Chloro­(pyrimidine-2-thiol­ato-κ2N,S)(triphenyl­phosphine-κP)palladium(II) methanol hemisolvate

Shaheen, F.; Najam-Ul-Haq, M.; Badshah, A.; Wurst, K.; Ali, S.

doi:10.1107/S1600536805041681

Chloro(pyrimidine-2-thiolato-κ²N,S)(triphenylphosphine-κP)palladium(II) methanol hemisolvate

F. Shaheen, M. Najam-Ul-Haq, A. Badshah, K. Wurst and S. Ali

In the title compound, [Pd(C₄H₃N₂S)Cl(C₁₈H₁₅P)]·0.5CH₃OH, the Pd atom is four-coordinate and exhibits a slightly distorted square-planar geometry with the S atom of the pyrimidine-2-thiolate ligand trans to the chloro ligand and the coordinated N atom trans to the phosphine. The compound crystallizes with two unique molecules and a disordered methanol solvent molecule in the asymmetric unit.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805041681/sj6164sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805041681/sj6164Isup2.hkl Contains datablock I

CCDC reference: 296654

checkCIF report

Key indicators

Single-crystal X-ray study
T = 233 K
Mean (C-C) = 0.004 Å
H-atom completeness 91%
Disorder in solvent or counterion
R factor = 0.033
wR factor = 0.074
Data-to-parameter ratio = 18.4

checkCIF/PLATON results

No syntax errors found



Alert level B
ABSTM02_ALERT_3_B  The ratio of Tmax/Tmin expected RT(exp) is > 1.20
            Absorption corrections should be applied.
            Tmin and Tmax expected:      0.717     0.913
            RT(exp) =      1.274
PLAT057_ALERT_3_B Correction for Absorption Required   RT(exp) ...       1.27

Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.96
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings    Differ ....          ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............       0.50 Ratio
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)...          ?
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       2.57 Ratio
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      33.00 Perc.
PLAT430_ALERT_2_C Short Inter D...A Contact  O1A    ..  O1A     ..       2.88 Ang.

Alert level G
FORMU01_ALERT_2_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and the formula from the _atom_site* data.
            Atom count from _chemical_formula_sum:C22.5 H20 Cl1 N2 O0.5 P1 Pd1 S
            Atom count from the _atom_site data:  C22.5 H18 Cl1 N2 O0.5 P1 Pd1 S
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
           From the CIF: _cell_formula_units_Z    8
           From the CIF: _chemical_formula_sum  C22.50 H20 Cl N2 O0.50 P Pd S
           TEST: Compare cell contents of formula and atom_site data

           atom    Z*formula  cif sites diff
           C        180.00    180.00    0.00
           H        160.00    144.00   16.00
           Cl         8.00      8.00    0.00
           N         16.00     16.00    0.00
           O          4.00      4.00    0.00
           P          8.00      8.00    0.00
           Pd         8.00      8.00    0.00
           S          8.00      8.00    0.00

   0 ALERT level A = In general: serious problem
   2 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   6 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

Palladium(II) complexes with heterocylic thione ligands are of current interest for the synthesis of clinically useful drugs (Raper et al., 1985). The crystal structures of four-coordinate palladium(II) complexes with N– and S-donor hetrocyclic 2-thionate ligands, such as Pd₂[2-Me₂NCH₂C₆H₄]₂(µ-OH)(µ-Br) (Ruiz et al., 1996) and (2-benzolpyridinethiosemicarbazone)palladium(II) have been extensively investigated (Rebolledo et al., 2005). The title compound, (I), exhibits antibacterial and antitumor activity (Krischner et al., 1966) due to the N—C—S group generated by deprotonation of the hetrocyclic thione (Santana et al., 2000). It has also been used as a pesticide (Fackler, 2002) and an antimicrobial agent (Ronconi et al.; 2005).

In the title compound, each Pd atom of the two unique molecules in the asymmetric unit is four coordinate and exhibits a slightly distorted square-planar geometry (Fig. 1). The two molecules are similar except for the conformational orientation of the triphenylphosphine ligand, shown by the torsion angles S1—Pd1—P1—C5 [5.4 (1)°] and S2—Pd2—P2—C27 [−19.9 (1)°]. The pyrimidine-2-thiolate ligand acts as a bidentate chelate, coordinating to Pd via the S1 atom and the adjacent pyrimidine N1 atom. Atom S1 is trans to the chloride anion and N1 is trans to the triphenylphosphine ligand (Table 1). The slightly distorted square-planar geometry of the Pd atoms is also revealed by the displacements of the Pd atoms from the mean plane through the ligand donor atoms of 0.0876 (7) Å for Pd1 and 0.0893 (6) Å for Pd2. These deviations may be related to weak intermolecular interactions between Pd1 and N3 [3.660 (2) Å], and between Pd2 and S1 [3.9498 (9) Å].

