trans-Di­bromido­tetra­kis­(5-methyl-1H-pyrazole-κN2)manganese(II)

Athan, M.; Krishnan, S.; Loganathan, N.

doi:10.1107/S2414314624002372

metal-organic compounds

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ISSN: 2414-3146

Volume 9| Part 3| March 2024| x240237

https://doi.org/10.1107/S2414314624002372

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trans-Dibromidotetrakis(5-methyl-1H-pyrazole-κN²)manganese(II)

Manikumar Athan,^a Soundararajan Krishnan ^b and Nagarajan Loganathan ^a,^c ^*

^aSchool of Chemistry, Bharathidasan University, Tiruchirappalli 620 024, Tamilnadu, India, ^bDepartment of Chemistry, Periyar Maniammai Institute of Science and Technology, Vallam-613403, Thanjavur, Tamil Nadu, India, and ^cUGC-Faculty Recharge Programme, University Grant Commission, New Delhi,India
^*Correspondence e-mail: l.nagarajan@bdu.ac.in

Edited by M. Zeller, Purdue University, USA (Received 16 January 2024; accepted 12 March 2024; online 19 March 2024)

The title compound, trans-dibromidotetrakis(5-methyl-1H-pyrazole-κN²)manganese(II), [MnBr₂(C₄H₆N₂)₄] or [Mn(3-MePzH)₄Br₂] (1) crystallizes in the triclinic P $[\overline{1}]$ space group with the cell parameters a = 7.6288 (3), b = 8.7530 (4), c = 9.3794 (4) Å and α = 90.707 (4), β = 106.138 (4), γ = 114.285 (5)°, V = 542.62 (5) Å³, T = 120 K. The asymmetric unit contains only half the molecule with the manganese atom is situated on a crystallographic inversion center. The 3-MePzH ligands are present in an AABB type manner with two methyl groups pointing up and the other two down. The supramolecular architecture is characterized by several intermolecular C—H⋯N, N—H⋯Br, and C—H⋯π interactions. Earlier, a polymorphic structure of [Mn(3-MePzH)₄Br₂] (2) with a similar geometry and also an AABB arrangement for the pyrazole ligands was described [Reedijk et al. (1971 ). Inorg. Chem. 10, 2594–2599; a = 8.802 (6), b = 9.695 (5), c = 7.613 (8) Å and α = 105.12 (4), β = 114.98 (4), γ = 92.90 (3)°, V = 558.826 (5) Å³, T = 295 K]. A varying supramolecular pattern was reported, with the structure of 1 featuring a herringbone type pattern while that of structure 2 shows a pillared network type of arrangement along the a axis. A nickel complex [Ni(3-MePzH)₄Br₂] isomorphic to 1 and the analogous chloro derivatives of Fe^II, Co^II and Cu^II are also known.

Keywords: manganese; coordination compound; crystal structure; heteroleptic complex; herringbone pattern; polymorphism.

CCDC reference: 2322181

Structure description

Earth-abundant transition metals such as manganese have received much attention owing to their numerous applications in biological, industrial, and material sciences (Constable et al., 2021 ; Rice et al., 2017 ; Zhang et al., 2007 ; Dell, 2000 ). Apart from these applications, several mixed-valent multinuclear manganese cages have been assembled to understand their single molecular magnetism (SMM) behavior (Zabala-Lekuona et al., 2021 ). In addition, the famous Jacobson catalyst consisting of an Mn^II–salen complex was developed for the enantioselective epoxidation of alkenes (Zhang et al., 1990 ) while Mn^I carbonyls containing imidazolyl-based ligands have been used for the electrocatalytic-disproportionation of CO₂ (Myren et al., 2020 ). Likewise, many Mn^I carbonyls containing various N-heterocyclic ligands were developed as biomimicking models for hydrogenase enzymes (Xu et al., 2016 ; Pan et al., 2020 .) and as CO-releasing molecules (Mann, 2012 ; Cheng & Hu, 2021 ). Pyrazoles are one of the important classes of organic ligands used in many facets of coordination and organometallic chemistry (Trofimenko, 1972 ; Halcrow, 2009 ).

