Hydrogen-bonded chains in three cis-dichloridoplatinum(II) complexes bearing piperidine and amine ligands

The crystal structures of cis-di­chlorido­(ethyl­amine-[kappa]N)(piperidine-[kappa]N)platinum(II), [PtCl₂(C₂H₇N)(C₅H₁₁N)], (I), cis-di­chlorido(3-meth­oxy­aniline-[kappa]N)­(piperidine-[kappa]N)plati­num(II), [PtCl₂(C₅H₁₁N)(C₇H₉NO)], (II), and cis-di­chlorido­(piperidine-[kappa]N)(quinoline-[kappa]N)platinum(II), [PtCl₂(C₅H₁₁N)(C₉H₇N)], (III), have been determined at 100 K in order to verify the influence of the nonpiperidine ligand on the geometry and crystal packing. The crystal packing is characterized by N-H...Cl hydrogen bonding, resulting in the formation of chains of mol­ecules connected in a head-to-tail fashion. Hydrogen-bonding inter­actions play a major role in the packing of (I), where the chains further aggregate into planes, but less so in the case of (II) and (III), where [pi]-[pi] stacking inter­actions are of greater importance.

S1. Introduction

Platinum complexes have been known for a long time and have important medical applications. Among them, Cisplatin (cis-[PtCl₂(NH₃)₂]) is one of the most effective anti­tumor agents used in chemotherapy to treat various types of human cancers (Klein & Hambley, 2009; Wong & Giandomenico, 1999). Recently, there has been an intense inter­est in developing platinum complexes bearing either piperidine (pip) or its derivatives as ligand, most of which exhibit promising anti­tumor activity (Ali et al., 2007; Da, 2001a,b; Mukhopadhyay et al., 2003; Rounaq Ali Khan et al., 2000a,b; Solin et al., 1982). However, crystal data of these complexes are very limited, e.g. the crystal structures of cis-[PtCl₂(pip)₂] (Rounaq Ali Khan et al., 2000a) [OK?], and trans-[PtCl₂(4-pic)(pip)] (4-pic is ????; Najajreh et al., 2005). Herein, we report the crystal structures and molecular arrangement of three compounds, namely cis-[PtCl₂(ethyl­amine)(pip)], (I), cis-[PtCl₂(m-anisidine)(pip)], (II), and cis-[PtCl₂(pip)(quinoline)], (III). They all contain the piperidine ligand and another amine. The latter in compound (I) is a primary amine with an aliphatic chain, while in compound (II) a larger aromatic ring is present. In compound (III), a heterocyclic aromatic amine (quinoline) without an amine H atom was studied for comparison with (I) and (II).

S2. Experimental

S2.1. Synthesis and crystallization

The title complexes were synthesized according to the methods described by Vu et al. (2002) and Da et al. (2005). K[PtCl₃(piperidine)] (0.425 g, 1 mmol), prepared according to the synthetic protocol of Da et al. (2001b), was dissolved in an aqueous ethanol solution (15 ml, 1:1 v/v) and then filtered to afford a saturated solution. To this solution, amine (1.5 mol) in an aqueous ethanol solution (5 ml, 1:1 v/v) was added gradually at 288–293 K for ethyl­amine, and at 298–303 K for m-anisidine (3-meth­oxy­aniline) and quinoline. The reaction mixture was stirred for 4–5 h. After cooling in an ice bath at 278 K for 30 min, the precipitated yellow substance was filtered off and washed with an aqueous ethanol solution (1:1 v/v). The products were first dried in air at room temperature for 1 h, and then in a vacuum at 323 K for 2 h. The yields of (I), (II) and (III) were 70, 60 and 75%, respectively. Single crystals suitable for X-ray diffraction analysis were obtained by recrystallization from ethanol–water (2.5:1 v/v) for (I) and (II), and from chloro­form–ethanol (1:3 v/v) for (III).

S2.2. Structure solution and refinement

All H atoms were placed in idealized positions and refined in riding mode with U_iso(H) values assigned as 1.2 times U_eq of the parent atoms (1.5 times for methyl groups), with C—H distances of 0.95 (aromatic), 0.98 (methyl) and 0.99 Å (methyl­ene) and N—H distances of 0.93 (NH) and 0.92 Å (NH₂).

S3. Results and discussion

Compounds (I)–(III) crystallize in three different space groups: Pbca, P1 and P2₁/c for (I), (II) and (III), respectively. The molecular structures are shown in Fig. 1, and selected bond lengths and angles are given in Table 2. The Pt^II atoms exhibit the usual square-planar coordination and are surrounded by two Cl atoms and two N atoms [one belonging to piperidine (pip) and the other to ethyl­amine in (I), m-anisidine in (II) or quinoline in (III)]. The structures show unambiguously the cis positions of the two Cl atoms. The angles between two adjacent coordinating atoms are close to the expected values of 90°. The Pt—Cl bond lengths vary from 2.3020 (8) to 2.3155 (12) Å and are in good agreement with the average Pt—Cl bond distance of 2.33 (4) Å for cis-platinum complexes present in the Cambridge Structural Database (CSD, Version 5.34; Allen, 2002). The Pt—N(piperidine) distances are between 2.057 (3) and 2.074 (3) Å, and agree well with the closely related compound [PtCl₂(pip)₂] (Rounaq Ali Khan et al., 2000a) [OK?]. All the piperidine rings adopt chair conformations, as expected based on the ¹H NMR results (Dinh & Da, 2003). Moreover, the piperidine ring in all three compounds are arranged perpendicular to the coordination plane of the Pt^II atom, thereby reducing the van der Waals repulsion [dihedral angles between best planes through the piperidine ring and the four atoms coordinating to Pt are 86.52 (13) and 86.13 (13)° in (I), 79.15 (14)° in (II) and 85.31 (19)° in (III). The ethyl­amine ligands in compound (I) exhibit different conformations: one shows an anti conformation [Pt1—N2—C6—C7 = 177.9 (2)°] and the other shows a gauche conformation [Pt2—N4—C13—C14 = -55.2 (3)°].

The crystal packing of (I) is dominated by hydrogen-bonding inter­actions of the N—H···Cl type (Table 3). The resulting corrugated layers parallel to the ab plane (Fig. 2a) are similar to those observed for cis-amminedi­chloro­ispropyl­amine­platinum(II) (Kirik et al., 2006). Between the layers only hydro­phobic inter­actions between piperidine rings and ethyl groups are observed. The molecules in these layers are arranged in a pseudo-anti­parallel β-sheet motif in which each strand is formed by a head-to-tail arrangement of molecules stabilized by hydrogen bonds between the Cl1/Cl2 and N3/N4 atoms, and betweenthe Cl3/Cl4 and N1/N2 atoms (green dotted lines in Fig. 2b; Table 3). Atoms N1 and N3 belong to the piperidine rings, and atoms N2 and N4 to the ethyl­amine ligands. The chains are linked to each other by hydrogen bonds between N2/N4 and Cl2/Cl4 (magenta dotted lines in Fig. 2b; Table 3). The unit cell contains eight voids of 32 ų each.

