Chlorido{N-[2-(diphenylphosphanyl)benz­ylidene]-2-(2-thienyl)ethanamine-κ2N,P}methylpalladium(II) dichloromethane hemisolvate

Onani, M.O.; Motswainyana, W.M.; Iwuoha, E.I.; Darkwa, J.; Lalancette, R.A.

doi:10.1107/S1600536810017824

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page m688

https://doi.org/10.1107/S1600536810017824

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Chlorido{N-[2-(diphenylphosphanyl)benzylidene]-2-(2-thienyl)ethanamine-κ²N,P}methylpalladium(II) dichloromethane hemisolvate

Martin O. Onani,^a ^* William M. Motswainyana,^a Emmanuel I. Iwuoha,^a James Darkwa ^b and Roger A. Lalancette ^c

^aUniversity of the Western Cape, Cape Town, Bellville 7535, South Africa, ^bUniversity of Johannesburg, Auckland Park Kingsway Campus, Johannesburg 2006, South Africa, and ^cDepartment of Chemistry, Rutgers State University, 73 Warren St, Newark, NJ 07102, USA
^*Correspondence e-mail: monani@uwc.ac.za

(Received 26 April 2010; accepted 14 May 2010; online 22 May 2010)

In the title compound, [Pd(CH₃)Cl(C₂₅H₂₂NPS)]·0.5C₂H₂Cl₂, the Pd^II atom is coordinated by the N,P-bidentate ligand, a methyl group and a chloride ion, generating a distorted square-planar PdCClNS coordination geometry, with the N and Cl atoms trans. The thiophene ring is equally disordered over two orientations and the dichloromethane solvent molecule is disordered about an inversion centre.

Related literature

For metal-organic compounds with ligands containing both pyridyl and phosphine donor groups and for typical Pd—C, Pd—Cl, Pd—P and Pd—N bond lengths, see: Shaffer & Schmidt (2009 ). For the properties of related compounds, see: Tongwa et al. (2009 ); Jun-Gill et al. (2009 ).

Experimental

Crystal data

[Pd(CH₃)Cl(C₂₅H₂₂NPS)]·0.5C₂H₂Cl₂
M_r = 598.81
Monoclinic, P 2₁ /n
a = 9.9960 (6) Å
b = 18.6584 (11) Å
c = 13.8167 (8) Å
β = 94.517 (1)°
V = 2568.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.09 mm⁻¹
T = 173 K
0.16 × 0.15 × 0.14 mm

Data collection

Bruker Kappa DUO APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ) T_min = 0.683, T_max = 0.746
31867 measured reflections
6376 independent reflections
5600 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.074
S = 1.03
6376 reflections
321 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 1.34 e Å⁻³
Δρ_min = −1.04 e Å⁻³

Table 1
Selected bond lengths (Å)

Pd1—C1	2.045 (2)
Pd1—N1	2.158 (2)
Pd1—P1	2.2039 (6)
Pd1—Cl1	2.3628 (6)

Data collection: SMART (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810017824/hb5421sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810017824/hb5421Isup2.hkl

checkCIF report

Comment top

The stucture of the title compound, (I), is shown below. Dimensions are available in the archived CIF. The solvent molecule dichloromethane exhibits high thermal motions and were refined isotropically with temperature factors in the range of 0.101 – 0.122. It is situated close to a centre of inversion. The five-membered ring was disordered and shows two orientations each at 50% s.o.f.: the first ring C7, C8A, C9A, C10A and S1A (ring A) and the second ring C7, C8B, C9B, C10B and S1B (ring B). Ring A and ring B share two common atom sites at C7 and C10A (or C10B). C10A and C10B are on the same site and refined anisotropically with the same temperature factors. The maximum and minimum deviations from the least-squares planes of both rings are 0.086 (4) Å and -0.084 (3) Å for C7 and S1A in ring A, 0.095 (5) Å and -0.090 (3) Å for C7 and S1B in ring B. Angle from the least-square plane of ring A to that of ring B is 36.2 (3)°.