We aim to synthesize various CO-releasing molecules of the manganese family containing pyrazoles as primary ligands. In one such an attempt, a simple room-temperature stirring reaction involving the combination of Mn(CO)₅Br, 5-methyl-1H-pyrazole and triethylamine base (1:2:4) was found to release all CO molecules and afforded yellow-colored crystals suitable for single-crystal X-ray diffraction analysis (SCXRD) from a dichloromethane-ethanol mixture (1:1) in quantitative yield. The SCXRD analysis reveals that it is trans-dibromo tetrakis(5-methyl-1H-pyrazole-κ²N)manganese(II) (1). In other words, Mn^I was oxidized in situ to Mn^II and an octahedral heteroleptic complex containing two bromo ligands trans to each other in the axial position and four neutral 5-methyl-1H-pyrazoles in the equatorial position was obtained (Fig. 1). The asymmetric unit contains half the molecule with the manganese atom located on a crystallographic inversion center. The 3-MePzH ligands of the asymmetric unit are arranged in an AABB pattern with two neighboring pyrazole pointing upwards and the other two (their counterparts by inversion) downwards. The analysis reveals that it is a distorted octahedral complex with the axial distances to the larger bromine atoms [Mn1—Br1 = 2.7274 (3) Å] longer than the equatorial distances [Mn1—N1 = 2.251 (2) Å and Mn1—N3 = 2.261 (2) Å]. Angles at the manganese atom are close to 90° [N1—Mn1—Br1 = 89.10 (5)° and N3—Mn1—Br1 = 91.45 (5)°] and neighboring 3-MePzH rings are mutually perpendicular to each other with the dihedral angle between their planes being 87.08 (2)°.

Figure 1
The molecular structure of the title compound 1 with 50% probability displacement ellipsoids. The unlabeled atoms are related by symmetry.

Earlier, many transition-metal pyrazoles were reported (Reedijk et al., 1971; Bieller et al., 2006 ; Cotton et al., 2002 ; Nelana et al., 2004 ; Khan et al., 2014 ; Al Isawi et al., 2023 ). In particular, Reedijk et al. (1971) synthesized many of the first transition-metal 5-methyl-1H-pyrazole complexes, including a polymorphic form of the title compound [Mn(3-MePzH)₄Br₂] (2), which was synthesized using MnBr₂ and ethyl orthoformate as a dehydrating agent. It is interesting to note that the crystal data for compound 1 were collected at 120 K [a = 7.6288 (3), b = 8.7530 (4), c = 9.3794 (4) Å and α = 90.707 (4), β = 106.138 (4), γ = 114.285 (5)°, V = 542.62 (5) Å³] while compound 2 data were collected at 295 K [a = 8.802 (6), b = 9.695 (5), c = 7.613 (8) Å and α = 105.12 (4), β = 114.98 (4), γ = 92.90 (3)°, V = 558.826 (5) Å³]. A root-mean-square (r.m.s.) overlay of the molecules of 1 and 2 using Mercury 4.0 (Macrae et al., 2020 ) is shown in Fig. 2 and reveals that in Reedijk's polymorphic form, the 3-MePzH units are also placed in an AABB pattern with an r.m.s. deviation of 0.0612 Å. The analogous Mn^II, Co^II, Ni^II, Cu^II bromo complexes isomorphic with Reedijk's polymorph 2 were reported (Cotton et al., 2002; Nelana et al., 2004; Khan et al., 2014) and the bond parameters of 1 and 2 are both in good agreement with those reported structures. Interestingly, the Ni^II bromo complex (Nelana et al., 2004) is isomorphic with compound 1. It was synthesized using (1,2-dimethoxyethane)₂NiBr₂ as the metal source.

