)	−0.002 (2)
C39	0.009 (2)	0.010 (2)	0.012 (3)	−0.0016 (18)	0.0006 (19)	−0.002 (2)
C40	0.014 (2)	0.009 (2)	0.010 (2)	0.001 (2)	0.0035 (19)	−0.001 (2)
N1	0.018 (2)	0.015 (3)	0.011 (2)	−0.004 (2)	0.0035 (19)	0.003 (2)
N2	0.018 (2)	0.011 (2)	0.014 (2)	−0.0024 (19)	0.0043 (19)	−0.001 (2)
N3	0.014 (2)	0.017 (3)	0.011 (2)	0.001 (2)	0.0052 (19)	0.005 (2)
N4	0.010 (2)	0.015 (3)	0.021 (3)	−0.0021 (19)	0.009 (2)	−0.001 (2)
N5	0.017 (2)	0.015 (3)	0.017 (3)	0.006 (2)	−0.002 (2)	−0.004 (2)
N6	0.014 (2)	0.014 (3)	0.013 (2)	0.0000 (19)	0.0049 (19)	0.002 (2)
O1	0.022 (2)	0.010 (2)	0.0090 (19)	−0.0003 (17)	0.0011 (16)	0.0011 (16)
O2	0.025 (3)	0.012 (2)	0.022 (3)	−0.001 (2)	−0.007 (2)	0.000 (2)
O3	0.020 (2)	0.012 (2)	0.015 (2)	−0.0001 (18)	0.0093 (17)	0.0026 (17)
O4	0.021 (2)	0.015 (2)	0.036 (3)	0.0031 (19)	0.014 (2)	0.001 (2)
O5	0.019 (2)	0.013 (2)	0.013 (2)	−0.0039 (17)	0.0079 (16)	−0.0012 (17)
O6	0.025 (2)	0.020 (3)	0.017 (2)	−0.009 (2)	0.009 (2)	−0.004 (2)
O7	0.0134 (19)	0.013 (2)	0.018 (2)	−0.0013 (16)	0.0073 (16)	0.0032 (18)
O8	0.015 (2)	0.014 (2)	0.021 (3)	0.0033 (17)	0.0051 (18)	0.0062 (19)

Geometric parameters (Å, º) top

Cu1—N1	1.939 (6)	C19—C20	1.433 (10)
Cu1—N3	1.942 (6)	C20—O3	1.314 (8)
Cu1—O3	2.049 (5)	C21—O5	1.305 (8)
Cu1—O1	2.074 (5)	C21—C26	1.417 (9)
Cu1—N2	2.228 (6)	C21—C22	1.434 (10)
Cu2—N4	1.936 (6)	C22—O6	1.362 (9)
Cu2—N6	1.948 (6)	C22—C23	1.384 (11)
Cu2—O5	2.050 (5)	C23—C24	1.392 (11)
Cu2—O7	2.084 (5)	C23—H23	0.9500
Cu2—N5	2.198 (6)	C24—C25	1.379 (12)
C1—O1	1.316 (8)	C24—H24	0.9500
C1—C2	1.423 (10)	C25—C26	1.419 (10)
C1—C6	1.428 (10)	C25—H25	0.9500
C2—O2	1.366 (10)	C26—C27	1.449 (10)
C2—C3	1.385 (11)	C27—N4	1.286 (10)
C3—C4	1.383 (13)	C27—H27	0.9500
C3—H3	0.9500	C28—N4	1.460 (9)
C4—C5	1.379 (12)	C28—C29	1.527 (12)
C4—H4	0.9500	C28—H28A	0.9900
C5—C6	1.420 (10)	C28—H28B	0.9900
C5—H5	0.9500	C29—C30	1.533 (14)
C6—C7	1.437 (11)	C29—H29A	0.9900
C7—N3	1.290 (9)	C29—H29B	0.9900
C7—H7	0.9500	C30—N5	1.479 (11)
C8—N3	1.466 (10)	C30—H30A	0.9900
C8—C9	1.542 (11)	C30—H30B	0.9900
C8—H8A	0.9900	C31—N5	1.477 (11)
C8—H8B	0.9900	C31—C32	1.514 (13)
C9—C10	1.524 (11)	C31—H31A	0.9900
C9—H9A	0.9900	C31—H31B	0.9900
C9—H9B	0.9900	C32—C33	1.543 (11)
C10—N2	1.471 (10)	C32—H32A	0.9900
C10—H10A	0.9900	C32—H32B	0.9900
C10—H10B	0.9900	C33—N6	1.471 (9)
C11—N2	1.478 (10)	C33—H33A	0.9900
C11—C12	1.521 (13)	C33—H33B	0.9900
C11—H11A	0.9900	C34—N6	1.274 (8)
C11—H11B	0.9900	C34—C35	1.434 (10)
C12—C13	1.522 (11)	C34—H34	0.9500
C12—H12A	0.9900	C35—C36	1.425 (9)
C12—H12B	0.9900	C35—C40	1.431 (9)
C13—N1	1.464 (10)	C36—C37	1.365 (11)
C13—H13A	0.9900	C36—H36	0.9500
C13—H13B	0.9900	C37—C38	1.403 (11)
C14—N1	1.294 (10)	C37—H37	0.9500
C14—C15	1.438 (11)	C38—C39	1.386 (9)
C14—H14	0.9500	C38—H38	0.9500
C15—C20	1.415 (10)	C39—O8	1.361 (8)
C15—C16	1.428 (10)	C39—C40	1.425 (9)
C16—C17	1.349 (14)	C40—O7	1.306 (8)
C16—H16	0.9500	N2—H2A	1.0000
C17—C18	1.379 (14)	N5—H5A	1.0000
C17—H17	0.9500	O2—H2	0.8400
C18—C19	1.391 (11)	O4—H4A	0.8400
C18—H18	0.9500	O6—H6	0.8400
C19—O4	1.357 (10)	O8—H8	0.8400

