(SC,RS)-Bromido­(N-{4-methyl-1-[(4-methyl­phenyl)sul­fan­yl]­pentan-2-yl}-N′-(pyridin-2-yl)imidazol-2-yl­idene)palladium(II) bromide

Zeng, X.; Xu, Y.; Guo, S.; Xiao, Y.; Yuan, J.; Yang, L.

doi:10.1107/S2414314624003602

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 9| Part 4| April 2024| x240360

https://doi.org/10.1107/S2414314624003602

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(S_C,R_S)-Bromido(N-{4-methyl-1-[(4-methylphenyl)sulfanyl]pentan-2-yl}-N′-(pyridin-2-yl)imidazol-2-ylidene)palladium(II) bromide

Xianggui Zeng,^a Yanze Xu,^a Shuling Guo,^a Yongmei Xiao,^a Jinwei Yuan ^a and Liangru Yang ^a ^*

^aSchool of Chemistry & Chemical Engineering, Henan University of Technology, Zhengzhou 450001, People's Republic of China
^*Correspondence e-mail: lryang@haut.edu.cn

Edited by M. Zeller, Purdue University, USA (Received 25 March 2024; accepted 21 April 2024; online 26 April 2024)

The molecule of the title NC_NHCS pincer N-heterocyclic carbene palladium(II) complex, [PdBr(C₂₁H₂₅N₃S)]Br, exhibits a slightly distorted square-planar coordination at the palladium(II) atom, with the five-membered chelate ring nearly planar. The six-membered chelate ring adopts an envelope conformation. Upon chelation, the sulfur atom becomes a stereogenic centre with an R_S configuration induced by the chiral carbon of the precursor imidazolium salt. There are intramolecular C—H⋯Br—Pd hydrogen bonds in the structure. The two interstitial Br atoms, as the counter-anion of the structure, are both located on crystallographic twofold axes and are connected to the complex cations via C—H⋯·Br hydrogen bonds.

Keywords: crystal structure; N-heterocyclic carbene; palladium(II); hydrogen bonds.

CCDC reference: 2312031

Structure description

N-Heterocyclic carbenes (NHCs) have been widely used as ancillary ligands in coordination chemistry and organic catalysis due to their characteristic electronic properties and easy structural modification (Hopkinson et al., 2014 ; Gardiner et al., 2018 ). Introduction of a coordinating heteroatom functional group to the N-atom substituents of the NHCs leads to the formation of a potentially chelating ligand, and facilitates the formation of stable pincer NHC–metal complexes that can possess catalytic activities. Metal complexes containing heteroatom donors, such as P, N, O and S, have been synthesized, characterized and employed extensively as catalysts for a variety of organic transformations (Ahrens et al., 2006 ; Bierenstiel & Cross, 2011 ; Meyer et al., 2012 ; Peris & Crabtree, 2004 ). Our group has investigated the synthesis and catalytic performance of a series of chelating NHC–palladium complexes derived from natural amino alcohols (Yang et al., 2015 , 2023 ; Yang, Zhang, Xiao & Mao, 2016 ; Yang, Zhang, Yuan et al., 2016 ; Meng et al., 2022 ). As part of our work on the study of NHC–metal complexes containing heteroatom-functionalized N-atom substituents, we present here the crystal structure of the title NC_NHCS pincer NHC palladium(II) complex (Fig. 1).

Figure 1
The molecular structure of the title complex, shown with 50% probability displacement ellipsoids.

In the title complex, the palladium(II) atom is coordinated to C8, N1, Br1, and S1, resulting in a slightly distorted square-planar coordination. The Pd1—C8, Pd1—N1, Pd1—Br1 and Pd1—S1 bond lengths are 1.946 (8), 2.093 (6), 2.4663 (10), and 2.2603 (17) Å, respectively. The five-membered chelate ring (C8/Pd1/N1/C5/N2) is almost planar, with Pd1—N1—C5—N2 and C5—N2—C8—Pd1 torsion angles of −0.3 (8) and 2.0 (8)°, respectively. The six-membered chelate ring (C8/Pd1/S1/C9/C10/N3) adopts an envelope conformation with puckering parameters of θ = 51.6 (6)° and φ= 125.4 (8)°, which are close to the expected values for this conformation (Boeyens, 1978 ).

