Chlorido{4-chloro-1-[2-(methyl­sulfan­yl)phenyl­diazen­yl]phenyl-κ³C,N,S}palladium(II): a second polymorph

The title compound, [Pd(C₁₃H₁₀ClN₂S)Cl], is the monoclinic form of a previously reported triclinic structure of the same compound. The bond distances and angles of the mol­ecule in the monoclinic form deviate slightly from those for the triclinic form. The Pd atom in this compound is tetracoordinated by a benzene C, a diazene N, a Cl and an S atom in an approximately square-planar geometry. The inter­molecular inter­actions are very similar in both polymorphs. The mol­ecules are found to dimerize through a nonbonding S...S inter­action [S...S = 3.438 (2) Å]. There are no hydrogen bonds and the crystal packing is stabilized by four inter­molecular π–π inter­actions; the distances between the centroids of the six-membered rings are 3.620 (3), 3.841 (3), 3.619 (3) and 3.842 (3) Å, and the perpendicular distances are 3.482, 3.482, 3.536 and 3.519 Å.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.050
• wR factor = 0.103
• Data-to-parameter ratio = 14.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          9

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Pd1         (2)       2.13

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

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

---

S1. Comment

We recently reported the structure of a first triclinic polymorph of [Pd(C₁₃H₁₀ClN₂S)Cl] in space group P1 (Bagchi et al., 2007). The title molecule, (I), was produced during a parallel crystallization process. The present crystal found to crystallize in monoclinic form with P2₁/c space group at room temperature. Herein we report the monoclinic crystal structure of (I).

The molecular structure of the title compound, (I), is shown in Fig. 1, with the atom numbering scheme. The palladium atom along with donor set of four atoms lie in an almost plane. Selected bond lengths and bond angles are listed in Table 1. The packing arrangement of (I) is shown in Fig. 2. The bond distances and bond angles of the molecule in the monoclinic form deviates slightly from those in the triclinic morphology (Bagchi et al., 2007). The molecules are found to dimerize through a nonbonded S···S interaction; having S···Sⁱ [Symmetry code: (i) -x, 2 - y, -z] distance of 3.438 (2) Å (Chattopadhyay et al., 1991) and is smaller than that in the triclinic crystal modification (Bagchi et al., 2007) (Fig. 3). Four intermolecular π—π interactions (Kubo et al., 2005; Bagchi & Bandyopadhyay, 2007) arrange the molecules in anti-parallel fashion (Fig. 4). The Cg3···Cg4ⁱⁱ, Cg3 ···Cg4ⁱⁱⁱ, Cg4···Cg3ⁱⁱ, Cg4 ···Cg3ⁱⁱⁱ [Symmetry codes: (ii) -x, 1 - y, -z; (iii) 1 - x, 1 - y, -z. Cg3 and Cg4 are the centroids of C1—C6 and C7—C12 rings, respectively] distances are 3.620 (3), 3.841 (3), 3.619 (3) and 3.842 (3) Å; the perpendicular distances are 3.482, 3.482, 3.536 and 3.519 Å, respectively, with no slippages; though the Cg···Cg distances are very close in both the polymorph but the perpendicular distances are greater in the monoclinic crystal modification.

Related literature

For related literature, see: Bagchi & Bandyopadhyay (2007); Bagchi et al. (2007); Chattopadhyay et al. (1991); Kubo et al. (2005).

S2. Experimental

The title compound (I) was prepared following a method reported in an earlier communication (Bagchi et al., 2007). Suitable crystals of (I) were grown from a dichloromethane-hexane solution by slow evaporation.

S3. Refinement

H atoms were included at calculated positions as riding atoms with C—H set to 0.93 Å for (aromatic) and 0.96 Å for (CH₃) H atoms, with U_iso(H) = 1.2U_eq(C) (1.5U_eq for methyl group).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The asymmetric unit of (I), with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. The molecular arrangement of (I) in the bc plane.
	Fig. 3. The intermolecular S···S interaction for (I), indicated by dotted line [Symmetry code: (i) -x, 2 - y, -z].
	Fig. 4. The intermolecular π—π interactions for (I), indicated by the blue and green dotted lines. [Symmetry code: (ii) -x, 1 - y, -z; (iii) 1 - x, 1 - y, -z.]. Cg3 and Cg4 are centroids of C1—C6 and C7—C12 rings, respectively.

