Tetra­methyl­phospho­nium chloride hydrate

Margraf, G.; Lerner, H.-W.; Bolte, M.

doi:10.1107/S1600536802006785

Tetramethylphosphonium chloride hydrate

[Me₄P]⁺·Cl^-·H₂O, shows an interesting hydrogen-bond pattern: two chloride ions and two water molecules are connected to form eight-membered rings.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802006785/cf6168sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536802006785/cf6168Isup2.hkl Contains datablock I

CCDC reference: 185793

checkCIF report

Key indicators

Single-crystal X-ray study
T = 173 K
Mean (P-C) = 0.004 Å
R factor = 0.054
wR factor = 0.130
Data-to-parameter ratio = 19.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level A:



DIFF_020  Alert A _diffrn_standards_interval_count and
          _diffrn_standards_interval_time are missing. Number of measurements
          between standards or time (min) between standards.


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           25.15
         From the CIF: _reflns_number_total               1407
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         1536
         Completeness (_total/calc)             91.60%
          Alert C: < 95% complete


 1 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

Comment top

Phosphonium salts, [R₄P]X, find applications in a wide range of chemistry. Up to now, only tetramethylphosphonium salts with large anions, such as I₃^-, have been structurally characterized by X-ray crystallography. We report here the synthesis and the X-ray crystal structure analysis of the phosphonium chloride [Me₄P]Cl. The synthesis of tetramethylphosphonium chloride was achieved by disproportionation of [Me₃PH]Cl, as indicated in the equation.

Geometric parameters in the title compound, [Me₄P]⁺Cl^-·H₂O, (I) (Fig. 1), are in the usual ranges. A search of the Cambridge Structural Database (Allen & Kennard, 1993) for the P(CH₃)₄ fragment yielded 16 hits, with a mean P—C bond distance of 1.78 (3) Å. The structure of (I) shows that two chloride ions and two water molecules are connected via hydrogen bonds to form eight-membered rings (Fig. 2).

Experimental top

The title compound was obtained by heating a solution of 0.2 mmol [Me₃PH]Cl in 1 ml CD₂Cl₂ at 323 K in a sealed NMR tube. Colourless crystals of [Me₄P]Cl were grown by storing this solution at ambient temperature for two days. The NMR spectra were recorded on a Bruker DPX 250 spectrometer. Me₄PCl: ¹H NMR (CD₂Cl₂, internal TMS): δ 1.414 (d, 4 Me, ²J_PH = 12.87 Hz). ¹³C{¹H} NMR (CD₂Cl₂, internal TMS): δ 18.4 (d, 4 Me, ¹J_PC = 69.81 Hz). ³¹P NMR (CD₂Cl₂, external H₃PO₄): δ 37.8 (m, ²J_HP = 12.87 Hz).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97.

Figures top

	Fig. 1. Perspective view of the title compound with the atom numbering; displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. Packing diagram of the title compound.

(I) top

Crystal data top

C₄H₁₂P⁺·Cl⁻·H₂O	F(000) = 624
M_r = 144.57	D_x = 1.127 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.762 (3) Å	Cell parameters from 2064 reflections
b = 8.628 (2) Å	θ = 3.5–25.2°
c = 17.604 (6) Å	µ = 0.55 mm⁻¹
β = 107.52 (2)°	T = 173 K
V = 1703.6 (8) Å³	Block, colourless
Z = 8	0.14 × 0.11 × 0.06 mm

Data collection top

Stoe IPDSII two-circle diffractometer	1407 independent reflections
Radiation source: fine-focus sealed tube	966 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.066
ω scans	θ_max = 25.2°, θ_min = 3.6°
Absorption correction: multi-scan (MULABS; Spek, 1990; Blessing, 1995)	h = −14→14
T_min = 0.927, T_max = 0.968	k = −10→8
3076 measured reflections	l = −21→16

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	w = 1/[σ²(F_o²) + (0.0671P)²] where P = (F_o² + 2F_c²)/3
1407 reflections	(Δ/σ)_max < 0.001
72 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₄H₁₂P⁺·Cl⁻·H₂O	V = 1703.6 (8) Å³
M_r = 144.57	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 11.762 (3) Å	µ = 0.55 mm⁻¹
b = 8.628 (2) Å	T = 173 K
c = 17.604 (6) Å	0.14 × 0.11 × 0.06 mm
β = 107.52 (2)°

Data collection top

Stoe IPDSII two-circle diffractometer	1407 independent reflections
Absorption correction: multi-scan (MULABS; Spek, 1990; Blessing, 1995)	966 reflections with I > 2σ(I)
T_min = 0.927, T_max = 0.968	R_int = 0.066
3076 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 0.98	Δρ_max = 0.34 e Å⁻³
1407 reflections	Δρ_min = −0.24 e Å⁻³
72 parameters

Special details top

Experimental. ;