Upon chelation, the sulfur atom becomes a stereogenic centre, resulting in the formation of molecules with an R_S configuration. This can be attributed to the chiral induction of the chiral carbon C(5), which retains the same S configuration as in the precursor imidazolium salt. The environment of the sulfur atoms of the molecule is approximately triangular pyramidal. This is indicated by the bond angles C9—S1—Pd1, C15—S1—Pd1 and C9—S1–15, which were found to be 106.2 (2), 111.0 (2), and 97.2 (3)°, respectively, with an average of 105.0°. In the crystal, intra- and intermolecular C—H⋯Br hydrogen bonds occur (Table 1, Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Br1	0.93	2.90	3.510 (10)	124
C6—H6⋯Br2ⁱ	0.93	2.74	3.661 (9)	173
C10—H10⋯Br3	0.98	2.78	3.624 (7)	144
C16—H16⋯Br3ⁱⁱ	0.93	3.11	3.742 (7)	127
Symmetry codes: (i) ; (ii) .

Figure 2
The C—H⋯Br interactions in the structure.

Synthesis and crystallization

A mixture of (S)-N-(4-methyl-1-(p-tolylthio)pentan-2-yl)-N′-(pyridin-2-yl)-1H-imidazolium bromide (1.0 mmol, 0.43 g), PdCl₂ (1.0 mmol, 0.18 g), NaOAc (1.0 mmol, 0.10 g), and NaBr (4 mmol, 0.41 g) in CH₃CN (10 ml) was heated at 80°C for 24 h, and then the volatiles were evaporated. Purification of the residue by column chromatography (silica gel, CH₂Cl₂/MeOH 15/1 ∼1:1, v/v) produced the title complex as a yellow solid (0.32 g, 60%). Crystallization of the solid from CH₃CN afforded the title complex as yellow crystals, m.p. 269–277°C. HR—MS (ESI) m/z calculated for C₂₁H₂₅BrN₃PdS⁺ (M – Br)⁺ 535.9987, found 535.9998. F T–IR (ATR mode): ν = 3388, 3012, 2910, 1681, 1496, 1376, 1316, 1144, 1014, 914, 806, 780, 738, 666, 448 cm^−1. [α]¹⁵₅₈₉: 8.3 (1.00, CH₂Cl₂).

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	[PdBr(C₂₁H₂₅N₃S)]Br
M_r	617.72
Crystal system, space group	Monoclinic, C2
Temperature (K)	293
a, b, c (Å)	25.8993 (7), 6.6206 (2), 13.4938 (3)
β (°)	96.425 (2)
V (Å³)	2299.23 (12)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	11.52
Crystal size (mm)	0.14 × 0.1 × 0.03

Data collection
Diffractometer	Xcalibur, Eos, Gemini
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.419, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	20069, 3950, 3693
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.611

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.072, 1.04
No. of reflections	3950
No. of parameters	258
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.38
Absolute structure	Flack x determined using 1371 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	−0.030 (7)
Computer programs: CrysAlis PRO (Rigaku OD, 2023 $[Rigaku OD (2023). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXS (Sheldrick, 2008 ), SHELXL (Sheldrick, 2015 ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2312031

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314624003602/zl4070sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314624003602/zl4070Isup3.hkl

checkCIF report

Computing details top

(S_C,R_S)-Bromido(N-{4-methyl-1-[(4-methylphenyl)sulfanyl]pentan-2-yl}-N'-(pyridin-2-yl)imidazol-2-ylidene)palladium(II) bromide top

