Crystal structure of a solvated dinuclear CuII complex derived from 3,3,3′,3′-tetraethyl-1,1′-(furan-2,5-dicarbonyl)bis(thiourea)

Le, C.D.; Nguyen, H.P.; Pham, C.T.

doi:10.1107/S2056989024010703

research communications

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 80| Part 12| December 2024| Pages 1266-1269

https://doi.org/10.1107/S2056989024010703

Open

access

Crystal structure of a solvated dinuclear Cu^II complex derived from 3,3,3′,3′-tetraethyl-1,1′-(furan-2,5-dicarbonyl)bis(thiourea)

Canh Dinh Le,^a Hoang Phuc Nguyen ^b and Chien Thang Pham ^b ^*

^aDepartment of Chemistry, Quy Nhon University, 170 An Duong Vuong, Quy Nhon, Vietnam, and ^bDepartment of Inorganic Chemistry, VNU University of Science, Vietnam National, University, Hanoi, 19 Le Thanh Tong, Hanoi, Vietnam
^*Correspondence e-mail: phamchienthang@hus.edu.vn

Edited by L. Suescun, Universidad de la República, Uruguay (Received 9 September 2024; accepted 4 November 2024; online 8 November 2024)

Reaction between equimolar amounts of 3,3,3′,3′-tetraethyl-1,1′-(furan-2,5-dicarbonyl)bis(thiourea) (H₂L) and CuCl₂·2H₂O in methanol in the presence of the supporting base Et₃N gave rise to a neutral dinuclear complex bis[μ-3,3,3′,3′-tetraethyl-1,1′-(furan-2,5-dicarbonyl)bis(thioureato)]dicopper(II) dichloromethane disolvate, [Cu₂(C₁₆H₂₂N₄O₃S₂)₂]·2CH₂Cl₂ or [Cu₂(L)₂]·2CH₂Cl₂. The aroylbis(thioureas) are doubly deprotonated and the resulting anions {L^2–} bond to metal ions through (S,O)-chelating moieties. The copper atoms adopt a virtually cis-square-planar environment. In the crystal, adjacent [Cu₂(L)₂]·2CH₂Cl₂ units are linked into polymeric chains along the a-axis direction by intermolecular coordinative Cu⋯S interactions. The co-crystallized solvent molecules play a vital role in the crystal packing. In particular, weak C—H_furan⋯Cl and C—H_ethyl⋯Cl contacts consolidate the three-dimensional supramolecular architecture.

Keywords: crystal structure; aroylbis(N,N-dialkylthioureas); Cu(II) complexes.

CCDC reference: 2400458

1. Chemical context

Benzoyl(N,N-dialkylthioureas) are versatile ligands forming stable complexes with a great number of transition-metal ions, in which the organic compounds mainly act as monoanionic and (S,O)-bidentate ligands (Fitzl et al., 1977 ; Knuuttila et al., 1982 ; Sieler et al., 1990 ; Bensch et al., 1995 ; Nguyen et al., 2007 ; Barnard et al., 2019 ; Pham et al., 2021 ). This coordination fashion also plays an important role in metal complexes of aroylbis(thioureas), such as homo-dinuclear complexes based on the bipodal iso-phthaloylbis(N,N-dialkylthioureas) (Koch et al., 2001 ; Rodenstein et al., 2008 ; Schwade et al., 2013 ; Schwade et al., 2020 ; Teixeira et al., 2020 ). The presence of potential donor atom(s) in the spacer between two aroylthiourea moieties, such as pyridine N or catechol O atoms, could enable the corresponding aroylbis(thioureas) to serve as building blocks for the construction of heteronuclear host–guest systems (Nguyen et al., 2016 ; Pham et al., 2017 , 2020 ; Le et al., 2019 ; Jesudas et al., 2020 ). However, it seems such aroylbis(thioureas) are not appropriate for the production of homonuclear systems. Indeed, all efforts to produce related homonuclear complexes, as in the case of iso-phthaloylbis(N,N-dialkylthioureas), have hitherto failed. Herein, we describe the synthesis and crystal structure of the first homonuclear complex derived from the novel 3,3,3′,3′-tetraethyl-1,1′-(furan-2,5-dicarbonyl)bis(thiourea) (H₂L), referred to as furan-2,5-dicarbonylbis(N,N-diethylthiourea), which possesses a potential furan O donor atom in the molecular backbone. The compound, [Cu₂(L)₂], potentially exhibits interesting magnetic and catalytic properties (Pham et al., 2019 ; Nath et al., 2020 ).

