Di-μ-thio-semicarbazide-κ(4)S:S-bis-[chlori-dobis(triphenyl-phosphane-κP)silver(I)].

The dinuclear title complex, [Ag(2)Cl(2)(CH(5)N(3)S)(2)(C(18)H(15)P)(2)], lies across an inversion center. The Ag(I) ion exhibits a slightly distorted tetra-hedral coordination geometry formed by a P atom from a triphenyl-phosphane ligand, two metal-bridging S atoms from thio-semicabazide ligands and one chloride ion. The S atoms bridge two symmetry-related Ag(I) ions, forming a strictly planar Ag(2)S(2) core with an Ag⋯Ag separation of 2.7802 (7) Å. There is an intra-molecular N-H⋯Cl hydrogen bond. In the crystal, N-H⋯Cl and N-H⋯S hydrogen bonds link complex mol-ecules, forming layers parallel to (001). These layers are connected through π-π stacking inter-actions [centroid-centroid distance = 3.665 (2) Å], leading to the formation of a three-dimensional network.

Related literature

For metal(I) complexes of phosphine ligands as precursors for the preparation of mixed-ligand complexes, see: Ferrari et al. (2007 ▶); Pakawatchai et al. (2012 ▶). For potential applications of thio­semicarbazide derivatives and their metal complexes, see: Pandeya et al. (1999 ▶); Wujec et al. (2009 ▶); Mohareb & Mohamed (2012 ▶); He et al. (2012 ▶). For examples of related discrete complexes, see: Wattanakanjana et al. (2012 ▶); Lobana et al. (2008 ▶).

Experimental

Crystal data

[Ag2Cl2(CH5N3S)2(C18H15P)2]

M = 993.46

Triclinic,

a = 8.7845 (4) Å

b = 9.4656 (4) Å

c = 13.7529 (6) Å

α = 109.276 (1)°

β = 98.306 (1)°

γ = 99.739 (1)°

V = 1038.94 (8) Å3

Z = 1

Mo Kα radiation

μ = 1.28 mm−1

T = 293 K

0.38 × 0.30 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T min = 0.638, T max = 0.880

14302 measured reflections

5026 independent reflections

4627 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.069

S = 1.06

5026 reflections

251 parameters

5 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.38 e Å−3

Δρmin = −0.55 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812051562/lh5573sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812051562/lh5573Isup2.hkl

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

[Ag2Cl2(CH5N3S)2(C18H15P)2]	Z = 1
Mr = 993.46	F(000) = 500
Triclinic, P1	Dx = 1.588 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.7845 (4) Å	Cell parameters from 9010 reflections
b = 9.4656 (4) Å	θ = 2.3–28.0°
c = 13.7529 (6) Å	µ = 1.28 mm−1
α = 109.276 (1)°	T = 293 K
β = 98.306 (1)°	Block, colorless
γ = 99.739 (1)°	0.38 × 0.30 × 0.10 mm
V = 1038.94 (8) Å3

Bruker SMART CCD diffractometer	5026 independent reflections
Radiation source: fine-focus sealed tube	4627 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.036
Full–matrix least–squares on F2 scans	θmax = 28.0°, θmin = 1.6°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −11→11
Tmin = 0.638, Tmax = 0.880	k = −12→12
14302 measured reflections	l = −18→18

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.026	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.069	w = 1/[σ2(Fo2) + (0.0293P)2 + 0.2733P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.003
5026 reflections	Δρmax = 0.38 e Å−3
251 parameters	Δρmin = −0.55 e Å−3
5 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0693 (18)