Crystal data top

[PdBr(C₂₁H₂₅N₃S)]Br	F(000) = 1216
M_r = 617.72	D_x = 1.785 Mg m⁻³
Monoclinic, C2	Cu Kα radiation, λ = 1.54184 Å
a = 25.8993 (7) Å	Cell parameters from 8595 reflections
b = 6.6206 (2) Å	θ = 4.5–70.1°
c = 13.4938 (3) Å	µ = 11.52 mm⁻¹
β = 96.425 (2)°	T = 293 K
V = 2299.23 (12) Å³	Plate, colourless
Z = 4	0.14 × 0.1 × 0.03 mm

Data collection top

Xcalibur, Eos, Gemini diffractometer	3950 independent reflections
Radiation source: fine-focus sealed X-ray tube, Enhance (Cu) X-ray Source	3693 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
Detector resolution: 16.2312 pixels mm^-1	θ_max = 70.5°, θ_min = 3.4°
ω scans	h = −31→31
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2023)	k = −8→6
T_min = 0.419, T_max = 1.000	l = −16→16
20069 measured reflections

Refinement top

Refinement on F²	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.033P)² + 2.7656P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.030	(Δ/σ)_max < 0.001
wR(F²) = 0.072	Δρ_max = 0.36 e Å⁻³
S = 1.04	Δρ_min = −0.38 e Å⁻³
3950 reflections	Extinction correction: SHELXL-2014/7 (Sheldrick, 2015), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
258 parameters	Extinction coefficient: 0.00034 (4)
1 restraint	Absolute structure: Flack x determined using 1371 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.030 (7)
Hydrogen site location: inferred from neighbouring sites

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. The H atoms on the carbons were positioned geometrically and constrained to ride on their parent atoms. C—H bond distances were constrained to 0.93 Å for aromatic and alkene C—H moieties, and to 0.98, 0.91 and 0.96 Å for aliphatic C—H, CH₂ and CH₃ moieties, respectively. Methyl CH₃ H atoms were allowed to rotate but not to tip to best fit the experimental electron density. U_iso(H) values were set to a multiple of U_eq(C) with 1.5 for CH₃, and 1.2 for C—H and CH₂ units, respectively.

