Dichlorido[μ-10,21-dimethyl-2,7,13,18-tetra­phenyl-3,6,14,17-tetra­aza­tricyclo­[17.3.1.18,12]tetra­cosa-1(23),2,6,8,10,12(24),13,17,19,21-deca­ene-23,24-diolato]dicopper(II) ethanol hemisolvate dihydrate

Gupta, S.K.; Anjana, C.; Butcher, R.J.; Sen, N.

doi:10.1107/S1600536810042248

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 12| December 2010| Pages m1531-m1532

https://doi.org/10.1107/S1600536810042248

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Dichlorido[μ-10,21-dimethyl-2,7,13,18-tetraphenyl-3,6,14,17-tetraazatricyclo[17.3.1.1^8,12]tetracosa-1(23),2,6,8,10,12(24),13,17,19,21-decaene-23,24-diolato]dicopper(II) ethanol hemisolvate dihydrate

Sushil K. Gupta,^a Chanda Anjana,^a Ray J. Butcher ^b ^* and Neha Sen ^a

^aSchool of Studies in Chemistry, Jiwaji University, Gwalior 474 011, India, and ^bDepartment of Chemistry, Howard University, 525 College Street NW, Washington, DC 20059, USA
^*Correspondence e-mail: rbutcher99@yahoo.com

(Received 15 October 2010; accepted 18 October 2010; online 10 November 2010)

The dinuclear title complex, [Cu₂(C₄₆H₃₈N₄O₂)Cl₂]·0.5C₂H₅OH·2H₂O, is located on crystallographic inversion centres with two half-molecules in the asymmetric unit. The two Cu^II atoms are coordinated by a hexadentate dianionic ligand formed in situ from the condensation of two tridentate ligands by four imine N atoms and two bridging phenolate O atoms along with two Cl atoms at axial positions. The coordination geometry around the metal atoms is distorted square-pyramidal (τ = 0.185 and 0.199). The non-bonding Cu⋯Cu distances are 2.9556 (12) and 2.9506 (12) Å in the two dimers. The packing is stabilized through solvent-mediated intermolecular O—H⋯O and O—H⋯Cl hydrogen bonds. The diamine chain of one of the dimers is disordered over two positions in a 0.680 (5):0.320 (5) ratio.

Related literature

For general background to phenol-based Schiff base metal complexes with N,N,O donors, see: Generex & Barton (2010 ); Fenton et al. (2010 ); Reisner et al. (2008 ). For related phenol-based Schiff base complexes, see: Gupta et al. (2002 , 2007 , 2008 ). For a description of the geometry of pentacoordinated atoms, see: Addison et al. (1984 ).

Experimental

Crystal data

[Cu₂(C₄₆H₃₈N₄O₂)Cl₂]·0.5C₂H₆O·2H₂O
M_r = 935.85
Monoclinic, P 2₁ /n
a = 15.1983 (4) Å
b = 16.2680 (5) Å
c = 19.3344 (5) Å
β = 103.964 (2)°
V = 4639.1 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.08 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ) T_min = 0.738, T_max = 0.813
36333 measured reflections
6669 independent reflections
4664 reflections with I > 2σ(I)
R_int = 0.054
θ_max = 23.3°

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.137
S = 1.05
6669 reflections
575 parameters
13 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H4⋯O2W	0.82	2.20	2.96 (2)	154
O1W—H1W1⋯Cl1ⁱ	0.82 (2)	2.54 (2)	3.355 (4)	171 (4)
O1W—H1W2⋯Cl2	0.82 (2)	2.56 (2)	3.374 (4)	174 (3)
O2W—H2W1⋯O3W	0.85	1.86	2.71 (3)	179
O2W—H2W2⋯O3	0.97	2.27	2.96 (2)	127
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810042248/bt5381sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810042248/bt5381Isup2.hkl

checkCIF report

Comment top

Phenol-based Schiff base metal complexes with NNO donors have recently drawn more attention due to their adjustable coordination ability and interesting application in bio-inorganic and therapeutic chemistry (Generex & Barton, 2010; Fenton et al., 2010; Reisner et al., 2008). As part of our investigations on the phenol based Schiff base complexes (Gupta et al., 2002, 2007, 2008), we herein report the synthesis and crystal structure of a dimeric copper (II) complex. The molecular structure of the complex is shown in Fig.1. The dimeric complex consists of [Cu₂Cl₂{(µ-O)C₆H₂(Me-4)PhCN(CH ₂)₂NCPh}₂].2H₂O. 0.5 EtOH wherein the copper (II) ion is five- coordinated with four imine N, two bridging phenolato O and two Cl at axial positions, giving a square pyramidal geometry [τ = 0.185 and 0.199 for Cu1 and Cu2, respectively (Addison et al., 1984)]. The copper atoms are displaced from the basal planes by 0.430 (1) and 0.436 (1) Å, respectively. The average Cu—Cl, Cu—O and Cu—N bond lengths are 2.428 (2), 1.931 (13) and 1.927 (4) A, respectively. the non-bonding Cu···..Cu distances are 2.9556 (12) and 2.9506 (12) Å. The packing is stabilized through solvent mediated intermolecular hydrogen bonds.

Related literature top

For general background to phenol-based Schiff base metal complexes with N,N,O donors, see: Generex & Barton (2010); Fenton et al., (2010); Reisner et al. (2008). For related phenol-based Schiff base complexes, see: Gupta et al. (2002, 2007, 2008). For a description of the geometry of pentacoordinated atoms, see: Addison et al. (1984).

Experimental top

Copper (II) chloride dihydrate (0.086 g, 0.51 mmol) dissolved in dry ethanol (20 ml) was added dropwise to an ethanol solution of tridentate ligand, 2-{N-(2-aminoethyl)benzimidoyl}-6-benzoyl-4-methylphenol (aebmpH) (0.365 g, 1.02 mmol) and heated to reflux. The clear solution so obtained was allowed to cool and dark green crystals suitable for X-ray diffraction were obtained in 40° yield.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2 and SAINT-Plus (Bruker, 2004); data reduction: SAINT and XPREP (Bruker, 2004); 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: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with the atom numbering scheme. Displacement ellipsoides are drawn at 50° probability level. Only one of the molecule in the asymmetric unit is shown for clarity. Solvent molecules are omitted.
	Fig. 2. The packing diagram of the molecules in the unit cell viewed down the a axis. The intermolecular H-bonding interactions are shown with dashed lines.

