Solvate-free bis-(triphenylphosphine)iminium chloride.

The title compound, C(36)H(30)NP(2) (+)·Cl(-), crystallized in the solvate-free form from a CH(3)CN/OEt(2) solution. The chloride anion and the N atom of the [(Ph(3)P)(2)N](+) cation are located on a twofold axis, yielding overall symmetry 2 for the cation. The central P-N-P angle [133.0 (3)°] is at the low end of the range of observed P-N-P angles.

Related literature

Several bis­(triphenyl­phosphine)iminium chloride structures containing solvate mol­ecules have been determined. For [(Ph3P)2N]Cl·B(OH)3, see: Andrews et al. (1983 ▶); for [(Ph3P)2N]Cl·CH3C6H5, see: Weller et al. (1993 ▶); for [(Ph3P)2N]Cl·CH2Cl2, see: Carroll et al. (1996 ▶); for [(Ph3P)2N]Cl·CH2Cl2·H2O, see: de Arellano (1997 ▶). Other bis­(triphenyl­phosphine)iminium halide structures have been determined: for [(Ph3P)2N]Br·CH3CN, see: Knapp & Uzun (2010 ▶); for [(Ph3P)2N]I, see: Beckett et al. (2010 ▶). For a discussion of the [(Ph3P)2N]+ cation, see: Lewis & Dance (2000 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶). For the synthesis, see: Ruff & Schlientz (1974 ▶).

Experimental

Crystal data

C36H30NP2 +·Cl−

M = 574.00

Monoclinic,

a = 15.094 (3) Å

b = 10.499 (2) Å

c = 18.615 (4) Å

β = 99.06 (3)°

V = 2913.0 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.27 mm−1

T = 123 K

0.30 × 0.23 × 0.23 mm

Data collection

Rigaku R-AXIS Spider diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 2001 ▶) T min = 0.924, T max = 0.941

7362 measured reflections

2551 independent reflections

2296 reflections with I > 2σ(I)

R int = 0.043

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.135

S = 1.24

2551 reflections

183 parameters

H-atom parameters constrained

Δρmax = 0.41 e Å−3

Δρmin = −0.42 e Å−3

Data collection: CrystalClear (Rigaku, 2007 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2010 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810046325/fi2099sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810046325/fi2099Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C36H30NP2+·Cl−	F(000) = 1200
Mr = 574.00	Dx = 1.309 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1435 reflections
a = 15.094 (3) Å	θ = 2.2–27.5°
b = 10.499 (2) Å	µ = 0.27 mm−1
c = 18.615 (4) Å	T = 123 K
β = 99.06 (3)°	Block, colourless
V = 2913.0 (10) Å3	0.30 × 0.23 × 0.23 mm
Z = 4

Rigaku R-AXIS Spider diffractometer	2551 independent reflections
Radiation source: sealed tube	2296 reflections with I > 2σ(I)
graphite	Rint = 0.043
Detector resolution: 10.0000 pixels mm-1	θmax = 25.0°, θmin = 2.2°
ω scans and/or φ scans	h = −17→17
Absorption correction: multi-scan (ABSCOR; Higashi, 2001)	k = −12→11
Tmin = 0.924, Tmax = 0.941	l = −20→22
7362 measured reflections

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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.135	H-atom parameters constrained
S = 1.24	w = 1/[σ2(Fo2) + 10.5312P] where P = (Fo2 + 2Fc2)/3
2551 reflections	(Δ/σ)max < 0.001
183 parameters	Δρmax = 0.41 e Å−3
0 restraints	Δρmin = −0.42 e Å−3

