Di-chlorido-(4-methyl-aniline-κN)[N-(4-methyl-phen-yl)-1-(thio-phen-2-yl)methanimine-κN]palladium(II).

The structure of a mono-amine PdII complex, [PdCl2(C7H9N)(C12H11NS)], which crystallizes in the triclinic space group, P , is reported. The primary geometry around the PdII atom closely resembles square planar (τ4' = 0.069). In the (E)-1-(thio-phen-2-yl)-N-(p-tol-yl)methanimine ligand, the phenyl and thio-phene rings are not coplanar, subtending a dihedral angle of 38.5 (1)° because of steric effects. The PdCl2N2 coordination plane is almost perpendicular to the planes of the coordinated o-toluidine and the NC2 fragment [dihedral angles of 84.7 (1) and 72.50 (4)°, respectively]. The Pd-NH2 length of 2.040 (2) Å is slightly shorter than the observed mean value for other complexes involving a Pd atom attached to the nitro-gen of an aniline derivative. The mol-ecules display an inter-esting supra-molecular synthon based on reciprocal inter-molecular N-H⋯Cl hydrogen-bonding inter-actions of the p-toluidine amine fragment, which results in centrosymmetric dimeric units. These units are further linked by C-H⋯Cl inter-actions, resulting in chains in the c-axis direction where the mean-planes of the repeating fragment are oriented in the (110) plane. © Butcher et al. 2022.

Chemical context

The chemistry of monodentate mono-amine PdII compounds with amine ligands is of inter­est because the hydrogen bond between the amine and the catalyst plays a key role in the catalytic transformation of simple, easily accessible amines into highly substituted, biologically important amine-containing mol­ecules and pharmaceutical agents (Calleja et al., 2015 ▸). While mono-amine PdII complexes are generally unstable and are formed as inter­mediates during the reaction, the corresponding bis­(amine) PdII complex is stable and ultimately hampers the utility of these compounds in the C—H activation reaction. Probably because of this, well-characterized mono-amine PdII complexes are relatively rare. In this article we report a well-characterized and room-temperature-stable mono-amine PdII complex.

Structural commentary

In the Schiff base ligand HL1 used [HL 1 = (E)-1-(thio­phen-2-yl)-N-(p-tol­yl)methanimine and L 2 = p-toluidine], we expected that the ortho proton of the tolyl ring of HL 1 could be acidic and thus could be employed for a metallation reaction. Ding and coworkers (Ding et al., 1992 ▸) have reported a series of mercuration reactions on similar Schiff base ligands through electrophilic substitution reactions. On the basis of these observations, we also envisaged that a palladation reaction should take place at the ortho position of the tolyl ring in the Schiff base ligand. To investigate this C—H activation step, we attempted to prepare the complex PdL 1 L 2Cl. However, when we treated 2-thio­phene­carboxaldehyde with two equivalents of p-toluidine in the presence of Na2PdCl4 in ethanol solvent at 343 K, none of the expected palladated mol­ecules, PdL 1Cl or PdL 1 L 2Cl were observed, and instead we directly isolated the corresponding mono-amine PdII complex Pd(HL 1)L 2Cl2,1, as red needles in good yield along with a small amount of a yellow solid. The isolated solid was not soluble in common organic solvents. The filtrate of the reaction mixture was allowed to evaporate at room temperature and afforded red needles of a mono-amine PdII complex. In the FTIR spectra, the C=N stretching frequency in the Pd complex shifts to lower values (1611 cm−1) with somewhat weaker intensity in comparison to those of the corresponding free ligand (1615 cm−1). Two singlets were also observed at 3777 and 3696 cm−1 for the asymmetric and symmetric N—H stretching frequencies, respectively, in the Pd complex. Both frequencies shift to longer wavelengths with weaker intensity in comparison to free p-toluidine (3421 and 3338 cm−1 for N—H) as a result of the presence of strong N—H⋯Cl hydrogen-bonding inter­actions. This observation was further supported by single-crystal X-ray studies.

