Diaquatetra­kis(μ-3-meth­oxy­benzoato-κ2O1:O1′)dicopper(II)

Srinivasan, B.R.; Bhargao, P.H.; Sudhadevi, P.K.

doi:10.1107/S2414314620004484

metal-organic compounds

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ISSN: 2414-3146

Volume 5| Part 4| April 2020| x200448

https://doi.org/10.1107/S2414314620004484

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Diaquatetrakis(μ-3-methoxybenzoato-κ²O¹:O^1′)dicopper(II)

Bikshandarkoil R. Srinivasan,^a ^* Pooja H. Bhargao ^a and P. K. Sudhadevi ^b

^aSchool of Chemical Sciences, Goa University, Goa 403206, India, and ^bSophisticated Analytical Instruments Facility (SAIF), Indian Institute of Technology Madras, Chennai 600036, India
^*Correspondence e-mail: srini@unigoa.ac.in

Edited by M. Weil, Vienna University of Technology, Austria (Received 17 March 2020; accepted 31 March 2020; online 7 April 2020)

The asymmetric unit of the binuclear title compound, [Cu₂(C₈H₇O₃)₄(H₂O)₂], comprises two halves of diaquatetrakis(μ-3-methoxybenzoato-κ²O¹:O^1′)dicopper(II) units. The paddle-wheel structure of each complex is completed by application of inversion symmetry, with the inversion centre situated at the midpoint between two Cu^II atoms in each dimer. The two Cu^II atoms of each centrosymmetric dimer are bridged by four 3-methoxybenzoate anions resulting in Cu⋯Cu separations of 2.5961 (11) and 2.6060 (12) Å, respectively. The square-pyramidal coordination sphere of each Cu^II atom is completed by an apical water molecule. Intermolecular O—H⋯O hydrogen bonds of weak nature link the complexes into layers parallel to (100). The three-dimensional network structure is accomplished by C—H⋯O hydrogen bonds interlinking adjacent layers.

Keywords: crystal structure; paddle-wheel structure; binuclear copper complex; hydrogen bonding.

CCDC reference: 1993956

Structure description

A very early structure investigation of cupric acetate monohydrate revealed that it is dimeric in nature, represented by the formula [Cu₂(CH₃COO)₄(H₂O)₂] (Van Niekerk & Schoening, 1953 ). In the dimer, each of the two cupric ions is bonded to four oxygen atoms of four bridging acetate ligands in addition to a terminal aqua ligand. This kind of coordination, wherein a pair of metal cations is bonded to four symmetrically bridging carboxylate anions, is referred to as a paddle-wheel structure and is well documented for several dimeric copper carboxylates (Doedens, 1976 ). The Cambridge Structural Database (CSD, version 5.40, update September 2019; Groom et al., 2016 ) lists the structures of several dicopper(II) compounds where the cupric cations are symmetrically bridged by four carboxylate ligands. The fifth ligand can be a terminal water molecule or any O– or N-donor ligand. A dinuclear copper compound with a paddle-wheel structure, viz. tetrakis(μ-3-methoxybenzoato- κ²O¹:O^1′)bis[acetonitrilecopper(II)] (2), was reported previously for the methoxybenzoate anion (Kar et al., 2011 ). In the present study, we describe the structure of a related dinuclear copper complex where the acetonitrile ligands are replaced by aqua ligands.

The crystal structure of the title compound, [Cu₂(C₈H₇O₃)₄(H₂O)₂], (1), consists of two crystallographically unique cupric cations, four crystallographically independent 3-methoxybenzoate anions and two terminal water molecules that build up two independent halves of a dimeric [Cu₂(C₈H₇O₃)₄(H₂O)₂] complex, the other halves being generated by inversion symmetry. The inversion centre is situated at the midpoint of the line connecting two Cu^II atoms in each of the dimers (Fig. 1). In each centrosymmetric dimer, a pair of Cu^II atoms is connected through four syn–syn bis-monodentate 3-methoxybenzoate bridges to generate a binuclear paddle-wheel unit. The fifth ligand, O7 on Cu1 and O14 on Cu2, is a terminal water molecule, defining an overall square-pyramidal coordination sphere around the central metal cation. Bond lengths and angles of the 3-methoxybenzoate anions are in normal ranges and are in agreement with reported data (Kar et al., 2011). The Cu—O_water bonds [2.171 (4) and 2.126 (4) Å for Cu1 and Cu2, respectively] are elongated as compared to the Cu—O_carboxylate distances ranging from 1.949 (4) to 1.959 (3) Å for Cu1 and from 1.936 (3) to 1.973 (3) Å for Cu2. The Cu⋯Cu separations in the dimers amount to 2.6060 (12) Å for Cu1 and 2.5961 (11) Å for Cu2, which are shorter than the Cu⋯Cu distance of 2.6433 (3) Å reported for (2) (Kar et al., 2011).

