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Tri­benzyl­phosphane, PBz3 (C21H21P), crystallizes in a notably different unit cell to its Group 15 analogues NBz3 and SbBz3. The packing is dominated by face-edge [pi]-inter­actions which result in infinite columns of mol­ecules parallel to the b axis; these columns are linked by further face-edge [pi]-inter­actions into sheets of columns parallel to the [101] direction. Its hydro­chloride salt, tri­benzyl­phospho­nium hydrogen di­chlo­ride-tri­benzyl­phosphane (1/1), lies on a threefold axis within a trigonal crystal system. It exists in the solid state as a hydrogen-bridged dimer with the composition [H(PBz3)2]+[HCl2]- (C42H43P2+·HCl2-). The cation is the first structurally authenticated example of a phosphane acting as a hydrogen-bond acceptor to a phospho­nium group and the cations are linked into a three-dimensional network through inter­molecular face-edge [pi]-inter­actions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113010226/yf3030sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113010226/yf3030Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270113010226/yf3030IIsup3.hkl
Contains datablock II

CCDC references: 950381; 950382

Comment top

Phosphanes are ubiquitous ligands in the coordination chemistry of transition metals, but their coordination chemistry with main group elements is less well explored. During recent work into the synthesis of phosphane complexes of halosilanes (Levason et al., 2013), we attempted the reaction of tribenzylphosphane, (I), with SiCl4 in CH2Cl2.

Although no complex was formed between (I) and SiCl4, colourless crystals of tribenzylphosphane (Fig. 1) were isolated instead by cooling a CH2Cl2 solution of the reaction mixture to 255 K for 16 h. Somewhat surprisingly, the solid-state structure of tribenzylphosphane had not previously been obtained despite its commercial availability and the presence of almost 100 metal complexes of tribenzylphosphane in the Cambridge Structural Database (CSD; November 2012 update; Allen, 2002).

Compound (I) crystallized in the monoclinic space group P21/n with the C—P bond lengths (Table 1) being unremarkable. The space group and cell dimensions of (I) were different to that of the antimony analogue tribenzylstibine (Becker et al., 2001), which crystallized in the orthorhombic space group Pbca. The cell dimensions were also notably different to the nitrogen analogue, tribenzylamine, which was twice determined to be monoclinic with different settings of the same space group. Determinations at 203 K as P21/a (Iwasaki & Iwasaki, 1972) and another at 120 K as P21/c (Nelson et al., 2008) contained β angles of 92.82 (1) (120 K) and 93.9 (2)° (203 K). It is notable that compound (I) has a β angle of 90.90 (1)°, indicating that as the atomic radius of the pnictogen increases, the β–angle decreases until it reaches 90° for tribenzylstibine. Analogues with the other pnictogens, tribenzylarsine and tribenzylbismuthine, have not been crystallographically characterized.

Analysis of the C—X—C bond angles (X = N, P or Sb) reveals that this series of molecules is consistent with classical VSEPR theory which holds that as the central atom gets larger, there is less steric repulsion between the electron pairs around the central atom, hence they move closer together. All determinations for NBz3 contain C—N—C angles of ~110°, very close to the ideal for a trigonal pyramidal structure, indicating that the lone pair on nitrogen is not significantly distorting the geometry of the molecule. In contrast, PBz3 and SbBz3 with larger central atoms both contain C—X—C bond angles <100°, much smaller than for an ideal trigonal pyramid.

The packing of compound (I) is dominated by face-edge π interactions between alternating up and down molecules (Fig. 2). The distances between the C—H donor and the acceptor (the mean plane defined by the six C atoms in the phenyl ring) range from 2.529 (4) [H10i–mean(C16–C21)] to 2.634 (4) Å [H3i–mean(C9–C14)]. The C16–C21 ring is also an acceptor from H13ii [2.578 (4) Å] and the fourth interaction is between H21ii and the C2–C7 ring [2.583 (3) Å] [symmetry codes: (i) -x+3/4, y+1/2, -z+1/2; (ii) -x+3/4, y-1/2, -z+1/2].

These alternating molecules form columns which stack parallel to the b axis (Fig. 3). The majority of the face-edge π-interactions are between neighbouring molecules within a single column, but a few intercolumnar interactions are present which cause the columns to align in a sheet parallel to the [101] direction. The intercolumnar interaction of 2.651 (4) Å is between H18iii (donor) and C2 (acceptor; the distance is calculated to the mean plane of the carbons in the entire C1–C7 benzyl group owing to the short H18iii–C1 interaction) and is slightly longer than the face-edge π-interactions which form the columns [symmetry code: (iii) -x+1, -y+1, -z+1]. Notably, this acceptor is external to the phenyl ring: similar interactions (albeit intramolecular) have been observed in the solid state structure of transition metal benzyl compounds (Rong et al., 2012, and references therein).

