Dichloro­(4,4'-dialkyl-2,2'-bipyridine-[kappa]²N,N')platinum(II), where alkyl is pentyl and heptyl

Dichloro­(4,4'-dipentyl-2,2'-bipyridine-[kappa]²N,N')platinum(II), [PtCl₂(C₂₀H₂₈N₂)], adopts a discrete [pi]-[pi] stacking structure, where the alkyl chains are located in a random manner. In contrast, dichloro­(4,4'-diheptyl-2,2'-bipyridine-[kappa]²N,N')platinum(II), [PtCl₂(C₂₄H₃₆N₂)], forms a layer structure comprised of alkyl chain layers and paired coordination sites, as observed for analogous complexes with longer alkyl chains.

S1. Comment

It is well known that long alkyl chains play an important role in controlling molecular arrangement. Such properties of long alkyl chains have been exploited in metal complexes in order to arrange them on the surface of matrices as monolayers or thin-layer films (Valenty et al., 1979; Borgarello et al., 1981). It is also known that square-planar Pt^II complexes are often stacked in the solid state so that they exhibit characteristic colours and intense luminescence (Houlding & Miskowski, 1991). Thus, the introduction of alkyl chains into Pt^II complexes would be expected to enhance and/or control their self-assembled properties. Such complexes are also expected to exhibit amphiphilic properties, which are induced by the combination of a hydrophilic coordination site and the hydrophobic alkyl chains. In fact, we recently reported the Langmuir–Blodgett film of dicyano(5,5'-diundecyl-2,2'-bipyridine)platinum(II), which exhibits characteristic luminescence based on Pt···Pt interactions with increasing surface pressure (Kobayashi et al., 2004). We have also determined the crystal structure of compound (III), the dichloro-Pt^II complex with 4,4'-dinonyl-2,2'-bipyridine (dC₉bpy) (Kato & Ikemori, 2003). In compound (III), the molecules are arranged in an orderly fashion to form an alternating layer structure of the alkyl-chain layers and paired coordination sites. Such layer arrangement indicates that the discrimination between the hydrophobic and hydrophilic sites is clear. In order to investigate the effect of the alkyl chains on the arrangement of such Pt^II complexes, we have now synthesized a series of Pt^II complexes bearing alkyl chains of different lengths. In this paper, we report the crystal structures of two dichloro-Pt^II complexes, (I) and (II), containing 4,4'-dipentyl-2,2'-bipyridine (dC₅bpy) and 4,4'-diheptyl-2,2'-bipyridine (dC₇bpy) ligands, respectively.

Fig. 1 shows the molecular structure of (I). The coordination geometry is planar, including the bipyridine moiety, with a deviation of 0.17 (1) Å For which atom?, but the two alkyl chains are located randomly out of the coordination plane. The complexes are stacked at the bipyridine moieties along the a axis, with an interplanar spacing of 3.27 (2) Å (Fig. 2). In this stack, the Pt···Pt distance is 5.1936 (5) Å. There is no particular orientation of the pentyl groups in the packing structure. For this complex, π–π stacking would be a main factor in controlling the packing structure. A similar stacking structure was reported for the analogous complex bearing tert-butyl groups, [PtCl₂(bu₂bpy)] (bu₂bpy = 4,4'-di-tert-butyl-2,2'-bipyridine; Achar & Catalano, 1997). The arrangement of the pentyl groups in compound (I) could be one of several conformations. In fact, a different crystal form, a solvate, was deposited from the same solution as used for the crystallization of complex (I).

In contrast to the above, complex (II) exhibits a well ordered arrangement of the alkyl chains. As shown in Fig. 3, the heptyl groups are extended in the same direction and the complex molecules are arranged to form a layer structure (Fig. 4). There is an alternating arrangement of the alkyl layers and the metal-coordination parts. No particular interactions are observed between the alkyl chains and the Cl⁻ ligands. There is no C—H···Cl distance shorter than 2.95 Å, the sum of the van der Waals radii of H and Cl (Reference?). The molecular arrangement of (II) is essentially the same as that of (III). In proportion to the length of the alkyl chain, the width of the alkyl layers for the dC₇bpy complex is narrower than that for the dC₉bpy complex. This is reflected in the smaller value of the lattice parameter of the a axis [15.102 (8) Å, space group P2₁/c] for (II) compared with that of the corresponding c axis for (III) [17.652 (2) Å, P2₁/a] while the other lattice parameters are similar. The coordination sites are arranged in a face-to-face fashion with an interplanar spacing of 3.40 (1) Å. The Pt···Pt distance is long enough to indicate no interaction between them [5.3416 (2) Å]. Thus, seven or more C atoms in the alkyl chains are necessary for the adoption of a layer arrangement.

Cocker & Bachman (2004) reported the crystal structures of Pt complexes containing a series of 4,4'-dialkyl-2,2'-bipyridines and a benzene-1,2-dithiolate ion. These complexes are roughly planar, including the extension of the alkyl chains, and are packed in an overlapping arrangement of the π–π stack of the coordination sites and the alkyl chains. These packing structures are different from the segregated and alternating layer structures of (II) and (III). Thus, the alternating layer structures of (II) and (III) would reflect good amphiphilic properties for dichloro Pt^II complexes. Further studies are in progress regarding related complexes bearing alkyl chains with even numbers of C atoms, in addition to those with odd numbers of C atoms.

