Electrostatic repulsion between the cations of (1-methyl-1H-imidazole-κN3)(2,2′:6′,2′′-terpyridine-κ3N,N′,N′′)platinum(II) perchlorate nitro­methane monosolvate prevents Pt⋯Pt inter­actions

Akerman, M.; Akerman, K.; Jaganyi, D.; Reddy, D.

doi:10.1107/S1600536811025475

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Pages m1075-m1076

doi:10.1107/S1600536811025475

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Electrostatic repulsion between the cations of (1-methyl-1H-imidazole-κN³)(2,2′:6′,2′′-terpyridine-κ³N,N′,N′′)platinum(II) perchlorate nitromethane monosolvate prevents Pt⋯Pt interactions

Matthew Akerman,^a ^* Kate Akerman,^a Deogratius Jaganyi ^a and Desigan Reddy ^a

^aSchool of Chemistry, University of KwaZulu-Natal, Private Bag X01, Pietermaritzburg 3209, South Africa
^*Correspondence e-mail: akermanm@ukzn.ac.za

(Received 7 May 2011; accepted 28 June 2011; online 9 July 2011)

The reaction between [Pt(terpy)Cl]·2H₂O (terpy = 2′,2′′:6′,2′′-terpyridine) and 1-methylimidazole (MIm) in the presence of two equivalents of AgClO₄ in nitromethane yields the title compound, [Pt(C₁₅H₁₁N₃)(C₄H₆N₂)](ClO₄)₂·CH₃NO₂. The dicationic complexes are arranged in a staggered configuration. The torsion angle subtended by the 1-methylimidazole ring relative to the terpyridine ring is 114.9 (5)°. Intermolecular C—H⋯O interactions between the perchlorate anions and the H atoms of the terpy ligand are observed. Consideration of related phenylbipyridyl complexes of platinum(II), which are monocationic, leads to the conclusion that the electrostatic repulsion between the dicationic chelates prevents the formation of Pt⋯Pt interactions. These interactions are a common feature associated with the monocationic species.

Related literature

For synthesis of the parent complex, chloro(2,2′:6′,2"-terpyridine)platinum(II)chloride dihydrate, [Pt(terpy)Cl]Cl·2H₂O, see: Pitteri et al. (1995 ). For the structure of the acetonitrile solvate of the title Pt(II) chelate, see: Roszak et al. (1996 ) and for a structure, which was devoid of solvent in the lattice, see: Müller et al. (2007 ). For studies of the luminescent properties and intermolecular Pt⋯Pt interactions of related compounds, see: Field et al. (2007 ). For a comprehensive review of Pt(II) terpyridines in general, see: Newkome et al. (2008 ). For Pt⋯Pt and Pt⋯π interactions in monocationic platinum(II) terpyridine and platinum(II) bipy complexes and the role they play in their unusual solid state emission properties, see: Connick et al. (1997 ); Field et al. (2003 ); Jaganyi & Reddy (2008 ).

Experimental

Crystal data

[Pt(C₁₅H₁₁N₃)(C₄H₆N₂)](ClO₄)₂·CH₃NO₂
M_r = 770.41
Monoclinic, P 2₁ /c
a = 16.389 (4) Å
b = 11.582 (5) Å
c = 14.538 (5) Å
β = 110.147 (5)°
V = 2590.7 (16) Å³
Z = 4
Mo Kα radiation
μ = 5.69 mm⁻¹
T = 296 K
0.60 × 0.60 × 0.60 mm

Data collection

Oxford Diffraction Xcalibur2 CCD diffractometer
Absorption correction: multi-scan (Blessing, 1995 ) T_min = 0.132, T_max = 0.132
17563 measured reflections
5102 independent reflections
3881 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.118
S = 0.98
5102 reflections
354 parameters
H-atom parameters constrained
Δρ_max = 1.59 e Å⁻³
Δρ_min = −2.64 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O7ⁱ	0.93	2.51	3.21 (2)	132 (1)
C8—H8⋯O7ⁱⁱ	0.93	2.56	3.42 (2)	153 (1)
C9—H9⋯O6ⁱⁱⁱ	0.93	2.54	3.34 (1)	144 (1)
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) -x+1, -y, -z+2; (iii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: WinGX (Farrugia, 1999 ); software used to prepare material for publication: WinGX (Farrugia, 1999).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811025475/fi2109sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025475/fi2109Isup2.hkl