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 > 2σ(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	0.5000	0.80128 (11)	0.7500	0.0264 (3)
P1	0.53916 (5)	0.32003 (8)	0.82724 (4)	0.0175 (2)
N1	0.5000	0.2594 (4)	0.7500	0.0200 (8)
C1	0.45695 (19)	0.4133 (3)	0.86442 (16)	0.0177 (6)
C2	0.4358 (2)	0.5349 (3)	0.83690 (17)	0.0206 (7)
H2	0.4700	0.5724	0.8038	0.030 (3)*
C3	0.3645 (2)	0.6011 (3)	0.85815 (19)	0.0262 (8)
H3	0.3505	0.6844	0.8399	0.030 (3)*
C4	0.3135 (2)	0.5461 (4)	0.90596 (19)	0.0293 (8)
H4	0.2639	0.5908	0.9193	0.030 (3)*
C5	0.3353 (2)	0.4258 (3)	0.9342 (2)	0.0288 (8)
H5	0.3009	0.3891	0.9675	0.030 (3)*
C6	0.4070 (2)	0.3582 (3)	0.91427 (18)	0.0258 (7)
H6	0.4220	0.2761	0.9340	0.030 (3)*
C7	0.57029 (19)	0.1897 (3)	0.88839 (17)	0.0182 (7)
C8	0.6079 (2)	0.2160 (3)	0.96055 (18)	0.0247 (7)
H8	0.6183	0.3018	0.9758	0.030 (3)*
C9	0.6297 (2)	0.1184 (3)	1.00954 (18)	0.0260 (7)
H9	0.6548	0.1365	1.0585	0.030 (3)*
C10	0.6148 (2)	−0.0064 (3)	0.98669 (19)	0.0261 (8)
H10	0.6298	−0.0738	1.0204	0.030 (3)*
C11	0.5784 (2)	−0.0344 (3)	0.91551 (19)	0.0242 (7)
H11	0.5685	−0.1204	0.9005	0.030 (3)*
C12	0.5563 (2)	0.0643 (3)	0.86618 (18)	0.0224 (7)
H12	0.5316	0.0457	0.8171	0.030 (3)*
C13	0.6391 (2)	0.4148 (3)	0.82560 (17)	0.0216 (7)
C14	0.6520 (2)	0.5357 (3)	0.85535 (18)	0.0232 (7)
H14	0.6081	0.5726	0.8804	0.030 (3)*
C15	0.7303 (2)	0.6030 (3)	0.8482 (2)	0.0299 (8)
H15	0.7385	0.6868	0.8674	0.030 (3)*
C16	0.7957 (2)	0.5487 (4)	0.8137 (2)	0.0314 (9)
H16	0.8488	0.5950	0.8098	0.030 (3)*
C17	0.7839 (2)	0.4266 (3)	0.78468 (19)	0.0275 (8)
H17	0.8292	0.3888	0.7616	0.030 (3)*
C18	0.7054 (2)	0.3602 (3)	0.78966 (18)	0.0249 (7)
H18	0.6964	0.2777	0.7688	0.030 (3)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0250 (6)	0.0205 (6)	0.0352 (7)	0.000	0.0095 (5)	0.000
P1	0.0157 (4)	0.0178 (4)	0.0194 (4)	0.0007 (3)	0.0037 (3)	0.0004 (3)
N1	0.0140 (17)	0.026 (2)	0.0199 (19)	0.000	0.0030 (14)	0.000
C1	0.0184 (15)	0.0189 (16)	0.0147 (14)	0.0012 (12)	−0.0006 (12)	−0.0041 (13)
C2	0.0217 (16)	0.0205 (17)	0.0194 (16)	−0.0022 (13)	0.0028 (13)	−0.0014 (14)
C3	0.0228 (16)	0.0240 (18)	0.0309 (18)	0.0045 (14)	0.0014 (14)	−0.0018 (15)
C4	0.0186 (16)	0.036 (2)	0.033 (2)	0.0056 (14)	0.0048 (14)	−0.0104 (17)
C5	0.0274 (18)	0.0265 (18)	0.036 (2)	−0.0023 (15)	0.0161 (15)	−0.0018 (17)
C6	0.0232 (17)	0.0279 (18)	0.0270 (18)	0.0008 (14)	0.0057 (14)	0.0038 (15)
C7	0.0161 (15)	0.0199 (16)	0.0192 (16)	0.0005 (12)	0.0044 (12)	0.0004 (13)
C8	0.0263 (17)	0.0210 (17)	0.0272 (18)	−0.0010 (14)	0.0055 (14)	0.0006 (15)
C9	0.0280 (18)	0.0304 (19)	0.0188 (16)	0.0008 (14)	0.0012 (13)	0.0025 (15)
C10	0.0230 (17)	0.0273 (18)	0.0287 (19)	0.0028 (14)	0.0062 (14)	0.0135 (15)
C11	0.0252 (17)	0.0151 (16)	0.0330 (19)	0.0000 (13)	0.0072 (14)	0.0033 (14)
C12	0.0177 (15)	0.0261 (18)	0.0236 (17)	−0.0016 (13)	0.0036 (13)	−0.0018 (15)
C13	0.0163 (15)	0.0246 (17)	0.0238 (17)	0.0001 (13)	0.0026 (12)	0.0033 (14)
C14	0.0235 (17)	0.0186 (16)	0.0276 (18)	−0.0014 (13)	0.0040 (13)	−0.0024 (14)
C15	0.0240 (17)	0.0280 (19)	0.036 (2)	−0.0052 (15)	−0.0003 (15)	−0.0018 (16)
C16	0.0163 (16)	0.043 (2)	0.033 (2)	−0.0046 (15)	−0.0021 (14)	0.0123 (17)
C17	0.0205 (16)	0.032 (2)	0.0305 (19)	0.0033 (14)	0.0050 (14)	0.0089 (16)
C18	0.0195 (16)	0.0311 (19)	0.0237 (17)	0.0026 (14)	0.0020 (13)	−0.0027 (15)

