Crystal structure of bis­[μ-bis­(di­phenyl­phosphan­yl)methane-κ2 P:P′]-μ-chlorido-chlorido-1κCl-(1-phenyl­thio­urea-2κS)disilver aceto­nitrile hemisolvate

Arunpatcha Nimthong-Roldán; Janejira Ratthiwal; Yupa Wattanakanjana

doi:10.1107/S2056989015008981

. 2015 May 23;71(Pt 6):m133–m134. doi: 10.1107/S2056989015008981

Crystal structure of bis[μ-bis(diphenylphosphanyl)methane-κ² P:P′]-μ-chlorido-chlorido-1κCl-(1-phenylthiourea-2κS)disilver acetonitrile hemisolvate

Arunpatcha Nimthong-Roldán ^a, Janejira Ratthiwal ^b, Yupa Wattanakanjana ^b,^*

PMCID: PMC4459320 PMID: 26090168

Abstract

In the dinuclear title complex, [Ag₂Cl₂(C₇H₈N₂S)(C₂₅H₂₂P₂)₂]·0.5CH₃CN, each Ag^I ion displays a distorted tetrahedral coordination geometry with two P atoms from two bis(diphenylphosphanyl)methane (dppm) ligands, one bridging chloride ion, one terminal chloride ion and one terminal S atom from the N,N′-phenylthiourea (ptu) ligand. The dppm ligands and the bridging chloride ion force the two Ag atoms into close proximity, with a short Ag⋯Ag separation of 3.2064 (2) Å. In the crystal, complex molecules are linked by N—H⋯Cl hydrogen bonds forming a dimer. The dimers are linked via weak C— H⋯Cl hydrogen bonds forming a two-dimensional supramolecular architecture in the yz plane. In addition, an intramolecular N—H⋯Cl hydrogen bond is observed.

Keywords: crystal structure; silver complex; N,N′-phenylthiourea; hydrogen bonding

Related literature

For the studies of silver(I) complexes containing phosphine and sulfur co-donor ligands, see: Zhang et al. (2003 ▸); Wattanakanjana et al. (2013 ▸). For their various applications such as antimicrobial activities, see: Isab et al. (2010 ▸); Nawaz et al. (2011 ▸). graphic file with name e-71-0m133-scheme1.jpg

Experimental

Crystal data

[Ag₂Cl₂(C₇H₈N₂S)(C₂₅H₂₂P₂)₂]·0.5C₂H₃N
M _r = 2456.22
Monoclinic,
a = 30.6130 (12) Å
b = 16.5078 (4) Å
c = 21.7975 (6) Å
β = 97.129 (2)°
V = 10930.3 (6) Å³
Z = 4
Mo Kα radiation
μ = 1.01 mm⁻¹
T = 100 K
0.38 × 0.27 × 0.05 mm

Data collection

Bruker AXS D8 Quest CMOS diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2014 ▸) T _min = 0.564, T _max = 0.746
43370 measured reflections
13309 independent reflections
11256 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.076
S = 1.09
13309 reflections
628 parameters
H-atom parameters constrained
Δρ_max = 1.11 e Å⁻³
Δρ_min = −0.82 e Å⁻³

Data collection: APEX2 (Bruker, 2014 ▸); cell refinement: SAINT (Bruker, 2014 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ▸) and SHELXLE (Hübschle et al., 2011 ▸); molecular graphics: Mercury (Macrae et al., 2008 ▸); software used to prepare material for publication: SHELXL2013.

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015008981/pj2019sup1.cif

e-71-0m133-sup1.cif^{(1.3MB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015008981/pj2019Isup2.hkl

e-71-0m133-Isup2.hkl^{(1MB, hkl)}

Click here for additional data file.^{(1.6MB, tif)}

. DOI: 10.1107/S2056989015008981/pj2019fig1.tif

The molecular structure with displacement ellipsoids drawn at the 50% probability level. The acetonitrile is omitted for clarity.

Click here for additional data file.^{(1.4MB, tif)}

. DOI: 10.1107/S2056989015008981/pj2019fig2.tif

Part of the crystal structure showing intra-intermolecular N—H⋯Cl hydrogen bonds forming a dimers as dashed lines.