Figure 1
The two centrosymmetric binuclear complexes in the crystal structure of [Cu₂(C₈H₇O₃)₄(H₂O)₂] with displacement ellipsoids drawn at the 30% probability level. [Symmetry codes: (i) −x + 1, −y + 1, −z; (ii) −x + 2, −y + 1, −z + 1.]

The water molecules, and the phenyl groups C23—H23 and C27—H27, respectively, function as hydrogen-bond donors, while the methoxy oxygen atoms O3, O6 and O13 and the carboxylate oxygen atoms O1, O5, O11 and O14 function as hydrogen-bond acceptors; parts of the O—H⋯O hydrogen bonds are bifurcated (Table 1). Each Cu1 dimer is linked to six other symmetry-related Cu1 dimers with the aid of three O—H⋯O hydrogen bonds, and each Cu2 dimer is hydrogen-bonded to six other symmetry-related Cu2 dimers (Fig. 2). As a result, O—H⋯O hydrogen-bonded layers parallel to (100) are formed. The two C—H⋯O hydrogen bonds interlink adjacent layers into a three-dimensional network (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O7—H7A⋯O3ⁱ	0.84 (2)	2.11 (3)	2.912 (6)	161 (5)
O7—H7B⋯O1ⁱⁱ	0.83 (2)	2.42 (5)	3.107 (6)	141 (7)
O7—H7B⋯O5ⁱⁱ	0.83 (2)	2.60 (5)	3.306 (6)	144 (6)
O14—H14B⋯O13ⁱⁱⁱ	0.84 (2)	2.00 (2)	2.831 (6)	169 (8)
O14—H14A⋯O11^iv	0.83 (2)	2.11 (3)	2.905 (5)	160 (6)
O14—H14A⋯O14^iv	0.83 (2)	2.57 (5)	3.055 (8)	118 (5)
C23—H23⋯O6^v	0.93	2.52	3.355 (7)	149
C27—H27⋯O6^vi	0.93	2.57	3.114 (7)	117
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y+2, -z; (iii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iv) -x+2, -y, -z+1; (v) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vi) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Figure 2
A view along [100] showing the O—H⋯O hydrogen bonds (dashed lines) around the Cu1 dimer (left) and the Cu2 dimer (right).

Figure 3
A view along [001] showing the interlinking of dimeric Cu1 units with adjacent dimeric Cu2 units with the aid of C—H⋯O hydrogen bonds.

Synthesis and crystallization

Cupric oxide (100 mg) was added in small portions to a hot aqueous solution of 3-methoxybenzoic acid (0.304 g, 2 mmol) in water (100 ml). The hot reaction mixture was continuously stirred to dissolve the oxide. When most of the oxide had dissolved, the blue reaction mixture was filtered to remove the insoluble matter. The blue filtrate thus obtained was left aside for crystallization. After a few days blue–greenish crystals of (1) slowly separated. The crystals were filtered and dried in air. Yield 35%.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The crystal under investigation was a two-component twin with a refined batch scale factor (BASF) of 0.47. The matrix that was used for overlapping the twin domains is (101 0 $[\overline{1}]$ 0 00 $[\overline{1}]$ ). H atoms of water molecules were discernible from a difference-Fourier map. To get a reasonable shape, water molecules were refined with a target value of 0.85 (2) Å for O—H bond lengths and of 1.35 (2) Å for H⋯H distances.

Table 2
Experimental details

Crystal data
Chemical formula	[Cu₂(C₈H₇O₃)₄(H₂O)₂]
M_r	767.65
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	22.515 (3), 7.5349 (6), 21.536 (2)
β (°)	118.429 (4)
V (Å³)	3213.0 (6)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.40
Crystal size (mm)	0.20 × 0.20 × 0.15

Data collection
Diffractometer	Bruker AXS Kappa APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2012 )
T_min, T_max	0.410, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	36309, 6704, 5194
R_int	0.082
(sin θ/λ)_max (Å⁻¹)	0.631

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.108, 1.02
No. of reflections	6704
No. of parameters	454
No. of restraints	6
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.90, −0.83
Computer programs: APEX2 and SAINT (Bruker, 2012), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), DIAMOND (Brandenburg, 1999 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1993956

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314620004484/wm4126sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620004484/wm4126Isup3.hkl

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2012); cell refinement: APEX2 (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: publCIF (Westrip, 2010).

