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Acta Cryst. (2005). E61, m2142-m2144
https://doi.org/10.1107/S1600536805030096
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Dichloro[8-(1,3-benzothia­zol-2-ylsulfanylmeth­yl)­quinoline-κN,N′]palladium(II)

R.-F. Song, J.-H. Liu, H. Qian and K.-Y. Zhao
In the mononuclear title complex, [Pd(C17H12N2S2)Cl2], the 8-(2-benzo­thia­zolyl­sulfanyl­meth­yl)­quinoline ligand chelates to PdCl2 through its N atoms, conferring a square planar geometry on Pd. The angles around the Pd atom range from 88.04 (6) to 92.76 (3)°.
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Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805030096/ng6202sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805030096/ng6202Isup2.hkl
Contains datablock I

CCDC reference: 287670

checkCIF report

Key indicators

  • Single-crystal X-ray study
  • T = 193 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.023
  • wR factor = 0.059
  • Data-to-parameter ratio = 14.5

checkCIF/PLATON results

No syntax errors found




Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.97
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT431_ALERT_2_C Short Inter HL..A Contact  Cl1    ..  S1      ..       3.40 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H9     ..  CL1     ..       2.94 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H8     ..  CL2     ..       2.84 Ang.
PLAT480_ALERT_4_C Long H...A H-Bond Reported H3     ..  CL1     ..       2.92 Ang.
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          8
            CL1 -PD1 -N2  -C16  -122.50  0.40   1.555   1.555   1.555   1.555


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

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

Square planar metal complexes have important applications in catalytic and bioinorganic systems (Fiallo & Garnier-Suillerot, 1986; Grundemann et al., 2001; Trost et al., 1995); for example, platinum(II) and palladium(II) complexes exhibit antitumour activity (Hay, 1987). The present study details the structure of a palladium dichloride adduct of a heterocyclic thioether ligand. A number of metal complexes of such ligands have been reported (Berry & Bebout, 2005; Song et al., 2003; Zou et al., 2004). The ligand used in this study is 8-(2-benzothiazolylsulfanylmethyl)quinoline.

The title PdCl2 adduct, (I), is a mononuclear compound (Fig. 1), and the Pd exists in a square planar geometry that is made up of two Cl atoms and the two N atoms of the ligand. The quinoline and benzothiazole rings of the ligand are twisted by 96.5 (1)°; the Pd lies 0.0387 (1) Å from the square plane. The bond distances are within the ranges expected for square planar palladium (Al-Mandhary et al., 2003; Buffin et al., 2003; Kita et al., 2002). The molecular packing in (I) is influenced by weak intermolecular C—H···Cl hydrogen bonds (Fig. 2 and Table 2).

Experimental top

The ligand (30.9 mg, 0.1 mmol) in CHCl3 (2 ml) was added to PdCl2 (17.8 mg, 0.1 mmol) dissolved in MeCN (20 ml). The mixture was stirred for 1 min, filtered and then set aside for the solvent to evaporate. Yield 34.5 mg (70%). Analysis found: C 42.10, H 2.46, N 5.76%; calculated for C17H12Cl2N2PdS2: C 42.03, H 2.49, N 5.77%.

