trans-Bis(5-amino-1,3,4-thia-diazol-2-thio-lato-κS(2))bis-(triphenyl-phosphane-κP)palladium(II) dimethyl sulfoxide disolvate hemihydrate.

The title complex, [Pd(C(2)H(2)N(3)S(2))(2)(C(18)H(15)P)(2)]·2C(2)H(6)OS·0.5H(2)O, was obtained from the reaction of trans-[(Ph(3)P)(2)PdCl(2)] with 5-amino-1,3,4-thia-diazole-2-thione (SSNH(2)) in a 2:1 molar ratio. The Pd(II) atom, located in a crystallographic center of symmetry, has a square-planar geometry with two triphenyl-phosphine P-coordinated mol-ecules and two SSNH(2) ligands with the S atoms in a trans conformation. The latter ligand exhibits N-H⋯N hydrogen-bonding contacts formed by the amino group with the thia-diazole ring, generating a chain along the c axis. The asymmetric unit contains one half of the complex mol-ecule along with disordered dimethyl sulfoxide and water mol-ecules.

Related literature

For background to the design and synthesis of ligands that contain efficient metal coordination sites and hydrogen-bonding functionalities, see: Beatty (2001 ▶). The SSNH2 (5-amino-1,3,4-thia­diazole-2-thiol) ligand exists in the thione and thiol forms and can converted into the thiol­ate form depending on the affinity of the metal, see: Tzeng et al. (1999 ▶). For SSNH2 acting as a ligand and as auxiliary in the construction of hydrogen bonds in coordination compounds with PdII, see: Tzeng, Lee et al. (2004 ▶), with PtII, see: Tannai et al. (2006 ▶), with CdII, see: Gao et al. (2009 ▶) and with AuI, see: Tzeng et al. (1999 ▶); Tzeng, Huang et al. (2004 ▶). For the thiol­ate form, see: Downie et al. (1972 ▶).

Experimental

Crystal data

[Pd(C2H2N3S2)2(C18H15P)2]·2C2H6OS·0.5H2O

M = 1060.58

Orthorhombic,

a = 14.6192 (18) Å

b = 13.2572 (16) Å

c = 25.707 (3) Å

V = 4982.3 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.73 mm−1

T = 298 K

0.24 × 0.16 × 0.13 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

38822 measured reflections

4590 independent reflections

2603 reflections with I > 2σ(I)

R int = 0.107

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.137

S = 0.95

4590 reflections

322 parameters

99 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.63 e Å−3

Δρmin = −0.37 e Å−3

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812011555/br2190sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812011555/br2190Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Pd(C2H2N3S2)2(C18H15P)2]·2C2H6OS·0.5H2O	F(000) = 2176
Mr = 1060.58	Dx = 1.414 Mg m−3
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2n 2ab	Cell parameters from 6520 reflections
a = 14.6192 (18) Å	θ = 2.2–25.0°
b = 13.2572 (16) Å	µ = 0.73 mm−1
c = 25.707 (3) Å	T = 298 K
V = 4982.3 (10) Å3	Prism, orange
Z = 4	0.24 × 0.16 × 0.13 mm

Bruker SMART APEX CCD area-detector diffractometer	2603 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.107
Graphite monochromator	θmax = 25.5°, θmin = 2.1°
Detector resolution: 0.83 pixels mm-1	h = −17→17
ω scans	k = −16→15
38822 measured reflections	l = −31→30
4590 independent reflections