Dichlorido[µ-10,21-dimethyl-2,7,13,18-tetraphenyl-3,6,14,17- tetraazatricyclo[17.3.1.1^8,12]tetracosa-1(23),2,6,8,10,12(24),13,17,19,21- decaene-23,24-diolato]dicopper(II) ethanol hemisolvate dihydrate top

Crystal data top

[Cu₂(C₄₆H₃₈N₄O₂)Cl₂]·0.5C₂H₆O·2H₂O	F(000) = 1932
M_r = 935.85	D_x = 1.340 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6395 reflections
a = 15.1983 (4) Å	θ = 2.1–22.5°
b = 16.2680 (5) Å	µ = 1.08 mm⁻¹
c = 19.3344 (5) Å	T = 293 K
β = 103.964 (2)°	Needle, brown
V = 4639.1 (2) Å³	0.30 × 0.20 × 0.20 mm
Z = 2

Data collection top

Bruker Kappa APEXII CCD diffractometer	6669 independent reflections
Radiation source: fine-focus sealed tube	4664 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
ω and φ scan	θ_max = 23.3°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −16→16
T_min = 0.738, T_max = 0.813	k = −18→18
36333 measured reflections	l = −21→21

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0717P)² + 3.5141P] where P = (F_o² + 2F_c²)/3
6669 reflections	(Δ/σ)_max = 0.001
575 parameters	Δρ_max = 0.51 e Å⁻³
13 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

[Cu₂(C₄₆H₃₈N₄O₂)Cl₂]·0.5C₂H₆O·2H₂O	V = 4639.1 (2) Å³
M_r = 935.85	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 15.1983 (4) Å	µ = 1.08 mm⁻¹
b = 16.2680 (5) Å	T = 293 K
c = 19.3344 (5) Å	0.30 × 0.20 × 0.20 mm
β = 103.964 (2)°

Data collection top

Bruker Kappa APEXII CCD diffractometer	6669 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1999)	4664 reflections with I > 2σ(I)
T_min = 0.738, T_max = 0.813	R_int = 0.054
36333 measured reflections	θ_max = 23.3°

Refinement top

R[F² > 2σ(F²)] = 0.044	13 restraints
wR(F²) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.51 e Å⁻³
6669 reflections	Δρ_min = −0.34 e Å⁻³
575 parameters