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
C1	0.71808 (17)	1.20926 (18)	0.50782 (12)	0.0350 (3)
C11	1.16762 (18)	0.7721 (2)	0.21780 (12)	0.0418 (3)
C12	1.2004 (2)	0.6279 (3)	0.18680 (16)	0.0564 (5)
H12	1.1194	0.5403	0.1675	0.068*
C13	1.3557 (3)	0.6145 (3)	0.18463 (19)	0.0701 (6)
H13	1.3781	0.5177	0.1635	0.084*
C14	1.4747 (3)	0.7429 (4)	0.21342 (19)	0.0712 (7)
H14	1.5778	0.7330	0.2111	0.085*
C15	1.4436 (2)	0.8871 (3)	0.24596 (17)	0.0628 (6)
H15	1.5255	0.9741	0.2657	0.075*
C16	1.2904 (2)	0.9025 (2)	0.24935 (14)	0.0481 (4)
H16	1.2695	0.9999	0.2727	0.058*
C21	0.84762 (18)	0.61752 (19)	0.20371 (13)	0.0404 (3)
C22	0.7696 (2)	0.5083 (2)	0.10569 (15)	0.0546 (4)
H22	0.7794	0.5284	0.0448	0.065*
C23	0.6776 (3)	0.3701 (3)	0.09818 (19)	0.0678 (6)
H23	0.6257	0.2977	0.0322	0.081*
C24	0.6619 (3)	0.3386 (3)	0.1867 (2)	0.0732 (6)
H24	0.6023	0.2439	0.1809	0.088*
C25	0.7351 (3)	0.4481 (3)	0.2851 (2)	0.0789 (7)
H25	0.7228	0.4276	0.3456	0.095*
C26	0.8265 (3)	0.5878 (3)	0.29402 (17)	0.0619 (5)
H26	0.8737	0.6618	0.3603	0.074*
C31	0.90601 (19)	0.8272 (2)	0.09696 (15)	0.0447 (4)
C32	0.9697 (3)	0.7705 (2)	0.00965 (15)	0.0562 (4)
H32	1.0525	0.7220	0.0147	0.067*
C33	0.9124 (3)	0.7846 (3)	−0.08519 (19)	0.0758 (7)
H33	0.9564	0.7463	−0.1433	0.091*
C34	0.7892 (4)	0.8561 (4)	−0.0922 (3)	0.0916 (10)
H34	0.7483	0.8642	−0.1559	0.110*
C35	0.7272 (3)	0.9150 (4)	−0.0065 (3)	0.0931 (10)
H35	0.6449	0.9639	−0.0121	0.112*
C36	0.7850 (2)	0.9031 (3)	0.0888 (2)	0.0666 (6)
H36	0.7432	0.9457	0.1472	0.080*
N1	0.82011 (18)	1.32995 (18)	0.51108 (14)	0.0474 (3)
N2	0.57728 (17)	1.22460 (17)	0.52697 (14)	0.0478 (3)
N3	0.5365 (2)	1.3672 (2)	0.54628 (19)	0.0609 (5)
P1	0.96967 (5)	0.80383 (5)	0.22142 (3)	0.03895 (10)
S1	0.75685 (4)	1.02919 (4)	0.47995 (3)	0.03889 (10)
Cl1	1.13857 (6)	1.28186 (5)	0.41121 (4)	0.05418 (12)
Ag1	0.977789 (17)	1.016088 (15)	0.381354 (12)	0.05737 (8)
H1A	0.912 (2)	1.320 (3)	0.4929 (19)	0.069*
H1B	0.797 (3)	1.417 (2)	0.530 (2)	0.069*
H2	0.518 (3)	1.146 (2)	0.526 (2)	0.069*
H3A	0.528 (3)	1.404 (3)	0.6102 (14)	0.069*
H3B	0.443 (2)	1.349 (3)	0.5070 (18)	0.069*