2. Structural commentary

The complex [Cu₂(L)₂] crystallizes as a solvated form in the centrosymmetric monoclinic space group P2₁/n with half of [Cu₂(L)₂]·2CH₂Cl₂ in the asymmetric unit. The molecular structure, including solvent molecules, is shown in Fig. 1. The complex consists of two Cu^II ions and two doubly deprotonated ligands {L}^2–, which bond to the metal ions through (S,O)-chelating aroylthiourea moieties. The Cu1—O bond lengths are Cu1—O10 = 1.9406 (15) Å and Cu1—O20 = 1.9431 (14) Å, while the Cu1—S10 and Cu1—S20 bond lengths are 2.2624 (6) and 2.2612 (6) Å, respectively. These bond distances fall in the same ranges for those observed in several copper(II) complexes with aroylmono(thioureas) (Wu et al., 2015 ; Selvakumaran et al., 2016 ; Binzet et al., 2018 ; Pham et al., 2021) and aroylbis(thioureas) (Rodenstein et al., 2008; Schwade et al., 2013; Teixeira et al., 2020). The metal⋯metal distance is 7.762 (3) Å and the midpoint between the two copper atoms is on the inversion center of the molecule. The two chelate planes Cu1/O10–S10 (r.m.s.d. = 0.075 Å) and Cu1/O20ⁱ–S10ⁱ (r.m.s.d. = 0.156 Å) form a dihedral angle of 15.32 (2)°. Thus, the four-coordinate Cu^II atoms adopt a flat isosceles trapezoid geometry due to the cis arrangement of the donor atoms. The atoms within the furan-2,5-dicarboxamide moieties and the copper atoms are nearly coplanar with a largest deviation of 0.298 (2) Å from the mean least-squares plane for the furan oxygen atoms. Two CH₂Cl₂ molecules are located on either side of the plane at a distance of 1.991 (5) Å from the plane to the solvent carbon atoms. One chlorine atom of the solvent molecule is disordered over two positions with occupancy factor of 0.6163 (9) for the atom labelled A. In addition, the solvent interacts with the complex through hydrogen bonds formed with the carbonyl oxygen atoms O10 (Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C30—H30A⋯O10	0.99	2.41	3.388 (3)	171
C30—H30B⋯O10ⁱ	0.99	2.45	3.428 (3)	171
C14—H14B⋯Cl1ⁱⁱ	0.99	2.83	3.627 (2)	138
C4—H4⋯Cl2Aⁱⁱⁱ	0.95	2.68	3.506 (8)	145
C4—H4⋯Cl2Bⁱⁱⁱ	0.95	2.60	3.446 (12)	149
Symmetry codes: (i) ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Figure 1
The molecular structure of the title compound [Cu₂(L)₂]·2CH₂Cl₂. (a) Top view with complete labeling of non-hydrogen atoms within the complex molecule. (b) Side view. Hydrogen atoms of the complex are omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level. The red dotted lines indicate the C—H⋯O hydrogen bonds. Symmetry code: (i) −x + 1, −y + 1, −z + 1.

3. Supramolecular features

Each [Cu₂(L)₂]·2CH₂Cl₂ unit interacts with two adjacent ones by long bonding interactions between the Cu^II ions and S20 atoms of adjacent blocks (Fig. 2a). These bonds, with a distance of 2.9884 (6) Å, are considerably longer than the coordinative Cu—S bonds within the [Cu₂(L)₂] unit. Such interactions between the units results in polymeric chains along the a-axis direction (Fig. 2b).

Figure 2
(a) Molecular packing of [Cu₂(L)₂]·2CH₂Cl₂ units by coordinative Cu⋯S interactions (dashed lines). Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (I)

x + 1, y, z; (II) −x + 2, −y + 1, −z + 1; (III) −x, −y + 1, −z + 1; (IV) x − 1, y, z. Ethyl groups are omitted for clarity. (b) Polymeric chains along the a-axis direction. Hydrogen atoms of ethyl groups are omitted for clarity.

Furthermore, intermolecular hydrogen bonds (Table 1) involving the solvent molecules and the C—H bonds of the furan rings and ethyl groups are responsible for aggregation of the polymeric chains (Fig. 3).

Figure 3
Crystal packing of the title compound shown in projection down the a-axis illustrating the aggregation of chains by C—H⋯Cl hydrogen bonding (green dotted lines). The central units are highlighted for clarity.