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. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Cu1	1.09084 (3)	0.47211 (2)	1.039422 (19)	0.04010 (11)
Cu2	0.52512 (3)	0.47246 (3)	0.57491 (2)	0.04566 (12)
Cl1	1.17520 (9)	0.59912 (7)	1.06780 (7)	0.0984 (4)
Cl2	0.53483 (9)	0.59915 (7)	0.64348 (7)	0.0943 (4)
O1	0.97493 (14)	0.50362 (14)	1.05664 (11)	0.0473 (6)
O2	0.58164 (14)	0.50367 (15)	0.49873 (11)	0.0519 (7)
O3	0.5295 (5)	0.5394 (8)	0.7957 (6)	0.283 (7)	0.50
H4	0.5485	0.5341	0.8389	0.425*	0.50
O1W	0.5206 (3)	0.7508 (3)	0.5223 (2)	0.1308 (15)
H1W1	0.5577 (17)	0.7868 (13)	0.538 (2)	0.196*
H1W2	0.526 (3)	0.7165 (15)	0.5540 (15)	0.196*
O2W	0.6367 (7)	0.4809 (11)	0.9357 (13)	0.370 (13)	0.50
H2W1	0.6163	0.4422	0.9569	0.555*	0.50
H2W2	0.6163	0.4649	0.8861	0.555*	0.50
O3W	0.5749 (10)	0.3569 (14)	1.0049 (11)	0.443 (12)	0.50
H3W1	0.5202	0.3669	0.9609	0.665*	0.50
H3W2	0.5644	0.3602	1.0442	0.665*	0.50
N1	1.12269 (17)	0.41850 (16)	1.13139 (13)	0.0396 (7)
N2	1.16146 (18)	0.39153 (17)	1.00425 (13)	0.0458 (8)
N3	0.63697 (17)	0.41998 (16)	0.62346 (13)	0.0435 (7)
N4	0.46031 (18)	0.39075 (18)	0.61374 (15)	0.0554 (9)
C1	1.04385 (19)	0.48096 (18)	0.88252 (15)	0.0341 (8)
C2	1.1145 (2)	0.42521 (19)	0.87872 (15)	0.0369 (8)
C3	1.1337 (2)	0.4126 (2)	0.81264 (16)	0.0443 (9)
H3	1.1805	0.3768	0.8101	0.053*
C4	1.0874 (2)	0.4498 (2)	0.75130 (16)	0.0446 (9)
C5	1.0176 (2)	0.50157 (19)	0.75585 (16)	0.0392 (8)
H5	0.9847	0.5265	0.7143	0.047*
C6	0.99364 (19)	0.51866 (18)	0.81944 (15)	0.0350 (8)
C7	0.9157 (2)	0.57477 (18)	0.81663 (15)	0.0362 (8)
C8	0.8847 (2)	0.62559 (19)	0.75101 (15)	0.0400 (9)
C9	0.9455 (3)	0.6785 (2)	0.73011 (16)	0.0494 (10)
H9	1.0064	0.6783	0.7543	0.059*
C10	0.9154 (3)	0.7317 (2)	0.67306 (19)	0.0651 (12)
H10	0.9557	0.7680	0.6599	0.078*
C11	0.8266 (3)	0.7308 (2)	0.63641 (19)	0.0720 (13)
H11	0.8068	0.7667	0.5984	0.086*
C12	0.7674 (3)	0.6784 (3)	0.65477 (19)	0.0695 (13)
H12	0.7073	0.6778	0.6288	0.083*
C13	0.7953 (2)	0.6251 (2)	0.71241 (17)	0.0513 (10)
H13	0.7540	0.5893	0.7248	0.062*
C14	1.2011 (2)	0.3657 (2)	1.13193 (18)	0.0608 (11)
H14A	1.2563	0.3972	1.1486	0.073*
H14B	1.2020	0.3207	1.1650	0.073*
C15	1.1991 (3)	0.3324 (3)	1.06185 (18)	0.0741 (13)
H15A	1.1627	0.2828	1.0546	0.089*
H15B	1.2602	0.3177	1.0596	0.089*
C16	1.1640 (2)	0.3759 (2)	0.93993 (16)	0.0393 (8)
C17	1.2154 (2)	0.3023 (2)	0.92484 (16)	0.0430 (9)
C18	1.1723 (3)	0.2301 (2)	0.90520 (18)	0.0561 (10)
H18	1.1095	0.2274	0.8970	0.067*
C19	1.2206 (3)	0.1607 (3)	0.8974 (2)	0.0750 (13)
H19	1.1905	0.1112	0.8847	0.090*
C20	1.3116 (3)	0.1643 (3)	0.9080 (2)	0.0838 (14)
H20	1.3441	0.1172	0.9029	0.101*
C21	1.3553 (3)	0.2362 (3)	0.9260 (2)	0.0807 (14)
H21	1.4179	0.2387	0.9323	0.097*
C22	1.3082 (2)	0.3061 (3)	0.93507 (19)	0.0614 (11)
H22	1.3388	0.3554	0.9480	0.074*
C23	1.1097 (3)	0.4335 (3)	0.68094 (18)	0.0719 (12)
H23A	1.1262	0.3769	0.6785	0.108*
H23B	1.1593	0.4679	0.6764	0.108*
H23C	1.0576	0.4455	0.6430	0.108*
C24	0.6667 (2)	0.52384 (19)	0.50571 (15)	0.0368 (8)
C25	0.3096 (2)	0.41742 (19)	0.54154 (15)	0.0372 (8)
C26	0.2183 (2)	0.39777 (19)	0.53150 (16)	0.0412 (9)
H26	0.2023	0.3592	0.5618	0.049*
C27	0.1505 (2)	0.4319 (2)	0.47948 (16)	0.0396 (8)
C28	0.1757 (2)	0.48855 (19)	0.43462 (16)	0.0387 (8)
H28	0.1305	0.5125	0.3992	0.046*
C29	0.7350 (2)	0.48847 (18)	0.56032 (15)	0.0356 (8)
C30	0.7164 (2)	0.42868 (19)	0.61303 (15)	0.0382 (8)
C31	0.7943 (2)	0.37859 (19)	0.65308 (17)	0.0424 (9)
C32	0.8411 (2)	0.3293 (2)	0.61612 (19)	0.0515 (10)
H32	0.8268	0.3307	0.5666	0.062*
C33	0.9089 (3)	0.2780 (2)	0.6522 (2)	0.0712 (13)
H33	0.9389	0.2439	0.6268	0.085*
C34	0.9321 (3)	0.2768 (3)	0.7248 (3)	0.0818 (15)
H34	0.9781	0.2422	0.7489	0.098*
C35	0.8880 (3)	0.3265 (3)	0.7621 (2)	0.0721 (13)
H35	0.9044	0.3260	0.8117	0.087*
C36	0.8191 (2)	0.3776 (2)	0.72694 (18)	0.0533 (10)
H36	0.7893	0.4113	0.7528	0.064*
C37	0.6168 (3)	0.3678 (4)	0.6819 (3)	0.0512 (14)	0.680 (5)
H37A	0.6141	0.4017	0.7226	0.061*	0.680 (5)
H37B	0.6638	0.3269	0.6970	0.061*	0.680 (5)
C38	0.5260 (3)	0.3264 (4)	0.6524 (3)	0.0598 (17)	0.680 (5)
H38A	0.5325	0.2828	0.6198	0.072*	0.680 (5)
H38B	0.5037	0.3026	0.6909	0.072*	0.680 (5)
C37'	0.6112 (7)	0.3476 (9)	0.6580 (6)	0.0512 (14)	0.320 (5)
H37C	0.6584	0.3347	0.7001	0.061*	0.320 (5)
H37D	0.6047	0.3011	0.6257	0.061*	0.320 (5)
C38'	0.5228 (7)	0.3623 (8)	0.6789 (7)	0.0598 (17)	0.320 (5)
H38C	0.5010	0.3119	0.6958	0.072*	0.320 (5)
H38D	0.5303	0.4036	0.7161	0.072*	0.320 (5)
C39	0.3754 (2)	0.3723 (2)	0.59562 (17)	0.0444 (9)
C40	0.3429 (2)	0.2996 (2)	0.62927 (18)	0.0482 (9)
C41	0.3327 (3)	0.2247 (2)	0.5969 (2)	0.0681 (12)
H41	0.3441	0.2184	0.5520	0.082*
C42	0.3054 (3)	0.1576 (3)	0.6310 (3)	0.0912 (17)
H42	0.3008	0.1059	0.6098	0.109*
C43	0.2855 (3)	0.1676 (3)	0.6957 (3)	0.0975 (16)
H43	0.2652	0.1230	0.7176	0.117*
C44	0.2948 (3)	0.2402 (3)	0.7275 (2)	0.0872 (15)
H44	0.2820	0.2458	0.7719	0.105*
C45	0.3234 (2)	0.3077 (3)	0.6954 (2)	0.0652 (12)
H45	0.3296	0.3585	0.7181	0.078*
C46	0.0538 (2)	0.4050 (2)	0.46937 (19)	0.0549 (10)
H46A	0.0382	0.4044	0.5146	0.082*