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.63119 (9)	0.53430 (13)	0.64042 (7)	0.0544 (3)
O1	0.4841 (3)	0.7183 (4)	0.4877 (3)	0.0668 (10)
H1O	0.446 (5)	0.644 (7)	0.451 (4)	0.084 (18)*
H2O	0.530 (4)	0.666 (6)	0.530 (4)	0.064 (16)*
P1	0.25342 (7)	0.50326 (11)	0.62478 (6)	0.0363 (3)
C1	0.3316 (3)	0.6802 (5)	0.6553 (3)	0.0476 (10)
H1A	0.2793	0.7677	0.6326	0.071*
H1B	0.4020	0.6832	0.6364	0.071*
H1C	0.3567	0.6871	0.7135	0.071*
C2	0.2055 (3)	0.4890 (5)	0.5195 (3)	0.0505 (10)
H2A	0.1531	0.5765	0.4969	0.076*
H2B	0.1619	0.3917	0.5035	0.076*
H2C	0.2750	0.4909	0.4997	0.076*
C3	0.1255 (3)	0.4976 (5)	0.6600 (3)	0.0467 (9)
H3A	0.0728	0.5849	0.6375	0.070*
H3B	0.1513	0.5049	0.7183	0.070*
H3C	0.0825	0.4000	0.6436	0.070*
C4	0.3494 (3)	0.3456 (5)	0.6662 (3)	0.0465 (10)
H4A	0.3071	0.2476	0.6495	0.070*
H4B	0.3743	0.3527	0.7245	0.070*
H4C	0.4199	0.3494	0.6476	0.070*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0507 (5)	0.0713 (7)	0.0397 (6)	−0.0058 (5)	0.0111 (4)	−0.0036 (5)
O1	0.077 (2)	0.047 (2)	0.070 (3)	0.0007 (17)	0.012 (2)	−0.0002 (19)
P1	0.0354 (4)	0.0389 (5)	0.0354 (5)	−0.0010 (4)	0.0121 (3)	0.0011 (4)
C1	0.049 (2)	0.044 (2)	0.050 (3)	−0.0047 (17)	0.016 (2)	−0.0011 (19)
C2	0.050 (2)	0.065 (3)	0.037 (2)	−0.0009 (18)	0.0144 (18)	0.000 (2)
C3	0.0429 (17)	0.055 (2)	0.045 (2)	0.0029 (17)	0.0186 (17)	0.0034 (18)
C4	0.0442 (19)	0.046 (2)	0.048 (3)	0.0010 (16)	0.0119 (18)	0.0008 (19)

Geometric parameters (Å, º) top

O1—H1O	0.93 (7)	C2—H2A	0.980
O1—H2O	0.90 (6)	C2—H2B	0.980
P1—C2	1.772 (4)	C2—H2C	0.980
P1—C4	1.779 (4)	C3—H3A	0.980
P1—C1	1.780 (4)	C3—H3B	0.980
P1—C3	1.792 (3)	C3—H3C	0.980
C1—H1A	0.980	C4—H4A	0.980
C1—H1B	0.980	C4—H4B	0.980
C1—H1C	0.980	C4—H4C	0.980

H1O—O1—H2O	106 (5)	P1—C2—H2C	109.5
C2—P1—C4	109.8 (2)	H2A—C2—H2C	109.5
C2—P1—C1	110.3 (2)	H2B—C2—H2C	109.5
C4—P1—C1	109.0 (2)	P1—C3—H3A	109.5
C2—P1—C3	108.94 (19)	P1—C3—H3B	109.5
C4—P1—C3	109.44 (19)	H3A—C3—H3B	109.5
C1—P1—C3	109.29 (19)	P1—C3—H3C	109.5
P1—C1—H1A	109.5	H3A—C3—H3C	109.5
P1—C1—H1B	109.5	H3B—C3—H3C	109.5
H1A—C1—H1B	109.5	P1—C4—H4A	109.5
P1—C1—H1C	109.5	P1—C4—H4B	109.5
H1A—C1—H1C	109.5	H4A—C4—H4B	109.5
H1B—C1—H1C	109.5	P1—C4—H4C	109.5
P1—C2—H2A	109.5	H4A—C4—H4C	109.5
P1—C2—H2B	109.5	H4B—C4—H4C	109.5
H2A—C2—H2B	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H2O···Cl1	0.90 (6)	2.25 (6)	3.153 (5)	175 (4)
O1—H1O···Cl1ⁱ	0.93 (7)	2.21 (7)	3.136 (4)	175 (4)

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₄H₁₂P⁺·Cl⁻·H₂O
M_r	144.57
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	11.762 (3), 8.628 (2), 17.604 (6)
β (°)	107.52 (2)
V (Å³)	1703.6 (8)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.55
Crystal size (mm)	0.14 × 0.11 × 0.06

Data collection
Diffractometer	Stoe IPDSII two-circle diffractometer
Absorption correction	Multi-scan (MULABS; Spek, 1990; Blessing, 1995)
T_min, T_max	0.927, 0.968
No. of measured, independent and observed [I > 2σ(I)] reflections	3076, 1407, 966
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.598

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.130, 0.98
No. of reflections	1407
No. of parameters	72
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.24

Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991), SHELXL97.

Selected geometric parameters (Å, º) top

P1—C2	1.772 (4)	P1—C1	1.780 (4)
P1—C4	1.779 (4)	P1—C3	1.792 (3)

C2—P1—C4	109.8 (2)	C2—P1—C3	108.94 (19)
C2—P1—C1	110.3 (2)	C4—P1—C3	109.44 (19)
C4—P1—C1	109.0 (2)	C1—P1—C3	109.29 (19)