4. Database survey

The crystal structures of neither the ligand nor its metal complexes are found in the Cambridge Structure Database (CSD version 5.45, update of June 2024; Groom et al., 2016 ). A search of the CSD for dinuclear copper(II) complexes derived from aroylbis(thioureas) reveals only five hits involving isophthaloyl derivatives: DIZTEM and DIZTEM1 (Rodenstein et al., 2008), BEWKAR (Schwade et al., 2013), DOMNIE (Selvakumaran et al., 2014 ) and YUFNUL (Teixeira et al., 2020). Across the series of metrics for these structures, all values regarding the coordination of copper(II) ions and aroylthiourea moieties are in accordance with those reported herein.

5. Synthesis and crystallization

H₂L (38.5 mg, 0.1 mmol) was added into a solution of CuCl₂·2H₂O (17.1 mg, 0.1 mmol) in 1 mL of MeOH. The reaction mixture was stirred at 313 K for 30 min before adding the supporting base Et₃N (0.03 mL, 0.2 mmol). A brown precipitate deposited immediately. After stirring for additional 1 h at 313 K, the product was filtered off, washed with MeOH, and dried under reduced pressure. Single crystals suitable for X-ray analysis were obtained by slow evaporation of a solution of the complex in a mixture of CH₂Cl₂ and MeOH. Under ambient conditions, the crystals slowly turned to powder due to the evaporation of the co-crystalized solvent.

IR (KBr, cm⁻¹): 2974 (w), 2931 (w), 1536 (s), 1492 (s), 1455 (m), 1399 (s), 1373 (s), 1348 (s), 1304 (s), 1262 (s), 1219 (m), 1148 (m), 1111 (m), 1074 (m), 1008 (s), 9722 (m), 880 (s), 813 (s), 767 (s), 665 (m), 6155 (w), 548 (w), 455 (m).

+ESI MS (m/z): 893.19 (calculated 893.09), 50% [Cu₂(L)₂ + H]⁺; 931.24 (calculated 931.05), 100% [Cu₂(L)₂ + K]⁺.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The H atoms were placed at calculated positions and refined in riding mode, with C—H distances of 0.95 Å (aromatic), 0.99 Å (CH₂) and 0.98 Å (CH₃), and isotropic displacement parameters equal to 1.2U_eq of the parent atoms (1.5U_eq for CH₃).

Table 2
Experimental details

Crystal data
Chemical formula	[Cu₂(C₁₆H₂₂N₄O₃S₂)₂]·2CH₂Cl₂
M_r	1061.92
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	140
a, b, c (Å)	10.2290 (9), 13.0681 (10), 16.9601 (15)
β (°)	98.377 (3)
V (Å³)	2242.9 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	1.42
Crystal size (mm)	0.14 × 0.08 × 0.05

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.686, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	29179, 5809, 4232
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.677

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.076, 1.03
No. of reflections	5809
No. of parameters	276
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.45
Computer programs: APEX2 ans SAINT (Bruker, 2014 ), SHELXT2014/5 (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Supporting information

CCDC reference: 2400458

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989024010703/oo2007sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024010703/oo2007Isup2.hkl

checkCIF report

Computing details top

Bis[µ-3,3,3',3'-tetraethyl-1,1'-(furan-2,5-dicarbonyl)bis(thioureato)]dicopper(II) dichloromethane disolvate top

Crystal data top

[Cu₂(C₁₆H₂₂N₄O₃S₂)₂]·2CH₂Cl₂	F(000) = 1092
M_r = 1061.92	D_x = 1.572 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.2290 (9) Å	Cell parameters from 8429 reflections
b = 13.0681 (10) Å	θ = 2.9–28.6°
c = 16.9601 (15) Å	µ = 1.42 mm⁻¹
β = 98.377 (3)°	T = 140 K
V = 2242.9 (3) Å³	Plate, red
Z = 2	0.14 × 0.08 × 0.05 mm

Data collection top

Bruker APEXII CCD diffractometer	4232 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.062
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θ_max = 28.8°, θ_min = 2.9°
T_min = 0.686, T_max = 0.746	h = −13→12
29179 measured reflections	k = −16→17
5809 independent reflections	l = −22→22

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.076	w = 1/[σ²(F_o²) + (0.0292P)² + 0.9669P] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max = 0.001
5809 reflections	Δρ_max = 0.50 e Å⁻³
276 parameters	Δρ_min = −0.44 e Å⁻³
0 restraints