Experimental top

Pyrimidine-2-thione (0.16 g, 1.14 mmol) dissolved in CH₂Cl₂ (10 ml) was added dropwise to a suspension of [PdCl₂(PPh₃)] (0.5 g, 1.14 mmol) (Kitano et al., 1983) in CH₂Cl₂ (20 ml). The resulting solution was refluxed for 2–3 h and a clear solution was obtained. Yellow crystals were obtained by slow evaporation of the solvent at room temperature.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXL97.

Figures top

Fig. 1. The structures of of the two unique molecules of (I), showing the atom-numbering scheme. Displacement elipsoids are drawn at the 50% probability level

Chloro(pyrimidine-2-thiolato-κ²N,S)(triphenylphosphine-κP)palladium(II) methanol solvate top

Crystal data top

[Pd(C₄H₃N₂S)Cl(C₁₈H₁₅P)]·0.5CH₄O	F(000) = 2136
M_r = 531.29	D_x = 1.591 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 398 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 16.1340 (2) Å	Cell parameters from 26420 reflections
b = 9.7020 (1) Å	θ = 1.0–27.5°
c = 29.0480 (4) Å	µ = 1.14 mm⁻¹
β = 102.617 (1)°	T = 233 K
V = 4437.14 (10) Å³	Prism, yellow
Z = 8	0.35 × 0.25 × 0.08 mm

Data collection top

Nonius KappaCCD diffractometer	8231 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.033
Graphite monochromator	θ_max = 27.5°, θ_min = 2.1°
ϕ and ω scans	h = −20→20
26420 measured reflections	k = −12→12
9812 independent reflections	l = −37→36

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.074	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0217P)² + 4.762P] where P = (F_o² + 2F_c²)/3
9812 reflections	(Δ/σ)_max = 0.002
532 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.63 e Å⁻³

Crystal data top

[Pd(C₄H₃N₂S)Cl(C₁₈H₁₅P)]·0.5CH₄O	V = 4437.14 (10) Å³
M_r = 531.29	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 16.1340 (2) Å	µ = 1.14 mm⁻¹
b = 9.7020 (1) Å	T = 233 K
c = 29.0480 (4) Å	0.35 × 0.25 × 0.08 mm
β = 102.617 (1)°

Data collection top

Nonius KappaCCD diffractometer	8231 reflections with I > 2σ(I)
26420 measured reflections	R_int = 0.033
9812 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	0 restraints
wR(F²) = 0.074	H-atom parameters constrained
S = 1.03	Δρ_max = 0.39 e Å⁻³
9812 reflections	Δρ_min = −0.63 e Å⁻³
532 parameters

Special details top

Experimental. The data set was not corrected for absorption. A number of redundant reflections were measured. Using these additional scans, a ϕ scan-like absorption correction will be achieved by the normal scaling process. Such a data set has a similar quality as corrected data based on procedures described by Blessing (1995).

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.