Related literature top

For metal-organic compounds with ligands containing both pyridyl and phosphine donor groups and for typical Pd—C, Pd—Cl, Pd—P and Pd—N bond distances, see: Shaffer & Schmidt (2009). For the properties of related compounds, see: Tongwa et al. (2009); Jun-Gill et al. (2009).

Experimental top

The iminophosphine heterocyclic ligand was prepared via the condensation reaction of 2-(diphenylphosphino)benzaldehyde with 2-thien-2-ylethanamine. The ligand was further refluxed with an equimolar Pd(cod)Cl₂ in dichloromethane and gave over 80% yield of a yellow complex. Light-yellow blocks of (I) were grown via slow diffusion of a dichloromethane solution of the complex in hexane a 4

Structure description top

The following shortfalls have been scrutinized and corrected. 1. ABSTRACT usually does not contain the description of synthesis and crystal preparation, which should be included in _publ_section_exptl_prep section. ABSTRACT should not contain the space group. true

2. _publ_section_exptl_prep section is missing.included

3. _publ_section_exptl_refinement section is missing, in which the treatment of H atoms should be given. rectified

4. _publ_section_figure_captions is missing. Avaialable

5. The solvent molecule in Scheme1 is incorrectly shown. rectified

6. References to published work must be cited in the correct format detailed in Notes for authors. sorted

7. Fig. 2 should show the cell-axis directions (labelled a, b, c) and the cell origin (labelled O). rectified

8. In CIF, the software for data collection is SAINT, and that for cell refinement and data reduction is DENZO-SMN; is it right?

SAINT

Computing details top

Data collection: SMART (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. : The molecular structure of (I) showing 30% displacement ellipsoids (all hydrogen atoms omitted for clarity). The solvent dichloromethane molecule is excluded.

Chlorido{N-[2-(diphenylphosphanyl)benzylidene]-2-(2-thienyl)ethanamine- κ²N,P}methylpalladium(II) dichloromethane hemisolvate top

Crystal data top

[Pd(CH₃)Cl(C₂₅H₂₂NPS)]·0.5C₂H₂Cl₂	F(000) = 1212
M_r = 598.81	D_x = 1.548 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 31867 reflections
a = 9.9960 (6) Å	θ = 2.2–28.3°
b = 18.6584 (11) Å	µ = 1.09 mm⁻¹
c = 13.8167 (8) Å	T = 173 K
β = 94.517 (1)°	Needle, light-yellow
V = 2568.9 (3) Å³	0.16 × 0.15 × 0.14 mm
Z = 4

Data collection top

Bruker Kappa DUO APEXII CCD diffractometer	6376 independent reflections
Radiation source: fine-focus sealed tube	5600 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
0.5° φ scans and ω scans	θ_max = 28.3°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −13→13
T_min = 0.683, T_max = 0.746	k = −24→24
31867 measured reflections	l = −18→18

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0301P)² + 3.2924P] where P = (F_o² + 2F_c²)/3
6376 reflections	(Δ/σ)_max = 0.002
321 parameters	Δρ_max = 1.34 e Å⁻³
2 restraints	Δρ_min = −1.04 e Å⁻³

Crystal data top

[Pd(CH₃)Cl(C₂₅H₂₂NPS)]·0.5C₂H₂Cl₂	V = 2568.9 (3) Å³
M_r = 598.81	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.9960 (6) Å	µ = 1.09 mm⁻¹
b = 18.6584 (11) Å	T = 173 K
c = 13.8167 (8) Å	0.16 × 0.15 × 0.14 mm
β = 94.517 (1)°

Data collection top

Bruker Kappa DUO APEXII CCD diffractometer	6376 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	5600 reflections with I > 2σ(I)
T_min = 0.683, T_max = 0.746	R_int = 0.028
31867 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	2 restraints
wR(F²) = 0.074	H-atom parameters constrained
S = 1.03	Δρ_max = 1.34 e Å⁻³
6376 reflections	Δρ_min = −1.04 e Å⁻³
321 parameters

Special details top

Experimental. Half sphere of data collected using SAINT strategy (Bruker, 2006). Crystal to detector distance = 50 mm; combination of φ and ω scans of 0.5°, 50 s per °, 2 iterations.