S2. Experimental

4,4'-Dipentyl-2,2'-bipyridine (dC₅bpy) and 4,4'-diheptyl-2,2'-bipyridine (dC₇bpy) were prepared by a similar method to that reported previously by Ellison & Iwamoto (1983), using 1-bromobutane for dC₅bpy and 1-bromohexane for dC₇bpy. The products were purified by silica-gel column chromatography (eluent: toluene–diethyl ether 1:1). For dC₅bpy, ¹H NMR (CDCl₃, δ, p.p.m.): 0.90 (t, 6H, CH₃), 1.36 (br, 8H, CH₂), 1.70 (m, 4H, CH₂), 2.69 (t, 4H, CH₂), 7.14 (d, 2H, bpy), 8.24 (s, 2H, bpy), 8.57 (d, 2H, bpy); ESI-MS: m/z 296 ([M+H]⁺). For dC₇bpy, ¹H NMR (CDCl₃, δ, p.p.m.): 0.88 (br, 6H, CH₃), 1.31 (br, 16H, CH₂), 1.69 (br, 4H, CH₂), 2.69 (t, 4H, CH₂), 7.13 (d, 2H, bpy), 8.23 (s, 2H, bpy), 8.56 (d, 2H, bpy); ESI-MS: m/z 353 ([M+H]⁺).

The Pt^II complexes were obtained by reaction of equimolar amounts of K₂[PtCl₄] and the respective ligands in an acidic aqueous solution at 343 K. After heating for 2 h, a yellow powder of (I) or (II) was deposited [yield: 30% for (I), 68% for (II)]. Recrystallization from N,N-dimethylformamide gave yellow needle crystals for (I) and yellow plate crystals for (II). For (I), ¹H NMR (CDCl₃, δ, p.p.m.): 0.93 (t, 3H, CH₃), 1.39 (br, 8H, CH₂), 1.75 (br, 4H, CH₂), 2.81 (t, 4H, CH₂), 7.20 (d, 2H, bpy), 7.90 (s, 2H, bpy), 9.20 (d, 2H, bpy); m.p. 483–484 K. For (II), ¹H NMR (CDCl₃, δ, p.p.m.): 0.90 (t, 6H, CH₃), 1.30 (br, 8H, CH₂), 1.36 (br, 8H, CH₂), 1.75 (br, 4H, CH₂), 2.81 (t, 4H, CH₂), 7.20 (d, 2H, bpy), 7.90 (s, 2H, bpy), 9.19 (d, 2H, bpy); m.p. 421–424 K.

S3. Refinement

H atoms were refined using a riding model, with C—H = 0.95, 0.98 and 0.99 Å for pyridyl, methyl and methylene groups, respectively, and with U_iso(H) = 1.2U_eq(C). For (I), the large ratio (3.7) of U_eq(max)/U_eq(min) for C is attributed to the fluctuation of the end of the pentyl groups. Several peaks of residual electron density (2.0–2.3 e Å⁻³) and the deepest hole of −3.5 e Å⁻³ were observed within 1.0 Å of atom Pt1 for (I). For (II), the peaks of 3.9 and 3.4 e Å⁻³ and the hole of −1.8 e Å⁻³ are located at 1.63, 1.78 and 0.73 Å from atoms C2, C24 and Pt1, respectively.

Computing details

For both compounds, data collection: CrystalClear (Rigaku, 2001); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: CrystalStructure.

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellispoids are plotted at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The packing structure of (I), viewed down the a axis. H atoms have been omitted for clarity.
	Fig. 3. The molecular structure of (II), showing the atom-numbering scheme. Displacement ellispoids are plotted at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. The packing structure of (II), viewed down the b axis. H atoms have been omitted for clarity.

(I) Dichloro(4,4'-dipentyl-2,2'-bipyridine-κ²N,N')platinum(II)

Crystal data

[PtCl2(C20H28N2)]	F(000) = 1096.00
Mr = 562.45	Dx = 1.828 Mg m^−3
Monoclinic, P21/c	Melting point = 483–484 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71070 Å
a = 7.1791 (19) Å	Cell parameters from 6090 reflections
b = 13.853 (4) Å	θ = 3.1–27.5°
c = 20.609 (5) Å	µ = 7.11 mm^−1
β = 94.3564 (9)°	T = 173 K
V = 2043.6 (9) Å^3	Needle, yellow
Z = 4	0.45 × 0.10 × 0.10 mm

Data collection

Rigaku Mercury CCD area-detector diffractometer	3263 reflections with F^2 > 2σ(F^2)
Detector resolution: 14.71 pixels mm^-1	Rint = 0.098
ω scans	θmax = 27.5°
Absorption correction: numerical (NUMABS; Higashi, 1999)	h = −9→8
Tmin = 0.578, Tmax = 0.868	k = −17→17
15324 measured reflections	l = −26→26
4537 independent reflections

Refinement

Refinement on F^2	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.067	w = 1/[σ^2(Fo^2) + (0.0864P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.180	(Δ/σ)max = 0.001
S = 0.97	Δρmax = 2.30 e Å^−3
4537 reflections	Δρmin = −3.54 e Å^−3
227 parameters