In contrast, SbBz3 packs in alternating ABAB columns which run parallel to the b axis. The face-edge π interactions of 2.71 Å are confined to molecules within a single column hence there are no intercolumnar interactions (Becker et al., 2001). The nitrogen analogue (P21/a) packs in a similar manner to compound (I), with columns of alternating up and down molecules running parallel to the b axis. Here, two types of intermolecular C—H···π interaction are present: one involving an aryl CH (2.580 Å to the neighbouring aryl ring) and the other involving one hydrogen from a benzyl CH2 group (2.826 Å to the neighbouring aryl ring) (Iwasaki & Iwasaki, 1972). The P21/c determination, however, only contains one CH–π interaction from an aryl CH donor (2.626 Å) with one of the benzyl CH2 H atoms being involved in a short contact (2.393 Å) to a neighbouring benzyl CH2 hydrogen (Nelson et al., 2008). A cocrystal of NBz3 and CBr4 has also been determined where the packing is dominated by dimers of NBz3 molecules linked by face-edge π interactions, one from an aryl CH (2.842 Å) and another from an alkyl CH2 group (2.860 Å). These dimers stack into columns which are bounded by columns of CBr4 molecules (Rosokha et al., 2006).

A second crop of colourless crystals was grown after keeping the same solution, from which (I) was obtained, for several weeks at 255 K. These had a different morphology to the previous crystals: the resulting product came from the partial hydrolysis of SiCl4 which formed the hydrochloride salt of tribenzylphosphane in situ.

The crystal system of (II) was determined as trigonal, with XPREP (Bruker, 2001) indicating the space group R3. The asymmetric unit consisted of one-third of a tribenzylphosphonium cation and one-third of a chloride anion lying on a C3 axis. The solution in this space group led to problems with short intermolecular P—H···H—P contacts (~1.4 Å), as well as stubbornly high R values (R[F2 > 2σ(F2)] > 0.1), hence it was redetermined in R3. The asymmetric unit now clearly showed the true formulation of (II), whereby one tribenzylphosphane moiety acts as a hydrogen-bond acceptor to a tribenzylphosphonium cation (Bz3P–H···PBz3) counterbalanced by a Cl—H···Cl anion (Fig. 4). The R values were also much more satisfactory (see below) despite the pseudosymmetry causing level B alerts in checkCIF.

The dichloride anion has been observed 30 times in the Cambridge Structural Database (CSD; February 2013 update; Allen, 2002) and in keeping with previously observed structures (bar those where the Cl—H bonds are related by symmetry), the Cl—H distances are significantly different to each other (Tables 2 and 3). The hydrogen(bisphosphane) cation group is unique; the only other molecule in the CSD with a P—H—P arrangement of atoms is bis(hexamethyldisilazido)phosphane (Olmstead et al., 1988) which exists as a hydrogen-bridged dimer in the solid state. However, the core of the molecule is a P2H2 ring, with P—H—P bond angles of 97 (2) and 99 (2)°, which contrasts to the P—H—P core of (II) which is linear.

Compound (II) is also the only structurally characterized example of a tribenzylphosphonium group. The C—P bond lengths (Table 2) appear to be slightly shorter than those in compound (I), but this can only be confirmed for the C1—P1 bond; the C2—P2 bond length is not significantly different from those in (I) within experimental error (Table 1). The C—P—C angles (Table 2) show two distinct P-atom environments. The phosphane acting as an acceptor (P1) has a C—P—C bond angle consistent with an ideal trigonal–pyramidal geometry, whereas the formal phosphonium cation (P2) has a C—P—C bond angle much smaller than for an ideal tetrahedral geometry. The distortion away from an ideal tetrahedron can also be seen in the C—P—H bond angle (Table 2), which is significantly larger than expected for an ideal tetrahedron. This is likely a result of the phosphane distorting to form the C—H···π interactions which are a major part of the structure.

Each aryl ring in compound (II) acts as both an acceptor and a donor, forming a circular network of C—H···π interactions around the core of the molecule (Fig. 4). The two distances of 2.663 (3) [H14iii···mean(C2–C7)] and 2.664 (5) Å [H3iii···mean(C9–C14)], which are not symmetry related, are identical [symmetry code: (iv) -x+y+1, -x+1, z]. These are longer than the intracolumnar face-edge π-interactions in (I), but are consistent with the length of the intercolumnar interactions. Also present are intermolecular interactions of 2.697 (5) [H10iv···mean(C2–C7)] and 2.683 (6) Å [H7v···mean(C9–C14)], the result of which is to form a three-dimensional network of interconnected cations (Fig. 5) [symmetry codes: (v) -x+y+4/3, -x+2/3, z-1/3; (vi) -x+y+2/3, -x+4/3, z+1/3]. The conformation of the benzyl groups in (II) is restricted by these donor–acceptor interactions such that the P—C—C—C torsion angles are all very close to 90° (Table 2). This contrasts to compound (I) where the lack of donor–acceptor interactions results in a much wider range of torsion angles, with large deviations (up to 20°) from 90° (Table 1).