Chlorido{4-chloro-1-[2-(methylsulfanyl)phenyldiazenyl]phenyl-\k³C,N,S}palladium(II)

Crystal data

[Pd(C13H10ClN2S)Cl]	F(000) = 792
Mr = 403.59	Dx = 1.955 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2420 reflections
a = 7.3978 (10) Å	θ = 2.0–25.0°
b = 8.8652 (12) Å	µ = 1.88 mm^−1
c = 20.978 (3) Å	T = 295 K
β = 94.668 (2)°	Block, red
V = 1371.2 (3) Å^3	0.42 × 0.30 × 0.19 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	2420 independent reflections
Radiation source: fine-focus sealed tube	2346 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
φ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
Tmin = 0.510, Tmax = 0.703	k = −10→10
12718 measured reflections	l = −24→24

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.103	H-atom parameters constrained
S = 1.31	w = 1/[σ^2(Fo^2) + (0.0356P)^2 + 3.6827P] where P = (Fo^2 + 2Fc^2)/3
2420 reflections	(Δ/σ)max = 0.001
173 parameters	Δρmax = 0.86 e Å^−3
0 restraints	Δρmin = −0.79 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
C5	0.3885 (8)	1.2353 (6)	0.3486 (3)	0.0398 (14)
H5	0.4174	1.3256	0.3293	0.048*
C13	0.2475 (9)	0.4991 (7)	0.5732 (3)	0.0496 (16)
H13A	0.3682	0.5370	0.5828	0.074*
H13B	0.2499	0.4190	0.5425	0.074*
H13C	0.2014	0.4615	0.6116	0.074*
Cl1	0.2324 (3)	0.60867 (17)	0.38218 (7)	0.0542 (5)
Cl2	0.4171 (3)	1.10947 (19)	0.23353 (7)	0.0532 (4)
Pd1	0.22575 (6)	0.79235 (4)	0.458724 (19)	0.03074 (16)
S1	0.1026 (2)	0.64961 (16)	0.54057 (7)	0.0363 (3)
N2	0.2277 (6)	0.9604 (5)	0.5206 (2)	0.0303 (10)
C7	0.1844 (7)	0.9369 (6)	0.5847 (3)	0.0314 (12)
C2	0.3027 (7)	0.9594 (6)	0.4043 (2)	0.0303 (12)
N1	0.2704 (6)	1.0932 (5)	0.5040 (2)	0.0342 (10)
C1	0.3119 (7)	1.0953 (6)	0.4398 (3)	0.0302 (12)
C8	0.1314 (8)	0.7914 (7)	0.6008 (3)	0.0360 (13)
C6	0.3554 (8)	1.2324 (6)	0.4122 (3)	0.0390 (13)
H6	0.3619	1.3204	0.4364	0.047*
C9	0.0915 (8)	0.7616 (7)	0.6630 (3)	0.0444 (15)
H9	0.0547	0.6655	0.6741	0.053*
C12	0.1965 (8)	1.0512 (7)	0.6304 (3)	0.0398 (14)
H12	0.2302	1.1482	0.6194	0.048*
C4	0.3786 (7)	1.1036 (6)	0.3140 (3)	0.0344 (12)
C3	0.3360 (7)	0.9653 (6)	0.3406 (3)	0.0365 (13)
H3	0.3301	0.8783	0.3158	0.044*
C11	0.1579 (9)	1.0191 (8)	0.6921 (3)	0.0481 (16)
H11	0.1662	1.0945	0.7230	0.058*
C10	0.1065 (8)	0.8739 (8)	0.7082 (3)	0.0490 (16)
H10	0.0820	0.8527	0.7501	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C5	0.047 (3)	0.028 (3)	0.045 (3)	−0.003 (3)	0.009 (3)	0.009 (3)
C13	0.062 (4)	0.036 (3)	0.049 (4)	0.002 (3)	−0.006 (3)	0.004 (3)
Cl1	0.0972 (13)	0.0283 (7)	0.0391 (8)	−0.0041 (8)	0.0176 (8)	−0.0051 (6)
Cl2	0.0783 (12)	0.0464 (9)	0.0363 (8)	−0.0009 (8)	0.0131 (8)	0.0081 (7)
Pd1	0.0413 (3)	0.0231 (2)	0.0281 (2)	−0.00143 (18)	0.00396 (17)	0.00059 (17)
S1	0.0453 (8)	0.0322 (7)	0.0308 (7)	−0.0094 (6)	0.0002 (6)	0.0013 (6)
N2	0.033 (2)	0.027 (2)	0.031 (2)	−0.0004 (19)	0.0008 (19)	−0.0012 (19)
C7	0.027 (3)	0.032 (3)	0.035 (3)	0.000 (2)	−0.001 (2)	−0.001 (2)
C2	0.032 (3)	0.028 (3)	0.031 (3)	0.006 (2)	0.002 (2)	0.005 (2)
N1	0.034 (2)	0.030 (2)	0.038 (3)	−0.001 (2)	0.006 (2)	−0.003 (2)
C1	0.028 (3)	0.027 (3)	0.036 (3)	0.004 (2)	0.001 (2)	0.000 (2)
C8	0.036 (3)	0.041 (3)	0.031 (3)	−0.004 (3)	0.003 (2)	−0.001 (3)
C6	0.043 (3)	0.026 (3)	0.047 (4)	−0.004 (2)	0.005 (3)	−0.001 (3)
C9	0.049 (4)	0.047 (4)	0.038 (3)	−0.004 (3)	0.007 (3)	0.004 (3)
C12	0.042 (3)	0.034 (3)	0.043 (3)	0.002 (3)	0.003 (3)	−0.011 (3)
C4	0.034 (3)	0.037 (3)	0.032 (3)	0.002 (2)	0.003 (2)	0.007 (2)
C3	0.039 (3)	0.033 (3)	0.038 (3)	0.000 (2)	0.003 (3)	0.001 (3)
C11	0.054 (4)	0.055 (4)	0.035 (3)	−0.003 (3)	0.003 (3)	−0.014 (3)
C10	0.049 (4)	0.066 (5)	0.032 (3)	−0.002 (3)	0.008 (3)	0.002 (3)