In the crystal packing of (II) chains of molecules are formed along the a axis by hydrogen bonding between the piperidine N2—H2A group and atom Cl2 (N2—H2A···Cl2ⁱ; Table 4 and green dotted lines in Fig. 3). The head-to-tail arrangement of two neighbouring chains is stabilized by hydrogen bonding between the m-anisidine N1—H1B group and atom Cl1 (N1—H1B···Cl1ⁱⁱ; Table 4 and red dotted lines in Fig. 3). Additionally, in the two other directions, hydro­phobic inter­actions are observed between aliphatic piperidine rings and π–π stacking of the benzene rings of the m-anisidine ligand [inter­planar distance = 3.373 (2) Å and centroid–centroid distance between benzene rings = 3.866 (2) Å; Fig. 3].

The crystal packing of (III) is much simpler than those of (I) and (II). Hydrogen-bonding contacts are limited compared to (I) and (II) due to the presence of the quinoline ligand having no amine H atom and the bulkier quinoline ring pushing molecules further away. As a result, each molecule contributes one donor (the amine H atom of piperidine) and one acceptor (Cl1) to the hydrogen-bonding network. However, a head-to-tail arrangement of molecules is still observed in this case and a chain of molecules along the b axis is formed by hydrogen bonding (N1—H1···Cl1ⁱ; Table 5 and Fig. 4). Two neighbouring chains are again anti­parallel, but this time the chains do not inter­acting by hydrogen bonding, but by π–π inter­actions between quinoline rings (Cg1···Cg2ⁱⁱ = 3.646 (3) Å; Cg1 and Cg2 are the centroids of the N2/C6–C9/C14 and C9–C14 rings, respectively; symmetry code: (ii) -x+2, -y+1, -z; Fig. 4).

The different nature of the nonpiperidine ligands characterizes the packing of (I), (II) and (III). For ethyl­amine in (I) with two amine H atoms and a small side chain, hydrogen bonds are dominant in the crystal packing. Replacing the aliphatic side chain with an aromatic side chain of m-anisidine in (II) decreases the number of hydrogen bonds and introduces π–π inter­actions between the aromatic rings in the crystal packing. Following this trend, compound (III), carrying a quinoline ligand, which has no amine H atom and a larger aromatic ring compared to that of (II), shows mainly π–π inter­actions. Although hydrogen bonds do not play a key role in the packing of (II) and (III), they are still responsible for the chain-building process.

Related literature

(type here to add)

For related literature, see: Ali et al. (2007); Allen (2002); Da (2001a,b); Da et al. (2005); Dinh & Da (2003); Dolomanov et al. (2009); Kirik et al. (2006); Klein & Hambley (2009); Mukhopadhyay et al. (2003); Najajreh et al. (2005); Rounaq Ali Khan et al. (2000a,b); Sheldrick (2008); Solin et al. (1982); Vu et al. (2002); Wong & Giandomenico (1999).

Computing details

For all compounds, data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures

	Fig. 1. Views of the asymmetric units in (a) (I), (b) (II) and (c) (III), showing the atom-labelling schemes. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. (a) The arrangement of layers in the crystal packing of (I), viewed along the c axis; (b) the hydrogen-bonding interactions between neighbouring chains in the layers of (I) (green dotted lines show H atoms bonds in a chain and magenta dotted lines show hydrogen bonds between chains). [Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x, -y+1/2, z-1/2; (iii) -x+1, y+1/2, -z+3/2.]
	Fig. 3. Hydrogen-bonding and π–π interactions in (II) (green dotted lines show H atoms bonds in a chain, red dotted lines show hydrogen bonds and π–π interactions between chains; Cg1 is the centroid of C1–C6 ring). [Symmetry codes: (i) x+1, y, z; (ii) -x+1, -y+1, z-1; (iii) -x, -y, -z+1.]
	Fig. 4. Hydrogen-bonding and π–π interactions in (III). [Symmetry codes: (i) -x+3/2, y-1/2, -z+1/2; (ii) -x+2, -y+1, -z.]

(I) cis-Dichlorido(ethylamine-κN)(piperidine-κN)platinum(II)

Crystal data

[PtCl2(C2H7N)(C5H11N)]	Dx = 2.216 Mg m^−3
Mr = 396.21	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 14625 reflections
a = 17.2910 (17) Å	θ = 3.4–29.1°
b = 12.5737 (5) Å	µ = 12.22 mm^−1
c = 21.8534 (5) Å	T = 100 K
V = 4751.2 (5) Å^3	Plate, yellow
Z = 16	0.3 × 0.1 × 0.05 mm
F(000) = 2976

Data collection

Agilent SuperNova (single source at offset, Eos detector) diffractometer	4847 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	4116 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.041
Detector resolution: 15.9631 pixels mm^-1	θmax = 26.4°, θmin = 2.7°
ω scans	h = −21→21
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −15→15
Tmin = 0.577, Tmax = 1.000	l = −27→27
46115 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.019	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.041	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0141P)^2 + 3.0137P] where P = (Fo^2 + 2Fc^2)/3
4847 reflections	(Δ/σ)max = 0.005
219 parameters	Δρmax = 0.92 e Å^−3
0 restraints	Δρmin = −0.72 e Å^−3