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	Occ. (<1)
Cu1	0.84517 (2)	0.55425 (2)	0.43977 (2)	0.01612 (8)
S20	−0.02763 (5)	0.36002 (4)	0.50470 (3)	0.01813 (12)
S10	0.92190 (5)	0.55137 (4)	0.32124 (3)	0.02175 (13)
Cl1	0.51955 (6)	0.24405 (4)	0.50494 (4)	0.02871 (14)
Cl2A	0.6845 (12)	0.3546 (8)	0.6351 (5)	0.0389 (13)	0.62 (6)
O1	0.43749 (13)	0.41530 (10)	0.37590 (8)	0.0148 (3)
O20	0.24820 (14)	0.42489 (11)	0.46961 (9)	0.0201 (3)
O10	0.67999 (14)	0.49014 (12)	0.39462 (9)	0.0234 (4)
N20	0.12097 (16)	0.30601 (13)	0.38549 (10)	0.0161 (4)
N10	0.72045 (17)	0.41079 (13)	0.27587 (11)	0.0171 (4)
N21	−0.06963 (17)	0.22096 (13)	0.39037 (11)	0.0174 (4)
N11	0.90007 (17)	0.40368 (13)	0.21277 (11)	0.0181 (4)
C20	0.2228 (2)	0.36677 (15)	0.40972 (12)	0.0155 (4)
C21	0.01399 (19)	0.29379 (15)	0.42245 (12)	0.0149 (4)
C10	0.6509 (2)	0.43597 (15)	0.33275 (12)	0.0146 (4)
C5	0.3243 (2)	0.35962 (15)	0.35652 (13)	0.0156 (4)
C2	0.5189 (2)	0.38896 (16)	0.32183 (12)	0.0150 (4)
C11	0.8417 (2)	0.44890 (16)	0.26910 (12)	0.0165 (4)
C4	0.3331 (2)	0.29970 (17)	0.29214 (14)	0.0226 (5)
H4	0.267641	0.253875	0.267244	0.027*
C12	1.0320 (2)	0.43485 (17)	0.19544 (14)	0.0221 (5)
H12A	1.076331	0.374578	0.175901	0.026*
H12B	1.085855	0.457912	0.245532	0.026*
C14	0.8325 (2)	0.31971 (17)	0.16420 (13)	0.0229 (5)
H14A	0.784256	0.276870	0.198538	0.027*
H14B	0.899900	0.276039	0.144445	0.027*
C3	0.4587 (2)	0.31868 (17)	0.26922 (13)	0.0218 (5)
H3	0.493828	0.288489	0.225885	0.026*
C22	−0.1906 (2)	0.19430 (17)	0.42337 (14)	0.0237 (5)
H22A	−0.255015	0.163290	0.380844	0.028*
H22B	−0.230516	0.257583	0.441381	0.028*
C30	0.5687 (2)	0.36547 (17)	0.54694 (14)	0.0244 (5)
H30A	0.608215	0.406292	0.507265	0.029*	0.62 (6)
H30B	0.489631	0.402474	0.559208	0.029*	0.62 (6)
H30C	0.620516	0.402930	0.511272	0.029*	0.38 (6)
H30D	0.489701	0.406736	0.553233	0.029*	0.38 (6)
C24	−0.0367 (2)	0.15816 (17)	0.32306 (14)	0.0233 (5)
H24A	−0.002603	0.203498	0.283944	0.028*
H24B	−0.118227	0.125169	0.296061	0.028*
C23	−0.1646 (3)	0.12006 (18)	0.49296 (16)	0.0324 (6)
H23A	−0.122811	0.057995	0.475893	0.049*
H23B	−0.248397	0.102117	0.511037	0.049*
H23C	−0.105823	0.152244	0.536775	0.049*
C15	0.7365 (3)	0.3571 (2)	0.09391 (15)	0.0333 (6)
H15A	0.784371	0.396006	0.057839	0.050*
H15B	0.670058	0.401186	0.112873	0.050*
H15C	0.692659	0.298337	0.065448	0.050*
C13	1.0272 (3)	0.5201 (2)	0.13398 (16)	0.0336 (6)
H13A	0.975577	0.497390	0.083784	0.050*
H13B	1.117258	0.536891	0.125049	0.050*
H13C	0.985739	0.580787	0.153507	0.050*
