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organic compounds
Bis(triphenyl-λ5-phosphanylidene)ammonium hydrogen dichloride
aInstitut für Anorganische und Analytische Chemie, Albert-Ludwigs-Universität Freiburg, Albertstrasse 21, 79104 Freiburg i. Br., Germany
*Correspondence e-mail: carsten.knapp@ac.uni-freiburg.de
In the title compound, [(Ph3P)2N]+·[Cl-H-Cl]− or C36H30NP2+·Cl2H−, the H atom of the [Cl—H—Cl]− anion and the N atom of the [(Ph3P)2N]+ cation are located on a twofold axis, yielding overall symmetry 2 for both the cation and the anion. The central P—N—P angle [144.12 (13)°] of the cation is in the expected range and indicates only weak cation–anion interactions. The almost linear [Cl—H—Cl]− anion is a rare example of a symmetric hydrogen bridge in a hydrogen dichloride anion. The Cl⋯Cl distance and two equal Cl—H bonds are typical of such a symmetric hydrogen dichloride anion.
Related literature
For selected examples containing the [Cl—H—Cl]− anion, see: Atwood et al. (1990); Mootz et al. (1981
); Habtemariam et al. (2001
); Swann et al. (1984
); Neumüller et al. (2005
). For other bis(triphenyl-λ5-phosphanylidene)ammonium halide structures, see: Knapp & Uzun (2010a
,b
); 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 of [(Ph3P)2N]Cl, see: Ruff & Schlientz (1974
).
Experimental
Crystal data
|
Refinement
|
|
Data collection: APEX2 (Bruker, 2007); cell SAINT (Bruker, 2007
); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
); molecular graphics: DIAMOND (Brandenburg & Putz, 2011
); software used to prepare material for publication: SHELXL97.
Supporting information
https://doi.org/10.1107/S1600536811035057/su2304sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811035057/su2304Isup2.hkl
Single crystals of the title compound, suitable for X-ray
were obtained as a by-product by layering a CH3CN solution of [(Ph3P)2N]Cl with diethyl ether.The carbon-bonded hydrogen atoms were positioned geometrically and refined using a riding model. The same Uiso value was used for all H atoms, which refined to 0.0226 (13) Å2. The coordinates for the hydrogen atom in the [Cl—H—Cl]- anion were taken from the Fourier map and the atom was refined isotropically.
The Cambridge Structural Database (Allen, 2002) currently contains more than 1200 structures containing the [(Ph3P)2N]+ cation ([(Ph3P)2N]+ = [PNP]+). Usually this cation is partnered by a bulky anion, while crystal structures containing small anions and especially halides are rare. The crystal structures of some solvate-free halides, [(Ph3P)2N]I (Beckett et al., 2010) and [(Ph3P)2N]Cl (Knapp & Uzun, 2010a), and the acetontrile solvate [(Ph3P)2N]Br.CH3CN (Knapp & Uzun, 2010b), were published only very recently.
Bis(triphenyl-λ5-phosphanylidene)ammonium chloride [(Ph3P)2N]Cl was synthesized according to a published method (Ruff et al., 1974). Solvate-free single crystals suitable for X-ray diffraction of the title compound were obtained as a by-product by layering a CH3CN solution with diethyl ether. The H atom of the [Cl—H—Cl]- anion and the N atom of the [(Ph3P)2N]+ cation are located on a twofold axis, yielding overall symmetry 2 for the cation. The central P—N—P angle [144.12 (13)°] and the P—N [1.5762 (7) Å] and P—C distances [1.7940 (16)–1.8028 (15) Å] are in the expected range for the [(Ph3P)2N]+ cation (Lewis & Dance, 2000).