N1—Cu1—N3	176.5 (3)	C22—C23—C24	121.1 (7)
N1—Cu1—O3	92.6 (2)	C22—C23—H23	119.5
N3—Cu1—O3	87.8 (2)	C24—C23—H23	119.5
N1—Cu1—O1	92.4 (2)	C25—C24—C23	119.7 (7)
N3—Cu1—O1	90.4 (2)	C25—C24—H24	120.1
O3—Cu1—O1	121.1 (2)	C23—C24—H24	120.1
N1—Cu1—N2	91.0 (2)	C24—C25—C26	120.0 (7)
N3—Cu1—N2	85.9 (2)	C24—C25—H25	120.0
O3—Cu1—N2	125.3 (2)	C26—C25—H25	120.0
O1—Cu1—N2	113.3 (2)	C21—C26—C25	121.7 (7)
N4—Cu2—N6	178.4 (3)	C21—C26—C27	123.2 (7)
N4—Cu2—O5	92.3 (2)	C25—C26—C27	115.1 (6)
N6—Cu2—O5	87.9 (2)	N4—C27—C26	128.1 (7)
N4—Cu2—O7	90.4 (2)	N4—C27—H27	115.9
N6—Cu2—O7	90.9 (2)	C26—C27—H27	115.9
O5—Cu2—O7	116.2 (2)	N4—C28—C29	111.8 (6)
N4—Cu2—N5	90.8 (3)	N4—C28—H28A	109.3
N6—Cu2—N5	87.7 (3)	C29—C28—H28A	109.3
O5—Cu2—N5	126.1 (2)	N4—C28—H28B	109.3
O7—Cu2—N5	117.5 (2)	C29—C28—H28B	109.3
O1—C1—C2	119.5 (7)	H28A—C28—H28B	107.9
O1—C1—C6	124.4 (6)	C28—C29—C30	114.1 (6)
C2—C1—C6	116.1 (6)	C28—C29—H29A	108.7
O2—C2—C3	117.4 (7)	C30—C29—H29A	108.7
O2—C2—C1	120.5 (6)	C28—C29—H29B	108.7
C3—C2—C1	122.0 (8)	C30—C29—H29B	108.7
C4—C3—C2	120.9 (7)	H29A—C29—H29B	107.6
C4—C3—H3	119.5	N5—C30—C29	114.7 (7)
C2—C3—H3	119.5	N5—C30—H30A	108.6
C5—C4—C3	119.8 (7)	C29—C30—H30A	108.6
C5—C4—H4	120.1	N5—C30—H30B	108.6
C3—C4—H4	120.1	C29—C30—H30B	108.6
C4—C5—C6	120.5 (8)	H30A—C30—H30B	107.6
C4—C5—H5	119.7	N5—C31—C32	114.3 (7)
C6—C5—H5	119.7	N5—C31—H31A	108.7
C5—C6—C1	120.6 (7)	C32—C31—H31A	108.7
C5—C6—C7	115.7 (7)	N5—C31—H31B	108.7
C1—C6—C7	123.7 (6)	C32—C31—H31B	108.7
N3—C7—C6	126.1 (7)	H31A—C31—H31B	107.6
N3—C7—H7	116.9	C31—C32—C33	114.1 (7)
C6—C7—H7	116.9	C31—C32—H32A	108.7
N3—C8—C9	109.0 (6)	C33—C32—H32A	108.7
N3—C8—H8A	109.9	C31—C32—H32B	108.7
C9—C8—H8A	109.9	C33—C32—H32B	108.7
N3—C8—H8B	109.9	H32A—C32—H32B	107.6
C9—C8—H8B	109.9	N6—C33—C32	110.1 (6)
H8A—C8—H8B	108.3	N6—C33—H33A	109.6
C10—C9—C8	113.4 (6)	C32—C33—H33A	109.6
C10—C9—H9A	108.9	N6—C33—H33B	109.6
C8—C9—H9A	108.9	C32—C33—H33B	109.6
C10—C9—H9B	108.9	H33A—C33—H33B	108.2
C8—C9—H9B	108.9	N6—C34—C35	126.8 (6)
H9A—C9—H9B	107.7	N6—C34—H34	116.6