Geometric parameters (Å, º)

C5—C4	1.374 (8)	C7—C8	1.397 (8)
C5—C6	1.375 (8)	C2—C3	1.380 (8)
C5—H5	0.9300	C2—C1	1.415 (7)
C13—S1	1.810 (6)	N1—C1	1.406 (7)
C13—H13A	0.9600	C1—C6	1.395 (8)
C13—H13B	0.9600	C8—C9	1.386 (8)
C13—H13C	0.9600	C6—H6	0.9300
Cl1—Pd1	2.2904 (15)	C9—C10	1.374 (9)
Cl2—C4	1.736 (6)	C9—H9	0.9300
Pd1—N2	1.975 (4)	C12—C11	1.378 (9)
Pd1—C2	1.981 (5)	C12—H12	0.9300
Pd1—S1	2.3735 (15)	C4—C3	1.394 (8)
S1—C8	1.783 (6)	C3—H3	0.9300
N2—N1	1.274 (6)	C11—C10	1.392 (10)
N2—C7	1.424 (7)	C11—H11	0.9300
C7—C12	1.393 (8)	C10—H10	0.9300
C4—C5—C6	119.3 (5)	C6—C1—N1	119.1 (5)
C4—C5—H5	120.3	C6—C1—C2	121.7 (5)
C6—C5—H5	120.3	N1—C1—C2	119.2 (5)
S1—C13—H13A	109.5	C9—C8—C7	119.3 (5)
S1—C13—H13B	109.5	C9—C8—S1	120.7 (5)
H13A—C13—H13B	109.5	C7—C8—S1	119.9 (4)
S1—C13—H13C	109.5	C5—C6—C1	119.0 (5)
H13A—C13—H13C	109.5	C5—C6—H6	120.5
H13B—C13—H13C	109.5	C1—C6—H6	120.5
N2—Pd1—C2	80.1 (2)	C10—C9—C8	120.0 (6)
N2—Pd1—Cl1	176.01 (14)	C10—C9—H9	120.0
C2—Pd1—Cl1	95.98 (16)	C8—C9—H9	120.0
N2—Pd1—S1	84.81 (13)	C11—C12—C7	119.3 (6)
C2—Pd1—S1	163.81 (16)	C11—C12—H12	120.3
Cl1—Pd1—S1	99.18 (6)	C7—C12—H12	120.3
C8—S1—C13	102.6 (3)	C5—C4—C3	122.7 (5)
C8—S1—Pd1	96.11 (19)	C5—C4—Cl2	118.8 (4)
C13—S1—Pd1	114.6 (2)	C3—C4—Cl2	118.4 (4)
N1—N2—C7	118.2 (4)	C2—C3—C4	119.0 (5)
N1—N2—Pd1	120.4 (4)	C2—C3—H3	120.5
C7—N2—Pd1	121.3 (3)	C4—C3—H3	120.5
C12—C7—C8	120.6 (5)	C12—C11—C10	120.0 (6)
