Di-μ-aqua-bis­[aqua­(2,2′-bi­pyridine)(4-nitro­benzoato)cobalt(II)] bis­(4-nitro­benzoate)

Srinivasan, B.R.; Harmalkar, S.S.; D'Souza, L.R.; Dhuri, S.N.

doi:10.1107/S2414314620007968

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 5| Part 6| June 2020| x200796

https://doi.org/10.1107/S2414314620007968

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Di-μ-aqua-bis[aqua(2,2′-bipyridine)(4-nitrobenzoato)cobalt(II)] bis(4-nitrobenzoate)

Bikshandarkoil R. Srinivasan,^a Sarvesh S. Harmalkar,^a Luann R. D'Souza ^a and Sunder N. Dhuri ^a ^*

^aSchool of Chemical Sciences, Goa University, Goa 403206, India
^*Correspondence e-mail: sndhuri@unigoa.ac.in

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 27 May 2020; accepted 13 June 2020; online 19 June 2020)

The title compound, [Co₂(C₇H₄NO₄)₂(C₁₀H₈N₂)₂(H₂O)₄](C₇H₄NO₄)₂, consists of a centrosymmetric bimetallic complex charge-balanced by free 4-nitrobenzoate anions. The Co^II ion exhibits a distorted cis-CoN₂O₄ octahedral coordination environment and the Co⋯Co separation is 3.326 (2) Å. In the crystal, the dications and anions are linked by O—H⋯O and C—H⋯O hydrogen bonds.

Keywords: crystal structure; bimetallic complex; divalent-metal 4-nitrobenzoate; hydrogen bonds.

CCDC reference: 2009578

Structure description

As part of an ongoing research program we are investigating the structural aspects of mixed-ligand compounds of divalent-metal 4-nitrobenzoates. Recently we described the structure of [Co(H₂O)₂(DMSO)₂(C₇H₄NO₄)](C₇H₄NO₄) 2 (DMSO = dimethylsulfoxide; C₇H₄NO₄ = 4-nitrobenzoate) containing a bidentate as well as a free 4-nitrobenzoate anion (Srinivasan et al., 2020 ). Our attempts to replace the cis-aqua ligands of 2 with 2,2′-bipyridine has resulted in the isolation of the diaqua-bridged title dinuclear compound. The Cambridge Structural Database (CSD, version 5.40, update September 2019; Groom et al., 2016 ) lists the structures of several cobalt 4-nitrobenzoates: of these, more than a dozen are mononuclear cobalt compounds (Srinivasan et al., 2004 , 2020; Chakravorty et al., 2011 ) while only four dinuclear compounds of 4-nitrobenzoate are known to date (Singh et al., 2007 ; Jung et al., 2009 ; Yang et al., 2011 ; Wang & Qi, 2014 ). The title compound is a new addition to the list of dimeric cobalt 4-nitrobenzoates.

The structure of the title compound, 1, consists of a crystallographically unique cobaltous ion and a 2,2′-bipyridine molecule, two crystallographically independent 4-nitrobenzoate ions and two unique aqua ligands (one terminal, one bridging). The Co^II ion, one 4-nitrobenzoate ion, one 2,2′-bipyridine molecule and each of a terminal and bridging water molecule build up one half of a dimeric dicationic species [Co₂(H₂O)₂(C₁₀H₈N₂)₂(C₇H₄NO₄)₂(μ₂-H₂O)₂]²⁺, the other half being generated by inversion symmetry (Fig. 1). The crystallographic inversion centre is situated at the midpoint of the line connecting the Co^II atoms in the dimer. A charge-balancing 4-nitrobenzoate ion completes the structure.

Figure 1
The dinuclear dication in 1 with displacement ellipsoids drawn at the 50% probability level. Intramolecular hydrogen bonds are shown as broken lines [Symmetry code: (i) 1 – x, 1 – y, 1 – z.]