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.

Refinement. The solvent molecule dichloromethane exhibits high thermal motions and were refined isotropically with temperature factors in the range of 0.101 C 0.122. It is modelled as a whole molecule with 50% s.o.f. The 5 member ring was disordered and shows two preferred orientations each at 50% s.o.f. All hydrogen atoms were positioned geometrically with C—H = 0.95 C 0.99 A and refined as riding on their parent atoms with Uiso (H) = 1.2 - 1.5 Ueq (C). 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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Pd1	0.636610 (16)	0.296906 (8)	0.583217 (12)	0.02079 (5)
Cl1	0.51346 (6)	0.20048 (3)	0.64253 (6)	0.03899 (15)
Cl2A	1.0260 (4)	0.55967 (18)	1.0814 (2)	0.1066 (9)*	0.50
Cl2B	0.9080 (4)	0.4537 (2)	0.9486 (3)	0.1223 (11)*	0.50
S1A	0.3721 (8)	0.3256 (4)	0.9098 (5)	0.0464 (12)	0.50
S1B	0.3499 (8)	0.3404 (4)	0.8969 (6)	0.0443 (12)	0.50
P1	0.76594 (5)	0.38331 (3)	0.53464 (4)	0.01817 (11)
N1	0.7551 (2)	0.30566 (11)	0.72019 (14)	0.0289 (4)
C1	0.5273 (2)	0.28695 (14)	0.45247 (18)	0.0316 (5)
H1A	0.5795	0.2602	0.4074	0.047*
H1B	0.5062	0.3347	0.4259	0.047*
H1C	0.4438	0.2612	0.4615	0.047*
C2	0.9364 (2)	0.34988 (11)	0.56117 (16)	0.0214 (4)
C3	0.9725 (2)	0.31802 (13)	0.65212 (17)	0.0268 (5)
C4	0.8828 (3)	0.31090 (14)	0.73071 (18)	0.0315 (5)
H4	0.9235	0.3101	0.7952	0.038*
C5	0.6819 (3)	0.30364 (16)	0.80910 (18)	0.0374 (6)
H5A	0.7465	0.3037	0.8672	0.045*
H5B	0.6275	0.2594	0.8100	0.045*
C6	0.5910 (3)	0.36912 (17)	0.81044 (19)	0.0402 (6)
H6A	0.6467	0.4130	0.8089	0.048*
H6B	0.5284	0.3689	0.7513	0.048*
C7	0.5115 (3)	0.37153 (19)	0.8982 (2)	0.0455 (7)
C8A	0.5216 (8)	0.4289 (5)	0.9701 (5)	0.0549 (18)	0.50
H8A	0.5839	0.4674	0.9708	0.066*	0.50
C8B	0.5611 (7)	0.3773 (5)	0.9925 (5)	0.059 (2)	0.50
H8B	0.6537	0.3845	1.0113	0.070*	0.50
C9A	0.4239 (8)	0.4189 (5)	1.0396 (5)	0.0569 (19)	0.50
H9A	0.4164	0.4492	1.0942	0.068*	0.50
C9B	0.4608 (7)	0.3717 (5)	1.0608 (4)	0.0522 (17)	0.50
H9B	0.4791	0.3767	1.1290	0.063*	0.50
C10A	0.3397 (3)	0.35877 (19)	1.0181 (2)	0.0497 (8)	0.50
