Crystal structure and Hirshfeld surface analysis of chlorido­(2,6-di­methyl­phenyl isocyanide)[N′-(2,6-di­methyl­phen­yl)-N-(pyridin-2-yl)carbamimido­yl]platinum(II)

Repina, O.V.; Nevskaya, E.Y.; Kritchenkov, I.S.; Khrustalev, V.N.; Novikov, A.S.; Tskhovrebov, A.G.; Shikhaliyev, N.Q.; Niyazova, A.A.; Akkurt, M.; Bhattarai, A.

doi:10.1107/S2056989025005079

research communications

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ISSN: 2056-9890

Volume 81| Part 7| July 2025| Pages 587-590

https://doi.org/10.1107/S2056989025005079

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Crystal structure and Hirshfeld surface analysis of chlorido(2,6-dimethylphenyl isocyanide)[N′-(2,6-dimethylphenyl)-N-(pyridin-2-yl)carbamimidoyl]platinum(II)

^aPeoples' Friendship University of Russia, 6 Miklukho-Maklaya Street, Moscow, 117198, Russian Federation, ^bZelinsky Institute of Organic Chemistry, Russian Academy of Sciences (RAS), Leninsky Prospect 47, 119991 Moscow, Russian Federation, ^cInstitute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7/9, 199034 Saint Petersburg, Russian Federation, ^dBaku Engineering University, Khirdalan City, 120 AZ0101 Hasan Aliyev Street, Baku, Azerbaijan, ^eAzerbaijan State University of Economics, M. Mukhtarov 194, 1001 Baku, Azerbaijan, ^fDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Türkiye, and ^gDepartment of Chemistry, M.M.A.M.C (Tribhuvan University) Biratnagar, Nepal
^*Correspondence e-mail: [email protected]

Edited by B. Therrien, University of Neuchâtel, Switzerland (Received 23 April 2025; accepted 4 June 2025; online 10 June 2025)

In the title compound, [Pt(C₁₄H₁₄N₃)Cl(C₉H₉N)], the platinum atom has a square-planar geometry. In the crystal, dimers with R²₂(8) motifs are formed by pairs of N—H⋯N hydrogen bonds. They are connected to each other through pairs of weak C—H⋯Cl interactions, forming a R²₂(16) motif, creating parallel ribbons along the [011] axis. The molecular pairs are also linked by C—H⋯π and by π–π interactions, the shortest centroid-centroid distance [3.513 (2) Å] being observed between pyridyl rings. These weak interactions form parallel ribbons along the [010] axis. The resulting three-dimensional network ensures the cohesion of the crystal structure. Hirshfeld two-dimensional fingerprint plots revealed that the most significant interactions are H⋯H (58.0%), C⋯H/H⋯C (17.9%), Cl⋯H/H⋯Cl (10.7%), N⋯H/H⋯N (6.9%), C⋯C (2.9%), Pt⋯H/H⋯Pt (2.6%), and N⋯C/C⋯N (1.1%) contacts.

Keywords: crystal structure; dimers; square-planar geometry; isocyanides; 2-aminopyridine; Hirshfeld surface analysis.

CCDC reference: 2456370

1. Chemical context

Acyclic diaminocarbenes (ADCs) are well-known for their strong σ-donating properties and their ability to coordinate to metals through the carbene C atom (Alder et al., 1996 ; Tskhovrebov et al., 2012 , 2013 , 2018 ; Luzyanin et al., 2009 ; Repina et al., 2025 ). Among the various methods for synthesizing N-acyclic carbene (NAC) metal complexes, the addition of amines to the activated CN triple bond of isocyanide ligands stands out, due to its simplicity and the versatility of ligands that can be accessed (Michelin et al., 2001 ).

N-Acyclic carbene complexes of platinum are of significant interest in applied science because of their potential applications in catalysis and photoluminescent materials and as anticancer agents (Kinzhalov & Luzyanin, 2022 ). For instance, palladium NAC complexes have been successfully utilized as Suzuki–Miyaura, Sonogashira, and Heck reaction catalysts (Mizoroki et al., 1971 ; Heck & Nolley, 1972 ; Miyaura et al., 1979 ; Suzuki, 1999 ). The ability of the Pd center to promote coupling between coordinated isocyanides and 2-aminopyridine was demonstrated earlier (Tskhovrebov et al., 2011 ; Mikhaylov et al., 2020 ). In our study, we aimed to adapt this synthetic approach to platinum.