In the centrosymmetric dimer, each Co^II ion exhibits a distorted octahedral environment and is bonded to a terminal aqua ligand, a monodentate 4-nitrobenzoate ligand disposed cis to the terminal aqua ligand and a bidentate 2,2′-bipyridine molecule. A pair of cis-aqua ligands bridges the metal centres and completes the hexa-coordination around the metal ions resulting in a Co⋯Co(1 – x, 1 – y, 1 – z) separation of 3.326 (2) Å. It is interesting to note that in three of the four known dinuclear cobalt compounds (Singh et al., 2007; Yang et al., 2011; Wang & Qi, 2014), the 4-nitrobenzoate anion functions as a monodentate ligand as in the title compound. One example each of a dinuclear (Jung et al., 2009) and a tetranuclear cobalt compound (Dimitrou et al., 2001 ) is known where the 4-nitrobenzoate ion functions as a symmetric bridging ligand.

The geometric parameters of 1 are in their normal ranges and are in agreement with reported data (Srinivasan et al., 2020). The Co—O_w (w = water) bonds [2.0743 (10) and 2.1617 (9) Å] are elongated as compared to the Co—O_c (c = carboxylate) distance, which is the shortest at 2.0494 (9) Å. The cis-O—Co—O and N—Co—N bond angles range between 77.97 (4) and 100.02 (4)°, while the trans bond angles deviate from ideal values, indicating a distortion of the {CoN₂O₄} octahedron.

All of the H atoms attached to the aqua ligands, and five of the other H atoms viz. H9, H14, H16, H17 and H21 bonded to C9, C14, C16, C17 and C21, respectively, function as hydrogen-bond donors, while the oxygen atoms O2, O3, O5, O6 and O7 of the 4-nitrobenzoate ions function as acceptors, resulting in a total of four O—H⋯O and five C—H⋯O hydrogen bonds (Table 1). Each free 4-nitrobenzoate anion is linked with four symmetry-related dications with the aid of two O—H⋯O hydrogen bonds and four C—H⋯O hydrogen bonds (Figs. 2 and 3). Each of the dinuclear dicobalt dicationic species is linked with two symmetry-related dications and eight symmetry-generated anions (Fig. 4), resulting in a three-dimensional supramolecular network.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2W—H2B⋯O5ⁱ	0.84 (2)	1.67 (2)	2.5101 (13)	173 (2)
O2W—H2A⋯O3	0.79 (2)	1.88 (2)	2.6483 (13)	164 (2)
O1W—H1B⋯O3ⁱⁱ	0.82 (2)	2.04 (2)	2.8477 (14)	174 (2)
O1W—H1A⋯O6ⁱⁱⁱ	0.81 (2)	1.88 (2)	2.6803 (14)	171 (2)
C21—H21⋯O2^iv	0.93	2.48	3.2219 (17)	137
C17—H17⋯O5ⁱ	0.93	2.24	3.1679 (16)	172
C16—H16⋯O2^v	0.93	2.57	3.4644 (17)	160
C14—H14⋯O6^vi	0.93	2.41	3.3126 (16)	164
C9—H9⋯O7^vii	0.93	2.64	3.5467 (18)	164
Symmetry codes: (i) x-1, y, z; (ii) -x, -y+1, -z+1; (iii) -x+1, -y+1, -z+1; (iv) x+1, y, z-1; (v) x, y, z-1; (vi) x, y+1, z; (vii) x, y+1, z+1.

Figure 2
The hydrogen-bonding scheme around the 4-nitrobenzoate anion showing the O—H⋯O and C—H⋯O hydrogen bonds as dashed lines. For symmetry codes see Table 1

Figure 3
Environment of the anion, showing its hydrogen bonds to four symmetrically related dications via O—H⋯O and C—H⋯O bonds.

Figure 4
The hydrogen-bonding scheme around the dication showing its linking with eight anions and two cations via O—H⋯O and C—H⋯O hydrogen bonds.

Synthesis and crystallization

Crystals of 2 (0.0292 g, 0.05 mmol) were taken in DMSO (3 ml) to obtain a purple solution. 2,2′-Bipyridine (0.0078 g, 0.05 mmol) was dissolved in DMSO (3 ml) in a separate beaker and then was added dropwise to the cobalt solution with continuous swirling. The pale-orange solution thus obtained was left undisturbed at room temperature. After to days, dark-orange blocks of 1 started forming in the solution, which were isolated by filtration and air dried. Yield 60%.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	[Co₂(C₇H₄NO₄)₂(C₁₀H₈N₂)₂(H₂O)₄](C₇H₄NO₄)₂
M_r	1166.74
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	296
a, b, c (Å)	7.2747 (5), 10.4927 (8), 16.3560 (12)
α, β, γ (°)	97.735 (2), 102.840 (2), 102.607 (2)
V (Å³)	1165.70 (15)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.81
Crystal size (mm)	0.45 × 0.32 × 0.21

