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

Yupa Wattanakanjana; Arunpatcha Nimthong-Roldán; Suthida Palavat; Walailak Puetpaiboon

doi:10.1107/S2056989015017120

. 2015 Oct 3;71(Pt 11):m187–m188. doi: 10.1107/S2056989015017120

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

Yupa Wattanakanjana ^a,^*, Arunpatcha Nimthong-Roldán ^b, Suthida Palavat ^a, Walailak Puetpaiboon ^a

PMCID: PMC4645055 PMID: 26594526

Abstract

The title complex, [Ag₃I₂(C₂₅H₂₂P₂)₃]I·C₇H₈N₂S, comprises a trinuclear [Ag₃I₂(C₂₅H₂₂P₂)₃]⁺ unit, an I⁻ anion and one N,N′-phenylthiourea molecule (ptu). Two μ₃-bridging I⁻ anions are linked by three Ag^I ions, leading to the formation of a dicapped triangular motif with Ag⋯Ag separations in the range 3.0823 (5)–3.2999 (5) Å. Each Ag^I atom exhibits a distorted tetrahedral geometry, with coordination to two I atoms and two P atoms from bis(diphenylphosphanyl)methane ligands. In the crystal, the I⁻ anion is linked to the ptu molecule through two N—H⋯I hydrogen bonds [graph-set motif R ₂ ¹(6)]. These N—H⋯I hydrogen bonds, in addition to weak C—H⋯S and C—H⋯I hydrogen bonds, form zigzag chains along [010]. Two of the phenyl rings of two dppm ligands are disordered over two sets of sites with refined occupancies of 0.557 (16) and 0.443 (16).

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

Related literature

For bis(diphenylphosphino)methane (dppm) complexes formed with metal(I) ions, see: Bera et al. (1998 ▸); Matsumoto et al. (2001 ▸); Nicola et al. (2005 ▸). For the complex [Ag₃(C₂₅H₂₂P₂)₃(μ₃-Br)₂]⁺, see: Nimthong-Roldán et al. (2015 ▸). graphic file with name e-71-0m187-scheme1.jpg

Experimental

Crystal data

[Ag₃I₂(C₂₅H₂₂P₂)₃]I·C₇H₈N₂S
M _r = 2009.62
Monoclinic,
a = 10.8177 (4) Å
b = 28.5680 (11) Å
c = 26.1639 (11) Å
β = 95.315 (2)°
V = 8050.9 (5) Å³
Z = 4
Cu Kα radiation
μ = 16.53 mm⁻¹
T = 296 K
0.14 × 0.04 × 0.03 mm

Data collection

Bruker Prospector CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2013 ▸) T _min = 0.394, T _max = 0.753
82145 measured reflections
14160 independent reflections
12277 reflections with I > 2σ(I)
R _int = 0.056

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.104
S = 1.08
14160 reflections
983 parameters
216 restraints
H-atom parameters constrained
Δρ_max = 1.16 e Å⁻³
Δρ_min = −1.04 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: SHELXL2014 (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. DOI: 10.1107/S2056989015017120/lh5785sup1.cif

e-71-0m187-sup1.cif^{(2.7MB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015017120/lh5785Isup2.hkl

e-71-0m187-Isup2.hkl^{(1.1MB, hkl)}

Click here for additional data file.^{(1.7MB, tif)}

. DOI: 10.1107/S2056989015017120/lh5785fig1.tif

The molecular structure with displacement ellipsoids drawn at the 50% probability level. All H atoms and the minor component of disorder are omitted for clarity.

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

. DOI: 10.1107/S2056989015017120/lh5785fig2.tif

Part of the crystal structure showing intermolecular N—H⋯I, C—H⋯S and C—H⋯I hydrogen bonds as dashed lines, forming a chain along [010].

CCDC reference: 1424053

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N1H1AI3	0.86	2.82	3.633(9)	159
N2H2AI3	0.86	2.72	3.568(6)	170
C53H53S1ⁱ	0.99	2.88	3.67(2)	143
C13H13BI3	0.99	3.04	3.933(4)	153

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Symmetry code: (i) Inline graphic .

Acknowledgments

We are grateful to Department of Chemistry, Faculty of Science, Prince of Songkla University, for financial assistance. We would like to thank Youngstown State University for access to their X-ray diffraction facility, funded in part by NSF Grant DMR 1337296.

supplementary crystallographic information

S1. Comment

Complexes of bis(diphenylphosphino)methane (dppm) with metal(I) ions have been extensively studied (Bera et al. 1998; Matsumoto et al. 2001; Nicola et al. 2005). Recently, we reported the complex which we prepared by reacting silver (I) bromide and dppm, followed by the addition of N,N'-phenylthiourea (ptu) in acetonitrile solvent. An unexpected complex [Ag₃(C₂₅H₂₂P₂)₃(µ₃-Br)₂]⁺ unit was formed with uncoordinated ptu (Nimthong-Roldán et al. 2015). Herein, we present the complex formed using silver(I) iodide instead of silver(I) bromide under the same conditions.

The title complex consists of a trinuclear [Ag₃(C₂₅H₂₂P₂)₃(µ₃-I)₂]⁺ unit, a discrete I^- anion and one N,N′-phenylthiourea molecule (ptu). Three Ag^I ions in the corners of the trianglular plane are linked via two bridging µ₃-I anions, forming a dicapped triangular geometry with a Ag···Ag separations range of 3.0823 (5)–3.2999 (5) Å. Each Ag^I ion coordinates to two iodide ions and two P atoms of two dppm ligands in a distorted tetrahedral geometry (Fig 1). In the crystal, two N—H···I hydrogen bonds exist between the iodide anion and ptu molecule [graph-set motif R²₁(6)] (Table 1). These hydrogen bonds are in turn connected via weak C—H···S and C—H···I hydrogen bonds, forming a zig-zag chain along [010] (Fig. 2, Table 1). Two of the phenyl rings from two dppm ligands are disordered over two sites with refined occupancies 0.557 (16) and 0.443 (16).

S2. Synthesis and crystallization

Bis(diphenylphosphino)methane, dppm, (0.1 g, 0.26 mmol) was dissolved in 30 ml of acetonitrile at 343 K and then silver(I) iodide, AgI, (0.06 g, 0.26 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.

S3. Refinement details

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 geometry of the minor component of each pair of disordered phenyl rings was restrained to be similar to that of the major componnet (within a standard deviation of 0.02 Å). 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 0.557 (16):0.443 (16).