Tris(2-methylphenyl)phosphonium tetrachloroborate

The title compound, C₂₁H₂₂P⁺·BCl₄^-, is the first structurally characterized example of the [HP(o-tolyl)₃]⁺ cation, presented here with BCl₄^- as the counter-ion. The cation has a near-tetrahedral P atom and the BCl₄^- anion is near-tetrahedral at boron. There are no unusually short cation-anion contacts.

Computing details

Data collection: SMART-NT (Bruker, 1998); cell refinement: SMART-NT; data reduction: SHELXTL-NT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT; software used to prepare material for publication: SHELXTL-NT.

tris(2-methylphenyl)phosphonium tetrachloroborate

Crystal data

C21H22P^+·BCl4^−	Z = 2
Mr = 457.97	F(000) = 472
Triclinic, P1	Dx = 1.390 Mg m^−3
a = 9.4160 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.4361 (3) Å	Cell parameters from 869 reflections
c = 11.5642 (3) Å	θ = 10.2–21.6°
α = 118.281 (1)°	µ = 0.62 mm^−1
β = 90.114 (1)°	T = 100 K
γ = 93.444 (1)°	Block, colourless
V = 1093.98 (5) Å^3	0.48 × 0.18 × 0.10 mm

Data collection

Model? CCD area-detector diffractometer	6059 independent reflections
Radiation source: fine-focus sealed tube	4302 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.042
ω scans	θmax = 30.5°, θmin = 2.0°
Absorption correction: empirical (using intensity measurements) (XPREP in SHELXTL-NT; Bruker, 1998)	h = −12→13
Tmin = 0.814, Tmax = 0.962	k = −15→15
14295 measured reflections	l = −16→16