Refinement top

H atoms were included in calculated positions and refined as riding on C, with C—H distances of 0.95 Å (aromatic H) and 0.99 Å (methylene H); Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: CrystalClear (Molecular Structure Corporation, 2000; Rigaku Corporation, 1999 ); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku & Rigaku/MSC, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. View of (I), shown with 30% probability displacement ellipsoids and small spheres for the H atoms.
[Figure 2] Fig. 2. The molecular packing of (I) viewed along the a axis. Dashed lines indicate hydrogen bonds.
(I) top
Crystal data top
[Pd(C17H12N2S2)Cl2]F(000) = 960
Mr = 485.71Dx = 1.867 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ybcCell parameters from 7287 reflections
a = 12.417 (3) Åθ = 3.3–25.3°
b = 10.152 (3) ŵ = 1.63 mm−1
c = 14.541 (5) ÅT = 193 K
β = 109.492 (5)°Block, orange
V = 1728.0 (8) Å30.46 × 0.35 × 0.23 mm
Z = 4
Data collection top
Rigaku Mercury
diffractometer		3157 independent reflections
Radiation source: fine-focus sealed tube3034 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.023
Detector resolution: 7.31 pixels mm-1θmax = 25.3°, θmin = 3.3°
ω scansh = −14→13
Absorption correction: multi-scan
(Jacobson, 1998)		k = −12→12
Tmin = 0.522, Tmax = 0.706l = −16→17
16474 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.059H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.0245P)2 + 2.5404P]
where P = (Fo2 + 2Fc2)/3
3157 reflections(Δ/σ)max = 0.001
218 parametersΔρmax = 0.55 e Å−3
0 restraintsΔρmin = −0.56 e Å−3
Crystal data top
[Pd(C17H12N2S2)Cl2]V = 1728.0 (8) Å3
Mr = 485.71Z = 4
Monoclinic, P21/cMo Kα radiation
a = 12.417 (3) ŵ = 1.63 mm−1
b = 10.152 (3) ÅT = 193 K
c = 14.541 (5) Å0.46 × 0.35 × 0.23 mm
β = 109.492 (5)°
Data collection top
Rigaku Mercury
diffractometer		3157 independent reflections
Absorption correction: multi-scan
(Jacobson, 1998)		3034 reflections with I > 2σ(I)
Tmin = 0.522, Tmax = 0.706Rint = 0.023
16474 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0230 restraints
wR(F2) = 0.059H-atom parameters constrained
S = 1.11Δρmax = 0.55 e Å−3
3157 reflectionsΔρmin = −0.56 e Å−3
218 parameters
Special details top