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Pd1	0.240964 (11)	0.66465 (2)	0.398828 (7)	0.03162 (6)
Pd2	0.199587 (12)	0.83808 (2)	0.246817 (7)	0.03306 (6)
S1	0.31967 (4)	0.58844 (8)	0.34683 (3)	0.04655 (18)
S2	0.10400 (4)	0.65839 (8)	0.24137 (3)	0.04725 (18)
P1	0.33454 (4)	0.82233 (7)	0.43539 (2)	0.03084 (14)
P2	0.25733 (4)	0.79040 (7)	0.18507 (2)	0.03063 (14)
Cl1	0.14491 (5)	0.68449 (9)	0.44749 (3)	0.0582 (2)
Cl2	0.27507 (5)	1.04153 (7)	0.26184 (3)	0.04819 (17)
N1	0.17786 (13)	0.5047 (2)	0.35862 (8)	0.0359 (5)
N2	0.22709 (15)	0.3745 (2)	0.30065 (9)	0.0441 (6)
N3	0.12661 (15)	0.8617 (3)	0.29720 (8)	0.0430 (6)
N4	0.00779 (16)	0.7263 (3)	0.30479 (12)	0.0673 (8)
C1	0.23438 (16)	0.4739 (3)	0.33231 (10)	0.0374 (6)
C2	0.10702 (17)	0.4311 (3)	0.35238 (11)	0.0450 (7)
H2	0.0667	0.4496	0.3705	0.054*
C3	0.09274 (19)	0.3273 (3)	0.31920 (12)	0.0519 (8)
H3	0.0425	0.2749	0.3138	0.062*
C4	0.15472 (19)	0.3032 (3)	0.29433 (11)	0.0489 (7)
H4	0.1456	0.2326	0.2716	0.059*
C5	0.42434 (16)	0.8379 (2)	0.40719 (9)	0.0340 (5)
C6	0.40771 (17)	0.8749 (3)	0.35961 (10)	0.0400 (6)
H6	0.3521	0.8983	0.3441	0.048*
C7	0.4722 (2)	0.8775 (3)	0.33511 (11)	0.0490 (7)
H7	0.4604	0.9033	0.3031	0.059*
C8	0.5531 (2)	0.8426 (3)	0.35745 (13)	0.0559 (9)
H8	0.5967	0.8425	0.3406	0.067*
C9	0.57100 (18)	0.8072 (3)	0.40484 (13)	0.0536 (8)
H9	0.6269	0.7846	0.4201	0.064*
C10	0.50693 (17)	0.8050 (3)	0.42981 (11)	0.0410 (6)
H10	0.5194	0.7813	0.4620	0.049*
C11	0.29712 (17)	0.9976 (3)	0.44036 (9)	0.0371 (6)
C12	0.3377 (2)	1.1097 (3)	0.42695 (14)	0.0606 (9)
H12	0.3853	1.0965	0.4137	0.073*
C13	0.3095 (3)	1.2425 (3)	0.43262 (15)	0.0720 (11)
H13	0.3386	1.3182	0.4236	0.086*
C14	0.2403 (2)	1.2640 (3)	0.45110 (13)	0.0622 (9)
H14	0.2212	1.3540	0.4549	0.075*
C15	0.1988 (3)	1.1532 (4)	0.46412 (16)	0.0740 (11)
H15	0.1507	1.1674	0.4768	0.089*
C16	0.2264 (2)	1.0204 (3)	0.45894 (14)	0.0613 (9)
H16	0.1969	0.9452	0.4681	0.074*
C17	0.38092 (15)	0.7669 (3)	0.49519 (9)	0.0325 (5)
C18	0.40159 (19)	0.8585 (3)	0.53233 (10)	0.0445 (7)
H18	0.3871	0.9521	0.5276	0.053*
C19	0.4437 (2)	0.8127 (4)	0.57652 (11)	0.0535 (8)
H19	0.4574	0.8753	0.6018	0.064*
C20	0.4653 (2)	0.6773 (4)	0.58341 (11)	0.0545 (8)
H20	0.4948	0.6471	0.6132	0.065*
C21	0.4441 (2)	0.5849 (3)	0.54702 (12)	0.0537 (8)
H21	0.4587	0.4915	0.5521	0.064*
C22	0.40118 (19)	0.6287 (3)	0.50283 (10)	0.0430 (6)
H22	0.3859	0.5648	0.4781	0.052*
C23	0.07384 (17)	0.7542 (3)	0.28565 (11)	0.0461 (7)
C24	0.1146 (2)	0.9486 (4)	0.33024 (11)	0.0575 (8)
H24	0.1516	1.0237	0.3388	0.069*
C25	0.0481 (3)	0.9292 (5)	0.35205 (13)	0.0720 (11)
H25	0.0381	0.9898	0.3755	0.086*
C26	−0.0030 (2)	0.8174 (5)	0.33807 (15)	0.0779 (13)
H26	−0.0489	0.8032	0.3527	0.094*
C27	0.24255 (15)	0.6118 (3)	0.16526 (10)	0.0355 (6)
C28	0.2221 (2)	0.5751 (3)	0.11794 (11)	0.0557 (8)
H28	0.2147	0.6433	0.0944	0.067*
C29	0.2125 (2)	0.4364 (4)	0.10564 (13)	0.0666 (10)
H29	0.1983	0.4113	0.0736	0.080*
