Crystal structure of tris­[μ2-bis­(di­phenyl­phosphan­yl)methane-κ2 P:P′]di-μ3-bromido-tris­ilver(I) bromide–N,N′-phenyl­thio­urea (1/1)

Arunpatcha Nimthong-Roldán; Yupa Wattanakanjana; Jintana Rodkeaw

doi:10.1107/S2056989015005150

. 2015 Mar 21;71(Pt 4):m89–m90. doi: 10.1107/S2056989015005150

Crystal structure of tris[μ₂-bis(diphenylphosphanyl)methane-κ² P:P′]di-μ₃-bromido-trisilver(I) bromide–N,N′-phenylthiourea (1/1)

Arunpatcha Nimthong-Roldán ^a, Yupa Wattanakanjana ^b,^*, Jintana Rodkeaw ^b

PMCID: PMC4438794 PMID: 26029416

Abstract

The title complex, [Ag₃Br₂(C₂₅H₂₂P₂)₃]Br·C₇H₈N₂S, comprises a trinuclear [Ag₃Br₂(C₂₅H₂₂P₂)₃]⁺ unit, a Br⁻ anion and one N,N′-dimethylthiourea molecule (ptu). Three Ag^I ions are linked via two μ₃-bridging Br atoms, leading to a distorted triangular bipyramid with an Ag⋯Ag separation range of 3.1046 (6)–3.3556 (6) Å. The triangular Ag₃ arrangement is stabilized by six P atoms from three chelating bis(diphenylphosphanyl)methane (dppm) ligands. The Ag^I ion presents a distorted tetrahedral coordination geometry. In the crystal, the bromide anion is connected to the ptu molecule through N—H⋯Br hydrogen bonds [graph-set motif R ₂ ¹(6)]. Each bromide/ptu aggregate links the complex ion via C—H⋯S and C—H⋯Br hydrogen bonds, leading to the formation of a three-dimensional network. Two phenyl rings from two dppm ligands were modelled as disordered over two sites.

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

Related literature

For studies of silver(I) complexes with diphosphane ligands, see: Matsumoto et al. (2001 ▸); Nicola et al. (2005 ▸, 2006 ▸). For their potential applications, see: Song et al. (2010 ▸); Sun et al. (2011 ▸). For applications of the coordination chemistry of silver(I) complexes with phosphorus- and sulfur-donor ligands, see: Isab et al. (2010 ▸). graphic file with name e-71-00m89-scheme1.jpg

Experimental

Crystal data

[Ag₃Br₂(C₂₅H₂₂P₂)₃]Br·C₇H₈N₂S
M _r = 1868.65
Monoclinic,
a = 10.550 (2) Å
b = 28.329 (6) Å
c = 25.622 (6) Å
β = 95.859 (4)°
V = 7618 (3) Å³
Z = 4
Mo Kα radiation
μ = 2.54 mm⁻¹
T = 100 K
0.22 × 0.15 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2013 ▸) T _min = 0.516, T _max = 0.746
54265 measured reflections
22914 independent reflections
16918 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.097
S = 0.99
22914 reflections
911 parameters
84 restraints
H-atom parameters constrained
Δρ_max = 1.48 e Å⁻³
Δρ_min = −0.67 e Å⁻³

Data collection: APEX2 (Bruker, 2013 ▸); cell refinement: SAINT (Bruker, 2013 ▸); 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: publCIF (Westrip, 2010 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015005150/nk2229sup1.cif

e-71-00m89-sup1.cif^{(1.6MB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015005150/nk2229Isup2.hkl

e-71-00m89-Isup2.hkl^{(1.2MB, hkl)}

Click here for additional data file.^{(1.9MB, tif)}

. DOI: 10.1107/S2056989015005150/nk2229fig1.tif

The molecular structure with displacement ellipsoids drawn at the 50% probability level. The minor component of disorder is omitted for clarity. The dashed lines show N—H⋯Br hydrogen bonds between the ptu and the bromide anion.

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

. DOI: 10.1107/S2056989015005150/nk2229fig2.tif

Part of the crystal structure showing intermolecular C—H⋯S and C—H⋯Br hydrogen bonds as dashed lines, forming a three-dimensional network.