Not only does this result contrast with those found for other Schiff base compounds (Dubey et al., 2019 ▸), which readily form a stable palladated complex, but this reaction is also a relatively rare example of a mono-amine PdII complex. A search of the Cambridge Structural Database (CSD, version 5.43, update of November 2021; Groom et al., 2016 ▸) for structures containing a Pd(NH2-phenyl derivative)Cl2 fragment gave 51 hits, of which 30 were bis­(amine)PdCl2 moieties and among these was the complex Pd(p-toluidine)2Cl2 (YOYWOB; Tay, 2019 ▸) which is relevant for comparison with the title compound. Of the remaining 21, 11 contained the NH2 group as part of a chelate ring and only 10 contained a monodentate mono-amine PdCl2 complex (BOCTIX, Hadzovic et al., 2008 ▸; HIPDEP, Vicente et al., 1998 ▸; KASNAU, Asma et al., 2005 ▸; OCATEV, OCATIZ, Xia et al., 2021 ▸; OCEPOE, Asma & Kaminsky, 2017 ▸; XEKFEZ, Randell et al., 2006 ▸; XIYLOG, Liu et al., 2002 ▸; XORVIM, Hu et al., 2019 ▸; and YELMOS, Asma et al., 2006 ▸). One of these structures (HIPDEP; Vicente et al., 1998 ▸) is particularly relevant as it contains an sp C donor attached to a PdCl2(o-toluidine) fragment where the major difference with the present structure is the substitution of the sp C for sp N.

An ORTEP view of the mol­ecular structure of Pd(HL 1)L 2Cl2, 1, is shown in Fig. 1 ▸ and selected bond lengths and bond angles are given in Table 1 ▸. This mono-amine PdII complex crystallizes in the triclinic space group, P . The primary geometry around the PdII atom closely resembles square planar (τ4′ = 0.069, where 0 = square planar and 1 = tetra­hedral; Okuniewski et al., 2015 ▸). In the (E)-1-(thio­phen-2-yl)-N-(p-tol­yl)methanimine ligand, the phenyl and thio­phene rings are not coplanar because of the steric clash of the hydrogen atoms attached to C5 and C7, exhibiting a dihedral angle of 38.5 (1)°. In addition, the coordination plane (Pd1, Cl1, Cl2, N1, and N2) is almost perpendicular to both the planes of the coordinated o-toluidine ring and the C5, C6, N1 fragment [dihedral angles of 84.7 (1) and 72.50 (4)°, respectively]. A search of the CSD (Groom et al., 2016 ▸) for structures containing a Pd(NH2-phenyl derivative)Cl2 fragment contained 90 observations of the Pd—NH2 bond with a mean value of 2.065 (35) Å and minimum and maximum values of 2.028 Å (Baldovino-Pantaleón et al., 2007 ▸) and 2.171 Å (Asma et al., 2005 ▸), respectively. Thus, the length of 2.040 (2) Å in the title compound is slightly shorter than the observed mean value.

Figure 1

Mol­ecular structure of Pd(HL 1)L 2Cl2 showing the atom-numbering scheme. Atomic displacement parameters are at the 30% probability level.

Table 1

Selected geometric parameters (Å, °)

Pd1—N1	2.015 (2)	Pd1—Cl2	2.3082 (7)
Pd1—N2	2.040 (2)	S1—C1	1.702 (3)
Pd1—Cl1	2.3067 (7)	S1—C4	1.721 (3)
N1—Pd1—N2	176.02 (9)	N2—Pd1—Cl2	91.00 (7)
N1—Pd1—Cl1	90.55 (6)	Cl1—Pd1—Cl2	174.53 (2)
N2—Pd1—Cl1	86.64 (7)	C1—S1—C4	91.29 (14)
N1—Pd1—Cl2	92.04 (6)

A related structure (HIPDEP; Vicente et al., 1998 ▸) contains an sp C donor attached to a PdCl2(o-toluidine) fragment where the major differences with the present structure are the substitution of the sp C atom for sp N, and the fact that there are cis Cl donors, which leads to a substantial trans effect involving the Pd—Cl distances. In this structure, the Pd—NH2 distance is 2.076 (2) Å. The other related structure (Tay, 2019 ▸) is trans-Pd(o-toluidine)2Cl2 in which the Pd—NH2 distance is 2.050 (3) Å.