2. Structural commentary

The bond lengths involving Pt are: Pt1—C15 = 1.910 (3), Pt1—C1 = 1.979 (3), Pt1—N1 = 2.048 (3) and Pt1—Cl1 = 2.3709 (9) Å, while the sum of the angles around the Pt atom [C1—Pt1—N1 = 80.71(12°), C15—Pt1—C1 = 98.97 (14)°, C15–Pt1—Cl1 = 85.69 (10) and N1—Pt1—Cl1 = 94.63 (9)°] is 360 (14)°, thus showing a typical square-planar geometry (Fig. 1). The Pt—C_carbene distance [1.910 (3) Å] is slightly shorter than Pt—C_amine [1.979 (3) Å]. The 2,6-dimethylphenyl fragments (A: C7–C12 and B: C16–C21) are almost perpendicular to the mean plane passing through the square-planar complex and the pyridyl-carbamimidoyl moiety, the interplanar angles being 81.55 (9) and 72.64 (11)°, respectively. The compound exhibits weak intramolecular C6—H6⋯Cl1 and C13—H13A⋯N3 interactions (Fig. 1; Table 1). The geometric parameters are normal and consistent with those of related compounds (see Database survey section).

Table 1
Hydrogen-bond geometry (Å, °)

Cg3 is the centroid of the C7–C12 benzene ring attached to the N3 atom.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N3ⁱ	0.80 (6)	2.15 (6)	2.943 (4)	173 (6)
C6—H6⋯Cl1	0.95	2.70	3.308 (4)	123
C13—H13A⋯N3	0.98	2.36	2.848 (5)	110
C22—H22B⋯Cl1ⁱⁱ	0.98	2.78	3.660 (5)	150
C3—H3⋯Cg3ⁱ	0.95	2.99	3.898 (4)	162
Symmetry codes: (i) ; (ii) .

Figure 1
Molecular structure of the title complex with displacement ellipsoids drawn at the 30% probability level.

3. Supramolecular features and Hirshfeld surface analysis

In the crystal, molecules are linked by pairs of N—H⋯N hydrogen bonds, forming inversion dimers with an R₂²(8) ring motif (Bernstein et al., 1995 ). The dimers are connected through pairs of weak C—H⋯Cl interactions, forming an R₂²(16) motif. Thus, parallel ribbons are formed along the [011] axis (Fig. 2; Table 1). Furthermore, the molecular pairs are also linked by C—H⋯π and π–π interactions [Cg2⋯Cg2^a = 3.513 (2) Å, slippage = 0.106 Å; symmetry code (a): 1 − x, −y, 1 − z; where Cg2 is the centroid of the N1/C2–C6 pyridine ring], forming parallel ribbons along the [010] axis (Table 1; Fig. 3). The three-dimensional network arising from N—H⋯N and C—H⋯Cl hydrogen bonds, C—H⋯π and π—π interactions, contribute to the cohesion of the crystal structure. Table 2 lists additional intermolecular hydrogen contacts.

Table 2
Interatomic contacts (Å)

Contact	Distance	Symmetry operation
H6⋯H13B	2.09	x, −1 + y, z
H13A⋯H11	2.32	−1 + x, y, z
H19⋯Cl1	2.96	2 − x, −y, −z
H22B⋯Cl1	2.78	1 − x, −y, −z
H2⋯N3	2.15	1 − x, 1 − y, 1 − z
H14B⋯H4	2.59	1 − x, −y, 1 − z
H4⋯C4	2.98	−x, −y, 1 − z
H18⋯H10	2.46	2 − x, 1 − y, −z
H14C⋯C14	2.94	2 − x, 1 − y, 1 − z

Figure 2
Hydrogen bonds (dotted lines) in the crystal, showing the N—H⋯N dimer and the C—H⋯Cl interactions.

Figure 3
A view along the a-axis showing the C—H⋯π interactions (dotted lines).

In order to quantify the intermolecular interactions in the crystal, Crystal Explorer 17.5 (Spackman et al., 2021 ) was used to generate Hirshfeld surfaces and two-dimensional fingerprint plots. The contributions of different intermolecular contacts to the Hirshfeld surface (Fig. 4) are following: H⋯H (58.0%; Fig. 4b), C⋯H/H⋯C (17.9%; Fig. 4c), Cl⋯H/H⋯Cl (10.7%; Fig. 4d), N⋯H/H⋯N (6.9%; Fig. 4e), C⋯C (2.9%; Fig. 4f), Pt⋯H/H⋯Pt (2.6%; Fig. 4g), and N⋯C/C⋯N (1.1%; Fig. 4h).

Figure 4
Two-dimensional fingerprint plots from a Hirshfeld surface analysis of the complex showing: (a) all contacts, (b) H⋯H (58.0%), (c) C⋯H/H⋯C (17.9%), (d) Cl⋯H/H⋯Cl (10.7%), (e) N⋯H/H⋯N (6.9%), (f) C⋯C (2.9%), (g) Pt⋯H/H⋯Pt (2.6%), (h) N⋯C/C⋯N (1.1%).

