1-Chloro-3,4-dimethyl-1-phenyl-3-phospho­lenium chloride

Both ions of the title compound, C₁₂H₁₅ClP⁺·Cl⁻, are located on a crystallographic mirror plane. The phospho­lene ring adopts an envelope conformation. The crystal structure is stabilized by C—H...Cl hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C)= 0.004 Å
• R factor = 0.032
• wR factor = 0.066
• Data-to-parameter ratio = 17.4

checkCIF/PLATON results

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Computing details

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SIR2002 (Burla et al., 2003); 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.

1-Chloro-3,4-Dimethyl-1-phenyl-3-phospholenium chloride

Crystal data

C12H15ClP^+·Cl^−	F(000) = 544
Mr = 261.11	Dx = 1.346 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 6837 reflections
a = 11.0359 (13) Å	θ = 3.6–26.5°
b = 7.0120 (12) Å	µ = 0.59 mm^−1
c = 16.657 (2) Å	T = 173 K
V = 1289.0 (3) Å^3	Needle, colourless
Z = 4	0.32 × 0.14 × 0.12 mm

Data collection

Stoe IPDS-II two-circle diffractometer	1441 independent reflections
Radiation source: fine-focus sealed tube	1081 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.085
ω scans	θmax = 26.5°, θmin = 3.9°
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)	h = −12→13
Tmin = 0.833, Tmax = 0.932	k = −8→8
9136 measured reflections	l = −20→20

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.066	H-atom parameters constrained
S = 0.91	w = 1/[σ^2(Fo^2) + (0.0273P)^2] where P = (Fo^2 + 2Fc^2)/3
1441 reflections	(Δ/σ)max < 0.001
83 parameters	Δρmax = 0.28 e Å^−3
0 restraints	Δρmin = −0.20 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.26347 (6)	0.7500	0.65235 (5)	0.03632 (18)
P1	0.44086 (6)	0.7500	0.67225 (4)	0.02346 (16)
C1	0.47482 (17)	0.5560 (2)	0.73850 (10)	0.0253 (4)
H1A	0.4108	0.4572	0.7369	0.030*
H1B	0.5538	0.4969	0.7253	0.030*
C2	0.47866 (16)	0.6548 (3)	0.81921 (11)	0.0255 (4)
C11	0.5167 (2)	0.7500	0.57751 (15)	0.0266 (5)
C12	0.6432 (3)	0.7500	0.57900 (19)	0.0407 (7)
H12	0.6857	0.7500	0.6286	0.049*
C13	0.7056 (3)	0.7500	0.50686 (19)	0.0438 (8)
H13	0.7916	0.7500	0.5072	0.053*
C14	0.6445 (3)	0.7500	0.43438 (19)	0.0388 (7)
H14	0.6882	0.7500	0.3852	0.047*
C15	0.5194 (3)	0.7500	0.43407 (17)	0.0332 (6)
H15	0.4770	0.7500	0.3844	0.040*
C16	0.4550 (3)	0.7500	0.50550 (16)	0.0288 (6)
H16	0.3689	0.7500	0.5049	0.035*
C21	0.4864 (2)	0.5242 (3)	0.89047 (12)	0.0373 (5)
H21A	0.4969	0.6000	0.9394	0.056*
H21B	0.5556	0.4381	0.8840	0.056*
H21C	0.4116	0.4493	0.8945	0.056*
Cl2	0.22744 (7)	0.2500	0.77838 (5)	0.03790 (19)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0237 (3)	0.0406 (4)	0.0446 (4)	0.000	−0.0023 (3)	0.000
P1	0.0231 (3)	0.0229 (3)	0.0244 (3)	0.000	−0.0004 (3)	0.000
C1	0.0285 (9)	0.0207 (8)	0.0267 (10)	0.0006 (7)	0.0019 (7)	0.0006 (6)
C2	0.0232 (8)	0.0265 (8)	0.0267 (10)	−0.0004 (7)	0.0005 (7)	0.0003 (7)
C11	0.0298 (13)	0.0250 (12)	0.0249 (13)	0.000	0.0004 (11)	0.000
C12	0.0280 (14)	0.065 (2)	0.0291 (16)	0.000	−0.0025 (12)	0.000
C13	0.0333 (17)	0.062 (2)	0.0357 (17)	0.000	0.0043 (13)	0.000
C14	0.0536 (19)	0.0342 (15)	0.0288 (15)	0.000	0.0073 (14)	0.000
C15	0.0496 (17)	0.0246 (12)	0.0254 (14)	0.000	−0.0059 (13)	0.000
C16	0.0336 (15)	0.0221 (12)	0.0307 (14)	0.000	−0.0049 (11)	0.000
C21	0.0493 (13)	0.0313 (10)	0.0312 (10)	−0.0008 (10)	−0.0009 (10)	0.0070 (8)
Cl2	0.0277 (3)	0.0319 (3)	0.0540 (5)	0.000	0.0074 (3)	0.000