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	w = 1/[σ2(Fo2) + (0.0611P)2] where P = (Fo2 + 2Fc2)/3
4590 reflections	(Δ/σ)max = 0.001
322 parameters	Δρmax = 0.63 e Å−3
99 restraints	Δρmin = −0.37 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Pd	0.5000	0.5000	0.5000	0.04092 (19)
S1	0.30706 (10)	0.43464 (14)	0.65323 (6)	0.0614 (5)
S2	0.35991 (9)	0.47537 (12)	0.54222 (5)	0.0494 (4)
C2	0.3886 (4)	0.4746 (4)	0.6078 (2)	0.0428 (14)
N3	0.4650 (3)	0.5019 (4)	0.62829 (17)	0.0527 (13)
N4	0.4655 (3)	0.4920 (4)	0.68230 (17)	0.0526 (13)
C5	0.3896 (4)	0.4590 (5)	0.7008 (2)	0.0561 (16)
N6	0.3726 (4)	0.4426 (5)	0.75160 (19)	0.0872 (19)
H6A	0.4270 (11)	0.444 (4)	0.7682 (6)	0.105*
H6B	0.331 (3)	0.489 (3)	0.7616 (8)	0.105*
P1	0.56548 (10)	0.35283 (12)	0.53336 (5)	0.0469 (4)
C7	0.6788 (4)	0.3827 (5)	0.5585 (2)	0.0524 (16)
C8	0.7562 (5)	0.3304 (6)	0.5456 (3)	0.084 (2)
H8	0.7521	0.2735	0.5246	0.101*
C9	0.8418 (5)	0.3621 (8)	0.5640 (3)	0.107 (3)
H9	0.8943	0.3276	0.5541	0.128*
C10	0.8482 (6)	0.4410 (8)	0.5954 (3)	0.105 (3)
H10	0.9050	0.4603	0.6083	0.126*
C11	0.7727 (5)	0.4936 (7)	0.6086 (3)	0.098 (3)
H11	0.7784	0.5496	0.6301	0.117*
C12	0.6866 (5)	0.4658 (6)	0.5906 (3)	0.073 (2)
H12	0.6351	0.5026	0.6000	0.088*
C13	0.5809 (4)	0.2545 (5)	0.4849 (2)	0.0536 (16)
C14	0.5676 (4)	0.2755 (5)	0.4331 (2)	0.0606 (17)
H14	0.5515	0.3401	0.4225	0.073*
C15	0.5787 (5)	0.1981 (6)	0.3965 (3)	0.076 (2)
H15	0.5712	0.2122	0.3613	0.092*
C16	0.5999 (5)	0.1033 (6)	0.4115 (4)	0.081 (2)
H16	0.6077	0.0531	0.3867	0.098*
C17	0.6099 (5)	0.0812 (6)	0.4624 (4)	0.092 (3)
H17	0.6226	0.0153	0.4726	0.110*
C18	0.6013 (5)	0.1553 (5)	0.4991 (3)	0.077 (2)
H18	0.6092	0.1395	0.5340	0.092*
C19	0.5104 (5)	0.2807 (4)	0.5842 (2)	0.0555 (16)
C20	0.4262 (5)	0.2343 (5)	0.5738 (3)	0.068 (2)
H20	0.3986	0.2451	0.5417	0.082*
C21	0.3831 (6)	0.1739 (6)	0.6093 (4)	0.096 (3)
H21	0.3275	0.1436	0.6012	0.115*
C22	0.4222 (9)	0.1586 (7)	0.6560 (4)	0.118 (4)
H22	0.3929	0.1177	0.6802	0.141*
C23	0.5037 (8)	0.2019 (7)	0.6685 (3)	0.114 (3)
H23	0.5299	0.1899	0.7009	0.137*
C24	0.5477 (5)	0.2642 (6)	0.6326 (3)	0.084 (2)
H24	0.6028	0.2948	0.6415	0.101*
S3	0.6482 (5)	0.2367 (6)	0.2460 (2)	0.148 (2)	0.555 (7)
O1	0.6973 (12)	0.2972 (13)	0.2789 (6)	0.205 (6)	0.555 (7)
C25	0.6929 (15)	0.1269 (10)	0.2344 (8)	0.153 (5)	0.555 (7)
H25A	0.7149	0.0982	0.2663	0.230*	0.555 (7)
H25B	0.7428	0.1343	0.2104	0.230*	0.555 (7)
H25C	0.6474	0.0834	0.2195	0.230*	0.555 (7)
C26	0.6108 (16)	0.2920 (16)	0.1935 (6)	0.168 (6)	0.555 (7)
H26A	0.5859	0.3568	0.2023	0.252*	0.555 (7)
H26B	0.5641	0.2513	0.1777	0.252*	0.555 (7)
H26C	0.6605	0.3006	0.1694	0.252*	0.555 (7)
S3A	0.7135 (7)	0.2550 (8)	0.2128 (3)	0.174 (3)	0.445 (7)
O1A	0.7568 (16)	0.3180 (16)	0.2464 (8)	0.219 (6)	0.445 (7)
C25A	0.6772 (18)	0.1491 (12)	0.2385 (10)	0.140 (5)	0.445 (7)
H25D	0.7254	0.1193	0.2588	0.210*	0.445 (7)
H25E	0.6595	0.1034	0.2113	0.210*	0.445 (7)
H25F	0.6256	0.1625	0.2605	0.210*	0.445 (7)
C26A	0.6357 (16)	0.307 (2)	0.1760 (10)	0.176 (7)	0.445 (7)
H26D	0.6588	0.3690	0.1620	0.264*	0.445 (7)
H26E	0.5819	0.3203	0.1963	0.264*	0.445 (7)
H26F	0.6205	0.2620	0.1480	0.264*	0.445 (7)
O2	0.5000	0.034 (2)	0.2500	0.263 (14)*	0.50