checkCIF report

Comment top

Platinum(II) polypyridine complexes are an important class of compounds in many areas of inorganic chemistry (Newkome et al., 2008). The most widely studied polypyridine ligands include 2,2'-bipyridine (bipy), 1,10-phenanthroline, 2,2':6',N''-terpyridine (terpy), 6-phenyl-2,2'-bipyridine and 2,2':6',2'':6'',2'''-quaterpyridine (Newkome et al., 2008). The substitution kinetics of platinum(II) polypyridines have been extensively studied. This is largely due to their redox stability and relatively fast reactivity (Jaganyi and Reddy, 2008). To develop the understanding of the binding mode of the incoming 1-methylimidazole ligand in substitution kinetics, the single-crystal X-ray structure of the title compound was elucidated. Upon examination it was evident that the structure was devoid of any Pt···Pt or Pt···π interactions. These interactions are ubiquitous with monocationic platinum(II) terpyridine (Field et al., 2007) and platinum(II) bipy complexes (Connick et al., 1997) and are, in part, responsible for their unusual solid state emission properties (Field et al., 2003).

Two variants of the title cation have been reported. Firstly, with an acetonitrile molecule in the lattice (Roszak et al., 1996) and secondly, a structure, which was devoid of solvent in the lattice (Müller et al., 2007). The title compound has a nitromethane molecule in the asymmetric unit.

The platinum(II) centre is nominally square planar with the tridentate terpy ligand and the monodentate 1-methylimidazole ligand, as expected for d⁸ platinum(II) complexes. The Pt— N1 and Pt— N3 bond distances are approximately equal, averaging 2.023 (8) Å. The Pt— N2 bond is 1.925 (5) Å. The Pt— N4 bond length is 2.013 (6) Å, these bond distances are equivalent to those previously reported. The MIm ligand is canted relative to the Pt(terpy) unit. The torsion angle defined by C(16)—N(4)—Pt—N(1) is 114.9 (5)°.This angle is equivalent to that reported by Roszak et al., 1996. The same torsion angle reported by Müller et al., 2007, is 107.2 (7)°. These data suggest that the identity of the solvent in the lattice is inconsequential in terms of its effect on the torsion angle of the ancillary ligand, but show that the presence of solvent influences the geometry of the cation. The platinum(II) chelates are arranged in a staggered configuration and are not parallel. Thus there are no Pt···Pt or Pt···π interactions in the solid state, which require interacting molecules to be parallel.

The crystal packing shows there to be no classical hydrogen bonding, however, there are unconventional hydrogen bonds between the perchlorate anions and the hydrogen atoms of the terpy ligand. The hydrogen bond parameters are given in Table 1.

Related literature top

For synthesis of the parent complex, chloro(2,2':6',2"-terpyridine)platinum(II)chloride dihydrate, [Pt(terpy)Cl]Cl.2H₂O, see: Pitteri et al. (1995). For the structure of the acetonitrile solvate of the title Pt(II) chelate, see: Roszak et al. (1996) and for a structure, which was devoid of solvent in the lattice, see: Müller et al. (2007). For studies of luminescent properties and intermolecular Pt···Pt interactions of related compounds, see: Field et al. (2007). For a comprehensive review of Pt(II) terpyridines in general, see: Newkome et al. (2008). For Pt···Pt and Pt···π interactions in monocationic platinum(II) terpyridine and platinum(II) bipy complexes and the role they play in their unusual solid state emission properties, see: Connick et al. (1997); Field et al. (2003); Jaganyi & Reddy (2008).