The formation of the novel hydrogenbis(phosphane) cation is probably driven by the ability of tribenzylphosphane to form a sterically bulky cage, stabilized by face-edge π-interactions, around the central P—H···P group. The flexibility, imparted by the methylene group, between the aryl ring and phosphorus in (II) is key to the formation of the cage; other phosphonium salts with aryl groups e.g. triphenylphosphonium cations (see, for example, Khan et al., 1986; Raveendran & Pal, 2008) do not contain this structural motif. It should also be noted that this cage is not the most stable arrangement of molecules of the type EBz3: it is not found in (I) (E = P) nor is it found in other Group 15 analogues (E = N or Sb), indicating that the combination of face-edge π-interactions and the P—H···P donor–acceptor group is required for the cage to form.

Related literature top

For related literature, see: Allen (2002); Becker et al. (2001); Bruker (2001); Iwasaki & Iwasaki (1972); Khan et al. (1986); Levason et al. (2013); Nelson et al. (2008); Olmstead et al. (1988); Raveendran & Pal (2008); Rong et al. (2012); Rosokha et al. (2006).

Experimental top

Under an inert atmosphere, SiCl4 (85 mg, 0.5 mmol) and tribenzylphosphane (304 mg, 1.0 mmol) were dissolved in CH2Cl2 (10 ml) and stirred at 295 K for 4 h. The solution was then concentrated to approximately 5 ml and cooled to 255 K. After 16 h, colourless blocks of (I) precipitated which were isolated by decanting the supernatant. Keeping the supernatant at 255 K for several weeks resulted in the precipitation of colourless plates of compound (II), which were isolated by decanting the supernatant.

Refinement top

H atoms attached to C atoms were placed in geometrically assigned positions, with C—H = 0.95 (CH) or 0.99 Å (CH2), and refined using a riding model, with Uiso(H) = 1.2Ueq(C). In (II), H atoms attached to heteroatoms were located in Fourier difference maps and the distances allowed to refine freely. However, the Uiso value of atom H2 (attached to phosphorus) was restrained to 1.2Ueq(P2).

The crystal system of (II) was determined as trigonal with the space group initially assigned as R3. However, the solution in this space group was clearly incorrect (short intermolecular P—H···H—P contacts and unsatisfactory R values), hence the space group was reassigned as R3, wherein the solution was routine.

Computing details top

Data collection: CrystalClear-SM Expert (Rigaku, 2012) for (I); CrystalClear-SM Expert (Rigaku, 2011) for (II). Cell refinement: CrystalClear-SM Expert (Rigaku, 2012) for (I); CrystalClear-SM Expert (Rigaku, 2011) for (II). Data reduction: CrystalClear-SM Expert (Rigaku, 2012) for (I); CrystalClear-SM Expert (Rigaku, 2011) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: PLATON (Spek, 2009), WinGX (Farrugia, 2012), enCIFer (Allen et al., 2004), publCIF (Westrip, 2010) and Mercury (Macrae et al., 2006).