	U11	U22	U33	U12	U13	U23
Pd	0.0372 (3)	0.0535 (4)	0.0320 (3)	0.0035 (3)	−0.0035 (3)	0.0020 (3)
S1	0.0524 (9)	0.0909 (13)	0.0409 (9)	−0.0164 (9)	0.0029 (8)	0.0012 (9)
S2	0.0407 (8)	0.0700 (11)	0.0374 (8)	−0.0005 (7)	−0.0034 (6)	0.0048 (7)
C2	0.044 (3)	0.047 (4)	0.037 (3)	0.004 (3)	0.002 (3)	0.005 (3)
N3	0.044 (3)	0.072 (3)	0.043 (3)	−0.004 (3)	−0.005 (2)	0.004 (3)
N4	0.051 (3)	0.070 (4)	0.037 (3)	−0.010 (3)	−0.003 (2)	0.005 (3)
C5	0.055 (4)	0.073 (5)	0.041 (4)	−0.006 (3)	−0.005 (3)	0.000 (3)
N6	0.070 (4)	0.154 (6)	0.037 (3)	−0.015 (4)	0.001 (3)	0.005 (4)
P1	0.0462 (9)	0.0563 (10)	0.0381 (8)	0.0086 (8)	−0.0024 (7)	0.0037 (8)
C7	0.046 (4)	0.071 (4)	0.040 (3)	0.012 (3)	−0.002 (3)	0.011 (3)
C8	0.063 (5)	0.128 (7)	0.062 (4)	0.024 (5)	−0.009 (4)	−0.018 (5)
C9	0.056 (5)	0.178 (10)	0.087 (6)	0.037 (6)	−0.016 (4)	−0.026 (6)
C10	0.053 (5)	0.178 (10)	0.084 (6)	0.010 (6)	−0.019 (4)	−0.009 (6)
C11	0.078 (6)	0.128 (7)	0.087 (6)	−0.015 (6)	−0.017 (5)	−0.023 (5)
C12	0.054 (4)	0.094 (6)	0.072 (5)	0.006 (4)	−0.013 (4)	−0.010 (4)
C13	0.048 (4)	0.071 (5)	0.041 (4)	0.005 (3)	0.007 (3)	−0.005 (3)
C14	0.059 (4)	0.058 (4)	0.064 (5)	−0.005 (3)	0.005 (4)	−0.003 (4)
C15	0.080 (5)	0.093 (6)	0.056 (4)	−0.010 (5)	0.014 (4)	−0.015 (5)
C16	0.076 (5)	0.069 (6)	0.100 (7)	−0.002 (4)	0.031 (5)	−0.030 (5)
C17	0.092 (6)	0.070 (6)	0.113 (7)	0.031 (5)	0.019 (5)	−0.006 (6)
C18	0.089 (5)	0.068 (5)	0.073 (5)	0.034 (4)	0.002 (4)	0.005 (5)
C19	0.073 (5)	0.048 (4)	0.046 (4)	0.016 (4)	0.007 (4)	0.001 (3)
C20	0.094 (6)	0.052 (4)	0.058 (4)	−0.002 (4)	0.022 (4)	0.002 (4)
C21	0.127 (8)	0.068 (6)	0.093 (6)	−0.024 (5)	0.035 (6)	−0.006 (5)
C22	0.186 (12)	0.069 (6)	0.099 (8)	−0.011 (7)	0.067 (8)	0.012 (6)
C23	0.188 (11)	0.100 (7)	0.054 (5)	0.009 (8)	0.019 (7)	0.027 (5)
C24	0.111 (6)	0.087 (6)	0.055 (5)	0.012 (5)	0.008 (4)	0.013 (4)
S3	0.146 (5)	0.196 (6)	0.104 (4)	0.051 (4)	−0.005 (4)	0.006 (4)
O1	0.245 (14)	0.220 (10)	0.149 (11)	−0.009 (10)	−0.024 (9)	−0.004 (9)
C25	0.122 (11)	0.218 (9)	0.120 (11)	0.086 (9)	−0.060 (9)	−0.007 (8)
C26	0.166 (11)	0.186 (10)	0.151 (10)	0.042 (10)	−0.020 (9)	0.042 (8)
S3A	0.169 (7)	0.230 (7)	0.123 (6)	0.024 (6)	−0.007 (5)	0.011 (5)
O1A	0.216 (14)	0.267 (12)	0.173 (13)	−0.040 (11)	−0.020 (10)	0.008 (10)
C25A	0.139 (11)	0.166 (10)	0.115 (10)	0.080 (8)	−0.025 (9)	−0.014 (8)
C26A	0.188 (14)	0.198 (13)	0.141 (13)	0.019 (11)	−0.003 (10)	0.046 (10)