N2—C10—C9	113.6 (6)	C35—C34—H34	116.6
N2—C10—H10A	108.8	C36—C35—C40	120.2 (6)
C9—C10—H10A	108.8	C36—C35—C34	116.1 (6)
N2—C10—H10B	108.8	C40—C35—C34	123.6 (6)
C9—C10—H10B	108.8	C37—C36—C35	122.1 (7)
H10A—C10—H10B	107.7	C37—C36—H36	118.9
N2—C11—C12	112.9 (7)	C35—C36—H36	118.9
N2—C11—H11A	109.0	C36—C37—C38	118.5 (6)
C12—C11—H11A	109.0	C36—C37—H37	120.8
N2—C11—H11B	109.0	C38—C37—H37	120.8
C12—C11—H11B	109.0	C39—C38—C37	121.0 (6)
H11A—C11—H11B	107.8	C39—C38—H38	119.5
C11—C12—C13	114.9 (6)	C37—C38—H38	119.5
C11—C12—H12A	108.6	O8—C39—C38	117.0 (6)
C13—C12—H12A	108.6	O8—C39—C40	120.7 (6)
C11—C12—H12B	108.6	C38—C39—C40	122.3 (6)
C13—C12—H12B	108.6	O7—C40—C39	119.2 (6)
H12A—C12—H12B	107.5	O7—C40—C35	125.1 (6)
N1—C13—C12	111.7 (6)	C39—C40—C35	115.8 (6)
N1—C13—H13A	109.3	C14—N1—C13	117.3 (6)
C12—C13—H13A	109.3	C14—N1—Cu1	125.0 (5)
N1—C13—H13B	109.3	C13—N1—Cu1	117.5 (5)
C12—C13—H13B	109.3	C10—N2—C11	109.4 (6)
H13A—C13—H13B	107.9	C10—N2—Cu1	110.6 (4)
N1—C14—C15	127.7 (7)	C11—N2—Cu1	112.1 (4)
N1—C14—H14	116.1	C10—N2—H2A	108.2
C15—C14—H14	116.1	C11—N2—H2A	108.2
C20—C15—C16	119.7 (7)	Cu1—N2—H2A	108.2
C20—C15—C14	124.1 (7)	C7—N3—C8	118.8 (6)
C16—C15—C14	116.2 (7)	C7—N3—Cu1	128.2 (5)
C17—C16—C15	121.3 (8)	C8—N3—Cu1	113.0 (5)
C17—C16—H16	119.4	C27—N4—C28	117.7 (6)
C15—C16—H16	119.4	C27—N4—Cu2	125.8 (5)
C16—C17—C18	120.3 (7)	C28—N4—Cu2	116.4 (5)
C16—C17—H17	119.8	C31—N5—C30	108.4 (6)
C18—C17—H17	119.8	C31—N5—Cu2	110.6 (4)
C17—C18—C19	121.0 (8)	C30—N5—Cu2	111.6 (5)
C17—C18—H18	119.5	C31—N5—H5A	108.7
C19—C18—H18	119.5	C30—N5—H5A	108.7
O4—C19—C18	117.3 (7)	Cu2—N5—H5A	108.7
O4—C19—C20	122.1 (7)	C34—N6—C33	119.6 (6)
C18—C19—C20	120.5 (8)	C34—N6—Cu2	127.1 (5)
O3—C20—C15	124.1 (6)	C33—N6—Cu2	113.0 (4)
O3—C20—C19	118.7 (6)	C1—O1—Cu1	124.8 (4)
C15—C20—C19	117.2 (7)	C2—O2—H2	109.5
O5—C21—C26	124.4 (6)	C20—O3—Cu1	125.0 (4)
O5—C21—C22	119.7 (6)	C19—O4—H4A	109.5
C26—C21—C22	115.9 (6)	C21—O5—Cu2	125.8 (4)
O6—C22—C23	117.1 (7)	C22—O6—H6	109.5
O6—C22—C21	121.3 (7)	C40—O7—Cu2	123.9 (4)
C23—C22—C21	121.6 (7)	C39—O8—H8	109.5