Special details

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

X-ray diffraction data were collected on an Agilent SuperNova diffractometer using mirror-monochromated Mo Kα radiation (λ = 0.71073 Å). Using OLEX2 (Dolomanov et al., 2009) the structures were solved by direct methods using SHELXS (Sheldrick, 2008) and refined by full-matrix least-squares methods based on F² using OLEX2 (Dolomanov et al., 2009). All non-hydrogen atoms were refined anisotropically.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.29677 (19)	0.2586 (3)	0.44488 (15)	0.0166 (8)
H1A	0.2670	0.2649	0.4834	0.020*
H1B	0.3285	0.1931	0.4473	0.020*
C2	0.2409 (2)	0.2498 (3)	0.39119 (16)	0.0225 (8)
H2A	0.2704	0.2362	0.3532	0.027*
H2B	0.2056	0.1889	0.3980	0.027*
C3	0.1937 (2)	0.3505 (3)	0.38370 (16)	0.0236 (9)
H3A	0.1591	0.3595	0.4194	0.028*
H3B	0.1612	0.3449	0.3466	0.028*
C4	0.2469 (2)	0.4464 (3)	0.37824 (16)	0.0242 (9)
H4A	0.2765	0.4417	0.3396	0.029*
H4B	0.2154	0.5122	0.3769	0.029*
C5	0.3028 (2)	0.4524 (3)	0.43185 (16)	0.0198 (8)
H5A	0.3385	0.5131	0.4257	0.024*
H5B	0.2734	0.4652	0.4700	0.024*
C6	0.5815 (2)	0.2868 (3)	0.45023 (16)	0.0258 (9)
H6A	0.5610	0.2134	0.4528	0.031*
H6B	0.6087	0.3026	0.4890	0.031*
C7	0.6381 (2)	0.2938 (3)	0.39770 (17)	0.0285 (9)
H7A	0.6121	0.2738	0.3596	0.043*
H7B	0.6815	0.2454	0.4052	0.043*
H7C	0.6575	0.3668	0.3943	0.043*
N1	0.34858 (15)	0.3526 (2)	0.43825 (12)	0.0133 (6)
H1	0.3755	0.3436	0.4018	0.016*
N2	0.51662 (15)	0.3616 (2)	0.44271 (12)	0.0143 (6)
H2C	0.4943	0.3481	0.4053	0.017*
H2D	0.5371	0.4291	0.4408	0.017*
Cl1	0.33257 (5)	0.37675 (7)	0.57835 (4)	0.01687 (18)
Cl2	0.52002 (5)	0.37554 (7)	0.58450 (4)	0.01634 (18)
Pt1	0.430069 (7)	0.363713 (10)	0.506495 (5)	0.01013 (4)
C8	0.34304 (19)	0.1193 (3)	0.66174 (15)	0.0181 (8)
H8A	0.2985	0.1649	0.6728	0.022*
H8B	0.3445	0.0589	0.6908	0.022*
C9	0.3317 (2)	0.0769 (3)	0.59713 (16)	0.0205 (8)
H9A	0.3244	0.1372	0.5685	0.025*
H9B	0.2845	0.0323	0.5957	0.025*
C10	0.4012 (2)	0.0111 (3)	0.57703 (16)	0.0222 (8)
H10A	0.4049	−0.0537	0.6026	0.027*
H10B	0.3945	−0.0111	0.5339	0.027*
C11	0.4749 (2)	0.0762 (3)	0.58336 (15)	0.0192 (8)
H11A	0.5200	0.0313	0.5728	0.023*
H11B	0.4734	0.1366	0.5544	0.023*
C12	0.48393 (19)	0.1180 (3)	0.64813 (15)	0.0176 (8)
H12A	0.4905	0.0573	0.6765	0.021*
H12B	0.5311	0.1624	0.6505	0.021*
C13	0.3470 (2)	0.4609 (3)	0.73897 (16)	0.0260 (9)
H13A	0.3434	0.5287	0.7161	0.031*
H13B	0.3556	0.4782	0.7826	0.031*
C14	0.2713 (2)	0.4009 (3)	0.73257 (17)	0.0318 (10)
H14A	0.2752	0.3326	0.7539	0.048*
H14B	0.2605	0.3884	0.6891	0.048*
H14C	0.2293	0.4430	0.7505	0.048*
N3	0.41593 (14)	0.1823 (2)	0.66766 (12)	0.0124 (6)
H3	0.4120	0.2382	0.6399	0.015*
N4	0.41404 (16)	0.3988 (2)	0.71569 (12)	0.0172 (6)
H4C	0.4583	0.4377	0.7226	0.021*
H4D	0.4087	0.3914	0.6740	0.021*
Cl3	0.44578 (5)	0.33064 (7)	0.84693 (4)	0.01915 (19)
Cl4	0.44297 (5)	0.08527 (7)	0.79815 (4)	0.01935 (19)
Pt2	0.429206 (7)	0.250441 (10)	0.752744 (5)	0.01126 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0172 (19)	0.0157 (19)	0.0169 (18)	−0.0011 (15)	−0.0015 (15)	−0.0009 (14)
C2	0.018 (2)	0.023 (2)	0.026 (2)	−0.0051 (16)	−0.0043 (16)	−0.0045 (16)
C3	0.0158 (19)	0.034 (2)	0.0208 (19)	−0.0004 (17)	−0.0046 (15)	0.0037 (17)
C4	0.021 (2)	0.026 (2)	0.025 (2)	−0.0021 (17)	−0.0107 (17)	0.0106 (17)
C5	0.0194 (19)	0.0165 (19)	0.0235 (19)	0.0010 (16)	−0.0061 (16)	0.0061 (16)
C6	0.024 (2)	0.035 (2)	0.0185 (19)	0.0158 (18)	−0.0031 (16)	0.0002 (17)
C7	0.017 (2)	0.031 (2)	0.038 (2)	0.0032 (18)	0.0026 (18)	−0.0068 (19)
N1	0.0090 (14)	0.0170 (16)	0.0137 (14)	0.0009 (12)	−0.0015 (11)	0.0022 (12)
N2	0.0124 (14)	0.0164 (16)	0.0143 (14)	−0.0021 (12)	−0.0002 (12)	0.0003 (12)
Cl1	0.0173 (4)	0.0213 (5)	0.0120 (4)	0.0031 (4)	0.0020 (3)	−0.0003 (3)
Cl2	0.0165 (4)	0.0206 (5)	0.0120 (4)	−0.0024 (4)	−0.0041 (3)	0.0006 (3)
Pt1	0.01166 (7)	0.01011 (7)	0.00862 (7)	0.00033 (5)	−0.00112 (5)	0.00066 (5)
C8	0.0149 (18)	0.016 (2)	0.0229 (19)	−0.0032 (15)	0.0005 (15)	0.0004 (15)
C9	0.0211 (19)	0.019 (2)	0.022 (2)	−0.0031 (16)	−0.0046 (16)	−0.0041 (16)
C10	0.033 (2)	0.0152 (19)	0.0185 (19)	−0.0004 (17)	−0.0039 (16)	−0.0029 (15)
C11	0.024 (2)	0.0165 (19)	0.0168 (18)	0.0038 (16)	0.0028 (16)	−0.0014 (15)
C12	0.0133 (17)	0.022 (2)	0.0178 (18)	0.0014 (15)	0.0032 (15)	−0.0007 (15)
C13	0.043 (3)	0.021 (2)	0.0140 (18)	0.0142 (19)	0.0028 (17)	0.0020 (16)
C14	0.037 (2)	0.040 (3)	0.018 (2)	0.018 (2)	0.0031 (18)	0.0072 (18)
N3	0.0122 (14)	0.0138 (15)	0.0111 (14)	−0.0010 (12)	−0.0009 (11)	0.0010 (11)
N4	0.0243 (17)	0.0165 (16)	0.0109 (14)	−0.0013 (13)	0.0016 (12)	0.0021 (12)
Cl3	0.0287 (5)	0.0178 (4)	0.0109 (4)	−0.0011 (4)	−0.0024 (4)	−0.0007 (3)
Cl4	0.0296 (5)	0.0149 (4)	0.0136 (4)	0.0055 (4)	−0.0001 (4)	0.0034 (3)
Pt2	0.01303 (8)	0.01170 (7)	0.00906 (7)	0.00013 (6)	0.00032 (5)	0.00102 (5)

Geometric parameters (Å, º)

