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The preparation and crystal structure of the title compound, cis-di­chloro­[6,9-dioxa-3,12-di­thia­bi­cyclo­[12.4.0]­octadeca-14,-16,­18(1)-tri­ene-S,S']­palladium(II), [PdCl2(C14H20O2S2)], are described. The Pd atom has a square-planar environment, coordinated to two S atoms of the di­thia­dioxa macrocycle and to two Cl- ions. The non-coordinating O atoms are oriented away from the metal coordination plane. Upon complexation, a bicyclic chelate structure, which consists of a seven- and an eleven-membered ring, is formed.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100004364/oa1097sup1.cif
Contains datablocks sad, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100004364/oa1097Isup2.hkl
Contains datablock I

CCDC reference: 147607

Comment top

The coordination chemistry of oxathia macrocycles is an intensive area of study, and complexes with numerous transition metals are known. As part of our continuing interest in the properties of both cyclic and acyclic oxathia ligands (Jung et al., 1999; Lee et al., 1995; Chung et al., 1997), the preparation and crystal structure of the PdII complex with the O2S2 donor-type macrocycle based on a monobenzo-subunit, (I), are described. \sch

The title compound crystallizes in the monoclinic space group P21/c. As shown in Fig. 1, the Pd atom essentially has four coordinates of a square-planar environment. The Pd atom lies above the plane at a perpendicular distance of 0.0882 (4) Å.

In Fig. 1, the macrocycle adopts a conformation in which two O donors are in endo and the two S donors are in exo orientations. Therefore, the macrocycle shows a syn conformation to facilitate coordination to Pd atom by two S atoms while preserving the two cis Pd—Cl bonds. Similar conformation of the donors for the oxathia macrocycles in free and complexed form with PdII ion have been given (Blake et al., 1995; Lai et al., 1997; Kickham & Loeb, 1994). Otherwise, two O atoms are oriented away from the Pd centre, precluding any Pd—O interaction. In fact, the distance from the Pd to O1 atom is 3.7872 (31) Å and to the O2 atom is 4.0008 (27) Å, greater than the sum of the van der Waals radii (3.10 Å) (Huheey et al., 1993). By the chelating of Pd—S, the seven- and eleven-membered bicyclic rings are formed, respectively.

The bond length of Pd—S is 2.3109 (7) and 2.3069 (7) Å and the Pd—Cl length is 2.3161 (8) and 2.3132 (7) Å. These bond lengths compare well with those Pd—S (2.301–2.317 Å) and Pd—Cl (2.318–2.330 Å) found in the PdII complex of 2,17-dioxa-5,14-dithia[6,6](1,2)cyclophane (Lai et al., 1997).

It is noted that the S—Pd—S bond angle of 104.46 (3)° is significantly larger than the Cl—Pd—Cl bond angle of 89.58 (3)°. The large difference in the two bond angles is believed to be a result of the conformational steric demand of the bicyclic rings consisting of seven- and eleven-membered ring formed by the chelating of PdII to two sulfur atoms.

Experimental top

The macrocycle was prepared in our laboratory by the coupling reaction of α,α'-dibromo-o-xylene and corresponding dithiol by high dilution condition and the synthetic detail will be reported elsewhere. The title compound was prepared by the reaction of equimolar amounts of the macrocycle and PdCl2(PhCN)2 in benzene. The yellow precipitate that formed immediately was filtered off, recrystallized from acetonitrile by slow evaporation to give orange-colored single crystals suitable for X-ray analysis, decomposition 505–507 K.