	U11	U22	U33	U12	U13	U23
C1	0.0332 (7)	0.0382 (7)	0.0346 (7)	0.0098 (6)	0.0061 (5)	0.0142 (6)
C11	0.0328 (7)	0.0549 (10)	0.0334 (7)	0.0156 (7)	0.0070 (6)	0.0082 (7)
C12	0.0476 (10)	0.0577 (11)	0.0546 (10)	0.0222 (9)	0.0088 (8)	0.0047 (9)
C13	0.0606 (13)	0.0856 (17)	0.0659 (13)	0.0444 (13)	0.0159 (10)	0.0154 (12)
C14	0.0395 (10)	0.116 (2)	0.0689 (13)	0.0367 (12)	0.0176 (9)	0.0363 (14)
C15	0.0352 (9)	0.0982 (17)	0.0597 (12)	0.0118 (10)	0.0102 (8)	0.0366 (12)
C16	0.0377 (8)	0.0630 (11)	0.0454 (9)	0.0119 (8)	0.0088 (7)	0.0218 (8)
C21	0.0336 (7)	0.0431 (8)	0.0419 (8)	0.0124 (6)	0.0080 (6)	0.0107 (7)
C22	0.0610 (11)	0.0483 (10)	0.0432 (9)	0.0011 (8)	0.0152 (8)	0.0063 (8)
C23	0.0743 (14)	0.0492 (11)	0.0610 (12)	−0.0057 (10)	0.0126 (11)	0.0063 (9)
C24	0.0709 (14)	0.0592 (13)	0.0896 (17)	0.0004 (11)	0.0118 (12)	0.0368 (13)
C25	0.0872 (17)	0.0848 (17)	0.0714 (15)	0.0060 (14)	0.0063 (13)	0.0483 (14)
C26	0.0638 (12)	0.0692 (13)	0.0483 (10)	0.0083 (10)	−0.0014 (9)	0.0249 (10)
C31	0.0343 (7)	0.0401 (8)	0.0552 (10)	0.0030 (6)	0.0044 (7)	0.0166 (7)
C32	0.0637 (12)	0.0529 (11)	0.0468 (10)	0.0099 (9)	0.0097 (8)	0.0141 (8)
C33	0.0969 (19)	0.0617 (13)	0.0547 (12)	−0.0107 (13)	0.0015 (12)	0.0234 (11)
C34	0.0875 (19)	0.0859 (19)	0.097 (2)	−0.0152 (15)	−0.0220 (16)	0.0621 (18)
C35	0.0588 (14)	0.100 (2)	0.138 (3)	0.0163 (14)	−0.0038 (16)	0.078 (2)
C36	0.0438 (10)	0.0688 (13)	0.1000 (17)	0.0183 (9)	0.0158 (11)	0.0442 (13)
N1	0.0388 (7)	0.0386 (7)	0.0699 (10)	0.0106 (6)	0.0169 (7)	0.0230 (7)
N2	0.0372 (7)	0.0396 (7)	0.0729 (10)	0.0145 (6)	0.0200 (7)	0.0226 (7)
N3	0.0468 (9)	0.0477 (9)	0.0920 (14)	0.0236 (7)	0.0164 (9)	0.0234 (9)
P1	0.03125 (19)	0.0388 (2)	0.0393 (2)	0.00988 (15)	0.00878 (15)	0.00323 (16)
S1	0.03454 (18)	0.03454 (19)	0.0490 (2)	0.01021 (14)	0.01279 (15)	0.01437 (16)
Cl1	0.0497 (2)	0.0406 (2)	0.0713 (3)	0.00658 (17)	0.0195 (2)	0.0183 (2)
Ag1	0.05604 (11)	0.04168 (10)	0.06025 (12)	0.00514 (6)	0.02583 (7)	−0.00213 (7)