Figures top
[Figure 1] Fig. 1. The molecular structure of tribenzylphosphane, (I), showing the atom numbering-scheme. Displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A view of a section of one column of (I), showing the intracolumnar π-interactions (blue) in the solid state structure of (I). [Symmetry codes: (i) -x+3/4, y+1/2, -z+1/2; (ii) -x+3/4, y-1/2, -z+1/2.]
[Figure 3] Fig. 3. A view of the packing of compound (I), viewed down the b axis. Dashed lines represent π-interactions.
[Figure 4] Fig. 4. The molecular structure of tribenzylphosphonium chloride, (II), showing the atom-numbering scheme. Dashed lines represent hydrogen bonds. Displacement ellipsoids are drawn at the 50% probability level and H atoms not involved in intramolecular hydrogen bonding have been omitted for clarity. [Symmetry codes: (iv) -x+y+1, -x+1, z; (vii) -y+1, x-y, z.]
[Figure 5] Fig. 5. A view of the packing of compound (II), showing the three-dimensional network of cations linked through intermolecular C—H···π interactions (dashed lines). The hydridodichloride anions are oriented along the P—H···P vector (parallel to the b axis) and lie between cations.
(I) Tribenzylphosphane top
Crystal data top
C21H21PF(000) = 648
Mr = 304.35Dx = 1.205 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3384 reflections
a = 10.9287 (8) Åθ = 2.5–27.5°
b = 9.5775 (7) ŵ = 0.16 mm1
c = 16.0272 (12) ÅT = 100 K
β = 91.051 (5)°Platelet, colourless
V = 1677.3 (2) Å30.09 × 0.04 × 0.01 mm
Z = 4
Data collection top
Rigaku Saturn724+ (2x2 bin mode)
diffractometer
3374 independent reflections
Radiation source: Rotating Anode2268 reflections with I > 2σ(I)
Confocal monochromatorRint = 0.048
Detector resolution: 28.5714 pixels mm-1θmax = 26.4°, θmin = 3.1°
profile data from ω scansh = 1213
Absorption correction: multi-scan
(CrystalClear-SM Expert; Rigaku, 2012)
k = 1111
Tmin = 0.986, Tmax = 0.998l = 1820
7381 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.049Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.109H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0391P)2 + 0.8781P]
where P = (Fo2 + 2Fc2)/3
3374 reflections(Δ/σ)max < 0.001
199 parametersΔρmax = 0.36 e Å3
0 restraintsΔρmin = 0.36 e Å3
Crystal data top
C21H21PV = 1677.3 (2) Å3
Mr = 304.35Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.9287 (8) ŵ = 0.16 mm1
b = 9.5775 (7) ÅT = 100 K
c = 16.0272 (12) Å0.09 × 0.04 × 0.01 mm
β = 91.051 (5)°
Data collection top
Rigaku Saturn724+ (2x2 bin mode)
diffractometer
3374 independent reflections
Absorption correction: multi-scan
(CrystalClear-SM Expert; Rigaku, 2012)
2268 reflections with I > 2σ(I)
Tmin = 0.986, Tmax = 0.998Rint = 0.048
7381 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0490 restraints
wR(F2) = 0.109H-atom parameters constrained
S = 1.01Δρmax = 0.36 e Å3
3374 reflectionsΔρmin = 0.36 e Å3
199 parameters
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.5006 (2)0.4221 (2)0.30990 (15)0.0200 (5)
H1A0.52090.43060.37010.024*
H1B0.42730.48030.29820.024*
C20.4701 (2)0.2722 (2)0.29062 (14)0.0173 (5)
C30.5304 (2)0.1643 (3)0.33218 (14)0.0195 (5)
H30.59130.18610.37320.023*
C40.5036 (2)0.0256 (3)0.31504 (14)0.0217 (5)
H40.54580.04690.34410.026*
C50.4146 (2)0.0068 (3)0.25502 (14)0.0230 (5)
H50.39530.10150.24310.028*
C60.3546 (2)0.0991 (3)0.21302 (15)0.0235 (6)
H60.29430.07690.17170.028*
C70.3812 (2)0.2375 (3)0.23029 (14)0.0203 (5)
H70.33880.30940.20090.024*
C80.5464 (2)0.5451 (3)0.15258 (14)0.0193 (5)
H8A0.50260.46340.12880.023*
H8B0.48460.61650.16680.023*
C90.6307 (2)0.6037 (2)0.08820 (14)0.0188 (5)
C100.6884 (2)0.5141 (3)0.03304 (14)0.0230 (5)
H100.67350.41650.03640.028*
C110.7669 (2)0.5643 (3)0.02667 (15)0.0259 (6)
H110.80550.50140.06370.031*
C120.7892 (2)0.7059 (3)0.03255 (15)0.0237 (6)
H120.84230.74070.07400.028*
C130.7338 (2)0.7969 (3)0.02228 (15)0.0219 (5)
