Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052932/hb2582sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052932/hb2582Isup2.hkl |
CCDC reference: 672803
The title compound was been prepared from the corresponding diphosphine, (PhCH2)2PCH2CH2P(CH2Ph)2, and 1,2-dibromoethane according to the procedure given by Hinton & Mann (1959). Colourless blocks of (I) were obtained from deuterated chloroform by slow evaporation at room temperature.
Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens, 2000); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
C32H36P22+·2Br−·2CDCl3 | F(000) = 1776 |
Mr = 883.08 | Dx = 1.595 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 8675 reflections |
a = 16.2692 (10) Å | θ = 2.3–30.4° |
b = 17.5649 (10) Å | µ = 2.75 mm−1 |
c = 13.9110 (8) Å | T = 133 K |
β = 112.350 (3)° | Block, colourless |
V = 3676.7 (4) Å3 | 0.38 × 0.30 × 0.29 mm |
Z = 4 |
Bruker SMART1000 CCD diffractometer | 5373 independent reflections |
Radiation source: fine-focus sealed tube | 4684 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
Detector resolution: 8.192 pixels mm-1 | θmax = 30.0°, θmin = 1.8° |
ω scans | h = −22→22 |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | k = −24→24 |
Tmin = 0.360, Tmax = 0.502 | l = −19→19 |
37985 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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0419P)2 + 6.1465P] where P = (Fo2 + 2Fc2)/3 |
5373 reflections | (Δ/σ)max < 0.001 |
200 parameters | Δρmax = 1.52 e Å−3 |
0 restraints | Δρmin = −1.05 e Å−3 |
C32H36P22+·2Br−·2CDCl3 | V = 3676.7 (4) Å3 |
Mr = 883.08 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 16.2692 (10) Å | µ = 2.75 mm−1 |
b = 17.5649 (10) Å | T = 133 K |
c = 13.9110 (8) Å | 0.38 × 0.30 × 0.29 mm |
β = 112.350 (3)° |
Bruker SMART1000 CCD diffractometer | 5373 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | 4684 reflections with I > 2σ(I) |
Tmin = 0.360, Tmax = 0.502 | Rint = 0.025 |
37985 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.083 | H-atom parameters constrained |
S = 1.05 | Δρmax = 1.52 e Å−3 |
5373 reflections | Δρmin = −1.05 e Å−3 |
200 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 | ||
Br1 | 0.0000 | 0.121056 (14) | 0.7500 | 0.02374 (7) | |
Br2 | 0.0000 | 0.209800 (15) | 0.2500 | 0.03136 (8) | |
P1 | 0.08262 (3) | 0.06365 (2) | 0.06148 (3) | 0.01914 (9) | |
C1 | 0.12293 (12) | 0.15385 (10) | 0.03500 (15) | 0.0246 (3) | |
H1A | 0.0881 | 0.1678 | −0.0382 | 0.030* | |
H1B | 0.1117 | 0.1932 | 0.0795 | 0.030* | |
C11 | 0.22023 (12) | 0.15556 (10) | 0.05260 (14) | 0.0238 (3) | |