C25	0.0658 (3)	0.07585 (18)	0.34959 (17)	0.0336 (6)
H25A	0.087206	0.038988	0.302800	0.050*
H25B	0.030115	0.027765	0.385352	0.050*
H25C	0.145957	0.107842	0.377676	0.050*
Cl2B	0.6656 (19)	0.3460 (10)	0.6407 (9)	0.044 (2)	0.38 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.01290 (13)	0.02103 (14)	0.01530 (14)	−0.00403 (10)	0.00497 (10)	−0.00410 (11)
S20	0.0141 (3)	0.0184 (3)	0.0231 (3)	−0.0034 (2)	0.0069 (2)	−0.0044 (2)
S10	0.0214 (3)	0.0267 (3)	0.0191 (3)	−0.0083 (2)	0.0096 (2)	−0.0042 (2)
Cl1	0.0350 (3)	0.0237 (3)	0.0301 (3)	0.0012 (2)	0.0136 (3)	0.0036 (2)
Cl2A	0.041 (2)	0.045 (2)	0.0275 (12)	0.006 (2)	−0.0045 (13)	0.0173 (14)
O1	0.0119 (7)	0.0207 (7)	0.0127 (8)	−0.0033 (6)	0.0046 (6)	−0.0045 (6)
O20	0.0158 (7)	0.0274 (8)	0.0184 (8)	−0.0086 (6)	0.0074 (6)	−0.0106 (6)
O10	0.0135 (8)	0.0379 (9)	0.0199 (9)	−0.0081 (7)	0.0067 (6)	−0.0118 (7)
N20	0.0125 (9)	0.0177 (9)	0.0181 (10)	−0.0029 (7)	0.0023 (7)	−0.0029 (7)
N10	0.0156 (9)	0.0200 (9)	0.0168 (10)	−0.0010 (7)	0.0063 (8)	−0.0021 (7)
N21	0.0133 (9)	0.0172 (9)	0.0217 (10)	−0.0030 (7)	0.0022 (7)	−0.0021 (7)
N11	0.0150 (9)	0.0240 (9)	0.0166 (10)	0.0002 (7)	0.0068 (8)	−0.0021 (8)
C20	0.0142 (10)	0.0174 (10)	0.0146 (11)	−0.0015 (8)	0.0014 (9)	−0.0008 (8)
C21	0.0124 (10)	0.0134 (10)	0.0184 (11)	0.0005 (8)	0.0010 (9)	0.0019 (8)
C10	0.0144 (10)	0.0163 (10)	0.0129 (11)	0.0013 (8)	0.0018 (8)	0.0019 (8)
C5	0.0124 (10)	0.0177 (10)	0.0165 (11)	−0.0032 (8)	0.0010 (8)	−0.0025 (8)
C2	0.0141 (10)	0.0204 (11)	0.0114 (11)	0.0029 (8)	0.0046 (8)	−0.0012 (8)
C11	0.0156 (10)	0.0199 (10)	0.0141 (11)	0.0012 (9)	0.0022 (8)	0.0026 (9)
C4	0.0173 (11)	0.0275 (12)	0.0232 (13)	−0.0066 (9)	0.0036 (10)	−0.0097 (10)
C12	0.0134 (11)	0.0320 (12)	0.0224 (12)	0.0028 (9)	0.0078 (9)	−0.0027 (10)
C14	0.0230 (12)	0.0251 (12)	0.0222 (13)	0.0030 (10)	0.0084 (10)	−0.0045 (9)
C3	0.0201 (11)	0.0279 (12)	0.0189 (12)	−0.0038 (9)	0.0079 (10)	−0.0092 (9)
C22	0.0142 (11)	0.0241 (12)	0.0331 (14)	−0.0086 (9)	0.0044 (10)	−0.0022 (10)
C30	0.0273 (13)	0.0233 (12)	0.0222 (13)	0.0032 (10)	0.0028 (10)	0.0042 (9)
C24	0.0221 (12)	0.0257 (12)	0.0215 (12)	−0.0086 (10)	0.0013 (10)	−0.0080 (9)
C23	0.0313 (14)	0.0234 (13)	0.0458 (17)	−0.0043 (11)	0.0165 (12)	0.0046 (11)
C15	0.0300 (14)	0.0382 (15)	0.0303 (15)	−0.0026 (11)	−0.0004 (11)	−0.0064 (11)
C13	0.0251 (13)	0.0474 (16)	0.0303 (15)	−0.0067 (12)	0.0108 (11)	0.0089 (12)
C25	0.0389 (15)	0.0242 (13)	0.0392 (16)	0.0012 (11)	0.0106 (13)	−0.0070 (11)
Cl2B	0.056 (4)	0.043 (2)	0.027 (3)	−0.021 (3)	−0.016 (3)	0.0175 (18)