H130.74950.89430.01890.026*
C140.6552 (2)0.7457 (3)0.08223 (15)0.0200 (5)
H140.61770.80880.11970.024*
C150.6419 (2)0.6646 (2)0.30018 (15)0.0207 (5)
H15A0.68250.73050.26200.025*
H15B0.55840.70030.31020.025*
C160.7123 (2)0.6607 (2)0.38159 (14)0.0170 (5)
C170.6551 (2)0.6783 (2)0.45773 (15)0.0204 (5)
H170.56910.69230.45900.025*
C180.7228 (2)0.6755 (3)0.53188 (15)0.0213 (5)
H180.68290.68770.58350.026*
C190.8479 (2)0.6552 (2)0.53089 (14)0.0206 (5)
H190.89410.65370.58170.025*
C200.9056 (2)0.6370 (2)0.45531 (14)0.0196 (5)
H200.99160.62290.45420.024*
C210.8383 (2)0.6394 (2)0.38182 (14)0.0179 (5)
H210.87850.62620.33040.021*
P10.63037 (6)0.49121 (7)0.24908 (4)0.01694 (16)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0231 (13)0.0185 (13)0.0183 (12)0.0008 (11)0.0012 (10)0.0004 (10)
C20.0201 (12)0.0170 (12)0.0148 (12)0.0019 (10)0.0035 (9)0.0006 (10)
C30.0216 (12)0.0205 (13)0.0163 (12)0.0022 (10)0.0015 (9)0.0020 (10)
C40.0269 (13)0.0187 (13)0.0196 (12)0.0003 (11)0.0030 (10)0.0032 (10)
C50.0306 (13)0.0174 (13)0.0212 (12)0.0070 (11)0.0046 (10)0.0027 (11)
C60.0226 (13)0.0279 (15)0.0201 (13)0.0083 (11)0.0030 (10)0.0021 (11)
C70.0203 (12)0.0235 (13)0.0172 (12)0.0004 (10)0.0006 (10)0.0017 (10)
C80.0206 (12)0.0181 (12)0.0190 (12)0.0010 (10)0.0047 (9)0.0001 (10)
C90.0195 (12)0.0206 (13)0.0161 (12)0.0012 (10)0.0064 (9)0.0023 (10)
C100.0320 (13)0.0174 (13)0.0195 (12)0.0026 (11)0.0005 (10)0.0004 (11)
C110.0333 (14)0.0247 (14)0.0197 (13)0.0004 (12)0.0005 (11)0.0025 (11)
C120.0234 (13)0.0299 (15)0.0175 (12)0.0020 (11)0.0028 (10)0.0063 (11)
C130.0243 (13)0.0160 (13)0.0249 (13)0.0006 (10)0.0094 (10)0.0047 (11)
C140.0222 (12)0.0186 (13)0.0191 (12)0.0029 (10)0.0059 (10)0.0000 (10)
C150.0254 (13)0.0129 (12)0.0234 (13)0.0001 (10)0.0059 (10)0.0012 (10)
C160.0208 (12)0.0091 (11)0.0209 (12)0.0009 (10)0.0014 (10)0.0009 (10)
C170.0200 (12)0.0145 (12)0.0268 (13)0.0003 (10)0.0017 (10)0.0008 (10)
C180.0306 (14)0.0159 (12)0.0176 (12)0.0031 (11)0.0067 (10)0.0009 (10)
C190.0333 (14)0.0149 (12)0.0135 (12)0.0020 (11)0.0059 (10)0.0017 (10)
C200.0234 (13)0.0146 (12)0.0208 (12)0.0013 (10)0.0022 (10)0.0018 (10)
C210.0235 (13)0.0128 (12)0.0175 (12)0.0006 (10)0.0020 (10)0.0002 (10)
P10.0197 (3)0.0146 (3)0.0165 (3)0.0011 (3)0.0016 (2)0.0001 (3)
Geometric parameters (Å, º) top
C1—C21.505 (3)C11—C121.381 (4)
C1—P11.858 (2)C11—H110.9500
C1—H1A0.9900C12—C131.385 (3)
C1—H1B0.9900C12—H120.9500
C2—C31.389 (3)C13—C141.390 (3)
C2—C71.398 (3)C13—H130.9500
C3—C41.387 (3)C14—H140.9500
C3—H30.9500C15—C161.503 (3)
C4—C51.391 (3)C15—P11.855 (2)
C4—H40.9500C15—H15A0.9900
C5—C61.376 (4)C15—H15B0.9900
C5—H50.9500C16—C171.391 (3)
C6—C71.385 (3)C16—C211.392 (3)
C6—H60.9500C17—C181.388 (3)
C7—H70.9500C17—H170.9500
C8—C91.504 (3)C18—C191.381 (3)
C8—P11.857 (2)C18—H180.9500
C8—H8A0.9900C19—C201.387 (3)
C8—H8B0.9900C19—H190.9500
C9—C141.391 (3)C20—C211.378 (3)
C9—C101.391 (3)C20—H200.9500
C10—C111.384 (3)C21—H210.9500
C10—H100.9500
C2—C1—P1113.61 (16)C10—C11—H11120.0
C2—C1—H1A108.8C11—C12—C13119.6 (2)
P1—C1—H1A108.8C11—C12—H12120.2
C2—C1—H1B108.8C13—C12—H12120.2
P1—C1—H1B108.8C12—C13—C14120.0 (2)
H1A—C1—H1B107.7C12—C13—H13120.0
C3—C2—C7118.2 (2)C14—C13—H13120.0
C3—C2—C1120.7 (2)C13—C14—C9121.0 (2)
C7—C2—C1121.1 (2)C13—C14—H14119.5
C4—C3—C2121.4 (2)C9—C14—H14119.5
C4—C3—H3119.3C16—C15—P1113.00 (16)
C2—C3—H3119.3C16—C15—H15A109.0
C3—C4—C5119.5 (2)P1—C15—H15A109.0
C3—C4—H4120.2C16—C15—H15B109.0
C5—C4—H4120.2P1—C15—H15B109.0
C6—C5—C4119.7 (2)H15A—C15—H15B107.8
C6—C5—H5120.2C17—C16—C21118.4 (2)
C4—C5—H5120.2C17—C16—C15121.9 (2)
C5—C6—C7120.7 (2)C21—C16—C15119.8 (2)
C5—C6—H6119.6C18—C17—C16120.5 (2)
C7—C6—H6119.6C18—C17—H17119.7
C6—C7—C2120.4 (2)C16—C17—H17119.7
C6—C7—H7119.8C19—C18—C17120.3 (2)
C2—C7—H7119.8C19—C18—H18119.9
C9—C8—P1112.04 (16)C17—C18—H18119.9
C9—C8—H8A109.2C18—C19—C20119.6 (2)