H10A	0.2753	0.3403	1.0586	0.060*	0.50
C10B	0.3397 (3)	0.35877 (19)	1.0181 (2)	0.0497 (8)	0.50
H10B	0.2589	0.3595	1.0499	0.060*	0.50
C11	1.0318 (2)	0.35515 (12)	0.49348 (17)	0.0263 (5)
H11	1.0084	0.3770	0.4324	0.032*
C12	1.1615 (2)	0.32884 (14)	0.5141 (2)	0.0323 (5)
H12	1.2250	0.3320	0.4666	0.039*
C13	1.1980 (3)	0.29822 (14)	0.6033 (2)	0.0380 (6)
H13	1.2863	0.2803	0.6175	0.046*
C14	1.1042 (3)	0.29394 (14)	0.6720 (2)	0.0358 (6)
H14	1.1301	0.2742	0.7340	0.043*
C15	0.7553 (2)	0.46247 (11)	0.61019 (15)	0.0195 (4)
C16	0.8684 (2)	0.49563 (12)	0.65553 (16)	0.0250 (4)
H16	0.9552	0.4770	0.6473	0.030*
C17	0.8542 (3)	0.55604 (13)	0.71283 (17)	0.0306 (5)
H17	0.9313	0.5782	0.7444	0.037*
C18	0.7276 (3)	0.58398 (13)	0.72402 (17)	0.0309 (5)
H18	0.7185	0.6258	0.7621	0.037*
C19	0.6147 (3)	0.55098 (13)	0.67984 (17)	0.0300 (5)
H19	0.5281	0.5699	0.6883	0.036*
C20	0.6280 (2)	0.49029 (12)	0.62321 (16)	0.0249 (4)
H20	0.5504	0.4676	0.5932	0.030*
C21	0.7591 (2)	0.41830 (11)	0.41116 (15)	0.0203 (4)
C22	0.7452 (2)	0.49174 (12)	0.39294 (16)	0.0243 (4)
H22	0.7424	0.5244	0.4455	0.029*
C23	0.7355 (3)	0.51719 (13)	0.29770 (17)	0.0312 (5)
H23	0.7263	0.5671	0.2856	0.037*
C24	0.7393 (3)	0.46996 (15)	0.22089 (17)	0.0328 (5)
H24	0.7310	0.4874	0.1561	0.039*
C25	0.7550 (3)	0.39725 (15)	0.23840 (17)	0.0320 (5)
H25	0.7593	0.3650	0.1855	0.038*
C26	0.7644 (2)	0.37123 (13)	0.33299 (17)	0.0268 (5)
H26	0.7744	0.3212	0.3445	0.032*
C27	0.9815 (11)	0.5338 (5)	0.9658 (6)	0.101 (3)*	0.50
H27A	0.9199	0.5705	0.9358	0.121*	0.50
H27B	1.0632	0.5342	0.9297	0.121*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.01711 (8)	0.01957 (8)	0.02575 (9)	0.00040 (6)	0.00207 (6)	0.00374 (6)
Cl1	0.0251 (3)	0.0310 (3)	0.0611 (4)	−0.0026 (2)	0.0048 (3)	0.0200 (3)
S1A	0.058 (3)	0.0360 (18)	0.048 (3)	−0.0159 (16)	0.022 (2)	−0.0098 (16)
S1B	0.0410 (17)	0.061 (4)	0.0305 (10)	−0.0139 (19)	0.0016 (10)	0.0018 (19)
P1	0.0166 (2)	0.0187 (2)	0.0192 (2)	0.00054 (19)	0.00097 (18)	0.00085 (19)
N1	0.0272 (10)	0.0343 (11)	0.0252 (10)	0.0028 (8)	0.0030 (8)	0.0106 (8)
C1	0.0256 (11)	0.0375 (13)	0.0310 (12)	−0.0099 (10)	−0.0026 (9)	−0.0016 (10)