4. Database survey

A search of the Cambridge Structural Database (CSD, Version 5.44. last update Jun 2023; Groom et al., 2016 ) for the complex yielded four closely related entries, viz. CSD refcodes ROJWOD (Luzyanin et al., 2008 ), ROJWUJ (Luzyanin et al., 2008), ROJXAQ (Luzyanin et al., 2008), and MUDJAZ (Mikhaylov et al., 2020). ROJWOD and ROJWUJ crystallize in the triclinic P $[\overline{1}]$ space group like the title complex, ROJXAQ in the monoclinic C2/c, and MUDJAZ in the monoclinic P2₁/c space group. In ROJWOD and MUDJAZ, the Pt^II atom has a square-planar geometry. In the crystals of ROJWUJ and ROJXAQ, both Pt^II centers exhibit a slightly distorted square-planar geometry and they have the same coordination environment. In MUDJAZ, the carbene and unreacted isocyanide ligands were located in mutually trans positions. Such an arrangement was unexpected since it did not follow the trans effect rule (Shaw et al., 2009 ). Consolidation of the unfavorable isomer was rationalized by intra-molecular hydrogen bonds.

5. Synthesis and crystallization

The title compound was prepared according to a modified literature procedure (Fig. 5; Gee et al., 2018 ). A solution of 2,6-dimethylphenylisocyanide (14 mg, 107 µmol) in 1,2-dichloroethane (2 mL) was added to a solution of dichloro (1,5-cyclooctadiene) platinum(II) (20 mg, 53 µmol) in 1,2-dichloroethane (2 mL), and the reaction mixture was stirred at room temperature for 30 minutes. After that, 2-aminopyridine (10 mg, 107 µmol) was added and the reaction mixture was stirred under reflux for 1 h. The course of the reaction was controlled by TLC. The solution was evaporated and the residue was purified by column chromatography (eluent: DCM), then evaporated and dried under vacuum. Yellow solid. Yield: 17 mg (55%). Crystals suitable for X-ray analysis were obtained by layering hexane over a dichloromethane solution of the target complex.

Figure 5
Synthesis of the title N-acyclic carbene complex of platinum(II).

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. The N-bound H atom was located in a difference-Fourier map [N2—H2 = 0.80 (6) Å] and refined with U_iso(H) =1.2U_eq(N). The C-bound H atoms were positioned geometrically (C—H= 0.93–0.98 Å) and refined as riding with fixed isotropic displacement parameters [U_iso(H) = 1.2 or 1.5U_eq(C)]. One of the methyl groups (C13) was found to be disordered; it was treated as an idealized disordered methyl group, with two positions rotated from each other by 60°, and the site-occupation factors were fixed at 0.5. Twelve reflections (−7 3 0, −8 4 0, −7 4 0, 7 − 6 1, −9 2 1, 5 − 7 2, 4 − 9 3, 5 − 9 3, −10 0 2, −11 − 2 3, 6 − 9 1 and −9 0 2) were omitted during refinement as they showed poor agreement. The remaining positive and negative residual electron densities are located near the platinum atom Pt1 (1.05 Å from Pt1) and the hydrogen atom H13D (0.88 Å from H13D), respectively.

Table 3
Experimental details

Crystal data
Chemical formula	[Pt(C₁₄H₁₄N₃)Cl(C₉H₉N)]
M_r	585.99
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	100
a, b, c (Å)	7.7053 (3), 9.7010 (3), 15.0316 (5)
α, β, γ (°)	104.535 (1), 95.922 (1), 90.227 (1)
V (Å³)	1081.31 (6)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	6.63
Crystal size (mm)	0.20 × 0.15 × 0.10

Data collection
Diffractometer	Bruker D8 QUEST PHOTON-III CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 ).
T_min, T_max	0.297, 0.495
No. of measured, independent and observed [I > 2σ(I)] reflections	26083, 7860, 6973
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.758

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.071, 1.09
No. of reflections	7860
No. of parameters	268
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	2.31, −1.84
Computer programs: APEX3 (Bruker, 2018 ), SAINT (Bruker, 2013 ), SHELXT2016/6 (Sheldrick, 2015a ), SHELXL2016/6 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC reference: 2456370

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2056989025005079/tx2098sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989025005079/tx2098Isup2.hkl

checkCIF report

Computing details top

Chlorido(2,6-dimethylphenyl isocyanide)[N'-(2,6-dimethylphenyl)-N-(pyridin-2-yl)carbamimidoyl]platinum(II) top