Special details

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement using reflections with F² > 2.0 σ(F²). The weighted R-factor(wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq
Pt1	0.29106 (5)	−0.07509 (3)	0.58358 (2)	0.02498 (15)
Cl1	0.2288 (4)	−0.0410 (2)	0.68869 (14)	0.0402 (6)
Cl2	0.4071 (4)	−0.2228 (2)	0.61712 (14)	0.0379 (6)
N1	0.2012 (11)	0.0540 (6)	0.5472 (4)	0.0253 (18)
N2	0.3287 (11)	−0.0951 (6)	0.4890 (4)	0.0276 (19)
C1	0.1427 (13)	0.1276 (8)	0.5823 (5)	0.028 (2)
C2	0.0892 (13)	0.2146 (7)	0.5532 (5)	0.028 (2)
C3	0.0913 (13)	0.2278 (7)	0.4871 (5)	0.028 (2)
C4	0.1536 (13)	0.1496 (7)	0.4508 (5)	0.026 (2)
C5	0.2090 (13)	0.0659 (6)	0.4818 (5)	0.0201 (19)
C6	0.2738 (13)	−0.0222 (7)	0.4485 (5)	0.027 (2)
C7	0.2851 (13)	−0.0283 (7)	0.3817 (5)	0.027 (2)
C8	0.3483 (14)	−0.1118 (8)	0.3550 (5)	0.029 (2)
C9	0.4084 (15)	−0.1847 (7)	0.3953 (5)	0.032 (2)
C10	0.3931 (14)	−0.1758 (7)	0.4618 (5)	0.028 (2)
C11	0.0335 (15)	0.3204 (7)	0.4548 (5)	0.030 (2)
C12	0.2009 (15)	0.3892 (8)	0.4492 (5)	0.033 (2)
C13	0.145 (2)	0.4801 (8)	0.4119 (7)	0.048 (3)
C14	0.305 (2)	0.5528 (9)	0.4137 (8)	0.054 (3)
C15	0.468 (2)	0.5176 (12)	0.3781 (8)	0.073 (5)
C16	0.3572 (16)	−0.1205 (9)	0.2813 (5)	0.038 (2)
C17	0.1605 (17)	−0.1332 (8)	0.2480 (5)	0.037 (2)
C18	0.0697 (15)	−0.2271 (8)	0.2671 (5)	0.033 (2)
C19	−0.1311 (17)	−0.2384 (9)	0.2385 (6)	0.043 (2)
C20	−0.223 (2)	−0.3309 (11)	0.2631 (7)	0.060 (4)
H1	0.1377	0.1203	0.6279	0.034*
H2	0.0504	0.2661	0.5794	0.034*
H4	0.1573	0.1550	0.4049	0.031*
H7	0.2491	0.0250	0.3546	0.033*
H9	0.4606	−0.2415	0.3782	0.038*
H10	0.4293	−0.2287	0.4893	0.033*
H11A	−0.0607	0.3524	0.4802	0.036*
H11B	−0.0254	0.3067	0.4108	0.036*
H12A	0.2538	0.4069	0.4934	0.039*
H12B	0.2994	0.3554	0.4269	0.039*
H13A	0.0364	0.5099	0.4310	0.058*
H13B	0.1071	0.4633	0.3661	0.058*
H14A	0.2587	0.6142	0.3938	0.065*
H14B	0.3484	0.5662	0.4596	0.065*
H15A	0.5649	0.5676	0.3793	0.088*
H15B	0.4260	0.5033	0.3328	0.088*
H15C	0.5196	0.4589	0.3992	0.088*
H16A	0.4355	−0.1765	0.2713	0.045*
H16B	0.4152	−0.0617	0.2644	0.045*