C1—H1A	0.9900	C8—H8A	0.9900
C1—H1B	0.9900	C8—H8B	0.9900
C1—C2	1.524 (4)	C8—C9	1.522 (5)
C1—N1	1.490 (4)	C8—N3	1.494 (4)
C2—H2A	0.9900	C9—H9A	0.9900
C2—H2B	0.9900	C9—H9B	0.9900
C2—C3	1.515 (5)	C9—C10	1.523 (5)
C3—H3A	0.9900	C10—H10A	0.9900
C3—H3B	0.9900	C10—H10B	0.9900
C3—C4	1.521 (5)	C10—C11	1.521 (5)
C4—H4A	0.9900	C11—H11A	0.9900
C4—H4B	0.9900	C11—H11B	0.9900
C4—C5	1.521 (4)	C11—C12	1.518 (4)
C5—H5A	0.9900	C12—H12A	0.9900
C5—H5B	0.9900	C12—H12B	0.9900
C5—N1	1.491 (4)	C12—N3	1.489 (4)
C6—H6A	0.9900	C13—H13A	0.9900
C6—H6B	0.9900	C13—H13B	0.9900
C6—C7	1.512 (5)	C13—C14	1.517 (5)
C6—N2	1.473 (4)	C13—N4	1.488 (4)
C7—H7A	0.9800	C14—H14A	0.9800
C7—H7B	0.9800	C14—H14B	0.9800
C7—H7C	0.9800	C14—H14C	0.9800
N1—H1	0.9300	N3—H3	0.9300
N1—Pt1	2.057 (3)	N3—Pt2	2.060 (3)
N2—H2C	0.9200	N4—H4C	0.9200
N2—H2D	0.9200	N4—H4D	0.9200
N2—Pt1	2.045 (3)	N4—Pt2	2.050 (3)
Cl1—Pt1	2.3097 (8)	Cl3—Pt2	2.3099 (8)
Cl2—Pt1	2.3124 (8)	Cl4—Pt2	2.3140 (8)
H1A—C1—H1B	108.0	H8A—C8—H8B	107.9
C2—C1—H1A	109.4	C9—C8—H8A	109.2
C2—C1—H1B	109.4	C9—C8—H8B	109.2
N1—C1—H1A	109.4	N3—C8—H8A	109.2
N1—C1—H1B	109.4	N3—C8—H8B	109.2
N1—C1—C2	111.3 (3)	N3—C8—C9	112.0 (3)
C1—C2—H2A	109.4	C8—C9—H9A	109.5
C1—C2—H2B	109.4	C8—C9—H9B	109.5
H2A—C2—H2B	108.0	C8—C9—C10	110.9 (3)
C3—C2—C1	111.4 (3)	H9A—C9—H9B	108.1
C3—C2—H2A	109.4	C10—C9—H9A	109.5
C3—C2—H2B	109.4	C10—C9—H9B	109.5
C2—C3—H3A	109.6	C9—C10—H10A	109.6
C2—C3—H3B	109.6	C9—C10—H10B	109.6
C2—C3—C4	110.2 (3)	H10A—C10—H10B	108.2
H3A—C3—H3B	108.1	C11—C10—C9	110.1 (3)
C4—C3—H3A	109.6	C11—C10—H10A	109.6
C4—C3—H3B	109.6	C11—C10—H10B	109.6
C3—C4—H4A	109.4	C10—C11—H11A	109.5
C3—C4—H4B	109.4	C10—C11—H11B	109.5
H4A—C4—H4B	108.0	H11A—C11—H11B	108.0
C5—C4—C3	111.3 (3)	C12—C11—C10	110.9 (3)
C5—C4—H4A	109.4	C12—C11—H11A	109.5
C5—C4—H4B	109.4	C12—C11—H11B	109.5
C4—C5—H5A	109.3	C11—C12—H12A	109.2
C4—C5—H5B	109.3	C11—C12—H12B	109.2
H5A—C5—H5B	108.0	H12A—C12—H12B	107.9
N1—C5—C4	111.6 (3)	N3—C12—C11	112.0 (3)
N1—C5—H5A	109.3	N3—C12—H12A	109.2
N1—C5—H5B	109.3	N3—C12—H12B	109.2
H6A—C6—H6B	107.9	H13A—C13—H13B	107.9
C7—C6—H6A	109.3	C14—C13—H13A	109.1
C7—C6—H6B	109.3	C14—C13—H13B	109.1
N2—C6—H6A	109.3	N4—C13—H13A	109.1
N2—C6—H6B	109.3	N4—C13—H13B	109.1
N2—C6—C7	111.8 (3)	N4—C13—C14	112.3 (3)
C6—C7—H7A	109.5	C13—C14—H14A	109.5
C6—C7—H7B	109.5	C13—C14—H14B	109.5
C6—C7—H7C	109.5	C13—C14—H14C	109.5
H7A—C7—H7B	109.5	H14A—C14—H14B	109.5
H7A—C7—H7C	109.5	H14A—C14—H14C	109.5
H7B—C7—H7C	109.5	H14B—C14—H14C	109.5
C1—N1—C5	111.0 (2)	C8—N3—H3	106.4
C1—N1—H1	106.7	C8—N3—Pt2	113.11 (19)
C1—N1—Pt1	113.30 (19)	C12—N3—C8	110.7 (3)
C5—N1—H1	106.7	C12—N3—H3	106.4
C5—N1—Pt1	112.0 (2)	C12—N3—Pt2	113.35 (19)
Pt1—N1—H1	106.7	Pt2—N3—H3	106.4
C6—N2—H2C	107.5	C13—N4—H4C	108.2
C6—N2—H2D	107.5	C13—N4—H4D	108.2
C6—N2—Pt1	119.3 (2)	C13—N4—Pt2	116.2 (2)
H2C—N2—H2D	107.0	H4C—N4—H4D	107.4
Pt1—N2—H2C	107.5	Pt2—N4—H4C	108.2
Pt1—N2—H2D	107.5	Pt2—N4—H4D	108.2
N1—Pt1—Cl1	89.88 (8)	N3—Pt2—Cl3	178.47 (8)
N1—Pt1—Cl2	178.98 (8)	N3—Pt2—Cl4	91.44 (8)
N2—Pt1—N1	90.36 (11)	N4—Pt2—N3	90.44 (11)
N2—Pt1—Cl1	176.67 (8)	N4—Pt2—Cl3	88.32 (8)
N2—Pt1—Cl2	90.64 (8)	N4—Pt2—Cl4	177.49 (8)
Cl1—Pt1—Cl2	89.15 (3)	Cl3—Pt2—Cl4	89.82 (3)
C1—C2—C3—C4	54.6 (4)	C8—C9—C10—C11	−55.0 (4)
C1—N1—Pt1—N2	122.5 (2)	C8—N3—Pt2—N4	−111.5 (2)
C1—N1—Pt1—Cl1	−60.8 (2)	C8—N3—Pt2—Cl4	66.8 (2)
C2—C1—N1—C5	56.7 (4)	C9—C8—N3—C12	−55.9 (4)
C2—C1—N1—Pt1	−176.4 (2)	C9—C8—N3—Pt2	175.7 (2)
C2—C3—C4—C5	−54.3 (4)	C9—C10—C11—C12	55.4 (4)
C3—C4—C5—N1	55.7 (4)	C10—C11—C12—N3	−56.5 (4)
C4—C5—N1—C1	−56.6 (4)	C11—C12—N3—C8	56.1 (4)
C4—C5—N1—Pt1	175.7 (2)	C11—C12—N3—Pt2	−175.5 (2)
C5—N1—Pt1—N2	−111.0 (2)	C12—N3—Pt2—N4	121.4 (2)
C5—N1—Pt1—Cl1	65.6 (2)	C12—N3—Pt2—Cl4	−60.2 (2)
C6—N2—Pt1—N1	−129.6 (3)	C13—N4—Pt2—N3	119.2 (2)
C6—N2—Pt1—Cl2	50.2 (2)	C13—N4—Pt2—Cl3	−61.8 (2)
C7—C6—N2—Pt1	177.9 (2)	C14—C13—N4—Pt2	−55.2 (3)
N1—C1—C2—C3	−56.2 (4)	N3—C8—C9—C10	55.9 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl3^i	0.93	2.78	3.481 (3)	133
N1—H1···Cl4^i	0.93	2.70	3.556 (3)	153
N2—H2C···Cl3^i	0.92	2.72	3.424 (3)	134
N2—H2C···Cl4^i	0.92	2.64	3.471 (3)	151
N2—H2D···Cl2^ii	0.92	2.70	3.417 (3)	135
N3—H3···Cl1	0.93	2.59	3.445 (3)	152
N3—H3···Cl2	0.93	2.82	3.528 (3)	134
N4—H4C···Cl4^iii	0.92	2.56	3.421 (3)	155
N4—H4D···Cl1	0.92	2.48	3.327 (3)	154
N4—H4D···Cl2	0.92	2.75	3.415 (3)	130