The number of structurally characterized hydrogen dichloride anions is still limited. Often disorder or low crystal quality does not allow to establish unequivically the position of the H atom. The Cl···Cl distances in all hydrogen dichloride anions deviate only slightly from an averaged distance of 3.10 Å. The anion in the title compound contains a symmetric hydrogen bridge with H—Cl distances of 1.56 (1) Å and a Cl···Cl distance of 3.1045 (9) Å. The anion is almost linear and a Cl—H—Cl angle of 173 (3)° is observed. A very similar hydrogen dichloride anion was found in the the
of [K(18 C-6)][Cl—H—Cl], where H—Cl is 1.56 Å and Cl···Cl 3.117 (1) Å (Atwood et al., 1990).For selected examples containing the [Cl—H—Cl]- anion, see: Atwood et al. (1990); Mootz et al. (1981); Habtemariam et al. (2001); Swann et al. (1984); Neumüller et al. (2005). For other Bis(triphenyl-λ5-phosphanylidene)ammonium halide structures, see: Knapp & Uzun (2010a,b); Beckett et al. (2010). For a discussion of the [(Ph3P)2N]+ cation, see: Lewis & Dance (2000). For a dsecription of the Cambridge Structural Database, see: Allen (2002). For the synthesis, see: Ruff & Schlientz (1974).
Data collection: APEX2 (Bruker, 2007); cell
SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2011); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).C36H30NP2+·Cl2H− | F(000) = 1272 |
Mr = 610.46 | Dx = 1.335 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 9956 reflections |
a = 11.6467 (3) Å | θ = 2.5–30.8° |
b = 16.5474 (4) Å | µ = 0.35 mm−1 |
c = 15.7584 (3) Å | T = 100 K |
V = 3037.00 (12) Å3 | Block, colourless |
Z = 4 | 0.18 × 0.14 × 0.09 mm |
Bruker APEXII CCD area-detector diffractometer | 2994 independent reflections |
Radiation source: microfocus sealed tube | 2671 reflections with I > 2σ(I) |
Multilayer mirro optics monochromator | Rint = 0.030 |
φ and ω scans | θmax = 26.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −14→14 |
Tmin = 0.940, Tmax = 0.970 | k = −19→20 |
28633 measured reflections | l = −19→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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0372P)2 + 2.5322P] where P = (Fo2 + 2Fc2)/3 |
2994 reflections | (Δ/σ)max < 0.001 |
189 parameters | Δρmax = 0.61 e Å−3 |
0 restraints | Δρmin = −0.79 e Å−3 |
C36H30NP2+·Cl2H− | V = 3037.00 (12) Å3 |
Mr = 610.46 | Z = 4 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 11.6467 (3) Å | µ = 0.35 mm−1 |
b = 16.5474 (4) Å | T = 100 K |
c = 15.7584 (3) Å | 0.18 × 0.14 × 0.09 mm |
Bruker APEXII CCD area-detector diffractometer | 2994 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 2671 reflections with I > 2σ(I) |
Tmin = 0.940, Tmax = 0.970 | Rint = 0.030 |