Data collection
Diffractometer	Bruker D8 Quest eco
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
No. of measured, independent and observed [I > 2σ(I)] reflections	26747, 5763, 5312
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.064, 1.05
No. of reflections	5763
No. of parameters	368
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.31
Computer programs: APEX3 and SAINT (Bruker, 2019 ), SHELXT2014/5 (Sheldrick, 20015a ), SHELXL2018 (Sheldrick, 2015b ), DIAMOND (Brandenburg, 1999 ) and shelXle (Hübschle et al., 2011 ).

Structural data

CCDC reference: 2009578

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314620007968/hb4348sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314620007968/hb4348Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2019); cell refinement: SAINT (Bruker, 2019); data reduction: SAINT (Bruker, 2019); program(s) used to solve structure: SHELXT2014/5 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: shelXle (Hübschle et al., 2011).

Di-µ-aqua-bis[aqua(2,2'-bipyridine)(4-nitrobenzoato)cobalt(II)] bis(4-nitrobenzoate) top

Crystal data top

[Co₂(C₇H₄NO₄)₂(C₁₀H₈N₂)₂(H₂O)₄](C₇H₄NO₄)₂	Z = 1
M_r = 1166.74	F(000) = 598
Triclinic, P1	D_x = 1.662 Mg m⁻³
a = 7.2747 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.4927 (8) Å	Cell parameters from 9978 reflections
c = 16.3560 (12) Å	θ = 2.9–28.2°
α = 97.735 (2)°	µ = 0.81 mm⁻¹
β = 102.840 (2)°	T = 296 K
γ = 102.607 (2)°	Block, orange
V = 1165.70 (15) Å³	0.45 × 0.32 × 0.21 mm

Data collection top

Bruker D8 Quest eco diffractometer	5312 reflections with I > 2σ(I)
Radiation source: Sealed Tube	R_int = 0.025
φ and ω scans	θ_max = 28.3°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −9→9
	k = −13→13
26747 measured reflections	l = −21→21
5763 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.064	w = 1/[σ²(F_o²) + (0.0255P)² + 0.6838P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.003
5763 reflections	Δρ_max = 0.36 e Å⁻³
368 parameters	Δρ_min = −0.31 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.