Supra­molecular features

The mol­ecules display an inter­esting supra­molecular synthon in the crystal. This synthon is based on reciprocal inter­molecular N—H⋯Cl hydrogen-bonding inter­actions (Table 2 ▸) of the p-toluidine amine fragment and results in centrosymmetric dimeric units (Fig. 2 ▸). These units are further linked by inter­molecular C—H⋯Cl inter­actions, resulting in chains in the c-axis direction where the mean-planes of the repeating fragment are oriented in the (110) plane.

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N2⋯Cl2i	0.85 (2)	2.45 (2)	3.273 (2)	163 (2)
C2—H2A⋯Cl1ii	0.95	2.97	3.779 (3)	144
C5—H5A⋯Cl1iii	0.95	2.98	3.759 (3)	140
C7—H7A⋯Cl1iii	0.95	2.80	3.629 (3)	147
C11—H11A⋯Cl2	0.95	2.96	3.711 (3)	137

Symmetry codes: (i) ; (ii) ; (iii) .

Figure 2

Packing diagram for Pd(HL 1)L 2Cl2 showing the inter­molecular N—H⋯Cl hydrogen-bonding inter­actions of the p-toluidine amine fragment resulting in centrosymmetric dimeric units that are further linked by inter­molecular C—H⋯Cl inter­actions, resulting in chains in the c-axis direction where the mean planes of the repeating fragment are oriented in the (110) plane.

Synthesis and crystallization

A solution of 2-thio­phene­carboxaldehyde (0.50 ml, 5 mmol) and 2 equivalent of p-toluidine (1.07 g, 10 mmol) in 20 ml of freshly distilled ethanol was allowed to stir at room temperature for 1 h. Then Na2PdCl4 (1.47 g, 10 mmol) was added. The reaction mixture was refluxed under stirring at 343 K for 2 h. A small amount of yellow solid gradually separated during the reaction. After stirring for 3 h the solid was filtered off and the filtrate underwent slow evaporation at room temperature to give red needles of (p-CH3C6H4NH2)SbHPdCl2; yield: 0.80 g, 33%, m.p. 533 K. FT–IR (KBr disk, cm−1): 3777 (NH), 3696 (NH), 3406, 2921, 2857, 1611 (CH=N), 1384, 1056, 754. Analysis calculated for C19H20N2Cl2PdS: C, 46.98; H, 4.15; N, 5.77. Found: C, 47.10; H, 4.30; N, 6.00%.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3 ▸. All hydrogen atoms were fixed geometrically with their U iso values set to 1.2 times that of the phenyl carbons and 1.5 times that of the methyl group. The hydrogen atoms attached to nitro­gen were refined isotropically.

Table 3

Experimental details

Crystal data
Chemical formula	[PdCl2(C7H9N)(C12H11NS)]
M r	485.73
Crystal system, space group	Triclinic, P
Temperature (K)	100
a, b, c (Å)	9.2135 (4), 9.4060 (4), 12.9032 (5)
α, β, γ (°)	79.866 (2), 70.000 (2), 67.753 (2)
V (Å3)	971.17 (7)
Z	2
Radiation type	Mo Kα
μ (mm−1)	1.34
Crystal size (mm)	0.21 × 0.16 × 0.10
Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 ▸)
T min, T max	0.622, 0.747
No. of measured, independent and observed [I > 2σ(I)] reflections	22977, 7379, 5166
R int	0.074
(sin θ/λ)max (Å−1)	0.771
Refinement
R[F 2 > 2σ(F 2)], wR(F 2), S	0.045, 0.090, 1.04
No. of reflections	7379
No. of parameters	236
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å−3)	0.75, −1.05

Computer programs: APEX2 (Bruker, 2005 ▸), SAINT (Bruker, 2002 ▸), SHELXT (Sheldrick, 2015a ▸), SHELXL2018/3 (Sheldrick, 2015b ▸) and SHELXTL (Sheldrick, 2008 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022004960/tx2049sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989022004960/tx2049Isup2.hkl

