Crystal structure of benzyl­tri­phenyl­phospho­nium chloride monohydrate

Jimmy Ahmad; Siti Nadiah Abdul Halim; Fiona N-F How

doi:10.1107/S2056989015009159

. 2015 May 20;71(Pt 6):o410–o411. doi: 10.1107/S2056989015009159

Crystal structure of benzyltriphenylphosphonium chloride monohydrate

Jimmy Ahmad ^a, Siti Nadiah Abdul Halim ^b, Fiona N-F How ^a,^*

PMCID: PMC4459357 PMID: 26090195

Abstract

The title compound, Ph₃(PhCH₂)P⁺·Cl⁻·H₂O, was obtained unintentionally as the product of an attempted synthesis of a silver dithiocarbamate complex using benzyltriphenylphosphonium as the counter-ion. The asymmetric unit consists of a phosphonium cation and a chloride anion, and a water molecule of crystallization. In the crystal, the chloride ion is linked to the water molecule by an O—H⋯Cl hydrogen bond. The three units are further linked via C—H⋯Cl and C—H⋯O hydrogen bonds and C—H⋯ π interactions, forming a three-dimensional structure.

Keywords: crystal structure, benzyltriphenylphosphonium, chloride, hydrogen bonding, C—H⋯ π interactions

Related literature

For some structures containing the Ph₃(PhCH₂)P⁺ cation, see: Li & He (2011 ▸); Fischer & Wiebelhaus (1997 ▸); Skapski & Stephens (1974 ▸). graphic file with name e-71-0o410-scheme1.jpg

Experimental

Crystal data

C₂₅H₂₂P⁺·Cl⁻·H₂O
M _r = 406.86
Monoclinic,
a = 9.7368 (8) Å
b = 19.7474 (17) Å
c = 11.4170 (9) Å
β = 109.728 (9)°
V = 2066.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 100 K
0.30 × 0.25 × 0.20 mm

Data collection

Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent 2013 ▸) T _min = 0.813, T _max = 1.000
12625 measured reflections
5434 independent reflections
3901 reflections with I > 2σ(I)
R _int = 0.067

Refinement

R[F ² > 2σ(F ²)] = 0.067
wR(F ²) = 0.194
S = 1.07
5434 reflections
256 parameters
H-atom parameters constrained
Δρ_max = 0.90 e Å⁻³
Δρ_min = −0.72 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2013 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: OLEX2.solve (Bourhis et al., 2015 ▸); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015 ▸); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▸); software used to prepare material for publication: publCIF (Westrip, 2010 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015009159/su5134sup1.cif

e-71-0o410-sup1.cif^{(275.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015009159/su5134Isup2.hkl

e-71-0o410-Isup2.hkl^{(297.9KB, hkl)}

Click here for additional data file.^{(7.4KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015009159/su5134Isup3.cml

Click here for additional data file.^{(1.3MB, tif)}

. DOI: 10.1107/S2056989015009159/su5134fig1.tif

The asymmetric unit of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 50% probability level. Dotted line denotes the O—H⋯Cl hydrogen bond (see Table 1 for details).

CCDC reference: 1400555

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

Table 1. Hydrogen-bond geometry (, ).

Cg2 and Cg4 are the centroids of rings C8-C13 and C20-C25, respectively.

DHA	DH	HA	D A	DHA
O1H1BCl1ⁱ	0.85	2.27	3.114(3)	170
C7H7ACl1	0.97	2.57	3.511(3)	162
C7H7BCl1ⁱⁱ	0.97	2.60	3.528(2)	160
C12H12O1ⁱⁱⁱ	0.93	2.47	3.207(5)	136
C17H17Cl1^iv	0.93	2.81	3.562(3)	139
C3H3Cg4^v	0.93	2.83	3.584(3)	139
C18H18Cg2^vi	0.93	2.98	3.720(3)	137

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

Acknowledgments

The authors gratefully acknowledge The Ministry of Higher Education (MOHE), Malaysia, for funding this research under the Fundamental Research Grant Scheme Grant No. FRGS12–064-0213 and the Universiti Malaya Research Grant.

supplementary crystallographic information

S1. Synthesis and crystallization

The title compound was obtained unintentionally as the product of an attempted synthesis of silver complex of dithiocarbamate using benzyltriphenylphosphonium as the counter ion. Colourless crystals were obtained upon slow evaporation of the methanolic solution at room temperature.

S2. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The H atoms of the water molecule were located in a Fourier difference map. The water molecule was then refined as a rigid group with U_iso(H) = 1.5U_eq(O). The C-bound H atoms were included in calculated positions and treated as riding atoms: C—H = 0.93 Å with U_iso(H) = 1.2U_eq(C).

S3. Results and discussion

The asymmetric unit of the title compound, shown in Fig. 1, consists of one independent cation, one independent anion and a hydrated water molecule. The central phosphine atom coordinates with the ligands in a slightly distorted tetrahedral environment. The C—P—C bond angles vary from 108.56 (12) to 110.51 (11) °, deviating slightly from the ideal tetrahedral angle of 109.5 °. The P–C bond distances, that vary from 1.792 (2) to 1.800 (3) Å, are comparable to values found for related compounds containing the Ph₃(PhCH₂)P⁺ cation (Li & He, 2011; Fischer & Wiebelhaus, 1997; Skapski & Stephens, 1974).

In the crystal, the chloride ion is linked to the water molecule by an O—H···Cl hydrogen bond (Table 1 and Fig. 1). The three units are further linked via C—H···Cl and C—H···O hydrogen bonds and C—H··· π interactions (Table 1) forming a three-dimensional structure.

S4. Experimental

The title compound was obtained unintentionally as the product of an attempted synthesis of silver complex of dithiocarbamate using benzyltriphenylphosphonium as the counter ion. The colourless crystal was obtained upon slow evaporation of the methanolic solution at room temperature.