P1—C8—H8A109.2C18—C19—H19120.2
C9—C8—H8B109.2C20—C19—H19120.2
P1—C8—H8B109.2C21—C20—C19120.0 (2)
H8A—C8—H8B107.9C21—C20—H20120.0
C14—C9—C10118.0 (2)C19—C20—H20120.0
C14—C9—C8122.2 (2)C20—C21—C16121.2 (2)
C10—C9—C8119.7 (2)C20—C21—H21119.4
C11—C10—C9121.2 (2)C16—C21—H21119.4
C11—C10—H10119.4C15—P1—C898.48 (11)
C9—C10—H10119.4C15—P1—C197.69 (11)
C12—C11—C10120.1 (2)C8—P1—C199.53 (11)
C12—C11—H11120.0
P1—C1—C2—C386.5 (2)C10—C9—C14—C130.8 (4)
P1—C1—C2—C793.1 (2)C8—C9—C14—C13179.8 (2)
C7—C2—C3—C40.3 (3)P1—C15—C16—C17109.5 (2)
C1—C2—C3—C4179.9 (2)P1—C15—C16—C2170.6 (3)
C2—C3—C4—C50.0 (3)C21—C16—C17—C180.5 (3)
C3—C4—C5—C60.4 (3)C15—C16—C17—C18179.4 (2)
C4—C5—C6—C70.5 (3)C16—C17—C18—C190.0 (4)
C5—C6—C7—C20.3 (4)C17—C18—C19—C200.2 (4)
C3—C2—C7—C60.1 (3)C18—C19—C20—C210.0 (4)
C1—C2—C7—C6179.7 (2)C19—C20—C21—C160.4 (4)
P1—C8—C9—C1492.7 (2)C17—C16—C21—C200.7 (3)
P1—C8—C9—C1086.4 (2)C15—C16—C21—C20179.2 (2)
C14—C9—C10—C110.6 (4)C16—C15—P1—C8177.50 (17)
C8—C9—C10—C11179.7 (2)C16—C15—P1—C181.60 (19)
C9—C10—C11—C120.1 (4)C9—C8—P1—C1582.23 (18)
C10—C11—C12—C130.8 (4)C9—C8—P1—C1178.44 (17)
C11—C12—C13—C140.7 (4)C2—C1—P1—C15174.85 (17)
C12—C13—C14—C90.1 (4)C2—C1—P1—C885.16 (19)
(II) Tribenzylphosphonium hydrogen dichloride–tribenzylphosphane (1/1) top
Crystal data top
C42H43P2+·HCl2Dx = 1.286 Mg m3
Mr = 681.61Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3Cell parameters from 2232 reflections
Hall symbol: R 3θ = 2.1–27.4°
a = 13.941 (5) ŵ = 0.31 mm1
c = 15.693 (7) ÅT = 100 K
V = 2641.3 (18) Å3Block, colourless
Z = 30.06 × 0.04 × 0.03 mm
F(000) = 1080
Data collection top
Rigaku Saturn724+ (2x2 bin mode)
diffractometer
1664 independent reflections
Radiation source: fine-focus sealed tube1414 reflections with I > 2σ(I)
Confocal monochromatorRint = 0.022
Detector resolution: 28.5714 pixels mm-1θmax = 27.4°, θmin = 3.1°
profile data from ω–scansh = 188
Absorption correction: multi-scan
(CrystalClear-SM Expert; Rigaku, 2011)
k = 1217
Tmin = 0.982, Tmax = 0.991l = 2011
2521 measured reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.099 w = 1/[σ2(Fo2) + (0.0533P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
1664 reflectionsΔρmax = 0.61 e Å3
142 parametersΔρmin = 0.57 e Å3
1 restraintAbsolute structure: Flack (1983), 325 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.34 (14)
Crystal data top
C42H43P2+·HCl2Z = 3
Mr = 681.61Mo Kα radiation
Trigonal, R3µ = 0.31 mm1
a = 13.941 (5) ÅT = 100 K
c = 15.693 (7) Å0.06 × 0.04 × 0.03 mm
V = 2641.3 (18) Å3
Data collection top
Rigaku Saturn724+ (2x2 bin mode)
diffractometer
1664 independent reflections
Absorption correction: multi-scan
(CrystalClear-SM Expert; Rigaku, 2011)
1414 reflections with I > 2σ(I)
Tmin = 0.982, Tmax = 0.991Rint = 0.022
2521 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.042H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.099Δρmax = 0.61 e Å3
S = 1.02Δρmin = 0.57 e Å3
1664 reflectionsAbsolute structure: Flack (1983), 325 Friedel pairs
142 parametersAbsolute structure parameter: 0.34 (14)
1 restraint
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.7408 (4)0.2664 (3)0.5748 (2)0.0219 (9)
H1A0.69620.18610.58700.026*
H1B0.75030.27570.51230.026*
C20.8536 (3)0.3121 (3)0.6161 (2)0.0179 (8)
C30.8675 (4)0.2586 (3)0.6871 (2)0.0188 (8)
H30.80540.19450.71000.023*
C40.9695 (4)0.2979 (4)0.7236 (2)0.0246 (10)
H40.97840.25990.77050.030*
C51.0613 (3)0.3944 (4)0.6917 (2)0.0215 (9)
H51.13200.42250.71750.026*
C61.0482 (4)0.4478 (4)0.6232 (2)0.0228 (9)
H61.10980.51310.60130.027*
C70.9445 (3)0.4062 (3)0.5858 (2)0.0209 (9)
H70.93630.44360.53820.025*
C80.5926 (4)0.3968 (4)0.9179 (2)0.0238 (9)
H8A0.58550.38010.97960.029*
H8B0.63630.47820.91090.029*
C90.4792 (3)0.3541 (3)0.8800 (2)0.0188 (8)
C100.3866 (3)0.2587 (3)0.9116 (2)0.0212 (9)
H100.39490.22100.95890.025*
C110.2836 (4)0.2187 (4)0.8749 (2)0.0225 (9)