H17A	0.0814	−0.0784	0.2599	0.045*
H17B	0.1678	−0.1320	0.2003	0.045*
H18A	0.0715	−0.2303	0.3152	0.040*
H18B	0.1446	−0.2819	0.2525	0.040*
H19A	−0.1326	−0.2407	0.1904	0.051*
H19B	−0.2047	−0.1815	0.2504	0.051*
H20A	−0.3507	−0.3361	0.2433	0.072*
H20B	−0.2247	−0.3280	0.3106	0.072*
H20C	−0.1505	−0.3874	0.2511	0.072*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
PT1	0.0229 (2)	0.0251 (2)	0.0259 (2)	−0.00473 (14)	−0.00454 (16)	0.00285 (16)
CL1	0.0521 (18)	0.0394 (15)	0.0288 (14)	−0.0014 (14)	0.0007 (12)	0.0029 (12)
CL2	0.0408 (15)	0.0307 (14)	0.0406 (15)	0.0015 (12)	−0.0067 (12)	0.0102 (12)
N1	0.022 (4)	0.022 (4)	0.031 (4)	−0.003 (3)	−0.007 (3)	0.001 (3)
N2	0.020 (4)	0.030 (4)	0.031 (4)	−0.000 (3)	−0.009 (3)	−0.009 (3)
C1	0.018 (4)	0.041 (6)	0.025 (5)	−0.006 (4)	0.003 (3)	−0.005 (4)
C2	0.020 (4)	0.025 (5)	0.039 (6)	−0.003 (4)	−0.000 (4)	−0.008 (4)
C3	0.021 (5)	0.024 (5)	0.037 (5)	−0.002 (4)	−0.002 (4)	−0.003 (4)
C4	0.016 (4)	0.035 (5)	0.025 (5)	0.001 (4)	−0.001 (3)	0.001 (4)
C5	0.016 (4)	0.018 (4)	0.026 (4)	−0.005 (3)	−0.002 (3)	0.010 (3)
C6	0.016 (4)	0.028 (5)	0.037 (5)	−0.006 (4)	−0.007 (4)	0.007 (4)
C7	0.021 (4)	0.027 (5)	0.032 (5)	−0.004 (4)	−0.008 (4)	0.010 (4)
C8	0.021 (5)	0.029 (5)	0.035 (5)	−0.004 (4)	−0.003 (4)	−0.004 (4)
C9	0.039 (6)	0.025 (5)	0.030 (5)	0.002 (4)	−0.002 (4)	−0.013 (4)
C10	0.027 (5)	0.023 (5)	0.034 (5)	0.004 (4)	0.009 (4)	0.009 (4)
C11	0.037 (6)	0.022 (5)	0.030 (5)	−0.001 (4)	−0.005 (4)	0.001 (4)
C12	0.035 (6)	0.030 (5)	0.032 (6)	−0.004 (4)	−0.001 (4)	−0.004 (4)
C13	0.057 (8)	0.026 (6)	0.062 (9)	−0.002 (6)	0.009 (6)	0.002 (6)
C14	0.058 (9)	0.032 (7)	0.073 (11)	−0.007 (6)	0.016 (7)	0.006 (6)
C15	0.095 (13)	0.057 (10)	0.072 (12)	−0.006 (9)	0.033 (10)	0.012 (9)
C16	0.036 (6)	0.038 (6)	0.038 (6)	−0.007 (5)	−0.002 (5)	0.007 (5)
C17	0.052 (7)	0.033 (6)	0.027 (5)	−0.006 (5)	0.001 (5)	−0.004 (4)
C18	0.030 (5)	0.042 (6)	0.027 (5)	−0.002 (5)	−0.005 (4)	−0.003 (5)
C19	0.046 (7)	0.040 (7)	0.040 (7)	−0.007 (5)	−0.004 (5)	−0.009 (5)
C20	0.044 (8)	0.068 (10)	0.068 (10)	−0.021 (7)	0.001 (7)	−0.020 (8)