Crystal data top

[Pt(C₁₄H₁₄N₃)Cl(C₉H₉N)]	Z = 2
M_r = 585.99	F(000) = 568
Triclinic, P1	D_x = 1.800 Mg m⁻³
a = 7.7053 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.7010 (3) Å	Cell parameters from 9990 reflections
c = 15.0316 (5) Å	θ = 2.7–32.6°
α = 104.535 (1)°	µ = 6.63 mm⁻¹
β = 95.922 (1)°	T = 100 K
γ = 90.227 (1)°	Prism, red
V = 1081.31 (6) Å³	0.20 × 0.15 × 0.10 mm

Data collection top

Bruker D8 QUEST PHOTON-III CCD diffractometer	6973 reflections with I > 2σ(I)
φ and ω scans	R_int = 0.036
Absorption correction: multi-scan (SADABS; Krause et al., 2015).	θ_max = 32.6°, θ_min = 2.3°
T_min = 0.297, T_max = 0.495	h = −11→11
26083 measured reflections	k = −14→14
7860 independent reflections	l = −22→22

Refinement top

Refinement on F²	Primary atom site location: difference Fourier map
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.030	Hydrogen site location: mixed
wR(F²) = 0.071	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0282P)² + 2.7164P] where P = (F_o² + 2F_c²)/3
7860 reflections	(Δ/σ)_max = 0.002
268 parameters	Δρ_max = 2.31 e Å⁻³
0 restraints	Δρ_min = −1.84 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	Occ. (<1)
Pt1	0.53441 (2)	0.13401 (2)	0.28812 (2)	0.01514 (4)
Cl1	0.51685 (14)	−0.09097 (9)	0.17919 (8)	0.0293 (2)
N1	0.3881 (4)	0.0699 (3)	0.3776 (2)	0.0167 (5)
N2	0.4380 (4)	0.3015 (3)	0.4560 (2)	0.0208 (6)
N3	0.6105 (4)	0.4395 (3)	0.3983 (2)	0.0205 (6)
N4	0.7598 (4)	0.2117 (3)	0.1508 (2)	0.0194 (6)
C1	0.5383 (4)	0.3147 (4)	0.3855 (2)	0.0167 (6)
C2	0.3667 (4)	0.1731 (4)	0.4533 (2)	0.0169 (6)
C3	0.2794 (5)	0.1459 (4)	0.5250 (3)	0.0204 (7)
H3	0.265681	0.219578	0.578710	0.024*
C4	0.2142 (5)	0.0100 (4)	0.5158 (3)	0.0215 (7)
H4	0.156299	−0.011383	0.563766	0.026*
C5	0.2336 (5)	−0.0964 (4)	0.4353 (3)	0.0240 (8)
H5	0.187654	−0.190204	0.427571	0.029*
C6	0.3199 (5)	−0.0627 (4)	0.3681 (3)	0.0226 (7)
H6	0.332495	−0.134323	0.313232	0.027*
C7	0.7334 (5)	0.4707 (3)	0.3421 (2)	0.0176 (6)
C8	0.6827 (5)	0.5520 (3)	0.2788 (2)	0.0175 (6)
C9	0.8120 (5)	0.6020 (4)	0.2349 (2)	0.0200 (7)
H9	0.780448	0.658775	0.192975	0.024*
C10	0.9859 (5)	0.5697 (4)	0.2517 (3)	0.0237 (7)
H10	1.072772	0.606706	0.222696	0.028*
C11	1.0329 (5)	0.4835 (4)	0.3108 (3)	0.0256 (8)
H11	1.151099	0.457850	0.319630	0.031*
C12	0.9076 (5)	0.4341 (4)	0.3573 (3)	0.0231 (7)
C13	0.4921 (5)	0.5789 (4)	0.2586 (3)	0.0238 (7)
H13A	0.423489	0.535280	0.296317	0.036*	0.5
H13B	0.474198	0.681757	0.273333	0.036*	0.5
H13C	0.454504	0.537103	0.192970	0.036*	0.5
H13D	0.477972	0.634147	0.212097	0.036*	0.5
H13E	0.427263	0.487670	0.235081	0.036*	0.5
H13F	0.446956	0.632323	0.315444	0.036*	0.5
C14	0.9594 (6)	0.3416 (5)	0.4217 (3)	0.0335 (10)
H14A	1.086152	0.349498	0.438079	0.050*
H14B	0.925098	0.242238	0.391146	0.050*
H14C	0.900736	0.372707	0.477880	0.050*
C15	0.6750 (4)	0.1938 (3)	0.2063 (3)	0.0182 (6)
C16	0.8932 (5)	0.2184 (4)	0.0958 (3)	0.0223 (7)
C17	0.8685 (5)	0.2968 (5)	0.0294 (3)	0.0268 (8)