Figure 2
Overlay of the compounds 1 and 2 showing a slight deviation of 0.0612 Å (Mercury; Macrae et al., 2020

Compound 1 contains various intra- and intermolecular interactions in the form of N—H⋯Br and C—H⋯N interactions as well as C—H⋯π interactions (see Table 1). A perspective view of the supramolecular architecture of 1 is given in Fig. 3, which shows the presence of the various C—H⋯π interactions, leading to the formation of a herringbone-type of arrangement (Fig. 4a) along the a axis. In contrast, a pillared network along the a axis is seen in the structure of 2 (Fig. 5a). Further investigation reveals that along the b axis, the Br—Mn—Br moieties are stacked one over another in compound 1 while in 2, they are arranged in a zigzag fashion (Fig. 4b and 5b). The view along c axis is also different in both the compounds (Fig. 4c and 5c). Overall, the supramolecular architectures clearly distinguish the two polymorphic forms 1 and 2.

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the N1/N2/C2–C4 and N3/N4/ C5–C7 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯Br1	0.84 (3)	2.70 (3)	3.343 (2)	134 (2)
C1—H1C⋯Br1ⁱ	0.98	3.11	3.951 (3)	145
N2—H2⋯Br1	0.84 (3)	2.70 (3)	3.343 (2)	134 (2)
N2—H2⋯Br1ⁱ	0.84 (3)	3.05 (3)	3.704 (2)	137 (2)
N4—H7⋯Br1ⁱⁱ	0.80 (3)	3.00 (3)	3.636 (2)	138 (3)
N4—H7⋯Br1ⁱⁱⁱ	0.80 (3)	2.76 (3)	3.351 (2)	132 (3)
C3—H3⋯N4^iv	0.95	2.76	3.659 (3)	158
C8—H8A⋯N2^v	0.98	2.86	3.744 (3)	151
C8—H8A⋯Cg1^v	0.98	2.61	3.586 (3)	173
C3—H3⋯Cg2^vi	0.95	2.84	3.667 (4)	146
Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Figure 3
Perspective view of the supramolecular pattern of compound 1 showing the presence of intermolecular C—H⋯π interactions.

Figure 4
Supramolecular architecture of compound 1. (a) View along the a axis showing a herringbone-type arrangement; (b) and (c) the stacking of Br—Mn—Br along the respective axes.

Figure 5
Supramolecular architecture of compound 2. (a) View along the a axis showing a pillared network arrangement; (b) a view along the b axis showing the zigzag pattern of Br—Mn—Br and (c) a view along the c axis.

Synthesis and crystallization

50 mg (0.19 mmol) of Mn(CO)₅Br [bromopentacarbonylmanganese(I)] and 30.6 µL (0.38 mmol) of 5-methyl-1H-pyrazole were dissolved in 20 ml of ethanol. After stirring for a few minutes, 105 µL (0.76 mmol) of triethylamine were added to the reaction mixture and the resultant straw-yellow-colored solution was stirred at room temperature for 20 h. Light-yellow crystals were obtained by the slow evaporation method of a 1:1 dichloromethane–ethanol solvent mixture. Crystal yield 60%. ESI–MS data: m/z 540.53290 [M – H]⁺.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	[MnBr₂(C₄H₆N₂)₄]
M_r	543.19
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	120
a, b, c (Å)	7.6288 (3), 8.7530 (4), 9.3794 (4)
α, β, γ (°)	90.707 (4), 106.138 (4), 114.285 (5)
V (Å³)	542.62 (5)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	4.31
Crystal size (mm)	0.17 × 0.14 × 0.12

Data collection
Diffractometer	XtaLAB AFC12 (RINC): Kappa single
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2017 $[Rigaku OD. (2017). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.706, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	11690, 2574, 2115
R_int	0.060
(sin θ/λ)_max (Å⁻¹)	0.680

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.064, 1.04
No. of reflections	2574
No. of parameters	134
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.50, −0.38
Computer programs: CrysAlis PRO (Rigaku OD, 2017 $[Rigaku OD. (2017). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2019/3 (Sheldrick, 2015b ), ORTEP-3 for Windows2020 (Farrugia, 2012 ), Diamond (Brandenburg et al., 2014 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 2322181

