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The title compound, C6H18P3+·CF3SO3, crystallizes in two polymorphic forms in the space groups P21/c and Pnma. In the ortho­rhom­bic form, the two crystallographically independent mol­ecular units lie across a crystallographic mirror plane. The compound lacks traditional hydrogen-bond donors and, hence, is held together by weak C—H...O and C—H...F inter­actions, forming layers. The second polymorph was obtained as a by-product from the reaction of 1,3-bis­(2,6-dimethyl­phen­yl)-2,4-ditriflato-1,3,2,4-diaza­diphosphetidine with tetra­methyl­diphosphine.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107006671/fa3074sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107006671/fa3074Isup2.hkl
Contains datablock I

CCDC reference: 641816

Comment top

P-donor ligands on PIII systems have recently become pivotal in the development of molecular main-group coordination chemistry. These donor–acceptor interactions are recognized as `homoatomic' coordination complexes in inter- and intramolecular phosphine–phosphonium complexes and are essentially unique to phosphorus (Burford et al., 2003). Facile synthetic methods for the diversification of catena-polyphosphorus cations yielded a series of new organo-substituted diphosphinophosphonium and cyclo-tetraphosphinodiphosphonium cations (Weigand et al., 2006). Recently, we reported the crystal structure of catena-hexamethyldiphosphinophosphonium trifluoromethanesulfonate, which crystallizes in the monoclinic crystal system P21/c (Burford et al., 2005). During our further investigation we obtained a second polymorph of the title compound, (I) [OTf- is trifluoromethanesulfonate (trifluoromethanesulfonate)], by chance, from the reaction of 1,3-bis(2,6-dimethylphenyl)-2,4-ditriflato-1,3,2,4-diazadiphosphetidine with tetramethyldiphosphine as a reaction by-product.

The orthorhombic polymorph crystallizes with two half-formula units in the asymmetric unit. A view of the molecular structures along with the numbering scheme is depicted in Fig. 1. X-ray investigation has shown that the bond lengths in (I) do not significantly differ from that found in the monoclinic polymorph. The same unusual eclipsed/staggered conformation (local molecular symmetry Cs) of the cation is observed. The geometries of the trifluoromethanesulfonate anions in (I) are in accordance with that previously determined (You & Zhu, 2004). The interatomic distances and bond angles in the two independent molecules are almost identical, and selected molecular parameters of the cations are presented in Table 1. The cations and anions lie across a crystallographic mirror plane passing through atoms P1–P6, S1, S2, C7 and C9.

Compound (I) lacks traditional hydrogen-bond donor groups; hence, the structure is stabilized by weak C—H···O and C—H···F interactions (Table 2). These C—H···O hydrogen bonds (C2—H4···O3, C2—H6···O1iii and C5—H14···O2; symmetry codes and geometry are given in Table 2) account for the observation of subunits consisting of two cations and two anions, and, together with the weak C—H···F interactions (C3—H8···F2 and C6—H16···F2v; Table 2), form two-dimensional sheets (Fig. 2). The two hydrogen bonds found between these sheets (C2—H5···O4ii and C5—H13···O1iv; Table 2) are the main contributors that lead to a lateral packing of the layers. The resulting layers are arranged in an antiparallel manner (ABA layer sequence), which is compatible with space group Pnma (Fig. 3). In the case of the monoclinic polymorph, a lateral packing of layers is found, similar to that of the orthorhombic polymorph. However, the layers are composed of alternating strands of cations and anions running along the c axis, stabilized by weak C—H···O and C—H···F interactions.

Related literature top

For related literature, see: Burford et al. (2003, 2005); Weigand et al. (2006); You & Zhu (2004).

Experimental top

All manipulations were performed under an inert atmosphere of dinitrogen. A solution of tetramethyldiphosphine (126 mg, 1 mmol) in CH2Cl2 (2 ml) was added to a solution of 1,3-bis(2,6-dimethylphenyl)-2,4-ditriflato-1,3,2,4-diazadiphosphetidine (300 mg, 0.5 mmol) in CH2Cl2 (3 ml) leading to the formation of a bright-yellow solution. Addition of Et2O resulted in the formation of a bright-yellow precipitate. Compound (I) was obtained as colorless needles from vapor diffusion of Et2O into a CH2Cl2/CH3CN solution of the yellow precipitate amidst copious amounts of a yellow oily material of unknown constitution. The analytical data are in agreement with that previously reported (Burford et al., 2005).