C30	0.2235 (2)	0.3358 (3)	0.13968 (15)	0.0595 (9)
H30	0.2169	0.2426	0.1309	0.071*
C31	0.24404 (19)	0.3711 (3)	0.18638 (13)	0.0501 (8)
H31	0.2522	0.3021	0.2097	0.060*
C32	0.25279 (17)	0.5088 (3)	0.19923 (10)	0.0400 (6)
H32	0.2658	0.5327	0.2314	0.048*
C33	0.20889 (16)	0.8957 (3)	0.13472 (9)	0.0353 (6)
C34	0.24838 (18)	0.9160 (3)	0.09736 (10)	0.0480 (7)
H34	0.3028	0.8792	0.0988	0.058*
C35	0.2083 (2)	0.9901 (4)	0.05790 (11)	0.0577 (8)
H35	0.2354	1.0033	0.0327	0.069*
C36	0.1289 (2)	1.0442 (4)	0.05577 (11)	0.0567 (8)
H36	0.1012	1.0929	0.0288	0.068*
C37	0.08991 (19)	1.0274 (3)	0.09281 (12)	0.0544 (8)
H37	0.0360	1.0660	0.0913	0.065*
C38	0.12933 (17)	0.9540 (3)	0.13243 (10)	0.0439 (7)
H38	0.1023	0.9435	0.1578	0.053*
C39	0.37140 (15)	0.8203 (2)	0.19397 (8)	0.0302 (5)
C40	0.40287 (17)	0.9534 (3)	0.19145 (9)	0.0369 (6)
H40	0.3650	1.0279	0.1841	0.044*
C41	0.48946 (17)	0.9761 (3)	0.19975 (10)	0.0389 (6)
H41	0.5102	1.0660	0.1976	0.047*
C42	0.54576 (16)	0.8679 (3)	0.21116 (10)	0.0403 (6)
H42	0.6046	0.8840	0.2170	0.048*
C43	0.51539 (16)	0.7363 (3)	0.21387 (10)	0.0411 (6)
H43	0.5536	0.6624	0.2216	0.049*
C44	0.42877 (16)	0.7120 (3)	0.20532 (10)	0.0375 (6)
H44	0.4086	0.6217	0.2072	0.045*
O1	−0.0032 (5)	0.8323 (10)	0.4912 (4)	0.211 (4)	0.75
O1A	0.0008 (17)	0.934 (3)	0.5445 (14)	0.31 (2)	0.25
C45	0.0398 (7)	0.8312 (14)	0.5332 (4)	0.259 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Pd1	0.02951 (10)	0.03379 (11)	0.03160 (11)	−0.00387 (7)	0.00678 (7)	−0.00325 (8)
Pd2	0.03246 (10)	0.03445 (11)	0.03351 (11)	0.00380 (8)	0.00989 (8)	0.00369 (8)
S1	0.0391 (4)	0.0477 (4)	0.0578 (5)	−0.0126 (3)	0.0214 (3)	−0.0192 (4)
S2	0.0342 (3)	0.0464 (4)	0.0609 (5)	−0.0010 (3)	0.0097 (3)	0.0043 (4)
P1	0.0326 (3)	0.0305 (3)	0.0297 (3)	−0.0032 (3)	0.0074 (3)	−0.0026 (3)
P2	0.0285 (3)	0.0319 (3)	0.0316 (3)	0.0025 (2)	0.0069 (2)	0.0022 (3)
Cl1	0.0558 (4)	0.0709 (5)	0.0564 (5)	−0.0127 (4)	0.0308 (4)	−0.0112 (4)
Cl2	0.0544 (4)	0.0373 (4)	0.0571 (4)	−0.0035 (3)	0.0214 (3)	−0.0063 (3)
N1	0.0303 (11)	0.0389 (12)	0.0378 (12)	−0.0044 (9)	0.0061 (9)	−0.0048 (10)
N2	0.0465 (13)	0.0378 (13)	0.0482 (14)	−0.0028 (10)	0.0108 (11)	−0.0119 (11)
N3	0.0436 (13)	0.0498 (14)	0.0404 (13)	0.0118 (11)	0.0194 (11)	0.0098 (11)
N4	0.0399 (14)	0.088 (2)	0.080 (2)	0.0100 (14)	0.0264 (14)	0.0254 (18)
C1	0.0331 (13)	0.0353 (14)	0.0429 (15)	−0.0015 (11)	0.0065 (11)	−0.0018 (12)
C2	0.0315 (14)	0.0507 (17)	0.0524 (17)	−0.0076 (12)	0.0081 (12)	−0.0037 (15)
C3	0.0410 (16)	0.0479 (18)	0.063 (2)	−0.0124 (13)	0.0040 (14)	−0.0089 (16)
C4	0.0505 (17)	0.0385 (16)	0.0534 (19)	−0.0053 (13)	0.0020 (14)	−0.0092 (14)
C5	0.0390 (13)	0.0270 (12)	0.0375 (14)	−0.0069 (10)	0.0118 (11)	−0.0038 (11)
C6	0.0433 (15)	0.0387 (14)	0.0394 (15)	−0.0101 (12)	0.0122 (12)	−0.0009 (12)
C7	0.065 (2)	0.0427 (16)	0.0449 (17)	−0.0137 (14)	0.0249 (15)	−0.0017 (14)
C8	0.061 (2)	0.0495 (18)	0.070 (2)	−0.0061 (15)	0.0406 (18)	−0.0021 (17)