Diaquatetrakis(µ-3-methoxybenzoato-κ²O¹:O^1')dicopper(II) top

Crystal data top

[Cu₂(C₈H₇O₃)₄(H₂O)₂]	F(000) = 1576
M_r = 767.65	D_x = 1.587 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 22.515 (3) Å	Cell parameters from 9989 reflections
b = 7.5349 (6) Å	θ = 2.2–26.2°
c = 21.536 (2) Å	µ = 1.40 mm⁻¹
β = 118.429 (4)°	T = 296 K
V = 3213.0 (6) Å³	Block, bluish green
Z = 4	0.20 × 0.20 × 0.15 mm

Data collection top

Bruker AXS Kappa APEXII CCD diffractometer	6704 independent reflections
Radiation source: fine-focus sealed tube	5194 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.082
ω and φ scan	θ_max = 26.6°, θ_min = 1.0°
Absorption correction: multi-scan (SADABS; Bruker, 2012)	h = −28→28
T_min = 0.410, T_max = 0.745	k = −9→9
36309 measured reflections	l = −26→26

Refinement top

Refinement on F²	6 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.108	w = 1/[σ²(F_o²) + (0.0351P)² + 3.0856P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.002
6704 reflections	Δρ_max = 0.90 e Å⁻³
454 parameters	Δρ_min = −0.83 e Å⁻³