Computing details top

Data collection: SMART (Siemens, 1996a); cell refinement: SAINT (Siemens, 1996a); data reduction: SHELXTL (Siemens, 1996b); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Perspective view of (I) with the atom numbering; displacement ellipsoids are drawn at the 30% probability level and H atoms have been omitted for clarity.
cis-Dichloro(5,8-dioxa-2,11-dithia[12]-o-cyclophane)palladium(II) top
Crystal data top
[PdCl2(C14H20O2S2)]F(000) = 928
Mr = 461.72Dx = 1.775 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 8.1698 (4) ÅCell parameters from 10792 reflections
b = 14.3745 (7) Åθ = 2.0–28.3°
c = 14.9238 (8) ŵ = 1.63 mm1
β = 99.649 (1)°T = 298 K
V = 1727.81 (15) Å3Plate, orange
Z = 40.4 × 0.3 × 0.08 mm
Data collection top
Siemens SMART CCD
diffractometer
4119 independent reflections
Radiation source: fine-focus sealed tube3758 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.032
ϕ and ω scansθmax = 28.3°, θmin = 2.0°
Absorption correction: multi-scan
Multi-scan (SADABS; Sheldrick, 1996)
h = 910
Tmin = 0.476, Tmax = 0.878k = 1915
10792 measured reflectionsl = 1919
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)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.082H atoms treated by a mixture of independent and constrained refinement
S = 1.05 w = 1/[σ2(Fo2) + (0.0387P)2 + 1.9613P]
where P = (Fo2 + 2Fc2)/3
4119 reflections(Δ/σ)max = 0.001
190 parametersΔρmax = 0.94 e Å3
0 restraintsΔρmin = 0.87 e Å3
Crystal data top
[PdCl2(C14H20O2S2)]V = 1727.81 (15) Å3
Mr = 461.72Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.1698 (4) ŵ = 1.63 mm1
b = 14.3745 (7) ÅT = 298 K
c = 14.9238 (8) Å0.4 × 0.3 × 0.08 mm
β = 99.649 (1)°
Data collection top
Siemens SMART CCD
diffractometer
4119 independent reflections
Absorption correction: multi-scan
Multi-scan (SADABS; Sheldrick, 1996)
3758 reflections with I > 2σ(I)
Tmin = 0.476, Tmax = 0.878Rint = 0.032
10792 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.082H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.94 e Å3
4119 reflectionsΔρmin = 0.87 e Å3
190 parameters
Special details top

Experimental. Data were collected over a hemisphere of reciprocal space, by a combination of three sets of exposures. Each set had a different ϕ angle for the crystal and each exposure of 30 s covered 0.30° in ω. The crystal-to-detector distance was 5.00 cm. The first 50 frames were retaken after complete data collection. The crystal showed no decay and no correction was applied for decay. The structure was solved by direct methods.

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.