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
xyzUiso*/Ueq
Pd10.854567 (15)0.392291 (18)0.572163 (13)0.01725 (8)
Cl10.80503 (5)0.58212 (6)0.63473 (5)0.02387 (14)
Cl21.04427 (5)0.41407 (6)0.66366 (5)0.02359 (14)
S10.47193 (5)0.31712 (7)0.45390 (5)0.02476 (15)
S20.64423 (6)0.20533 (7)0.63061 (5)0.02863 (16)
N10.68609 (17)0.3664 (2)0.49472 (15)0.0191 (4)
N20.89341 (17)0.2353 (2)0.50081 (15)0.0189 (4)
C10.6146 (2)0.3006 (2)0.52567 (19)0.0209 (5)
C20.5116 (2)0.4209 (3)0.37529 (19)0.0213 (5)
C30.4430 (2)0.4856 (3)0.2921 (2)0.0295 (6)
H30.36230.47630.27010.035*
C40.4965 (3)0.5641 (3)0.2423 (2)0.0328 (7)
H40.45170.60850.18480.039*
C50.6154 (3)0.5789 (3)0.2756 (2)0.0298 (6)
H50.64980.63420.24060.036*
C60.6837 (2)0.5146 (3)0.35822 (19)0.0237 (6)
H60.76430.52470.38020.028*
C70.6309 (2)0.4348 (2)0.40841 (18)0.0197 (5)
C80.9543 (2)0.2701 (3)0.44479 (18)0.0235 (6)
H80.98770.35540.45340.028*
C90.9718 (2)0.1879 (3)0.37409 (19)0.0253 (6)
H91.01620.21690.33590.030*
C100.9242 (2)0.0660 (3)0.36078 (18)0.0237 (6)
H100.93400.00910.31230.028*
C110.8597 (2)0.0241 (3)0.41974 (18)0.0206 (5)
C120.8107 (2)−0.1036 (3)0.4075 (2)0.0254 (6)
H120.8186−0.16050.35830.030*
C130.7520 (2)−0.1444 (3)0.4671 (2)0.0299 (6)
H130.7166−0.22870.45780.036*
C140.7442 (2)−0.0622 (3)0.5414 (2)0.0276 (6)
H140.7052−0.09340.58320.033*
C150.7907 (2)0.0628 (3)0.55676 (18)0.0205 (5)
C160.8475 (2)0.1097 (2)0.49262 (18)0.0182 (5)
C170.7848 (2)0.1369 (3)0.64452 (19)0.0225 (5)
H17A0.84100.20970.65880.027*
H17B0.80730.07670.70140.027*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.01430 (12)0.01718 (11)0.02025 (12)−0.00108 (7)0.00573 (8)0.00097 (7)
Cl10.0229 (3)0.0203 (3)0.0277 (3)0.0020 (2)0.0075 (3)−0.0012 (2)
Cl20.0148 (3)0.0294 (3)0.0250 (3)−0.0034 (2)0.0045 (2)−0.0011 (3)
S10.0163 (3)0.0263 (3)0.0322 (4)−0.0043 (3)0.0088 (3)−0.0006 (3)
S20.0289 (4)0.0292 (4)0.0347 (4)0.0066 (3)0.0199 (3)0.0105 (3)
N10.0171 (10)0.0195 (11)0.0215 (11)−0.0012 (8)0.0074 (9)−0.0007 (9)
N20.0155 (10)0.0216 (11)0.0199 (10)−0.0003 (8)0.0064 (8)0.0010 (8)
C10.0203 (13)0.0187 (12)0.0258 (13)0.0017 (10)0.0105 (10)−0.0012 (10)
C20.0195 (13)0.0216 (13)0.0239 (13)−0.0024 (10)0.0085 (10)−0.0046 (10)
C30.0182 (13)0.0380 (16)0.0277 (14)0.0026 (12)0.0016 (11)−0.0026 (12)
C40.0327 (16)0.0388 (17)0.0239 (14)0.0074 (13)0.0054 (12)0.0044 (13)
C50.0341 (16)0.0326 (15)0.0266 (14)0.0018 (12)0.0150 (12)0.0030 (12)
C60.0210 (13)0.0245 (14)0.0277 (14)−0.0007 (11)0.0111 (11)−0.0003 (11)
C70.0200 (13)0.0179 (12)0.0212 (12)0.0009 (10)0.0069 (10)−0.0033 (10)
C80.0204 (13)0.0258 (14)0.0240 (13)−0.0037 (11)0.0072 (10)0.0035 (11)
C90.0219 (13)0.0333 (15)0.0232 (13)−0.0010 (11)0.0108 (11)0.0019 (11)
C100.0212 (13)0.0314 (15)0.0180 (13)0.0021 (11)0.0058 (10)−0.0027 (11)
C110.0170 (12)0.0233 (13)0.0194 (12)0.0030 (10)0.0032 (10)0.0016 (10)