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

	x	y	z	U_iso*/U_eq
Co1	0.43361 (2)	0.63922 (2)	0.52457 (2)	0.01063 (5)
O1	0.43137 (17)	0.71403 (11)	1.06326 (6)	0.0261 (2)
N1	0.32901 (17)	0.60682 (12)	1.01984 (7)	0.0180 (2)
C1	0.32850 (19)	0.57702 (13)	0.92928 (8)	0.0147 (2)
O2	0.22558 (18)	0.52407 (11)	1.04780 (7)	0.0289 (2)
N2	0.61203 (16)	0.83416 (10)	0.57038 (7)	0.0131 (2)
C2	0.45366 (19)	0.66787 (13)	0.89966 (8)	0.0168 (3)
H2	0.539777	0.742960	0.936466	0.020*
O3	0.19021 (13)	0.40968 (9)	0.61539 (6)	0.01502 (18)
N3	0.44762 (16)	0.70799 (11)	0.41050 (7)	0.0130 (2)
C3	0.44682 (19)	0.64358 (13)	0.81350 (8)	0.0161 (2)
H3	0.529735	0.703100	0.792083	0.019*
O4	0.43133 (13)	0.59742 (9)	0.64323 (6)	0.01478 (18)
N4	0.82411 (18)	0.08005 (12)	−0.06413 (8)	0.0207 (2)
C4	0.31743 (18)	0.53122 (12)	0.75861 (8)	0.0129 (2)
C5	0.1950 (2)	0.44082 (13)	0.79086 (8)	0.0169 (3)
H5	0.109775	0.365050	0.754405	0.020*
O5	1.07575 (15)	0.36007 (10)	0.32867 (6)	0.0211 (2)
C6	0.1994 (2)	0.46313 (13)	0.87707 (8)	0.0180 (3)
H6	0.118041	0.403405	0.899036	0.022*
O6	0.85644 (15)	0.18061 (9)	0.33776 (6)	0.0203 (2)
C7	0.31025 (18)	0.51044 (12)	0.66454 (8)	0.0127 (2)
O7	0.91826 (18)	0.15271 (12)	−0.10126 (7)	0.0317 (3)
C8	0.6889 (2)	0.89288 (13)	0.65249 (8)	0.0167 (3)
H8	0.650756	0.848993	0.694104	0.020*
O8	0.70001 (17)	−0.02340 (11)	−0.10076 (7)	0.0297 (2)
C9	0.8231 (2)	1.01652 (13)	0.67843 (9)	0.0188 (3)
H9	0.874547	1.054302	0.736112	0.023*
C10	0.8785 (2)	1.08205 (13)	0.61629 (9)	0.0191 (3)
H10	0.967902	1.164988	0.631700	0.023*
C11	0.79935 (19)	1.02285 (13)	0.53093 (9)	0.0165 (2)
H11	0.834491	1.065696	0.488378	0.020*
C12	0.66666 (18)	0.89850 (12)	0.50973 (8)	0.0131 (2)
C13	0.57188 (18)	0.82847 (12)	0.41994 (8)	0.0130 (2)
C14	0.6047 (2)	0.88285 (13)	0.34951 (9)	0.0176 (3)
H14	0.691802	0.965414	0.356946	0.021*
C15	0.5048 (2)	0.81138 (14)	0.26838 (9)	0.0206 (3)
H15	0.525861	0.845041	0.220521	0.025*
C16	0.3734 (2)	0.68944 (14)	0.25880 (9)	0.0188 (3)
H16	0.302949	0.641070	0.204804	0.023*
C17	0.34957 (19)	0.64140 (13)	0.33163 (8)	0.0155 (2)
H17	0.261827	0.559500	0.325489	0.019*
C18	0.95292 (19)	0.24975 (13)	0.29757 (8)	0.0146 (2)
C19	0.92261 (19)	0.20072 (13)	0.20274 (8)	0.0149 (2)
C20	1.03275 (19)	0.27527 (13)	0.15766 (9)	0.0173 (3)
H20	1.127507	0.352694	0.186407	0.021*
O1W	0.16527 (15)	0.68171 (11)	0.51582 (7)	0.0186 (2)
C21	1.0024 (2)	0.23507 (14)	0.07020 (9)	0.0189 (3)
H21	1.075168	0.284846	0.039878	0.023*
C22	0.8611 (2)	0.11911 (13)	0.02938 (9)	0.0178 (3)
C23	0.7511 (2)	0.04133 (14)	0.07225 (9)	0.0218 (3)
H23	0.658049	−0.036827	0.043395	0.026*
C24	0.7839 (2)	0.08360 (14)	0.15973 (9)	0.0203 (3)
H24	0.712092	0.032818	0.189930	0.024*
O2W	0.30828 (13)	0.43132 (9)	0.47476 (6)	0.01185 (17)
H1A	0.148 (3)	0.718 (2)	0.5594 (15)	0.042 (6)*
H1B	0.066 (3)	0.650 (2)	0.4773 (14)	0.039 (6)*
H2A	0.264 (3)	0.410 (2)	0.5123 (15)	0.045 (6)*
