Tetrakis(chloromethyl)phosphonium chloride monohydrate, C
4H
8Cl
4P
+·Cl
−·H
2O or P(CH
2Cl)
4+·Cl
−·H
2O, is the first crystal structure determination of a tetrakis(halogenomethyl)phosphonium compound to date. The only comparable structures known so far are of phosphonium ions containing just one halogenomethyl group. The solvent water molecule interacts with the Cl
− anion
via hydrogen bonds, with O
Cl distances of 3.230 (2) and 3.309 (2) Å. The structure also contains several C—H
Cl
− and C—H
O contacts, though with longer
DA distances [
DA 3.286 (3)–3.662 (2) Å] or bent
D—H
A angles. For these reasons, the C—H
Cl
− and C—H
O interactions should not be considered as strong hydrogen bonds.
Supporting information
CCDC reference: 183035
Tetrakis(chloromethyl)phosphonium chloride (100 mg) was prepared by the method
of Hoffman (1921, 1930) and Reeves et al. (1955), and dissolved in a
mixture of methanol and ethyl acetate (3:16; 50 ml). The solvent was slowly
removed at room temperature in an open vessel. After 5 d, colourless
prism-shaped crystals of (I) formed (m.p. 401 K).
All H-atom positions were found on the difference Fourier map and refined
independently with isotropic displacement parameters.
Data collection: COLLECT (Nonius, 1999); cell refinement: SCALEPACK (Otwinowski & Minor 1997); data reduction: DENZO (Otwinowski & Minor 1997) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97.
Tetrakis(chloromethyl)phosphonium chloride monohydrate
top
Crystal data top
C4H8Cl4P+·Cl−·H2O | Dx = 1.705 Mg m−3 |
Mr = 282.34 | Melting point: 401 K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 36817 reflections |
a = 13.0928 (2) Å | θ = 1.0–26.0° |
b = 12.6946 (2) Å | µ = 1.41 mm−1 |
c = 13.2335 (2) Å | T = 293 K |
V = 2199.51 (6) Å3 | Prismatic block, colourless |
Z = 8 | 0.12 × 0.10 × 0.10 mm |
F(000) = 1136 | |
Data collection top
Nonius KappaCCD area-detector Query diffractometer | 1929 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.058 |
Horizonally mounted graphite crystal monochromator | θmax = 26.0°, θmin = 2.7° |
Detector resolution: 9 pixels mm-1 | h = −16→16 |
CCD scans | k = −15→15 |
50779 measured reflections | l = −16→16 |
2171 independent reflections | |
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)] = 0.026 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.062 | All H-atom parameters refined |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0246P)2 + 1.3871P] where P = (Fo2 + 2Fc2)/3 |
2171 reflections | (Δ/σ)max < 0.001 |
140 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
Crystal data top
C4H8Cl4P+·Cl−·H2O | V = 2199.51 (6) Å3 |
Mr = 282.34 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 13.0928 (2) Å | µ = 1.41 mm−1 |