C120.0265 (15)0.0221 (14)0.0249 (14)0.0011 (11)0.0050 (11)−0.0038 (11)
C130.0333 (16)0.0201 (13)0.0356 (16)−0.0071 (12)0.0106 (13)−0.0023 (12)
C140.0300 (15)0.0240 (14)0.0313 (15)−0.0032 (12)0.0137 (12)0.0043 (12)
C150.0172 (12)0.0215 (13)0.0225 (13)0.0033 (10)0.0063 (10)0.0035 (10)
C160.0148 (12)0.0189 (12)0.0189 (12)0.0007 (9)0.0030 (10)0.0028 (10)
C170.0229 (13)0.0239 (13)0.0227 (13)0.0028 (11)0.0104 (11)0.0059 (11)
Geometric parameters (Å, º) top
Pd1—N12.035 (2)C6—C71.393 (4)
Pd1—N22.045 (2)C6—H60.9500
Pd1—Cl22.2971 (8)C8—C91.396 (4)
Pd1—Cl12.3007 (8)C8—H80.9500
S1—C11.738 (3)C9—C101.357 (4)
S1—C21.742 (3)C9—H90.9500
S2—C11.739 (3)C10—C111.420 (4)
S2—C171.826 (3)C10—H100.9500
N1—C11.306 (3)C11—C161.417 (4)
N1—C71.397 (3)C11—C121.417 (4)
N2—C81.331 (3)C12—C131.370 (4)
N2—C161.386 (3)C12—H120.9500
C2—C31.390 (4)C13—C141.394 (4)
C2—C71.403 (4)C13—H130.9500
C3—C41.385 (4)C14—C151.381 (4)
C3—H30.9500C14—H140.9500
C4—C51.400 (4)C15—C161.426 (4)
C4—H40.9500C15—C171.504 (4)
C5—C61.382 (4)C17—H17A0.9900
C5—H50.9500C17—H17B0.9900
N1—Pd1—N289.52 (8)N1—C7—C2113.8 (2)
N1—Pd1—Cl2177.58 (6)N2—C8—C9123.5 (2)
N2—Pd1—Cl289.94 (6)N2—C8—H8118.3
N1—Pd1—Cl188.04 (6)C9—C8—H8118.3
N2—Pd1—Cl1173.08 (6)C10—C9—C8118.9 (2)
Cl2—Pd1—Cl192.76 (3)C10—C9—H9120.6
C1—S1—C289.87 (12)C8—C9—H9120.6
C1—S2—C17102.92 (12)C9—C10—C11119.6 (2)
C1—N1—C7112.2 (2)C9—C10—H10120.2
C1—N1—Pd1124.55 (18)C11—C10—H10120.2
C7—N1—Pd1122.60 (16)C16—C11—C12120.4 (2)
C8—N2—C16119.6 (2)C16—C11—C10119.3 (2)
C8—N2—Pd1112.45 (17)C12—C11—C10120.2 (2)
C16—N2—Pd1126.94 (16)C13—C12—C11119.6 (3)
N1—C1—S1114.69 (19)C13—C12—H12120.2
N1—C1—S2128.2 (2)C11—C12—H12120.2
S1—C1—S2117.10 (15)C12—C13—C14119.9 (3)
C3—C2—C7121.4 (2)C12—C13—H13120.1
C3—C2—S1129.2 (2)C14—C13—H13120.1
C7—C2—S1109.41 (19)C15—C14—C13122.9 (3)
C4—C3—C2117.7 (3)C15—C14—H14118.6
C4—C3—H3121.1C13—C14—H14118.6
C2—C3—H3121.1C14—C15—C16118.2 (2)
C3—C4—C5121.0 (3)C14—C15—C17117.4 (2)
C3—C4—H4119.5C16—C15—C17124.3 (2)
C5—C4—H4119.5N2—C16—C11119.0 (2)
C6—C5—C4121.3 (3)N2—C16—C15122.0 (2)
C6—C5—H5119.3C11—C16—C15118.9 (2)
C4—C5—H5119.3C15—C17—S2114.33 (18)
C5—C6—C7118.1 (3)C15—C17—H17A108.7
C5—C6—H6120.9S2—C17—H17A108.7
C7—C6—H6120.9C15—C17—H17B108.7
C6—C7—N1125.7 (2)S2—C17—H17B108.7
C6—C7—C2120.4 (2)H17A—C17—H17B107.6
N2—Pd1—N1—C195.8 (2)S1—C2—C7—C6−179.2 (2)
Cl1—Pd1—N1—C1−90.7 (2)C3—C2—C7—N1178.0 (2)
N2—Pd1—N1—C7−94.34 (19)S1—C2—C7—N1−1.4 (3)
Cl1—Pd1—N1—C779.18 (19)C16—N2—C8—C92.5 (4)
N1—Pd1—N2—C8114.82 (18)Pd1—N2—C8—C9−166.5 (2)
Cl2—Pd1—N2—C8−67.54 (17)N2—C8—C9—C100.3 (4)
Cl2—Pd1—N2—C16124.42 (19)C8—C9—C10—C11−1.0 (4)
Cl1—Pd1—N2—C16−122.5 (4)C9—C10—C11—C16−0.9 (4)
C7—N1—C1—S1−1.0 (3)C9—C10—C11—C12−179.2 (2)
Pd1—N1—C1—S1169.75 (12)C16—C11—C12—C13−0.4 (4)
C7—N1—C1—S2−178.38 (19)C10—C11—C12—C13177.8 (2)
Pd1—N1—C1—S2−7.6 (3)C11—C12—C13—C14−2.3 (4)