H110.22160.15350.89650.027*
C120.2708 (3)0.2744 (4)0.8057 (2)0.0234 (9)
H120.19980.24820.78100.028*
C130.3610 (4)0.3671 (4)0.7734 (2)0.0225 (10)
H130.35240.40430.72590.027*
C140.4654 (4)0.4070 (4)0.8102 (2)0.0244 (10)
H140.52760.47080.78710.029*
P10.66670.33330.61180 (14)0.0249 (4)
P20.66670.33330.86636 (12)0.0258 (5)
Cl10.66670.33330.15629 (12)0.0371 (5)
Cl20.66670.33330.35858 (12)0.0363 (5)
H10.66670.33330.273 (4)0.05 (2)*
H20.66670.33330.790 (5)0.064*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.023 (2)0.021 (2)0.026 (2)0.014 (2)0.0001 (16)0.0016 (16)
C20.024 (2)0.018 (2)0.0178 (17)0.0151 (19)0.0015 (15)0.0048 (14)
C30.017 (2)0.015 (2)0.0218 (18)0.0064 (18)0.0028 (15)0.0004 (15)
C40.030 (3)0.026 (3)0.021 (2)0.017 (2)0.0033 (17)0.0015 (16)
C50.018 (2)0.024 (2)0.0222 (19)0.0100 (19)0.0035 (16)0.0067 (16)
C60.023 (2)0.020 (2)0.0229 (19)0.009 (2)0.0072 (16)0.0011 (16)
C70.025 (2)0.024 (2)0.0168 (17)0.014 (2)0.0026 (15)0.0003 (15)
C80.022 (2)0.023 (2)0.0232 (19)0.009 (2)0.0015 (16)0.0005 (16)
C90.018 (2)0.020 (2)0.0195 (18)0.0106 (18)0.0013 (15)0.0038 (15)
C100.021 (2)0.025 (2)0.0199 (19)0.014 (2)0.0017 (16)0.0001 (15)
C110.021 (2)0.024 (2)0.022 (2)0.011 (2)0.0026 (16)0.0005 (16)
C120.021 (2)0.032 (3)0.025 (2)0.018 (2)0.0031 (16)0.0066 (17)
C130.032 (3)0.022 (2)0.0192 (19)0.018 (2)0.0010 (16)0.0017 (15)
C140.030 (3)0.024 (2)0.0221 (19)0.016 (2)0.0032 (16)0.0013 (16)
P10.0183 (6)0.0183 (6)0.0381 (9)0.0092 (3)0.0000.000
P20.0168 (6)0.0168 (6)0.0436 (13)0.0084 (3)0.0000.000
Cl10.0305 (7)0.0305 (7)0.0502 (11)0.0152 (4)0.0000.000
Cl20.0282 (7)0.0282 (7)0.0526 (13)0.0141 (3)0.0000.000
Geometric parameters (Å, º) top
C1—C21.515 (5)C8—H8B0.9900
C1—P11.800 (4)C9—C141.386 (5)
C1—H1A0.9900C9—C101.402 (5)
C1—H1B0.9900C10—C111.380 (6)
C2—C71.376 (5)C10—H100.9500
C2—C31.407 (5)C11—C121.397 (5)
C3—C41.368 (6)C11—H110.9500
C3—H30.9500C12—C131.372 (6)
C4—C51.405 (6)C12—H120.9500
C4—H40.9500C13—C141.397 (6)
C5—C61.371 (5)C13—H130.9500
C5—H50.9500C14—H140.9500
C6—C71.389 (6)P1—C1i1.800 (4)
C6—H60.9500P1—C1ii1.800 (4)
C7—H70.9500P2—C8ii1.847 (4)
C8—C91.506 (5)P2—C8i1.847 (4)
C8—P21.847 (4)P2—H21.19 (7)
C8—H8A0.9900Cl2—H11.35 (7)
C2—C1—P1112.9 (3)H8A—C8—H8B108.0
C2—C1—H1A109.0C14—C9—C10118.5 (4)
P1—C1—H1A109.0C14—C9—C8119.9 (4)
C2—C1—H1B109.0C10—C9—C8121.5 (3)
P1—C1—H1B109.0C11—C10—C9120.9 (4)
H1A—C1—H1B107.8C11—C10—H10119.5
C7—C2—C3118.3 (4)C9—C10—H10119.5
C7—C2—C1121.4 (3)C10—C11—C12119.7 (4)
C3—C2—C1120.3 (4)C10—C11—H11120.1
C4—C3—C2120.7 (4)C12—C11—H11120.1
C4—C3—H3119.7C13—C12—C11119.9 (4)
C2—C3—H3119.7C13—C12—H12120.0
C3—C4—C5120.1 (4)C11—C12—H12120.0
C3—C4—H4120.0C12—C13—C14120.3 (4)
C5—C4—H4120.0C12—C13—H13119.9
C6—C5—C4119.6 (4)C14—C13—H13119.9
C6—C5—H5120.2C9—C14—C13120.6 (4)
C4—C5—H5120.2C9—C14—H14119.7
C5—C6—C7119.9 (4)C13—C14—H14119.7
C5—C6—H6120.1C1—P1—C1i110.14 (15)
C7—C6—H6120.1C1—P1—C1ii110.14 (15)
C2—C7—C6121.5 (4)C1i—P1—C1ii110.14 (15)
C2—C7—H7119.3C8ii—P2—C8i102.28 (16)
C6—C7—H7119.3C8ii—P2—C8102.28 (16)
C9—C8—P2111.5 (3)C8i—P2—C8102.28 (16)
C9—C8—H8A109.3C8ii—P2—H2115.95 (14)
P2—C8—H8A109.3C8i—P2—H2115.95 (14)
C9—C8—H8B109.3C8—P2—H2115.95 (13)
P2—C8—H8B109.3
P1—C1—C2—C783.3 (4)C14—C9—C10—C110.8 (6)
P1—C1—C2—C396.5 (4)C8—C9—C10—C11178.2 (4)
C7—C2—C3—C41.6 (6)C9—C10—C11—C120.6 (6)
C1—C2—C3—C4178.5 (3)C10—C11—C12—C131.5 (6)
C2—C3—C4—C51.8 (6)C11—C12—C13—C140.9 (6)
C3—C4—C5—C61.0 (6)C10—C9—C14—C131.4 (6)
C4—C5—C6—C70.0 (6)C8—C9—C14—C13178.8 (4)
C3—C2—C7—C60.6 (6)C12—C13—C14—C90.5 (6)
C1—C2—C7—C6179.5 (3)C2—C1—P1—C1i169.8 (3)
C5—C6—C7—C20.2 (6)C2—C1—P1—C1ii68.5 (4)
P2—C8—C9—C1488.9 (4)C9—C8—P2—C8ii78.7 (4)
P2—C8—C9—C1088.5 (4)C9—C8—P2—C8i175.6 (3)
Symmetry codes: (i) x+y+1, x+1, z; (ii) y+1, xy, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
Cl2—H1···Cl11.35 (7)1.83 (7)3.175 (3)180
P2—H2···P11.19 (7)2.80 (7)3.995 (3)180 (1)