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

	x	y	z	U_iso*/U_eq
Pd1	0.37598 (2)	0.06095 (8)	0.28758 (3)	0.03701 (15)
S1	0.40637 (6)	−0.0902 (3)	0.15555 (12)	0.0381 (4)
N1	0.3574 (2)	0.2356 (11)	0.4079 (4)	0.0443 (16)
N2	0.4255 (2)	0.4165 (10)	0.3607 (4)	0.0413 (14)
N3	0.4680 (2)	0.3203 (10)	0.2419 (4)	0.0381 (13)
C1	0.3187 (3)	0.2026 (16)	0.4635 (6)	0.057 (2)
H1	0.2972	0.0912	0.4501	0.069*
C2	0.3100 (4)	0.3329 (18)	0.5414 (7)	0.069 (3)
H2	0.2832	0.3085	0.5804	0.083*
C3	0.3414 (4)	0.4954 (18)	0.5587 (7)	0.074 (3)
H3	0.3359	0.5840	0.6099	0.089*
C4	0.3813 (3)	0.5318 (18)	0.5021 (6)	0.061 (2)
H4	0.4033	0.6422	0.5144	0.073*
C5	0.3873 (3)	0.3975 (13)	0.4263 (5)	0.0450 (18)
C6	0.4650 (3)	0.5562 (15)	0.3556 (5)	0.0478 (16)
H6	0.4719	0.6686	0.3963	0.057*
C7	0.4911 (3)	0.4978 (13)	0.2812 (6)	0.049 (2)
H7	0.5195	0.5632	0.2593	0.059*
C8	0.4280 (2)	0.2737 (13)	0.2911 (5)	0.0393 (16)
C9	0.4434 (2)	0.1033 (12)	0.0964 (5)	0.0415 (18)
H9A	0.4574	0.0439	0.0394	0.050*
H9B	0.4199	0.2108	0.0720	0.050*
C10	0.4877 (3)	0.1938 (11)	0.1649 (5)	0.0366 (15)
H10	0.5072	0.2821	0.1242	0.044*
C11	0.5255 (2)	0.0360 (13)	0.2122 (5)	0.0397 (16)
H11A	0.5325	−0.0599	0.1610	0.048*
H11B	0.5085	−0.0373	0.2617	0.048*
C12	0.5777 (3)	0.1161 (12)	0.2623 (5)	0.0441 (19)
H12	0.5707	0.2109	0.3150	0.053*
C13	0.6081 (3)	−0.0612 (16)	0.3099 (7)	0.065 (3)
H13A	0.5892	−0.1208	0.3598	0.097*
H13B	0.6413	−0.0150	0.3404	0.097*
H13C	0.6132	−0.1599	0.2598	0.097*
C14	0.6090 (3)	0.2258 (18)	0.1894 (7)	0.072 (3)
H14A	0.6092	0.1467	0.1298	0.108*
H14B	0.6440	0.2448	0.2196	0.108*
H14C	0.5935	0.3549	0.1729	0.108*
C15	0.3558 (3)	−0.1214 (13)	0.0549 (5)	0.0428 (18)
C16	0.3572 (3)	−0.2944 (13)	−0.0012 (6)	0.0494 (19)
H16	0.3814	−0.3949	0.0174	0.059*
C17	0.3221 (3)	−0.3171 (14)	−0.0853 (6)	0.054 (2)
H17	0.3225	−0.4353	−0.1224	0.064*
C18	0.2862 (3)	−0.1665 (14)	−0.1157 (5)	0.048 (2)
C19	0.2848 (3)	0.0021 (14)	−0.0560 (5)	0.051 (2)
H19	0.2601	0.1015	−0.0734	0.061*
C20	0.3190 (3)	0.0263 (14)	0.0282 (5)	0.049 (2)
H20	0.3176	0.1415	0.0672	0.059*
C21	0.2512 (3)	−0.1845 (17)	−0.2126 (6)	0.067 (3)
H21A	0.2684	−0.1290	−0.2659	0.101*
H21B	0.2195	−0.1116	−0.2075	0.101*
H21C	0.2433	−0.3242	−0.2261	0.101*
Br1	0.30979 (4)	−0.20451 (15)	0.29589 (7)	0.0603 (3)
Br2	0.5000	0.0140 (2)	0.5000	0.0609 (4)
Br3	0.5000	0.61892 (17)	0.0000	0.0480 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.0397 (2)	0.0390 (3)	0.0327 (2)	−0.0004 (2)	0.00594 (15)	−0.0005 (2)
S1	0.0391 (8)	0.0388 (11)	0.0362 (8)	0.0001 (7)	0.0032 (6)	−0.0042 (8)
N1	0.050 (3)	0.054 (5)	0.030 (3)	0.012 (3)	0.009 (2)	−0.007 (3)
N2	0.050 (3)	0.036 (4)	0.038 (3)	0.007 (3)	0.003 (2)	−0.007 (3)
N3	0.042 (3)	0.031 (4)	0.042 (3)	−0.003 (3)	0.006 (2)	0.002 (3)
C1	0.054 (4)	0.073 (7)	0.047 (4)	0.009 (4)	0.015 (3)	−0.002 (4)
C2	0.063 (5)	0.091 (9)	0.055 (5)	0.018 (5)	0.019 (4)	0.003 (5)
C3	0.089 (7)	0.087 (9)	0.050 (4)	0.020 (6)	0.019 (4)	−0.017 (5)
C4	0.071 (5)	0.058 (7)	0.054 (4)	0.012 (5)	0.010 (3)	−0.019 (5)
C5	0.051 (4)	0.043 (5)	0.038 (4)	0.010 (4)	−0.006 (3)	−0.007 (4)
C6	0.061 (4)	0.030 (4)	0.050 (4)	−0.001 (4)	−0.001 (3)	−0.008 (4)
C7	0.052 (4)	0.038 (5)	0.055 (4)	−0.011 (3)	0.003 (3)	0.000 (4)
C8	0.042 (3)	0.037 (5)	0.036 (3)	0.005 (3)	−0.003 (3)	−0.002 (3)
C9	0.042 (3)	0.047 (6)	0.035 (3)	0.001 (3)	0.003 (2)	−0.001 (3)
C10	0.045 (3)	0.031 (4)	0.034 (3)	−0.002 (3)	0.008 (3)	−0.001 (3)
C11	0.049 (3)	0.032 (4)	0.039 (3)	0.002 (3)	0.009 (2)	0.000 (4)
C12	0.043 (3)	0.048 (6)	0.041 (3)	−0.005 (3)	0.004 (3)	−0.001 (3)
C13	0.051 (4)	0.073 (7)	0.068 (5)	0.007 (4)	−0.005 (4)	0.010 (5)
C14	0.051 (5)	0.096 (9)	0.069 (6)	−0.019 (5)	0.006 (4)	0.022 (6)
C15	0.038 (3)	0.051 (5)	0.039 (3)	−0.001 (3)	0.003 (3)	−0.009 (4)
C16	0.047 (4)	0.038 (5)	0.062 (5)	0.003 (3)	0.001 (3)	−0.009 (4)
C17	0.056 (4)	0.051 (6)	0.051 (4)	−0.001 (4)	−0.006 (3)	−0.020 (4)
C18	0.036 (3)	0.058 (6)	0.048 (4)	−0.011 (3)	0.004 (3)	−0.006 (4)
C19	0.042 (4)	0.060 (7)	0.050 (4)	0.007 (3)	0.002 (3)	0.000 (4)
C20	0.051 (4)	0.046 (6)	0.051 (4)	0.014 (4)	0.004 (3)	−0.011 (4)
C21	0.058 (5)	0.079 (8)	0.061 (5)	−0.003 (5)	−0.014 (4)	−0.006 (5)
Br1	0.0612 (5)	0.0547 (7)	0.0674 (5)	−0.0142 (4)	0.0173 (4)	0.0042 (5)
Br2	0.0953 (9)	0.0421 (9)	0.0444 (5)	0.000	0.0037 (5)	0.000
Br3	0.0607 (6)	0.0392 (8)	0.0460 (5)	0.000	0.0141 (4)	0.000