CCDC reference: 2171669

Additional supporting information: crystallographic information; 3D view; checkCIF report

[PdCl2(C7H9N)(C12H11NS)]	Z = 2
Mr = 485.73	F(000) = 488
Triclinic, P1	Dx = 1.661 Mg m−3
a = 9.2135 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.4060 (4) Å	Cell parameters from 7754 reflections
c = 12.9032 (5) Å	θ = 2.6–31.6°
α = 79.866 (2)°	µ = 1.34 mm−1
β = 70.000 (2)°	T = 100 K
γ = 67.753 (2)°	Prism, red-orange
V = 971.17 (7) Å3	0.21 × 0.16 × 0.10 mm

Bruker APEXII CCD diffractometer	5166 reflections with I > 2σ(I)
φ and ω scans	Rint = 0.074
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	θmax = 33.2°, θmin = 2.6°
Tmin = 0.622, Tmax = 0.747	h = −14→14
22977 measured reflections	k = −14→14
7379 independent reflections	l = −19→19

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: mixed
wR(F2) = 0.090	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0211P)2 + 0.1526P] where P = (Fo2 + 2Fc2)/3
7379 reflections	(Δ/σ)max = 0.001
236 parameters	Δρmax = 0.75 e Å−3
3 restraints	Δρmin = −1.04 e Å−3

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.

	x	y	z	Uiso*/Ueq
Pd1	0.53572 (2)	0.53405 (2)	0.70240 (2)	0.01680 (6)
Cl1	0.33922 (8)	0.70208 (8)	0.83363 (6)	0.02463 (14)
Cl2	0.71210 (8)	0.36598 (7)	0.56567 (5)	0.02350 (14)
S1	0.85995 (9)	0.55990 (9)	0.70536 (6)	0.02886 (16)
N1	0.6002 (3)	0.3778 (2)	0.82190 (18)	0.0176 (4)
N2	0.4704 (3)	0.7036 (3)	0.5873 (2)	0.0220 (5)
H2N1	0.377 (3)	0.770 (3)	0.622 (2)	0.032 (9)*
H2N2	0.444 (3)	0.674 (3)	0.5400 (19)	0.028 (9)*
C1	1.0173 (4)	0.5879 (3)	0.7297 (3)	0.0305 (7)
H1A	1.076419	0.650381	0.682505	0.037*
C2	1.0496 (3)	0.5118 (3)	0.8234 (3)	0.0298 (7)
H2A	1.133321	0.516183	0.848589	0.036*
C3	0.9467 (3)	0.4256 (3)	0.8798 (2)	0.0198 (5)
H3A	0.952608	0.364962	0.946424	0.024*
C4	0.8334 (3)	0.4419 (3)	0.8232 (2)	0.0197 (5)
C5	0.7160 (3)	0.3650 (3)	0.8615 (2)	0.0198 (5)
H5A	0.724011	0.295542	0.924122	0.024*
C6	0.4938 (3)	0.2900 (3)	0.8769 (2)	0.0192 (5)
C7	0.4335 (3)	0.2799 (3)	0.9911 (2)	0.0227 (6)
H7A	0.463677	0.329462	1.034377	0.027*
C8	0.3296 (3)	0.1977 (3)	1.0415 (2)	0.0238 (6)
H8A	0.288941	0.191174	1.119823	0.029*
C9	0.2829 (3)	0.1243 (3)	0.9811 (2)	0.0225 (6)
C10	0.3476 (3)	0.1323 (3)	0.8664 (2)	0.0258 (6)
H10A	0.320210	0.079781	0.823403	0.031*
C11	0.4510 (3)	0.2156 (3)	0.8141 (2)	0.0240 (6)
H11A	0.492453	0.221808	0.735826	0.029*
C12	0.1631 (3)	0.0410 (3)	1.0382 (3)	0.0301 (7)
H12A	0.190105	−0.017694	1.103815	0.045*
H12B	0.169958	−0.029332	0.987540	0.045*
H12C	0.051154	0.115955	1.060209	0.045*
C13	0.5932 (3)	0.7750 (3)	0.5331 (2)	0.0198 (5)
C14	0.6077 (3)	0.8804 (3)	0.5877 (2)	0.0223 (6)
H14A	0.539342	0.903607	0.661152	0.027*
C15	0.7222 (3)	0.9519 (3)	0.5351 (2)	0.0240 (6)
H15A	0.731007	1.025059	0.572709	0.029*
C16	0.8240 (3)	0.9187 (3)	0.4286 (2)	0.0257 (6)
C17	0.8092 (4)	0.8100 (3)	0.3760 (2)	0.0287 (6)
H17A	0.878381	0.785164	0.303024	0.034*
C18	0.6952 (3)	0.7373 (3)	0.4283 (2)	0.0253 (6)
H18A	0.687823	0.661983	0.391948	0.030*
C19	0.9476 (4)	0.9977 (4)	0.3690 (3)	0.0348 (7)
H19A	0.938923	1.073179	0.416289	0.052*
H19B	0.925215	1.050022	0.300474	0.052*
H19C	1.058806	0.921028	0.351413	0.052*