H2B	0.223 (3)	0.404 (2)	0.4276 (14)	0.039 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.01158 (9)	0.01116 (8)	0.00889 (8)	0.00091 (6)	0.00424 (6)	0.00170 (6)
O1	0.0363 (6)	0.0240 (5)	0.0128 (5)	0.0000 (5)	0.0064 (4)	−0.0016 (4)
N1	0.0228 (6)	0.0209 (6)	0.0115 (5)	0.0064 (5)	0.0061 (4)	0.0034 (4)
C1	0.0187 (6)	0.0180 (6)	0.0092 (6)	0.0061 (5)	0.0056 (5)	0.0031 (5)
O2	0.0405 (6)	0.0285 (6)	0.0170 (5)	−0.0013 (5)	0.0154 (5)	0.0056 (4)
N2	0.0144 (5)	0.0128 (5)	0.0126 (5)	0.0034 (4)	0.0045 (4)	0.0024 (4)
C2	0.0173 (6)	0.0177 (6)	0.0128 (6)	0.0004 (5)	0.0037 (5)	0.0011 (5)
O3	0.0163 (4)	0.0161 (4)	0.0111 (4)	0.0010 (3)	0.0048 (3)	0.0008 (3)
N3	0.0136 (5)	0.0141 (5)	0.0118 (5)	0.0033 (4)	0.0047 (4)	0.0025 (4)
C3	0.0166 (6)	0.0180 (6)	0.0130 (6)	0.0003 (5)	0.0061 (5)	0.0032 (5)
O4	0.0174 (4)	0.0162 (4)	0.0112 (4)	0.0019 (4)	0.0065 (3)	0.0032 (3)
N4	0.0239 (6)	0.0204 (6)	0.0168 (6)	0.0057 (5)	0.0054 (5)	0.0002 (5)
C4	0.0139 (6)	0.0156 (6)	0.0108 (6)	0.0051 (5)	0.0049 (4)	0.0028 (5)
C5	0.0200 (6)	0.0154 (6)	0.0135 (6)	0.0003 (5)	0.0063 (5)	0.0008 (5)
O5	0.0234 (5)	0.0185 (5)	0.0136 (5)	−0.0051 (4)	−0.0005 (4)	0.0027 (4)
C6	0.0230 (7)	0.0176 (6)	0.0141 (6)	0.0014 (5)	0.0092 (5)	0.0041 (5)
O6	0.0241 (5)	0.0161 (4)	0.0205 (5)	−0.0001 (4)	0.0116 (4)	0.0012 (4)
C7	0.0139 (6)	0.0154 (6)	0.0109 (6)	0.0056 (5)	0.0053 (4)	0.0037 (5)
O7	0.0416 (7)	0.0307 (6)	0.0202 (5)	−0.0008 (5)	0.0134 (5)	0.0028 (5)
C8	0.0194 (6)	0.0161 (6)	0.0143 (6)	0.0047 (5)	0.0046 (5)	0.0016 (5)
O8	0.0345 (6)	0.0258 (5)	0.0202 (5)	−0.0017 (5)	0.0046 (5)	−0.0046 (4)
C9	0.0200 (6)	0.0174 (6)	0.0156 (6)	0.0047 (5)	0.0011 (5)	−0.0023 (5)
C10	0.0165 (6)	0.0137 (6)	0.0240 (7)	0.0017 (5)	0.0038 (5)	−0.0003 (5)
C11	0.0163 (6)	0.0135 (6)	0.0199 (6)	0.0024 (5)	0.0065 (5)	0.0036 (5)
C12	0.0126 (6)	0.0133 (6)	0.0141 (6)	0.0038 (5)	0.0042 (5)	0.0026 (5)
C13	0.0125 (6)	0.0130 (5)	0.0134 (6)	0.0027 (4)	0.0041 (5)	0.0022 (5)
C14	0.0194 (6)	0.0159 (6)	0.0173 (6)	0.0008 (5)	0.0069 (5)	0.0047 (5)
C15	0.0271 (7)	0.0216 (7)	0.0138 (6)	0.0032 (6)	0.0079 (5)	0.0064 (5)
C16	0.0234 (7)	0.0194 (6)	0.0125 (6)	0.0036 (5)	0.0050 (5)	0.0025 (5)
C17	0.0174 (6)	0.0138 (6)	0.0135 (6)	0.0009 (5)	0.0045 (5)	0.0014 (5)
C18	0.0140 (6)	0.0137 (6)	0.0155 (6)	0.0039 (5)	0.0030 (5)	0.0024 (5)
C19	0.0137 (6)	0.0146 (6)	0.0161 (6)	0.0037 (5)	0.0033 (5)	0.0024 (5)
C20	0.0149 (6)	0.0162 (6)	0.0178 (6)	−0.0001 (5)	0.0036 (5)	0.0013 (5)
O1W	0.0149 (5)	0.0254 (5)	0.0154 (5)	0.0058 (4)	0.0049 (4)	0.0004 (4)
C21	0.0190 (6)	0.0185 (6)	0.0188 (7)	0.0015 (5)	0.0071 (5)	0.0039 (5)
C22	0.0199 (6)	0.0178 (6)	0.0153 (6)	0.0055 (5)	0.0047 (5)	0.0003 (5)
C23	0.0242 (7)	0.0156 (6)	0.0194 (7)	−0.0032 (5)	0.0044 (5)	−0.0018 (5)
C24	0.0235 (7)	0.0159 (6)	0.0183 (7)	−0.0019 (5)	0.0068 (5)	0.0013 (5)
O2W	0.0120 (4)	0.0137 (4)	0.0085 (4)	0.0000 (3)	0.0036 (3)	0.0012 (3)