C12—C7—N2	122.5 (5)	C12—C11—H11	120.0
C8—C7—N2	116.9 (5)	C10—C11—H11	120.0
C3—C2—C1	118.2 (5)	C9—C10—C11	120.8 (6)
C3—C2—Pd1	131.9 (4)	C9—C10—H10	119.6
C1—C2—Pd1	109.7 (4)	C11—C10—H10	119.6
N2—N1—C1	110.6 (4)
N2—Pd1—S1—C8	−7.4 (2)	C3—C2—C1—N1	177.1 (5)
C2—Pd1—S1—C8	−28.3 (6)	Pd1—C2—C1—N1	0.7 (6)
Cl1—Pd1—S1—C8	172.5 (2)	C12—C7—C8—C9	−0.3 (8)
N2—Pd1—S1—C13	−114.3 (3)	N2—C7—C8—C9	178.6 (5)
C2—Pd1—S1—C13	−135.2 (6)	C12—C7—C8—S1	176.0 (4)
Cl1—Pd1—S1—C13	65.6 (2)	N2—C7—C8—S1	−5.1 (7)
C2—Pd1—N2—N1	0.4 (4)	C13—S1—C8—C9	−58.1 (6)
S1—Pd1—N2—N1	−173.8 (4)	Pd1—S1—C8—C9	−175.0 (5)
C2—Pd1—N2—C7	−178.6 (4)	C13—S1—C8—C7	125.7 (5)
S1—Pd1—N2—C7	7.1 (4)	Pd1—S1—C8—C7	8.8 (5)
N1—N2—C7—C12	−3.5 (7)	C4—C5—C6—C1	−0.2 (9)
Pd1—N2—C7—C12	175.6 (4)	N1—C1—C6—C5	−177.3 (5)
N1—N2—C7—C8	177.6 (5)	C2—C1—C6—C5	0.6 (9)
Pd1—N2—C7—C8	−3.3 (6)	C7—C8—C9—C10	−0.8 (9)
N2—Pd1—C2—C3	−176.3 (6)	S1—C8—C9—C10	−177.0 (5)
Cl1—Pd1—C2—C3	4.2 (5)	C8—C7—C12—C11	0.9 (9)
S1—Pd1—C2—C3	−155.2 (4)	N2—C7—C12—C11	−178.0 (5)
N2—Pd1—C2—C1	−0.6 (4)	C6—C5—C4—C3	0.0 (9)
Cl1—Pd1—C2—C1	180.0 (3)	C6—C5—C4—Cl2	179.0 (5)
S1—Pd1—C2—C1	20.6 (8)	C1—C2—C3—C4	0.6 (8)
C7—N2—N1—C1	178.9 (4)	Pd1—C2—C3—C4	176.1 (4)
Pd1—N2—N1—C1	−0.2 (6)	C5—C4—C3—C2	−0.2 (9)
N2—N1—C1—C6	177.6 (5)	Cl2—C4—C3—C2	−179.2 (4)
N2—N1—C1—C2	−0.4 (7)	C7—C12—C11—C10	−0.4 (9)
C3—C2—C1—C6	−0.8 (8)	C8—C9—C10—C11	1.3 (10)
Pd1—C2—C1—C6	−177.3 (4)	C12—C11—C10—C9	−0.7 (10)