	U11	U22	U33	U12	U13	U23
Pd1	0.01898 (10)	0.01641 (10)	0.01739 (10)	−0.00721 (7)	−0.00816 (8)	0.00119 (7)
Cl1	0.0253 (3)	0.0249 (3)	0.0226 (3)	−0.0071 (3)	−0.0069 (3)	−0.0032 (3)
Cl2	0.0275 (3)	0.0217 (3)	0.0215 (3)	−0.0066 (3)	−0.0086 (3)	−0.0033 (2)
S1	0.0309 (4)	0.0297 (4)	0.0300 (4)	−0.0159 (3)	−0.0113 (3)	0.0054 (3)
N1	0.0217 (11)	0.0162 (10)	0.0173 (11)	−0.0082 (9)	−0.0082 (9)	0.0017 (8)
N2	0.0245 (12)	0.0213 (12)	0.0232 (13)	−0.0078 (10)	−0.0127 (11)	0.0022 (9)
C1	0.0253 (15)	0.0279 (15)	0.0389 (18)	−0.0150 (12)	−0.0021 (14)	−0.0050 (13)
C2	0.0245 (15)	0.0322 (16)	0.0368 (18)	−0.0118 (12)	−0.0078 (14)	−0.0103 (13)
C3	0.0145 (12)	0.0182 (12)	0.0269 (14)	−0.0071 (10)	−0.0031 (11)	−0.0047 (10)
C4	0.0219 (13)	0.0195 (12)	0.0178 (13)	−0.0081 (10)	−0.0056 (11)	0.0005 (10)
C5	0.0224 (13)	0.0167 (12)	0.0198 (13)	−0.0055 (10)	−0.0075 (11)	−0.0003 (10)
C6	0.0196 (13)	0.0165 (12)	0.0222 (14)	−0.0061 (10)	−0.0089 (11)	0.0022 (10)
C7	0.0232 (14)	0.0246 (14)	0.0227 (14)	−0.0104 (11)	−0.0066 (12)	−0.0026 (11)
C8	0.0229 (14)	0.0250 (14)	0.0215 (14)	−0.0082 (11)	−0.0035 (12)	−0.0024 (11)
C9	0.0189 (13)	0.0171 (12)	0.0296 (15)	−0.0052 (10)	−0.0069 (12)	0.0002 (11)
C10	0.0300 (15)	0.0237 (14)	0.0287 (16)	−0.0128 (12)	−0.0105 (13)	−0.0021 (11)
C11	0.0280 (15)	0.0282 (14)	0.0194 (14)	−0.0127 (12)	−0.0092 (12)	0.0007 (11)
C12	0.0258 (15)	0.0242 (14)	0.0398 (18)	−0.0128 (12)	−0.0059 (14)	0.0010 (13)
C13	0.0224 (13)	0.0169 (12)	0.0200 (13)	−0.0059 (10)	−0.0096 (11)	0.0034 (10)
C14	0.0253 (14)	0.0191 (13)	0.0202 (14)	−0.0061 (11)	−0.0068 (12)	0.0013 (10)
C15	0.0293 (15)	0.0194 (13)	0.0265 (15)	−0.0089 (11)	−0.0127 (13)	0.0011 (11)
C16	0.0211 (13)	0.0239 (14)	0.0301 (16)	−0.0059 (11)	−0.0118 (13)	0.0075 (11)
C17	0.0262 (15)	0.0281 (15)	0.0234 (15)	−0.0030 (12)	−0.0036 (13)	−0.0030 (12)
C18	0.0314 (15)	0.0232 (14)	0.0210 (14)	−0.0081 (12)	−0.0080 (13)	−0.0029 (11)
C19	0.0290 (16)	0.0328 (17)	0.0409 (19)	−0.0140 (13)	−0.0093 (15)	0.0073 (14)