O1—C1—C2—O2	−1.2 (10)	N4—C28—C29—C30	67.5 (8)
C6—C1—C2—O2	178.3 (6)	C28—C29—C30—N5	−65.0 (9)
O1—C1—C2—C3	−177.2 (7)	N5—C31—C32—C33	51.3 (9)
C6—C1—C2—C3	2.4 (10)	C31—C32—C33—N6	24.4 (10)
O2—C2—C3—C4	−177.0 (7)	N6—C34—C35—C36	−177.5 (7)
C1—C2—C3—C4	−0.9 (12)	N6—C34—C35—C40	2.5 (12)
C2—C3—C4—C5	−1.3 (12)	C40—C35—C36—C37	1.8 (10)
C3—C4—C5—C6	1.8 (11)	C34—C35—C36—C37	−178.2 (7)
C4—C5—C6—C1	−0.3 (10)	C35—C36—C37—C38	0.1 (11)
C4—C5—C6—C7	179.0 (7)	C36—C37—C38—C39	−0.3 (11)
O1—C1—C6—C5	177.7 (6)	C37—C38—C39—O8	−179.1 (6)
C2—C1—C6—C5	−1.8 (9)	C37—C38—C39—C40	−1.4 (10)
O1—C1—C6—C7	−1.5 (10)	O8—C39—C40—O7	0.8 (9)
C2—C1—C6—C7	179.0 (6)	C38—C39—C40—O7	−176.9 (6)
C5—C6—C7—N3	−174.3 (7)	O8—C39—C40—C35	−179.4 (6)
C1—C6—C7—N3	4.9 (11)	C38—C39—C40—C35	3.0 (9)
N3—C8—C9—C10	26.9 (8)	C36—C35—C40—O7	176.7 (6)
C8—C9—C10—N2	50.2 (8)	C34—C35—C40—O7	−3.4 (11)
N2—C11—C12—C13	−68.3 (9)	C36—C35—C40—C39	−3.2 (9)
C11—C12—C13—N1	69.7 (9)	C34—C35—C40—C39	176.8 (6)
N1—C14—C15—C20	2.6 (11)	C15—C14—N1—C13	−178.0 (6)
N1—C14—C15—C16	−179.7 (7)	C15—C14—N1—Cu1	8.0 (10)
C20—C15—C16—C17	2.5 (10)	C12—C13—N1—C14	119.7 (7)
C14—C15—C16—C17	−175.4 (7)	C12—C13—N1—Cu1	−65.8 (7)
C15—C16—C17—C18	−0.5 (11)	C9—C10—N2—C11	169.2 (6)
C16—C17—C18—C19	−0.9 (11)	C9—C10—N2—Cu1	−66.8 (6)
C17—C18—C19—O4	−177.3 (7)	C12—C11—N2—C10	179.7 (6)
C17—C18—C19—C20	0.3 (11)	C12—C11—N2—Cu1	56.7 (7)
C16—C15—C20—O3	178.6 (6)	C6—C7—N3—C8	−174.8 (6)
C14—C15—C20—O3	−3.7 (10)	C6—C7—N3—Cu1	6.3 (10)
C16—C15—C20—C19	−2.9 (9)	C9—C8—N3—C7	96.8 (7)
C14—C15—C20—C19	174.7 (6)	C9—C8—N3—Cu1	−84.1 (6)
O4—C19—C20—O3	−2.4 (10)	C26—C27—N4—C28	179.8 (7)
C18—C19—C20—O3	−179.8 (6)	C26—C27—N4—Cu2	4.6 (11)
O4—C19—C20—C15	179.0 (6)	C29—C28—N4—C27	115.9 (8)
C18—C19—C20—C15	1.6 (10)	C29—C28—N4—Cu2	−68.4 (6)