Geometric parameters (Å, º)

Pt1—Cl1	2.294 (3)	C12—C13	1.513 (17)
Pt1—Cl2	2.295 (2)	C12—H12A	0.990
Pt1—N1	2.026 (8)	C12—H12B	0.990
Pt1—N2	2.007 (9)	C13—C14	1.53 (2)
N1—C1	1.336 (14)	C13—H13A	0.990
N1—C5	1.362 (13)	C13—H13B	0.990
N2—C6	1.350 (13)	C14—C15	1.51 (2)
N2—C10	1.348 (13)	C14—H14A	0.990
C1—C2	1.387 (15)	C14—H14B	0.990
C1—H1	0.950	C15—H15A	0.980
C2—C3	1.375 (15)	C15—H15B	0.980
C2—H2	0.950	C15—H15C	0.980
C3—C4	1.409 (15)	C16—C17	1.532 (16)
C3—C11	1.490 (14)	C16—H16A	0.990
C4—C5	1.370 (14)	C16—H16B	0.990
C4—H4	0.950	C17—C18	1.521 (17)
C5—C6	1.491 (14)	C17—H17A	0.990
C6—C7	1.388 (15)	C17—H17B	0.990
C7—C8	1.372 (15)	C18—C19	1.524 (16)
C7—H7	0.950	C18—H18A	0.990
C8—C9	1.358 (15)	C18—H18B	0.990
C8—C16	1.529 (16)	C19—C20	1.54 (2)
C9—C10	1.389 (16)	C19—H19A	0.990
C9—H9	0.950	C19—H19B	0.990
C10—H10	0.950	C20—H20A	0.980
C11—C12	1.546 (15)	C20—H20B	0.980
C11—H11A	0.990	C20—H20C	0.980
C11—H11B	0.990
Cl1—Pt1—Cl2	89.50 (11)	C13—C12—H12A	109.2
Cl1—Pt1—N1	95.1 (2)	C13—C12—H12B	109.2
Cl1—Pt1—N2	174.7 (2)	H12A—C12—H12B	107.9
Cl2—Pt1—N1	175.1 (2)	C12—C13—C14	111.5 (11)
Cl2—Pt1—N2	95.6 (2)	C12—C13—H13A	109.3
N1—Pt1—N2	79.9 (3)	C12—C13—H13B	109.3
Pt1—N1—C1	125.3 (7)	C14—C13—H13A	109.3
Pt1—N1—C5	115.9 (6)	C14—C13—H13B	109.3
C1—N1—C5	118.8 (8)	H13A—C13—H13B	108.0
PT1—N2—C6	116.2 (7)	C13—C14—C15	112.6 (12)
PT1—N2—C10	126.4 (7)	C13—C14—H14A	109.1
C6—N2—C10	117.2 (9)	C13—C14—H14B	109.1
N1—C1—C2	121.1 (9)	C15—C14—H14A	109.1
N1—C1—H1	119.4	C15—C14—H14B	109.1
C2—C1—H1	119.4	H14A—C14—H14B	107.8
C1—C2—C3	121.3 (10)	C14—C15—H15A	109.5
C1—C2—H2	119.3	C14—C15—H15B	109.5
C3—C2—H2	119.3	C14—C15—H15C	109.5
C2—C3—C4	116.9 (9)	H15A—C15—H15B	109.5
C2—C3—C11	122.2 (9)	H15A—C15—H15C	109.5
C4—C3—C11	120.9 (9)	H15B—C15—H15C	109.5
C3—C4—C5	119.7 (9)	C8—C16—C17	110.3 (9)
C3—C4—H4	120.2	C8—C16—H16A	109.6
C5—C4—H4	120.2	C8—C16—H16B	109.6
N1—C5—C4	122.2 (9)	C17—C16—H16A	109.6
N1—C5—C6	113.2 (8)	C17—C16—H16B	109.6
C4—C5—C6	124.6 (9)	H16A—C16—H16B	108.1
N2—C6—C5	114.5 (9)	C16—C17—C18	112.4 (9)
N2—C6—C7	122.1 (9)	C16—C17—H17A	109.1
C5—C6—C7	123.4 (9)	C16—C17—H17B	109.1
C6—C7—C8	119.7 (10)	C18—C17—H17A	109.1
C6—C7—H7	120.1	C18—C17—H17B	109.1
C8—C7—H7	120.1	H17A—C17—H17B	107.9
C7—C8—C9	118.7 (10)	C17—C18—C19	113.5 (9)
C7—C8—C16	120.3 (10)	C17—C18—H18A	108.9
C9—C8—C16	120.9 (10)	C17—C18—H18B	108.9
C8—C9—C10	119.5 (10)	C19—C18—H18A	108.9
C8—C9—H9	120.2	C19—C18—H18B	108.9
C10—C9—H9	120.3	H18A—C18—H18B	107.7
N2—C10—C9	122.6 (9)	C18—C19—C20	111.8 (10)
N2—C10—H10	118.7	C18—C19—H19A	109.3
C9—C10—H10	118.7	C18—C19—H19B	109.3
C3—C11—C12	111.9 (8)	C20—C19—H19A	109.3
C3—C11—H11A	109.2	C20—C19—H19B	109.3
C3—C11—H11B	109.2	H19A—C19—H19B	107.9
C12—C11—H11A	109.2	C19—C20—H20A	109.5
C12—C11—H11B	109.2	C19—C20—H20B	109.5
H11A—C11—H11B	107.9	C19—C20—H20C	109.5
C11—C12—C13	112.0 (9)	H20A—C20—H20B	109.5
C11—C12—H12A	109.2	H20A—C20—H20C	109.5
C11—C12—H12B	109.2	H20B—C20—H20C	109.5

(II) dichloro(4,4'-diheptyl-2,2'-bipyridine-κ²N,N')platinum(II)

Crystal data

[PtCl2(C24H36N2)]	F(000) = 1224.00
Mr = 618.56	Dx = 1.654 Mg m^−3
Monoclinic, P21/c	Melting point = 421–424 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71070 Å
a = 15.102 (8) Å	Cell parameters from 7972 reflections
b = 10.781 (6) Å	θ = 3.1–27.5°
c = 16.525 (10) Å	µ = 5.85 mm^−1
β = 112.570 (3)°	T = 173 K
V = 2484 (2) Å^3	Plate, yellow
Z = 4	0.37 × 0.30 × 0.17 mm

Data collection

Rigaku Mercury CCD area-detector diffractometer	4970 reflections with F^2 > 2σ(F^2)
Detector resolution: 7.31 pixels mm^-1	Rint = 0.027
ω scans	θmax = 27.5°
Absorption correction: numerical (NUMABS; Higashi, 1999)	h = −19→17
Tmin = 0.182, Tmax = 0.363	k = −14→14
18483 measured reflections	l = −17→21
5522 independent reflections

Refinement

Refinement on F^2	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.041	w = 1/[σ^2(Fo^2) + (0.0723P)^2 + 0.9111P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.115	(Δ/σ)max = 0.001
S = 1.12	Δρmax = 3.87 e Å^−3
5522 reflections	Δρmin = −1.83 e Å^−3
263 parameters

Special details

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement using reflections with F² > 2.0 σ(F²). The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 σ(F²) is used only for calculating R-factor (gt).