Special details top

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

Refinement. Refined as a two-component twin

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

	x	y	z	U_iso*/U_eq
Cu1	0.50684 (3)	0.65510 (8)	−0.02260 (3)	0.03022 (19)
C1	0.5402 (2)	0.6223 (7)	0.1219 (3)	0.0341 (12)
C2	0.5610 (2)	0.7024 (8)	0.1931 (3)	0.0352 (12)
C3	0.5619 (3)	0.8829 (7)	0.2013 (3)	0.0473 (14)
H3	0.553854	0.957326	0.163685	0.057*
C4	0.5745 (3)	0.9535 (8)	0.2649 (3)	0.0565 (16)
H4	0.572505	1.075719	0.269696	0.068*
C5	0.5900 (3)	0.8450 (8)	0.3216 (3)	0.0483 (15)
H5	0.598563	0.893345	0.364783	0.058*
C6	0.5929 (3)	0.6635 (7)	0.3145 (3)	0.0451 (14)
C7	0.5772 (3)	0.5917 (8)	0.2496 (3)	0.0409 (13)
H7	0.577578	0.469341	0.244079	0.049*
C8	0.6299 (5)	0.3893 (9)	0.3737 (4)	0.095 (3)
H8A	0.594361	0.328194	0.334527	0.142*
H8B	0.637957	0.332541	0.416971	0.142*
H8C	0.670353	0.385973	0.369359	0.142*
C9	0.3827 (2)	0.5945 (7)	−0.0264 (3)	0.0370 (11)
C10	0.3150 (3)	0.6464 (7)	−0.0354 (3)	0.0381 (12)
C11	0.2869 (3)	0.8092 (8)	−0.0627 (3)	0.0465 (14)
H11	0.308308	0.886444	−0.079308	0.056*
C12	0.2266 (3)	0.8568 (8)	−0.0650 (3)	0.0604 (17)
H12	0.206701	0.964655	−0.085164	0.073*
C13	0.1958 (3)	0.7476 (9)	−0.0382 (4)	0.0584 (19)
H13	0.155816	0.782540	−0.038909	0.070*
C14	0.2244 (3)	0.5856 (9)	−0.0100 (3)	0.0526 (15)
C15	0.2829 (3)	0.5331 (8)	−0.0094 (3)	0.0457 (13)
H15	0.301205	0.422211	0.008402	0.055*
C16	0.2158 (4)	0.3189 (9)	0.0455 (5)	0.083 (2)
H16A	0.211575	0.238074	0.009184	0.124*
H16B	0.191200	0.273485	0.068286	0.124*
H16C	0.262557	0.331491	0.079654	0.124*
O1	0.53588 (19)	0.7269 (5)	0.0746 (2)	0.0403 (10)
O2	0.52749 (18)	0.4584 (4)	0.11476 (17)	0.0380 (8)
O3	0.6108 (2)	0.5671 (5)	0.3743 (2)	0.0639 (12)
O4	0.40388 (17)	0.4427 (5)	−0.00258 (19)	0.0419 (9)
O5	0.41505 (18)	0.7099 (5)	−0.04147 (19)	0.0412 (8)
O6	0.1892 (2)	0.4862 (6)	0.0153 (2)	0.0651 (12)
O7	0.5378 (3)	0.9096 (5)	−0.0449 (3)	0.0582 (11)
H7A	0.566 (2)	0.927 (7)	−0.059 (3)	0.050 (18)*
H7B	0.530 (3)	1.005 (5)	−0.031 (4)	0.10 (3)*
Cu2	1.00357 (3)	0.34185 (7)	0.52545 (3)	0.02704 (17)
C17	0.8821 (2)	0.4364 (7)	0.4052 (3)	0.0344 (11)
C18	0.8143 (2)	0.3902 (6)	0.3454 (3)	0.0335 (11)
C19	0.7823 (2)	0.5098 (7)	0.2908 (3)	0.0378 (11)
H19	0.800444	0.622163	0.293246	0.045*
C20	0.7232 (3)	0.4598 (7)	0.2326 (3)	0.0416 (12)
C21	0.6958 (3)	0.2923 (9)	0.2304 (3)	0.0511 (15)
H21	0.655720	0.258591	0.191294	0.061*
C22	0.7275 (3)	0.1787 (7)	0.2854 (3)	0.0509 (14)
H22	0.708932	0.067457	0.283747	0.061*
C23	0.7873 (3)	0.2266 (8)	0.3437 (3)	0.0450 (15)
H23	0.808799	0.148658	0.381440	0.054*
C24	0.7133 (3)	0.7314 (10)	0.1710 (4)	0.073 (2)
H24A	0.721094	0.799866	0.211808	0.110*
H24B	0.680916	0.791342	0.129157	0.110*
H24C	0.754901	0.717887	0.169388	0.110*
C25	1.0434 (2)	0.3824 (7)	0.4183 (2)	0.0327 (11)
C26	1.0650 (2)	0.3142 (7)	0.3676 (3)	0.0334 (11)
C27	1.0786 (3)	0.1352 (7)	0.3666 (3)	0.0438 (13)
H27	1.077861	0.058767	0.400195	0.053*
C28	1.0931 (3)	0.0720 (8)	0.3153 (3)	0.0532 (16)
H28	1.101825	−0.048261	0.314230	0.064*
C29	1.0948 (3)	0.1821 (8)	0.2661 (3)	0.0499 (15)
H29	1.103129	0.136388	0.230861	0.060*
C30	1.0841 (3)	0.3626 (7)	0.2686 (3)	0.0400 (13)
C31	1.0693 (2)	0.4274 (7)	0.3186 (3)	0.0342 (12)
H31	1.061863	0.548415	0.320089	0.041*
C32	1.1014 (4)	0.6486 (8)	0.2328 (4)	0.0647 (18)
H32A	1.063753	0.700448	0.235440	0.097*
H32B	1.106403	0.703643	0.195349	0.097*
H32C	1.141820	0.666487	0.276769	0.097*
O8	0.91180 (17)	0.3186 (4)	0.44982 (19)	0.0428 (9)
O9	0.90509 (18)	0.5881 (4)	0.40517 (17)	0.0416 (9)
O10	0.68798 (18)	0.5618 (5)	0.1750 (2)	0.0544 (10)