C2	0.0186 (9)	0.0199 (9)	0.0257 (10)	0.0007 (8)	0.0004 (8)	−0.0008 (8)
C3	0.0216 (11)	0.0281 (11)	0.0303 (12)	0.0032 (9)	−0.0013 (9)	0.0041 (9)
C4	0.0290 (12)	0.0395 (13)	0.0254 (11)	0.0054 (10)	−0.0024 (9)	0.0104 (10)
C5	0.0343 (13)	0.0532 (16)	0.0253 (12)	0.0016 (12)	0.0052 (10)	0.0140 (11)
C6	0.0427 (15)	0.0537 (17)	0.0254 (12)	0.0045 (13)	0.0099 (11)	0.0064 (11)
C7	0.0359 (14)	0.074 (2)	0.0269 (13)	−0.0073 (14)	0.0076 (11)	−0.0028 (13)
C8A	0.054 (4)	0.072 (5)	0.042 (4)	−0.028 (4)	0.018 (3)	−0.014 (3)
C8B	0.032 (3)	0.114 (7)	0.031 (3)	−0.017 (4)	0.010 (2)	−0.018 (4)
C9A	0.065 (5)	0.075 (5)	0.034 (3)	−0.019 (4)	0.022 (3)	−0.016 (3)
C9B	0.045 (4)	0.089 (6)	0.024 (3)	−0.014 (4)	0.010 (2)	−0.010 (3)
C10A	0.0469 (17)	0.067 (2)	0.0378 (15)	−0.0110 (15)	0.0179 (13)	−0.0025 (14)
C10B	0.0469 (17)	0.067 (2)	0.0378 (15)	−0.0110 (15)	0.0179 (13)	−0.0025 (14)
C11	0.0225 (11)	0.0270 (11)	0.0295 (11)	0.0006 (9)	0.0025 (9)	−0.0015 (9)
C12	0.0209 (11)	0.0333 (12)	0.0434 (14)	0.0029 (9)	0.0072 (10)	−0.0065 (11)
C13	0.0214 (11)	0.0363 (13)	0.0559 (17)	0.0080 (10)	−0.0001 (11)	0.0021 (12)
C14	0.0263 (12)	0.0386 (14)	0.0413 (14)	0.0075 (10)	−0.0057 (10)	0.0095 (11)
C15	0.0212 (10)	0.0198 (9)	0.0178 (9)	−0.0001 (8)	0.0030 (7)	0.0008 (7)
C16	0.0220 (10)	0.0264 (11)	0.0265 (11)	−0.0005 (8)	0.0025 (8)	−0.0032 (9)
C17	0.0325 (12)	0.0308 (12)	0.0285 (12)	−0.0069 (10)	0.0022 (9)	−0.0070 (9)
C18	0.0439 (14)	0.0256 (11)	0.0246 (11)	−0.0011 (10)	0.0107 (10)	−0.0051 (9)
C19	0.0307 (12)	0.0294 (11)	0.0310 (12)	0.0074 (10)	0.0097 (10)	−0.0001 (9)
C20	0.0211 (10)	0.0277 (11)	0.0261 (11)	0.0021 (8)	0.0029 (8)	0.0011 (9)
C21	0.0165 (9)	0.0240 (10)	0.0204 (10)	0.0002 (8)	0.0012 (7)	0.0012 (8)
C22	0.0262 (11)	0.0237 (10)	0.0228 (10)	−0.0029 (8)	0.0009 (8)	0.0007 (8)
C23	0.0344 (13)	0.0294 (12)	0.0295 (12)	−0.0015 (10)	0.0008 (10)	0.0079 (9)
C24	0.0313 (12)	0.0450 (14)	0.0224 (11)	0.0006 (11)	0.0041 (9)	0.0051 (10)
C25	0.0310 (12)	0.0434 (14)	0.0219 (11)	0.0052 (11)	0.0032 (9)	−0.0050 (10)
C26	0.0258 (11)	0.0279 (11)	0.0267 (11)	0.0052 (9)	0.0027 (9)	−0.0022 (9)