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314624002372/zl4064sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314624002372/zl4064Isup2.hkl

checkCIF report

Computing details top

trans-Dibromidotetrakis(5-methyl-1H-pyrazole-κN²)\ manganese(II) top

Crystal data top

[MnBr₂(C₄H₆N₂)₄]	Z = 1
M_r = 543.19	F(000) = 271
Triclinic, P1	D_x = 1.662 Mg m⁻³
a = 7.6288 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.7530 (4) Å	Cell parameters from 4000 reflections
c = 9.3794 (4) Å	θ = 3.1–28.0°
α = 90.707 (4)°	µ = 4.31 mm⁻¹
β = 106.138 (4)°	T = 120 K
γ = 114.285 (5)°	Block, yellow
V = 542.62 (5) Å³	0.17 × 0.14 × 0.12 mm

Data collection top

XtaLAB AFC12 (RINC): Kappa single diffractometer	R_int = 0.060
Radiation source: fine-focus sealed X-ray tube	θ_max = 28.9°, θ_min = 3.1°
ω scans	h = −10→10
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2017)	k = −10→11
T_min = 0.706, T_max = 1.000	l = −12→11
11690 measured reflections	3 standard reflections every 20 reflections
2574 independent reflections	intensity decay: none
2115 reflections with I > 2σ(I)

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.032	Hydrogen site location: mixed
wR(F²) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0225P)² + 0.1264P] where P = (F_o² + 2F_c²)/3
2574 reflections	(Δ/σ)_max < 0.001
134 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.37 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
C1	0.8781 (4)	−0.4193 (4)	0.2379 (3)	0.0248 (6)
H1A	0.841583	−0.535204	0.195589	0.037*
H1B	0.924272	−0.407646	0.347700	0.037*
H1C	0.986772	−0.339348	0.203390	0.037*
C2	0.6971 (4)	−0.3823 (3)	0.1878 (3)	0.0177 (5)
C3	0.5014 (4)	−0.4665 (3)	0.1909 (3)	0.0196 (6)
H3	0.443446	−0.571543	0.225950	0.024*
C4	0.4061 (4)	−0.3654 (3)	0.1319 (3)	0.0191 (5)
H4	0.268506	−0.392289	0.120452	0.023*
C5	0.6662 (4)	0.1767 (4)	0.3552 (3)	0.0234 (6)
H5	0.803196	0.199834	0.368271	0.028*
C6	0.5970 (4)	0.2174 (4)	0.4670 (3)	0.0251 (6)
H6	0.675254	0.271808	0.566727	0.030*
C7	0.3930 (4)	0.1625 (3)	0.4026 (3)	0.0201 (6)
C8	0.2336 (4)	0.1681 (4)	0.4618 (3)	0.0329 (7)
H8A	0.264306	0.152549	0.567683	0.049*
H8B	0.101977	0.077534	0.404452	0.049*
H8C	0.229412	0.278049	0.452166	0.049*
Br1	0.91038 (4)	0.16217 (3)	0.06734 (3)	0.01922 (10)
Mn1	0.500000	0.000000	0.000000	0.01496 (13)
N1	0.5313 (3)	−0.2264 (3)	0.0935 (2)	0.0169 (4)
N2	0.7090 (3)	−0.2395 (3)	0.1301 (2)	0.0177 (5)
N3	0.5156 (3)	0.1016 (3)	0.2283 (2)	0.0175 (5)
N4	0.3507 (3)	0.0941 (3)	0.2610 (2)	0.0193 (5)
H2	0.804 (4)	−0.166 (4)	0.106 (3)	0.013 (7)*
H7	0.244 (5)	0.058 (4)	0.196 (3)	0.025 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0248 (15)	0.0259 (15)	0.0293 (15)	0.0154 (13)	0.0098 (12)	0.0085 (12)
C2	0.0219 (13)	0.0169 (13)	0.0145 (12)	0.0100 (11)	0.0038 (10)	0.0005 (10)
C3	0.0258 (14)	0.0163 (13)	0.0177 (13)	0.0092 (11)	0.0079 (11)	0.0036 (10)
C4	0.0184 (13)	0.0187 (14)	0.0208 (13)	0.0069 (11)	0.0088 (10)	0.0018 (10)
C5	0.0165 (13)	0.0293 (16)	0.0253 (14)	0.0116 (12)	0.0052 (11)	0.0054 (12)
C6	0.0237 (14)	0.0349 (17)	0.0161 (13)	0.0124 (13)	0.0058 (11)	0.0008 (11)
C7	0.0216 (14)	0.0229 (14)	0.0165 (13)	0.0086 (11)	0.0087 (11)	0.0027 (10)
C8	0.0276 (16)	0.055 (2)	0.0204 (14)	0.0201 (15)	0.0104 (12)	0.0017 (13)
Br1	0.01626 (14)	0.01839 (15)	0.02480 (15)	0.00854 (11)	0.00746 (10)	0.00161 (10)
Mn1	0.0161 (3)	0.0151 (3)	0.0174 (3)	0.0090 (2)	0.0070 (2)	0.0023 (2)
N1	0.0180 (11)	0.0168 (11)	0.0181 (11)	0.0106 (9)	0.0042 (9)	0.0020 (8)
N2	0.0148 (11)	0.0175 (12)	0.0208 (12)	0.0061 (10)	0.0065 (9)	0.0040 (9)
N3	0.0163 (11)	0.0204 (12)	0.0203 (11)	0.0098 (9)	0.0092 (9)	0.0030 (9)
N4	0.0159 (12)	0.0201 (12)	0.0195 (12)	0.0054 (10)	0.0056 (10)	0.0013 (9)