C18	1.0081 (7)	0.3038 (7)	−0.0215 (3)	0.0468 (14)
H18	0.998231	0.356724	−0.066964	0.056*
C19	1.1612 (7)	0.2343 (8)	−0.0066 (3)	0.0505 (15)
H19	1.255256	0.241513	−0.041498	0.061*
C20	1.1796 (6)	0.1548 (6)	0.0582 (3)	0.0365 (11)
H20	1.284531	0.106110	0.066206	0.044*
C21	1.0446 (5)	0.1458 (4)	0.1116 (3)	0.0267 (8)
C22	0.6990 (6)	0.3677 (5)	0.0129 (3)	0.0314 (9)
H22A	0.661132	0.418583	0.072357	0.047*
H22B	0.609921	0.295356	−0.019962	0.047*
H22C	0.715665	0.435391	−0.024357	0.047*
C23	1.0591 (6)	0.0627 (5)	0.1833 (4)	0.0386 (11)
H23A	1.162807	0.004344	0.176843	0.058*
H23B	0.954809	0.000691	0.175119	0.058*
H23C	1.069049	0.128459	0.244974	0.058*
H2	0.434 (8)	0.372 (6)	0.497 (4)	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pt1	0.01269 (5)	0.01191 (5)	0.02260 (7)	−0.00027 (4)	0.00389 (4)	0.00688 (4)
Cl1	0.0335 (5)	0.0139 (3)	0.0412 (6)	−0.0005 (3)	0.0197 (4)	0.0019 (3)
N1	0.0123 (12)	0.0144 (12)	0.0263 (15)	0.0002 (10)	0.0036 (11)	0.0097 (11)
N2	0.0271 (15)	0.0177 (13)	0.0174 (14)	−0.0097 (12)	0.0016 (12)	0.0046 (11)
N3	0.0285 (15)	0.0171 (13)	0.0179 (14)	−0.0074 (11)	0.0034 (12)	0.0077 (11)
N4	0.0175 (13)	0.0155 (12)	0.0247 (15)	−0.0017 (10)	0.0043 (11)	0.0030 (11)
C1	0.0181 (15)	0.0157 (14)	0.0176 (15)	−0.0041 (11)	−0.0017 (12)	0.0082 (12)
C2	0.0158 (14)	0.0186 (14)	0.0178 (15)	−0.0061 (11)	−0.0010 (12)	0.0085 (12)
C3	0.0204 (16)	0.0249 (16)	0.0177 (16)	−0.0078 (13)	−0.0011 (12)	0.0101 (13)
C4	0.0199 (16)	0.0233 (16)	0.0264 (18)	−0.0028 (13)	0.0016 (13)	0.0159 (14)
C5	0.0199 (16)	0.0153 (14)	0.041 (2)	−0.0001 (12)	0.0094 (15)	0.0126 (15)
C6	0.0214 (16)	0.0136 (14)	0.035 (2)	−0.0003 (12)	0.0100 (15)	0.0068 (14)
C7	0.0257 (16)	0.0146 (13)	0.0127 (14)	−0.0069 (12)	0.0013 (12)	0.0041 (11)
C8	0.0237 (16)	0.0138 (13)	0.0150 (15)	−0.0029 (12)	0.0024 (12)	0.0037 (11)
C9	0.0280 (17)	0.0181 (14)	0.0154 (15)	−0.0044 (13)	0.0055 (13)	0.0054 (12)
C10	0.0248 (17)	0.0261 (17)	0.0211 (17)	−0.0098 (14)	0.0033 (14)	0.0076 (14)
C11	0.0210 (17)	0.0272 (18)	0.030 (2)	−0.0083 (14)	−0.0032 (14)	0.0125 (16)
C12	0.0238 (17)	0.0245 (16)	0.0217 (17)	−0.0102 (14)	−0.0055 (14)	0.0107 (14)
C13	0.0234 (17)	0.0226 (16)	0.0281 (19)	0.0018 (14)	0.0070 (15)	0.0100 (15)
C14	0.0262 (19)	0.039 (2)	0.040 (2)	−0.0144 (17)	−0.0116 (17)	0.025 (2)
C15	0.0154 (14)	0.0140 (13)	0.0248 (17)	0.0000 (11)	0.0043 (13)	0.0036 (12)
C16	0.0201 (16)	0.0214 (15)	0.0216 (17)	−0.0060 (13)	0.0092 (13)	−0.0040 (13)
C17	0.0255 (18)	0.040 (2)	0.0127 (16)	−0.0054 (16)	0.0041 (13)	0.0028 (15)
C18	0.033 (2)	0.093 (4)	0.0161 (19)	−0.002 (3)	0.0097 (17)	0.016 (2)
C19	0.029 (2)	0.096 (5)	0.024 (2)	−0.003 (3)	0.0153 (18)	0.006 (3)
C20	0.0187 (18)	0.051 (3)	0.031 (2)	0.0007 (18)	0.0075 (16)	−0.007 (2)
C21	0.0205 (17)	0.0224 (16)	0.032 (2)	−0.0028 (13)	0.0060 (15)	−0.0046 (15)
C22	0.028 (2)	0.048 (3)	0.0192 (18)	−0.0027 (18)	0.0010 (15)	0.0124 (18)
C23	0.025 (2)	0.028 (2)	0.065 (3)	0.0054 (16)	0.007 (2)	0.016 (2)