Pd—P1i	2.3363 (15)	C16—H16	0.9300
Pd—P1	2.3364 (15)	C17—C18	1.368 (9)
Pd—S2i	2.3407 (14)	C17—H17	0.9300
Pd—S2	2.3407 (14)	C18—H18	0.9300
S1—C5	1.748 (6)	C19—C24	1.377 (8)
S1—C2	1.751 (5)	C19—C20	1.402 (8)
S2—C2	1.736 (5)	C20—C21	1.367 (9)
C2—N3	1.288 (7)	C20—H20	0.9300
N3—N4	1.394 (6)	C21—C22	1.344 (12)
N4—C5	1.284 (7)	C21—H21	0.9300
C5—N6	1.348 (7)	C22—C23	1.362 (12)
N6—H6A	0.904 (10)	C22—H22	0.9300
N6—H6B	0.899 (10)	C23—C24	1.396 (10)
P1—C19	1.807 (6)	C23—H23	0.9300
P1—C13	1.817 (6)	C24—H24	0.9300
P1—C7	1.821 (6)	S3—O1	1.369 (12)
C7—C8	1.367 (8)	S3—C25	1.623 (8)
C7—C12	1.382 (8)	S3—C26	1.632 (7)
C8—C9	1.402 (10)	C25—H25A	0.9600
C8—H8	0.9300	C25—H25B	0.9600
C9—C10	1.324 (11)	C25—H25C	0.9600
C9—H9	0.9300	C26—H26A	0.9600
C10—C11	1.348 (10)	C26—H26B	0.9600
C10—H10	0.9300	C26—H26C	0.9600
C11—C12	1.391 (9)	S3A—O1A	1.358 (12)
C11—H11	0.9300	S3A—C26A	1.633 (8)
C12—H12	0.9300	S3A—C25A	1.640 (8)
C13—C14	1.374 (7)	C25A—H25D	0.9600
C13—C18	1.397 (8)	C25A—H25E	0.9600
C14—C15	1.401 (8)	C25A—H25F	0.9600
C14—H14	0.9300	C26A—H26D	0.9600
C15—C16	1.351 (10)	C26A—H26E	0.9600
C15—H15	0.9300	C26A—H26F	0.9600
C16—C17	1.348 (10)
P1i—Pd—P1	180.0	C16—C17—C18	120.1 (7)
P1i—Pd—S2i	94.12 (5)	C16—C17—H17	119.9
P1—Pd—S2i	85.88 (5)	C18—C17—H17	119.9
P1i—Pd—S2	85.89 (5)	C17—C18—C13	121.1 (7)
P1—Pd—S2	94.12 (5)	C17—C18—H18	119.4
S2i—Pd—S2	180.0	C13—C18—H18	119.4
C5—S1—C2	86.6 (3)	C24—C19—C20	116.7 (6)
C2—S2—Pd	103.87 (19)	C24—C19—P1	124.2 (6)
N3—C2—S2	127.2 (4)	C20—C19—P1	119.1 (5)
N3—C2—S1	113.7 (4)	C21—C20—C19	122.4 (7)
S2—C2—S1	119.0 (3)	C21—C20—H20	118.8
C2—N3—N4	112.7 (5)	C19—C20—H20	118.8
C5—N4—N3	113.3 (5)	C22—C21—C20	119.2 (9)
N4—C5—N6	125.0 (5)	C22—C21—H21	120.4
N4—C5—S1	113.6 (4)	C20—C21—H21	120.4
N6—C5—S1	121.4 (5)	C21—C22—C23	121.4 (9)
C5—N6—H6A	107.1 (13)	C21—C22—H22	119.3