Geometric parameters (Å, º) top

Cu1—S20ⁱ	2.2612 (6)	C12—H12B	0.9900
Cu1—S10	2.2624 (6)	C12—C13	1.521 (3)
Cu1—O20ⁱ	1.9431 (14)	C14—H14A	0.9900
Cu1—O10	1.9406 (15)	C14—H14B	0.9900
S20—C21	1.746 (2)	C14—C15	1.511 (3)
S10—C11	1.743 (2)	C3—H3	0.9500
Cl1—C30	1.781 (2)	C22—H22A	0.9900
Cl2A—C30	1.773 (8)	C22—H22B	0.9900
O1—C5	1.366 (2)	C22—C23	1.521 (3)
O1—C2	1.369 (2)	C30—H30A	0.9900
O20—C20	1.265 (2)	C30—H30B	0.9900
O10—C10	1.265 (2)	C30—H30C	0.9900
N20—C20	1.326 (3)	C30—H30D	0.9900
N20—C21	1.347 (3)	C30—Cl2B	1.766 (13)
N10—C10	1.321 (3)	C24—H24A	0.9900
N10—C11	1.357 (3)	C24—H24B	0.9900
N21—C21	1.341 (3)	C24—C25	1.523 (3)
N21—C22	1.472 (3)	C23—H23A	0.9800
N21—C24	1.484 (3)	C23—H23B	0.9800
N11—C11	1.336 (3)	C23—H23C	0.9800
N11—C12	1.479 (3)	C15—H15A	0.9800
N11—C14	1.481 (3)	C15—H15B	0.9800
C20—C5	1.475 (3)	C15—H15C	0.9800
C10—C2	1.471 (3)	C13—H13A	0.9800
C5—C4	1.357 (3)	C13—H13B	0.9800
C2—C3	1.363 (3)	C13—H13C	0.9800
C4—H4	0.9500	C25—H25A	0.9800
C4—C3	1.417 (3)	C25—H25B	0.9800
C12—H12A	0.9900	C25—H25C	0.9800

S20ⁱ—Cu1—S10	90.35 (2)	C2—C3—C4	106.24 (19)
O20ⁱ—Cu1—S20ⁱ	94.14 (4)	C2—C3—H3	126.9
O20ⁱ—Cu1—S10	168.29 (5)	C4—C3—H3	126.9
O10—Cu1—S20ⁱ	175.25 (5)	N21—C22—H22A	109.1
O10—Cu1—S10	92.12 (5)	N21—C22—H22B	109.1
O10—Cu1—O20ⁱ	82.68 (6)	N21—C22—C23	112.59 (19)
C21—S20—Cu1ⁱ	107.20 (7)	H22A—C22—H22B	107.8
C11—S10—Cu1	105.37 (7)	C23—C22—H22A	109.1
C5—O1—C2	106.35 (15)	C23—C22—H22B	109.1
C20—O20—Cu1ⁱ	130.70 (13)	Cl1—C30—H30A	109.1
C10—O10—Cu1	130.91 (13)	Cl1—C30—H30B	109.1
C20—N20—C21	125.52 (18)	Cl1—C30—H30C	110.0
C10—N10—C11	124.50 (18)	Cl1—C30—H30D	110.0
C21—N21—C22	122.38 (18)	Cl2A—C30—Cl1	112.4 (4)
C21—N21—C24	120.11 (17)	Cl2A—C30—H30A	109.1
C22—N21—C24	117.34 (17)	Cl2A—C30—H30B	109.1
C11—N11—C12	122.41 (18)	H30A—C30—H30B	107.9
C11—N11—C14	120.30 (17)	H30C—C30—H30D	108.3
C12—N11—C14	117.29 (17)	Cl2B—C30—Cl1	108.7 (5)
O20—C20—N20	131.98 (19)	Cl2B—C30—H30C	110.0
O20—C20—C5	116.66 (17)	Cl2B—C30—H30D	110.0
N20—C20—C5	111.33 (18)	N21—C24—H24A	109.0
N20—C21—S20	128.46 (16)	N21—C24—H24B	109.0
N21—C21—S20	117.42 (15)	N21—C24—C25	112.76 (19)
N21—C21—N20	114.12 (18)	H24A—C24—H24B	107.8
O10—C10—N10	131.22 (19)	C25—C24—H24A	109.0
O10—C10—C2	116.03 (17)	C25—C24—H24B	109.0
N10—C10—C2	112.72 (18)	C22—C23—H23A	109.5
O1—C5—C20	117.82 (17)	C22—C23—H23B	109.5
C4—C5—O1	110.36 (17)	C22—C23—H23C	109.5
C4—C5—C20	131.58 (19)	H23A—C23—H23B	109.5
O1—C2—C10	116.58 (17)	H23A—C23—H23C	109.5
C3—C2—O1	110.28 (18)	H23B—C23—H23C	109.5
C3—C2—C10	133.07 (19)	C14—C15—H15A	109.5
N10—C11—S10	127.42 (16)	C14—C15—H15B	109.5
N11—C11—S10	118.44 (15)	C14—C15—H15C	109.5
N11—C11—N10	114.05 (18)	H15A—C15—H15B	109.5
C5—C4—H4	126.6	H15A—C15—H15C	109.5
C5—C4—C3	106.76 (19)	H15B—C15—H15C	109.5
C3—C4—H4	126.6	C12—C13—H13A	109.5
N11—C12—H12A	108.9	C12—C13—H13B	109.5
N11—C12—H12B	108.9	C12—C13—H13C	109.5
N11—C12—C13	113.50 (19)	H13A—C13—H13B	109.5
H12A—C12—H12B	107.7	H13A—C13—H13C	109.5
C13—C12—H12A	108.9	H13B—C13—H13C	109.5
C13—C12—H12B	108.9	C24—C25—H25A	109.5
N11—C14—H14A	108.9	C24—C25—H25B	109.5
N11—C14—H14B	108.9	C24—C25—H25C	109.5
N11—C14—C15	113.34 (19)	H25A—C25—H25B	109.5
H14A—C14—H14B	107.7	H25A—C25—H25C	109.5
C15—C14—H14A	108.9	H25B—C25—H25C	109.5
C15—C14—H14B	108.9