Geometric parameters (Å, º) top

C1—C2	1.497 (3)	C7—N4	1.346 (3)
C1—H1A	0.9800	C7—C8	1.488 (4)
C1—H1B	0.9800	C8—H8A	0.9800
C1—H1C	0.9800	C8—H8B	0.9800
C2—N2	1.348 (3)	C8—H8C	0.9800
C2—C3	1.376 (4)	Br1—Br1	0.0000 (10)
C3—C4	1.391 (4)	Br1—Mn1	2.7274 (3)
C3—H3	0.9500	Mn1—N1	2.251 (2)
C4—N1	1.330 (3)	Mn1—N1ⁱ	2.251 (2)
C4—H4	0.9500	Mn1—N3	2.2612 (19)
C5—N3	1.330 (3)	Mn1—N3ⁱ	2.2613 (19)
C5—C6	1.400 (4)	N1—N2	1.356 (3)
C5—H5	0.9500	N2—H2	0.84 (3)
C6—C7	1.368 (4)	N3—N4	1.352 (3)
C6—H6	0.9500	N4—H7	0.80 (3)

C2—C1—H1A	109.5	N1—Mn1—N3	89.74 (7)
C2—C1—H1B	109.5	N1ⁱ—Mn1—N3	90.26 (7)
H1A—C1—H1B	109.5	N1—Mn1—N3ⁱ	90.26 (7)
C2—C1—H1C	109.5	N1ⁱ—Mn1—N3ⁱ	89.74 (7)
H1A—C1—H1C	109.5	N3—Mn1—N3ⁱ	180.0
H1B—C1—H1C	109.5	N1—Mn1—Br1	89.10 (5)
N2—C2—C3	105.9 (2)	N1ⁱ—Mn1—Br1	90.90 (5)
N2—C2—C1	121.2 (2)	N3—Mn1—Br1	91.45 (5)
C3—C2—C1	132.9 (2)	N3ⁱ—Mn1—Br1	88.55 (5)
C2—C3—C4	105.5 (2)	N1—Mn1—Br1	89.10 (5)
C2—C3—H3	127.3	N1ⁱ—Mn1—Br1	90.90 (5)
C4—C3—H3	127.3	N3—Mn1—Br1	91.45 (5)
N1—C4—C3	111.7 (2)	N3ⁱ—Mn1—Br1	88.55 (5)
N1—C4—H4	124.1	Br1—Mn1—Br1	0.000 (16)
C3—C4—H4	124.1	N1—Mn1—Br1ⁱ	90.90 (5)
N3—C5—C6	111.3 (2)	N1ⁱ—Mn1—Br1ⁱ	89.10 (5)
N3—C5—H5	124.3	N3—Mn1—Br1ⁱ	88.55 (5)
C6—C5—H5	124.3	N3ⁱ—Mn1—Br1ⁱ	91.45 (5)
C7—C6—C5	105.6 (2)	Br1—Mn1—Br1ⁱ	180.0
C7—C6—H6	127.2	Br1—Mn1—Br1ⁱ	180.0
C5—C6—H6	127.2	C4—N1—N2	104.0 (2)
N4—C7—C6	105.9 (2)	C4—N1—Mn1	133.75 (17)
N4—C7—C8	122.0 (2)	N2—N1—Mn1	122.16 (16)
C6—C7—C8	132.1 (2)	C2—N2—N1	112.9 (2)
C7—C8—H8A	109.5	C2—N2—H2	129.5 (18)