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.090	All H-atom parameters refined
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0446P)^2] where P = (Fo^2 + 2Fc^2)/3
6059 reflections	(Δ/σ)max = 0.001
332 parameters	Δρmax = 0.43 e Å^−3
0 restraints	Δρmin = −0.38 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
P1	0.12580 (5)	0.28906 (5)	0.13724 (5)	0.01455 (10)
H1	0.180 (2)	0.4099 (18)	0.1992 (19)	0.016 (5)*
C1	0.13986 (19)	0.23344 (18)	−0.03610 (18)	0.0163 (4)
C2	0.0186 (2)	0.17154 (19)	−0.11863 (19)	0.0203 (4)
H2A	−0.065 (2)	0.1594 (19)	−0.086 (2)	0.017 (5)*
C3	0.0264 (2)	0.1250 (2)	−0.2527 (2)	0.0267 (5)
H3A	−0.055 (3)	0.084 (2)	−0.310 (2)	0.035 (6)*
C4	0.1558 (2)	0.1388 (2)	−0.3047 (2)	0.0290 (5)
H4A	0.161 (2)	0.107 (2)	−0.395 (2)	0.026 (6)*
C5	0.2758 (2)	0.2001 (2)	−0.2237 (2)	0.0255 (4)
H5A	0.361 (3)	0.213 (2)	−0.262 (2)	0.033 (6)*
C6	0.2707 (2)	0.24948 (19)	−0.08780 (19)	0.0203 (4)
C7	0.4021 (2)	0.3179 (2)	−0.0006 (2)	0.0262 (5)
H7C	0.390 (3)	0.408 (3)	0.065 (3)	0.040 (7)*
H7B	0.481 (3)	0.319 (2)	−0.052 (2)	0.037 (7)*
H7A	0.434 (3)	0.273 (2)	0.051 (2)	0.043 (7)*
C8	−0.05727 (18)	0.28897 (18)	0.18104 (17)	0.0162 (4)
C9	−0.1087 (2)	0.1964 (2)	0.22114 (18)	0.0195 (4)
H9A	−0.048 (2)	0.1343 (19)	0.2270 (19)	0.015 (5)*
C10	−0.2489 (2)	0.1955 (2)	0.25757 (19)	0.0248 (4)
H10A	−0.283 (2)	0.130 (2)	0.2847 (19)	0.018 (5)*
C11	−0.3370 (2)	0.2864 (2)	0.2539 (2)	0.0274 (5)
H11A	−0.426 (3)	0.286 (2)	0.279 (2)	0.046 (7)*
C12	−0.2873 (2)	0.3775 (2)	0.21338 (19)	0.0240 (4)
H12A	−0.347 (2)	0.443 (2)	0.213 (2)	0.025 (6)*
C13	−0.14654 (19)	0.38127 (18)	0.17546 (17)	0.0177 (4)
C14	−0.0967 (2)	0.4789 (2)	0.1293 (2)	0.0215 (4)
H14C	−0.078 (3)	0.438 (2)	0.041 (3)	0.036 (7)*
H14A	−0.157 (3)	0.549 (3)	0.152 (3)	0.055 (8)*
H14B	−0.009 (3)	0.527 (3)	0.171 (3)	0.069 (9)*
C15	0.22398 (18)	0.18655 (17)	0.18314 (18)	0.0162 (4)
C16	0.2712 (2)	0.06804 (19)	0.0823 (2)	0.0197 (4)
H16A	0.252 (2)	0.0465 (19)	0.000 (2)	0.012 (5)*
C17	0.3474 (2)	−0.0151 (2)	0.1116 (2)	0.0238 (4)
H17A	0.375 (2)	−0.097 (2)	0.041 (2)	0.022 (5)*
C18	0.3773 (2)	0.0200 (2)	0.2422 (2)	0.0239 (4)
H18A	0.432 (2)	−0.039 (2)	0.264 (2)	0.030 (6)*
C19	0.3311 (2)	0.1373 (2)	0.3428 (2)	0.0218 (4)
H19A	0.353 (2)	0.161 (2)	0.429 (2)	0.025 (6)*
C20	0.25343 (19)	0.22353 (18)	0.31668 (18)	0.0172 (4)
C21	0.2057 (2)	0.3495 (2)	0.4286 (2)	0.0226 (4)
H21C	0.113 (3)	0.362 (3)	0.421 (3)	0.065 (9)*
