Poly[[μ(3)-chlorido-bis(μ(2)-thio-urea-κS)disilver(I)] nitrate].

The mol-ecular structure of the title polymeric complex, {[Ag(2)Cl(CH(4)N(2)S)(2)]NO(3)}(n), consists of a binuclear cationic complex and a nitrate counter-ion. The cationic complex contains two bridging thio-urea (Tu) ligands and a triply bridging μ(3)-Cl anion. The latter is probably released from 2-amino-ethane-thiol hydro-chloride during the synthesis. The coordination environment around the two Ag(I) atoms is different; one is trigonal planar, being coordinated by two thio-urea ligands through the S atoms and to one Cl(-) ion, while in the other the Ag(I) atom is tetra-hedrally coordinated by two thio-urea ligands through the S atoms and to two Cl(-) ions. These units aggregate through the Cl(-) anion and the Tu S atoms, forming a chain propagating in [100]. In the crystal structure, the polymeric chains are linked via N-H⋯O and N-H⋯Cl hydrogen bonds, forming a double layer two-dimensional network propagating in (011).

Related literature

For silver(I) complexes with sulfur-containing ligands with applications in medicine and analytical chemistry, see: Raper (1996 ▶); Akrivos (2001 ▶). For silver(I) complexes containing thio­nes, see: Stocker et al. (2000 ▶); Pakawatchai et al. (1996 ▶); Casas et al. (1996 ▶); Aslandis et al. (2005 ▶); Ashraf et al. (2004 ▶); Isab et al. (2002 ▶). For silver(I) complexes containing thiol­ates, see: Nomiya et al. (2000 ▶); Zachariadis et al. (2003 ▶); Tsyba et al. (2003 ▶). For argentophilic inter­actions, see: Nomiya et al. (2000 ▶); Zachariadis et al. (2003 ▶); Tsyba et al. (2003 ▶). For the structures of some silver(I) complexes of thio­urea, see: Udupa et al. (1976 ▶); Hanif et al. (2007 ▶).

Experimental

Crystal data

[Ag2Cl(CH4N2S)2]NO3

M = 465.44

Triclinic,

a = 6.3981 (8) Å

b = 7.7060 (9) Å

c = 11.8478 (14) Å

α = 83.041 (14)°

β = 82.868 (14)°

γ = 77.312 (14)°

V = 562.80 (12) Å3

Z = 2

Mo Kα radiation

μ = 4.08 mm−1

T = 173 K

0.34 × 0.23 × 0.12 mm

Data collection

Stoe IPDS diffractometer

Absorption correction: multi-scan (MULscanABS in PLATON; Spek, 2009 ▶) T min = 0.771, T max = 1.353

4473 measured reflections

2055 independent reflections

1682 reflections with I > 2σ(I)

R int = 0.056

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.114

S = 0.98

2055 reflections

136 parameters

H-atom parameters constrained

Δρmax = 1.49 e Å−3

Δρmin = −1.27 e Å−3

Data collection: EXPOSE (Stoe & Cie, 2004 ▶); cell refinement: CELL (Stoe & Cie, 2004 ▶); data reduction: INTEGRATE (Stoe & Cie, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: PLATON and SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810030953/bt5309sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810030953/bt5309Isup2.hkl

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

[Ag2Cl(CH4N2S)2]NO3	Z = 2
Mr = 465.44	F(000) = 444
Triclinic, P1	Dx = 2.747 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.3981 (8) Å	Cell parameters from 5310 reflections
b = 7.7060 (9) Å	θ = 2.7–26.0°
c = 11.8478 (14) Å	µ = 4.08 mm−1
α = 83.041 (14)°	T = 173 K
β = 82.868 (14)°	Plate, colourless
γ = 77.312 (14)°	0.34 × 0.23 × 0.12 mm
V = 562.80 (12) Å3

Stoe IPDS diffractometer	2055 independent reflections
Radiation source: fine-focus sealed tube	1682 reflections with I > 2σ(I)
graphite	Rint = 0.056
φ scans	θmax = 26.0°, θmin = 2.7°
Absorption correction: multi-scan (MULscanABS in PLATON; Spek, 2009)	h = −7→7
Tmin = 0.771, Tmax = 1.353	k = −9→8
4473 measured reflections	l = −14→13

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.114	H-atom parameters constrained
S = 0.98	w = 1/[σ2(Fo2) + (0.0795P)2] where P = (Fo2 + 2Fc2)/3
2055 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 1.49 e Å−3
0 restraints	Δρmin = −1.27 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. The NH2H-atoms were included in calculated positions and treated as riding atoms: N—H 0.88 Å with Uiso(H) = 1.2Ueq(parent N-atom).