H46B	0.0465	0.3509	0.4490	0.082*
H46C	0.0147	0.4426	0.4380	0.082*
C47	0.3985 (7)	0.4819 (7)	0.8194 (8)	0.250 (11)	0.50
H47A	0.3347	0.4744	0.7997	0.375*	0.50
H47B	0.4088	0.4974	0.8686	0.375*	0.50
H47C	0.4298	0.4314	0.8157	0.375*	0.50
C48	0.4334 (9)	0.5483 (9)	0.7789 (9)	0.292 (9)	0.50
H48A	0.4084	0.5420	0.7280	0.350*	0.50
H48B	0.4167	0.6021	0.7932	0.350*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0408 (2)	0.0455 (2)	0.03363 (19)	0.01844 (18)	0.00837 (16)	0.00292 (17)
Cu2	0.0359 (2)	0.0530 (2)	0.0464 (2)	−0.00232 (19)	0.00656 (18)	0.02143 (19)
Cl1	0.1143 (9)	0.0656 (7)	0.1098 (9)	−0.0300 (7)	0.0164 (8)	−0.0062 (7)
Cl2	0.1024 (9)	0.0662 (7)	0.1126 (9)	0.0039 (7)	0.0227 (8)	−0.0161 (7)
O1	0.0457 (12)	0.0634 (14)	0.0318 (11)	0.0272 (11)	0.0076 (10)	0.0027 (10)
O2	0.0329 (12)	0.0715 (15)	0.0484 (13)	−0.0072 (11)	0.0040 (10)	0.0273 (12)
O3	0.356 (14)	0.345 (15)	0.188 (9)	0.215 (12)	0.141 (10)	0.125 (9)
O1W	0.115 (3)	0.156 (3)	0.126 (3)	−0.016 (3)	0.037 (2)	0.023 (3)
O2W	0.065 (6)	0.325 (19)	0.71 (4)	0.021 (9)	0.071 (12)	0.06 (2)
O3W	0.179 (12)	0.61 (3)	0.51 (2)	0.054 (16)	0.029 (14)	−0.38 (2)
N1	0.0407 (14)	0.0414 (15)	0.0360 (13)	0.0166 (12)	0.0075 (12)	0.0054 (12)
N2	0.0478 (15)	0.0525 (16)	0.0367 (14)	0.0245 (13)	0.0094 (12)	0.0040 (12)
N3	0.0389 (14)	0.0464 (15)	0.0441 (14)	−0.0024 (13)	0.0079 (12)	0.0175 (13)
N4	0.0385 (15)	0.0663 (19)	0.0591 (17)	−0.0008 (14)	0.0074 (13)	0.0333 (15)
C1	0.0316 (15)	0.0389 (17)	0.0325 (15)	0.0062 (14)	0.0090 (13)	0.0023 (14)
C2	0.0344 (16)	0.0396 (17)	0.0377 (16)	0.0095 (14)	0.0106 (13)	−0.0003 (14)
C3	0.0442 (17)	0.0458 (19)	0.0465 (18)	0.0181 (16)	0.0179 (15)	0.0028 (15)
C4	0.0471 (18)	0.052 (2)	0.0375 (17)	0.0124 (16)	0.0164 (15)	0.0008 (15)
C5	0.0440 (18)	0.0428 (18)	0.0294 (15)	0.0084 (15)	0.0065 (14)	−0.0006 (14)
C6	0.0312 (16)	0.0340 (17)	0.0392 (16)	0.0051 (14)	0.0072 (13)	−0.0050 (14)
C7	0.0375 (16)	0.0336 (16)	0.0331 (16)	0.0081 (14)	0.0000 (14)	−0.0052 (14)
C8	0.0495 (19)	0.0389 (17)	0.0285 (15)	0.0117 (16)	0.0032 (14)	−0.0051 (14)
C9	0.066 (2)	0.0419 (19)	0.0377 (17)	0.0053 (18)	0.0082 (16)	−0.0042 (15)
C10	0.105 (3)	0.046 (2)	0.049 (2)	0.007 (2)	0.026 (2)	0.0054 (17)
C11	0.105 (3)	0.062 (2)	0.041 (2)	0.033 (2)	0.003 (2)	0.0060 (19)
C12	0.077 (3)	0.075 (3)	0.045 (2)	0.034 (2)	−0.009 (2)	−0.003 (2)
C13	0.050 (2)	0.054 (2)	0.0442 (19)	0.0151 (18)	0.0004 (16)	−0.0048 (17)
C14	0.061 (2)	0.072 (2)	0.054 (2)	0.0405 (19)	0.0219 (17)	0.0171 (18)
C15	0.094 (3)	0.085 (3)	0.045 (2)	0.059 (2)	0.0195 (19)	0.0149 (19)
C16	0.0315 (16)	0.0468 (18)	0.0407 (17)	0.0097 (15)	0.0112 (14)	0.0001 (15)
C17	0.0429 (18)	0.051 (2)	0.0375 (16)	0.0212 (16)	0.0149 (14)	0.0071 (15)
C18	0.061 (2)	0.051 (2)	0.062 (2)	0.0161 (19)	0.0267 (18)	0.0044 (18)
C19	0.105 (3)	0.054 (2)	0.071 (2)	0.023 (2)	0.031 (2)	0.005 (2)
C20	0.115 (3)	0.077 (3)	0.066 (2)	0.061 (3)	0.032 (2)	0.010 (2)
C21	0.063 (2)	0.112 (3)	0.072 (3)	0.053 (2)	0.025 (2)	0.008 (2)
C22	0.050 (2)	0.076 (3)	0.061 (2)	0.023 (2)	0.0181 (18)	0.001 (2)
C23	0.084 (3)	0.094 (3)	0.0438 (19)	0.040 (2)	0.0275 (19)	0.006 (2)
C24	0.0306 (16)	0.0436 (18)	0.0364 (16)	−0.0036 (15)	0.0082 (13)	0.0047 (14)
C25	0.0341 (16)	0.0409 (17)	0.0376 (16)	−0.0016 (15)	0.0106 (13)	0.0034 (14)
C26	0.0467 (18)	0.0422 (18)	0.0395 (16)	−0.0061 (15)	0.0196 (14)	0.0023 (14)
C27	0.0346 (16)	0.0431 (18)	0.0406 (17)	−0.0060 (15)	0.0080 (14)	−0.0016 (15)
C28	0.0357 (17)	0.0415 (18)	0.0360 (16)	−0.0005 (15)	0.0027 (14)	−0.0007 (14)
C29	0.0374 (17)	0.0324 (16)	0.0368 (16)	−0.0027 (14)	0.0085 (14)	0.0005 (13)
C30	0.0400 (17)	0.0355 (17)	0.0359 (16)	−0.0073 (15)	0.0029 (14)	0.0010 (14)
C31	0.0374 (18)	0.0356 (17)	0.0480 (19)	−0.0053 (15)	−0.0019 (15)	0.0076 (15)
C32	0.049 (2)	0.0409 (19)	0.060 (2)	−0.0059 (17)	0.0038 (17)	0.0013 (17)
C33	0.052 (2)	0.051 (2)	0.105 (3)	0.008 (2)	0.007 (2)	0.002 (2)
C34	0.058 (2)	0.067 (3)	0.102 (3)	0.009 (2)	−0.015 (2)	0.029 (3)
C35	0.066 (3)	0.077 (3)	0.058 (2)	−0.015 (2)	−0.014 (2)	0.024 (2)
C36	0.051 (2)	0.054 (2)	0.048 (2)	−0.0067 (18)	−0.0026 (17)	0.0053 (17)
C37	0.046 (2)	0.067 (3)	0.040 (3)	0.006 (2)	0.008 (2)	0.024 (2)
C38	0.042 (2)	0.061 (4)	0.076 (4)	0.008 (3)	0.014 (2)	0.035 (3)
C37'	0.046 (2)	0.067 (3)	0.040 (3)	0.006 (2)	0.008 (2)	0.024 (2)
C38'	0.042 (2)	0.061 (4)	0.076 (4)	0.008 (3)	0.014 (2)	0.035 (3)
C39	0.0420 (18)	0.0497 (19)	0.0457 (18)	−0.0010 (16)	0.0190 (15)	0.0100 (15)
C40	0.0364 (17)	0.054 (2)	0.057 (2)	0.0025 (16)	0.0180 (15)	0.0226 (17)
C41	0.066 (2)	0.058 (2)	0.085 (3)	−0.003 (2)	0.028 (2)	0.012 (2)
C42	0.071 (3)	0.055 (3)	0.149 (4)	−0.005 (2)	0.029 (3)	0.020 (3)
C43	0.075 (3)	0.086 (3)	0.140 (4)	0.004 (3)	0.044 (3)	0.064 (3)
C44	0.080 (3)	0.108 (4)	0.085 (3)	0.010 (3)	0.042 (2)	0.048 (3)
C45	0.060 (2)	0.074 (3)	0.067 (2)	0.010 (2)	0.0260 (19)	0.025 (2)
C46	0.0427 (19)	0.066 (2)	0.057 (2)	−0.0076 (18)	0.0131 (17)	0.0036 (18)
C47	0.201 (18)	0.156 (13)	0.35 (3)	0.001 (13)	−0.019 (18)	−0.134 (15)
C48	0.346 (18)	0.231 (17)	0.39 (2)	0.177 (15)	0.275 (16)	0.174 (15)