H21A	0.219 (3)	0.352 (3)	0.505 (3)	0.053 (8)*
H21B	0.261 (4)	0.421 (3)	0.437 (3)	0.072 (10)*
B1	0.2995 (2)	0.7055 (2)	0.3632 (2)	0.0177 (4)
Cl1	0.43203 (5)	0.59574 (5)	0.37333 (5)	0.02568 (12)
Cl2	0.27768 (5)	0.66849 (5)	0.18846 (4)	0.02309 (11)
Cl3	0.36421 (5)	0.88104 (4)	0.46513 (5)	0.02352 (11)
Cl4	0.12567 (5)	0.67182 (5)	0.42017 (5)	0.02366 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
P1	0.0106 (2)	0.0171 (2)	0.0166 (2)	0.00171 (17)	0.00080 (17)	0.00841 (19)
C1	0.0146 (9)	0.0182 (9)	0.0189 (9)	0.0044 (7)	0.0042 (7)	0.0107 (7)
C2	0.0175 (10)	0.0215 (10)	0.0215 (10)	0.0041 (8)	0.0012 (8)	0.0095 (8)
C3	0.0252 (11)	0.0325 (11)	0.0206 (10)	0.0083 (9)	−0.0009 (8)	0.0103 (9)
C4	0.0353 (12)	0.0341 (12)	0.0187 (10)	0.0144 (10)	0.0075 (9)	0.0122 (9)
C5	0.0251 (11)	0.0308 (11)	0.0265 (10)	0.0136 (9)	0.0122 (9)	0.0170 (9)
C6	0.0179 (9)	0.0214 (9)	0.0252 (10)	0.0076 (7)	0.0068 (8)	0.0133 (8)
C7	0.0148 (10)	0.0301 (12)	0.0333 (12)	0.0012 (8)	0.0070 (8)	0.0148 (10)
C8	0.0128 (8)	0.0194 (9)	0.0139 (8)	0.0015 (7)	0.0022 (7)	0.0057 (7)
C9	0.0176 (9)	0.0240 (10)	0.0171 (9)	−0.0014 (8)	−0.0002 (7)	0.0103 (8)
C10	0.0210 (10)	0.0348 (12)	0.0193 (10)	−0.0084 (9)	−0.0001 (8)	0.0145 (9)
C11	0.0134 (9)	0.0406 (13)	0.0210 (10)	−0.0018 (9)	0.0032 (8)	0.0093 (9)
C12	0.0150 (9)	0.0283 (11)	0.0216 (10)	0.0037 (8)	−0.0008 (7)	0.0059 (8)
C13	0.0154 (9)	0.0188 (9)	0.0140 (8)	0.0018 (7)	−0.0014 (7)	0.0038 (7)
C14	0.0210 (10)	0.0195 (10)	0.0248 (11)	0.0028 (8)	−0.0024 (8)	0.0112 (9)
C15	0.0103 (8)	0.0185 (9)	0.0212 (9)	−0.0007 (7)	−0.0011 (7)	0.0108 (8)
C16	0.0159 (9)	0.0222 (10)	0.0212 (10)	0.0012 (7)	−0.0002 (7)	0.0104 (8)
C17	0.0213 (10)	0.0210 (10)	0.0296 (11)	0.0054 (8)	0.0017 (8)	0.0121 (9)
C18	0.0178 (10)	0.0261 (10)	0.0347 (12)	0.0019 (8)	−0.0018 (8)	0.0200 (9)
C19	0.0161 (9)	0.0286 (10)	0.0244 (10)	−0.0031 (8)	−0.0037 (8)	0.0161 (9)
C20	0.0114 (8)	0.0202 (9)	0.0205 (9)	−0.0032 (7)	0.0004 (7)	0.0106 (8)
C21	0.0204 (10)	0.0275 (11)	0.0207 (10)	0.0005 (9)	0.0004 (8)	0.0122 (9)
B1	0.0147 (10)	0.0197 (10)	0.0175 (10)	−0.0007 (8)	0.0000 (8)	0.0081 (8)
Cl1	0.0195 (2)	0.0253 (2)	0.0324 (3)	0.00640 (19)	0.00046 (19)	0.0133 (2)
Cl2	0.0198 (2)	0.0307 (3)	0.0175 (2)	−0.00005 (19)	0.00204 (17)	0.01050 (19)
Cl3	0.0264 (3)	0.0183 (2)	0.0234 (2)	−0.00297 (19)	−0.00277 (19)	0.00841 (19)
Cl4	0.0145 (2)	0.0335 (3)	0.0216 (2)	−0.00216 (19)	0.00285 (17)	0.0124 (2)