C2—S1—C1—N10.2 (2)C12—C13—C14—C152.0 (4)
C2—S1—C1—S2177.87 (16)C13—C14—C15—C161.0 (4)
C17—S2—C1—N1−33.4 (3)C13—C14—C15—C17−175.0 (3)
C17—S2—C1—S1149.33 (15)C8—N2—C16—C11−4.4 (3)
C1—S1—C2—C3−178.6 (3)Pd1—N2—C16—C11162.83 (17)
C1—S1—C2—C70.66 (19)C8—N2—C16—C15174.0 (2)
C7—C2—C3—C40.3 (4)Pd1—N2—C16—C15−18.7 (3)
S1—C2—C3—C4179.6 (2)C12—C11—C16—N2−178.1 (2)
C2—C3—C4—C5−0.8 (4)C10—C11—C16—N23.7 (3)
C3—C4—C5—C60.8 (5)C12—C11—C16—C153.4 (4)
C4—C5—C6—C7−0.4 (4)C10—C11—C16—C15−174.9 (2)
C5—C6—C7—N1−177.7 (2)C14—C15—C16—N2177.9 (2)
C5—C6—C7—C2−0.1 (4)C17—C15—C16—N2−6.4 (4)
C1—N1—C7—C6179.3 (2)C14—C15—C16—C11−3.6 (4)
Pd1—N1—C7—C68.3 (3)C17—C15—C16—C11172.1 (2)
C1—N1—C7—C21.6 (3)C14—C15—C17—S2−76.4 (3)
Pd1—N1—C7—C2−169.43 (17)C16—C15—C17—S2107.9 (2)
C3—C2—C7—C60.1 (4)C1—S2—C17—C15−55.5 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C17—H17b···Cl2i0.992.753.667 (3)154
C10—H10···Cl1ii0.952.713.466 (3)137
C9—H9···Cl1iii0.952.943.658 (3)133
C8—H8···Cl2iii0.952.843.575 (3)135
C6—H6···Cl2iii0.952.733.571 (3)148
C3—H3···Cl1iv0.952.923.644 (3)134
Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) x, −y+1/2, z−1/2; (iii) −x+2, −y+1, −z+1; (iv) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula[Pd(C17H12N2S2)Cl2]
Mr485.71
Crystal system, space groupMonoclinic, P21/c
Temperature (K)193
a, b, c (Å)12.417 (3), 10.152 (3), 14.541 (5)
β (°) 109.492 (5)
V (Å3)1728.0 (8)
Z4
Radiation typeMo Kα
µ (mm−1)1.63
Crystal size (mm)0.46 × 0.35 × 0.23
Data collection
DiffractometerRigaku Mercury
diffractometer
Absorption correctionMulti-scan
(Jacobson, 1998)
Tmin, Tmax0.522, 0.706
No. of measured, independent and
observed [I > 2σ(I)] reflections		16474, 3157, 3034
Rint0.023
(sin θ/λ)max (Å−1)0.602
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.023, 0.059, 1.11
No. of reflections3157
No. of parameters218
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.55, −0.56

Computer programs: CrystalClear (Molecular Structure Corporation, 2000; Rigaku Corporation, 1999 ), CrystalClear, CrystalStructure (Rigaku & Rigaku/MSC, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL.

Selected geometric parameters (Å, º) top
Pd1—N12.035 (2)Pd1—Cl22.2971 (8)
Pd1—N22.045 (2)Pd1—Cl12.3007 (8)
N1—Pd1—N289.52 (8)N1—Pd1—Cl188.04 (6)
N1—Pd1—Cl2177.58 (6)N2—Pd1—Cl1173.08 (6)
N2—Pd1—Cl289.94 (6)Cl2—Pd1—Cl192.76 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C17—H17b···Cl2i0.992.753.667 (3)154.4
C10—H10···Cl1ii0.952.713.466 (3)137.2
C9—H9···Cl1iii0.952.943.658 (3)133.4
C8—H8···Cl2iii0.952.843.575 (3)134.8
C6—H6···Cl2iii0.952.733.571 (3)148.0
C3—H3···Cl1iv0.952.923.644 (3)134.4
Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) x, −y+1/2, z−1/2; (iii) −x+2, −y+1, −z+1; (iv) −x+1, −y+1, −z+1.
 

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