H atoms were added at calculated positions and refined using a riding model. Anisotropic displacement parameters were used for all non-H atoms. H atoms were given isotropic displacement parameters equal to 1.2 times the equivalent isotropic displacement parameter of the atom to which they are attached.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Pd0.28253 (2)0.046182 (13)0.213437 (13)0.03100 (8)
Cl10.16068 (12)0.19209 (5)0.19887 (7)0.0587 (2)
Cl20.46482 (10)0.09251 (5)0.11901 (6)0.05077 (19)
S10.08987 (9)0.02049 (5)0.30781 (5)0.03833 (15)
S20.44810 (8)0.08476 (5)0.23034 (5)0.03694 (15)
O10.0958 (4)0.1077 (2)0.15148 (18)0.0697 (7)
O20.1726 (3)0.2075 (2)0.11036 (17)0.0616 (6)
C10.1026 (6)0.1490 (4)0.0638 (3)0.0906 (17)
H1A0.21390.16970.04180.109*
H1B0.07420.10330.02220.109*
C20.1274 (4)0.0126 (3)0.1441 (2)0.0585 (9)
H2A0.23690.00220.11080.070*
H2B0.04900.01660.11180.070*
C30.1134 (4)0.0285 (2)0.2370 (3)0.0519 (8)
H3A0.19240.00190.26800.062*
H3B0.14390.09290.23090.062*
C40.0859 (4)0.0973 (2)0.3533 (2)0.0486 (7)
H4A0.00820.10480.38350.058*
H4B0.07750.14200.30490.058*
C50.2441 (4)0.1123 (2)0.4194 (2)0.0445 (7)
C60.2513 (5)0.0859 (2)0.5101 (2)0.0564 (8)
H60.15450.06060.52970.068*
C70.3970 (6)0.0960 (3)0.5721 (2)0.0625 (10)
H70.40110.07730.63420.075*
C80.5360 (5)0.1330 (2)0.5443 (2)0.0585 (9)
H80.63720.13950.58700.070*
C90.5301 (5)0.1606 (2)0.4554 (2)0.0514 (7)
H90.62710.18700.43690.062*
C100.3845 (4)0.15077 (19)0.3919 (2)0.0436 (6)
C110.3828 (5)0.1812 (2)0.2953 (2)0.0480 (7)
H11A0.27300.20070.26870.058*
H11B0.45670.23300.29410.058*
C120.4417 (4)0.1409 (2)0.1206 (2)0.0492 (7)
H12A0.50980.10580.08630.059*
H12B0.49030.20160.13060.059*
C130.2727 (5)0.1514 (3)0.0640 (2)0.0577 (9)
H13A0.22240.09130.05230.069*
H13B0.28240.17940.00670.069*
C140.0055 (5)0.2241 (4)0.0667 (3)0.0852 (15)
H14A0.00780.24400.00550.102*
H14B0.03850.27460.09750.102*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd0.03254 (12)0.02570 (11)0.03515 (12)0.00081 (7)0.00682 (8)0.00057 (7)
Cl10.0672 (5)0.0338 (4)0.0796 (6)0.0157 (3)0.0252 (4)0.0099 (4)
Cl20.0526 (4)0.0432 (4)0.0619 (4)0.0014 (3)0.0251 (4)0.0077 (3)
S10.0382 (3)0.0352 (3)0.0435 (4)0.0003 (3)0.0124 (3)0.0017 (3)
S20.0356 (3)0.0300 (3)0.0456 (4)0.0035 (2)0.0081 (3)0.0011 (3)
O10.0712 (17)0.0776 (19)0.0566 (15)0.0161 (14)0.0002 (12)0.0171 (13)
O20.0482 (13)0.0820 (18)0.0544 (13)0.0019 (12)0.0079 (10)0.0151 (13)
C10.063 (3)0.129 (4)0.073 (3)0.017 (3)0.008 (2)0.045 (3)
C20.0357 (15)0.081 (3)0.0566 (19)0.0017 (16)0.0005 (14)0.0081 (18)
C30.0326 (14)0.0477 (17)0.076 (2)0.0078 (12)0.0122 (14)0.0013 (15)
C40.0477 (17)0.0444 (17)0.0532 (17)0.0099 (13)0.0069 (14)0.0090 (13)
C50.0564 (17)0.0335 (14)0.0415 (14)0.0098 (12)0.0019 (13)0.0069 (11)
C60.076 (2)0.0472 (18)0.0485 (17)0.0068 (16)0.0173 (16)0.0037 (14)
C70.093 (3)0.052 (2)0.0389 (16)0.0145 (19)0.0003 (17)0.0008 (14)
C80.071 (2)0.0466 (18)0.0499 (18)0.0153 (17)0.0141 (16)0.0095 (14)
C90.0593 (19)0.0360 (15)0.0551 (18)0.0014 (13)0.0011 (15)0.0095 (13)
C100.0596 (18)0.0270 (12)0.0418 (14)0.0046 (12)0.0020 (13)0.0046 (11)
C110.068 (2)0.0288 (13)0.0453 (16)0.0015 (13)0.0054 (14)0.0035 (11)
C120.0572 (18)0.0406 (16)0.0565 (17)0.0000 (13)0.0290 (15)0.0090 (13)
C130.081 (2)0.0485 (18)0.0430 (16)0.0052 (17)0.0101 (16)0.0090 (14)
C140.060 (2)0.108 (4)0.081 (3)0.004 (2)0.007 (2)0.043 (3)
Geometric parameters (Å, º) top
Pd—S22.3069 (7)C1—C141.391 (7)
Pd—S12.3109 (7)C2—C31.494 (5)
Pd—Cl22.3132 (7)C4—C51.504 (4)
Pd—Cl12.3161 (8)C5—C101.396 (5)
S1—C31.816 (3)C5—C61.397 (4)
S1—C41.827 (3)C6—C71.388 (5)
S2—C121.819 (3)C7—C81.379 (6)
S2—C111.822 (3)C8—C91.377 (5)
O1—C21.391 (5)C9—C101.399 (4)
O1—C11.430 (5)C10—C111.504 (4)
O2—C131.410 (5)C12—C131.500 (5)
O2—C141.430 (5)
S2—Pd—S1104.46 (3)C2—C3—S1115.8 (2)
S2—Pd—Cl282.87 (3)C5—C4—S1108.0 (2)
S1—Pd—Cl2172.35 (3)C10—C5—C6119.3 (3)
S2—Pd—Cl1169.74 (3)C10—C5—C4121.4 (3)
S1—Pd—Cl182.88 (3)C6—C5—C4119.3 (3)
Cl2—Pd—Cl189.58 (3)C7—C6—C5120.6 (4)
C3—S1—C4101.72 (15)C8—C7—C6119.8 (3)
C3—S1—Pd106.56 (12)C9—C8—C7120.2 (3)
C4—S1—Pd115.53 (12)C8—C9—C10120.8 (4)
C12—S2—C11100.06 (15)C5—C10—C9119.2 (3)
C12—S2—Pd109.61 (12)C5—C10—C11121.4 (3)
C11—S2—Pd117.41 (11)C9—C10—C11119.4 (3)
C2—O1—C1110.9 (4)C10—C11—S2109.4 (2)
C13—O2—C14117.4 (4)C13—C12—S2115.9 (2)
C14—C1—O1111.5 (4)O2—C13—C12109.6 (3)
O1—C2—C3109.3 (3)C1—C14—O2115.9 (4)
C2—C3—S1—Pd38.8 (3)C10—C11—S2—Pd63.4 (3)
C5—C4—S1—Pd68.9 (2)C13—C12—S2—Pd45.5 (3)