Geometric parameters (Å, º)

Cl1—P1	1.9855 (10)	C12—H12	0.9500
P1—C11	1.786 (3)	C13—C14	1.383 (5)
P1—C1	1.7914 (18)	C13—H13	0.9500
P1—C1^i	1.7914 (18)	C14—C15	1.380 (5)
C1—C2	1.513 (2)	C14—H14	0.9500
C1—H1A	0.9900	C15—C16	1.386 (4)
C1—H1B	0.9900	C15—H15	0.9500
C2—C2^i	1.335 (4)	C16—H16	0.9500
C2—C21	1.502 (3)	C21—H21A	0.9800
C11—C16	1.379 (4)	C21—H21B	0.9800
C11—C12	1.397 (4)	C21—H21C	0.9800
C12—C13	1.385 (4)
C11—P1—C1	116.51 (8)	C11—C12—H12	120.6
C11—P1—C1^i	116.51 (8)	C14—C13—C12	121.0 (3)
C1—P1—C1^i	98.82 (12)	C14—C13—H13	119.5
C11—P1—Cl1	108.31 (10)	C12—C13—H13	119.5
C1—P1—Cl1	108.01 (7)	C15—C14—C13	119.4 (3)
C1^i—P1—Cl1	108.01 (7)	C15—C14—H14	120.3
C2—C1—P1	101.85 (12)	C13—C14—H14	120.3
C2—C1—H1A	111.4	C14—C15—C16	120.6 (3)
P1—C1—H1A	111.4	C14—C15—H15	119.7
C2—C1—H1B	111.4	C16—C15—H15	119.7
P1—C1—H1B	111.4	C11—C16—C15	119.6 (3)
H1A—C1—H1B	109.3	C11—C16—H16	120.2
C2^i—C2—C21	127.58 (11)	C15—C16—H16	120.2
C2^i—C2—C1	117.27 (9)	C2—C21—H21A	109.5
C21—C2—C1	115.12 (15)	C2—C21—H21B	109.5
C16—C11—C12	120.6 (3)	H21A—C21—H21B	109.5
C16—C11—P1	122.5 (2)	C2—C21—H21C	109.5
C12—C11—P1	116.9 (2)	H21A—C21—H21C	109.5
C13—C12—C11	118.8 (3)	H21B—C21—H21C	109.5
C13—C12—H12	120.6
C11—P1—C1—C2	140.96 (13)	Cl1—P1—C11—C12	180.0
C1^i—P1—C1—C2	15.36 (17)	C16—C11—C12—C13	0.0
Cl1—P1—C1—C2	−96.94 (11)	P1—C11—C12—C13	180.0
P1—C1—C2—C2^i	−11.18 (13)	C11—C12—C13—C14	0.0
P1—C1—C2—C21	170.83 (15)	C12—C13—C14—C15	0.0
C1—P1—C11—C16	121.94 (8)	C13—C14—C15—C16	0.0
C1^i—P1—C11—C16	−121.94 (8)	C12—C11—C16—C15	0.0
Cl1—P1—C11—C16	0.0	P1—C11—C16—C15	180.0
C1—P1—C11—C12	−58.06 (8)	C14—C15—C16—C11	0.0
C1^i—P1—C11—C12	58.06 (8)

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···Cl1	0.95	2.72	3.233 (3)	115
C1—H1A···Cl2	0.99	2.59	3.535 (2)	161
C1—H1B···Cl2^ii	0.99	2.58	3.529 (2)	160

Symmetry code: (ii) x+1/2, y, −z+3/2.