C9	0.0380 (16)	0.0508 (18)	0.075 (2)	−0.0002 (13)	0.0195 (15)	0.0055 (17)
C10	0.0357 (14)	0.0388 (15)	0.0495 (17)	−0.0041 (11)	0.0115 (12)	0.0002 (13)
C11	0.0415 (14)	0.0338 (14)	0.0353 (14)	0.0006 (11)	0.0071 (11)	−0.0013 (12)
C12	0.063 (2)	0.0357 (16)	0.090 (3)	0.0004 (14)	0.0323 (19)	0.0029 (17)
C13	0.091 (3)	0.0345 (17)	0.097 (3)	0.0035 (17)	0.034 (2)	0.0065 (19)
C14	0.089 (3)	0.0402 (18)	0.055 (2)	0.0181 (17)	0.0120 (18)	−0.0076 (16)
C15	0.080 (3)	0.060 (2)	0.093 (3)	0.0155 (19)	0.043 (2)	−0.012 (2)
C16	0.068 (2)	0.0443 (18)	0.082 (3)	0.0028 (16)	0.0389 (19)	−0.0043 (18)
C17	0.0305 (12)	0.0363 (14)	0.0315 (13)	−0.0053 (10)	0.0084 (10)	−0.0014 (11)
C18	0.0519 (17)	0.0434 (16)	0.0359 (15)	−0.0075 (13)	0.0045 (12)	−0.0024 (13)
C19	0.0606 (19)	0.064 (2)	0.0334 (16)	−0.0155 (16)	0.0056 (14)	−0.0044 (15)
C20	0.0497 (17)	0.079 (2)	0.0343 (16)	−0.0061 (16)	0.0084 (13)	0.0155 (16)
C21	0.0617 (19)	0.0511 (18)	0.0506 (19)	0.0103 (15)	0.0176 (15)	0.0190 (16)
C22	0.0515 (16)	0.0378 (15)	0.0412 (16)	0.0000 (12)	0.0133 (13)	−0.0003 (13)
C23	0.0344 (14)	0.0553 (18)	0.0494 (17)	0.0108 (13)	0.0107 (12)	0.0177 (15)
C24	0.070 (2)	0.062 (2)	0.0463 (18)	0.0176 (17)	0.0248 (16)	0.0086 (16)
C25	0.079 (3)	0.092 (3)	0.057 (2)	0.031 (2)	0.040 (2)	0.016 (2)
C26	0.054 (2)	0.117 (4)	0.074 (3)	0.029 (2)	0.039 (2)	0.033 (3)
C27	0.0282 (12)	0.0374 (14)	0.0405 (15)	0.0007 (10)	0.0067 (10)	−0.0036 (12)
C28	0.066 (2)	0.0540 (19)	0.0429 (17)	0.0018 (16)	0.0035 (15)	−0.0080 (16)
C29	0.074 (2)	0.064 (2)	0.057 (2)	−0.0027 (18)	0.0018 (17)	−0.0275 (19)
C30	0.0504 (18)	0.0431 (18)	0.087 (3)	−0.0072 (14)	0.0191 (17)	−0.0211 (19)
C31	0.0437 (16)	0.0377 (15)	0.073 (2)	−0.0027 (12)	0.0223 (15)	−0.0042 (16)
C32	0.0374 (14)	0.0340 (14)	0.0501 (17)	−0.0029 (11)	0.0127 (12)	−0.0028 (13)
C33	0.0325 (13)	0.0360 (14)	0.0360 (14)	0.0029 (10)	0.0045 (10)	0.0039 (12)
C34	0.0438 (16)	0.0603 (19)	0.0419 (16)	0.0119 (14)	0.0138 (13)	0.0095 (15)
C35	0.063 (2)	0.073 (2)	0.0389 (16)	0.0088 (17)	0.0150 (14)	0.0149 (17)
C36	0.059 (2)	0.063 (2)	0.0426 (17)	0.0089 (16)	0.0007 (14)	0.0175 (16)
C37	0.0393 (16)	0.062 (2)	0.060 (2)	0.0128 (14)	0.0072 (14)	0.0178 (17)
C38	0.0360 (14)	0.0499 (17)	0.0465 (16)	0.0057 (12)	0.0106 (12)	0.0104 (14)
C39	0.0290 (12)	0.0341 (13)	0.0279 (12)	0.0016 (10)	0.0067 (9)	0.0006 (10)
C40	0.0424 (14)	0.0308 (13)	0.0392 (15)	0.0032 (11)	0.0126 (11)	−0.0005 (12)
C41	0.0417 (14)	0.0394 (15)	0.0377 (15)	−0.0096 (12)	0.0135 (11)	−0.0041 (12)
C42	0.0296 (13)	0.0561 (17)	0.0347 (14)	−0.0051 (12)	0.0059 (10)	−0.0010 (13)
C43	0.0313 (13)	0.0453 (16)	0.0462 (16)	0.0061 (11)	0.0073 (11)	0.0082 (13)
C44	0.0371 (14)	0.0338 (13)	0.0412 (15)	0.0018 (11)	0.0077 (11)	0.0045 (12)
O1	0.115 (5)	0.258 (10)	0.263 (11)	0.002 (5)	0.049 (6)	−0.087 (8)
O1A	0.18 (2)	0.27 (3)	0.51 (6)	−0.02 (2)	0.15 (3)	−0.26 (4)
C45	0.164 (9)	0.344 (16)	0.224 (12)	0.086 (9)	−0.057 (8)	−0.138 (11)