P1—N1	1.5984 (18)	C8—H8	0.9500
P1—C7	1.795 (3)	C9—C10	1.385 (5)
P1—C1	1.802 (3)	C9—H9	0.9500
P1—C13	1.811 (3)	C10—C11	1.384 (5)
N1—P1i	1.5984 (18)	C10—H10	0.9500
C1—C2	1.394 (4)	C11—C12	1.390 (5)
C1—C6	1.409 (5)	C11—H11	0.9500
C2—C3	1.390 (5)	C12—H12	0.9500
C2—H2	0.9500	C13—C14	1.386 (5)
C3—C4	1.390 (5)	C13—C18	1.410 (4)
C3—H3	0.9500	C14—C15	1.401 (5)
C4—C5	1.387 (5)	C14—H14	0.9500
C4—H4	0.9500	C15—C16	1.383 (5)
C5—C6	1.392 (5)	C15—H15	0.9500
C5—H5	0.9500	C16—C17	1.392 (5)
C6—H6	0.9500	C16—H16	0.9500
C7—C12	1.386 (4)	C17—C18	1.391 (5)
C7—C8	1.401 (4)	C17—H17	0.9500
C8—C9	1.377 (5)	C18—H18	0.9500
N1—P1—C7	106.82 (17)	C8—C9—C10	119.3 (3)
N1—P1—C1	112.50 (12)	C8—C9—H9	120.3
C7—P1—C1	107.33 (15)	C10—C9—H9	120.3
N1—P1—C13	113.24 (13)	C11—C10—C9	121.1 (3)
C7—P1—C13	107.11 (14)	C11—C10—H10	119.5
C1—P1—C13	109.49 (15)	C9—C10—H10	119.5
P1—N1—P1i	133.0 (3)	C10—C11—C12	119.5 (3)
C2—C1—C6	120.2 (3)	C10—C11—H11	120.3
C2—C1—P1	119.2 (2)	C12—C11—H11	120.3
C6—C1—P1	120.2 (2)	C7—C12—C11	120.1 (3)
C3—C2—C1	119.7 (3)	C7—C12—H12	119.9
C3—C2—H2	120.1	C11—C12—H12	119.9
C1—C2—H2	120.1	C14—C13—C18	119.7 (3)
C4—C3—C2	120.4 (3)	C14—C13—P1	124.1 (2)
C4—C3—H3	119.8	C18—C13—P1	116.1 (3)
C2—C3—H3	119.8	C13—C14—C15	119.5 (3)
C5—C4—C3	119.9 (3)	C13—C14—H14	120.3
C5—C4—H4	120.0	C15—C14—H14	120.3
C3—C4—H4	120.0	C16—C15—C14	120.7 (3)
C4—C5—C6	120.7 (3)	C16—C15—H15	119.6
C4—C5—H5	119.6	C14—C15—H15	119.6
C6—C5—H5	119.6	C15—C16—C17	120.2 (3)