C12 | 0.27929 (14) | 0.19798 (11) | 0.13390 (16) | 0.0291 (4) | |
H12 | 0.2580 | 0.2269 | 0.1773 | 0.035* | |
C13 | 0.36960 (15) | 0.19821 (13) | 0.15203 (19) | 0.0380 (5) | |
H13 | 0.4098 | 0.2274 | 0.2076 | 0.046* | |
C14 | 0.40056 (16) | 0.15622 (14) | 0.0894 (2) | 0.0421 (5) | |
H14 | 0.4624 | 0.1551 | 0.1032 | 0.050* | |
C15 | 0.34194 (17) | 0.11551 (13) | 0.0062 (2) | 0.0401 (5) | |
H15 | 0.3633 | 0.0875 | −0.0379 | 0.048* | |
C16 | 0.25188 (15) | 0.11585 (12) | −0.01245 (17) | 0.0316 (4) | |
H16 | 0.2116 | 0.0887 | −0.0702 | 0.038* | |
C2 | 0.13706 (12) | 0.03240 (10) | 0.19539 (14) | 0.0223 (3) | |
H2A | 0.1500 | 0.0777 | 0.2411 | 0.027* | |
H2B | 0.0952 | −0.0001 | 0.2132 | 0.027* | |
C21 | 0.22303 (11) | −0.01158 (10) | 0.21883 (13) | 0.0217 (3) | |
C22 | 0.30491 (13) | 0.02553 (12) | 0.25009 (15) | 0.0279 (4) | |
H22 | 0.3076 | 0.0793 | 0.2580 | 0.033* | |
C23 | 0.38249 (13) | −0.01563 (13) | 0.26965 (17) | 0.0331 (4) | |
H23 | 0.4379 | 0.0101 | 0.2912 | 0.040* | |
C24 | 0.37956 (13) | −0.09415 (13) | 0.25799 (16) | 0.0323 (4) | |
H24 | 0.4327 | −0.1220 | 0.2704 | 0.039* | |
C25 | 0.29897 (14) | −0.13164 (12) | 0.22824 (16) | 0.0293 (4) | |
H25 | 0.2968 | −0.1854 | 0.2204 | 0.035* | |
C26 | 0.22100 (12) | −0.09085 (11) | 0.20968 (14) | 0.0247 (3) | |
H26 | 0.1660 | −0.1171 | 0.1907 | 0.030* | |
C3 | −0.03415 (11) | 0.07968 (10) | 0.03025 (14) | 0.0222 (3) | |
H3A | −0.0403 | 0.1155 | 0.0821 | 0.027* | |
H3B | −0.0593 | 0.1050 | −0.0384 | 0.027* | |
C4 | −0.09037 (11) | 0.00863 (10) | 0.02692 (14) | 0.0214 (3) | |
H4A | −0.1533 | 0.0240 | 0.0059 | 0.026* | |
H4B | −0.0708 | −0.0133 | 0.0977 | 0.026* | |
Cl1 | −0.10604 (4) | 0.26705 (3) | −0.07399 (5) | 0.03723 (12) | |
Cl2 | −0.09062 (6) | 0.41535 (4) | 0.01860 (5) | 0.05499 (18) | |
Cl3 | −0.26168 (4) | 0.33812 (4) | −0.06513 (5) | 0.04406 (15) | |
C99 | −0.14538 (14) | 0.32753 (12) | 0.00011 (16) | 0.0311 (4) | |
H99 | −0.1329 | 0.3035 | 0.0694 | 0.037* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.02504 (12) | 0.02263 (12) | 0.02072 (12) | 0.000 | 0.00553 (9) | 0.000 |
Br2 | 0.04348 (16) | 0.02395 (13) | 0.02526 (14) | 0.000 | 0.01151 (11) | 0.000 |
P1 | 0.01808 (19) | 0.01810 (19) | 0.0191 (2) | −0.00022 (15) | 0.00459 (15) | −0.00208 (14) |
C1 | 0.0265 (8) | 0.0204 (8) | 0.0244 (9) | −0.0010 (6) | 0.0069 (7) | 0.0010 (6) |
C11 | 0.0285 (8) | 0.0206 (8) | 0.0227 (8) | −0.0028 (6) | 0.0101 (7) | 0.0015 (6) |
C12 | 0.0354 (10) | 0.0241 (8) | 0.0280 (10) | −0.0065 (7) | 0.0121 (8) | −0.0021 (7) |
C13 | 0.0337 (10) | 0.0371 (11) | 0.0396 (12) | −0.0147 (9) | 0.0099 (9) | 0.0022 (9) |