Geometric parameters (Å, º) top

Pt1—C15	1.910 (3)	C11—C12	1.398 (5)
Pt1—C1	1.979 (3)	C11—H11	0.9500
Pt1—N1	2.048 (3)	C12—C14	1.504 (5)
Pt1—Cl1	2.3709 (9)	C13—H13A	0.9800
N1—C2	1.340 (5)	C13—H13B	0.9800
N1—C6	1.355 (4)	C13—H13C	0.9800
N2—C2	1.350 (4)	C13—H13D	0.9800
N2—C1	1.404 (4)	C13—H13E	0.9800
N2—H2	0.80 (6)	C13—H13F	0.9800
N3—C1	1.291 (4)	C14—H14A	0.9800
N3—C7	1.413 (4)	C14—H14B	0.9800
N4—C15	1.157 (5)	C14—H14C	0.9800
N4—C16	1.394 (4)	C16—C21	1.396 (6)
C2—C3	1.405 (5)	C16—C17	1.398 (6)
C3—C4	1.377 (5)	C17—C18	1.394 (6)
C3—H3	0.9500	C17—C22	1.505 (6)
C4—C5	1.401 (6)	C18—C19	1.387 (8)
C4—H4	0.9500	C18—H18	0.9500
C5—C6	1.369 (5)	C19—C20	1.382 (8)
C5—H5	0.9500	C19—H19	0.9500
C6—H6	0.9500	C20—C21	1.394 (6)
C7—C12	1.401 (5)	C20—H20	0.9500
C7—C8	1.408 (5)	C21—C23	1.496 (7)
C8—C9	1.399 (5)	C22—H22A	0.9800
C8—C13	1.506 (5)	C22—H22B	0.9800
C9—C10	1.390 (6)	C22—H22C	0.9800
C9—H9	0.9500	C23—H23A	0.9800
C10—C11	1.389 (5)	C23—H23B	0.9800
C10—H10	0.9500	C23—H23C	0.9800

C15—Pt1—C1	98.97 (14)	C11—C12—C14	120.3 (4)
C15—Pt1—N1	178.85 (14)	C7—C12—C14	120.7 (3)
C1—Pt1—N1	80.71 (12)	C8—C13—H13A	109.5
C15—Pt1—Cl1	85.69 (10)	C8—C13—H13B	109.5
C1—Pt1—Cl1	175.33 (10)	H13A—C13—H13B	109.5
N1—Pt1—Cl1	94.63 (9)	C8—C13—H13C	109.5
C2—N1—C6	119.7 (3)	H13A—C13—H13C	109.5
C2—N1—Pt1	113.5 (2)	H13B—C13—H13C	109.5
C6—N1—Pt1	126.8 (3)	H13D—C13—H13E	109.5
C2—N2—C1	119.2 (3)	H13D—C13—H13F	109.5
C2—N2—H2	125 (4)	H13E—C13—H13F	109.5
C1—N2—H2	115 (4)	C12—C14—H14A	109.5
C1—N3—C7	123.1 (3)	C12—C14—H14B	109.5
C15—N4—C16	166.0 (4)	H14A—C14—H14B	109.5
N3—C1—N2	114.0 (3)	C12—C14—H14C	109.5
N3—C1—Pt1	134.9 (3)	H14A—C14—H14C	109.5
N2—C1—Pt1	111.2 (2)	H14B—C14—H14C	109.5
N1—C2—N2	115.2 (3)	N4—C15—Pt1	171.2 (3)
N1—C2—C3	121.3 (3)	N4—C16—C21	117.0 (4)
N2—C2—C3	123.4 (3)	N4—C16—C17	118.8 (4)
C4—C3—C2	118.6 (3)	C21—C16—C17	124.2 (4)
C4—C3—H3	120.7	C18—C17—C16	116.4 (4)
C2—C3—H3	120.7	C18—C17—C22	121.9 (4)
C3—C4—C5	119.7 (3)	C16—C17—C22	121.7 (3)
C3—C4—H4	120.2	C19—C18—C17	120.8 (5)
C5—C4—H4	120.2	C19—C18—H18	119.6
C6—C5—C4	118.7 (3)	C17—C18—H18	119.6
C6—C5—H5	120.6	C20—C19—C18	121.3 (4)
C4—C5—H5	120.6	C20—C19—H19	119.4
N1—C6—C5	122.0 (4)	C18—C19—H19	119.4
N1—C6—H6	119.0	C19—C20—C21	120.2 (4)
C5—C6—H6	119.0	C19—C20—H20	119.9
C12—C7—C8	121.0 (3)	C21—C20—H20	119.9
C12—C7—N3	119.4 (3)	C20—C21—C16	117.2 (4)
C8—C7—N3	119.2 (3)	C20—C21—C23	122.2 (4)
C9—C8—C7	118.4 (3)	C16—C21—C23	120.6 (4)
C9—C8—C13	122.2 (3)	C17—C22—H22A	109.5
C7—C8—C13	119.4 (3)	C17—C22—H22B	109.5
C10—C9—C8	120.9 (3)	H22A—C22—H22B	109.5
C10—C9—H9	119.5	C17—C22—H22C	109.5
C8—C9—H9	119.5	H22A—C22—H22C	109.5
C11—C10—C9	120.0 (3)	H22B—C22—H22C	109.5
C11—C10—H10	120.0	C21—C23—H23A	109.5
C9—C10—H10	120.0	C21—C23—H23B	109.5
C10—C11—C12	120.5 (4)	H23A—C23—H23B	109.5
C10—C11—H11	119.7	C21—C23—H23C	109.5
C12—C11—H11	119.7	H23A—C23—H23C	109.5
C11—C12—C7	119.0 (3)	H23B—C23—H23C	109.5