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

(II) cis-Dichlorido(3-methoxyaniline-κN)(piperidine-κN)platinum(II)

Crystal data

[PtCl2(C5H11N)(C7H9NO)]	Z = 2
Mr = 474.29	F(000) = 452
Triclinic, P1	Dx = 2.162 Mg m^−3
a = 6.3800 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.9376 (9) Å	Cell parameters from 3469 reflections
c = 12.7899 (8) Å	θ = 3.3–29.0°
α = 108.733 (7)°	µ = 9.99 mm^−1
β = 91.463 (5)°	T = 100 K
γ = 106.893 (7)°	Block, yellow
V = 728.46 (9) Å^3	0.35 × 0.15 × 0.1 mm

Data collection

Agilent SuperNova (single source at offset, Eos detector) diffractometer	2911 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2762 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.027
Detector resolution: 15.9631 pixels mm^-1	θmax = 26.4°, θmin = 3.3°
ω scans	h = −7→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −11→12
Tmin = 0.493, Tmax = 1.000	l = −15→15
5750 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.019	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.038	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0085P)^2] where P = (Fo^2 + 2Fc^2)/3
2911 reflections	(Δ/σ)max = 0.005
164 parameters	Δρmax = 1.07 e Å^−3
0 restraints	Δρmin = −1.08 e Å^−3

Special details

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

X-ray diffraction data were collected on an Agilent SuperNova diffractometer using mirror-monochromated Mo Kα radiation (λ = 0.71073 Å). Using OLEX2 (Dolomanov et al., 2009) the structures were solved by direct methods using SHELXS (Sheldrick, 2008) and refined by full-matrix least-squares methods based on F² using OLEX2 (Dolomanov et al., 2009). All non-hydrogen atoms were refined anisotropically.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.1098 (6)	0.1280 (4)	0.3890 (3)	0.0108 (7)
C2	0.2058 (6)	0.0317 (4)	0.4135 (3)	0.0143 (8)
H2	0.3426	0.0699	0.4606	0.017*
C3	0.1005 (6)	−0.1205 (4)	0.3685 (3)	0.0161 (8)
H3	0.1653	−0.1872	0.3853	0.019*
C4	−0.0980 (6)	−0.1775 (4)	0.2993 (3)	0.0168 (8)
H4	−0.1684	−0.2827	0.2684	0.020*
C5	−0.1949 (6)	−0.0789 (4)	0.2751 (3)	0.0123 (8)
C6	−0.0902 (6)	0.0746 (4)	0.3195 (3)	0.0120 (7)
H6	−0.1536	0.1420	0.3028	0.014*
C7	−0.4896 (6)	−0.0485 (4)	0.1755 (3)	0.0205 (9)
H7A	−0.6284	−0.1082	0.1261	0.031*
H7B	−0.3872	0.0067	0.1365	0.031*
H7C	−0.5191	0.0225	0.2423	0.031*
C8	0.2589 (6)	0.2151 (4)	0.1233 (3)	0.0134 (8)
H8A	0.1962	0.1245	0.1434	0.016*
H8B	0.4028	0.2128	0.0969	0.016*
C9	0.1038 (6)	0.2120 (4)	0.0299 (3)	0.0158 (8)
H9A	−0.0451	0.2023	0.0532	0.019*
H9B	0.0917	0.1235	−0.0366	0.019*
C10	0.1847 (6)	0.3531 (4)	0.0000 (3)	0.0163 (8)
H10A	0.0746	0.3510	−0.0570	0.020*
H10B	0.3252	0.3569	−0.0320	0.020*
C11	0.2204 (6)	0.4918 (4)	0.1030 (3)	0.0157 (8)
H11A	0.2841	0.5826	0.0833	0.019*
H11B	0.0762	0.4941	0.1290	0.019*
C12	0.3747 (6)	0.4934 (4)	0.1967 (3)	0.0139 (8)
H12A	0.5244	0.5046	0.1741	0.017*
H12B	0.3851	0.5807	0.2638	0.017*
N1	0.2228 (4)	0.2887 (3)	0.4335 (2)	0.0104 (6)
H1A	0.2675	0.3169	0.5085	0.013*
H1B	0.1261	0.3385	0.4249	0.013*
N2	0.2950 (4)	0.3517 (3)	0.2247 (2)	0.0097 (6)
H2A	0.1574	0.3477	0.2484	0.012*
O1	−0.3933 (4)	−0.1455 (3)	0.2071 (2)	0.0186 (6)
Cl1	0.71152 (14)	0.34972 (10)	0.50180 (7)	0.01352 (18)
Cl2	0.80064 (14)	0.40292 (10)	0.26551 (7)	0.01604 (19)
Pt1	0.49406 (2)	0.349543 (15)	0.354443 (10)	0.00847 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0143 (18)	0.0085 (19)	0.0086 (16)	0.0024 (15)	0.0068 (14)	0.0022 (14)
C2	0.0137 (19)	0.017 (2)	0.0158 (18)	0.0063 (17)	0.0030 (15)	0.0088 (17)
C3	0.022 (2)	0.016 (2)	0.0177 (19)	0.0107 (18)	0.0080 (16)	0.0109 (17)
C4	0.022 (2)	0.011 (2)	0.0177 (19)	0.0061 (17)	0.0073 (17)	0.0052 (16)
C5	0.0107 (18)	0.012 (2)	0.0136 (18)	0.0038 (16)	0.0051 (15)	0.0040 (16)
C6	0.0158 (19)	0.0110 (19)	0.0111 (17)	0.0065 (16)	0.0034 (15)	0.0042 (15)
C7	0.018 (2)	0.020 (2)	0.020 (2)	0.0061 (18)	−0.0034 (16)	0.0021 (17)
C8	0.0144 (19)	0.0094 (19)	0.0129 (17)	0.0020 (16)	−0.0008 (15)	0.0010 (15)
C9	0.0155 (19)	0.015 (2)	0.0149 (18)	0.0023 (17)	−0.0013 (15)	0.0051 (16)
C10	0.0165 (19)	0.021 (2)	0.0146 (18)	0.0081 (17)	0.0021 (16)	0.0086 (17)
C11	0.0149 (19)	0.018 (2)	0.0192 (19)	0.0061 (17)	0.0075 (16)	0.0124 (17)
C12	0.0146 (19)	0.012 (2)	0.0166 (18)	0.0051 (16)	0.0035 (15)	0.0054 (16)
N1	0.0112 (15)	0.0113 (16)	0.0081 (14)	0.0040 (13)	0.0016 (12)	0.0020 (13)
N2	0.0070 (14)	0.0108 (16)	0.0133 (15)	0.0042 (13)	0.0037 (12)	0.0052 (13)
O1	0.0163 (14)	0.0114 (14)	0.0239 (14)	0.0036 (12)	−0.0038 (11)	0.0018 (12)
Cl1	0.0139 (4)	0.0135 (5)	0.0125 (4)	0.0063 (4)	−0.0016 (3)	0.0020 (4)
Cl2	0.0100 (4)	0.0201 (5)	0.0233 (5)	0.0065 (4)	0.0069 (4)	0.0124 (4)
Pt1	0.00807 (8)	0.00719 (8)	0.00964 (7)	0.00287 (6)	0.00125 (5)	0.00180 (6)