28633 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.085 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.61 e Å−3 |
2994 reflections | Δρmin = −0.79 e Å−3 |
189 parameters |
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 | ||
P1 | 0.37492 (3) | 0.47726 (2) | 0.22743 (2) | 0.01086 (11) | |
N1 | 0.5000 | 0.44792 (11) | 0.2500 | 0.0142 (4) | |
C1 | 0.32847 (13) | 0.42600 (9) | 0.13289 (10) | 0.0136 (3) | |
C2 | 0.37451 (13) | 0.35003 (10) | 0.11482 (10) | 0.0163 (3) | |
H2 | 0.4320 | 0.3275 | 0.1505 | 0.0226 (13)* | |
C3 | 0.33594 (15) | 0.30750 (10) | 0.04441 (11) | 0.0203 (4) | |
H3 | 0.3678 | 0.2561 | 0.0315 | 0.0226 (13)* | |
C4 | 0.25109 (16) | 0.33988 (10) | −0.00703 (11) | 0.0227 (4) | |
H4 | 0.2247 | 0.3104 | −0.0549 | 0.0226 (13)* | |
C5 | 0.20431 (15) | 0.41512 (11) | 0.01091 (11) | 0.0224 (4) | |
H5 | 0.1460 | 0.4369 | −0.0245 | 0.0226 (13)* | |
C6 | 0.24288 (14) | 0.45863 (10) | 0.08092 (10) | 0.0173 (3) | |
H6 | 0.2112 | 0.5102 | 0.0933 | 0.0226 (13)* | |
C7 | 0.36204 (12) | 0.58392 (9) | 0.20936 (10) | 0.0126 (3) | |
C8 | 0.43189 (13) | 0.61829 (10) | 0.14660 (10) | 0.0171 (3) | |
H8 | 0.4784 | 0.5847 | 0.1118 | 0.0226 (13)* | |
C9 | 0.43306 (14) | 0.70100 (10) | 0.13533 (11) | 0.0203 (4) | |
H9 | 0.4809 | 0.7243 | 0.0931 | 0.0226 (13)* | |
C10 | 0.36455 (14) | 0.75028 (10) | 0.18551 (11) | 0.0204 (4) | |
H10 | 0.3661 | 0.8072 | 0.1778 | 0.0226 (13)* | |
C11 | 0.29393 (15) | 0.71670 (10) | 0.24675 (11) | 0.0210 (4) | |
H11 | 0.2462 | 0.7505 | 0.2803 | 0.0226 (13)* | |
C12 | 0.29273 (14) | 0.63361 (10) | 0.25912 (10) | 0.0169 (3) | |
H12 | 0.2447 | 0.6107 | 0.3015 | 0.0226 (13)* | |
C13 | 0.27637 (13) | 0.44720 (9) | 0.30980 (10) | 0.0128 (3) | |
C14 | 0.15825 (13) | 0.45901 (10) | 0.30003 (10) | 0.0162 (3) | |
H14 | 0.1295 | 0.4861 | 0.2513 | 0.0226 (13)* | |
C15 | 0.08307 (14) | 0.43109 (10) | 0.36169 (11) | 0.0189 (3) | |
H15 | 0.0028 | 0.4391 | 0.3550 | 0.0226 (13)* | |
C16 | 0.12438 (14) | 0.39159 (10) | 0.43294 (10) | 0.0179 (3) | |
H16 | 0.0724 | 0.3723 | 0.4748 | 0.0226 (13)* | |
C17 | 0.24172 (14) | 0.38023 (10) | 0.44327 (10) | 0.0174 (3) | |
H17 | 0.2700 | 0.3534 | 0.4923 | 0.0226 (13)* | |
C18 | 0.31776 (13) | 0.40806 (9) | 0.38184 (10) | 0.0149 (3) | |
H18 | 0.3980 | 0.4004 | 0.3890 | 0.0226 (13)* | |
Cl1 | 0.49306 (4) | 0.14372 (3) | 0.15163 (3) | 0.03665 (15) | |
H1 | 0.5000 | 0.149 (3) | 0.2500 | 0.087 (15)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.0108 (2) | 0.0097 (2) | 0.0120 (2) | −0.00044 (14) | −0.00017 (14) | −0.00049 (14) |
N1 | 0.0123 (9) | 0.0108 (9) | 0.0196 (10) | 0.000 | −0.0001 (7) | 0.000 |
C1 | 0.0144 (7) | 0.0138 (8) | 0.0127 (7) | −0.0053 (6) | 0.0026 (6) | −0.0011 (6) |