Experimental details

Crystal data
Chemical formula[PdCl2(C14H20O2S2)]
Mr461.72
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)8.1698 (4), 14.3745 (7), 14.9238 (8)
β (°) 99.649 (1)
V3)1727.81 (15)
Z4
Radiation typeMo Kα
µ (mm1)1.63
Crystal size (mm)0.4 × 0.3 × 0.08
Data collection
DiffractometerSiemens SMART CCD
diffractometer
Absorption correctionMulti-scan
Multi-scan (SADABS; Sheldrick, 1996)
Tmin, Tmax0.476, 0.878
No. of measured, independent and
observed [I > 2σ(I)] reflections
10792, 4119, 3758
Rint0.032
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.082, 1.05
No. of reflections4119
No. of parameters190
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.94, 0.87

Computer programs: SMART (Siemens, 1996a), SAINT (Siemens, 1996a), SHELXTL (Siemens, 1996b), SHELXTL.

Selected geometric parameters (Å, º) top
Pd—S22.3069 (7)Pd—Cl22.3132 (7)
Pd—S12.3109 (7)Pd—Cl12.3161 (8)
S2—Pd—S1104.46 (3)S2—Pd—Cl1169.74 (3)
S2—Pd—Cl282.87 (3)S1—Pd—Cl182.88 (3)
S1—Pd—Cl2172.35 (3)Cl2—Pd—Cl189.58 (3)
C2—C3—S1—Pd38.8 (3)C10—C11—S2—Pd63.4 (3)
C5—C4—S1—Pd68.9 (2)C13—C12—S2—Pd45.5 (3)
 

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