C14 | 0.0327 (11) | 0.0446 (13) | 0.0539 (15) | −0.0049 (9) | 0.0220 (10) | 0.0125 (11) |
C15 | 0.0479 (13) | 0.0375 (11) | 0.0479 (14) | −0.0006 (10) | 0.0329 (11) | 0.0038 (10) |
C16 | 0.0393 (11) | 0.0315 (10) | 0.0281 (10) | −0.0047 (8) | 0.0174 (8) | −0.0017 (7) |
C2 | 0.0225 (8) | 0.0241 (8) | 0.0193 (8) | 0.0018 (6) | 0.0069 (6) | −0.0002 (6) |
C21 | 0.0218 (8) | 0.0252 (8) | 0.0176 (8) | 0.0008 (6) | 0.0067 (6) | 0.0024 (6) |
C22 | 0.0262 (9) | 0.0288 (9) | 0.0260 (9) | −0.0028 (7) | 0.0069 (7) | 0.0036 (7) |
C23 | 0.0228 (9) | 0.0431 (11) | 0.0335 (11) | −0.0030 (8) | 0.0107 (8) | 0.0043 (9) |
C24 | 0.0273 (9) | 0.0427 (11) | 0.0294 (10) | 0.0093 (8) | 0.0138 (8) | 0.0051 (8) |
C25 | 0.0331 (10) | 0.0286 (9) | 0.0261 (9) | 0.0054 (8) | 0.0113 (7) | 0.0024 (7) |
C26 | 0.0238 (8) | 0.0261 (8) | 0.0225 (8) | −0.0006 (7) | 0.0067 (6) | 0.0009 (6) |
C3 | 0.0202 (7) | 0.0193 (8) | 0.0243 (8) | 0.0026 (6) | 0.0053 (6) | −0.0025 (6) |
C4 | 0.0213 (8) | 0.0214 (8) | 0.0208 (8) | 0.0012 (6) | 0.0070 (6) | −0.0020 (6) |
Cl1 | 0.0334 (2) | 0.0369 (3) | 0.0452 (3) | 0.0021 (2) | 0.0192 (2) | 0.0015 (2) |
Cl2 | 0.0842 (5) | 0.0376 (3) | 0.0367 (3) | −0.0212 (3) | 0.0157 (3) | −0.0044 (2) |
Cl3 | 0.0367 (3) | 0.0499 (3) | 0.0516 (3) | 0.0161 (2) | 0.0235 (2) | 0.0209 (3) |
C99 | 0.0363 (10) | 0.0303 (10) | 0.0264 (10) | −0.0011 (8) | 0.0115 (8) | 0.0040 (7) |
P1—C3 | 1.8027 (18) | Cl2—C99 | 1.751 (2) |
P1—C4i | 1.8050 (18) | Cl3—C99 | 1.770 (2) |
P1—C1 | 1.8053 (18) | C1—H1A | 0.9900 |
P1—C2 | 1.8170 (18) | C1—H1B | 0.9900 |
C1—C11 | 1.507 (3) | C12—H12 | 0.9500 |
C11—C16 | 1.387 (3) | C13—H13 | 0.9500 |
C11—C12 | 1.389 (3) | C14—H14 | 0.9500 |
C12—C13 | 1.393 (3) | C15—H15 | 0.9500 |
C13—C14 | 1.375 (4) | C16—H16 | 0.9500 |
C14—C15 | 1.386 (4) | C2—H2A | 0.9900 |
C15—C16 | 1.387 (3) | C2—H2B | 0.9900 |
C2—C21 | 1.521 (2) | C22—H22 | 0.9500 |
C21—C22 | 1.396 (3) | C23—H23 | 0.9500 |
C21—C26 | 1.397 (3) | C24—H24 | 0.9500 |
C22—C23 | 1.389 (3) | C25—H25 | 0.9500 |
C23—C24 | 1.387 (3) | C26—H26 | 0.9500 |
C24—C25 | 1.383 (3) | C3—H3A | 0.9900 |
C25—C26 | 1.393 (3) | C3—H3B | 0.9900 |
C3—C4 | 1.538 (2) | C4—H4A | 0.9900 |
C4—P1i | 1.8049 (18) | C4—H4B | 0.9900 |
Cl1—C99 | 1.761 (2) | C99—H99 | 1.0000 |
C3—P1—C4i | 106.61 (8) | C14—C13—H13 | 120.0 |
C3—P1—C1 | 104.19 (8) | C12—C13—H13 | 120.0 |
C4i—P1—C1 | 110.70 (9) | C13—C14—H14 | 119.9 |
C3—P1—C2 | 110.63 (9) | C15—C14—H14 | 119.9 |
C4i—P1—C2 | 110.66 (8) | C14—C15—H15 | 120.1 |
C1—P1—C2 | 113.65 (8) | C16—C15—H15 | 120.1 |
C11—C1—P1 | 115.15 (13) | C11—C16—H16 | 119.7 |
C16—C11—C12 | 119.16 (19) | C15—C16—H16 | 119.7 |