Geometric parameters (Å, º) top

Cu1—N2	1.920 (3)	C18—H18	0.9300
Cu1—O1ⁱ	1.9258 (19)	C19—C20	1.349 (6)
Cu1—N1	1.934 (2)	C19—H19	0.9300
Cu1—O1	1.939 (2)	C20—C21	1.350 (6)
Cu1—Cl1	2.4238 (12)	C20—H20	0.9300
Cu1—Cu1ⁱ	2.9563 (7)	C21—C22	1.377 (6)
Cu2—N4	1.913 (3)	C21—H21	0.9300
Cu2—O2ⁱⁱ	1.922 (2)	C22—H22	0.9300
Cu2—N3	1.931 (2)	C23—H23A	0.9600
Cu2—O2	1.943 (2)	C23—H23B	0.9600
Cu2—Cl2	2.4356 (13)	C23—H23C	0.9600
Cu2—Cu2ⁱⁱ	2.9512 (8)	C24—C29	1.412 (4)
O1—C1ⁱ	1.300 (4)	C24—C25ⁱⁱ	1.427 (4)
O1—Cu1ⁱ	1.9258 (19)	C25—C26	1.391 (4)
O2—C24	1.309 (4)	C25—C24ⁱⁱ	1.427 (4)
O2—Cu2ⁱⁱ	1.922 (2)	C25—C39	1.458 (4)
O3—C48	1.425 (13)	C26—C27	1.372 (4)
O3—H4	0.8200	C26—H26	0.9300
O1W—H1W1	0.820 (17)	C27—C28	1.382 (4)
O1W—H1W2	0.818 (17)	C27—C46	1.500 (4)
O2W—H2W1	0.8494	C28—C29ⁱⁱ	1.388 (4)
O2W—H2W2	0.9688	C28—H28	0.9300
O3W—H3W1	1.0487	C29—C28ⁱⁱ	1.388 (4)
O3W—H3W2	0.8157	C29—C30	1.485 (4)
N1—C7ⁱ	1.282 (4)	C30—C31	1.491 (4)
N1—C14	1.467 (4)	C31—C32	1.380 (5)
N2—C16	1.279 (4)	C31—C36	1.386 (5)
N2—C15	1.478 (4)	C32—C33	1.378 (5)
N3—C30	1.279 (4)	C32—H32	0.9300
N3—C37'	1.453 (13)	C33—C34	1.363 (6)
N3—C37	1.502 (6)	C33—H33	0.9300
N4—C39	1.289 (4)	C34—C35	1.363 (6)
N4—C38'	1.458 (12)	C34—H34	0.9300
N4—C38	1.514 (6)	C35—C36	1.380 (5)
C1—O1ⁱ	1.300 (4)	C35—H35	0.9300
C1—C6	1.413 (4)	C36—H36	0.9300
C1—C2	1.421 (4)	C37—C38	1.517 (7)
C2—C3	1.393 (4)	C37—H37A	0.9700
C2—C16	1.476 (4)	C37—H37B	0.9700
C3—C4	1.366 (4)	C38—H38A	0.9700
C3—H3	0.9300	C38—H38B	0.9700
C4—C5	1.374 (5)	C37'—C38'	1.512 (13)
C4—C23	1.502 (5)	C37'—H37C	0.9700
C5—C6	1.392 (4)	C37'—H37D	0.9700
C5—H5	0.9300	C38'—H38C	0.9700
C6—C7	1.486 (4)	C38'—H38D	0.9700
C7—N1ⁱ	1.282 (4)	C39—C40	1.490 (5)
C7—C8	1.492 (4)	C40—C41	1.363 (5)
C8—C13	1.384 (4)	C40—C45	1.386 (5)
C8—C9	1.392 (5)	C41—C42	1.389 (6)
C9—C10	1.390 (5)	C41—H41	0.9300
C9—H9	0.9300	C42—C43	1.366 (7)
C10—C11	1.363 (6)	C42—H42	0.9300
C10—H10	0.9300	C43—C44	1.323 (7)
C11—C12	1.348 (6)	C43—H43	0.9300
C11—H11	0.9300	C44—C45	1.382 (6)
C12—C13	1.395 (5)	C44—H44	0.9300
C12—H12	0.9300	C45—H45	0.9300
C13—H13	0.9300	C46—H46A	0.9600
C14—C15	1.452 (5)	C46—H46B	0.9600
C14—H14A	0.9700	C46—H46C	0.9600
C14—H14B	0.9700	C47—C48	1.505 (10)
C15—H15A	0.9700	C47—H47A	0.9600
C15—H15B	0.9700	C47—H47B	0.9600
C16—C17	1.496 (4)	C47—H47C	0.9600
C17—C18	1.354 (5)	C48—H48A	0.9700
C17—C22	1.378 (5)	C48—H48B	0.9700
C18—C19	1.374 (5)