C7—C8—H8B	109.5	N1—N2—H2	117.2 (18)
H8A—C8—H8B	109.5	C5—N3—N4	104.0 (2)
C7—C8—H8C	109.5	C5—N3—Mn1	133.35 (17)
H8A—C8—H8C	109.5	N4—N3—Mn1	122.65 (15)
H8B—C8—H8C	109.5	C7—N4—N3	113.2 (2)
Br1—Br1—Mn1	0.00 (2)	C7—N4—H7	127 (2)
N1—Mn1—N1ⁱ	180.0	N3—N4—H7	119 (2)

N2—C2—C3—C4	0.4 (3)	C1—C2—N2—N1	−178.9 (2)
C1—C2—C3—C4	178.2 (3)	C4—N1—N2—C2	0.8 (3)
C2—C3—C4—N1	0.1 (3)	Mn1—N1—N2—C2	178.32 (15)
N3—C5—C6—C7	0.3 (3)	C6—C5—N3—N4	−0.4 (3)
C5—C6—C7—N4	0.0 (3)	C6—C5—N3—Mn1	179.66 (18)
C5—C6—C7—C8	−180.0 (3)	C6—C7—N4—N3	−0.3 (3)
C3—C4—N1—N2	−0.5 (3)	C8—C7—N4—N3	179.7 (2)
C3—C4—N1—Mn1	−177.60 (16)	C5—N3—N4—C7	0.4 (3)
C3—C2—N2—N1	−0.8 (3)	Mn1—N3—N4—C7	−179.64 (17)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the N1/N2/C2–C4 and N3/N4/ C5–C7 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Br1	0.84 (3)	2.70 (3)	3.343 (2)	134 (2)
C1—H1C···Br1ⁱⁱ	0.98	3.11	3.951 (3)	145
N2—H2···Br1	0.84 (3)	2.70 (3)	3.343 (2)	134 (2)
N2—H2···Br1ⁱⁱ	0.84 (3)	3.05 (3)	3.704 (2)	137 (2)
N4—H7···Br1ⁱⁱⁱ	0.80 (3)	3.00 (3)	3.636 (2)	138 (3)
N4—H7···Br1ⁱ	0.80 (3)	2.76 (3)	3.351 (2)	132 (3)
C3—H3···N4^iv	0.95	2.76	3.659 (3)	158
C8—H8A···N2^v	0.98	2.86	3.744 (3)	151
C8—H8A···Cg1^v	0.98	2.61	3.586 (3)	173
C3—H3···Cg2^vi	0.95	2.84	3.667 (4)	146

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

Acknowledgements

Dr Orbett Alexander, Department of Chemistry, University of Western Cape, South Africa, is thanked for crystallographic software assistance.