Geometric parameters (Å, º)

C1—C2	1.383 (4)	C9—H9A	0.9900
C1—C6	1.395 (5)	C9—H9B	0.9900
C1—N1	1.456 (4)	C9—C10	1.521 (5)
C2—H2	0.9500	C10—H10A	0.9900
C2—C3	1.379 (5)	C10—H10B	0.9900
C3—H3	0.9500	C10—C11	1.525 (5)
C3—C4	1.383 (5)	C11—H11A	0.9900
C4—H4	0.9500	C11—H11B	0.9900
C4—C5	1.406 (5)	C11—C12	1.525 (5)
C5—C6	1.389 (5)	C12—H12A	0.9900
C5—O1	1.373 (4)	C12—H12B	0.9900
C6—H6	0.9500	C12—N2	1.512 (4)
C7—H7A	0.9800	N1—H1A	0.9200
C7—H7B	0.9800	N1—H1B	0.9200
C7—H7C	0.9800	N1—Pt1	2.063 (3)
C7—O1	1.432 (4)	N2—H2A	0.9300
C8—H8A	0.9900	N2—Pt1	2.074 (3)
C8—H8B	0.9900	Cl1—Pt1	2.3109 (8)
C8—C9	1.518 (4)	Cl2—Pt1	2.3020 (8)
C8—N2	1.500 (4)
C2—C1—C6	121.5 (3)	C9—C10—H10B	109.6
C2—C1—N1	119.5 (3)	C9—C10—C11	110.4 (3)
C6—C1—N1	118.9 (3)	H10A—C10—H10B	108.1
C1—C2—H2	120.4	C11—C10—H10A	109.6
C3—C2—C1	119.1 (3)	C11—C10—H10B	109.6
C3—C2—H2	120.4	C10—C11—H11A	109.3
C2—C3—H3	119.5	C10—C11—H11B	109.3
C2—C3—C4	121.0 (3)	H11A—C11—H11B	108.0
C4—C3—H3	119.5	C12—C11—C10	111.5 (3)
C3—C4—H4	120.2	C12—C11—H11A	109.3
C3—C4—C5	119.6 (4)	C12—C11—H11B	109.3
C5—C4—H4	120.2	C11—C12—H12A	109.2
C6—C5—C4	120.0 (3)	C11—C12—H12B	109.2
O1—C5—C4	115.5 (3)	H12A—C12—H12B	107.9
O1—C5—C6	124.5 (3)	N2—C12—C11	111.9 (3)
C1—C6—H6	120.6	N2—C12—H12A	109.2
C5—C6—C1	118.8 (3)	N2—C12—H12B	109.2
C5—C6—H6	120.6	C1—N1—H1A	109.3
H7A—C7—H7B	109.5	C1—N1—H1B	109.3
H7A—C7—H7C	109.5	C1—N1—Pt1	111.7 (2)
H7B—C7—H7C	109.5	H1A—N1—H1B	107.9
O1—C7—H7A	109.5	Pt1—N1—H1A	109.3
O1—C7—H7B	109.5	Pt1—N1—H1B	109.3
O1—C7—H7C	109.5	C8—N2—C12	111.3 (3)
H8A—C8—H8B	107.9	C8—N2—H2A	106.6
C9—C8—H8A	109.2	C8—N2—Pt1	111.67 (19)
C9—C8—H8B	109.2	C12—N2—H2A	106.6
N2—C8—H8A	109.2	C12—N2—Pt1	113.7 (2)
N2—C8—H8B	109.2	Pt1—N2—H2A	106.6
N2—C8—C9	112.0 (3)	C5—O1—C7	116.7 (3)
C8—C9—H9A	109.3	N1—Pt1—N2	91.00 (11)
C8—C9—H9B	109.3	N1—Pt1—Cl1	88.07 (8)
C8—C9—C10	111.7 (3)	N1—Pt1—Cl2	176.25 (8)
H9A—C9—H9B	107.9	N2—Pt1—Cl1	178.74 (8)
C10—C9—H9A	109.3	N2—Pt1—Cl2	90.78 (8)
C10—C9—H9B	109.3	Cl2—Pt1—Cl1	90.19 (3)
C9—C10—H10A	109.6
C1—C2—C3—C4	0.3 (5)	C8—N2—Pt1—N1	−103.2 (2)
C1—N1—Pt1—N2	82.6 (2)	C8—N2—Pt1—Cl2	73.5 (2)
C1—N1—Pt1—Cl1	−98.3 (2)	C9—C8—N2—C12	−54.7 (4)
C2—C1—C6—C5	0.6 (5)	C9—C8—N2—Pt1	177.1 (2)
C2—C1—N1—Pt1	72.6 (3)	C9—C10—C11—C12	54.6 (4)
C2—C3—C4—C5	−0.5 (5)	C10—C11—C12—N2	−54.7 (4)
C3—C4—C5—C6	0.7 (5)	C11—C12—N2—C8	54.3 (4)
C3—C4—C5—O1	−179.1 (3)	C11—C12—N2—Pt1	−178.5 (2)
C4—C5—C6—C1	−0.8 (5)	C12—N2—Pt1—N1	129.8 (2)
C4—C5—O1—C7	−176.4 (3)	C12—N2—Pt1—Cl2	−53.5 (2)
C6—C1—C2—C3	−0.4 (5)	N1—C1—C2—C3	−178.3 (3)
C6—C1—N1—Pt1	−105.3 (3)	N1—C1—C6—C5	178.5 (3)
C6—C5—O1—C7	3.8 (5)	N2—C8—C9—C10	55.6 (4)
C8—C9—C10—C11	−55.0 (4)	O1—C5—C6—C1	179.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Cl1^i	0.92	2.79	3.312 (3)	117
N2—H2A···Cl2^ii	0.93	2.49	3.365 (3)	157

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

(III) cis-dichlorido(piperidine-κN)(quinoline-κN)platinum(II)