Experimental top

The complex, chloro(2,2':6',2"-terpyridine)platinum(II)chloride dihydrate, [Pt(terpy)C1]C1.2H₂O was synthesized using previously reported methods (Pitteri et al., 1995). [Pt(terpy)Cl]Cl.2H₂O (70 mg, 0.13 mmol) was dissolved in nitromethane (4 ml) and AgClO₄ (54 mg, 0.26 mmol) was added to the stirred platinum solution at ca. 50 ^oC. The reaction mixture was stirred for 1 h over which time it turned a pale yellow in colour with a white silver(I)chloride precipitate. The precipitate was removed by filtration. One equivalent of 1-methylimidazole (11 mg, 0.13 mmol) was added to the filtrate, which immediately turned orange in colour. Orange crystals of [Pt(terpy)MIm](ClO₄)₂(CH₃NO₂) were grown via vapour diffusion of diethylether into the nitromethane solution of the desired product (yield 73%).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis CCD (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: WinGX (Farrugia, 1999); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. Molecular structure (50% probability surfaces) of [Pt(terpy)MIm](ClO₄)₂(CH₃NO₂). Hydrogen atoms have been omitted for clarity.

(1-methyl-1H-imidazole-κN³)(2,2':6',2''- terpyridine-κ³N,N',N'')platinum(II) perchlorate nitromethane monosolvate top

Crystal data top

[Pt(C₁₅H₁₁N₃)(C₄H₆N₂)](ClO₄)₂·CH₃NO₂	F(000) = 1496
M_r = 770.41	D_x = 1.975 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5102 reflections
a = 16.389 (4) Å	θ = 2.8–26.1°
b = 11.582 (5) Å	µ = 5.69 mm⁻¹
c = 14.538 (5) Å	T = 296 K
β = 110.147 (5)°	Cubic, orange
V = 2590.7 (16) Å³	0.60 × 0.60 × 0.60 mm
Z = 4

Data collection top

Oxford Diffraction Xcalibur2 CCD diffractometer	5102 independent reflections
Radiation source: fine-focus sealed tube	3881 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
ω scans at fixed θ angles	θ_max = 26.1°, θ_min = 2.8°
Absorption correction: multi-scan (Blessing, 1995)	h = −20→20
T_min = 0.132, T_max = 0.132	k = −14→14
17563 measured reflections	l = −17→14

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 0.98	w = 1/[σ²(F_o²) + (0.082P)²] where P = (F_o² + 2F_c²)/3
5102 reflections	(Δ/σ)_max = 0.001
354 parameters	Δρ_max = 1.59 e Å⁻³
0 restraints	Δρ_min = −2.64 e Å⁻³

Crystal data top

[Pt(C₁₅H₁₁N₃)(C₄H₆N₂)](ClO₄)₂·CH₃NO₂	V = 2590.7 (16) Å³
M_r = 770.41	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.389 (4) Å	µ = 5.69 mm⁻¹
b = 11.582 (5) Å	T = 296 K
c = 14.538 (5) Å	0.60 × 0.60 × 0.60 mm
β = 110.147 (5)°