C7—N3—C1—N2	172.0 (3)	C8—C9—C10—C11	1.8 (6)
C7—N3—C1—Pt1	−8.2 (6)	C9—C10—C11—C12	−3.1 (6)
C2—N2—C1—N3	−175.3 (3)	C10—C11—C12—C7	1.2 (6)
C2—N2—C1—Pt1	4.9 (4)	C10—C11—C12—C14	−179.6 (4)
C6—N1—C2—N2	−179.5 (3)	C8—C7—C12—C11	2.0 (6)
Pt1—N1—C2—N2	2.6 (4)	N3—C7—C12—C11	−170.8 (3)
C6—N1—C2—C3	2.1 (5)	C8—C7—C12—C14	−177.2 (4)
Pt1—N1—C2—C3	−175.9 (3)	N3—C7—C12—C14	10.0 (5)
C1—N2—C2—N1	−5.0 (5)	C15—N4—C16—C21	9.9 (16)
C1—N2—C2—C3	173.4 (3)	C15—N4—C16—C17	−169.7 (13)
N1—C2—C3—C4	−0.5 (5)	N4—C16—C17—C18	177.9 (4)
N2—C2—C3—C4	−178.8 (4)	C21—C16—C17—C18	−1.6 (6)
C2—C3—C4—C5	−1.0 (6)	N4—C16—C17—C22	−3.0 (6)
C3—C4—C5—C6	1.0 (6)	C21—C16—C17—C22	177.4 (4)
C2—N1—C6—C5	−2.1 (6)	C16—C17—C18—C19	0.7 (8)
Pt1—N1—C6—C5	175.6 (3)	C22—C17—C18—C19	−178.3 (5)
C4—C5—C6—N1	0.6 (6)	C17—C18—C19—C20	0.8 (9)
C1—N3—C7—C12	−80.3 (5)	C18—C19—C20—C21	−1.5 (8)
C1—N3—C7—C8	106.8 (4)	C19—C20—C21—C16	0.7 (7)
C12—C7—C8—C9	−3.3 (5)	C19—C20—C21—C23	−179.2 (5)
N3—C7—C8—C9	169.5 (3)	N4—C16—C21—C20	−178.6 (3)
C12—C7—C8—C13	175.0 (3)	C17—C16—C21—C20	1.0 (6)
N3—C7—C8—C13	−12.2 (5)	N4—C16—C21—C23	1.2 (6)
C7—C8—C9—C10	1.4 (5)	C17—C16—C21—C23	−179.2 (4)
C13—C8—C9—C10	−176.9 (3)

Hydrogen-bond geometry (Å, º) top

Cg3 is the centroid of the C7–C12 benzene ring attached to the N3 atom.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N3ⁱ	0.80 (6)	2.15 (6)	2.943 (4)	173 (6)
C6—H6···Cl1	0.95	2.70	3.308 (4)	123
C13—H13A···N3	0.98	2.36	2.848 (5)	110
C22—H22B···Cl1ⁱⁱ	0.98	2.78	3.660 (5)	150
C3—H3···Cg3ⁱ	0.95	2.99	3.898 (4)	162