Geometric parameters (Å, º) top

Pd1—C1	2.045 (2)	C9A—H9A	0.9500
Pd1—N1	2.158 (2)	C9B—H9B	0.9500
Pd1—P1	2.2039 (6)	C10A—H10A	0.9500
Pd1—Cl1	2.3628 (6)	C11—C12	1.394 (3)
Cl2A—C27	1.695 (7)	C11—H11	0.9500
Cl2B—C27	1.673 (8)	C12—C13	1.381 (4)
S1A—C7	1.655 (9)	C12—H12	0.9500
S1A—C10A	1.673 (9)	C13—C14	1.388 (4)
S1B—C7	1.715 (9)	C13—H13	0.9500
P1—C15	1.817 (2)	C14—H14	0.9500
P1—C21	1.823 (2)	C15—C16	1.394 (3)
P1—C2	1.825 (2)	C15—C20	1.398 (3)
N1—C4	1.278 (3)	C16—C17	1.391 (3)
N1—C5	1.479 (3)	C16—H16	0.9500
C1—H1A	0.9800	C17—C18	1.388 (4)
C1—H1B	0.9800	C17—H17	0.9500
C1—H1C	0.9800	C18—C19	1.384 (4)
C2—C11	1.391 (3)	C18—H18	0.9500
C2—C3	1.411 (3)	C19—C20	1.389 (3)
C3—C14	1.397 (3)	C19—H19	0.9500
C3—C4	1.467 (3)	C20—H20	0.9500
C4—H4	0.9500	C21—C26	1.396 (3)
C5—C6	1.523 (4)	C21—C22	1.398 (3)
C5—H5A	0.9900	C22—C23	1.395 (3)
C5—H5B	0.9900	C22—H22	0.9500
C6—C7	1.502 (4)	C23—C24	1.382 (4)
C6—H6A	0.9900	C23—H23	0.9500
C6—H6B	0.9900	C24—C25	1.385 (4)
C7—C8B	1.362 (7)	C24—H24	0.9500
C7—C8A	1.459 (8)	C25—C26	1.390 (3)
C8A—C9A	1.434 (9)	C25—H25	0.9500
C8A—H8A	0.9500	C26—H26	0.9500
C8B—C9B	1.434 (8)	C27—H27A	0.9900
C8B—H8B	0.9500	C27—H27B	0.9900
C9A—C10A	1.420 (8)

C1—Pd1—N1	178.73 (9)	C10A—C9A—H9A	123.7
C1—Pd1—P1	94.76 (7)	C8A—C9A—H9A	123.7
N1—Pd1—P1	85.25 (6)	C8B—C9B—H9B	123.8
C1—Pd1—Cl1	88.88 (7)	C9A—C10A—S1A	109.1 (4)
N1—Pd1—Cl1	91.05 (6)	C9A—C10A—H10A	125.5
P1—Pd1—Cl1	175.36 (2)	S1A—C10A—H10A	125.5
C7—S1A—C10A	96.8 (4)	C2—C11—C12	120.9 (2)
C15—P1—C21	104.30 (10)	C2—C11—H11	119.6
C15—P1—C2	104.99 (10)	C12—C11—H11	119.6
C21—P1—C2	106.03 (10)	C13—C12—C11	120.3 (2)
C15—P1—Pd1	110.94 (7)	C13—C12—H12	119.9
C21—P1—Pd1	124.56 (7)	C11—C12—H12	119.9
C2—P1—Pd1	104.47 (7)	C12—C13—C14	119.3 (2)
C4—N1—C5	117.6 (2)	C12—C13—H13	120.4