Refinement top

H atoms were located in a difference Fourier map and their coordinates were refined in the riding mode [Uiso(H) = 1.2Ueq(C)]. The data set for (I) was truncated at 2Θ = 60° as only statistically insignificant data were present above the limit.

Computing details top

Data collection: PROCESS (Rigaku, 1996); cell refinement: PROCESS; data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: CRYSTALS (Watkin et al., 1996); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: CrystalStructure.

Figures top
[Figure 1] Fig. 1. A view of the molecular structure of (I), showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of an arbitrary radius. [Symmetry code: (i) x, -y + 1/2, z].
[Figure 2] Fig. 2. The arrangement of the ions of (I), viewed along the [010] axis. The weak C—H···O and C—H···F interactions are represented by dashed lines. H atoms not involved in these interactions have been omitted for clarity [Symmetry codes: (iii) x + 1/2, -y + 1/2, -z + 1/2; (v) x, -y + 1/2, z + 1.]
[Figure 3] Fig. 3. The arrangement of the ions of (I), viewed along the [001] axis. The weak C—H···O interactions between the sheets are represented by dashed lines. H atoms not involved in these interactions have been omitted for clarity [Symmetry codes: (i) x, -y + 1/2, z; (vi) -x + 1/2, -y + 1, z + 1/2; (vii) -x, y + 1/2, -z + 1].
bis(dimethylphosphino)dimethylphosphonium trifluoromethanesulfonate top
Crystal data top
C6H18P3+·CF3O3SF(000) = 1376.00
Mr = 332.19Dx = 1.450 Mg m3
Orthorhombic, PnmaMo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ac 2nCell parameters from 12587 reflections
a = 23.5972 (7) Åθ = 5.0–35.7°
b = 10.7419 (4) ŵ = 0.55 mm1
c = 12.0086 (4) ÅT = 123 K
V = 3043.9 (2) Å3Needle, colourless
Z = 80.40 × 0.17 × 0.12 mm
Data collection top
Rigaku R-AXIS
diffractometer
Rint = 0.080
Detector resolution: 10.00 pixels mm-1θmax = 35.7°
ω scansh = 3735
25123 measured reflectionsk = 1517
6230 independent reflectionsl = 1913
2682 reflections with F2 > 2σ(F2)
Refinement top
Refinement on FH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.052 Chebychev polynomial with three parameters (Carruthers & Watkin, 1979): 22.3826, -11.8310 and 17.0026
wR(F2) = 0.063(Δ/σ)max < 0.001
S = 1.06Δρmax = 1.08 e Å3
2682 reflectionsΔρmin = 0.62 e Å3
193 parameters
Crystal data top
C6H18P3+·CF3O3SV = 3043.9 (2) Å3
Mr = 332.19Z = 8
Orthorhombic, PnmaMo Kα radiation
a = 23.5972 (7) ŵ = 0.55 mm1
b = 10.7419 (4) ÅT = 123 K
c = 12.0086 (4) Å0.40 × 0.17 × 0.12 mm
Data collection top
Rigaku R-AXIS
diffractometer
2682 reflections with F2 > 2σ(F2)
25123 measured reflectionsRint = 0.080
6230 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.052193 parameters
wR(F2) = 0.063H-atom parameters constrained
S = 1.06Δρmax = 1.08 e Å3
2682 reflectionsΔρmin = 0.62 e Å3
Special details top

Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY

Refinement. Refinement using reflections with F2 > 3.0 σ(F2). The weighted R-factor(wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.02148 (4)0.25000.29420 (9)0.0309 (3)
S20.26489 (4)0.25000.59125 (9)0.0279 (2)
P10.30491 (5)0.25000.00516 (10)0.0373 (3)
P20.27412 (4)0.25000.17720 (8)0.0234 (2)
P30.18032 (4)0.25000.17526 (9)0.0277 (3)
P40.01508 (5)0.25000.69750 (10)0.0362 (3)
P50.07646 (5)0.25000.65808 (10)0.0314 (3)
P60.12354 (5)0.25000.81492 (12)0.0488 (4)
F10.0377 (2)0.25000.0796 (4)0.143 (3)
F20.0360 (2)0.1538 (7)0.1336 (3)0.182 (2)
F30.3624 (2)0.1508 (4)0.5432 (4)0.1076 (13)
F40.3591 (2)0.25000.6997 (6)0.123 (2)
O10.0544 (1)0.3615 (3)0.3004 (3)0.0622 (9)
O20.0296 (2)0.25000.3590 (3)0.0447 (10)
O30.2501 (2)0.25000.4765 (3)0.067 (2)
O40.25075 (13)0.1376 (3)0.6490 (3)0.0550 (8)
C10.2627 (2)0.3816 (4)0.0477 (3)0.0431 (9)
C20.30363 (13)0.1159 (3)0.2446 (3)0.0320 (7)
C30.1660 (1)0.1190 (3)0.2687 (3)0.0420 (9)
C40.0386 (2)0.1174 (4)0.6123 (4)0.0445 (9)
C50.0985 (1)0.1158 (4)0.5799 (3)0.0395 (8)
C60.0880 (2)0.3820 (4)0.8810 (3)0.0516 (11)
C70.0040 (3)0.25000.1521 (6)0.107 (3)
C90.3412 (2)0.25000.5920 (7)0.063 (2)
H10.27630.45690.01580.052*
H20.26620.38570.12650.052*
H30.22410.37010.02820.052*
H40.29550.11930.32200.039*
H50.28750.04260.21360.038*
H60.34350.11480.23390.038*
H70.18140.13610.34020.050*
H80.12630.10710.27480.051*
H90.18300.04580.23940.051*
H100.02690.12980.53740.053*
H110.02220.04290.64020.053*
H120.07870.11130.61530.053*
H130.08850.04240.61940.047*
H140.08020.11600.50940.047*
H150.13840.11810.56960.048*
H160.10320.39470.95330.062*
H170.09360.45470.83730.062*
H180.04850.36510.88650.062*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0247 (5)0.0394 (6)0.0285 (5)0.00000.0005 (4)0.0000
S20.0291 (5)0.0286 (5)0.0260 (5)0.00000.0014 (4)0.0000
P10.0313 (6)0.0552 (8)0.0256 (5)0.00000.0052 (4)0.0000
P20.0225 (4)0.0256 (5)0.0221 (4)0.00000.0006 (4)0.0000
P30.0223 (5)0.0340 (6)0.0267 (5)0.00000.0010 (4)0.0000
P40.0243 (5)0.0497 (7)0.0345 (6)0.00000.0010 (5)0.0000
P50.0239 (5)0.0413 (7)0.0290 (5)0.00000.0005 (4)0.0000
P60.0299 (6)0.0857 (11)0.0309 (6)0.00000.0038 (5)0.0000
F10.056 (3)0.331 (10)0.041 (2)0.00000.021 (2)0.0000
F20.071 (2)0.400 (9)0.077 (2)0.076 (3)0.002 (2)0.108 (4)
F30.060 (2)0.098 (3)0.165 (4)0.030 (2)0.040 (2)0.012 (3)
F40.065 (3)0.174 (6)0.129 (5)0.00000.062 (3)0.0000
O10.054 (2)0.046 (2)0.086 (2)0.015 (1)0.012 (2)0.005 (2)
O20.031 (2)0.067 (3)0.036 (2)0.00000.007 (1)0.0000
O30.077 (3)0.092 (4)0.032 (2)0.00000.016 (2)0.0000
O40.061 (2)0.041 (2)0.063 (2)0.005 (1)0.014 (1)0.014 (1)
C10.061 (2)0.039 (2)0.029 (2)0.005 (2)0.003 (2)0.005 (1)
C20.032 (1)0.030 (2)0.034 (1)0.0038 (12)0.0018 (12)0.0026 (12)