C5—C6—C1	119.0 (3)	C15—C16—H16	119.9
C5—C6—H6	120.5	C17—C16—H16	119.9
C1—C6—H6	120.5	C18—C17—C16	119.6 (3)
C12—C7—C8	119.5 (3)	C18—C17—H17	120.2
C12—C7—P1	121.5 (2)	C16—C17—H17	120.2
C8—C7—P1	118.9 (2)	C17—C18—C13	120.3 (3)
C9—C8—C7	120.5 (3)	C17—C18—H18	119.9
C9—C8—H8	119.8	C13—C18—H18	119.9
C7—C8—H8	119.8
C7—P1—N1—P1i	−179.94 (11)	C12—C7—C8—C9	−0.9 (5)
C1—P1—N1—P1i	62.54 (12)	P1—C7—C8—C9	177.8 (2)
C13—P1—N1—P1i	−62.27 (13)	C7—C8—C9—C10	0.4 (5)
N1—P1—C1—C2	−76.9 (3)	C8—C9—C10—C11	0.1 (5)
C7—P1—C1—C2	165.9 (2)	C9—C10—C11—C12	−0.1 (5)
C13—P1—C1—C2	50.0 (3)	C8—C7—C12—C11	0.9 (5)
N1—P1—C1—C6	95.5 (3)	P1—C7—C12—C11	−177.8 (2)
C7—P1—C1—C6	−21.7 (3)	C10—C11—C12—C7	−0.4 (5)
C13—P1—C1—C6	−137.7 (3)	N1—P1—C13—C14	132.3 (3)
C6—C1—C2—C3	−0.8 (5)	C7—P1—C13—C14	−110.2 (3)
P1—C1—C2—C3	171.6 (2)	C1—P1—C13—C14	5.9 (3)
C1—C2—C3—C4	−0.8 (5)	N1—P1—C13—C18	−46.0 (3)
C2—C3—C4—C5	1.7 (5)	C7—P1—C13—C18	71.5 (3)
C3—C4—C5—C6	−1.0 (5)	C1—P1—C13—C18	−172.5 (2)
C4—C5—C6—C1	−0.5 (5)	C18—C13—C14—C15	1.1 (5)
C2—C1—C6—C5	1.4 (5)	P1—C13—C14—C15	−177.2 (3)
P1—C1—C6—C5	−170.9 (3)	C13—C14—C15—C16	−1.8 (5)
N1—P1—C7—C12	−2.0 (3)	C14—C15—C16—C17	0.8 (5)
C1—P1—C7—C12	118.9 (3)	C15—C16—C17—C18	1.0 (5)
C13—P1—C7—C12	−123.6 (3)	C16—C17—C18—C13	−1.7 (5)
N1—P1—C7—C8	179.3 (2)	C14—C13—C18—C17	0.7 (5)
C1—P1—C7—C8	−59.8 (3)	P1—C13—C18—C17	179.1 (3)
C13—P1—C7—C8	57.7 (3)

P1—N1	1.5984 (18)
P1—C7	1.795 (3)
P1—C1	1.802 (3)
P1—C13	1.811 (3)

P1—N1—P1i

133.0 (3)

Symmetry code: (i) .