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

	x	y	z	Uiso*/Ueq
Pt1	0.446840 (10)	0.16345 (2)	−0.134610 (10)	0.03174 (10)
Cl1	0.32866 (11)	0.31121 (13)	−0.16840 (10)	0.0498 (3)
Cl2	0.37236 (10)	0.07920 (12)	−0.27224 (8)	0.0433 (3)
N1	0.5161 (2)	0.2210 (3)	−0.0101 (2)	0.0327 (8)
N2	0.5551 (2)	0.0398 (3)	−0.0947 (2)	0.0331 (8)
C1	0.4923 (4)	0.3180 (4)	0.0291 (4)	0.0392 (11)
C2	0.5399 (4)	0.3420 (4)	0.1174 (4)	0.0409 (13)
C3	0.6134 (3)	0.2651 (4)	0.1700 (3)	0.0349 (10)
C4	0.6398 (3)	0.1672 (3)	0.1279 (3)	0.0329 (10)
C5	0.5923 (3)	0.1484 (4)	0.0393 (3)	0.0307 (10)
C6	0.6156 (3)	0.0476 (4)	−0.0097 (3)	0.0303 (9)
C7	0.6926 (3)	−0.0328 (4)	0.0264 (3)	0.0335 (10)
C8	0.7090 (3)	−0.1245 (4)	−0.0252 (3)	0.0354 (10)
C9	0.6469 (4)	−0.1305 (4)	−0.1120 (3)	0.0378 (11)
C10	0.5717 (3)	−0.0497 (4)	−0.1450 (3)	0.0377 (11)
C11	0.6633 (4)	0.2855 (5)	0.2676 (3)	0.0403 (11)
C12	0.7387 (3)	0.3885 (5)	0.2910 (3)	0.0402 (11)
C13	0.8204 (4)	0.3587 (6)	0.2633 (4)	0.0509 (14)
C14	0.8956 (4)	0.4607 (6)	0.2840 (4)	0.0580 (16)
C15	0.9792 (5)	0.4176 (6)	0.2529 (4)	0.0670 (18)
C16	1.0505 (5)	0.5127 (7)	0.2619 (5)	0.0704 (19)
C17	1.1215 (4)	0.4689 (7)	0.2240 (4)	0.0661 (18)
C18	0.7929 (3)	−0.2129 (4)	0.0109 (3)	0.0398 (11)
C19	0.8754 (4)	−0.1766 (4)	−0.0164 (4)	0.0393 (12)
C20	0.9563 (3)	−0.2710 (5)	0.0117 (3)	0.0410 (11)
C21	1.0399 (3)	−0.2374 (4)	−0.0137 (3)	0.0405 (11)
C22	1.1160 (4)	−0.3383 (4)	0.0073 (3)	0.0362 (11)
C23	1.2027 (4)	−0.3043 (5)	−0.0133 (3)	0.0409 (11)
C24	1.2703 (4)	−0.4139 (5)	−0.0030 (4)	0.0528 (15)
H1	0.4414	0.3711	−0.0049	0.047*
H2	0.5222	0.4122	0.1426	0.049*
H4	0.6908	0.1136	0.1608	0.039*
H7	0.7340	−0.0251	0.0863	0.040*
H9	0.6565	−0.1916	−0.1492	0.045*
H10	0.5299	−0.0564	−0.2049	0.045*
H11A	0.6946	0.2072	0.2954	0.048*
H11B	0.6147	0.3067	0.2920	0.048*
H12A	0.7077	0.4665	0.2623	0.048*
H12B	0.7644	0.4022	0.3551	0.048*
H13A	0.7942	0.3430	0.1993	0.061*
H13B	0.8518	0.2815	0.2929	0.061*
H14A	0.9227	0.4774	0.3478	0.070*
H14B	0.8658	0.5380	0.2533	0.070*
H15A	1.0117	0.3442	0.2877	0.080*
H15B	0.9500	0.3919	0.1907	0.080*
H16A	1.0848	0.5331	0.3247	0.085*
H16B	1.0182	0.5889	0.2312	0.085*
H17A	1.1691	0.5341	0.2309	0.079*
H17B	1.0876	0.4503	0.1615	0.079*
H17C	1.1538	0.3940	0.2548	0.079*
H18A	0.7711	−0.2978	−0.0104	0.048*
H18B	0.8162	−0.2139	0.0756	0.048*
H19A	0.8505	−0.1674	−0.0809	0.047*
H19B	0.9012	−0.0951	0.0098	0.047*