C5—N6—H6B	107.0 (13)	C23—C22—H22	119.3
H6A—N6—H6B	116.7 (19)	C22—C23—C24	119.7 (9)
C19—P1—C13	99.9 (3)	C22—C23—H23	120.2
C19—P1—C7	105.3 (3)	C24—C23—H23	120.2
C13—P1—C7	106.6 (3)	C19—C24—C23	120.7 (8)
C19—P1—Pd	121.6 (2)	C19—C24—H24	119.7
C13—P1—Pd	113.4 (2)	C23—C24—H24	119.7
C7—P1—Pd	108.7 (2)	O1—S3—C25	115.4 (8)
C8—C7—C12	118.7 (6)	O1—S3—C26	115.0 (9)
C8—C7—P1	123.9 (6)	C25—S3—C26	112.7 (9)
C12—C7—P1	117.4 (5)	S3—C25—H25A	109.5
C7—C8—C9	120.3 (7)	S3—C25—H25B	109.5
C7—C8—H8	119.8	H25A—C25—H25B	109.5
C9—C8—H8	119.8	S3—C25—H25C	109.5
C10—C9—C8	120.4 (8)	H25A—C25—H25C	109.5
C10—C9—H9	119.8	H25B—C25—H25C	109.5
C8—C9—H9	119.8	S3—C26—H26A	109.5
C9—C10—C11	120.2 (8)	S3—C26—H26B	109.5
C9—C10—H10	119.9	H26A—C26—H26B	109.5
C11—C10—H10	119.9	S3—C26—H26C	109.5
C10—C11—C12	121.4 (8)	H26A—C26—H26C	109.5
C10—C11—H11	119.3	H26B—C26—H26C	109.5
C12—C11—H11	119.3	O1A—S3A—C26A	115.7 (10)
C7—C12—C11	119.0 (7)	O1A—S3A—C25A	114.9 (9)
C7—C12—H12	120.5	C26A—S3A—C25A	111.7 (10)
C11—C12—H12	120.5	S3A—C25A—H25D	109.5
C14—C13—C18	118.2 (6)	S3A—C25A—H25E	109.5
C14—C13—P1	120.2 (5)	H25D—C25A—H25E	109.5
C18—C13—P1	121.5 (5)	S3A—C25A—H25F	109.5
C13—C14—C15	119.1 (6)	H25D—C25A—H25F	109.5
C13—C14—H14	120.4	H25E—C25A—H25F	109.5
C15—C14—H14	120.4	S3A—C26A—H26D	109.5
C16—C15—C14	121.1 (7)	S3A—C26A—H26E	109.5
C16—C15—H15	119.5	H26D—C26A—H26E	109.5
C14—C15—H15	119.5	S3A—C26A—H26F	109.5
C17—C16—C15	120.3 (7)	H26D—C26A—H26F	109.5
C17—C16—H16	119.8	H26E—C26A—H26F	109.5
C15—C16—H16	119.8

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6A···N4ii	0.90 (1)	2.12 (2)	2.986 (7)	160 (5)

Table 1

Selected bond lengths (Å)

Pd—P1	2.3364 (15)
Pd—S2	2.3407 (14)
S2—C2	1.736 (5)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6—H6A⋯N4i	0.90 (1)	2.12 (2)	2.986 (7)	160 (5)

Symmetry code: (i) .