C4—N1—Pd1	125.45 (17)	C14—C13—H13	120.4
C5—N1—Pd1	116.96 (16)	C13—C14—C3	121.6 (2)
Pd1—C1—H1A	109.5	C13—C14—H14	119.2
Pd1—C1—H1B	109.5	C3—C14—H14	119.2
H1A—C1—H1B	109.5	C16—C15—C20	119.4 (2)
Pd1—C1—H1C	109.5	C16—C15—P1	122.46 (16)
H1A—C1—H1C	109.5	C20—C15—P1	118.09 (16)
H1B—C1—H1C	109.5	C17—C16—C15	120.0 (2)
C11—C2—C3	119.2 (2)	C17—C16—H16	120.0
C11—C2—P1	121.32 (17)	C15—C16—H16	120.0
C3—C2—P1	119.46 (17)	C18—C17—C16	120.2 (2)
C14—C3—C2	118.7 (2)	C18—C17—H17	119.9
C14—C3—C4	116.5 (2)	C16—C17—H17	119.9
C2—C3—C4	124.7 (2)	C19—C18—C17	120.2 (2)
N1—C4—C3	125.9 (2)	C19—C18—H18	119.9
N1—C4—H4	117.1	C17—C18—H18	119.9
C3—C4—H4	117.1	C18—C19—C20	120.0 (2)
N1—C5—C6	108.9 (2)	C18—C19—H19	120.0
N1—C5—H5A	109.9	C20—C19—H19	120.0
C6—C5—H5A	109.9	C19—C20—C15	120.2 (2)
N1—C5—H5B	109.9	C19—C20—H20	119.9
C6—C5—H5B	109.9	C15—C20—H20	119.9
H5A—C5—H5B	108.3	C26—C21—C22	119.1 (2)
C7—C6—C5	112.8 (2)	C26—C21—P1	119.85 (17)
C7—C6—H6A	109.0	C22—C21—P1	121.03 (16)
C5—C6—H6A	109.0	C23—C22—C21	120.1 (2)
C7—C6—H6B	109.0	C23—C22—H22	119.9
C5—C6—H6B	109.0	C21—C22—H22	119.9
H6A—C6—H6B	107.8	C24—C23—C22	120.2 (2)
C8B—C7—C8A	44.7 (4)	C24—C23—H23	119.9
C8B—C7—C6	126.8 (4)	C22—C23—H23	119.9
C8A—C7—C6	124.0 (4)	C23—C24—C25	120.0 (2)
C8B—C7—S1A	101.2 (4)	C23—C24—H24	120.0
C8A—C7—S1A	109.1 (4)	C25—C24—H24	120.0
C6—C7—S1A	124.5 (4)	C24—C25—C26	120.3 (2)
C8B—C7—S1B	108.0 (4)	C24—C25—H25	119.8
C8A—C7—S1B	105.6 (4)	C26—C25—H25	119.8
C6—C7—S1B	122.7 (4)	C25—C26—C21	120.2 (2)
S1A—C7—S1B	13.1 (3)	C25—C26—H26	119.9
C9A—C8A—C7	110.3 (6)	C21—C26—H26	119.9
C9A—C8A—H8A	124.8	Cl2B—C27—Cl2A	117.9 (6)
C7—C8A—H8A	124.8	Cl2B—C27—H27A	107.8
C7—C8B—C9B	113.8 (5)	Cl2A—C27—H27A	107.8
C7—C8B—H8B	123.1	Cl2B—C27—H27B	107.8
C9B—C8B—H8B	123.1	Cl2A—C27—H27B	107.8
C10A—C9A—C8A	112.7 (6)	H27A—C27—H27B	107.2