Data collection top

Oxford Diffraction Xcalibur2 CCD diffractometer	5102 independent reflections
Absorption correction: multi-scan (Blessing, 1995)	3881 reflections with I > 2σ(I)
T_min = 0.132, T_max = 0.132	R_int = 0.053
17563 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 0.98	Δρ_max = 1.59 e Å⁻³
5102 reflections	Δρ_min = −2.64 e Å⁻³
354 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
C1	0.6697 (5)	0.4867 (7)	1.0042 (6)	0.059 (2)
H1	0.6976	0.5318	0.9712	0.071*
C1S	0.9475 (7)	0.0921 (12)	1.0904 (9)	0.118 (4)
H1S1	0.9664	0.0286	1.1351	0.176*
H1S2	0.9972	0.1356	1.0896	0.176*
H1S3	0.9167	0.0633	1.0258	0.176*
C2	0.6293 (6)	0.5379 (8)	1.0631 (6)	0.069 (2)
H2	0.6308	0.6179	1.0693	0.082*
C3	0.5873 (5)	0.4746 (9)	1.1124 (6)	0.071 (3)
H3	0.5594	0.5097	1.1509	0.086*
C4	0.5882 (5)	0.3568 (9)	1.1025 (6)	0.063 (2)
H4	0.5614	0.3110	1.1363	0.076*
C5	0.6272 (4)	0.3058 (7)	1.0446 (5)	0.0450 (17)
C6	0.6301 (4)	0.1792 (8)	1.0298 (5)	0.0483 (18)
C7	0.5995 (5)	0.0928 (9)	1.0705 (6)	0.060 (2)
H7	0.5695	0.1096	1.1128	0.072*
C8	0.6121 (5)	−0.0197 (8)	1.0502 (6)	0.061 (2)
H8	0.5911	−0.0782	1.0798	0.073*
C9	0.6548 (5)	−0.0487 (7)	0.9871 (5)	0.059 (2)
H9	0.6620	−0.1253	0.9721	0.070*
C10	0.6871 (4)	0.0424 (6)	0.9465 (5)	0.0435 (16)
C11	0.7363 (4)	0.0341 (6)	0.8776 (5)	0.0452 (17)
C12	0.7570 (5)	−0.0665 (7)	0.8412 (6)	0.062 (2)
H12	0.7398	−0.1371	0.8590	0.074*
C13	0.8024 (6)	−0.0627 (7)	0.7794 (7)	0.069 (2)
H13	0.8190	−0.1310	0.7572	0.083*
C14	0.8241 (5)	0.0410 (8)	0.7494 (6)	0.067 (2)
H14	0.8527	0.0440	0.7042	0.080*
C15	0.8030 (4)	0.1402 (7)	0.7870 (6)	0.0525 (19)
H15	0.8195	0.2107	0.7684	0.063*
C16	0.8566 (4)	0.4276 (6)	0.8775 (5)	0.0430 (16)
H16	0.9022	0.3812	0.9149	0.052*
C17	0.7844 (6)	0.5684 (7)	0.7859 (6)	0.061 (2)
H17	0.7717	0.6360	0.7491	0.073*
C18	0.7266 (5)	0.4945 (6)	0.8026 (5)	0.0475 (17)
H18	0.6665	0.5028	0.7788	0.057*
C19	0.9464 (5)	0.5765 (8)	0.8392 (7)	0.080 (3)
H19A	0.9931	0.5231	0.8681	0.121*
H19B	0.9556	0.6450	0.8786	0.121*
H19C	0.9446	0.5962	0.7744	0.121*
N1	0.6682 (4)	0.3704 (6)	0.9951 (4)	0.0453 (14)
N1S	0.8913 (5)	0.1653 (8)	1.1213 (6)	0.072 (2)
N2	0.6734 (4)	0.1509 (5)	0.9674 (4)	0.0429 (14)
N3	0.7591 (4)	0.1392 (5)	0.8502 (4)	0.0438 (14)
N4	0.7711 (4)	0.4065 (5)	0.8597 (4)	0.0399 (13)
N5	0.8647 (4)	0.5235 (5)	0.8340 (4)	0.0469 (14)
O1	0.941 (2)	0.7727 (17)	1.039 (3)	0.38 (2)
O1S	0.8411 (5)	0.1229 (7)	1.1517 (5)	0.102 (2)
O2	0.8371 (10)	0.7867 (13)	1.1015 (11)	0.203 (7)
O2S	0.8951 (5)	0.2668 (7)	1.1098 (8)	0.114 (3)
O3	0.8708 (12)	0.6230 (12)	1.0429 (10)	0.252 (8)
O4	0.9562 (13)	0.7038 (14)	1.1756 (10)	0.261 (10)
O5	0.4957 (4)	0.1229 (6)	0.7854 (5)	0.092 (2)
O6	0.4009 (6)	0.2158 (7)	0.6530 (6)	0.104 (3)
O7	0.3906 (7)	0.2504 (6)	0.8042 (7)	0.096 (3)
O8	0.5069 (5)	0.3205 (8)	0.7608 (7)	0.109 (3)