O11	1.0361 (2)	0.2734 (4)	0.4584 (2)	0.0385 (9)
O12	1.0316 (2)	0.5454 (4)	0.41646 (19)	0.0408 (9)
O13	1.0901 (2)	0.4638 (5)	0.2193 (2)	0.0610 (12)
O14	1.0181 (3)	0.0849 (5)	0.5712 (2)	0.0567 (12)
H14B	1.034 (4)	0.074 (8)	0.6150 (11)	0.10 (3)*
H14A	0.998 (3)	−0.009 (6)	0.552 (3)	0.09 (2)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0338 (4)	0.0263 (3)	0.0275 (4)	0.0029 (2)	0.0122 (3)	0.0011 (2)
C1	0.019 (2)	0.050 (3)	0.029 (3)	0.004 (2)	0.008 (2)	−0.002 (2)
C2	0.025 (3)	0.050 (3)	0.027 (3)	−0.004 (2)	0.010 (2)	−0.001 (2)
C3	0.051 (3)	0.044 (3)	0.043 (3)	−0.001 (3)	0.019 (3)	0.000 (3)
C4	0.066 (4)	0.043 (3)	0.059 (4)	−0.001 (3)	0.029 (3)	−0.017 (3)
C5	0.045 (3)	0.061 (4)	0.034 (3)	0.001 (3)	0.014 (3)	−0.016 (3)
C6	0.041 (3)	0.058 (3)	0.035 (3)	0.001 (3)	0.017 (3)	0.000 (3)
C7	0.045 (3)	0.047 (3)	0.033 (3)	0.000 (2)	0.020 (3)	−0.007 (2)
C8	0.157 (8)	0.080 (5)	0.048 (4)	0.050 (5)	0.050 (5)	0.021 (4)
C9	0.032 (3)	0.049 (3)	0.025 (2)	0.007 (2)	0.009 (2)	−0.004 (2)
C10	0.032 (3)	0.045 (3)	0.029 (3)	0.006 (2)	0.008 (2)	−0.005 (2)
C11	0.038 (3)	0.056 (4)	0.038 (3)	0.011 (3)	0.012 (2)	0.004 (3)
C12	0.040 (3)	0.068 (4)	0.060 (4)	0.025 (3)	0.013 (3)	−0.003 (3)
C13	0.033 (4)	0.086 (5)	0.056 (4)	0.008 (3)	0.020 (3)	−0.016 (3)
C14	0.034 (3)	0.075 (4)	0.048 (3)	0.000 (3)	0.018 (3)	−0.014 (3)
C15	0.039 (3)	0.055 (3)	0.036 (3)	0.001 (3)	0.012 (2)	−0.010 (3)
C16	0.080 (5)	0.078 (5)	0.103 (7)	−0.007 (4)	0.053 (5)	0.010 (5)
O1	0.047 (3)	0.0385 (19)	0.030 (2)	−0.0018 (16)	0.0142 (19)	−0.0012 (16)
O2	0.044 (2)	0.0358 (19)	0.0291 (19)	−0.0007 (16)	0.0129 (16)	−0.0034 (15)
O3	0.095 (3)	0.066 (3)	0.035 (2)	0.022 (2)	0.034 (2)	0.004 (2)
O4	0.0324 (18)	0.044 (2)	0.046 (2)	0.0060 (16)	0.0161 (16)	0.0035 (17)
O5	0.040 (2)	0.042 (2)	0.045 (2)	0.0090 (17)	0.0218 (18)	0.0052 (17)
O6	0.047 (2)	0.082 (3)	0.072 (3)	−0.008 (2)	0.033 (2)	−0.015 (3)
O7	0.092 (4)	0.031 (2)	0.070 (3)	0.001 (2)	0.053 (3)	0.009 (2)
Cu2	0.0363 (4)	0.0242 (3)	0.0232 (3)	−0.0029 (2)	0.0163 (3)	−0.0015 (2)
C17	0.033 (3)	0.044 (3)	0.030 (3)	0.000 (2)	0.018 (2)	−0.005 (2)
C18	0.031 (2)	0.040 (3)	0.033 (3)	−0.005 (2)	0.018 (2)	−0.005 (2)
C19	0.033 (3)	0.044 (3)	0.034 (3)	−0.005 (2)	0.014 (2)	−0.007 (2)
C20	0.033 (3)	0.058 (3)	0.030 (3)	0.004 (2)	0.012 (2)	−0.001 (2)
C21	0.042 (4)	0.062 (4)	0.041 (4)	−0.008 (3)	0.014 (3)	−0.010 (3)
C22	0.045 (3)	0.053 (3)	0.046 (3)	−0.019 (3)	0.015 (3)	−0.005 (3)
C23	0.045 (4)	0.051 (3)	0.034 (3)	−0.009 (3)	0.016 (3)	−0.005 (3)
C24	0.065 (4)	0.065 (4)	0.070 (5)	−0.001 (4)	0.016 (4)	0.018 (4)
C25	0.036 (3)	0.041 (3)	0.021 (2)	−0.005 (2)	0.014 (2)	−0.004 (2)
C26	0.032 (3)	0.041 (3)	0.033 (3)	−0.007 (2)	0.019 (2)	−0.009 (2)
C27	0.054 (3)	0.043 (3)	0.038 (3)	0.005 (3)	0.025 (3)	−0.001 (2)
C28	0.074 (4)	0.042 (3)	0.054 (4)	0.011 (3)	0.039 (3)	−0.004 (3)
C29	0.063 (4)	0.059 (4)	0.042 (3)	0.004 (3)	0.037 (3)	−0.011 (3)
C30	0.045 (3)	0.049 (3)	0.032 (3)	−0.010 (3)	0.023 (3)	−0.010 (2)
C31	0.039 (3)	0.035 (3)	0.029 (3)	−0.004 (2)	0.016 (2)	−0.002 (2)
C32	0.084 (5)	0.062 (4)	0.060 (4)	−0.022 (3)	0.044 (4)	−0.005 (3)
O8	0.038 (2)	0.044 (2)	0.038 (2)	−0.0101 (17)	0.0114 (17)	−0.0004 (17)
O9	0.041 (2)	0.0380 (18)	0.0358 (19)	−0.0083 (16)	0.0105 (17)	−0.0045 (16)
O10	0.044 (2)	0.059 (2)	0.042 (2)	0.0012 (18)	0.0057 (18)	0.0023 (19)
O11	0.060 (3)	0.0358 (18)	0.033 (2)	−0.0010 (17)	0.033 (2)	−0.0042 (15)
O12	0.065 (3)	0.0319 (19)	0.040 (2)	−0.0024 (17)	0.036 (2)	−0.0039 (15)
O13	0.099 (3)	0.058 (2)	0.047 (2)	−0.019 (2)	0.051 (2)	−0.013 (2)
O14	0.106 (4)	0.0252 (19)	0.036 (2)	−0.012 (2)	0.032 (2)	−0.0034 (17)