Geometric parameters (Å, º) top

Pd1—N1	2.071 (2)	C16—H16	0.9400
Pd1—P1	2.2467 (7)	C17—C18	1.381 (4)
Pd1—S1	2.2975 (7)	C17—C22	1.387 (4)
Pd1—Cl1	2.3225 (8)	C18—C19	1.388 (4)
Pd1—N3	3.660 (2)	C18—H18	0.9400
Pd2—N3	2.082 (2)	C19—C20	1.363 (5)
Pd2—P2	2.2424 (7)	C19—H19	0.9400
Pd2—S2	2.3100 (7)	C20—C21	1.371 (5)
Pd2—Cl2	2.3104 (7)	C20—H20	0.9400
Pd2—S1	3.9498 (9)	C21—C22	1.385 (4)
S1—C1	1.747 (3)	C21—H21	0.9400
S2—C23	1.740 (3)	C22—H22	0.9400
P1—C17	1.816 (3)	C24—C25	1.374 (5)
P1—C5	1.820 (3)	C24—H24	0.9400
P1—C11	1.821 (3)	C25—C26	1.369 (6)
P2—C33	1.815 (3)	C25—H25	0.9400
P2—C39	1.825 (2)	C26—H26	0.9400
P2—C27	1.825 (3)	C27—C28	1.388 (4)
N1—C2	1.326 (3)	C27—C32	1.389 (4)
N1—C1	1.345 (3)	C28—C29	1.393 (5)
N2—C1	1.320 (3)	C28—H28	0.9400
N2—C4	1.335 (4)	C29—C30	1.373 (5)
N3—C24	1.323 (4)	C29—H29	0.9400
N3—C23	1.342 (4)	C30—C31	1.368 (5)
N4—C23	1.333 (4)	C30—H30	0.9400
N4—C26	1.349 (5)	C31—C32	1.386 (4)
C2—C3	1.378 (4)	C31—H31	0.9400
C2—H2	0.9400	C32—H32	0.9400
C3—C4	1.375 (5)	C33—C34	1.387 (4)
C3—H3	0.9400	C33—C38	1.391 (4)
C4—H4	0.9400	C34—C35	1.388 (4)
C5—C10	1.388 (4)	C34—H34	0.9400
C5—C6	1.396 (4)	C35—C36	1.373 (5)
C6—C7	1.383 (4)	C35—H35	0.9400
C6—H6	0.9400	C36—C37	1.369 (5)
C7—C8	1.367 (5)	C36—H36	0.9400
C7—H7	0.9400	C37—C38	1.384 (4)
C8—C9	1.387 (5)	C37—H37	0.9400
C8—H8	0.9400	C38—H38	0.9400
C9—C10	1.387 (4)	C39—C44	1.391 (3)
C9—H9	0.9400	C39—C40	1.396 (3)
C10—H10	0.9400	C40—C41	1.383 (4)
C11—C12	1.369 (4)	C40—H40	0.9400
C11—C16	1.383 (4)	C41—C42	1.381 (4)
C12—C13	1.388 (5)	C41—H41	0.9400
C12—H12	0.9400	C42—C43	1.376 (4)
C13—C14	1.356 (5)	C42—H42	0.9400
C13—H13	0.9400	C43—C44	1.385 (4)
C14—C15	1.363 (5)	C43—H43	0.9400
C14—H14	0.9400	C44—H44	0.9400
C15—C16	1.382 (5)	O1—C45	1.266 (12)
C15—H15	0.9400	O1A—C45	1.26 (2)