	x	y	z	Uiso*/Ueq
Ag1	0.48799 (7)	0.87109 (6)	0.15613 (4)	0.0303 (2)
Ag2	1.07497 (7)	1.16730 (7)	0.06513 (4)	0.0327 (2)
Cl1	0.6808 (2)	1.16001 (19)	0.05756 (13)	0.0245 (4)
S1	0.7764 (2)	0.63258 (18)	0.08944 (12)	0.0197 (4)
S2	0.2032 (2)	1.07487 (18)	0.25782 (13)	0.0201 (4)
N1	1.1617 (8)	0.5710 (7)	0.1682 (5)	0.0264 (16)
N2	0.8858 (7)	0.5149 (7)	0.2959 (5)	0.0271 (16)
N3	0.0979 (8)	0.8245 (7)	0.4138 (5)	0.0319 (16)
N4	−0.1790 (8)	0.9882 (7)	0.3218 (5)	0.0276 (16)
C1	0.9560 (8)	0.5703 (7)	0.1930 (5)	0.0179 (14)
C2	0.0266 (8)	0.9512 (7)	0.3359 (5)	0.0183 (17)
O1	0.1853 (6)	0.3896 (6)	0.4594 (4)	0.0303 (15)
O2	0.4735 (7)	0.2157 (7)	0.5106 (5)	0.0440 (16)
O3	0.4800 (8)	0.3913 (8)	0.3521 (5)	0.0481 (18)
N5	0.3826 (7)	0.3331 (7)	0.4412 (5)	0.0268 (16)
H1A	1.25110	0.53410	0.22110	0.0320*
H1B	1.21010	0.60840	0.09880	0.0320*
H2A	0.97600	0.47810	0.34840	0.0330*
H2B	0.74820	0.51410	0.31310	0.0330*
H3A	0.00830	0.76530	0.45590	0.0380*
H3B	0.23560	0.79830	0.42420	0.0380*
H4A	−0.26680	0.92790	0.36460	0.0330*
H4B	−0.22930	1.07330	0.26960	0.0330*

	U11	U22	U33	U12	U13	U23
Ag1	0.0177 (3)	0.0356 (3)	0.0341 (3)	−0.0027 (2)	0.0032 (2)	−0.0001 (2)
Ag2	0.0266 (3)	0.0465 (3)	0.0235 (3)	−0.0128 (2)	−0.0058 (2)	0.0155 (2)
Cl1	0.0214 (6)	0.0313 (7)	0.0219 (8)	−0.0123 (5)	−0.0056 (5)	0.0089 (6)
S1	0.0155 (6)	0.0263 (7)	0.0163 (8)	−0.0040 (5)	−0.0036 (5)	0.0038 (6)
S2	0.0160 (6)	0.0234 (7)	0.0198 (8)	−0.0062 (5)	−0.0013 (5)	0.0057 (6)
N1	0.024 (2)	0.036 (3)	0.019 (3)	−0.010 (2)	−0.0043 (19)	0.007 (2)
N2	0.014 (2)	0.043 (3)	0.022 (3)	−0.007 (2)	−0.0018 (19)	0.008 (2)
N3	0.019 (2)	0.042 (3)	0.029 (3)	−0.005 (2)	−0.005 (2)	0.019 (3)
N4	0.018 (2)	0.041 (3)	0.022 (3)	−0.011 (2)	−0.0029 (19)	0.014 (2)
C1	0.018 (2)	0.016 (2)	0.019 (3)	−0.0056 (19)	−0.002 (2)	0.005 (2)
C2	0.019 (3)	0.022 (3)	0.012 (3)	−0.001 (2)	−0.001 (2)	−0.001 (2)
O1	0.0158 (18)	0.044 (3)	0.024 (3)	0.0012 (17)	−0.0020 (16)	0.011 (2)
O2	0.022 (2)	0.056 (3)	0.047 (3)	−0.001 (2)	−0.013 (2)	0.019 (3)
O3	0.028 (2)	0.071 (4)	0.041 (3)	−0.020 (2)	0.010 (2)	0.016 (3)
N5	0.016 (2)	0.035 (3)	0.028 (3)	−0.008 (2)	−0.002 (2)	0.007 (2)