Geometric parameters (Å, º) top

Cu1—O1	1.949 (4)	Cu2—O8	1.936 (3)
Cu1—O2ⁱ	1.951 (3)	Cu2—O9ⁱⁱ	1.953 (3)
Cu1—O5	1.951 (3)	Cu2—O12ⁱⁱ	1.964 (3)
Cu1—O4ⁱ	1.959 (3)	Cu2—O11	1.973 (3)
Cu1—O7	2.171 (4)	Cu2—O14	2.126 (4)
Cu1—Cu1ⁱ	2.6060 (12)	Cu2—Cu2ⁱⁱ	2.5961 (11)
C1—O1	1.254 (6)	C17—O8	1.244 (6)
C1—O2	1.261 (6)	C17—O9	1.255 (6)
C1—C2	1.500 (7)	C17—C18	1.496 (7)
C2—C3	1.370 (7)	C18—C23	1.367 (7)
C2—C7	1.374 (8)	C18—C19	1.381 (7)
C3—C4	1.367 (9)	C19—C20	1.377 (7)
C3—H3	0.9300	C19—H19	0.9300
C4—C5	1.369 (8)	C20—O10	1.351 (6)
C4—H4	0.9300	C20—C21	1.396 (8)
C5—C6	1.381 (7)	C21—C22	1.355 (8)
C5—H5	0.9300	C21—H21	0.9300
C6—O3	1.362 (7)	C22—C23	1.382 (8)
C6—C7	1.378 (8)	C22—H22	0.9300
C7—H7	0.9300	C23—H23	0.9300
C8—O3	1.409 (7)	C24—O10	1.418 (8)
C8—H8A	0.9600	C24—H24A	0.9600
C8—H8B	0.9600	C24—H24B	0.9600
C8—H8C	0.9600	C24—H24C	0.9600
C9—O4	1.252 (6)	C25—O12	1.253 (6)
C9—O5	1.272 (6)	C25—O11	1.258 (6)
C9—C10	1.495 (7)	C25—C26	1.484 (7)
C10—C11	1.377 (7)	C26—C27	1.385 (7)
C10—C15	1.397 (7)	C26—C31	1.395 (7)
C11—C12	1.380 (8)	C27—C28	1.379 (8)
C11—H11	0.9300	C27—H27	0.9300
C12—C13	1.370 (9)	C28—C29	1.361 (8)
C12—H12	0.9300	C28—H28	0.9300
C13—C14	1.379 (9)	C29—C30	1.387 (8)
C13—H13	0.9300	C29—H29	0.9300
C14—C15	1.369 (8)	C30—C31	1.361 (7)
C14—O6	1.376 (7)	C30—O13	1.365 (7)
C15—H15	0.9300	C31—H31	0.9300
C16—O6	1.414 (8)	C32—O13	1.420 (6)
C16—H16A	0.9600	C32—H32A	0.9600
C16—H16B	0.9600	C32—H32B	0.9600
C16—H16C	0.9600	C32—H32C	0.9600
O7—H7A	0.835 (19)	O14—H14B	0.84 (2)
O7—H7B	0.830 (19)	O14—H14A	0.832 (19)