Cu1ⁱ—S20—C21—N20	−14.0 (2)	C10—N10—C11—S10	−11.0 (3)
Cu1ⁱ—S20—C21—N21	166.21 (14)	C10—N10—C11—N11	172.43 (19)
Cu1—S10—C11—N10	29.0 (2)	C10—C2—C3—C4	176.6 (2)
Cu1—S10—C11—N11	−154.56 (15)	C5—O1—C2—C10	−177.26 (17)
Cu1ⁱ—O20—C20—N20	5.2 (4)	C5—O1—C2—C3	0.3 (2)
Cu1ⁱ—O20—C20—C5	−172.26 (14)	C5—C4—C3—C2	0.4 (3)
Cu1—O10—C10—N10	−5.1 (3)	C2—O1—C5—C20	175.01 (18)
Cu1—O10—C10—C2	172.61 (14)	C2—O1—C5—C4	0.0 (2)
O1—C5—C4—C3	−0.2 (3)	C11—N10—C10—O10	−6.7 (4)
O1—C2—C3—C4	−0.4 (3)	C11—N10—C10—C2	175.57 (19)
O20—C20—C5—O1	0.3 (3)	C11—N11—C12—C13	−88.5 (3)
O20—C20—C5—C4	174.1 (2)	C11—N11—C14—C15	83.8 (2)
O10—C10—C2—O1	5.2 (3)	C12—N11—C11—S10	2.4 (3)
O10—C10—C2—C3	−171.6 (2)	C12—N11—C11—N10	179.34 (18)
N20—C20—C5—O1	−177.58 (17)	C12—N11—C14—C15	−95.6 (2)
N20—C20—C5—C4	−3.8 (3)	C14—N11—C11—S10	−176.94 (15)
N10—C10—C2—O1	−176.69 (17)	C14—N11—C11—N10	0.0 (3)
N10—C10—C2—C3	6.5 (3)	C14—N11—C12—C13	90.9 (2)
C20—N20—C21—S20	6.1 (3)	C22—N21—C21—S20	−1.7 (3)
C20—N20—C21—N21	−174.10 (19)	C22—N21—C21—N20	178.48 (18)
C20—C5—C4—C3	−174.3 (2)	C22—N21—C24—C25	−98.7 (2)
C21—N20—C20—O20	0.9 (4)	C24—N21—C21—S20	−176.80 (15)
C21—N20—C20—C5	178.46 (19)	C24—N21—C21—N20	3.4 (3)
C21—N21—C22—C23	−82.9 (2)	C24—N21—C22—C23	92.4 (2)
C21—N21—C24—C25	76.7 (2)

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
C30—H30A···O10	0.99	2.41	3.388 (3)	171
C30—H30B···O10ⁱ	0.99	2.45	3.428 (3)	171
C14—H14B···Cl1ⁱⁱ	0.99	2.83	3.627 (2)	138
C4—H4···Cl2Aⁱⁱⁱ	0.95	2.68	3.506 (8)	145
C4—H4···Cl2Bⁱⁱⁱ	0.95	2.60	3.446 (12)	149

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

Funding information

Funding for this research was provided by: The Asia Research Center at Vietnam National University, Hanoi (grant No. CA.22.06A to Chien Thang Pham).