Pd1—N1	2.015 (2)	C8—H8A	0.9500
Pd1—N2	2.040 (2)	C9—C10	1.394 (4)
Pd1—Cl1	2.3067 (7)	C9—C12	1.507 (4)
Pd1—Cl2	2.3082 (7)	C10—C11	1.384 (4)
S1—C1	1.702 (3)	C10—H10A	0.9500
S1—C4	1.721 (3)	C11—H11A	0.9500
N1—C5	1.291 (3)	C12—H12A	0.9800
N1—C6	1.442 (3)	C12—H12B	0.9800
N2—C13	1.446 (3)	C12—H12C	0.9800
N2—H2N1	0.868 (16)	C13—C18	1.372 (4)
N2—H2N2	0.848 (16)	C13—C14	1.382 (4)
C1—C2	1.358 (4)	C14—C15	1.383 (4)
C1—H1A	0.9500	C14—H14A	0.9500
C2—C3	1.410 (4)	C15—C16	1.384 (4)
C2—H2A	0.9500	C15—H15A	0.9500
C3—C4	1.417 (4)	C16—C17	1.392 (4)
C3—H3A	0.9500	C16—C19	1.509 (4)
C4—C5	1.429 (3)	C17—C18	1.386 (4)
C5—H5A	0.9500	C17—H17A	0.9500
C6—C7	1.386 (4)	C18—H18A	0.9500
C6—C11	1.388 (4)	C19—H19A	0.9800
C7—C8	1.376 (4)	C19—H19B	0.9800
C7—H7A	0.9500	C19—H19C	0.9800
C8—C9	1.383 (4)
N1—Pd1—N2	176.02 (9)	C8—C9—C10	118.0 (2)
N1—Pd1—Cl1	90.55 (6)	C8—C9—C12	120.7 (3)
N2—Pd1—Cl1	86.64 (7)	C10—C9—C12	121.3 (3)
N1—Pd1—Cl2	92.04 (6)	C11—C10—C9	121.1 (3)
N2—Pd1—Cl2	91.00 (7)	C11—C10—H10A	119.5
Cl1—Pd1—Cl2	174.53 (2)	C9—C10—H10A	119.5
C1—S1—C4	91.29 (14)	C10—C11—C6	119.6 (3)
C5—N1—C6	118.0 (2)	C10—C11—H11A	120.2
C5—N1—Pd1	124.71 (18)	C6—C11—H11A	120.2
C6—N1—Pd1	116.66 (15)	C9—C12—H12A	109.5
C13—N2—Pd1	113.09 (16)	C9—C12—H12B	109.5
C13—N2—H2N1	112 (2)	H12A—C12—H12B	109.5
Pd1—N2—H2N1	106 (2)	C9—C12—H12C	109.5
C13—N2—H2N2	110 (2)	H12A—C12—H12C	109.5
Pd1—N2—H2N2	113 (2)	H12B—C12—H12C	109.5
H2N1—N2—H2N2	102 (2)	C18—C13—C14	120.4 (3)
C2—C1—S1	113.1 (2)	C18—C13—N2	120.1 (2)
C2—C1—H1A	123.4	C14—C13—N2	119.5 (2)
S1—C1—H1A	123.4	C13—C14—C15	119.7 (3)
C1—C2—C3	113.4 (3)	C13—C14—H14A	120.1
C1—C2—H2A	123.3	C15—C14—H14A	120.1
C3—C2—H2A	123.3	C14—C15—C16	121.1 (3)
C2—C3—C4	110.5 (2)	C14—C15—H15A	119.4
C2—C3—H3A	124.7	C16—C15—H15A	119.4