H20A	0.9302	−0.3521	−0.0148	0.049*
H20B	0.9804	−0.2806	0.0761	0.049*
H21A	1.0702	−0.1605	0.0174	0.049*
H21B	1.0151	−0.2199	−0.0774	0.049*
H23A	1.2383	−0.2366	0.0263	0.049*
H23B	1.1806	−0.2730	−0.0742	0.049*
H24A	1.3248	−0.3873	−0.0170	0.063*
H24B	1.2358	−0.4807	−0.0429	0.063*
H24C	1.2936	−0.4441	0.0576	0.063*
H22A	1.1380	−0.3589	0.0703	0.043*
H22B	1.0862	−0.4138	−0.0262	0.043*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pt1	0.03402 (14)	0.03214 (12)	0.03065 (14)	−0.00164 (6)	0.01417 (11)	0.00531 (6)
Cl1	0.0503 (8)	0.0526 (7)	0.0443 (8)	0.0167 (6)	0.0156 (6)	0.0123 (6)
Cl2	0.0495 (7)	0.0450 (6)	0.0308 (6)	−0.0046 (5)	0.0102 (5)	0.0043 (5)
N1	0.036 (2)	0.035 (2)	0.031 (2)	−0.0005 (16)	0.0169 (18)	0.0040 (16)
N2	0.037 (2)	0.0300 (19)	0.037 (2)	−0.0037 (15)	0.0199 (19)	0.0020 (15)
C1	0.040 (2)	0.039 (2)	0.045 (3)	0.005 (2)	0.022 (2)	0.001 (2)
C2	0.042 (3)	0.041 (3)	0.049 (3)	0.002 (2)	0.028 (2)	−0.006 (2)
C3	0.041 (2)	0.033 (2)	0.035 (2)	−0.0015 (19)	0.020 (2)	−0.0042 (19)
C4	0.033 (2)	0.034 (2)	0.035 (2)	−0.0018 (17)	0.016 (2)	0.0014 (17)
C5	0.031 (2)	0.031 (2)	0.034 (2)	−0.0045 (17)	0.017 (2)	0.0020 (17)
C6	0.033 (2)	0.030 (2)	0.032 (2)	−0.0075 (17)	0.017 (2)	−0.0014 (17)
C7	0.035 (2)	0.035 (2)	0.032 (2)	−0.0004 (19)	0.015 (2)	0.0005 (18)
C8	0.040 (2)	0.030 (2)	0.041 (2)	−0.003 (2)	0.022 (2)	0.003 (2)
C9	0.043 (3)	0.037 (2)	0.037 (3)	−0.001 (2)	0.019 (2)	−0.007 (2)
C10	0.051 (3)	0.033 (2)	0.035 (2)	−0.002 (2)	0.023 (2)	−0.0022 (19)
C11	0.045 (3)	0.043 (2)	0.040 (3)	−0.005 (2)	0.024 (2)	−0.002 (2)
C12	0.044 (3)	0.043 (2)	0.034 (2)	0.002 (2)	0.016 (2)	−0.003 (2)
C13	0.041 (3)	0.076 (4)	0.039 (3)	−0.001 (2)	0.019 (2)	−0.011 (2)
C14	0.043 (3)	0.085 (4)	0.042 (3)	−0.009 (3)	0.013 (2)	0.005 (3)
C15	0.091 (5)	0.059 (4)	0.050 (3)	−0.020 (3)	0.025 (3)	−0.007 (3)
C16	0.064 (4)	0.073 (4)	0.067 (4)	−0.011 (3)	0.017 (3)	0.003 (3)
C17	0.048 (3)	0.097 (5)	0.055 (4)	−0.006 (3)	0.023 (3)	0.001 (3)
C18	0.042 (2)	0.032 (2)	0.047 (3)	0.004 (2)	0.019 (2)	0.003 (2)
C19	0.039 (3)	0.036 (2)	0.047 (3)	0.0013 (19)	0.022 (2)	0.002 (2)
C20	0.044 (3)	0.043 (2)	0.041 (2)	0.004 (2)	0.022 (2)	0.003 (2)
C21	0.042 (2)	0.037 (2)	0.048 (3)	0.001 (2)	0.023 (2)	0.001 (2)
C22	0.041 (3)	0.035 (2)	0.040 (3)	0.0027 (18)	0.023 (2)	0.0045 (18)
C23	0.045 (3)	0.042 (2)	0.040 (3)	−0.005 (2)	0.022 (2)	0.000 (2)
C24	0.041 (3)	0.051 (3)	0.073 (4)	0.005 (2)	0.029 (3)	0.007 (3)

