Crystal structure of bis­[μ-1,2-bis­(di­phenyl­phosphan­yl)ethane-κ2 P:P′]bis[(N,N′-di­ethyl­thio­urea-κS)iodidocopper(I)]

Ladawan Khongsichan; Arunpatcha Nimthong-Roldán; Chaveng Pakawatchai; Sumpun Wongnawa

doi:10.1107/S2056989015014176

. 2015 Aug 6;71(Pt 9):m154–m155. doi: 10.1107/S2056989015014176

Crystal structure of bis[μ-1,2-bis(diphenylphosphanyl)ethane-κ² P:P′]bis[(N,N′-diethylthiourea-κS)iodidocopper(I)]

Ladawan Khongsichan ^a, Arunpatcha Nimthong-Roldán ^b, Chaveng Pakawatchai ^a, Sumpun Wongnawa ^a,^*

PMCID: PMC4555430 PMID: 26396862

Abstract

The binuclear title complex, [Cu₂I₂(C₂₆H₂₄P₂)₂(C₅H₁₂N₂S)₂], lies about an inversion centre. The Cu^I atom displays a distorted tetrahedral coordination geometry defined by one S atom of an N,N′-diethylthiourea ligand, two P atoms derived from two bridging 1,2-bis(diphenylphosphanyl)ethane (dppe) ligands and one iodide ion. The dppe ligand bridges two symmetry-related Cu^I ions, forming a 10-membered Cu₂P₄C₄ ring. An intramolecular N—H⋯I hydrogen bond is noted. In the crystal, N—H⋯I hydrogen bonds link complex molecules into layers parallel to (-101).

Keywords: crystal structure; copper(I) complex; N,N′-diethylthiourea; N—H⋯I hydrogen bonding

Related literature

For background to the coordination chemistry of copper(I) halides and pseudohalides, see: Dennehy et al. (2011 ▸); Oshio et al. (1996 ▸); Seward et al. (2003 ▸). For their potential applications, see: Corey et al. (1987 ▸); Dias et al. (2006 ▸). For relevant examples of discrete complexes, see: Dennehy et al. (2009 ▸). graphic file with name e-71-0m154-scheme1.jpg

Experimental

Crystal data

[Cu₂I₂(C₂₆H₂₄P₂)₂(C₅H₁₂N₂S)₂]
M _r = 1442.11
Monoclinic,
a = 12.2150 (8) Å
b = 15.1836 (9) Å
c = 17.1801 (10) Å
β = 96.414 (2)°
V = 3166.4 (3) Å³
Z = 2
Cu Kα radiation
μ = 10.37 mm⁻¹
T = 100 K
0.16 × 0.15 × 0.08 mm

Data collection

Bruker Prospector CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2013 ▸) T _min = 0.433, T _max = 0.753
23236 measured reflections
5564 independent reflections
5556 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.063
S = 1.13
5564 reflections
345 parameters
H-atom parameters constrained
Δρ_max = 0.98 e Å⁻³
Δρ_min = −0.92 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: SHELXL2015 (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/S2056989015014176/tk5371sup1.cif

e-71-0m154-sup1.cif^{(801.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015014176/tk5371Isup2.hkl

e-71-0m154-Isup2.hkl^{(442.7KB, hkl)}

Click here for additional data file.^{(2.7MB, tif)}

. DOI: 10.1107/S2056989015014176/tk5371fig1.tif

The structure of title complex with displacement ellipsoids drawn at the 50% propbability level. All H atoms are omitted for clarity.

Click here for additional data file.^{(2.3MB, tif)}

. DOI: 10.1107/S2056989015014176/tk5371fig2.tif

Part of the crystal structure showing intra/inter-molecular N—H⋯I hydrogen bonds forming a layers as dashed lines.

CCDC reference: 1415379

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N1H1I1ⁱ	0.88	2.80	3.622(2)	156
N2H2I1	0.88	2.70	3.5517(19)	162

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Symmetry code: (i) Inline graphic .

Acknowledgments

We gratefully acknowledge financial support from the Strategic Scholarships Fellowships Frontier Research Networks (Specific for Southern Region), the Commission on Higher Education, Ministry of Education, and the Department of Chemistry and Graduate School, Prince of Songkla University. LK would like to thank Dr Matthias Zeller of Youngstown State University, Ohio, USA, for suggestions and assistance with the X-ray structure refinement.

supplementary crystallographic information

S0.1. Synthesis and crystallization

N,N'-Diethylthiourea (0.07 g, 0.5 mmol) was dissolved in 30 cm³ of acetonitrile in a round flask equipped with reflux condenser and magnetic stirrer at 333 K and then CuI (0.1 g, 0.5 mmol) was added. The mixture was stirred for 2 h. 1,2-bis(diphenylphosphanyl)ethane (0.2 g, 0.5 mmol) was added and the reaction mixture was heated under reflux for 5 h where upon the precipitate gradually disappeared. The resulting clear solution was filtered and left to evaporate at room temperature. The colorless crystals, which deposited after standing for several days were filtered off and washed with acetone and dried in vacuo (M. pt = 557 K). Elemental analysis, calculated for [Cu₂I₂(C₂₆H₂₄P₂)₂(C₅H₁₂N₂S)₂]: C, 51.59; H, 4.97; N, 3.88; S, 4.44%, found: C, 55.69; H, 5.22; N, 3.62; S, 4.61%.

S0.2. Refinement

The (-1 8 3) reflection was affected by the beam-stop and was omitted from the final cycles of refinement. H atoms bonded to C and N atoms were included in their calculated positions and were refined using a riding model using bond lengths of 0.95–0.99 Å and U_iso(H) = 1.2–1.5U_eq(C), and N—H = 0.88 Å (NH) and U_iso(H) = 1.2U_eq(N). The (-1 8 3) reflection was omitted owing to poor agreement.

S1. Comment

Coordination complexes of copper(I) halides or pseudo-halides with mixed P and S donor ligands have been of interest in coordination chemistry (Dennehy et al., 2011; Oshio et al., 1996; Sewead et al., 2003) due to their applications such as magnetism (Oshio et al., 1996) and biological or medicinal activities (Corey et al., 1987; Dias et al., 2006). In this work, a mixed ligand complex of copper(I) iodide with 1,2-bis(diphenylphosphanyl)ethane (dppe) and N,N'-diethylthiourea (detu) is reported. The binuclear copper(I) complex lies across an inversion center. The µ₂-dppe bridges between Cu^I centers leads to a 10-membered Cu₂P₄C₄ rhomboid, see Fig. 1. The Cu1—P1 and Cu1—P2 bond lengths are 2.2681 (6) and 2.2813 (6)Å, respectively. These values are slightly shorter than the equivalent distances found in [Cu(tsac)(PPh₃)₂], [Cu₄(tsac)₄(PPh₃)₃], [Cu₂(tsac)₂(dppm)₂] and [Cu₄(tsac)₄(dppm)₂], which are in the range 2.2799 (5) and 2.3119 (5) Å (Dennehy et al., 2009). There is an intramolecular N2—H2···I1 hydrogen bond. In the crystal, intermolecular N1—H1···I1 hydrogen bonds link complex molecules into a two-dimensional supramolecular network parallel to (-101) (Fig. 2. and Table 1)