Geometric parameters (Å, º) top

Co1—O4	2.0494 (9)	C8—H8	0.9300
Co1—O1W	2.0743 (10)	C9—C10	1.385 (2)
Co1—N2	2.1038 (11)	C9—H9	0.9300
Co1—N3	2.1039 (11)	C10—C11	1.386 (2)
Co1—O2W	2.1394 (9)	C10—H10	0.9300
Co1—O2Wⁱ	2.1617 (9)	C11—C12	1.3908 (17)
O1—N1	1.2282 (16)	C11—H11	0.9300
N1—O2	1.2262 (15)	C12—C13	1.4868 (18)
N1—C1	1.4712 (16)	C13—C14	1.3960 (18)
C1—C2	1.3833 (18)	C14—C15	1.3845 (19)
C1—C6	1.3851 (19)	C14—H14	0.9300
N2—C8	1.3376 (17)	C15—C16	1.3861 (19)
N2—C12	1.3550 (16)	C15—H15	0.9300
C2—C3	1.3857 (18)	C16—C17	1.3851 (18)
C2—H2	0.9300	C16—H16	0.9300
O3—C7	1.2581 (16)	C17—H17	0.9300
N3—C17	1.3386 (16)	C18—C19	1.5176 (18)
N3—C13	1.3511 (16)	C19—C24	1.3906 (18)
C3—C4	1.3918 (18)	C19—C20	1.3934 (18)
C3—H3	0.9300	C20—C21	1.3890 (19)
O4—C7	1.2655 (15)	C20—H20	0.9300
N4—O7	1.2251 (16)	O1W—H1A	0.81 (2)
N4—O8	1.2284 (16)	O1W—H1B	0.82 (2)
N4—C22	1.4763 (17)	C21—C22	1.3831 (19)
C4—C5	1.3951 (17)	C21—H21	0.9300
C4—C7	1.5121 (17)	C22—C23	1.3844 (19)
C5—C6	1.3900 (18)	C23—C24	1.390 (2)
C5—H5	0.9300	C23—H23	0.9300
O5—C18	1.2590 (16)	C24—H24	0.9300
C6—H6	0.9300	O2W—H2A	0.79 (2)
O6—C18	1.2499 (16)	O2W—H2B	0.84 (2)
C8—C9	1.3897 (19)