Cl1	0.89895 (18)	0.7258 (2)	1.08438 (18)	0.0666 (6)
Cl2	0.45100 (13)	0.22848 (15)	0.75630 (14)	0.0472 (4)
Pt	0.720986 (15)	0.27470 (2)	0.913208 (17)	0.03619 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.069 (5)	0.040 (5)	0.072 (5)	−0.007 (4)	0.030 (4)	−0.012 (4)
C1S	0.088 (8)	0.126 (12)	0.134 (10)	0.026 (8)	0.032 (8)	−0.005 (9)
C2	0.073 (6)	0.056 (6)	0.076 (6)	0.005 (5)	0.025 (5)	−0.022 (5)
C3	0.064 (6)	0.082 (7)	0.072 (5)	0.003 (5)	0.028 (5)	−0.020 (5)
C4	0.049 (5)	0.087 (8)	0.059 (5)	−0.011 (4)	0.025 (4)	−0.006 (4)
C5	0.030 (4)	0.052 (5)	0.054 (4)	−0.003 (3)	0.016 (3)	0.003 (3)
C6	0.032 (4)	0.066 (5)	0.045 (4)	−0.009 (4)	0.011 (3)	0.006 (4)
C7	0.043 (4)	0.076 (7)	0.055 (4)	−0.016 (4)	0.012 (4)	0.009 (4)
C8	0.050 (5)	0.070 (6)	0.057 (5)	−0.019 (4)	0.010 (4)	0.014 (4)
C9	0.059 (5)	0.044 (5)	0.061 (5)	−0.020 (4)	0.005 (4)	0.004 (4)
C10	0.034 (4)	0.040 (4)	0.047 (4)	−0.010 (3)	0.002 (3)	0.002 (3)
C11	0.035 (4)	0.041 (4)	0.054 (4)	0.000 (3)	0.008 (3)	0.004 (3)
C12	0.065 (5)	0.035 (4)	0.079 (6)	−0.003 (4)	0.018 (5)	−0.009 (4)
C13	0.066 (6)	0.040 (5)	0.107 (7)	−0.005 (4)	0.037 (5)	−0.023 (5)
C14	0.060 (5)	0.063 (6)	0.088 (6)	−0.006 (4)	0.038 (5)	−0.021 (5)
C15	0.036 (4)	0.051 (5)	0.074 (5)	−0.010 (3)	0.024 (4)	−0.011 (4)
C16	0.044 (4)	0.035 (4)	0.048 (4)	−0.003 (3)	0.012 (3)	0.004 (3)
C17	0.081 (6)	0.035 (4)	0.067 (5)	0.001 (4)	0.027 (5)	0.005 (4)
C18	0.044 (4)	0.044 (4)	0.051 (4)	0.009 (3)	0.012 (3)	0.005 (3)
C19	0.071 (6)	0.068 (6)	0.107 (7)	−0.032 (5)	0.038 (5)	0.006 (5)
N1	0.035 (3)	0.050 (4)	0.050 (3)	0.006 (3)	0.013 (3)	−0.004 (3)
N1S	0.051 (5)	0.068 (6)	0.082 (5)	−0.017 (4)	0.005 (4)	0.012 (4)
N2	0.032 (3)	0.039 (4)	0.057 (3)	−0.011 (2)	0.013 (3)	0.002 (3)
N3	0.031 (3)	0.036 (3)	0.065 (4)	−0.001 (2)	0.017 (3)	0.001 (3)
N4	0.043 (3)	0.030 (3)	0.046 (3)	0.001 (3)	0.014 (3)	−0.001 (2)
N5	0.048 (4)	0.037 (3)	0.058 (3)	−0.014 (3)	0.021 (3)	−0.006 (3)
O1	0.44 (4)	0.27 (2)	0.64 (5)	0.02 (2)	0.43 (4)	0.16 (2)
O1S	0.083 (5)	0.123 (7)	0.107 (5)	−0.020 (5)	0.041 (4)	0.026 (5)
O2	0.140 (11)	0.250 (16)	0.216 (15)	0.098 (11)	0.057 (10)	−0.020 (11)
O2S	0.060 (5)	0.095 (7)	0.164 (9)	−0.006 (4)	0.011 (5)	0.015 (6)
O3	0.39 (2)	0.153 (12)	0.218 (13)	−0.087 (13)	0.112 (14)	−0.097 (11)
O4	0.33 (2)	0.270 (18)	0.130 (10)	0.168 (17)	0.016 (12)	−0.018 (11)
O5	0.082 (5)	0.066 (4)	0.123 (6)	0.030 (4)	0.030 (4)	0.016 (4)
O6	0.098 (6)	0.116 (7)	0.084 (5)	0.006 (4)	0.013 (4)	0.006 (4)
O7	0.125 (7)	0.074 (5)	0.125 (7)	0.016 (4)	0.088 (6)	0.001 (4)
O8	0.095 (6)	0.076 (5)	0.167 (7)	−0.038 (5)	0.057 (5)	−0.016 (5)
Cl1	0.0814 (17)	0.0584 (13)	0.0685 (13)	0.0075 (12)	0.0366 (12)	−0.0004 (10)
Cl2	0.0475 (11)	0.0368 (9)	0.0627 (11)	0.0040 (8)	0.0258 (9)	0.0044 (8)
Pt	0.02992 (17)	0.03339 (17)	0.04422 (17)	−0.00357 (11)	0.01146 (12)	0.00027 (11)