CCDC reference: 1053790

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N1H1Br3	0.88	2.46	3.328(3)	167
N2H2ABr3	0.88	2.57	3.390(3)	155
C6H6Br3ⁱ	0.95	2.93	3.855(3)	166
C13H13ABr3ⁱ	0.99	2.80	3.705(3)	152
C47H47S1ⁱⁱ	0.95	2.81	3.645(9)	147
C78H78S1	0.95	2.70	3.259(4)	118

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Symmetry codes: (i) Inline graphic ; (ii) .

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. Comment

The studies of silver(I) complexes with diphosphane has been receiving more attention (Matsumoto et al., 2001; Nicola et al., 2005; Nicola et al., 2006) because of their potential applications such as show interesting luminescence properties (Song et al., 2010; Sun et al., 2011). The coordination chemistry of silver(I) complexes with phosphorus and sulfur donor ligands, on the other hand have been of increasing interest due to their potential applications such as antimicrobial activities (Isab et al., 2010). Herein, the title complex was prepared by reacting silver (I) bromide and dppm ligand, followed by the addition of ptu in acetonitrile solvent. An unexpexted complex [Ag₃(C₂₅H₂₂P₂)₃(µ₃-Br)₂]⁺ unit was formed in the uncoordinated of ptu.

The title complex comprises of a trinuclear [Ag₃(C₂₅H₂₂P₂)₃(µ₃-Br)₂]⁺ unit, Br anion and one N,N'-dimethylthiourea molecule (ptu). The bromide anion forms a triple bridge from the both side of the Ag-3 plane leading to distorted triangular bipyramid with an Ag···Ag separation of 3.1046 (6)-3.3556 (6) Å. A triangular Ag₃ arrangement stabilized by six P atoms from three chelating dppm ligands (Fig.1). The Ag^I ion presents a distorted tetrahedral coordination geometry. In the crystal, The bromide anions is connected to ptu ligand with N—H···Br hydrogen bonds between the ptu NH2 and NHPh moieties and the bromide anion [graph-set motif R¹₂(6)] (Fig.1 and Table 1). The dimers are in turn connected with complex ion via C—H···S and C—H···Br hydrogen bonds [C63(sp³)—H63A···S1, with H63A···S1 = 2.8858 (5) Å, C63(sp³)···S1 = 3.8147 (7) Å and C63(sp³)—H63A···S1 = 156.604 (4)°; C47(sp²)—H47···S1ⁱ, with H47···S1ⁱ = 2.8085 (4) Å, C47(sp²)···S1ⁱ = 3.6448 (6) Å and C47(sp²)—H47···S1ⁱ = 147.374 (7)°; C13(sp³)—H13A···Br3ⁱⁱ, with H13A···Br3ⁱⁱ = 2.8043 (5) Å, C13(sp³)···Br3ⁱⁱ = 3.7048 (7) Å and C13(sp³)—H13A···Br3ⁱⁱ = 151.555 (6)°; C6(sp²)—H6···Br3ⁱⁱ, with H6···Br3ⁱⁱ = 2.9249 (5) Å, C6(sp²)···Br3ⁱⁱ = 3.8550 (6) Å and C6(sp²)—H6···Br3ⁱⁱ = 166.483 (2)°; C73(sp²)—H73···Br3ⁱⁱⁱ, with H73···Br3ⁱⁱⁱ = 3.0296 (5) Å, C73(sp²)···Br3ⁱⁱ = 3.7706 (5) Å and C73(sp²)—H73···Br3ⁱⁱⁱ = 135.934 (6)°, symmetry code: (i) 1-x,1-y, 1-z, (ii) 1/2+x, 1/2-y, 1/2+z, (iii) 1+x, y, z] leading to the formation of a three-dimensional network, Fig. 2. In complex, two phenyl rings from two dppm ligands are disordered over two sites with refined occupancies 0.516 (3):0.484 (3).

S2. 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) bromide, AgBr, (0.05 g, 0.27 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 (Mp = 490-492 K).

S2.1. 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). Two phenyl rings from two dppm ligands are disordered. The ADPs of ipso carbon atoms were constrained to be identical for each disordered pair of phenyl rings. The geometry of the minor moiety of each pair of disordered phenyl rings was restrained to be similar to that of the major moiety (within a standard deviation of 0.02 Angstroms). Carbon atoms of one phenyl ring were restrained with effective standard deviation 0.01 to have the same Uij components. To ensure satisfactory refinement the atoms of each disorder component of the phenyl rings were restrained to lie within a common plane. The overall ratio of the two components of disorder, refined with the same free variable, is 0.516:0.484 (3).