N2—Cu1—O1ⁱ	90.16 (10)	C18—C19—H19	119.9
N2—Cu1—N1	88.88 (11)	C19—C20—C21	119.9 (4)
O1ⁱ—Cu1—N1	159.32 (11)	C19—C20—H20	120.0
N2—Cu1—O1	148.23 (11)	C21—C20—H20	120.0
O1ⁱ—Cu1—O1	80.20 (10)	C20—C21—C22	120.7 (4)
N1—Cu1—O1	89.86 (10)	C20—C21—H21	119.7
N2—Cu1—Cl1	110.60 (9)	C22—C21—H21	119.7
O1ⁱ—Cu1—Cl1	99.59 (8)	C21—C22—C17	119.4 (4)
N1—Cu1—Cl1	100.07 (8)	C21—C22—H22	120.3
O1—Cu1—Cl1	100.87 (8)	C17—C22—H22	120.3
N2—Cu1—Cu1ⁱ	124.02 (7)	C4—C23—H23A	109.5
O1ⁱ—Cu1—Cu1ⁱ	40.26 (7)	C4—C23—H23B	109.5
N1—Cu1—Cu1ⁱ	127.43 (8)	H23A—C23—H23B	109.5
O1—Cu1—Cu1ⁱ	39.93 (6)	C4—C23—H23C	109.5
Cl1—Cu1—Cu1ⁱ	103.43 (4)	H23A—C23—H23C	109.5
N4—Cu2—O2ⁱⁱ	90.49 (10)	H23B—C23—H23C	109.5
N4—Cu2—N3	88.75 (11)	O2—C24—C29	120.3 (3)
O2ⁱⁱ—Cu2—N3	159.37 (11)	O2—C24—C25ⁱⁱ	119.8 (3)
N4—Cu2—O2	147.45 (12)	C29—C24—C25ⁱⁱ	119.9 (3)
O2ⁱⁱ—Cu2—O2	80.47 (10)	C26—C25—C24ⁱⁱ	117.5 (3)
N3—Cu2—O2	89.18 (10)	C26—C25—C39	118.2 (3)
N4—Cu2—Cl2	110.11 (10)	C24ⁱⁱ—C25—C39	124.2 (3)
O2ⁱⁱ—Cu2—Cl2	99.31 (8)	C27—C26—C25	123.9 (3)
N3—Cu2—Cl2	100.31 (9)	C27—C26—H26	118.1
O2—Cu2—Cl2	102.22 (8)	C25—C26—H26	118.1
N4—Cu2—Cu2ⁱⁱ	124.09 (8)	C26—C27—C28	117.2 (3)
O2ⁱⁱ—Cu2—Cu2ⁱⁱ	40.49 (7)	C26—C27—C46	121.1 (3)
N3—Cu2—Cu2ⁱⁱ	126.88 (8)	C28—C27—C46	121.6 (3)
O2—Cu2—Cu2ⁱⁱ	39.97 (6)	C27—C28—C29ⁱⁱ	123.4 (3)
Cl2—Cu2—Cu2ⁱⁱ	104.16 (4)	C27—C28—H28	118.3
C1ⁱ—O1—Cu1ⁱ	131.06 (19)	C29ⁱⁱ—C28—H28	118.3
C1ⁱ—O1—Cu1	127.82 (18)	C28ⁱⁱ—C29—C24	118.2 (3)
Cu1ⁱ—O1—Cu1	99.80 (10)	C28ⁱⁱ—C29—C30	118.2 (3)
C24—O2—Cu2ⁱⁱ	131.45 (19)	C24—C29—C30	123.6 (3)
C24—O2—Cu2	126.42 (19)	N3—C30—C29	121.6 (3)
Cu2ⁱⁱ—O2—Cu2	99.54 (10)	N3—C30—C31	121.3 (3)
C48—O3—H4	109.5	C29—C30—C31	117.1 (3)
H1W1—O1W—H1W2	105 (3)	C32—C31—C36	118.7 (3)
H2W1—O2W—H2W2	102.3	C32—C31—C30	119.5 (3)
H3W1—O3W—H3W2	116.8	C36—C31—C30	121.7 (3)
C7ⁱ—N1—C14	124.5 (3)	C33—C32—C31	120.4 (4)
C7ⁱ—N1—Cu1	128.4 (2)	C33—C32—H32	119.8
C14—N1—Cu1	107.0 (2)	C31—C32—H32	119.8
C16—N2—C15	120.4 (3)	C34—C33—C32	120.4 (4)
C16—N2—Cu1	129.1 (2)	C34—C33—H33	119.8
C15—N2—Cu1	109.0 (2)	C32—C33—H33	119.8
C30—N3—C37'	122.1 (5)	C35—C34—C33	119.9 (4)
C30—N3—C37	123.6 (3)	C35—C34—H34	120.0
C30—N3—Cu2	128.9 (2)	C33—C34—H34	120.0
C37'—N3—Cu2	106.2 (4)	C34—C35—C36	120.5 (4)
C37—N3—Cu2	107.4 (2)	C34—C35—H35	119.7
C39—N4—C38'	124.2 (5)	C36—C35—H35	119.7
C39—N4—C38	118.2 (3)	C35—C36—C31	120.0 (4)
C39—N4—Cu2	129.2 (2)	C35—C36—H36	120.0
C38'—N4—Cu2	105.7 (5)	C31—C36—H36	120.0
C38—N4—Cu2	109.5 (3)	N3—C37—C38	107.5 (4)
O1ⁱ—C1—C6	120.4 (3)	N3—C37—H37A	110.2
O1ⁱ—C1—C2	120.2 (2)	C38—C37—H37A	110.2
C6—C1—C2	119.3 (3)	N3—C37—H37B	110.2
C3—C2—C1	118.0 (3)	C38—C37—H37B	110.2
C3—C2—C16	118.4 (3)	H37A—C37—H37B	108.5
C1—C2—C16	123.4 (3)	N4—C38—C37	108.1 (4)
C4—C3—C2	123.6 (3)	N4—C38—H38A	110.1
C4—C3—H3	118.2	C37—C38—H38A	110.1
C2—C3—H3	118.2	N4—C38—H38B	110.1
C3—C4—C5	117.4 (3)	C37—C38—H38B	110.1
C3—C4—C23	121.8 (3)	H38A—C38—H38B	108.4
C5—C4—C23	120.8 (3)	N3—C37'—C38'	110.5 (10)
C4—C5—C6	123.4 (3)	N3—C37'—H37C	109.6
C4—C5—H5	118.3	C38'—C37'—H37C	109.6
C6—C5—H5	118.3	N3—C37'—H37D	109.6
C5—C6—C1	118.3 (3)	C38'—C37'—H37D	109.6
C5—C6—C7	117.8 (3)	H37C—C37'—H37D	108.1
C1—C6—C7	123.9 (3)	N4—C38'—C37'	104.8 (9)
N1ⁱ—C7—C6	122.2 (3)	N4—C38'—H38C	110.8
N1ⁱ—C7—C8	120.6 (3)	C37'—C38'—H38C	110.8
C6—C7—C8	117.1 (3)	N4—C38'—H38D	110.8
C13—C8—C9	118.8 (3)	C37'—C38'—H38D	110.8
C13—C8—C7	121.5 (3)	H38C—C38'—H38D	108.9
C9—C8—C7	119.6 (3)	N4—C39—C25	123.1 (3)
C10—C9—C8	120.0 (3)	N4—C39—C40	118.8 (3)
C10—C9—H9	120.0	C25—C39—C40	118.1 (3)
C8—C9—H9	120.0	C41—C40—C45	118.9 (3)
C11—C10—C9	120.1 (4)	C41—C40—C39	121.5 (3)
C11—C10—H10	120.0	C45—C40—C39	119.6 (3)
C9—C10—H10	120.0	C40—C41—C42	119.9 (4)
C12—C11—C10	120.6 (4)	C40—C41—H41	120.0
C12—C11—H11	119.7	C42—C41—H41	120.0
C10—C11—H11	119.7	C43—C42—C41	119.8 (5)
C11—C12—C13	120.7 (4)	C43—C42—H42	120.1
C11—C12—H12	119.7	C41—C42—H42	120.1
C13—C12—H12	119.7	C44—C43—C42	120.7 (4)
C8—C13—C12	119.8 (4)	C44—C43—H43	119.6
C8—C13—H13	120.1	C42—C43—H43	119.6
C12—C13—H13	120.1	C43—C44—C45	120.7 (5)
C15—C14—N1	112.2 (3)	C43—C44—H44	119.7
C15—C14—H14A	109.2	C45—C44—H44	119.7
N1—C14—H14A	109.2	C44—C45—C40	119.9 (4)
C15—C14—H14B	109.2	C44—C45—H45	120.0
N1—C14—H14B	109.2	C40—C45—H45	120.0
H14A—C14—H14B	107.9	C27—C46—H46A	109.5
C14—C15—N2	112.2 (3)	C27—C46—H46B	109.5
C14—C15—H15A	109.2	H46A—C46—H46B	109.5
N2—C15—H15A	109.2	C27—C46—H46C	109.5
C14—C15—H15B	109.2	H46A—C46—H46C	109.5
N2—C15—H15B	109.2	H46B—C46—H46C	109.5
H15A—C15—H15B	107.9	C48—C47—H47A	109.5
N2—C16—C2	122.8 (3)	C48—C47—H47B	109.5
N2—C16—C17	119.2 (3)	H47A—C47—H47B	109.5
C2—C16—C17	117.9 (3)	C48—C47—H47C	109.5
C18—C17—C22	119.2 (3)	H47A—C47—H47C	109.5
C18—C17—C16	120.6 (3)	H47B—C47—H47C	109.5
C22—C17—C16	120.0 (3)	O3—C48—C47	106.2 (9)
C17—C18—C19	120.5 (4)	O3—C48—H48A	110.5
C17—C18—H18	119.7	C47—C48—H48A	110.5
C19—C18—H18	119.7	O3—C48—H48B	110.5
C20—C19—C18	120.3 (4)	C47—C48—H48B	110.5
C20—C19—H19	119.9	H48A—C48—H48B	108.7