C16—C11—C1 | 120.75 (17) | C21—C2—H2A | 108.5 |
C12—C11—C1 | 120.09 (17) | P1—C2—H2A | 108.5 |
C11—C12—C13 | 120.3 (2) | C21—C2—H2B | 108.5 |
C14—C13—C12 | 119.9 (2) | P1—C2—H2B | 108.5 |
C13—C14—C15 | 120.3 (2) | H2A—C2—H2B | 107.5 |
C14—C15—C16 | 119.8 (2) | C23—C22—H22 | 119.8 |
C11—C16—C15 | 120.5 (2) | C21—C22—H22 | 119.8 |
C21—C2—P1 | 115.04 (12) | C24—C23—H23 | 119.8 |
C22—C21—C26 | 118.72 (17) | C22—C23—H23 | 119.8 |
C22—C21—C2 | 121.37 (17) | C25—C24—H24 | 120.2 |
C26—C21—C2 | 119.91 (16) | C23—C24—H24 | 120.2 |
C23—C22—C21 | 120.44 (19) | C24—C25—H25 | 119.9 |
C24—C23—C22 | 120.42 (19) | C26—C25—H25 | 119.9 |
C25—C24—C23 | 119.67 (18) | C25—C26—H26 | 119.8 |
C24—C25—C26 | 120.25 (19) | C21—C26—H26 | 119.8 |
C25—C26—C21 | 120.48 (17) | C4—C3—H3A | 108.2 |
C4—C3—P1 | 116.16 (12) | P1—C3—H3A | 108.2 |
C3—C4—P1i | 113.36 (12) | C4—C3—H3B | 108.2 |
Cl2—C99—Cl1 | 109.85 (12) | P1—C3—H3B | 108.2 |
Cl2—C99—Cl3 | 111.58 (12) | H3A—C3—H3B | 107.4 |
Cl1—C99—Cl3 | 108.59 (12) | C3—C4—H4A | 108.9 |
C11—C1—H1A | 108.5 | P1i—C4—H4A | 108.9 |
P1—C1—H1A | 108.5 | C3—C4—H4B | 108.9 |
C11—C1—H1B | 108.5 | P1i—C4—H4B | 108.9 |
P1—C1—H1B | 108.5 | H4A—C4—H4B | 107.7 |
H1A—C1—H1B | 107.5 | Cl2—C99—H99 | 108.9 |
C11—C12—H12 | 119.9 | Cl1—C99—H99 | 108.9 |
C13—C12—H12 | 119.9 | Cl3—C99—H99 | 108.9 |
C3—P1—C1—C11 | −178.60 (14) | C1—P1—C2—C21 | −86.12 (15) |
C4i—P1—C1—C11 | −64.34 (16) | P1—C2—C21—C22 | 89.50 (19) |
C2—P1—C1—C11 | 60.91 (16) | P1—C2—C21—C26 | −90.81 (18) |
P1—C1—C11—C16 | 69.5 (2) | C26—C21—C22—C23 | 1.2 (3) |
P1—C1—C11—C12 | −111.24 (18) | C2—C21—C22—C23 | −179.06 (18) |
C16—C11—C12—C13 | −2.4 (3) | C21—C22—C23—C24 | 0.3 (3) |
C1—C11—C12—C13 | 178.39 (18) | C22—C23—C24—C25 | −1.0 (3) |
C11—C12—C13—C14 | −0.1 (3) | C23—C24—C25—C26 | 0.2 (3) |
C12—C13—C14—C15 | 2.1 (3) | C24—C25—C26—C21 | 1.3 (3) |
C13—C14—C15—C16 | −1.5 (4) | C22—C21—C26—C25 | −2.0 (3) |
C12—C11—C16—C15 | 3.0 (3) | C2—C21—C26—C25 | 178.29 (17) |
C1—C11—C16—C15 | −177.79 (19) | C4i—P1—C3—C4 | 52.58 (17) |
C14—C15—C16—C11 | −1.1 (3) | C1—P1—C3—C4 | 169.70 (13) |
C3—P1—C2—C21 | 157.08 (13) | C2—P1—C3—C4 | −67.81 (15) |
C4i—P1—C2—C21 | 39.15 (16) | P1—C3—C4—P1i | −56.00 (16) |
Symmetry code: (i) −x, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···Cl3ii | 0.99 | 2.93 | 3.8486 (19) | 155 |
C14—H14···Cl1iii | 0.95 | 2.87 | 3.686 (2) | 145 |
C13—H13···Br1iv | 0.95 | 2.99 | 3.773 (2) | 141 |
C2—H2B···Br1v | 0.99 | 2.79 | 3.7553 (18) | 166 |
C4—H4B···Br1v | 0.99 | 2.75 | 3.6757 (18) | 157 |
C1—H1A···Br1vi | 0.99 | 2.86 | 3.7443 (19) | 149 |