C30.034 (2)0.033 (2)0.059 (2)0.0021 (13)0.008 (2)0.008 (2)
C40.032 (2)0.043 (2)0.059 (2)0.001 (1)0.007 (2)0.000 (2)
C50.033 (2)0.045 (2)0.040 (2)0.004 (1)0.0031 (13)0.001 (2)
C60.067 (3)0.053 (2)0.035 (2)0.019 (2)0.003 (2)0.002 (2)
C70.035 (3)0.26 (1)0.029 (3)0.00000.005 (2)0.0000
C90.030 (3)0.073 (5)0.086 (5)0.00000.005 (3)0.0000
Geometric parameters (Å, º) top
S1—O11.429 (3)F4—C91.36 (1)
S1—O21.435 (4)C1—H10.9500
S1—C71.809 (7)C1—H20.9500
S2—O31.422 (4)C1—H30.9501
S2—O41.431 (3)C2—H40.9500
S2—C91.801 (6)C2—H50.9500
P1—P22.190 (2)C2—H60.9499
P2—P32.214 (1)C3—H70.9501
P1—C11.842 (4)C3—H80.9500
P2—C21.793 (3)C3—H90.9500
P3—C31.830 (4)C4—H100.9500
P5—P62.187 (2)C4—H110.9500
P4—P52.211 (2)C4—H120.9499
P6—C61.828 (4)C5—H130.9501
P5—C51.797 (4)C5—H140.9500
P4—C41.839 (4)C5—H150.9500
F1—C71.313 (8)C6—H160.9500
F2—C71.299 (7)C6—H170.9501
F3—C91.314 (6)C6—H180.9501
O1i—S1—O1113.8 (2)P1—C1—H3109.4866
O2—S1—O1115.4 (2)P2—C2—H4109.4204
C7—S1—O1103.3 (2)P2—C2—H5109.5124
C7—S1—O2103.4 (3)P2—C2—H6109.4839
S1—C7—F1112.1 (5)P3—C3—H7109.5619
S1—C7—F2110.7 (4)P3—C3—H9109.3910
O4—S2—O3114.3 (2)P3—C3—H8109.4549
C9—S2—O3104.5 (3)P4—C4—H10109.3786
O4i—S2—O4115.0 (2)P4—C4—H11109.5485
C9—S2—O4103.3 (2)P4—C4—H12109.4839
S2—C9—F3112.2 (3)P5—C5—H15109.5405
S2—C9—F4108.3 (5)P5—C5—H13109.4586
P1—P2—P3108.77 (6)P5—C5—H14109.4083
P1—P2—C2107.3 (1)P6—C6—H18109.3889
P2—P3—C3100.2 (1)P6—C6—H17109.4726
C1—P1—P298.4 (1)P6—C6—H16109.5483
C2—P2—P3113.2 (1)H2—C1—H1109.4710
C1i—P1—C1100.3 (2)H3—C1—H1109.4783
C2i—P2—C2106.9 (2)H3—C1—H2109.4663
C3i—P3—C3100.4 (2)H5—C2—H4109.4699
P4—P5—P6108.17 (7)H6—C2—H4109.4677
C5—P5—P6107.6 (1)H6—C2—H5109.4729
C4—P4—P5100.1 (1)H9—C3—H7109.4754
P5—P6—C698.1 (1)H8—C3—H7109.4750
P4—P5—C5113.2 (1)H9—C3—H8109.4691
C6i—P6—C6101.6 (2)H11—C4—H10109.4738
C5i—P5—C5106.7 (2)H12—C4—H10109.4735
C4i—P4—C4101.5 (2)H12—C4—H11109.4690
F1—C7—F2108.8 (4)H15—C5—H13109.4784
F2—C7—F2i105.4 (6)H14—C5—H13109.4729
F3—C9—F3i108.3 (6)H15—C5—H14109.4686
F3—C9—F4107.8 (4)H18—C6—H16109.4776
P1—C1—H1109.4466H17—C6—H16109.4685
P1—C1—H2109.4784H18—C6—H17109.4713
O1—S1—C7—F159.4 (4)C1—P1—P2—P350.9 (3)
O1—S1—C7—F2178.9 (4)C1—P1—P2—C2173.6 (2)
O2—S1—C7—F1180.0P1—P2—P3—C3128.7 (2)
O2—S1—C7—F258.3 (5)C2—P2—P3—C39.6 (2)
O3—S2—C9—F361.1 (6)C4—P4—P5—P6128.1 (2)
O3—S2—C9—F4180.0C4—P4—P5—C58.9 (2)
O4—S2—C9—F358.8 (6)P4—P5—P6—C651.5 (3)
O4—S2—C9—F460.1 (4)C5—P5—P6—C6174.2 (2)
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H4···O30.952.563.380 (5)145
C2—H5···O4ii0.952.273.222 (5)177
C2—H6···O1iii0.952.463.402 (4)173
C5—H13···O1iv0.952.313.258 (5)173
C5—H14···O20.952.603.429 (5)146
C3—H8···F20.952.773.491 (5)134
C6—H16···F2v0.952.733.295 (5)119
Symmetry codes: (ii) x+1/2, y, z1/2; (iii) x+1/2, y+1/2, z+1/2; (iv) x, y1/2, z+1; (v) x, y+1/2, z+1.