C1—N1	1.311 (2)	C25—H25	0.9300
C1—N2	1.323 (2)	C26—H26	0.9300
C1—S1	1.7236 (16)	C31—C32	1.383 (3)
C11—C12	1.383 (3)	C31—C36	1.391 (3)
C11—C16	1.391 (3)	C31—P1	1.8184 (18)
C11—P1	1.8189 (16)	C32—C33	1.386 (3)
C12—C13	1.394 (3)	C32—H32	0.9300
C12—H12	0.9300	C33—C34	1.377 (4)
C13—C14	1.364 (4)	C33—H33	0.9300
C13—H13	0.9300	C34—C35	1.360 (5)
C14—C15	1.377 (4)	C34—H34	0.9300
C14—H14	0.9300	C35—C36	1.383 (4)
C15—C16	1.384 (3)	C35—H35	0.9300
C15—H15	0.9300	C36—H36	0.9300
C16—H16	0.9300	N1—H1A	0.888 (16)
C21—C22	1.389 (2)	N1—H1B	0.851 (17)
C21—C26	1.391 (3)	N2—N3	1.406 (2)
C21—P1	1.8221 (18)	N2—H2	0.834 (16)
C22—C23	1.381 (3)	N3—H3A	0.851 (16)
C22—H22	0.9300	N3—H3B	0.870 (16)
C23—C24	1.366 (4)	P1—Ag1	2.4225 (4)
C23—H23	0.9300	S1—Ag1	2.5202 (4)
C24—C25	1.384 (4)	Cl1—Ag1	2.5378 (5)
C24—H24	0.9300	Ag1—Ag1i	3.3502 (4)
C25—C26	1.383 (3)
N1—C1—N2	119.02 (15)	C32—C31—P1	123.22 (14)
N1—C1—S1	123.57 (12)	C36—C31—P1	118.21 (17)
N2—C1—S1	117.41 (12)	C31—C32—C33	121.2 (2)
C12—C11—C16	119.68 (16)	C31—C32—H32	119.4
C12—C11—P1	123.64 (15)	C33—C32—H32	119.4
C16—C11—P1	116.68 (13)	C34—C33—C32	119.1 (3)
C11—C12—C13	119.7 (2)	C34—C33—H33	120.5
C11—C12—H12	120.2	C32—C33—H33	120.5
C13—C12—H12	120.2	C35—C34—C33	120.4 (2)
C14—C13—C12	120.2 (2)	C35—C34—H34	119.8
C14—C13—H13	119.9	C33—C34—H34	119.8
C12—C13—H13	119.9	C34—C35—C36	120.9 (3)
C13—C14—C15	120.57 (19)	C34—C35—H35	119.6
C13—C14—H14	119.7	C36—C35—H35	119.6
C15—C14—H14	119.7	C35—C36—C31	119.8 (3)
C14—C15—C16	120.0 (2)	C35—C36—H36	120.1
C14—C15—H15	120.0	C31—C36—H36	120.1
C16—C15—H15	120.0	C1—N1—H1A	120.0 (17)
C15—C16—C11	119.9 (2)	C1—N1—H1B	119.0 (18)
C15—C16—H16	120.1	H1A—N1—H1B	121 (2)
C11—C16—H16	120.1	C1—N2—N3	120.06 (15)
C22—C21—C26	118.97 (18)	C1—N2—H2	115.7 (18)
C22—C21—P1	123.40 (14)	N3—N2—H2	124.3 (19)
C26—C21—P1	117.55 (14)	N2—N3—H3A	109.2 (19)
C23—C22—C21	120.31 (19)	N2—N3—H3B	106.8 (18)
C23—C22—H22	119.8	H3A—N3—H3B	107 (2)
C21—C22—H22	119.8	C31—P1—C11	103.77 (8)
C24—C23—C22	120.6 (2)	C31—P1—C21	103.33 (8)
C24—C23—H23	119.7	C11—P1—C21	105.00 (8)
C22—C23—H23	119.7	C31—P1—Ag1	117.05 (6)
C23—C24—C25	119.7 (2)	C11—P1—Ag1	109.59 (5)
C23—C24—H24	120.1	C21—P1—Ag1	116.71 (6)
C25—C24—H24	120.1	C1—S1—Ag1	108.17 (5)
C26—C25—C24	120.3 (2)	P1—Ag1—S1	123.445 (15)