Geometric parameters (Å, º) top

C1—N1	1.353 (10)	C14—C15	1.368 (11)
C1—C2	1.382 (11)	C14—H14	0.9300
C1—H1	0.9300	C15—N3	1.349 (9)
C1S—N1S	1.434 (13)	C15—H15	0.9300
C1S—H1S1	0.9600	C16—N5	1.307 (8)
C1S—H1S2	0.9600	C16—N4	1.356 (8)
C1S—H1S3	0.9600	C16—H16	0.9300
C2—C3	1.366 (13)	C17—C18	1.359 (11)
C2—H2	0.9300	C17—N5	1.363 (10)
C3—C4	1.372 (13)	C17—H17	0.9300
C3—H3	0.9300	C18—N4	1.357 (9)
C4—C5	1.356 (10)	C18—H18	0.9300
C4—H4	0.9300	C19—N5	1.452 (8)
C5—N1	1.365 (9)	C19—H19A	0.9600
C5—C6	1.485 (13)	C19—H19B	0.9600
C6—C7	1.345 (11)	C19—H19C	0.9600
C6—N2	1.372 (9)	N1—Pt	2.025 (6)
C7—C8	1.367 (13)	N1S—O1S	1.168 (9)
C7—H7	0.9300	N1S—O2S	1.192 (11)
C8—C9	1.374 (11)	N2—Pt	1.925 (5)
C8—H8	0.9300	N3—Pt	2.021 (6)
C9—C10	1.400 (10)	N4—Pt	2.013 (6)
C9—H9	0.9300	O1—Cl1	1.234 (16)
C10—N2	1.330 (9)	O2—Cl1	1.327 (11)
C10—C11	1.489 (10)	O3—Cl1	1.343 (12)
C11—C12	1.369 (11)	O4—Cl1	1.359 (14)
C11—N3	1.372 (9)	O5—Cl2	1.413 (7)
C12—C13	1.351 (12)	O6—Cl2	1.450 (8)
C12—H12	0.9300	O7—Cl2	1.415 (8)
C13—C14	1.366 (12)	O8—Cl2	1.393 (7)
C13—H13	0.9300