O1—Cu1—O2ⁱ	169.12 (15)	O8—Cu2—O9ⁱⁱ	168.91 (14)
O1—Cu1—O5	86.87 (16)	O8—Cu2—O12ⁱⁱ	89.02 (16)
O2ⁱ—Cu1—O5	90.77 (15)	O9ⁱⁱ—Cu2—O12ⁱⁱ	89.57 (16)
O1—Cu1—O4ⁱ	91.82 (16)	O8—Cu2—O11	88.84 (16)
O2ⁱ—Cu1—O4ⁱ	88.52 (15)	O9ⁱⁱ—Cu2—O11	90.47 (16)
O5—Cu1—O4ⁱ	169.26 (15)	O12ⁱⁱ—Cu2—O11	169.05 (14)
O1—Cu1—O7	90.79 (17)	O8—Cu2—O14	100.04 (17)
O2ⁱ—Cu1—O7	100.09 (17)	O9ⁱⁱ—Cu2—O14	91.05 (17)
O5—Cu1—O7	100.79 (17)	O12ⁱⁱ—Cu2—O14	96.79 (16)
O4ⁱ—Cu1—O7	89.89 (17)	O11—Cu2—O14	94.16 (15)
O1—Cu1—Cu1ⁱ	83.50 (11)	O8—Cu2—Cu2ⁱⁱ	84.33 (10)
O2ⁱ—Cu1—Cu1ⁱ	85.81 (10)	O9ⁱⁱ—Cu2—Cu2ⁱⁱ	84.59 (10)
O5—Cu1—Cu1ⁱ	88.03 (11)	O12ⁱⁱ—Cu2—Cu2ⁱⁱ	84.78 (10)
O4ⁱ—Cu1—Cu1ⁱ	81.23 (11)	O11—Cu2—Cu2ⁱⁱ	84.32 (11)
O7—Cu1—Cu1ⁱ	169.25 (15)	O14—Cu2—Cu2ⁱⁱ	175.37 (14)
O1—C1—O2	126.3 (5)	O8—C17—O9	125.4 (5)
O1—C1—C2	116.3 (5)	O8—C17—C18	116.9 (4)
O2—C1—C2	117.4 (5)	O9—C17—C18	117.6 (5)
C3—C2—C7	120.4 (5)	C23—C18—C19	121.4 (5)
C3—C2—C1	120.7 (5)	C23—C18—C17	119.4 (5)
C7—C2—C1	118.9 (5)	C19—C18—C17	119.1 (4)
C4—C3—C2	120.0 (6)	C20—C19—C18	118.8 (5)
C4—C3—H3	120.0	C20—C19—H19	120.6
C2—C3—H3	120.0	C18—C19—H19	120.6
C3—C4—C5	120.2 (5)	O10—C20—C19	124.8 (5)
C3—C4—H4	119.9	O10—C20—C21	115.3 (5)
C5—C4—H4	119.9	C19—C20—C21	119.9 (5)
C4—C5—C6	119.9 (5)	C22—C21—C20	120.0 (5)
C4—C5—H5	120.1	C22—C21—H21	120.0
C6—C5—H5	120.1	C20—C21—H21	120.0
O3—C6—C7	124.6 (5)	C21—C22—C23	120.6 (5)
O3—C6—C5	115.5 (5)	C21—C22—H22	119.7
C7—C6—C5	119.9 (5)	C23—C22—H22	119.7
C2—C7—C6	119.4 (5)	C18—C23—C22	119.2 (6)
C2—C7—H7	120.3	C18—C23—H23	120.4
C6—C7—H7	120.3	C22—C23—H23	120.4
O3—C8—H8A	109.5	O10—C24—H24A	109.5
O3—C8—H8B	109.5	O10—C24—H24B	109.5
H8A—C8—H8B	109.5	H24A—C24—H24B	109.5
O3—C8—H8C	109.5	O10—C24—H24C	109.5
H8A—C8—H8C	109.5	H24A—C24—H24C	109.5
H8B—C8—H8C	109.5	H24B—C24—H24C	109.5
O4—C9—O5	125.2 (5)	O12—C25—O11	124.5 (5)
O4—C9—C10	117.3 (5)	O12—C25—C26	117.1 (4)
O5—C9—C10	117.4 (5)	O11—C25—C26	118.4 (4)
C11—C10—C15	119.7 (5)	C27—C26—C31	119.3 (5)
C11—C10—C9	121.5 (5)	C27—C26—C25	119.9 (5)
C15—C10—C9	118.6 (5)	C31—C26—C25	120.7 (4)
C10—C11—C12	119.4 (6)	C28—C27—C26	119.1 (5)
C10—C11—H11	120.3	C28—C27—H27	120.5
C12—C11—H11	120.3	C26—C27—H27	120.5
C13—C12—C11	121.0 (6)	C29—C28—C27	121.3 (5)
C13—C12—H12	119.5	C29—C28—H28	119.3
C11—C12—H12	119.5	C27—C28—H28	119.3
C12—C13—C14	119.5 (6)	C28—C29—C30	119.8 (5)
C12—C13—H13	120.2	C28—C29—H29	120.1
C14—C13—H13	120.2	C30—C29—H29	120.1
C15—C14—O6	124.8 (6)	C31—C30—O13	124.5 (5)
C15—C14—C13	120.4 (6)	C31—C30—C29	119.7 (5)
O6—C14—C13	114.8 (5)	O13—C30—C29	115.8 (5)
C14—C15—C10	119.9 (5)	C30—C31—C26	120.6 (5)
C14—C15—H15	120.0	C30—C31—H31	119.7
C10—C15—H15	120.0	C26—C31—H31	119.7
O6—C16—H16A	109.5	O13—C32—H32A	109.5
O6—C16—H16B	109.5	O13—C32—H32B	109.5
H16A—C16—H16B	109.5	H32A—C32—H32B	109.5
O6—C16—H16C	109.5	O13—C32—H32C	109.5
H16A—C16—H16C	109.5	H32A—C32—H32C	109.5
H16B—C16—H16C	109.5	H32B—C32—H32C	109.5
C1—O1—Cu1	123.6 (3)	C17—O8—Cu2	123.5 (3)
C1—O2—Cu1ⁱ	120.6 (3)	C17—O9—Cu2ⁱⁱ	122.0 (3)
C6—O3—C8	117.0 (5)	C20—O10—C24	119.4 (5)
C9—O4—Cu1ⁱ	126.7 (3)	C25—O11—Cu2	123.2 (3)
C9—O5—Cu1	118.7 (3)	C25—O12—Cu2ⁱⁱ	123.2 (3)
C14—O6—C16	118.1 (5)	C30—O13—C32	117.6 (4)
Cu1—O7—H7A	127 (4)	Cu2—O14—H14B	120 (4)
Cu1—O7—H7B	123 (4)	Cu2—O14—H14A	128 (4)
H7A—O7—H7B	109 (3)	H14B—O14—H14A	108 (3)