Crystal data

[PtCl2(C5H11N)(C9H7N)]	F(000) = 912
Mr = 480.29	Dx = 2.128 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.8920 (19) Å	Cell parameters from 12819 reflections
b = 11.3011 (8) Å	θ = 3.3–30.0°
c = 13.199 (3) Å	µ = 9.70 mm^−1
β = 112.68 (2)°	T = 100 K
V = 1499.0 (4) Å^3	Block, yellow
Z = 4	0.35 × 0.35 × 0.2 mm

Data collection

Agilent SuperNova (single source at offset, Eos detector) diffractometer	3072 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2779 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.076
Detector resolution: 15.9631 pixels mm^-1	θmax = 26.4°, θmin = 2.8°
ω scans	h = −13→13
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	k = −14→14
Tmin = 0.304, Tmax = 1.000	l = −16→16
30516 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.061	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.0231P)^2 + 6.243P] where P = (Fo^2 + 2Fc^2)/3
3072 reflections	(Δ/σ)max = 0.001
172 parameters	Δρmax = 2.14 e Å^−3
0 restraints	Δρmin = −2.09 e Å^−3

Special details

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

X-ray diffraction data were collected on an Agilent SuperNova diffractometer using mirror-monochromated Mo Kα radiation (λ = 0.71073 Å). Using OLEX2 (Dolomanov et al., 2009) the structures were solved by direct methods using SHELXS (Sheldrick, 2008) and refined by full-matrix least-squares methods based on F² using OLEX2 (Dolomanov et al., 2009). All non-hydrogen atoms were refined anisotropically.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.5797 (4)	0.5091 (4)	0.2663 (4)	0.0186 (10)
H1A	0.5345	0.5561	0.1987	0.022*
H1B	0.5227	0.4401	0.2640	0.022*
C2	0.5947 (5)	0.5842 (4)	0.3650 (4)	0.0190 (10)
H2A	0.5055	0.6064	0.3620	0.023*
H2B	0.6428	0.6579	0.3628	0.023*
C3	0.6700 (5)	0.5195 (5)	0.4719 (4)	0.0227 (10)
H3A	0.6840	0.5730	0.5347	0.027*
H3B	0.6174	0.4507	0.4786	0.027*
C4	0.8030 (4)	0.4780 (4)	0.4739 (4)	0.0196 (10)
H4A	0.8486	0.4311	0.5415	0.024*
H4B	0.8590	0.5477	0.4764	0.024*
C5	0.7890 (5)	0.4026 (5)	0.3741 (4)	0.0178 (9)
H5A	0.8786	0.3825	0.3767	0.021*
H5B	0.7430	0.3278	0.3768	0.021*
C6	0.6942 (5)	0.5850 (4)	0.0008 (4)	0.0160 (9)
H6	0.6001	0.5786	−0.0246	0.019*
C7	0.7480 (5)	0.6747 (4)	−0.0421 (4)	0.0226 (10)
H7	0.6917	0.7266	−0.0969	0.027*
C8	0.8842 (5)	0.6866 (4)	−0.0034 (5)	0.0256 (11)
H8	0.9227	0.7470	−0.0317	0.031*
C9	0.9654 (5)	0.6099 (4)	0.0772 (4)	0.0212 (11)
C10	1.1065 (5)	0.6171 (5)	0.1218 (5)	0.0286 (13)
H10	1.1488	0.6779	0.0974	0.034*
C11	1.1816 (5)	0.5394 (6)	0.1983 (5)	0.0354 (15)
H11	1.2758	0.5464	0.2277	0.043*
C12	1.1207 (5)	0.4480 (5)	0.2346 (4)	0.0284 (12)
H12	1.1748	0.3936	0.2881	0.034*
C13	0.9851 (4)	0.4358 (5)	0.1944 (4)	0.0205 (10)
H13	0.9454	0.3733	0.2191	0.025*
C14	0.9054 (4)	0.5175 (4)	0.1159 (4)	0.0169 (9)
Cl1	0.58542 (10)	0.21935 (10)	0.18339 (9)	0.0174 (2)
Cl2	0.62666 (10)	0.28692 (10)	−0.04494 (9)	0.0166 (2)
N1	0.7119 (3)	0.4659 (3)	0.2681 (3)	0.0128 (7)
H1	0.7608	0.5329	0.2668	0.015*
N2	0.7684 (4)	0.5081 (3)	0.0756 (3)	0.0150 (8)
Pt1	0.679720 (15)	0.374755 (15)	0.125207 (13)	0.01080 (7)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.015 (2)	0.023 (3)	0.017 (2)	0.0043 (19)	0.0053 (18)	0.001 (2)
C2	0.019 (2)	0.009 (2)	0.025 (3)	−0.0012 (18)	0.0049 (19)	−0.007 (2)
C3	0.028 (3)	0.021 (3)	0.018 (2)	−0.003 (2)	0.009 (2)	−0.003 (2)
C4	0.020 (2)	0.018 (2)	0.014 (2)	−0.0017 (19)	−0.0015 (18)	−0.0008 (19)
C5	0.020 (2)	0.020 (2)	0.011 (2)	−0.001 (2)	0.0039 (17)	0.0043 (19)
C6	0.021 (2)	0.015 (2)	0.015 (2)	0.0020 (19)	0.0095 (18)	−0.0008 (19)
C7	0.034 (3)	0.012 (2)	0.029 (3)	0.001 (2)	0.020 (2)	0.001 (2)
C8	0.041 (3)	0.013 (2)	0.035 (3)	−0.008 (2)	0.028 (2)	−0.009 (2)
C9	0.023 (2)	0.024 (3)	0.024 (3)	−0.007 (2)	0.016 (2)	−0.011 (2)
C10	0.030 (3)	0.031 (3)	0.034 (3)	−0.015 (2)	0.022 (3)	−0.022 (2)
C11	0.018 (2)	0.054 (4)	0.037 (3)	−0.013 (3)	0.014 (2)	−0.029 (3)
C12	0.016 (2)	0.046 (4)	0.020 (3)	0.001 (2)	0.003 (2)	−0.010 (2)
C13	0.015 (2)	0.029 (3)	0.016 (2)	0.000 (2)	0.0052 (18)	−0.003 (2)
C14	0.014 (2)	0.020 (2)	0.018 (2)	−0.0049 (18)	0.0077 (18)	−0.011 (2)
Cl1	0.0213 (5)	0.0139 (5)	0.0194 (5)	−0.0038 (4)	0.0104 (4)	0.0008 (4)
Cl2	0.0193 (5)	0.0161 (5)	0.0134 (5)	−0.0015 (4)	0.0052 (4)	−0.0014 (4)
N1	0.0122 (17)	0.0103 (18)	0.0154 (18)	−0.0001 (14)	0.0048 (14)	0.0012 (15)
N2	0.0147 (17)	0.0141 (19)	0.0153 (18)	−0.0013 (15)	0.0049 (15)	−0.0027 (16)
Pt1	0.01041 (10)	0.01048 (11)	0.01166 (11)	−0.00040 (6)	0.00443 (7)	0.00026 (6)

Geometric parameters (Å, º)