N2—Cu1—O1—C1ⁱ	117.9 (3)	C11—C12—C13—C8	−0.3 (6)
O1ⁱ—Cu1—O1—C1ⁱ	−168.0 (3)	C7ⁱ—N1—C14—C15	146.7 (3)
N1—Cu1—O1—C1ⁱ	30.2 (3)	Cu1—N1—C14—C15	−32.8 (4)
Cl1—Cu1—O1—C1ⁱ	−70.0 (3)	N1—C14—C15—N2	35.9 (5)
Cu1ⁱ—Cu1—O1—C1ⁱ	−168.0 (3)	C16—N2—C15—C14	172.2 (3)
N2—Cu1—O1—Cu1ⁱ	−74.1 (2)	Cu1—N2—C15—C14	−20.5 (4)
O1ⁱ—Cu1—O1—Cu1ⁱ	0.0	C15—N2—C16—C2	169.5 (3)
N1—Cu1—O1—Cu1ⁱ	−161.78 (11)	Cu1—N2—C16—C2	5.0 (5)
Cl1—Cu1—O1—Cu1ⁱ	97.99 (9)	C15—N2—C16—C17	−7.4 (5)
N4—Cu2—O2—C24	−121.0 (3)	Cu1—N2—C16—C17	−171.8 (2)
O2ⁱⁱ—Cu2—O2—C24	163.3 (3)	C3—C2—C16—N2	169.0 (3)
N3—Cu2—O2—C24	−34.6 (3)	C1—C2—C16—N2	−15.4 (5)
Cl2—Cu2—O2—C24	65.8 (3)	C3—C2—C16—C17	−14.1 (4)
Cu2ⁱⁱ—Cu2—O2—C24	163.3 (3)	C1—C2—C16—C17	161.5 (3)
N4—Cu2—O2—Cu2ⁱⁱ	75.7 (2)	N2—C16—C17—C18	95.3 (4)
O2ⁱⁱ—Cu2—O2—Cu2ⁱⁱ	0.0	C2—C16—C17—C18	−81.7 (4)
N3—Cu2—O2—Cu2ⁱⁱ	162.08 (12)	N2—C16—C17—C22	−80.7 (4)
Cl2—Cu2—O2—Cu2ⁱⁱ	−97.55 (9)	C2—C16—C17—C22	102.3 (4)
N2—Cu1—N1—C7ⁱ	−162.5 (3)	C22—C17—C18—C19	1.7 (5)
O1ⁱ—Cu1—N1—C7ⁱ	−75.0 (4)	C16—C17—C18—C19	−174.4 (3)
O1—Cu1—N1—C7ⁱ	−14.2 (3)	C17—C18—C19—C20	−1.2 (6)
Cl1—Cu1—N1—C7ⁱ	86.8 (3)	C18—C19—C20—C21	−0.4 (6)
Cu1ⁱ—Cu1—N1—C7ⁱ	−28.9 (3)	C19—C20—C21—C22	1.3 (7)
N2—Cu1—N1—C14	17.0 (2)	C20—C21—C22—C17	−0.7 (6)
O1ⁱ—Cu1—N1—C14	104.5 (3)	C18—C17—C22—C21	−0.8 (5)
O1—Cu1—N1—C14	165.2 (2)	C16—C17—C22—C21	175.3 (3)
Cl1—Cu1—N1—C14	−93.8 (2)	Cu2ⁱⁱ—O2—C24—C29	−170.8 (2)
Cu1ⁱ—Cu1—N1—C14	150.57 (19)	Cu2—O2—C24—C29	31.4 (4)
O1ⁱ—Cu1—N2—C16	8.0 (3)	Cu2ⁱⁱ—O2—C24—C25ⁱⁱ	10.0 (5)
N1—Cu1—N2—C16	167.4 (3)	Cu2—O2—C24—C25ⁱⁱ	−147.8 (2)
O1—Cu1—N2—C16	79.5 (4)	C24ⁱⁱ—C25—C26—C27	−0.5 (5)
Cl1—Cu1—N2—C16	−92.3 (3)	C39—C25—C26—C27	−175.7 (3)
Cu1ⁱ—Cu1—N2—C16	31.3 (3)	C25—C26—C27—C28	0.5 (5)
O1ⁱ—Cu1—N2—C15	−157.8 (2)	C25—C26—C27—C46	177.1 (3)
N1—Cu1—N2—C15	1.5 (2)	C26—C27—C28—C29ⁱⁱ	0.3 (5)
O1—Cu1—N2—C15	−86.4 (3)	C46—C27—C28—C29ⁱⁱ	−176.2 (3)
Cl1—Cu1—N2—C15	101.9 (2)	O2—C24—C29—C28ⁱⁱ	179.7 (3)
Cu1ⁱ—Cu1—N2—C15	−134.6 (2)	C25ⁱⁱ—C24—C29—C28ⁱⁱ	−1.1 (5)
N4—Cu2—N3—C30	164.0 (3)	O2—C24—C29—C30	−0.9 (5)
O2ⁱⁱ—Cu2—N3—C30	75.9 (4)	C25ⁱⁱ—C24—C29—C30	178.3 (3)
O2—Cu2—N3—C30	16.4 (3)	C37'—N3—C30—C29	161.7 (6)
Cl2—Cu2—N3—C30	−85.8 (3)	C37—N3—C30—C29	−172.6 (3)
Cu2ⁱⁱ—Cu2—N3—C30	30.8 (3)	Cu2—N3—C30—C29	3.5 (4)
N4—Cu2—N3—C37'	3.1 (6)	C37'—N3—C30—C31	−17.9 (7)
O2ⁱⁱ—Cu2—N3—C37'	−85.0 (6)	C37—N3—C30—C31	7.9 (5)
O2—Cu2—N3—C37'	−144.4 (6)	Cu2—N3—C30—C31	−176.1 (2)
Cl2—Cu2—N3—C37'	113.3 (6)	C28ⁱⁱ—C29—C30—N3	162.3 (3)
Cu2ⁱⁱ—Cu2—N3—C37'	−130.1 (6)	C24—C29—C30—N3	−17.1 (5)
N4—Cu2—N3—C37	−19.5 (3)	C28ⁱⁱ—C29—C30—C31	−18.1 (4)
O2ⁱⁱ—Cu2—N3—C37	−107.6 (4)	C24—C29—C30—C31	162.5 (3)
O2—Cu2—N3—C37	−167.0 (3)	N3—C30—C31—C32	121.2 (4)
Cl2—Cu2—N3—C37	90.7 (3)	C29—C30—C31—C32	−58.4 (4)
Cu2ⁱⁱ—Cu2—N3—C37	−152.7 (2)	N3—C30—C31—C36	−56.2 (4)
O2ⁱⁱ—Cu2—N4—C39	−6.0 (3)	C29—C30—C31—C36	124.2 (3)
N3—Cu2—N4—C39	−165.3 (3)	C36—C31—C32—C33	2.3 (5)
O2—Cu2—N4—C39	−78.8 (4)	C30—C31—C32—C33	−175.2 (3)
Cl2—Cu2—N4—C39	94.1 (3)	C31—C32—C33—C34	−1.7 (6)
Cu2ⁱⁱ—Cu2—N4—C39	−30.1 (4)	C32—C33—C34—C35	0.2 (6)
O2ⁱⁱ—Cu2—N4—C38'	−175.0 (6)	C33—C34—C35—C36	0.7 (6)
N3—Cu2—N4—C38'	25.6 (6)	C34—C35—C36—C31	0.0 (6)
O2—Cu2—N4—C38'	112.1 (6)	C32—C31—C36—C35	−1.5 (5)
Cl2—Cu2—N4—C38'	−74.9 (6)	C30—C31—C36—C35	176.0 (3)
Cu2ⁱⁱ—Cu2—N4—C38'	160.9 (6)	C30—N3—C37—C38	−142.6 (4)
O2ⁱⁱ—Cu2—N4—C38	153.1 (3)	C37'—N3—C37—C38	−49.3 (12)
N3—Cu2—N4—C38	−6.2 (3)	Cu2—N3—C37—C38	40.7 (5)
O2—Cu2—N4—C38	80.3 (3)	C39—N4—C38—C37	−167.8 (4)
Cl2—Cu2—N4—C38	−106.8 (3)	C38'—N4—C38—C37	−57.4 (10)
Cu2ⁱⁱ—Cu2—N4—C38	129.0 (3)	Cu2—N4—C38—C37	30.5 (5)
O1ⁱ—C1—C2—C3	−178.2 (3)	N3—C37—C38—N4	−46.5 (6)
C6—C1—C2—C3	2.5 (4)	C30—N3—C37'—C38'	166.6 (7)
O1ⁱ—C1—C2—C16	6.2 (5)	C37—N3—C37'—C38'	65.7 (14)
C6—C1—C2—C16	−173.1 (3)	Cu2—N3—C37'—C38'	−30.9 (10)
C1—C2—C3—C4	−1.0 (5)	C39—N4—C38'—C37'	143.6 (8)
C16—C2—C3—C4	174.8 (3)	C38—N4—C38'—C37'	55.2 (10)
C2—C3—C4—C5	−0.9 (5)	Cu2—N4—C38'—C37'	−46.7 (10)
C2—C3—C4—C23	−179.2 (3)	N3—C37'—C38'—N4	52.5 (12)
C3—C4—C5—C6	1.3 (5)	C38'—N4—C39—C25	163.2 (7)
C23—C4—C5—C6	179.7 (3)	C38—N4—C39—C25	−161.6 (4)
C4—C5—C6—C1	0.2 (5)	Cu2—N4—C39—C25	−4.0 (5)
C4—C5—C6—C7	−179.0 (3)	C38'—N4—C39—C40	−19.2 (8)
O1ⁱ—C1—C6—C5	178.6 (3)	C38—N4—C39—C40	16.0 (5)
C2—C1—C6—C5	−2.1 (4)	Cu2—N4—C39—C40	173.6 (2)
O1ⁱ—C1—C6—C7	−2.3 (5)	C26—C25—C39—N4	−173.4 (3)
C2—C1—C6—C7	177.0 (3)	C24ⁱⁱ—C25—C39—N4	11.7 (5)
C5—C6—C7—N1ⁱ	165.9 (3)	C26—C25—C39—C40	9.0 (5)
C1—C6—C7—N1ⁱ	−13.2 (5)	C24ⁱⁱ—C25—C39—C40	−165.9 (3)
C5—C6—C7—C8	−15.8 (4)	N4—C39—C40—C41	−95.9 (4)
C1—C6—C7—C8	165.1 (3)	C25—C39—C40—C41	81.8 (4)
N1ⁱ—C7—C8—C13	−55.5 (4)	N4—C39—C40—C45	83.3 (4)
C6—C7—C8—C13	126.2 (3)	C25—C39—C40—C45	−99.0 (4)
N1ⁱ—C7—C8—C9	120.7 (3)	C45—C40—C41—C42	−1.5 (5)
C6—C7—C8—C9	−57.6 (4)	C39—C40—C41—C42	177.6 (3)
C13—C8—C9—C10	2.4 (5)	C40—C41—C42—C43	2.5 (6)
C7—C8—C9—C10	−173.9 (3)	C41—C42—C43—C44	−2.3 (7)
C8—C9—C10—C11	−1.6 (5)	C42—C43—C44—C45	1.2 (7)
C9—C10—C11—C12	−0.2 (6)	C43—C44—C45—C40	−0.2 (6)
C10—C11—C12—C13	1.1 (6)	C41—C40—C45—C44	0.4 (5)
C9—C8—C13—C12	−1.5 (5)	C39—C40—C45—C44	−178.8 (3)
C7—C8—C13—C12	174.7 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H4···O2W	0.82	2.20	2.96 (2)	154
O1W—H1W1···Cl1ⁱⁱⁱ	0.82 (2)	2.54 (2)	3.355 (4)	171 (4)
O1W—H1W2···Cl2	0.82 (2)	2.56 (2)	3.374 (4)	174 (3)
O2W—H2W1···O3W	0.85	1.86	2.71 (3)	179
O2W—H2W2···O3	0.97	2.27	2.96 (2)	127