Experimental details

Crystal data
Chemical formulaC6H18P3+·CF3O3S
Mr332.19
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)123
a, b, c (Å)23.5972 (7), 10.7419 (4), 12.0086 (4)
V3)3043.9 (2)
Z8
Radiation typeMo Kα
µ (mm1)0.55
Crystal size (mm)0.40 × 0.17 × 0.12
Data collection
DiffractometerRigaku R-AXIS
diffractometer
Absorption correction
No. of measured, independent and
observed [F2 > 2σ(F2)] reflections
25123, 6230, 2682
Rint0.080
(sin θ/λ)max1)0.820
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.063, 1.06
No. of reflections2682
No. of parameters193
No. of restraints?
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.08, 0.62

Computer programs: PROCESS (Rigaku, 1996), PROCESS, CrystalStructure (Rigaku/MSC, 2004), SHELXS86 (Sheldrick, 1985), CRYSTALS (Watkin et al., 1996), DIAMOND (Brandenburg, 2000), CrystalStructure.

Selected geometric parameters (Å, º) top
P1—P22.190 (2)P4—P52.211 (2)
P2—P32.214 (1)P6—C61.828 (4)
P1—C11.842 (4)P5—C51.797 (4)
P2—C21.793 (3)P4—C41.839 (4)
P3—C31.830 (4)F1—C71.313 (8)
P5—P62.187 (2)F2—C71.299 (7)
P1—P2—P3108.77 (6)P4—P5—P6108.17 (7)
P1—P2—C2107.3 (1)C5—P5—P6107.6 (1)
P2—P3—C3100.2 (1)C4—P4—P5100.1 (1)
C1—P1—P298.4 (1)P5—P6—C698.1 (1)
C2—P2—P3113.2 (1)P4—P5—C5113.2 (1)
C1i—P1—C1100.3 (2)C6i—P6—C6101.6 (2)
C2i—P2—C2106.9 (2)C5i—P5—C5106.7 (2)
C3i—P3—C3100.4 (2)C4i—P4—C4101.5 (2)
Symmetry code: (i) x, y+1/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H4···O30.952.563.380 (5)145
C2—H5···O4ii0.952.273.222 (5)177
C2—H6···O1iii0.952.463.402 (4)173
C5—H13···O1iv0.952.313.258 (5)173
C5—H14···O20.952.603.429 (5)146
C3—H8···F20.952.773.491 (5)134
C6—H16···F2v0.952.733.295 (5)119
Symmetry codes: (ii) x+1/2, y, z1/2; (iii) x+1/2, y+1/2, z+1/2; (iv) x, y1/2, z+1; (v) x, y+1/2, z+1.
 

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