C1—H1A	0.9900	C7—C8	1.376 (7)
C1—H1B	0.9900	C8—H8	0.9500
C1—C2	1.510 (6)	C8—C9	1.393 (8)
C1—N1	1.512 (5)	C9—C10	1.421 (7)
C2—H2A	0.9900	C9—C14	1.426 (7)
C2—H2B	0.9900	C10—H10	0.9500
C2—C3	1.518 (7)	C10—C11	1.350 (9)
C3—H3A	0.9900	C11—H11	0.9500
C3—H3B	0.9900	C11—C12	1.408 (8)
C3—C4	1.512 (7)	C12—H12	0.9500
C4—H4A	0.9900	C12—C13	1.371 (6)
C4—H4B	0.9900	C13—H13	0.9500
C4—C5	1.526 (7)	C13—C14	1.409 (7)
C5—H5A	0.9900	C14—N2	1.381 (5)
C5—H5B	0.9900	Cl1—Pt1	2.3102 (11)
C5—N1	1.506 (6)	Cl2—Pt1	2.3155 (12)
C6—H6	0.9500	N1—H1	0.9300
C6—C7	1.396 (7)	N1—Pt1	2.057 (4)
C6—N2	1.330 (6)	N2—Pt1	2.029 (4)
C7—H7	0.9500
H1A—C1—H1B	107.8	C7—C8—H8	120.0
C2—C1—H1A	109.1	C7—C8—C9	119.9 (5)
C2—C1—H1B	109.1	C9—C8—H8	120.0
C2—C1—N1	112.5 (4)	C8—C9—C10	123.2 (5)
N1—C1—H1A	109.1	C8—C9—C14	119.0 (4)
N1—C1—H1B	109.1	C10—C9—C14	117.8 (5)
C1—C2—H2A	109.3	C9—C10—H10	119.4
C1—C2—H2B	109.3	C11—C10—C9	121.3 (5)
C1—C2—C3	111.8 (4)	C11—C10—H10	119.4
H2A—C2—H2B	107.9	C10—C11—H11	119.9
C3—C2—H2A	109.3	C10—C11—C12	120.2 (5)
C3—C2—H2B	109.3	C12—C11—H11	119.9
C2—C3—H3A	109.7	C11—C12—H12	119.3
C2—C3—H3B	109.7	C13—C12—C11	121.4 (5)
H3A—C3—H3B	108.2	C13—C12—H12	119.3
C4—C3—C2	109.7 (4)	C12—C13—H13	120.5
C4—C3—H3A	109.7	C12—C13—C14	119.1 (5)
C4—C3—H3B	109.7	C14—C13—H13	120.5
C3—C4—H4A	109.1	C13—C14—C9	120.4 (4)
C3—C4—H4B	109.1	N2—C14—C9	119.7 (4)
C3—C4—C5	112.4 (4)	N2—C14—C13	120.0 (4)
H4A—C4—H4B	107.9	C1—N1—H1	106.6
C5—C4—H4A	109.1	C1—N1—Pt1	108.8 (3)
C5—C4—H4B	109.1	C5—N1—C1	110.8 (3)
C4—C5—H5A	109.3	C5—N1—H1	106.6
C4—C5—H5B	109.3	C5—N1—Pt1	116.8 (3)
H5A—C5—H5B	107.9	Pt1—N1—H1	106.6
N1—C5—C4	111.8 (4)	C6—N2—C14	119.5 (4)
N1—C5—H5A	109.3	C6—N2—Pt1	119.7 (3)
N1—C5—H5B	109.3	C14—N2—Pt1	120.7 (3)
C7—C6—H6	118.5	Cl1—Pt1—Cl2	91.14 (4)
N2—C6—H6	118.5	N1—Pt1—Cl1	90.92 (11)
N2—C6—C7	123.1 (4)	N1—Pt1—Cl2	173.98 (10)
C6—C7—H7	120.6	N2—Pt1—Cl1	178.04 (11)
C8—C7—C6	118.8 (5)	N2—Pt1—Cl2	88.70 (11)
C8—C7—H7	120.6	N2—Pt1—N1	89.43 (15)
C1—C2—C3—C4	55.2 (5)	C8—C9—C14—C13	177.6 (4)
C1—N1—Pt1—Cl1	−71.7 (3)	C8—C9—C14—N2	−2.2 (7)
C1—N1—Pt1—N2	110.2 (3)	C9—C10—C11—C12	0.7 (8)
C2—C1—N1—C5	54.1 (5)	C9—C14—N2—C6	0.4 (6)
C2—C1—N1—Pt1	−176.2 (3)	C9—C14—N2—Pt1	178.1 (3)
C2—C3—C4—C5	−54.9 (5)	C10—C9—C14—C13	−1.0 (7)
C3—C4—C5—N1	54.9 (5)	C10—C9—C14—N2	179.2 (4)
C4—C5—N1—C1	−53.1 (5)	C10—C11—C12—C13	−0.4 (8)
C4—C5—N1—Pt1	−178.5 (3)	C11—C12—C13—C14	−0.6 (7)
C5—N1—Pt1—Cl1	54.6 (3)	C12—C13—C14—C9	1.3 (7)
C5—N1—Pt1—N2	−123.5 (3)	C12—C13—C14—N2	−178.9 (4)
C6—C7—C8—C9	−0.1 (7)	C13—C14—N2—C6	−179.4 (4)
C6—N2—Pt1—Cl2	71.1 (3)	C13—C14—N2—Pt1	−1.7 (6)
C6—N2—Pt1—N1	−103.2 (3)	C14—C9—C10—C11	0.0 (7)
C7—C6—N2—C14	1.6 (7)	C14—N2—Pt1—Cl2	−106.6 (3)
C7—C6—N2—Pt1	−176.1 (4)	C14—N2—Pt1—N1	79.1 (3)
C7—C8—C9—C10	−179.5 (5)	N1—C1—C2—C3	−55.8 (5)
C7—C8—C9—C14	2.0 (7)	N2—C6—C7—C8	−1.8 (7)
C8—C9—C10—C11	−178.6 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1^i	0.93	2.61	3.521 (3)	166

Symmetry code: (i) −x+3/2, y+1/2, −z+1/2.

Selected bond lengths (Å) and angles (°) for (I), (II) and (III).

	(I)	(II)	(III)
Pt1—N1	2.057 (3)	2.063 (3)	2.057 (4)
Pt1—N2	2.045 (3)	2.074 (3)	2.029 (4)
Pt1—Cl1	2.3097 (8)	2.3109 (8)	2.3102 (11)
Pt1—Cl2	2.3124 (8)	2.3020 (8)	2.3155 (12)
Pt2—N3	2.060 (3)
Pt2–N4	2.050 (3)
Pt1—Cl3	2.3099 (8)
Pt2—Cl4	2.3140 (8)
Cl1—Pt1—Cl2	89.15 (3)	90.19 (3)	91.14 (4)
N1—Pt1—N2	90.36 (11)	91.00 (11)	89.43 (15)
N1—Pt1—Cl1	89.88 (8)	88.07 (8)	90.92 (11)
N2—Pt1—Cl2	90.64 (8)	90.78 (8)	88.70 (11)
Cl3—Pt2—Cl4	89.82 (3)
N3—Pt2—N4	90.44 (11)
N3—Pt2—Cl4	91.44 (8)
N4—Pt2—Cl3	88.32 (8)