Click here for additional data file.^{(2.2MB, tif)}

. DOI: 10.1107/S2056989015008981/pj2019fig3.tif

Part of the crystal structure showing intermolecular C—H⋯Cl hydrogen bonds as dashed lines, forming a two-dimensional network parallel to (100).

CCDC reference: 1064097

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N1H1Cl2ⁱ	0.88	2.32	3.1910(19)	172
N2H2ACl1ⁱ	0.88	2.56	3.1618(19)	126
N2H2ACl2ⁱ	0.88	2.84	3.595(2)	144
N2H2BCl1	0.88	2.52	3.328(2)	152

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Symmetry code: (i) Inline graphic .

Acknowledgments

Financial support from the Department of Chemistry, Prince of Songkla University, is gratefully acknowledged. We would like to thank Dr Matthias Zeller for valuable suggestions and assistance with the X-ray structure determination and use of structure refinement programs.

supplementary crystallographic information

S1. Experimental

Bis(diphenylphosphanyl)methane, dppm, (0.1 g, 0.26 mmol) was dissolved in 30 ml of acetonitrile at 343 K and then silver(I) chloride, AgCl, (0.04 g, 0.28 mmol) was added. The mixture was stirred for 4 hr and then N,N′-phenylthiourea, ptu, (0.04 g, 0.26 mmol) was added and the new reaction mixture was heated under reflux for 6 hr during which the precipitate gradually disappeared. The resulting clear solution was filtered and left to evaporate at room temperature. The crystalline complex, which deposited upon standing for several days, was filtered off and dried in vacuo.

S1.1. Refinement

H atoms bonded to C and N atoms were included in calculated positions and were refined with a riding model using distances of 0.95 Å (aryl H), and U_iso(H) = 1.2U_eq(C); 0.99 Å (CH₂) and U_iso(H) = 1.5U_eq(C); 0.88 Å (NH), and U_iso(H) = 1.2U_eq(N).

S2. Results and discussion

Silver(I) complexes containing phosphine and sulfur co-donor ligands have been studied in recent years (Zhang et al., 2003; Wattanakanjana et al., 2013) because of their various applications such as antimicrobial activities (Isab et al., 2010; Nawaz et al., 2011). Herein, the crystal structure of a dinuclear silver(I) chloride complex containing both dppm and ptu is described.

The title complex is dinuclear in which the Ag^I ions adopt distorted tetrahedral geometries. Bis(diphenylphosphanyl)methane (dppm) affords a dinuclear metal complex in the µ-dppm form. There are two kinds of coordination environment around the Ag^I centres. In one of the Ag centre, the silver atom, Ag1, is tetrahedrally coordinated to two P atoms of two dppm ligands, one bridging chloride ion and a terminal S atom of N,N'-phenylthiourea (ptu) ligand. In the second centre, the silver atom, Ag2, is bound to two P atoms of two dppm ligands and two chloride ions form the bridging and a terminal Cl atom in a tetrahedral environment as shown in Fig. 1. The dppm ligands and the bridging chloride ion force the two Ag atoms into close proximity with a short Ag···Ag separation of 3.2064 (2) Å. In the crystal, N1—H1···Cl2ⁱ and N2—H2A···Cl1ⁱ hydrogen bonds are linked molecules into dimers (Fig. 2 and Table 1). The dimers are connected via a weak C10— H10A···Cl2ⁱⁱ hydrogen bonds [C10(sp³)—H10A···Cl2ⁱⁱ, with H10A···Cl2ⁱⁱ = 2.6379 (6) Å, C10(sp³)···Cl2ⁱⁱ, = 3.581 (2) Å and C10(sp³)—H10A···Cl2ⁱⁱ, = 159.20 (14)°, symmetry code: (ii) 1/2 - x,-1/2 + y, 1/2 - z], leading to the formation of a two-dimensional network parallel to (100), Fig. 3. In addition, an intramolecular N2—H2B···Cl1 hydrogen bond is observed.