C2 | 0.0148 (7) | 0.0154 (8) | 0.0188 (8) | −0.0027 (6) | 0.0026 (6) | −0.0021 (6) |
C3 | 0.0231 (8) | 0.0158 (8) | 0.0219 (9) | −0.0040 (7) | 0.0065 (7) | −0.0059 (7) |
C4 | 0.0334 (9) | 0.0200 (9) | 0.0146 (8) | −0.0099 (7) | 0.0004 (7) | −0.0030 (7) |
C5 | 0.0300 (9) | 0.0212 (9) | 0.0160 (8) | −0.0063 (7) | −0.0066 (7) | 0.0041 (7) |
C6 | 0.0229 (8) | 0.0135 (8) | 0.0155 (8) | −0.0021 (6) | −0.0011 (6) | 0.0015 (6) |
C7 | 0.0126 (7) | 0.0118 (7) | 0.0134 (7) | 0.0000 (6) | −0.0044 (6) | −0.0001 (6) |
C8 | 0.0160 (7) | 0.0169 (8) | 0.0184 (8) | 0.0015 (6) | 0.0007 (6) | 0.0006 (6) |
C9 | 0.0187 (8) | 0.0174 (9) | 0.0247 (9) | −0.0021 (7) | −0.0007 (7) | 0.0067 (7) |
C10 | 0.0218 (8) | 0.0118 (8) | 0.0276 (9) | 0.0007 (6) | −0.0076 (7) | 0.0019 (7) |
C11 | 0.0231 (8) | 0.0158 (8) | 0.0240 (9) | 0.0054 (7) | −0.0021 (7) | −0.0027 (7) |
C12 | 0.0173 (8) | 0.0166 (8) | 0.0169 (8) | 0.0019 (6) | 0.0003 (6) | 0.0001 (6) |
C13 | 0.0148 (7) | 0.0106 (7) | 0.0130 (8) | −0.0014 (6) | 0.0006 (6) | −0.0023 (6) |
C14 | 0.0155 (7) | 0.0185 (8) | 0.0147 (8) | −0.0014 (6) | −0.0018 (6) | 0.0002 (6) |
C15 | 0.0133 (7) | 0.0214 (9) | 0.0219 (9) | −0.0024 (6) | 0.0001 (6) | −0.0006 (7) |
C16 | 0.0202 (8) | 0.0153 (8) | 0.0180 (8) | −0.0039 (6) | 0.0047 (6) | 0.0001 (6) |
C17 | 0.0230 (8) | 0.0142 (8) | 0.0149 (8) | 0.0002 (6) | −0.0009 (6) | 0.0022 (6) |
C18 | 0.0151 (7) | 0.0127 (8) | 0.0168 (8) | 0.0008 (6) | −0.0009 (6) | −0.0005 (6) |
Cl1 | 0.0363 (3) | 0.0556 (3) | 0.0181 (2) | 0.0236 (2) | −0.00128 (18) | −0.0032 (2) |
P1—N1 | 1.5762 (7) | C9—C10 | 1.388 (2) |
P1—C7 | 1.7940 (16) | C9—H9 | 0.9500 |
P1—C1 | 1.7976 (16) | C10—C11 | 1.384 (2) |
P1—C13 | 1.8028 (15) | C10—H10 | 0.9500 |
N1—P1i | 1.5761 (7) | C11—C12 | 1.389 (2) |
C1—C2 | 1.396 (2) | C11—H11 | 0.9500 |
C1—C6 | 1.399 (2) | C12—H12 | 0.9500 |
C2—C3 | 1.389 (2) | C13—C18 | 1.393 (2) |
C2—H2 | 0.9500 | C13—C14 | 1.398 (2) |
C3—C4 | 1.386 (3) | C14—C15 | 1.387 (2) |
C3—H3 | 0.9500 | C14—H14 | 0.9500 |
C4—C5 | 1.388 (3) | C15—C16 | 1.386 (2) |
C4—H4 | 0.9500 | C15—H15 | 0.9500 |
C5—C6 | 1.392 (2) | C16—C17 | 1.389 (2) |
C5—H5 | 0.9500 | C16—H16 | 0.9500 |
C6—H6 | 0.9500 | C17—C18 | 1.390 (2) |
C7—C12 | 1.394 (2) | C17—H17 | 0.9500 |
C7—C8 | 1.401 (2) | C18—H18 | 0.9500 |
C8—C9 | 1.380 (2) | Cl1—H1 | 1.555 (3) |
C8—H8 | 0.9500 | ||
N1—P1—C7 | 114.59 (8) | C8—C9—C10 | 120.24 (16) |
N1—P1—C1 | 108.65 (7) | C8—C9—H9 | 119.9 |
C7—P1—C1 | 107.91 (7) | C10—C9—H9 | 119.9 |
N1—P1—C13 | 109.93 (6) | C11—C10—C9 | 120.19 (15) |
C7—P1—C13 | 109.42 (7) | C11—C10—H10 | 119.9 |
C1—P1—C13 | 105.96 (7) | C9—C10—H10 | 119.9 |
P1i—N1—P1 | 144.12 (13) | C10—C11—C12 | 120.08 (16) |
C2—C1—C6 | 120.13 (14) | C10—C11—H11 | 120.0 |