Geometric parameters (Å, º) top

Pd1—S1	2.2603 (17)	C10—H10	0.9800
Pd1—N1	2.093 (6)	C10—C11	1.522 (10)
Pd1—C8	1.946 (8)	C11—H11A	0.9700
Pd1—Br1	2.4663 (10)	C11—H11B	0.9700
S1—C9	1.836 (7)	C11—C12	1.537 (9)
S1—C15	1.789 (7)	C12—H12	0.9800
N1—C1	1.335 (9)	C12—C13	1.517 (11)
N1—C5	1.330 (10)	C12—C14	1.527 (10)
N2—C5	1.405 (9)	C13—H13A	0.9600
N2—C6	1.387 (10)	C13—H13B	0.9600
N2—C8	1.340 (9)	C13—H13C	0.9600
N3—C7	1.396 (10)	C14—H14A	0.9600
N3—C8	1.328 (9)	C14—H14B	0.9600
N3—C10	1.470 (9)	C14—H14C	0.9600
C1—H1	0.9300	C15—C16	1.376 (11)
C1—C2	1.397 (13)	C15—C20	1.384 (11)
C2—H2	0.9300	C16—H16	0.9300
C2—C3	1.354 (15)	C16—C17	1.380 (11)
C3—H3	0.9300	C17—H17	0.9300
C3—C4	1.373 (12)	C17—C18	1.393 (12)
C4—H4	0.9300	C18—C19	1.379 (11)
C4—C5	1.376 (11)	C18—C21	1.511 (10)
C6—H6	0.9300	C19—H19	0.9300
C6—C7	1.329 (10)	C19—C20	1.370 (10)
C7—H7	0.9300	C20—H20	0.9300
C9—H9A	0.9700	C21—H21A	0.9600
C9—H9B	0.9700	C21—H21B	0.9600
C9—C10	1.513 (9)	C21—H21C	0.9600