Ag1—Cl1	2.8393 (15)	N1—C1	1.314 (8)
Ag1—S1	2.4305 (15)	N2—C1	1.301 (8)
Ag1—S2	2.4278 (15)	N3—C2	1.305 (8)
Ag1—Cl1i	2.9280 (16)	N4—C2	1.311 (8)
Ag2—Cl1	2.5477 (14)	N1—H1A	0.8800
Ag2—S2ii	2.4913 (16)	N1—H1B	0.8800
Ag2—S1iii	2.4827 (15)	N2—H2B	0.8800
S1—C1	1.738 (6)	N2—H2A	0.8800
S2—C2	1.744 (6)	N3—H3A	0.8800
O1—N5	1.242 (6)	N3—H3B	0.8800
O2—N5	1.241 (8)	N4—H4A	0.8800
O3—N5	1.244 (8)	N4—H4B	0.8800
Cl1—Ag1—S1	96.91 (5)	C1—N1—H1A	120.00
Cl1—Ag1—S2	90.60 (5)	C1—N2—H2A	120.00
Cl1—Ag1—Cl1i	92.64 (5)	H2A—N2—H2B	120.00
S1—Ag1—S2	169.00 (5)	C1—N2—H2B	120.00
Cl1i—Ag1—S1	82.74 (5)	C2—N3—H3A	120.00
Cl1i—Ag1—S2	105.01 (5)	H3A—N3—H3B	120.00
Cl1—Ag2—S2ii	114.00 (5)	C2—N3—H3B	120.00
Cl1—Ag2—S1iii	114.55 (5)	C2—N4—H4B	120.00
S1iii—Ag2—S2ii	126.77 (5)	H4A—N4—H4B	120.00
Ag1—Cl1—Ag2	123.99 (6)	C2—N4—H4A	120.00
Ag1—Cl1—Ag1i	87.36 (4)	O2—N5—O3	122.5 (5)
Ag1i—Cl1—Ag2	121.83 (6)	O1—N5—O2	118.6 (5)
Ag1—S1—C1	108.15 (19)	O1—N5—O3	118.8 (5)
Ag1—S1—Ag2iii	93.38 (5)	S1—C1—N1	121.4 (5)
Ag2iii—S1—C1	108.74 (19)	S1—C1—N2	119.0 (4)
Ag1—S2—C2	108.27 (19)	N1—C1—N2	119.6 (5)
Ag1—S2—Ag2iv	83.91 (5)	S2—C2—N3	119.6 (4)
Ag2iv—S2—C2	107.4 (2)	S2—C2—N4	121.3 (4)
C1—N1—H1B	120.00	N3—C2—N4	119.0 (5)
H1A—N1—H1B	120.00
S1—Ag1—Cl1—Ag2	−44.29 (8)	S2—Ag1—Cl1i—Ag1i	91.33 (5)
S1—Ag1—Cl1—Ag1i	83.00 (5)	S2—Ag1—Cl1i—Ag2i	−37.73 (8)
S2—Ag1—Cl1—Ag2	127.66 (7)	S2ii—Ag2—Cl1—Ag1	−46.44 (8)
S2—Ag1—Cl1—Ag1i	−105.06 (5)	S2ii—Ag2—Cl1—Ag1i	−157.13 (6)
Cl1i—Ag1—Cl1—Ag2	−127.29 (7)	S1iii—Ag2—Cl1—Ag1	156.10 (6)
Cl1i—Ag1—Cl1—Ag1i	−0.02 (9)	S1iii—Ag2—Cl1—Ag1i	45.41 (8)
Cl1—Ag1—S1—C1	90.6 (2)	Cl1—Ag2—S2ii—Ag1ii	127.70 (5)
Cl1—Ag1—S1—Ag2iii	−20.40 (5)	Cl1—Ag2—S2ii—C2ii	20.4 (2)
Cl1i—Ag1—S1—C1	−177.6 (2)	Cl1—Ag2—S1iii—Ag1iii	−123.22 (5)
Cl1i—Ag1—S1—Ag2iii	71.40 (5)	Cl1—Ag2—S1iii—C1iii	−12.8 (2)
Cl1—Ag1—S2—C2	179.2 (2)	Ag1—S1—C1—N1	−124.7 (4)
Cl1—Ag1—S2—Ag2iv	72.83 (5)	Ag1—S1—C1—N2	58.3 (5)
Cl1i—Ag1—S2—C2	86.3 (2)	Ag2iii—S1—C1—N1	−24.5 (5)
Cl1i—Ag1—S2—Ag2iv	−20.06 (5)	Ag2iii—S1—C1—N2	158.4 (4)
Cl1—Ag1—Cl1i—Ag1i	0.02 (10)	Ag1—S2—C2—N3	60.2 (5)
Cl1—Ag1—Cl1i—Ag2i	−129.06 (7)	Ag1—S2—C2—N4	−123.1 (5)
S1—Ag1—Cl1i—Ag1i	−96.64 (5)	Ag2iv—S2—C2—N3	149.4 (4)
S1—Ag1—Cl1i—Ag2i	134.30 (7)	Ag2iv—S2—C2—N4	−33.8 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ii	0.88	2.28	3.153 (8)	170
N2—H2A···O1ii	0.88	1.95	2.831 (7)	177
N2—H2B···O3	0.88	2.11	2.932 (7)	155
N3—H3A···O1v	0.88	2.00	2.881 (7)	174
N3—H3B···O2vi	0.88	2.08	2.930 (7)	163
N4—H4A···O2v	0.88	2.22	3.095 (8)	173
N1—H1B···Cl1iii	0.88	2.56	3.372 (6)	155
N4—H4B···Cl1iv	0.88	2.62	3.396 (6)	147

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3i	0.88	2.28	3.153 (8)	170
N2—H2A⋯O1i	0.88	1.95	2.831 (7)	177
N2—H2B⋯O3	0.88	2.11	2.932 (7)	155
N3—H3A⋯O1ii	0.88	2.00	2.881 (7)	174
N3—H3B⋯O2iii	0.88	2.08	2.930 (7)	163
N4—H4A⋯O2ii	0.88	2.22	3.095 (8)	173
N1—H1B⋯Cl1iv	0.88	2.56	3.372 (6)	155
N4—H4B⋯Cl1v	0.88	2.62	3.396 (6)	147

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