Funding information

Funding for this research was provided by: Science and Engineering Research Board, India, Early Career Research Award (award No. ECR/2016/001966 to Nagarajan Loganathan; grant No. EEQ2018/001373); Rashtriya Uchchatar Shiksha Abhiyan, Physical Sciences 2.0 (grant to Nagarajan Loganathan).

References

Al Isawi, W. A., Zeller, M. & Mezei, G. (2023). Acta Cryst. E79, 1199–1206. CSD CrossRef IUCr Journals Google Scholar
Bieller, S., Haghiri, A., Bolte, M., Bats, J. W., Wagner, M. & Lerner, H.-W. (2006). Inorg. Chim. Acta, 359, 1559–1572. Web of Science CSD CrossRef CAS Google Scholar
Brandenburg, K., Berndt, M. & Putz, H. (2014). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Cheng, J. & Hu, J. (2021). ChemMedChem, 16, 3628–3634. CrossRef CAS PubMed Google Scholar
Constable, E. C., Parkin, G. & Que, L. Jr (2021). Editors. Comprehensive coordination chemistry III, Vol 5. Amsterdam: Elsevier. Google Scholar
Cotton, S. A., Franckevicius, V. & Fawcett, J. (2002). Polyhedron, 21, 2055–2061. CSD CrossRef CAS Google Scholar
Dell, R. M. (2000). Solid State Ionics, 134, 139–158. CrossRef CAS Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Halcrow, M. A. (2009). Dalton Trans. pp. 2059–2073. Web of Science CrossRef Google Scholar
Khan, S. A., Noor, A., Kempe, R., Subhan, H., Shah, A. & Khan, E. (2014). J. Coord. Chem. 67, 2425–2434. CSD CrossRef CAS Google Scholar
Macrae, C. F., Sovago, I., Cottrell, S. J., Galek, P. T. A., McCabe, P., Pidcock, E., Platings, M., Shields, G. P., Stevens, J. S., Towler, M. & Wood, P. A. (2020). J. Appl. Cryst. 53, 226–235. Web of Science CrossRef CAS IUCr Journals Google Scholar
Mann, B. E. (2012). Organometallics, 31, 5728–5735. CrossRef CAS Google Scholar
Myren, T. H. T., Alherz, A., Thurston, J. R., Stinson, T. A., Huntzinger, C. G., Musgrave, C. B. & Luca, O. R. (2020). ACS Catal. 10, 1961–1968. CrossRef CAS Google Scholar
Nelana, S. M., Darkwa, J., Guzei, I. A. & Mapolie, S. F. (2004). J. Organomet. Chem. 689, 1835–1842. Web of Science CSD CrossRef CAS Google Scholar
Pan, H.-J. & Hu, X. (2020). Angew. Chem. Int. Ed. 59, 4942–4946. CSD CrossRef CAS Google Scholar
Reedijk, J., Stork-Blaisse, B. A. & Verschoor, G. C. (1971). Inorg. Chem. 10, 2594–2599. CSD CrossRef CAS Google Scholar
Rice, D. B., Massie, A. A. & Jackson, T. A. (2017). Acc. Chem. Res. 50, 2706–2717. CrossRef CAS PubMed Google Scholar
Rigaku OD. (2017). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England. 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
Trofimenko, S. (1972). Chem. Rev. 72, 497–509. CrossRef CAS Web of Science Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xu, T., Yin, C. M., Wodrich, M. D., Mazza, S., Schultz, K. M., Scopelliti, R. & Hu, X. (2016). J. Am. Chem. Soc. 138, 3270–3273. CSD CrossRef CAS PubMed Google Scholar
Zabala-Lekuona, A., Seco, J. M. & Colacio, E. (2021). Coord. Chem. Rev. 441, 213984. Google Scholar
Zhang, W. & Cheng, C. Y. (2007). Hydrometallurgy, 89, 137–159. CrossRef CAS Google Scholar
Zhang, W., Loebach, J. L., Wilson, S. R. & Jacobsen, E. N. (1990). J. Am. Chem. Soc. 112, 2801–2803. CSD CrossRef CAS Web of Science Google Scholar