C2—C1—P1 | 118.58 (12) | C12—C11—H11 | 120.0 |
C6—C1—P1 | 121.17 (12) | C11—C12—C7 | 119.95 (16) |
C3—C2—C1 | 119.67 (15) | C11—C12—H12 | 120.0 |
C3—C2—H2 | 120.2 | C7—C12—H12 | 120.0 |
C1—C2—H2 | 120.2 | C18—C13—C14 | 119.68 (14) |
C4—C3—C2 | 120.14 (16) | C18—C13—P1 | 119.66 (11) |
C4—C3—H3 | 119.9 | C14—C13—P1 | 120.57 (12) |
C2—C3—H3 | 119.9 | C15—C14—C13 | 119.84 (15) |
C3—C4—C5 | 120.49 (16) | C15—C14—H14 | 120.1 |
C3—C4—H4 | 119.8 | C13—C14—H14 | 120.1 |
C5—C4—H4 | 119.8 | C16—C15—C14 | 120.37 (15) |
C4—C5—C6 | 119.92 (16) | C16—C15—H15 | 119.8 |
C4—C5—H5 | 120.0 | C14—C15—H15 | 119.8 |
C6—C5—H5 | 120.0 | C15—C16—C17 | 120.03 (15) |
C5—C6—C1 | 119.63 (16) | C15—C16—H16 | 120.0 |
C5—C6—H6 | 120.2 | C17—C16—H16 | 120.0 |
C1—C6—H6 | 120.2 | C16—C17—C18 | 120.02 (15) |
C12—C7—C8 | 119.59 (15) | C16—C17—H17 | 120.0 |
C12—C7—P1 | 122.65 (12) | C18—C17—H17 | 120.0 |
C8—C7—P1 | 117.57 (12) | C17—C18—C13 | 120.06 (14) |
C9—C8—C7 | 119.94 (15) | C17—C18—H18 | 120.0 |
C9—C8—H8 | 120.0 | C13—C18—H18 | 120.0 |
C7—C8—H8 | 120.0 | ||
C7—P1—N1—P1i | 8.50 (6) | C12—C7—C8—C9 | 1.0 (2) |
C1—P1—N1—P1i | 129.26 (6) | P1—C7—C8—C9 | −174.15 (13) |
C13—P1—N1—P1i | −115.21 (6) | C7—C8—C9—C10 | −0.5 (2) |
N1—P1—C1—C2 | 27.31 (14) | C8—C9—C10—C11 | −0.5 (3) |
C7—P1—C1—C2 | 152.11 (12) | C9—C10—C11—C12 | 1.0 (3) |
C13—P1—C1—C2 | −90.78 (13) | C10—C11—C12—C7 | −0.5 (2) |
N1—P1—C1—C6 | −156.65 (13) | C8—C7—C12—C11 | −0.5 (2) |
C7—P1—C1—C6 | −31.85 (15) | P1—C7—C12—C11 | 174.41 (13) |
C13—P1—C1—C6 | 85.26 (14) | N1—P1—C13—C18 | 3.27 (15) |
C6—C1—C2—C3 | 0.8 (2) | C7—P1—C13—C18 | −123.40 (13) |
P1—C1—C2—C3 | 176.89 (12) | C1—P1—C13—C18 | 120.50 (13) |
C1—C2—C3—C4 | −0.8 (2) | N1—P1—C13—C14 | −173.36 (13) |
C2—C3—C4—C5 | 0.4 (3) | C7—P1—C13—C14 | 59.97 (14) |
C3—C4—C5—C6 | 0.2 (3) | C1—P1—C13—C14 | −56.13 (14) |
C4—C5—C6—C1 | −0.2 (2) | C18—C13—C14—C15 | −0.6 (2) |
C2—C1—C6—C5 | −0.3 (2) | P1—C13—C14—C15 | 176.07 (12) |
P1—C1—C6—C5 | −176.29 (12) | C13—C14—C15—C16 | 0.0 (2) |
N1—P1—C7—C12 | −118.52 (12) | C14—C15—C16—C17 | 0.4 (3) |
C1—P1—C7—C12 | 120.31 (13) | C15—C16—C17—C18 | −0.4 (2) |
C13—P1—C7—C12 | 5.46 (15) | C16—C17—C18—C13 | −0.1 (2) |
N1—P1—C7—C8 | 56.51 (13) | C14—C13—C18—C17 | 0.6 (2) |
C1—P1—C7—C8 | −64.66 (13) | P1—C13—C18—C17 | −176.05 (12) |
C13—P1—C7—C8 | −179.52 (12) |
Symmetry code: (i) −x+1, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
Cl1—H1···Cl1i | 1.56 (1) | 1.56 (1) | 3.1045 (9) | 173 (3) |
Symmetry code: (i) −x+1, y, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C36H30NP2+·Cl2H− |
Mr | 610.46 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 100 |
a, b, c (Å) | 11.6467 (3), 16.5474 (4), 15.7584 (3) |
V (Å3) | 3037.00 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.35 |