Symmetry codes: (ii) x+1/2, −y+1/2, z+1/2; (iii) −x+1/2, −y+1/2, −z; (iv) −x+1/2, −y+1/2, −z+1; (v) −x, −y, −z+1; (vi) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C32H36P22+·2Br−·2CDCl3 |
Mr | 883.08 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 133 |
a, b, c (Å) | 16.2692 (10), 17.5649 (10), 13.9110 (8) |
β (°) | 112.350 (3) |
V (Å3) | 3676.7 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.75 |
Crystal size (mm) | 0.38 × 0.30 × 0.29 |
Data collection | |
Diffractometer | Bruker SMART1000 CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.360, 0.502 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 37985, 5373, 4684 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.704 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.083, 1.05 |
No. of reflections | 5373 |
No. of parameters | 200 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.52, −1.05 |
Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP (Siemens, 2000).
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···Cl3ii | 0.99 | 2.93 | 3.8486 (19) | 155 |
C14—H14···Cl1iii | 0.95 | 2.87 | 3.686 (2) | 145 |
C13—H13···Br1iv | 0.95 | 2.99 | 3.773 (2) | 141 |
C2—H2B···Br1v | 0.99 | 2.79 | 3.7553 (18) | 166 |
C4—H4B···Br1v | 0.99 | 2.75 | 3.6757 (18) | 157 |
C1—H1A···Br1vi | 0.99 | 2.86 | 3.7443 (19) | 149 |
Symmetry codes: (ii) x+1/2, −y+1/2, z+1/2; (iii) −x+1/2, −y+1/2, −z; (iv) −x+1/2, −y+1/2, −z+1; (v) −x, −y, −z+1; (vi) x, y, z−1. |
Similar to the homologue structures known in the literature (Brown & Trefonas, 1972; Matt et al., 1996; Duraczynska & Nelson, 2005) the diphosphonium ring, in the title compound, (I), which sits on a crystallographic center of symmetry, is in a chair conformation with the torsion angles of 52.58 (17)° (C4i—P—C3—C4) and -56.00 (16)° (P—C3—C4—Pi) (i: -x,-y,-z). Each phosphorus atom has two benzyl groups attached, one of which is equatorial and the other axial. The mean P—C bond distance in (I) of 1.80 (18) Å is in accordance with the reported data for other cyclic diphosphonium salts. The P atom in (I) displays a slightly distorted tetrahedral geometry with C—P—C angles ranging from 106.61 (8)° to 113.65 (8)°. The C2—P1—C1 angle is intermediate between that of phenyl (Brown & Trefonas, 1972; Matt et al., 1996) and cyclohexyl substituted derivatives (Duraczynska & Nelson, 2005). The phenyl rings are tilted to each other with an angle of 47.42 (10)°.
Unlike the phenyl analog (Matt et al., 1996), the packing for (I) is consolidated by weak C—H···Cl and C—H···Br interactions (Table 1), linking the dication, the anions, and the deuterated solvent molecule.