b = 12.6946 (2) Å | T = 293 K |
c = 13.2335 (2) Å | 0.12 × 0.10 × 0.10 mm |
Data collection top
Nonius KappaCCD area-detector Query diffractometer | 1929 reflections with I > 2σ(I) |
50779 measured reflections | Rint = 0.058 |
2171 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.062 | All H-atom parameters refined |
S = 1.08 | Δρmax = 0.32 e Å−3 |
2171 reflections | Δρmin = −0.28 e Å−3 |
140 parameters | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
P | 0.80754 (4) | 0.19360 (4) | 0.73775 (3) | 0.03078 (12) | |
C1 | 0.74423 (19) | 0.08177 (17) | 0.68164 (17) | 0.0447 (5) | |
C2 | 0.72919 (16) | 0.25806 (18) | 0.83104 (15) | 0.0409 (5) | |
C3 | 0.91916 (16) | 0.14611 (18) | 0.80310 (16) | 0.0399 (4) | |
C4 | 0.84662 (17) | 0.28509 (15) | 0.64102 (14) | 0.0361 (4) | |
Cl1 | 0.65833 (5) | 0.12073 (5) | 0.58499 (5) | 0.05981 (18) | |
Cl2 | 0.62403 (4) | 0.32148 (4) | 0.77219 (4) | 0.04772 (14) | |
Cl3 | 0.87950 (5) | 0.06122 (4) | 0.90195 (4) | 0.05011 (15) | |
Cl4 | 0.92205 (5) | 0.21361 (5) | 0.55343 (4) | 0.05577 (17) | |
Cl5 | 0.43240 (4) | 0.44884 (4) | 0.66460 (4) | 0.04540 (14) | |
O | 0.35820 (15) | 0.58451 (15) | 0.47165 (16) | 0.0578 (4) | |
H1A | 0.7955 (18) | 0.0402 (18) | 0.6498 (18) | 0.052 (7)* | |
H1B | 0.710 (2) | 0.046 (2) | 0.728 (2) | 0.067 (8)* | |
H2A | 0.695 (2) | 0.213 (2) | 0.877 (2) | 0.066 (8)* | |
H2B | 0.7722 (18) | 0.3103 (18) | 0.8615 (18) | 0.052 (7)* | |
H3A | 0.9546 (17) | 0.2079 (18) | 0.8340 (17) | 0.049 (6)* | |
H3B | 0.9587 (19) | 0.108 (2) | 0.762 (2) | 0.060 (7)* | |
H4A | 0.7856 (18) | 0.3134 (17) | 0.6056 (18) | 0.049 (6)* | |
H4B | 0.8889 (17) | 0.3394 (19) | 0.6668 (17) | 0.049 (6)* | |
H5 | 0.373 (2) | 0.548 (2) | 0.527 (3) | 0.087 (11)* | |
H6 | 0.408 (2) | 0.581 (2) | 0.440 (2) | 0.064 (9)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
P | 0.0313 (2) | 0.0327 (2) | 0.0283 (2) | 0.00104 (19) | 0.00338 (19) | −0.00134 (18) |
C1 | 0.0474 (12) | 0.0418 (11) | 0.0448 (11) | −0.0094 (10) | 0.0042 (10) | −0.0068 (10) |
C2 | 0.0392 (11) | 0.0475 (12) | 0.0360 (10) | 0.0047 (9) | 0.0056 (9) | −0.0037 (9) |
C3 | 0.0392 (11) | 0.0447 (11) | 0.0357 (10) | 0.0045 (9) | 0.0022 (9) | 0.0079 (9) |
C4 | 0.0436 (11) | 0.0344 (10) | 0.0303 (9) | 0.0021 (9) | 0.0041 (8) | −0.0007 (8) |
Cl1 | 0.0506 (3) | 0.0761 (4) | 0.0527 (3) | −0.0038 (3) | −0.0090 (3) | −0.0244 (3) |
Cl2 | 0.0404 (3) | 0.0454 (3) | 0.0573 (3) | 0.0082 (2) | 0.0009 (2) | −0.0092 (2) |
Cl3 | 0.0689 (4) | 0.0416 (3) | 0.0398 (3) | −0.0007 (2) | 0.0021 (2) | 0.0093 (2) |
Cl4 | 0.0728 (4) | 0.0542 (3) | 0.0403 (3) | 0.0142 (3) | 0.0231 (3) | 0.0056 (2) |
Cl5 | 0.0476 (3) | 0.0482 (3) | 0.0404 (3) | −0.0009 (2) | 0.0023 (2) | 0.0016 (2) |