S1—Pd1—Br1	91.46 (5)	C9—C10—H10	107.3
N1—Pd1—S1	170.64 (19)	C9—C10—C11	113.1 (6)
N1—Pd1—Br1	97.90 (19)	C11—C10—H10	107.3
C8—Pd1—S1	92.2 (2)	C10—C11—H11A	108.3
C8—Pd1—N1	78.4 (3)	C10—C11—H11B	108.3
C8—Pd1—Br1	175.9 (2)	C10—C11—C12	116.1 (7)
C9—S1—Pd1	106.2 (2)	H11A—C11—H11B	107.4
C15—S1—Pd1	111.0 (2)	C12—C11—H11A	108.3
C15—S1—C9	97.2 (3)	C12—C11—H11B	108.3
C1—N1—Pd1	126.7 (6)	C11—C12—H12	108.5
C5—N1—Pd1	114.3 (5)	C13—C12—C11	108.0 (7)
C5—N1—C1	119.0 (7)	C13—C12—H12	108.5
C6—N2—C5	131.8 (6)	C13—C12—C14	110.6 (7)
C8—N2—C5	118.1 (7)	C14—C12—C11	112.7 (6)
C8—N2—C6	110.0 (6)	C14—C12—H12	108.5
C7—N3—C10	125.5 (6)	C12—C13—H13A	109.5
C8—N3—C7	109.3 (6)	C12—C13—H13B	109.5
C8—N3—C10	124.9 (6)	C12—C13—H13C	109.5
N1—C1—H1	119.5	H13A—C13—H13B	109.5
N1—C1—C2	121.1 (9)	H13A—C13—H13C	109.5
C2—C1—H1	119.5	H13B—C13—H13C	109.5
C1—C2—H2	120.8	C12—C14—H14A	109.5
C3—C2—C1	118.4 (8)	C12—C14—H14B	109.5
C3—C2—H2	120.8	C12—C14—H14C	109.5
C2—C3—H3	119.4	H14A—C14—H14B	109.5
C2—C3—C4	121.3 (9)	H14A—C14—H14C	109.5
C4—C3—H3	119.4	H14B—C14—H14C	109.5
C3—C4—H4	121.5	C16—C15—S1	116.9 (6)
C3—C4—C5	117.0 (10)	C16—C15—C20	120.2 (7)
C5—C4—H4	121.5	C20—C15—S1	122.7 (6)
N1—C5—N2	113.0 (6)	C15—C16—H16	120.4
N1—C5—C4	123.2 (8)	C15—C16—C17	119.2 (8)
C4—C5—N2	123.8 (8)	C17—C16—H16	120.4
N2—C6—H6	126.8	C16—C17—H17	119.3
C7—C6—N2	106.5 (7)	C16—C17—C18	121.4 (8)
C7—C6—H6	126.8	C18—C17—H17	119.3
N3—C7—H7	126.3	C17—C18—C21	121.0 (8)
C6—C7—N3	107.4 (7)	C19—C18—C17	117.9 (7)
C6—C7—H7	126.3	C19—C18—C21	121.1 (8)
N2—C8—Pd1	116.1 (5)	C18—C19—H19	119.3
N3—C8—Pd1	137.2 (6)	C20—C19—C18	121.5 (8)
N3—C8—N2	106.7 (7)	C20—C19—H19	119.3
S1—C9—H9A	108.7	C15—C20—H20	120.1
S1—C9—H9B	108.7	C19—C20—C15	119.7 (8)
H9A—C9—H9B	107.6	C19—C20—H20	120.1
C10—C9—S1	114.1 (5)	C18—C21—H21A	109.5
C10—C9—H9A	108.7	C18—C21—H21B	109.5
C10—C9—H9B	108.7	C18—C21—H21C	109.5
N3—C10—C9	111.0 (5)	H21A—C21—H21B	109.5
N3—C10—H10	107.3	H21A—C21—H21C	109.5
N3—C10—C11	110.6 (5)	H21B—C21—H21C	109.5