Experimental details

(I)(II)
Crystal data
Chemical formulaC21H21PC42H43P2+·HCl2
Mr304.35681.61
Crystal system, space groupMonoclinic, P21/nTrigonal, R3
Temperature (K)100100
a, b, c (Å)10.9287 (8), 9.5775 (7), 16.0272 (12)13.941 (5), 13.941 (5), 15.693 (7)
α, β, γ (°)90, 91.051 (5), 9090, 90, 120
V3)1677.3 (2)2641.3 (18)
Z43
Radiation typeMo KαMo Kα
µ (mm1)0.160.31
Crystal size (mm)0.09 × 0.04 × 0.010.06 × 0.04 × 0.03
Data collection
DiffractometerRigaku Saturn724+ (2x2 bin mode)
diffractometer
Rigaku Saturn724+ (2x2 bin mode)
diffractometer
Absorption correctionMulti-scan
(CrystalClear-SM Expert; Rigaku, 2012)
Multi-scan
(CrystalClear-SM Expert; Rigaku, 2011)
Tmin, Tmax0.986, 0.9980.982, 0.991
No. of measured, independent and
observed [I > 2σ(I)] reflections
7381, 3374, 2268 2521, 1664, 1414
Rint0.0480.022
(sin θ/λ)max1)0.6250.648
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.109, 1.01 0.042, 0.099, 1.02
No. of reflections33741664
No. of parameters199142
No. of restraints01
H-atom treatmentH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.36, 0.360.61, 0.57
Absolute structure?Flack (1983), 325 Friedel pairs
Absolute structure parameter?0.34 (14)

Computer programs: CrystalClear-SM Expert (Rigaku, 2012), CrystalClear-SM Expert (Rigaku, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012), PLATON (Spek, 2009), WinGX (Farrugia, 2012), enCIFer (Allen et al., 2004), publCIF (Westrip, 2010) and Mercury (Macrae et al., 2006)..

Selected geometric parameters (Å, º) for (I) top
C1—P11.858 (2)C15—P11.855 (2)
C8—P11.857 (2)
C15—P1—C898.48 (11)C8—P1—C199.53 (11)
C15—P1—C197.69 (11)
P1—C1—C2—C386.5 (2)P1—C8—C9—C1086.4 (2)
P1—C1—C2—C793.1 (2)P1—C15—C16—C17109.5 (2)
P1—C8—C9—C1492.7 (2)P1—C15—C16—C2170.6 (3)
Selected geometric parameters (Å, º) for (II) top
C1—P11.800 (4)P2—H21.19 (7)
C8—P21.847 (4)Cl2—H11.35 (7)
C1—P1—C1i110.14 (15)C8—P2—H2115.95 (13)
C8i—P2—C8102.28 (16)
P1—C1—C2—C783.3 (4)P2—C8—C9—C1488.9 (4)
P1—C1—C2—C396.5 (4)P2—C8—C9—C1088.5 (4)
Symmetry code: (i) x+y+1, x+1, z.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
Cl2—H1···Cl11.35 (7)1.83 (7)3.175 (3)180.0
P2—H2···P11.19 (7)2.80 (7)3.995 (3)180.000 (1)
 

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