C26—C25—H25	119.8	P1—Ag1—Cl1	119.164 (17)
C24—C25—H25	119.8	S1—Ag1—Cl1	111.851 (15)
C25—C26—C21	120.0 (2)	P1—Ag1—Ag1i	122.531 (13)
C25—C26—H26	120.0	S1—Ag1—Ag1i	58.885 (10)
C21—C26—H26	120.0	Cl1—Ag1—Ag1i	105.880 (14)
C32—C31—C36	118.6 (2)
C16—C11—C12—C13	−1.8 (3)	C36—C31—P1—C21	91.93 (16)
P1—C11—C12—C13	178.80 (17)	C32—C31—P1—Ag1	143.54 (15)
C11—C12—C13—C14	0.3 (4)	C36—C31—P1—Ag1	−37.84 (17)
C12—C13—C14—C15	0.7 (4)	C12—C11—P1—C31	−96.91 (17)
C13—C14—C15—C16	−0.2 (3)	C16—C11—P1—C31	83.68 (14)
C14—C15—C16—C11	−1.3 (3)	C12—C11—P1—C21	11.23 (18)
C12—C11—C16—C15	2.3 (3)	C16—C11—P1—C21	−168.18 (13)
P1—C11—C16—C15	−178.27 (14)	C12—C11—P1—Ag1	137.34 (15)
C26—C21—C22—C23	−2.5 (3)	C16—C11—P1—Ag1	−42.07 (14)
P1—C21—C22—C23	−179.27 (18)	C22—C21—P1—C31	18.41 (17)
C21—C22—C23—C24	0.0 (4)	C26—C21—P1—C31	−158.39 (15)
C22—C23—C24—C25	2.0 (4)	C22—C21—P1—C11	−90.05 (16)
C23—C24—C25—C26	−1.3 (5)	C26—C21—P1—C11	93.14 (16)
C24—C25—C26—C21	−1.3 (4)	C22—C21—P1—Ag1	148.38 (14)
C22—C21—C26—C25	3.1 (3)	C26—C21—P1—Ag1	−28.42 (16)
P1—C21—C26—C25	−179.9 (2)	N1—C1—S1—Ag1	−21.93 (16)
C36—C31—C32—C33	−1.7 (3)	N2—C1—S1—Ag1	158.21 (12)
P1—C31—C32—C33	176.89 (16)	C31—P1—Ag1—S1	96.31 (6)
C31—C32—C33—C34	−0.2 (3)	C11—P1—Ag1—S1	−145.95 (6)
C32—C33—C34—C35	1.4 (4)	C21—P1—Ag1—S1	−26.83 (6)
C33—C34—C35—C36	−0.7 (4)	C31—P1—Ag1—Cl1	−55.26 (7)
C34—C35—C36—C31	−1.3 (4)	C11—P1—Ag1—Cl1	62.48 (7)
C32—C31—C36—C35	2.5 (3)	C21—P1—Ag1—Cl1	−178.40 (6)
P1—C31—C36—C35	−176.20 (19)	C31—P1—Ag1—Ag1i	168.06 (6)
N1—C1—N2—N3	2.5 (3)	C11—P1—Ag1—Ag1i	−74.21 (7)
S1—C1—N2—N3	−177.61 (15)	C21—P1—Ag1—Ag1i	44.92 (6)
C32—C31—P1—C11	22.69 (18)	C1—S1—Ag1—P1	−132.43 (5)
C36—C31—P1—C11	−158.69 (16)	C1—S1—Ag1—Cl1	20.96 (6)
C32—C31—P1—C21	−86.69 (17)	C1—S1—Ag1—Ag1i	116.84 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···Cl1ii	0.87 (2)	2.67 (2)	3.535 (2)	171 (2)
N2—H2···S1iii	0.83 (2)	2.66 (2)	3.4320 (15)	155 (2)
N1—H1B···Cl1iv	0.85 (2)	2.63 (2)	3.4088 (16)	154 (2)
N1—H1A···Cl1	0.89 (2)	2.45 (2)	3.3239 (16)	170 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3B⋯Cl1i	0.87 (2)	2.67 (2)	3.535 (2)	171 (2)
N2—H2⋯S1ii	0.83 (2)	2.66 (2)	3.4320 (15)	155 (2)
N1—H1B⋯Cl1iii	0.85 (2)	2.63 (2)	3.4088 (16)	154 (2)
N1—H1A⋯Cl1	0.89 (2)	2.45 (2)	3.3239 (16)	170 (2)

Symmetry codes: (i) ; (ii) ; (iii) .