Pd1—S1—C9—C10	58.1 (5)	C7—N3—C8—Pd1	−179.7 (6)
Pd1—S1—C15—C16	−143.9 (5)	C7—N3—C8—N2	−0.4 (8)
Pd1—S1—C15—C20	41.2 (7)	C7—N3—C10—C9	−144.6 (7)
Pd1—N1—C1—C2	−179.1 (6)	C7—N3—C10—C11	89.0 (8)
Pd1—N1—C5—N2	−0.3 (8)	C8—N2—C5—N1	−1.1 (9)
Pd1—N1—C5—C4	179.8 (6)	C8—N2—C5—C4	178.8 (8)
S1—C9—C10—N3	−69.7 (7)	C8—N2—C6—C7	0.8 (9)
S1—C9—C10—C11	55.2 (7)	C8—N3—C7—C6	0.9 (9)
S1—C15—C16—C17	−173.9 (6)	C8—N3—C10—C9	41.5 (9)
S1—C15—C20—C19	173.0 (6)	C8—N3—C10—C11	−84.8 (8)
N1—C1—C2—C3	0.7 (14)	C9—S1—C15—C16	105.7 (6)
N2—C6—C7—N3	−1.0 (9)	C9—S1—C15—C20	−69.3 (7)
N3—C10—C11—C12	−68.7 (7)	C9—C10—C11—C12	166.1 (5)
C1—N1—C5—N2	−178.3 (7)	C10—N3—C7—C6	−173.7 (7)
C1—N1—C5—C4	1.8 (12)	C10—N3—C8—Pd1	−5.0 (11)
C1—C2—C3—C4	−0.5 (15)	C10—N3—C8—N2	174.3 (6)
C2—C3—C4—C5	0.9 (15)	C10—C11—C12—C13	176.6 (6)
C3—C4—C5—N1	−1.6 (13)	C10—C11—C12—C14	−60.9 (9)
C3—C4—C5—N2	178.6 (8)	C15—S1—C9—C10	172.5 (5)
C5—N1—C1—C2	−1.3 (12)	C15—C16—C17—C18	1.5 (13)
C5—N2—C6—C7	177.4 (7)	C16—C15—C20—C19	−1.8 (12)
C5—N2—C8—Pd1	2.0 (8)	C16—C17—C18—C19	−3.5 (12)
C5—N2—C8—N3	−177.4 (6)	C16—C17—C18—C21	174.6 (8)
C6—N2—C5—N1	−177.5 (7)	C17—C18—C19—C20	2.9 (12)
C6—N2—C5—C4	2.4 (13)	C18—C19—C20—C15	−0.3 (12)
C6—N2—C8—Pd1	179.2 (5)	C20—C15—C16—C17	1.2 (12)
C6—N2—C8—N3	−0.2 (8)	C21—C18—C19—C20	−175.2 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···Br1	0.93	2.90	3.510 (10)	124
C6—H6···Br2ⁱ	0.93	2.74	3.661 (9)	173
C10—H10···Br3	0.98	2.78	3.624 (7)	144
C16—H16···Br3ⁱⁱ	0.93	3.11	3.742 (7)	127

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

Acknowledgements

The authors thank Ms Y. Zhu for technical assistance.

Funding information

Funding for this research was provided by: the Natural Science Foundation of Henan Province (grant No. 242300420186).

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