C4—C3—H3A	124.7	C15—C16—C17	118.1 (3)
C3—C4—C5	122.3 (2)	C15—C16—C19	121.9 (3)
C3—C4—S1	111.66 (19)	C17—C16—C19	120.0 (3)
C5—C4—S1	126.0 (2)	C18—C17—C16	121.2 (3)
N1—C5—C4	128.2 (2)	C18—C17—H17A	119.4
N1—C5—H5A	115.9	C16—C17—H17A	119.4
C4—C5—H5A	115.9	C13—C18—C17	119.5 (3)
C7—C6—C11	119.9 (2)	C13—C18—H18A	120.3
C7—C6—N1	120.8 (2)	C17—C18—H18A	120.3
C11—C6—N1	119.3 (2)	C16—C19—H19A	109.5
C8—C7—C6	119.6 (3)	C16—C19—H19B	109.5
C8—C7—H7A	120.2	H19A—C19—H19B	109.5
C6—C7—H7A	120.2	C16—C19—H19C	109.5
C7—C8—C9	121.8 (3)	H19A—C19—H19C	109.5
C7—C8—H8A	119.1	H19B—C19—H19C	109.5
C9—C8—H8A	119.1
C4—S1—C1—C2	−0.2 (3)	C7—C8—C9—C12	−177.2 (2)
S1—C1—C2—C3	0.4 (3)	C8—C9—C10—C11	−2.2 (4)
C1—C2—C3—C4	−0.4 (3)	C12—C9—C10—C11	176.6 (3)
C2—C3—C4—C5	179.1 (2)	C9—C10—C11—C6	1.2 (4)
C2—C3—C4—S1	0.3 (3)	C7—C6—C11—C10	0.3 (4)
C1—S1—C4—C3	−0.1 (2)	N1—C6—C11—C10	−179.4 (2)
C1—S1—C4—C5	−178.9 (3)	Pd1—N2—C13—C18	102.6 (2)
C6—N1—C5—C4	−178.6 (2)	Pd1—N2—C13—C14	−76.9 (3)
Pd1—N1—C5—C4	−7.9 (4)	C18—C13—C14—C15	2.1 (4)
C3—C4—C5—N1	175.2 (3)	N2—C13—C14—C15	−178.3 (2)
S1—C4—C5—N1	−6.2 (4)	C13—C14—C15—C16	−0.6 (4)
C5—N1—C6—C7	43.1 (3)	C14—C15—C16—C17	−0.6 (4)
Pd1—N1—C6—C7	−128.3 (2)	C14—C15—C16—C19	178.9 (2)
C5—N1—C6—C11	−137.2 (3)	C15—C16—C17—C18	0.3 (4)
Pd1—N1—C6—C11	51.4 (3)	C19—C16—C17—C18	−179.1 (3)
C11—C6—C7—C8	−0.9 (4)	C14—C13—C18—C17	−2.4 (4)
N1—C6—C7—C8	178.8 (2)	N2—C13—C18—C17	178.1 (2)
C6—C7—C8—C9	−0.1 (4)	C16—C17—C18—C13	1.1 (4)
C7—C8—C9—C10	1.6 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N2···Cl2i	0.85 (2)	2.45 (2)	3.273 (2)	163 (2)
C2—H2A···Cl1ii	0.95	2.97	3.779 (3)	144
C5—H5A···Cl1iii	0.95	2.98	3.759 (3)	140
C7—H7A···Cl1iii	0.95	2.80	3.629 (3)	147
C11—H11A···Cl2	0.95	2.96	3.711 (3)	137