O4—Co1—O1W	88.78 (4)	C9—C10—C11	119.35 (12)
O4—Co1—N2	95.06 (4)	C9—C10—H10	120.3
O1W—Co1—N2	98.21 (4)	C11—C10—H10	120.3
O4—Co1—N3	172.65 (4)	C10—C11—C12	119.11 (12)
O1W—Co1—N3	89.91 (4)	C10—C11—H11	120.4
N2—Co1—N3	77.97 (4)	C12—C11—H11	120.4
O4—Co1—O2W	87.29 (4)	N2—C12—C11	121.70 (12)
O1W—Co1—O2W	93.78 (4)	N2—C12—C13	115.43 (11)
N2—Co1—O2W	167.83 (4)	C11—C12—C13	122.86 (12)
N3—Co1—O2W	100.02 (4)	N3—C13—C14	121.59 (12)
O4—Co1—O2Wⁱ	91.60 (4)	N3—C13—C12	115.34 (11)
O1W—Co1—O2Wⁱ	172.46 (4)	C14—C13—C12	123.07 (11)
N2—Co1—O2Wⁱ	89.26 (4)	C15—C14—C13	118.67 (12)
N3—Co1—O2Wⁱ	90.64 (4)	C15—C14—H14	120.7
O2W—Co1—O2Wⁱ	78.72 (4)	C13—C14—H14	120.7
O2—N1—O1	123.42 (12)	C14—C15—C16	119.70 (12)
O2—N1—C1	118.33 (11)	C14—C15—H15	120.2
O1—N1—C1	118.23 (11)	C16—C15—H15	120.2
C2—C1—C6	123.04 (12)	C17—C16—C15	118.36 (13)
C2—C1—N1	117.76 (12)	C17—C16—H16	120.8
C6—C1—N1	119.15 (11)	C15—C16—H16	120.8
C8—N2—C12	118.50 (11)	N3—C17—C16	122.72 (12)
C8—N2—Co1	126.05 (9)	N3—C17—H17	118.6
C12—N2—Co1	115.11 (8)	C16—C17—H17	118.6
C1—C2—C3	117.98 (12)	O6—C18—O5	125.68 (12)
C1—C2—H2	121.0	O6—C18—C19	119.05 (12)
C3—C2—H2	121.0	O5—C18—C19	115.27 (11)
C17—N3—C13	118.93 (11)	C24—C19—C20	119.42 (12)
C17—N3—Co1	125.64 (9)	C24—C19—C18	120.96 (12)
C13—N3—Co1	115.41 (8)	C20—C19—C18	119.60 (12)
C2—C3—C4	120.82 (12)	C21—C20—C19	120.64 (12)
C2—C3—H3	119.6	C21—C20—H20	119.7
C4—C3—H3	119.6	C19—C20—H20	119.7
C7—O4—Co1	129.34 (8)	Co1—O1W—H1A	116.9 (15)
O7—N4—O8	123.35 (12)	Co1—O1W—H1B	127.0 (15)
O7—N4—C22	118.32 (12)	H1A—O1W—H1B	114 (2)
O8—N4—C22	118.33 (12)	C22—C21—C20	118.29 (13)
C3—C4—C5	119.66 (12)	C22—C21—H21	120.9
C3—C4—C7	119.19 (11)	C20—C21—H21	120.9
C5—C4—C7	121.15 (11)	C21—C22—C23	122.70 (13)
C6—C5—C4	120.51 (12)	C21—C22—N4	117.93 (12)
C6—C5—H5	119.7	C23—C22—N4	119.34 (12)
C4—C5—H5	119.7	C22—C23—C24	117.98 (13)
C1—C6—C5	117.98 (12)	C22—C23—H23	121.0
C1—C6—H6	121.0	C24—C23—H23	121.0
C5—C6—H6	121.0	C23—C24—C19	120.94 (13)
O3—C7—O4	126.09 (11)	C23—C24—H24	119.5
O3—C7—C4	118.54 (11)	C19—C24—H24	119.5
O4—C7—C4	115.36 (11)	Co1—O2W—Co1ⁱ	101.28 (4)
N2—C8—C9	122.98 (12)	Co1—O2W—H2A	100.6 (16)
N2—C8—H8	118.5	Co1ⁱ—O2W—H2A	110.0 (16)
C9—C8—H8	118.5	Co1—O2W—H2B	121.6 (14)
C10—C9—C8	118.37 (13)	Co1ⁱ—O2W—H2B	112.2 (14)
C10—C9—H9	120.8	H2A—O2W—H2B	110 (2)
C8—C9—H9	120.8

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2W—H2B···O5ⁱⁱ	0.84 (2)	1.67 (2)	2.5101 (13)	173 (2)
O2W—H2A···O3	0.79 (2)	1.88 (2)	2.6483 (13)	164 (2)
O1W—H1B···O3ⁱⁱⁱ	0.82 (2)	2.04 (2)	2.8477 (14)	174 (2)
O1W—H1A···O6ⁱ	0.81 (2)	1.88 (2)	2.6803 (14)	171 (2)
C21—H21···O2^iv	0.93	2.48	3.2219 (17)	137
C17—H17···O5ⁱⁱ	0.93	2.24	3.1679 (16)	172
C16—H16···O2^v	0.93	2.57	3.4644 (17)	160
C14—H14···O6^vi	0.93	2.41	3.3126 (16)	164
C9—H9···O7^vii	0.93	2.64	3.5467 (18)	164

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, y, z; (iii) −x, −y+1, −z+1; (iv) x+1, y, z−1; (v) x, y, z−1; (vi) x, y+1, z; (vii) x, y+1, z+1.

Funding information

We thank Council of Scientific and Industrial Research (CSIR) New Delhi, for financial support.

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