N1—Pd1—P1	166.81 (6)	C14—C15—H15	119.5
N1—Pd1—S1	70.26 (6)	C16—C15—H15	119.5
P1—Pd1—S1	96.84 (2)	C15—C16—C11	120.3 (3)
N1—Pd1—Cl1	95.41 (6)	C15—C16—H16	119.9
P1—Pd1—Cl1	97.16 (3)	C11—C16—H16	119.9
S1—Pd1—Cl1	164.78 (3)	C18—C17—C22	119.3 (3)
N1—Pd1—N3	80.66 (7)	C18—C17—P1	122.3 (2)
P1—Pd1—N3	101.18 (4)	C22—C17—P1	118.2 (2)
S1—Pd1—N3	83.77 (4)	C17—C18—C19	120.2 (3)
Cl1—Pd1—N3	99.31 (4)	C17—C18—H18	119.9
N3—Pd2—P2	169.30 (7)	C19—C18—H18	119.9
N3—Pd2—S2	70.10 (7)	C20—C19—C18	120.1 (3)
P2—Pd2—S2	100.22 (3)	C20—C19—H19	119.9
N3—Pd2—Cl2	97.40 (7)	C18—C19—H19	119.9
P2—Pd2—Cl2	91.91 (3)	C19—C20—C21	120.3 (3)
S2—Pd2—Cl2	166.96 (3)	C19—C20—H20	119.9
N3—Pd2—S1	79.19 (6)	C21—C20—H20	119.9
P2—Pd2—S1	103.83 (2)	C20—C21—C22	120.3 (3)
S2—Pd2—S1	78.49 (2)	C20—C21—H21	119.9
Cl2—Pd2—S1	103.38 (2)	C22—C21—H21	119.9
C1—S1—Pd1	81.03 (9)	C21—C22—C17	119.8 (3)
C1—S1—Pd2	88.77 (9)	C21—C22—H22	120.1
Pd1—S1—Pd2	91.92 (2)	C17—C22—H22	120.1
C23—S2—Pd2	80.59 (10)	N4—C23—N3	125.1 (3)
C17—P1—C5	104.65 (12)	N4—C23—S2	125.3 (3)
C17—P1—C11	105.99 (12)	N3—C23—S2	109.6 (2)
C5—P1—C11	105.58 (12)	N3—C24—C25	120.0 (4)
C17—P1—Pd1	110.14 (8)	N3—C24—H24	120.0
C5—P1—Pd1	111.26 (8)	C25—C24—H24	120.0
C11—P1—Pd1	118.24 (9)	C26—C25—C24	116.9 (4)
C33—P2—C39	105.56 (12)	C26—C25—H25	121.5
C33—P2—C27	106.07 (12)	C24—C25—H25	121.5
C39—P2—C27	104.69 (11)	N4—C26—C25	124.6 (3)
C33—P2—Pd2	110.32 (9)	N4—C26—H26	117.7
C39—P2—Pd2	115.87 (8)	C25—C26—H26	117.7
C27—P2—Pd2	113.55 (9)	C28—C27—C32	119.0 (3)
C2—N1—C1	118.3 (2)	C28—C27—P2	122.8 (2)
C2—N1—Pd1	141.6 (2)	C32—C27—P2	118.2 (2)
C1—N1—Pd1	100.12 (16)	C27—C28—C29	119.4 (3)
C1—N2—C4	114.6 (2)	C27—C28—H28	120.3
C24—N3—C23	119.4 (3)	C29—C28—H28	120.3
C24—N3—Pd2	140.8 (2)	C30—C29—C28	120.8 (3)
C23—N3—Pd2	99.43 (18)	C30—C29—H29	119.6
C24—N3—Pd1	82.85 (18)	C28—C29—H29	119.6
C23—N3—Pd1	88.62 (16)	C31—C30—C29	120.1 (3)
Pd2—N3—Pd1	104.27 (8)	C31—C30—H30	119.9
C23—N4—C26	113.9 (3)	C29—C30—H30	119.9
N2—C1—N1	126.1 (2)	C30—C31—C32	119.7 (3)
N2—C1—S1	125.3 (2)	C30—C31—H31	120.1
N1—C1—S1	108.54 (19)	C32—C31—H31	120.1
N1—C2—C3	119.8 (3)	C31—C32—C27	120.9 (3)
N1—C2—H2	120.1	C31—C32—H32	119.6
C3—C2—H2	120.1	C27—C32—H32	119.6
C4—C3—C2	117.5 (3)	C34—C33—C38	118.8 (2)
C4—C3—H3	121.2	C34—C33—P2	121.3 (2)
C2—C3—H3	121.2	C38—C33—P2	119.9 (2)
N2—C4—C3	123.6 (3)	C33—C34—C35	120.6 (3)
N2—C4—H4	118.2	C33—C34—H34	119.7
C3—C4—H4	118.2	C35—C34—H34	119.7
C10—C5—C6	119.0 (2)	C36—C35—C34	119.8 (3)
C10—C5—P1	123.0 (2)	C36—C35—H35	120.1
C6—C5—P1	117.9 (2)	C34—C35—H35	120.1
C7—C6—C5	120.7 (3)	C37—C36—C35	120.2 (3)
C7—C6—H6	119.7	C37—C36—H36	119.9
C5—C6—H6	119.7	C35—C36—H36	119.9
C8—C7—C6	119.9 (3)	C36—C37—C38	120.5 (3)
C8—C7—H7	120.0	C36—C37—H37	119.7
C6—C7—H7	120.0	C38—C37—H37	119.7
C7—C8—C9	120.2 (3)	C37—C38—C33	120.0 (3)
C7—C8—H8	119.9	C37—C38—H38	120.0
C9—C8—H8	119.9	C33—C38—H38	120.0
C8—C9—C10	120.4 (3)	C44—C39—C40	118.7 (2)
C8—C9—H9	119.8	C44—C39—P2	120.79 (19)
C10—C9—H9	119.8	C40—C39—P2	120.44 (18)
C9—C10—C5	119.8 (3)	C41—C40—C39	120.3 (2)
C9—C10—H10	120.1	C41—C40—H40	119.9
C5—C10—H10	120.1	C39—C40—H40	119.9
C12—C11—C16	118.1 (3)	C42—C41—C40	120.5 (2)
C12—C11—P1	122.1 (2)	C42—C41—H41	119.8
C16—C11—P1	119.8 (2)	C40—C41—H41	119.8
C11—C12—C13	120.9 (3)	C43—C42—C41	119.7 (2)
C11—C12—H12	119.5	C43—C42—H42	120.1
C13—C12—H12	119.5	C41—C42—H42	120.1
C14—C13—C12	120.6 (3)	C42—C43—C44	120.4 (2)
C14—C13—H13	119.7	C42—C43—H43	119.8
C12—C13—H13	119.7	C44—C43—H43	119.8
C13—C14—C15	119.0 (3)	C43—C44—C39	120.5 (2)
C13—C14—H14	120.5	C43—C44—H44	119.8
C15—C14—H14	120.5	C39—C44—H44	119.8
C14—C15—C16	121.1 (3)	O1A—C45—O1	93 (2)