Geometric parameters (Å, º)

P1—C15	1.7968 (18)	C11—H11A	0.89 (3)
P1—C8	1.7977 (18)	C12—C13	1.402 (3)
P1—C1	1.8009 (18)	C12—H12A	0.97 (2)
P1—H1	1.289 (19)	C13—C14	1.502 (3)
C1—C2	1.405 (3)	C14—H14C	0.92 (2)
C1—C6	1.411 (3)	C14—H14A	0.94 (3)
C2—C3	1.384 (3)	C14—H14B	0.95 (3)
C2—H2A	0.90 (2)	C15—C16	1.404 (3)
C3—C4	1.393 (3)	C15—C20	1.416 (2)
C3—H3A	0.96 (2)	C16—C17	1.385 (3)
C4—C5	1.387 (3)	C16—H16A	0.88 (2)
C4—H4A	0.93 (2)	C17—C18	1.389 (3)
C5—C6	1.397 (3)	C17—H17A	0.95 (2)
C5—H5A	0.95 (2)	C18—C19	1.391 (3)
C6—C7	1.513 (3)	C18—H18A	1.00 (2)
C7—H7C	0.96 (2)	C19—C20	1.402 (3)
C7—H7B	0.95 (3)	C19—H19A	0.92 (2)
C7—H7A	1.00 (2)	C20—C21	1.505 (3)
C8—C9	1.405 (3)	C21—H21C	0.90 (3)
C8—C13	1.413 (3)	C21—H21A	0.88 (3)
C9—C10	1.388 (3)	C21—H21B	0.91 (3)
C9—H9A	0.96 (2)	B1—Cl3	1.843 (2)
C10—C11	1.384 (3)	B1—Cl4	1.853 (2)
C10—H10A	0.98 (2)	B1—Cl1	1.864 (2)
C11—C12	1.389 (3)	B1—Cl2	1.865 (2)
C15—P1—C8	111.09 (9)	C11—C12—C13	121.40 (19)
C15—P1—C1	109.90 (8)	C11—C12—H12A	121.6 (13)
C8—P1—C1	111.07 (8)	C13—C12—H12A	117.0 (13)
C15—P1—H1	109.1 (8)	C12—C13—C8	117.09 (17)
C8—P1—H1	107.8 (8)	C12—C13—C14	120.21 (17)
C1—P1—H1	107.8 (8)	C8—C13—C14	122.69 (17)
C2—C1—C6	120.91 (17)	C13—C14—H14C	112.2 (15)
C2—C1—P1	118.57 (14)	C13—C14—H14A	113.4 (17)
C6—C1—P1	120.51 (14)	H14C—C14—H14A	112 (2)
C3—C2—C1	120.09 (19)	C13—C14—H14B	112.7 (18)
C3—C2—H2A	118.8 (13)	H14C—C14—H14B	104 (2)
C1—C2—H2A	121.1 (13)	H14A—C14—H14B	102 (2)
C2—C3—C4	119.3 (2)	C16—C15—C20	120.69 (17)
C2—C3—H3A	121.5 (14)	C16—C15—P1	117.95 (14)
C4—C3—H3A	119.2 (14)	C20—C15—P1	121.36 (14)
C5—C4—C3	120.8 (2)	C17—C16—C15	120.58 (19)
C5—C4—H4A	119.9 (14)	C17—C16—H16A	119.7 (13)
C3—C4—H4A	119.3 (14)	C15—C16—H16A	119.7 (13)
C4—C5—C6	121.2 (2)	C16—C17—C18	119.39 (19)
C4—C5—H5A	118.5 (14)	C16—C17—H17A	118.9 (13)
C6—C5—H5A	120.2 (14)	C18—C17—H17A	121.7 (13)
C5—C6—C1	117.68 (18)	C17—C18—C19	120.46 (18)
C5—C6—C7	120.46 (18)	C17—C18—H18A	119.8 (13)
C1—C6—C7	121.86 (18)	C19—C18—H18A	119.7 (13)
C6—C7—H7C	113.9 (15)	C18—C19—C20	121.67 (19)
C6—C7—H7B	110.6 (15)	C18—C19—H19A	120.4 (13)
H7C—C7—H7B	108 (2)	C20—C19—H19A	117.9 (13)
C6—C7—H7A	114.0 (15)	C19—C20—C15	117.21 (17)
H7C—C7—H7A	104 (2)	C19—C20—C21	119.87 (18)
H7B—C7—H7A	105.6 (19)	C15—C20—C21	122.92 (17)
C9—C8—C13	121.13 (16)	C20—C21—H21C	113.4 (19)
C9—C8—P1	118.82 (14)	C20—C21—H21A	112.0 (17)
C13—C8—P1	120.05 (14)	H21C—C21—H21A	108 (3)
C10—C9—C8	120.08 (18)	C20—C21—H21B	111 (2)
C10—C9—H9A	118.1 (12)	H21C—C21—H21B	110 (3)
C8—C9—H9A	121.8 (12)	H21A—C21—H21B	102 (3)
C11—C10—C9	119.33 (19)	Cl3—B1—Cl4	110.40 (11)
C11—C10—H10A	121.8 (12)	Cl3—B1—Cl1	109.36 (11)
C9—C10—H10A	118.8 (12)	Cl4—B1—Cl1	109.68 (11)
C10—C11—C12	120.96 (19)	Cl3—B1—Cl2	109.66 (11)
C10—C11—H11A	118.5 (16)	Cl4—B1—Cl2	108.94 (10)
C12—C11—H11A	120.5 (16)	Cl1—B1—Cl2	108.78 (11)
C15—P1—C1—C2	109.96 (15)	C10—C11—C12—C13	−0.4 (3)
C8—P1—C1—C2	−13.39 (17)	C11—C12—C13—C8	−0.4 (3)
C15—P1—C1—C6	−68.78 (17)	C11—C12—C13—C14	178.68 (18)
C8—P1—C1—C6	167.88 (14)	C9—C8—C13—C12	0.9 (3)
C6—C1—C2—C3	0.1 (3)	P1—C8—C13—C12	−178.79 (13)
P1—C1—C2—C3	−178.60 (15)	C9—C8—C13—C14	−178.11 (17)
C1—C2—C3—C4	0.7 (3)	P1—C8—C13—C14	2.2 (2)
C2—C3—C4—C5	−0.8 (3)	C8—P1—C15—C16	111.14 (15)
C3—C4—C5—C6	0.0 (3)	C1—P1—C15—C16	−12.19 (17)
C4—C5—C6—C1	0.8 (3)	C8—P1—C15—C20	−68.95 (16)
C4—C5—C6—C7	−179.02 (19)	C1—P1—C15—C20	167.73 (14)
C2—C1—C6—C5	−0.9 (3)	C20—C15—C16—C17	0.1 (3)
P1—C1—C6—C5	177.82 (14)	P1—C15—C16—C17	−179.99 (15)
C2—C1—C6—C7	178.93 (18)	C15—C16—C17—C18	−0.2 (3)
P1—C1—C6—C7	−2.4 (3)	C16—C17—C18—C19	0.1 (3)
C15—P1—C8—C9	−11.11 (17)	C17—C18—C19—C20	0.0 (3)
C1—P1—C8—C9	111.54 (15)	C18—C19—C20—C15	−0.1 (3)
C15—P1—C8—C13	168.58 (14)	C18—C19—C20—C21	−179.95 (19)
C1—P1—C8—C13	−68.77 (16)	C16—C15—C20—C19	0.1 (3)
C13—C8—C9—C10	−0.7 (3)	P1—C15—C20—C19	−179.84 (14)
P1—C8—C9—C10	178.95 (14)	C16—C15—C20—C21	179.88 (18)
C8—C9—C10—C11	0.0 (3)	P1—C15—C20—C21	0.0 (2)
C9—C10—C11—C12	0.5 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···Cl2^i	0.95 (3)	2.81 (3)	3.758 (2)	177 (2)
C14—H14B···Cl4	0.95 (3)	2.80 (3)	3.599 (2)	141 (2)
C12—H12A···Cl1^ii	0.97 (2)	2.86 (2)	3.616 (2)	135.6 (16)
C21—H21B···Cl1	0.91 (3)	2.85 (3)	3.725 (2)	161 (3)

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1, y, z.