O | 0.0512 (11) | 0.0659 (11) | 0.0562 (11) | 0.0027 (9) | −0.0008 (9) | 0.0112 (9) |
Geometric parameters (Å, º) top
P—C1 | 1.804 (2) | C1—H1B | 0.89 (3) |
P—C2 | 1.802 (2) | C2—H2A | 0.95 (3) |
P—C3 | 1.802 (2) | C2—H2B | 0.96 (2) |
P—C4 | 1.803 (2) | C3—H3A | 1.00 (2) |
C1—Cl1 | 1.774 (2) | C3—H3B | 0.89 (3) |
C2—Cl2 | 1.775 (2) | C4—H4A | 0.99 (2) |
C3—Cl3 | 1.773 (2) | C4—H4B | 0.95 (2) |
C4—Cl4 | 1.7726 (19) | O—H5 | 0.88 (3) |
C1—H1A | 0.95 (2) | O—H6 | 0.78 (3) |
| | | |
C1—P—C2 | 112.20 (11) | P—C2—H2A | 115.4 (16) |
C1—P—C3 | 107.88 (11) | Cl2—C2—H2B | 109.0 (14) |
C1—P—C4 | 110.19 (10) | P—C2—H2B | 105.6 (14) |
C2—P—C3 | 106.55 (10) | H2A—C2—H2B | 115 (2) |
C2—P—C4 | 110.83 (10) | Cl3—C3—H3A | 108.2 (13) |
C3—P—C4 | 109.04 (10) | P—C3—H3A | 108.1 (13) |
P—C1—Cl1 | 111.64 (12) | Cl3—C3—H3B | 107.0 (16) |
P—C2—Cl2 | 110.30 (11) | P—C3—H3B | 111.1 (17) |
P—C3—Cl3 | 108.66 (11) | H3A—C3—H3B | 114 (2) |
P—C4—Cl4 | 107.02 (10) | Cl4—C4—H4A | 109.0 (13) |
Cl1—C1—H1A | 106.4 (14) | P—C4—H4A | 109.8 (13) |
P—C1—H1A | 107.1 (14) | Cl4—C4—H4B | 106.5 (14) |
Cl1—C1—H1B | 109.0 (17) | P—C4—H4B | 112.3 (14) |
P—C1—H1B | 110.5 (17) | H4A—C4—H4B | 112.1 (19) |
H1A—C1—H1B | 112 (2) | H5—O—H6 | 103 (3) |
Cl2—C2—H2A | 101.0 (16) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O—H5···Cl5 | 0.88 (3) | 2.35 (3) | 3.230 (2) | 173 (3) |
O—H6···Cl5i | 0.78 (3) | 2.53 (3) | 3.309 (2) | 175 (3) |
C1—H1B···Cl5ii | 0.89 (3) | 2.65 (3) | 3.512 (2) | 165 (2) |
C2—H2B···Cl5iii | 0.96 (2) | 2.76 (2) | 3.598 (2) | 146.6 (19) |
C3—H3B···Cl5iv | 0.89 (3) | 2.79 (3) | 3.662 (2) | 166 (2) |
C4—H4B···Cl5iii | 0.95 (2) | 2.69 (2) | 3.493 (2) | 142.9 (18) |
C1—H1A···Ov | 0.95 (2) | 2.40 (2) | 3.286 (3) | 154.5 (19) |
C4—H4A···Oi | 0.99 (2) | 2.50 (2) | 3.486 (3) | 169.9 (18) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+3/2; (iii) x+1/2, y, −z+3/2; (iv) −x+3/2, y−1/2, z; (v) x+1/2, −y+1/2, −z+1. |
Experimental details
Crystal data |
Chemical formula | C4H8Cl4P+·Cl−·H2O |
Mr | 282.34 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 13.0928 (2), 12.6946 (2), 13.2335 (2) |
V (Å3) | 2199.51 (6) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.41 |
Crystal size (mm) | 0.12 × 0.10 × 0.10 |
|
Data collection |
Diffractometer | Nonius KappaCCD area-detector Query diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 50779, 2171, 1929 |
Rint | 0.058 |
(sin θ/λ)max (Å−1) | 0.617 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.062, 1.08 |
No. of reflections | 2171 |
No. of parameters | 140 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.32, −0.28 |
Selected geometric parameters (Å, º) topP—C1 | 1.804 (2) | C1—Cl1 | 1.774 (2) |
P—C2 | 1.802 (2) | C2—Cl2 | 1.775 (2) |