O1—C1—C2—C3	12.5 (7)	O8—C17—C18—C23	2.6 (7)
O2—C1—C2—C3	−166.2 (5)	O9—C17—C18—C23	−179.6 (5)
O1—C1—C2—C7	−169.6 (5)	O8—C17—C18—C19	−173.4 (5)
O2—C1—C2—C7	11.8 (7)	O9—C17—C18—C19	4.4 (7)
C7—C2—C3—C4	−4.4 (9)	C23—C18—C19—C20	−2.3 (8)
C1—C2—C3—C4	173.6 (5)	C17—C18—C19—C20	173.7 (5)
C2—C3—C4—C5	3.6 (10)	C18—C19—C20—O10	−178.2 (5)
C3—C4—C5—C6	0.0 (10)	C18—C19—C20—C21	1.6 (8)
C4—C5—C6—O3	178.1 (6)	O10—C20—C21—C22	179.4 (5)
C4—C5—C6—C7	−2.9 (10)	C19—C20—C21—C22	−0.4 (9)
C3—C2—C7—C6	1.4 (8)	C20—C21—C22—C23	−0.3 (10)
C1—C2—C7—C6	−176.5 (5)	C19—C18—C23—C22	1.6 (9)
O3—C6—C7—C2	−178.9 (5)	C17—C18—C23—C22	−174.3 (5)
C5—C6—C7—C2	2.2 (9)	C21—C22—C23—C18	−0.3 (10)
O4—C9—C10—C11	−178.6 (5)	O12—C25—C26—C27	−179.6 (5)
O5—C9—C10—C11	3.5 (7)	O11—C25—C26—C27	−2.0 (7)
O4—C9—C10—C15	7.5 (7)	O12—C25—C26—C31	−2.3 (7)
O5—C9—C10—C15	−170.4 (5)	O11—C25—C26—C31	175.4 (5)
C15—C10—C11—C12	−1.2 (8)	C31—C26—C27—C28	−2.8 (8)
C9—C10—C11—C12	−175.1 (5)	C25—C26—C27—C28	174.6 (5)
C10—C11—C12—C13	2.6 (9)	C26—C27—C28—C29	0.5 (10)
C11—C12—C13—C14	−1.7 (10)	C27—C28—C29—C30	2.2 (10)
C12—C13—C14—C15	−0.6 (9)	C28—C29—C30—C31	−2.6 (9)
C12—C13—C14—O6	−179.8 (6)	C28—C29—C30—O13	176.8 (6)
O6—C14—C15—C10	−179.0 (5)	O13—C30—C31—C26	−179.1 (5)
C13—C14—C15—C10	1.9 (8)	C29—C30—C31—C26	0.3 (8)
C11—C10—C15—C14	−1.0 (8)	C27—C26—C31—C30	2.4 (8)
C9—C10—C15—C14	173.0 (5)	C25—C26—C31—C30	−175.0 (5)
O2—C1—O1—Cu1	0.7 (7)	O9—C17—O8—Cu2	−4.5 (7)
C2—C1—O1—Cu1	−177.8 (3)	C18—C17—O8—Cu2	173.2 (3)
O1—C1—O2—Cu1ⁱ	−3.4 (7)	O8—C17—O9—Cu2ⁱⁱ	3.9 (7)
C2—C1—O2—Cu1ⁱ	175.1 (3)	C18—C17—O9—Cu2ⁱⁱ	−173.8 (3)
C7—C6—O3—C8	15.7 (10)	C19—C20—O10—C24	2.3 (8)
C5—C6—O3—C8	−165.3 (6)	C21—C20—O10—C24	−177.5 (6)
O5—C9—O4—Cu1ⁱ	3.4 (7)	O12—C25—O11—Cu2	0.4 (7)
C10—C9—O4—Cu1ⁱ	−174.3 (3)	C26—C25—O11—Cu2	−177.1 (3)
O4—C9—O5—Cu1	−3.0 (7)	O11—C25—O12—Cu2ⁱⁱ	−1.9 (7)
C10—C9—O5—Cu1	174.7 (3)	C26—C25—O12—Cu2ⁱⁱ	175.6 (3)
C15—C14—O6—C16	1.4 (9)	C31—C30—O13—C32	19.3 (9)
C13—C14—O6—C16	−179.5 (6)	C29—C30—O13—C32	−160.1 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O7—H7A···O3ⁱⁱⁱ	0.84 (2)	2.11 (3)	2.912 (6)	161 (5)
O7—H7B···O1^iv	0.83 (2)	2.42 (5)	3.107 (6)	141 (7)
O7—H7B···O5^iv	0.83 (2)	2.60 (5)	3.306 (6)	144 (6)
O14—H14B···O13^v	0.84 (2)	2.00 (2)	2.831 (6)	169 (8)
O14—H14A···O11^vi	0.83 (2)	2.11 (3)	2.905 (5)	160 (6)
O14—H14A···O14^vi	0.83 (2)	2.57 (5)	3.055 (8)	118 (5)
C23—H23···O6^vii	0.93	2.52	3.355 (7)	149
C27—H27···O6^viii	0.93	2.57	3.114 (7)	117

Symmetry codes: (iii) x, −y+3/2, z−1/2; (iv) −x+1, −y+2, −z; (v) x, −y+1/2, z+1/2; (vi) −x+2, −y, −z+1; (vii) −x+1, y−1/2, −z+1/2; (viii) x+1, −y+1/2, z+1/2.

Acknowledgements

BRS acknowledges the Sophisticated Analytical Instrument Facility (SAIF), Indian Institute of Technology (IIT), Madras, for the single-crystal X-ray data collection.

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