References

Barnard, I. & Koch, K. R. (2019). Inorg. Chim. Acta, 495, 119019. Web of Science CSD CrossRef Google Scholar
Bensch, W. & Schuster, M. (1995). Z. Kristallogr. Cryst. Mater. 210, 68–68. CSD CrossRef CAS Web of Science Google Scholar
Binzet, G., Gumus, I., Dogen, A., Flörke, U., Kulcu, N. & Arslan, H. (2018). J. Mol. Struct. 1161, 519–529. Web of Science CSD CrossRef CAS Google Scholar
Bruker (2014). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Fitzl, G., Beyer, L., Sieler, J., Richter, R., Kaiser, J. & Hoyer, E. (1977). Z. Anorg. Allg. Chem. 433, 237–241. CSD CrossRef CAS Web of Science Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Jesudas, J. J., Pham, C. T., Hagenbach, A., Abram, U. & Nguyen, H. H. (2020). Inorg. Chem. 59, 386–395. Web of Science CSD CrossRef CAS PubMed Google Scholar
Knuuttila, P., Knuuttila, H., Hennig, H. & Beyer, L. (1982). Acta Chem. Scand. A, 36, 541–545. CSD CrossRef Web of Science Google Scholar
Koch, K. R., Hallale, O., Bourne, S. A., Miller, J. & Bacsa, J. (2001). J. Mol. Struct. 561, 185–196. Web of Science CSD CrossRef CAS Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Le, C. D., Pham, C. T. & Nguyen, H. H. (2019). Polyhedron, 173, 114143–114147. Web of Science CSD CrossRef CAS Google Scholar
Nath, B. D., Takaishi, K. & Ema, T. (2020). Catal. Sci. Technol. 10, 12–34. Web of Science CrossRef CAS Google Scholar
Nguyen, H. H. & Abram, U. (2007). Inorg. Chem. 46, 5310–5319. Web of Science CrossRef PubMed Google Scholar
Nguyen, H. H., Jegathesh, J. J., Takiden, A., Hauenstein, D., Pham, C. T., Le, C. D. & Abram, U. (2016). Dalton Trans. 45, 10771–10779. Web of Science CSD CrossRef CAS PubMed Google Scholar
Pham, C. T., Barnard, I., Nguyen, H. H., Abram, U. & Koch, K. R. (2020). Inorg. Chem. 59, 1183–1192. Web of Science CSD CrossRef CAS PubMed Google Scholar
Pham, C. T., Nguyen, H. H., Hagenbach, A. & Abram, U. (2017). Inorg. Chem. 56, 11406–11416. Web of Science CSD CrossRef CAS PubMed Google Scholar
Pham, C. T., Nguyen, T. H., Matsumoto, K. & Nguyen, H. H. (2019). Eur. J. Inorg. Chem. 2019, 4142–4146. Web of Science CSD CrossRef CAS Google Scholar
Pham, C. T., Pham, T. T., Nguyen, V. H., Trieu, T. N. & Nguyen, H. H. (2021). Z. Anorg. Allg. Chem. 647, 1383–1391. Web of Science CrossRef ICSD Google Scholar
Rodenstein, A., Griebel, J., Richter, R. & Kirmse, R. (2008). Z. Anorg. Allg. Chem. 634, 867–874. Web of Science CSD CrossRef CAS Google Scholar
Schwade, V. D., Kirsten, L., Hagenbach, A., Schulz Lang, E. & Abram, U. (2013). Polyhedron, 55, 155–161. Web of Science CSD CrossRef CAS Google Scholar
Schwade, V. D., Teixeira, E. I., dos Santos, F. A., Bortolotto, T., Tirloni, B. & Abram, U. (2020). New J. Chem. 44, 19598–19611. Web of Science CSD CrossRef CAS Google Scholar
Selvakumaran, N., Bhuvanesh, N. S. P. & Karvembu, R. (2014). Dalton Trans. 43, 16395–16410. Web of Science CSD CrossRef CAS PubMed Google Scholar
Selvakumaran, N., Sandhiya, L., Bhuvanesh, N. S. P., Senthilkumar, K. & Karvembu, R. (2016). New J. Chem. 40, 5401–5413. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sieler, J., Richter, R., Hoyer, E., Beyer, L., Lindqvist, O. & Andersen, L. (1990). Z. Anorg. Allg. Chem. 580, 167–174. CSD CrossRef CAS Web of Science Google Scholar
Teixeira, E. I., Schwalm, C. S., Casagrande, G. A., Tirloni, B. & Schwade, V. D. (2020). J. Mol. Struct. 1210, 127999. Web of Science CSD CrossRef Google Scholar
Wu, S.-Y., Zhao, X.-Y., Li, H.-P., Yang, Y. & Roesky, H. W. (2015). Z. Anorg. Allg. Chem. 641, 883–889. Web of Science CSD CrossRef CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.