S1—Pd1—P1—C5	5.44 (10)	S2—Pd2—P2—C27	−19.90 (9)

Experimental details

Crystal data
Chemical formula	[Pd(C₄H₃N₂S)Cl(C₁₈H₁₅P)]·0.5CH₄O
M_r	531.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	233
a, b, c (Å)	16.1340 (2), 9.7020 (1), 29.0480 (4)
β (°)	102.617 (1)
V (Å³)	4437.14 (10)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	1.14
Crystal size (mm)	0.35 × 0.25 × 0.08

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	26420, 9812, 8231
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.074, 1.03
No. of reflections	9812
No. of parameters	532
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.63

Computer programs: COLLECT (Nonius, 1998), SCALEPACK (Otwinowski & Minor, 1997), DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXL97.

Selected geometric parameters (Å, º) top

Pd1—N1	2.071 (2)	Pd2—Cl2	2.3104 (7)
Pd1—P1	2.2467 (7)	S1—C1	1.747 (3)
Pd1—S1	2.2975 (7)	S2—C23	1.740 (3)
Pd1—Cl1	2.3225 (8)	N1—C1	1.345 (3)
Pd2—N3	2.082 (2)	N2—C1	1.320 (3)
Pd2—P2	2.2424 (7)	N3—C23	1.342 (4)
Pd2—S2	2.3100 (7)	N4—C23	1.333 (4)

N1—Pd1—P1	166.81 (6)	S2—Pd2—Cl2	166.96 (3)
N1—Pd1—S1	70.26 (6)	C1—S1—Pd1	81.03 (9)
P1—Pd1—S1	96.84 (2)	C23—S2—Pd2	80.59 (10)
N1—Pd1—Cl1	95.41 (6)	C1—N1—Pd1	100.12 (16)
P1—Pd1—Cl1	97.16 (3)	C23—N3—Pd1	88.62 (16)
S1—Pd1—Cl1	164.78 (3)	N2—C1—N1	126.1 (2)
N3—Pd2—P2	169.30 (7)	N2—C1—S1	125.3 (2)
N3—Pd2—S2	70.10 (7)	N1—C1—S1	108.54 (19)
P2—Pd2—S2	100.22 (3)	N4—C23—N3	125.1 (3)
N3—Pd2—Cl2	97.40 (7)	N4—C23—S2	125.3 (3)
P2—Pd2—Cl2	91.91 (3)	N3—C23—S2	109.6 (2)

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

Chloro­(pyrimidine-2-thiol­ato-κ2N,S)(triphenyl­phosphine-κP)palladium(II) methanol hemisolvate

Supporting information

Key indicators

checkCIF/PLATON results

Chloro(pyrimidine-2-thiolato-κ²N,S)(triphenylphosphine-κP)palladium(II) methanol hemisolvate