O5—C21—C22—O6	−2.7 (10)	C32—C31—N5—C30	171.7 (6)
C26—C21—C22—O6	177.6 (6)	C32—C31—N5—Cu2	−65.7 (7)
O5—C21—C22—C23	179.1 (7)	C29—C30—N5—C31	178.6 (6)
C26—C21—C22—C23	−0.7 (10)	C29—C30—N5—Cu2	56.5 (7)
O6—C22—C23—C24	−176.5 (7)	C35—C34—N6—C33	−176.2 (7)
C21—C22—C23—C24	1.8 (12)	C35—C34—N6—Cu2	10.9 (11)
C22—C23—C24—C25	−1.5 (12)	C32—C33—N6—C34	105.9 (8)
C23—C24—C25—C26	0.1 (12)	C32—C33—N6—Cu2	−80.2 (7)
O5—C21—C26—C25	179.5 (6)	C2—C1—O1—Cu1	168.1 (5)
C22—C21—C26—C25	−0.8 (9)	C6—C1—O1—Cu1	−11.4 (9)
O5—C21—C26—C27	−3.6 (10)	C15—C20—O3—Cu1	−5.4 (9)
C22—C21—C26—C27	176.1 (6)	C19—C20—O3—Cu1	176.2 (4)
C24—C25—C26—C21	1.1 (11)	C26—C21—O5—Cu2	−0.7 (9)
C24—C25—C26—C27	−176.1 (7)	C22—C21—O5—Cu2	179.5 (5)
C21—C26—C27—N4	1.7 (12)	C39—C40—O7—Cu2	171.7 (4)
C25—C26—C27—N4	178.8 (7)	C35—C40—O7—Cu2	−8.1 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3ⁱ	0.84	1.95	2.699 (8)	147
O4—H4A···O1ⁱⁱ	0.84	1.90	2.686 (8)	156
O6—H6···O7ⁱ	0.84	2.08	2.758 (8)	137
O6—H6···O8ⁱ	0.84	2.40	3.101 (8)	142
O8—H8···O5ⁱⁱ	0.84	2.05	2.806 (7)	149
N2—H2A···O6	1.00	2.36	3.163 (8)	137

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3ⁱ	0.84	1.95	2.699 (8)	147
O4—H4A···O1ⁱⁱ	0.84	1.90	2.686 (8)	156
O6—H6···O7ⁱ	0.84	2.08	2.758 (8)	137
O6—H6···O8ⁱ	0.84	2.40	3.101 (8)	142
O8—H8···O5ⁱⁱ	0.84	2.05	2.806 (7)	149
N2—H2A···O6	1.00	2.36	3.163 (8)	137

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

Acknowledgements

This work was supported by grants from Department of Science and Technology, SERB, New Delhi, India (SERB/F/815/2014-15). SN thanks the Chairman of the Department of Chemistry, Aligarh Muslim University, India, who facilitated this research.

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