Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802006785/cf6168sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802006785/cf6168Isup2.hkl |
CCDC reference: 185793
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
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, 2JPH = 12.87 Hz). 13C{1H} NMR (CD2Cl2, internal TMS): δ 18.4 (d, 4 Me, 1JPC = 69.81 Hz). 31P NMR (CD2Cl2, external H3PO4): δ 37.8 (m, 2JHP = 12.87 Hz).
All H atoms were located in a difference Fourier synthesis. Methyl H atoms were refined with fixed individual displacement parameters [U(H) = 1.5Ueq(C)] using a riding model with C—H = 0.98 Å. The water H atoms were refined freely.
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.
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. |
C4H12P+·Cl−·H2O | F(000) = 624 |
Mr = 144.57 | Dx = 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 |
Stoe IPDSII two-circle diffractometer | 1407 independent reflections |
Radiation source: fine-focus sealed tube | 966 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.066 |
ω scans | θmax = 25.2°, θmin = 3.6° |
Absorption correction: multi-scan (MULABS; Spek, 1990; Blessing, 1995) | h = −14→14 |
Tmin = 0.927, Tmax = 0.968 | k = −10→8 |
3076 measured reflections | l = −21→16 |
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(Fo2) + (0.0671P)2] where P = (Fo2 + 2Fc2)/3 |
1407 reflections | (Δ/σ)max < 0.001 |
72 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C4H12P+·Cl−·H2O | V = 1703.6 (8) Å3 |
Mr = 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)° |
Stoe IPDSII two-circle diffractometer | 1407 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 1990; Blessing, 1995) | 966 reflections with I > 2σ(I) |
Tmin = 0.927, Tmax = 0.968 | Rint = 0.066 |
3076 measured reflections |
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 | Δρmax = 0.34 e Å−3 |
1407 reflections | Δρmin = −0.24 e Å−3 |
72 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
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* |
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) |
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 |
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 |
Mr | 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) |
Tmin, Tmax | 0.927, 0.968 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3076, 1407, 966 |
Rint | 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 |
Δρmax, Δρmin (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.
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) |
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. |
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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).