P—C3 | 1.802 (2) | C3—Cl3 | 1.773 (2) |
P—C4 | 1.803 (2) | C4—Cl4 | 1.7726 (19) |
| | | |
C1—P—C2 | 112.20 (11) | C3—P—C4 | 109.04 (10) |
C1—P—C3 | 107.88 (11) | P—C1—Cl1 | 111.64 (12) |
C1—P—C4 | 110.19 (10) | P—C2—Cl2 | 110.30 (11) |
C2—P—C3 | 106.55 (10) | P—C3—Cl3 | 108.66 (11) |
C2—P—C4 | 110.83 (10) | P—C4—Cl4 | 107.02 (10) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O—H5···Cl5 | 0.88 (3) | 2.35 (3) | 3.230 (2) | 173 (3) |
O—H6···Cl5i | 0.78 (3) | 2.53 (3) | 3.309 (2) | 175 (3) |
C1—H1B···Cl5ii | 0.89 (3) | 2.65 (3) | 3.512 (2) | 165 (2) |
C2—H2B···Cl5iii | 0.96 (2) | 2.76 (2) | 3.598 (2) | 146.6 (19) |
C3—H3B···Cl5iv | 0.89 (3) | 2.79 (3) | 3.662 (2) | 166 (2) |
C4—H4B···Cl5iii | 0.95 (2) | 2.69 (2) | 3.493 (2) | 142.9 (18) |
C1—H1A···Ov | 0.95 (2) | 2.40 (2) | 3.286 (3) | 154.5 (19) |
C4—H4A···Oi | 0.99 (2) | 2.50 (2) | 3.486 (3) | 169.9 (18) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, y−1/2, −z+3/2; (iii) x+1/2, y, −z+3/2; (iv) −x+3/2, y−1/2, z; (v) x+1/2, −y+1/2, −z+1. |
Hoffman (1921, 1930) reported on the formation of tetrakis(chloromethyl)phosphonium chloride as water-free needle-shaped crystals which melt at 466 K. We have now discovered that tetrakis(chloromethyl)phosphonium chloride also forms the title monohydrate, (I). Compound (I) can be obtained by dissolving tetrakis(chloromethyl)phosphonium chloride in organic solvents and then slowly removing the solvent in air. Monohydrate (I) can be distinguished from the anhydrous compound by the crystal habit and melting point. By recrystallization of (I) from methanol/ethyl acetate (3:16), needle-shaped crystals of the anhydrous material are recovered. \sch
The present structure determination of (I) is the first such to date, and the only comparable structures known so far are of phosphonium ions containing just one halogenomethyl group (Cambridge Structural Database, Version 5.22 Query; Allen & Kennard, 1993).
In the cation of (I), P is coordinated tetrahedrally by C atoms (Fig. 1). The Cl—C—PR2—R conformations are all staggered, with torsion angles ranging from 161.8 (1) to 179.6 (1)°. The coordination of the Cl- anions by water molecules presents an interesting feature, which is shown in Fig. 2. The O—H···Cl- hydrogen bonds establish an approximately planar eight-membered ring, with a maximum deviation of 0.04 (2) Å from the best plane For which atom?. The O—H···Cl- hydrogen bonds are nearly linear.
Additional coordination of Cl- ions via C—H···Cl- interactions should be weaker than the O—H···Cl- bonds for polarization reasons. This is confirmed by the longer H···Cl- distances and the bent C—H···Cl angle, compared with the geometry of the O—H···Cl- contacts (Table 2).