N1—C1—C2	119.5 (8)	N5—C16—N4	109.3 (6)
N1—C1—H1	120.2	N5—C16—H16	125.3
C2—C1—H1	120.2	N4—C16—H16	125.3
N1S—C1S—H1S1	109.5	C18—C17—N5	106.0 (7)
N1S—C1S—H1S2	109.5	C18—C17—H17	127.0
H1S1—C1S—H1S2	109.5	N5—C17—H17	127.0
N1S—C1S—H1S3	109.5	N4—C18—C17	108.8 (7)
H1S1—C1S—H1S3	109.5	N4—C18—H18	125.6
H1S2—C1S—H1S3	109.5	C17—C18—H18	125.6
C3—C2—C1	122.0 (9)	N5—C19—H19A	109.5
C3—C2—H2	119.0	N5—C19—H19B	109.5
C1—C2—H2	119.0	H19A—C19—H19B	109.5
C2—C3—C4	117.0 (8)	N5—C19—H19C	109.5
C2—C3—H3	121.5	H19A—C19—H19C	109.5
C4—C3—H3	121.5	H19B—C19—H19C	109.5
C5—C4—C3	121.5 (8)	C1—N1—C5	119.3 (6)
C5—C4—H4	119.3	C1—N1—Pt	127.3 (5)
C3—C4—H4	119.3	C5—N1—Pt	113.4 (5)
C4—C5—N1	120.8 (8)	O1S—N1S—O2S	123.1 (10)
C4—C5—C6	124.4 (7)	O1S—N1S—C1S	118.9 (10)
N1—C5—C6	114.8 (6)	O2S—N1S—C1S	117.9 (9)
C7—C6—N2	118.1 (8)	C10—N2—C6	122.9 (6)
C7—C6—C5	129.6 (7)	C10—N2—Pt	119.1 (5)
N2—C6—C5	112.3 (6)	C6—N2—Pt	117.9 (5)
C6—C7—C8	120.4 (8)	C15—N3—C11	117.9 (7)
C6—C7—H7	119.8	C15—N3—Pt	128.5 (5)
C8—C7—H7	119.8	C11—N3—Pt	113.6 (5)
C7—C8—C9	121.9 (8)	C16—N4—C18	106.5 (6)
C7—C8—H8	119.1	C16—N4—Pt	126.5 (4)
C9—C8—H8	119.1	C18—N4—Pt	127.0 (5)
C8—C9—C10	116.8 (8)	C16—N5—C17	109.4 (6)
C8—C9—H9	121.6	C16—N5—C19	125.4 (7)
C10—C9—H9	121.6	C17—N5—C19	125.1 (7)
N2—C10—C9	119.9 (7)	O1—Cl1—O2	118.1 (12)
N2—C10—C11	112.8 (6)	O1—Cl1—O3	108.6 (15)
C9—C10—C11	127.3 (7)	O2—Cl1—O3	112.9 (11)
C12—C11—N3	121.0 (7)	O1—Cl1—O4	106.3 (19)
C12—C11—C10	125.3 (7)	O2—Cl1—O4	103.3 (9)
N3—C11—C10	113.7 (6)	O3—Cl1—O4	106.7 (10)
C13—C12—C11	119.7 (8)	O8—Cl2—O5	112.5 (6)
C13—C12—H12	120.2	O8—Cl2—O7	113.6 (5)
C11—C12—H12	120.2	O5—Cl2—O7	112.7 (5)
C12—C13—C14	120.4 (8)	O8—Cl2—O6	104.8 (5)
C12—C13—H13	119.8	O5—Cl2—O6	105.8 (5)
C14—C13—H13	119.8	O7—Cl2—O6	106.6 (6)
C13—C14—C15	118.7 (8)	N2—Pt—N4	178.5 (2)
C13—C14—H14	120.6	N2—Pt—N3	80.7 (3)
C15—C14—H14	120.6	N4—Pt—N3	100.6 (2)
N3—C15—C14	122.3 (8)	N2—Pt—N1	81.5 (3)
N3—C15—H15	118.9	N4—Pt—N1	97.2 (2)
C14—C15—H15	118.9	N3—Pt—N1	162.2 (2)