C1—Pd1—P1—C15	122.52 (11)	S1B—C7—C8A—C9A	24.7 (8)
N1—Pd1—P1—C15	−58.75 (9)	C8A—C7—C8B—C9B	81.6 (9)
Cl1—Pd1—P1—C15	−96.0 (3)	C6—C7—C8B—C9B	−174.7 (6)
C1—Pd1—P1—C21	−3.25 (11)	S1A—C7—C8B—C9B	−24.3 (9)
N1—Pd1—P1—C21	175.47 (10)	S1B—C7—C8B—C9B	−12.7 (10)
Cl1—Pd1—P1—C21	138.3 (3)	C7—C8A—C9A—C10A	−2.9 (10)
C1—Pd1—P1—C2	−124.85 (11)	C8A—C9A—C10A—S1A	−6.9 (9)
N1—Pd1—P1—C2	53.87 (9)	C7—S1A—C10A—C9A	12.1 (6)
Cl1—Pd1—P1—C2	16.7 (3)	C3—C2—C11—C12	0.6 (3)
C1—Pd1—N1—C4	46 (4)	P1—C2—C11—C12	−179.39 (18)
P1—Pd1—N1—C4	−44.6 (2)	C2—C11—C12—C13	−1.2 (4)
Cl1—Pd1—N1—C4	132.6 (2)	C11—C12—C13—C14	0.0 (4)
C1—Pd1—N1—C5	−133 (4)	C12—C13—C14—C3	1.9 (4)
P1—Pd1—N1—C5	136.99 (18)	C2—C3—C14—C13	−2.5 (4)
Cl1—Pd1—N1—C5	−45.81 (17)	C4—C3—C14—C13	−179.8 (2)
C15—P1—C2—C11	−109.01 (19)	C21—P1—C15—C16	−96.92 (19)
C21—P1—C2—C11	1.0 (2)	C2—P1—C15—C16	14.4 (2)
Pd1—P1—C2—C11	134.17 (17)	Pd1—P1—C15—C16	126.67 (17)
C15—P1—C2—C3	70.99 (19)	C21—P1—C15—C20	83.53 (18)
C21—P1—C2—C3	−178.95 (18)	C2—P1—C15—C20	−165.18 (17)
Pd1—P1—C2—C3	−45.83 (19)	Pd1—P1—C15—C20	−52.88 (18)
C11—C2—C3—C14	1.2 (3)	C20—C15—C16—C17	−0.3 (3)
P1—C2—C3—C14	−178.79 (19)	P1—C15—C16—C17	−179.81 (18)
C11—C2—C3—C4	178.3 (2)	C15—C16—C17—C18	−0.8 (4)
P1—C2—C3—C4	−1.7 (3)	C16—C17—C18—C19	1.3 (4)
C5—N1—C4—C3	−176.1 (2)	C17—C18—C19—C20	−0.8 (4)
Pd1—N1—C4—C3	5.4 (4)	C18—C19—C20—C15	−0.3 (4)
C14—C3—C4—N1	−154.4 (3)	C16—C15—C20—C19	0.8 (3)
C2—C3—C4—N1	28.5 (4)	P1—C15—C20—C19	−179.61 (17)
C4—N1—C5—C6	116.9 (3)	C15—P1—C21—C26	−179.72 (17)
Pd1—N1—C5—C6	−64.6 (3)	C2—P1—C21—C26	69.74 (19)
N1—C5—C6—C7	179.6 (2)	Pd1—P1—C21—C26	−51.2 (2)
C5—C6—C7—C8B	63.5 (7)	C15—P1—C21—C22	−1.3 (2)
C5—C6—C7—C8A	119.0 (5)	C2—P1—C21—C22	−111.86 (18)
C5—C6—C7—S1A	−80.4 (4)	Pd1—P1—C21—C22	127.25 (16)
C5—C6—C7—S1B	−96.0 (4)	C26—C21—C22—C23	0.6 (3)
C10A—S1A—C7—C8B	32.0 (5)	P1—C21—C22—C23	−177.78 (18)
C10A—S1A—C7—C8A	−13.7 (5)	C21—C22—C23—C24	0.1 (4)
C10A—S1A—C7—C6	−176.8 (3)	C22—C23—C24—C25	−1.1 (4)
C10A—S1A—C7—S1B	−90 (3)	C23—C24—C25—C26	1.3 (4)
C8B—C7—C8A—C9A	−75.3 (8)	C24—C25—C26—C21	−0.5 (4)
C6—C7—C8A—C9A	174.6 (6)	C22—C21—C26—C25	−0.5 (3)
S1A—C7—C8A—C9A	11.4 (8)	P1—C21—C26—C25	177.97 (18)

Experimental details

Crystal data
Chemical formula	[Pd(CH₃)Cl(C₂₅H₂₂NPS)]·0.5C₂H₂Cl₂
M_r	598.81
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	9.9960 (6), 18.6584 (11), 13.8167 (8)
β (°)	94.517 (1)
V (Å³)	2568.9 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.09
Crystal size (mm)	0.16 × 0.15 × 0.14

Data collection
Diffractometer	Bruker Kappa DUO APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2006)
T_min, T_max	0.683, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	31867, 6376, 5600
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.029, 0.074, 1.03
No. of reflections	6376
No. of parameters	321
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.34, −1.04

Computer programs: SMART (Bruker, 2006), SAINT (Bruker, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001).

Selected bond lengths (Å) top

Pd1—C1	2.045 (2)	Pd1—P1	2.2039 (6)
Pd1—N1	2.158 (2)	Pd1—Cl1	2.3628 (6)

Acknowledgements

We acknowledge the University of the Western Cape and the Ministry of Health of Botswana (WMM) for funding.

References

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