Crystal size (mm) | 0.18 × 0.14 × 0.09 |
Data collection | |
Diffractometer | Bruker APEXII CCD area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.940, 0.970 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28633, 2994, 2671 |
Rint | 0.030 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.085, 1.08 |
No. of reflections | 2994 |
No. of parameters | 189 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.61, −0.79 |
Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2011).
D—H···A | D—H | H···A | D···A | D—H···A |
Cl1—H1···Cl1i | 1.555 (3) | 1.555 (3) | 3.1045 (9) | 173 (3) |
Symmetry code: (i) −x+1, y, −z+1/2. |
Acknowledgements
Financial support from the Deutsche Forschungsgemeinschaft (DFG) and Universität Freiburg is gratefully acknowledged.
References
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The Cambridge Structural Database (Allen, 2002) currently contains more than 1200 structures containing the [(Ph3P)2N]+ cation ([(Ph3P)2N]+ = [PNP]+). Usually this cation is partnered by a bulky anion, while crystal structures containing small anions and especially halides are rare. The crystal structures of some solvate-free halides, [(Ph3P)2N]I (Beckett et al., 2010) and [(Ph3P)2N]Cl (Knapp & Uzun, 2010a), and the acetontrile solvate [(Ph3P)2N]Br.CH3CN (Knapp & Uzun, 2010b), were published only very recently.
Bis(triphenyl-λ5-phosphanylidene)ammonium chloride [(Ph3P)2N]Cl was synthesized according to a published method (Ruff et al., 1974). Solvate-free single crystals suitable for X-ray diffraction of the title compound were obtained as a by-product by layering a CH3CN solution with diethyl ether. The H atom of the [Cl—H—Cl]- anion and the N atom of the [(Ph3P)2N]+ cation are located on a twofold axis, yielding overall symmetry 2 for the cation. The central P—N—P angle [144.12 (13)°] and the P—N [1.5762 (7) Å] and P—C distances [1.7940 (16)–1.8028 (15) Å] are in the expected range for the [(Ph3P)2N]+ cation (Lewis & Dance, 2000).
The number of structurally characterized hydrogen dichloride anions is still limited. Often disorder or low crystal quality does not allow to establish unequivically the position of the H atom. The Cl···Cl distances in all hydrogen dichloride anions deviate only slightly from an averaged distance of 3.10 Å. The anion in the title compound contains a symmetric hydrogen bridge with H—Cl distances of 1.56 (1) Å and a Cl···Cl distance of 3.1045 (9) Å. The anion is almost linear and a Cl—H—Cl angle of 173 (3)° is observed. A very similar hydrogen dichloride anion was found in the the crystal structure of [K(18 C-6)][Cl—H—Cl], where H—Cl is 1.56 Å and Cl···Cl 3.117 (1) Å (Atwood et al., 1990).