Symmetry code: (iii) x−1/2, −y+3/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[Cu₂(C₄₆H₃₈N₄O₂)Cl₂]·0.5C₂H₆O·2H₂O
M_r	935.85
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	15.1983 (4), 16.2680 (5), 19.3344 (5)
β (°)	103.964 (2)
V (Å³)	4639.1 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.08
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 1999)
T_min, T_max	0.738, 0.813
No. of measured, independent and observed [I > 2σ(I)] reflections	36333, 6669, 4664
R_int	0.054
θ_max (°)	23.3
(sin θ/λ)_max (Å⁻¹)	0.557

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.137, 1.05
No. of reflections	6669
No. of parameters	575
No. of restraints	13
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.34

Computer programs: APEX2 (Bruker, 2004), APEX2 and SAINT-Plus (Bruker, 2004), SAINT and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H4···O2W	0.82	2.20	2.96 (2)	154.3
O1W—H1W1···Cl1ⁱ	0.820 (17)	2.543 (16)	3.355 (4)	171 (4)
O1W—H1W2···Cl2	0.818 (17)	2.559 (17)	3.374 (4)	174 (3)
O2W—H2W1···O3W	0.85	1.86	2.71 (3)	178.5
O2W—H2W2···O3	0.97	2.27	2.96 (2)	127.3

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

Acknowledgements

The authors thank the DST (grant No. SR/S1/IC-38/2007) and the UGC [grant No. F.37–500/2009(SR)] for financial support and the SAIF at IIT Madras for the use of the X-ray diffractometer.

References

Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356. CSD CrossRef Web of Science Google Scholar
Bruker (1999). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). APEX2, SAINT-Plus and XPREP. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Fenton, H., Tidmash, I. S. & Ward, M. D. (2010). Dalton Trans. pp. 3805–3815. Web of Science CSD CrossRef Google Scholar
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Gupta, S. K., Hitchock, P. B. & Argal, G. S. (2008). Inorg. Chim. Acta, 361, 2139–2146. Web of Science CSD CrossRef CAS Google Scholar
Gupta, S. K., Hitchock, P. B. & Kushwah, Y. S. (2002). Polyhedron, 21, 1787–1793. Web of Science CrossRef CAS Google Scholar
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Volume 66| Part 12| December 2010| Pages m1531-m1532

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Di­chlorido[μ-10,21-di­methyl-2,7,13,18-tetra­phenyl-3,6,14,17-tetra­aza­tri­cyclo­[17.3.1.18,12]tetra­cosa-1(23),2,6,8,10,12(24),13,17,19,21-deca­ene-23,24-diolato]dicopper(II) ethanol hemisolvate dihydrate

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Dichlorido[μ-10,21-dimethyl-2,7,13,18-tetraphenyl-3,6,14,17-tetraazatricyclo[17.3.1.1^8,12]tetracosa-1(23),2,6,8,10,12(24),13,17,19,21-decaene-23,24-diolato]dicopper(II) ethanol hemisolvate dihydrate