Geometric parameters (Å, º)

Pt1—Cl1	2.2956 (15)	C14—C15	1.604 (11)
Pt1—Cl2	2.3019 (11)	C14—H14A	0.990
Pt1—N1	2.015 (3)	C14—H14B	0.990
Pt1—N2	2.014 (3)	C15—C16	1.452 (11)
N1—C1	1.350 (7)	C15—H15A	0.990
N1—C5	1.373 (5)	C15—H15B	0.990
N2—C6	1.353 (5)	C16—C17	1.511 (12)
N2—C10	1.358 (7)	C16—H16A	0.990
C1—C2	1.381 (8)	C16—H16B	0.990
C1—H1	0.950	C17—H17A	0.980
C2—C3	1.392 (7)	C17—H17B	0.980
C2—H2	0.950	C17—H17C	0.980
C3—C4	1.403 (7)	C18—C19	1.531 (9)
C3—C11	1.511 (7)	C18—H18A	0.990
C4—C5	1.376 (7)	C18—H18B	0.990
C4—H4	0.950	C19—C20	1.518 (7)
C5—C6	1.476 (7)	C19—H19A	0.990
C6—C7	1.387 (6)	C19—H19B	0.990
C7—C8	1.388 (7)	C20—C21	1.520 (9)
C7—H7	0.950	C20—H20A	0.990
C8—C9	1.382 (6)	C20—H20B	0.990
C8—C18	1.513 (7)	C21—C22	1.523 (7)
C9—C10	1.367 (7)	C21—H21A	0.990
C9—H9	0.950	C21—H21B	0.990
C10—H10	0.950	C22—C23	1.519 (9)
C11—C12	1.530 (7)	C22—H22A	0.990
C11—H11A	0.990	C22—H22B	0.990
C11—H11B	0.990	C23—C24	1.528 (8)
C12—C13	1.507 (10)	C23—H23A	0.990
C12—H12A	0.990	C23—H23B	0.990
C12—H12B	0.990	C24—H24A	0.980
C13—C14	1.522 (9)	C24—H24B	0.980
C13—H13A	0.990	C24—H24C	0.980
C13—H13B	0.990
Cl1—Pt1—Cl2	89.66 (5)	C15—C14—H14A	109.8
Cl1—Pt1—N1	94.88 (12)	C15—C14—H14B	109.8
Cl1—Pt1—N2	175.19 (12)	H14A—C14—H14B	108.3
Cl2—Pt1—N1	174.64 (11)	C14—C15—C16	114.0 (6)
Cl2—Pt1—N2	95.14 (11)	C14—C15—H15A	108.8
N1—Pt1—N2	80.31 (16)	C14—C15—H15B	108.8
Pt1—N1—C1	126.8 (3)	C16—C15—H15A	108.8
Pt1—N1—C5	114.8 (3)	C16—C15—H15B	108.8
C1—N1—C5	118.3 (4)	H15A—C15—H15B	107.7
Pt1—N2—C6	116.0 (3)	C15—C16—C17	110.7 (6)
Pt1—N2—C10	126.0 (2)	C15—C16—H16A	109.5
C6—N2—C10	118.0 (3)	C15—C16—H16B	109.5
N1—C1—C2	121.7 (4)	C17—C16—H16A	109.5
N1—C1—H1	119.1	C17—C16—H16B	109.5
C2—C1—H1	119.1	H16A—C16—H16B	108.1
C1—C2—C3	121.0 (5)	C16—C17—H17A	109.5
C1—C2—H2	119.5	C16—C17—H17B	109.5
C3—C2—H2	119.5	C16—C17—H17C	109.5
C2—C3—C4	116.7 (4)	H17A—C17—H17B	109.5
C2—C3—C11	122.1 (5)	H17A—C17—H17C	109.5
C4—C3—C11	121.2 (4)	H17B—C17—H17C	109.5
C3—C4—C5	120.5 (4)	C8—C18—C19	112.1 (4)
C3—C4—H4	119.7	C8—C18—H18A	109.2
C5—C4—H4	119.7	C8—C18—H18B	109.2
N1—C5—C4	121.6 (4)	C19—C18—H18A	109.2
N1—C5—C6	114.6 (4)	C19—C18—H18B	109.2
C4—C5—C6	123.8 (4)	H18A—C18—H18B	107.9
N2—C6—C5	114.0 (3)	C18—C19—C20	112.9 (4)
N2—C6—C7	121.9 (4)	C18—C19—H19A	109.0
C5—C6—C7	124.1 (4)	C18—C19—H19B	109.0
C6—C7—C8	119.9 (4)	C20—C19—H19A	109.0
C6—C7—H7	120.1	C20—C19—H19B	109.0
C8—C7—H7	120.1	H19A—C19—H19B	107.8
C7—C8—C9	117.4 (4)	C19—C20—C21	114.3 (4)
C7—C8—C18	121.8 (4)	C19—C20—H20A	108.7
C9—C8—C18	120.7 (5)	C19—C20—H20B	108.7
C8—C9—C10	120.9 (5)	C21—C20—H20A	108.7
C8—C9—H9	119.6	C21—C20—H20B	108.7
C10—C9—H9	119.6	H20A—C20—H20B	107.6
N2—C10—C9	121.9 (4)	C20—C21—C22	113.7 (4)
N2—C10—H10	119.1	C20—C21—H21A	108.8
C9—C10—H10	119.0	C20—C21—H21B	108.8
C3—C11—C12	113.1 (5)	C22—C21—H21A	108.8
C3—C11—H11A	109.0	C22—C21—H21B	108.8
C3—C11—H11B	109.0	H21A—C21—H21B	107.7
C12—C11—H11A	108.9	C21—C22—C23	114.6 (4)
C12—C11—H11B	108.9	C21—C22—H22A	108.6
H11A—C11—H11B	107.8	C21—C22—H22B	108.6
C11—C12—C13	112.7 (5)	C23—C22—H22A	108.6
C11—C12—H12A	109.1	C23—C22—H22B	108.6
C11—C12—H12B	109.1	H22A—C22—H22B	107.6
C13—C12—H12A	109.1	C22—C23—C24	112.6 (4)
C13—C12—H12B	109.0	C22—C23—H23A	109.1
H12A—C12—H12B	107.8	C22—C23—H23B	109.1
C12—C13—C14	113.9 (5)	C24—C23—H23A	109.1
C12—C13—H13A	108.8	C24—C23—H23B	109.1
C12—C13—H13B	108.8	H23A—C23—H23B	107.8
C14—C13—H13A	108.8	C23—C24—H24A	109.5
C14—C13—H13B	108.8	C23—C24—H24B	109.5
H13A—C13—H13B	107.7	C23—C24—H24C	109.5
C13—C14—C15	109.3 (5)	H24A—C24—H24B	109.5
C13—C14—H14A	109.8	H24A—C24—H24C	109.5
C13—C14—H14B	109.8	H24B—C24—H24C	109.5