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

Interatomic contacts (Å) top

Contact	Distance	Symmetry operation
H6···H13B	2.09	x, -1 + y, z
H13A···H11	2.32	-1 + x, y, z
H19···Cl1	2.96	2 - x, -y, -z
H22B···Cl1	2.78	1 - x, -y, -z
H2···N3	2.15	1 - x, 1 - y, 1 - z
H14B···H4	2.59	1 - x, -y, 1 - z
H4···C4	2.98	-x, -y, 1 - z
H18···H10	2.46	2 - x, 1 - y, -z
H14C···C14	2.94	2 - x, 1 - y, 1 - z

Acknowledgements

The author's contributions are as follows. Conceptualization, NQS, MA and AB; synthesis, AAS, EAD, ASK and ASN; X-ray analysis, VNK and MA; writing (review and editing of the manuscript) MMG, MA and AB; funding acquisition, NQS, EVD and MRK; supervision, NQS and AGT.

Funding information

This work was performed with the support of the Russian Science Foundation (award No. 25–23-00043).

References

Alder, R. W., Allen, P. R., Murray, M. & Orpen, A. G. (1996). Angew. Chem. Int. Ed. Engl. 35, 1121–1123. CSD CrossRef Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bruker (2013). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2018). APEX3. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gee, J. C., Fuller, B. A., Lockett, H.-M., Sedghi, G., Robertson, C. M. & Luzyanin, K. V. (2018). Chem. Commun. 54, 9450–9453. CSD CrossRef 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
Heck, R. F. & Nolley, J. P. (1972). J. Org. Chem. 37, 2320–2322. CrossRef CAS Web of Science Google Scholar
Kinzhalov, M. A. & Luzyanin, K. V. (2022). Russ. J. Inorg. Chem. 67, 48–90. CrossRef 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
Luzyanin, K. V., Pombeiro, A. J. L., Haukka, M. & Kukushkin, V. Yu. (2008). Organometallics 27, 5379–5389. CSD CrossRef Google Scholar
Luzyanin, K. V., Tskhovrebov, A. G., Carias, M. C., Guedes da Silva, M. F. C., Pombeiro, A. J. L. & Kukushkin, V. Y. (2009). Organometallics 28, 6559–6566. CSD CrossRef Google Scholar
Michelin, R. A., Pombeiro, A. J. L. & Guedes da Silva, M. F. (2001). Coord. Chem. Rev. 218, 75–112. CrossRef Google Scholar
Mikhaylov, V. N., Sorokoumov, V. N., Novikov, A. S., Melnik, M. V., Tskhovrebov, A. G. & Balova, I. A. (2020). J. Organomet. Chem. 912, 121174. CSD CrossRef Google Scholar
Miyaura, N., Yamada, K. & Suzuki, A. (1979). Tetrahedron Lett. 20, 3437–3440. CrossRef Web of Science Google Scholar
Mizoroki, T., Mori, T. & Ozaki, A. (1971). Bull. Chem. Soc. Jpn 44, 581–581. CrossRef Google Scholar
Repina, O. V., Kubasov, A. S., Vologzhanina, A. V., Borisov, A. V., Kritchenkov, I. S., Voroshilkina, K. M., Nazarov, A. A., Shchevnikov, D. M., Grudova, M. V., Gomila, R. M., Frontera, A., Nenajdenko, V. G., Kritchenkov, A. S. & Tskhovrebov, A. G. (2025). Int. J. Mol. Sci. https://doi. org/10.3390/ijms26020483. Google Scholar
Shaw, J. L., Dockery, C. R., Lewis, S. E., Harris, L. & Bettis, R. (2009). J. Chem. Educ. 86, 1416–1418. CrossRef 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
Spackman, P. R., Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Jayatilaka, D. & Spackman, M. A. (2021). J. Appl. Cryst. 54, 1006–1011. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
Suzuki, A. (1999). J. Organomet. Chem. 576, 147–168. Web of Science CrossRef CAS Google Scholar
Tskhovrebov, A., Solari, E., Scopelliti, R. & Severin, K. (2013). Inorg. Chem. 52, 11688–11690. CSD CrossRef PubMed Google Scholar
Tskhovrebov, A. G., Goddard, R. & Fürstner, A. (2018). Angew. Chem. Int. Ed. 57, 8089–8094. CSD CrossRef CAS Google Scholar
Tskhovrebov, A. G., Luzyanin, K. V., Dolgushin, F. M., Guedes da Silva, M. F. C., Pombeiro, A. J. L. & Kukushkin, V. Y. (2011). Organometallics 30, 3362–3370. CrossRef Google Scholar
Tskhovrebov, A. G., Luzyanin, K. V., Haukka, M. & Kukushkin, V. Y. (2012). J. Chem. Crystallogr. 42, 1170–1175. CSD CrossRef CAS Google Scholar

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