N1—C1—C2—C3	−0.3 (14)	C7—C6—N2—Pt	−177.7 (5)
C1—C2—C3—C4	1.2 (14)	C5—C6—N2—Pt	0.3 (7)
C2—C3—C4—C5	−1.5 (13)	C14—C15—N3—C11	0.8 (11)
C3—C4—C5—N1	1.0 (12)	C14—C15—N3—Pt	−179.5 (6)
C3—C4—C5—C6	−179.5 (7)	C12—C11—N3—C15	−0.5 (10)
C4—C5—C6—C7	−2.5 (12)	C10—C11—N3—C15	−179.3 (6)
N1—C5—C6—C7	177.0 (7)	C12—C11—N3—Pt	179.8 (6)
C4—C5—C6—N2	179.8 (7)	C10—C11—N3—Pt	1.0 (7)
N1—C5—C6—N2	−0.6 (8)	N5—C16—N4—C18	0.1 (7)
N2—C6—C7—C8	0.4 (11)	N5—C16—N4—Pt	−177.2 (4)
C5—C6—C7—C8	−177.1 (7)	C17—C18—N4—C16	0.0 (8)
C6—C7—C8—C9	−0.9 (12)	C17—C18—N4—Pt	177.2 (5)
C7—C8—C9—C10	1.7 (11)	N4—C16—N5—C17	−0.1 (8)
C8—C9—C10—N2	−1.9 (10)	N4—C16—N5—C19	177.6 (7)
C8—C9—C10—C11	179.2 (7)	C18—C17—N5—C16	0.0 (9)
N2—C10—C11—C12	−177.8 (7)	C18—C17—N5—C19	−177.7 (7)
C9—C10—C11—C12	1.1 (12)	C10—N2—Pt—N3	2.5 (5)
N2—C10—C11—N3	0.9 (9)	C6—N2—Pt—N3	179.6 (5)
C9—C10—C11—N3	179.8 (6)	C10—N2—Pt—N1	−177.0 (5)
N3—C11—C12—C13	1.7 (12)	C6—N2—Pt—N1	0.0 (5)
C10—C11—C12—C13	−179.7 (7)	C16—N4—Pt—N3	−64.4 (6)
C11—C12—C13—C14	−3.2 (14)	C18—N4—Pt—N3	119.0 (6)
C12—C13—C14—C15	3.4 (14)	C16—N4—Pt—N1	114.9 (5)
C13—C14—C15—N3	−2.2 (13)	C18—N4—Pt—N1	−61.7 (6)
N5—C17—C18—N4	0.0 (8)	C15—N3—Pt—N2	178.5 (7)
C2—C1—N1—C5	−0.3 (11)	C11—N3—Pt—N2	−1.8 (4)
C2—C1—N1—Pt	179.4 (6)	C15—N3—Pt—N4	−2.2 (7)
C4—C5—N1—C1	0.0 (11)	C11—N3—Pt—N4	177.4 (5)
C6—C5—N1—C1	−179.6 (6)	C15—N3—Pt—N1	−179.9 (7)
C4—C5—N1—Pt	−179.8 (6)	C11—N3—Pt—N1	−0.2 (10)
C6—C5—N1—Pt	0.6 (7)	C1—N1—Pt—N2	179.9 (6)
C9—C10—N2—C6	1.5 (10)	C5—N1—Pt—N2	−0.4 (5)
C11—C10—N2—C6	−179.5 (6)	C1—N1—Pt—N4	0.6 (7)
C9—C10—N2—Pt	178.4 (5)	C5—N1—Pt—N4	−179.7 (5)
C11—C10—N2—Pt	−2.5 (8)	C1—N1—Pt—N3	178.3 (7)
C7—C6—N2—C10	−0.7 (10)	C5—N1—Pt—N3	−2.0 (10)
C5—C6—N2—C10	177.2 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O7ⁱ	0.93	2.51	3.21 (2)	132 (1)
C8—H8···O7ⁱⁱ	0.93	2.56	3.42 (2)	153 (1)
C9—H9···O6ⁱⁱⁱ	0.93	2.54	3.34 (1)	144 (1)

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y, −z+2; (iii) −x+1, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Pt(C₁₅H₁₁N₃)(C₄H₆N₂)](ClO₄)₂·CH₃NO₂
M_r	770.41
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	16.389 (4), 11.582 (5), 14.538 (5)
β (°)	110.147 (5)
V (Å³)	2590.7 (16)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.69
Crystal size (mm)	0.60 × 0.60 × 0.60

Data collection
Diffractometer	Oxford Diffraction Xcalibur2 CCD diffractometer
Absorption correction	Multi-scan (Blessing, 1995)
T_min, T_max	0.132, 0.132
No. of measured, independent and observed [I > 2σ(I)] reflections	17563, 5102, 3881
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.118, 0.98
No. of reflections	5102
No. of parameters	354
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.59, −2.64

Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O7ⁱ	0.93	2.51	3.21 (2)	132 (1)
C8—H8···O7ⁱⁱ	0.93	2.562	3.42 (2)	153 (1)
C9—H9···O6ⁱⁱⁱ	0.93	2.543	3.34 (1)	144 (1)

Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+1, −y, −z+2; (iii) −x+1, y−1/2, −z+3/2.

Acknowledgements

We thank the University of KwaZulu-Natal and the National Research Foundation for their financial support.

References

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