organic compounds
[4-(Bromomethyl)benzyl]triphenylphosphonium bromide acetonitrile monosolvate
aDepartment of Chemistry, University of Hull, Hull, HU6 7RX, UK
*Correspondence e-mail: s.j.archibald@hull.ac.uk
In the title compound, C26H23BrP+·Br−·C2H3N, the dihedral angles between the plane of the benzylic phenyl ring attached to the P atom and the planes of the three directly attached phenyl rings are 34.04 (12), 45.48 (13) and 87.18 (9)°. In the crystal, centrosymmetric pairs of cations and anions are linked into dimeric aggregates via C—H⋯Br hydrogen bonds. There is also a C—H⋯N hydrogen bond to the acetonitrile solvent molecule.
Related literature
For background to the biological activity of alkyltriphenylphosphonium derivatives, see: Modica-Napolitano & Aprille (2001); Modica-Napolitano & Singh (2002); Wang et al. (2007); Kim et al. (2008, 2012); Madar et al. (2007). For the synthesis of triphenylphosphonium salts, see: Wang et al. (2007).
Experimental
Crystal data
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Refinement
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Data collection: X-AREA (Stoe & Cie, 2002); cell X-AREA; data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 and WinGX (Farrugia, 1999).
Supporting information
10.1107/S1600536812042341/rz5012sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812042341/rz5012Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812042341/rz5012Isup3.cdx
Supporting information file. DOI: 10.1107/S1600536812042341/rz5012Isup4.cml
The synthetic procedure was completed following literature methods (Wang et al., 2007). Triphenylphosphine (2 g, 7.73 mmol) in toluene (25 ml) was added dropwise to a stirred solution of α,α-dibromo-p-xylene (2.01 g, 7.73 mmol) in toluene (25 ml). The mixture was heated under reflux for 18 h. The reaction was cooled to room temperature, filtered and washed with toluene (20 ml) and diethyl ether (20 ml) to as a white solid (3.35 g, 82%). 1H-NMR (CDCl3): δ 4.39 (s, 2H, CH2—Br), 5.48 (d, 2H, CH2—P, J = 14.7 Hz), 7.10 (s, 4H, CH—Ar), 7.61 (m, 6H, CH—Ar), 7.76 (m, 9H, CH—Ar). 13C-NMR (CDCl3): δ 30.22 (CH2—P), 30.68 (CH2—P), 32.98 (CH2—P), 117.35 (CH—Ar), 118.21 (CH—Ar), 127.75 (C—Ar), 127.83 (C—Ar), 129.48 (CH—Ar), 130.18 (CH—Ar), 130.30 (CH—Ar), 132.10 (CH—Ar), 134.56 (CH—Ar), 135.09 (CH—Ar), 138.17 (C—Ar). 31P-NMR (CDCl3): δ 24.09 (s, PPh3). The crystals were grown by vapour diffusion of diethyl ether into an acetonitrile solution of the title compound at room temperature.
All H atoms were positioned geometrically and treated as riding, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms, with C—H = 0.99 Å and Uiso(H) = 1.2Ueq(C) for methylene H atoms and with C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C) for methyl H atoms.
Data collection: X-AREA (Stoe & Cie, 2002); cell
X-AREA (Stoe & Cie, 2002); data reduction: X-RED (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1999).C26H23BrP·Br·C2H3N | Z = 2 |
Mr = 567.29 | F(000) = 572 |
Triclinic, P1 | Dx = 1.481 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.588 (2) Å | Cell parameters from 8439 reflections |
b = 12.333 (3) Å | θ = 2.5–31.3° |
c = 12.393 (3) Å | µ = 3.26 mm−1 |
α = 74.961 (19)° | T = 150 K |
β = 70.051 (18)° | Block, colourless |
γ = 69.293 (19)° | 0.2 × 0.2 × 0.1 mm |
V = 1272.4 (5) Å3 |
Stoe IPDSII diffractometer | 4473 independent reflections |
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | 2659 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.069 |
Detector resolution: 6.67 pixels mm-1 | θmax = 25.0°, θmin = 2.5° |
rotation method scans | h = −11→11 |
Absorption correction: integration (X-AREA; Stoe & Cie, 2002) | k = −14→14 |
Tmin = 0.336, Tmax = 0.661 | l = −14→14 |
9761 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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.051 | H-atom parameters constrained |
S = 0.68 | w = 1/[σ2(Fo2) + (0.006P)2] where P = (Fo2 + 2Fc2)/3 |
4473 reflections | (Δ/σ)max = 0.001 |
290 parameters | Δρmax = 0.41 e Å−3 |
0 restraints | Δρmin = −0.36 e Å−3 |
C26H23BrP·Br·C2H3N | γ = 69.293 (19)° |
Mr = 567.29 | V = 1272.4 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.588 (2) Å | Mo Kα radiation |
b = 12.333 (3) Å | µ = 3.26 mm−1 |
c = 12.393 (3) Å | T = 150 K |
α = 74.961 (19)° | 0.2 × 0.2 × 0.1 mm |
β = 70.051 (18)° |
Stoe IPDSII diffractometer | 4473 independent reflections |
Absorption correction: integration (X-AREA; Stoe & Cie, 2002) | 2659 reflections with I > 2σ(I) |
Tmin = 0.336, Tmax = 0.661 | Rint = 0.069 |
9761 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.051 | H-atom parameters constrained |
S = 0.68 | Δρmax = 0.41 e Å−3 |
4473 reflections | Δρmin = −0.36 e Å−3 |
290 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 | −0.52982 (5) | 1.49983 (4) | 0.20248 (4) | 0.04070 (13) | |
P1 | 0.06715 (11) | 0.85342 (8) | 0.29654 (7) | 0.0195 (2) | |
C1 | −0.3828 (5) | 1.3828 (3) | 0.1005 (3) | 0.0329 (9) | |
H1A | −0.4412 | 1.3555 | 0.0661 | 0.04* | |
H1B | −0.3108 | 1.4201 | 0.0363 | 0.04* | |
C2 | −0.2931 (4) | 1.2814 (3) | 0.1680 (3) | 0.0236 (8) | |
C3 | −0.1400 (5) | 1.2690 (3) | 0.1579 (3) | 0.0294 (9) | |
H3 | −0.0933 | 1.3272 | 0.1085 | 0.035* | |
C4 | −0.0535 (4) | 1.1727 (3) | 0.2190 (3) | 0.0241 (8) | |
H4 | 0.0523 | 1.1643 | 0.2091 | 0.029* | |
C5 | −0.1216 (4) | 1.0885 (3) | 0.2945 (3) | 0.0218 (8) | |
C6 | −0.2768 (4) | 1.1031 (3) | 0.3071 (3) | 0.0217 (8) | |
H6 | −0.3252 | 1.0469 | 0.3593 | 0.026* | |
C7 | −0.3611 (4) | 1.1972 (3) | 0.2453 (3) | 0.0251 (8) | |
H7 | −0.4668 | 1.2053 | 0.2552 | 0.03* | |
C8 | −0.0296 (4) | 0.9850 (3) | 0.3620 (3) | 0.0227 (8) | |
H8A | −0.1004 | 0.9652 | 0.4387 | 0.027* | |
H8B | 0.0498 | 1.0093 | 0.3762 | 0.027* | |
C9 | 0.2092 (4) | 0.8782 (3) | 0.1619 (3) | 0.0204 (8) | |
C10 | 0.3660 (4) | 0.8213 (3) | 0.1497 (3) | 0.0244 (8) | |
H10 | 0.3989 | 0.7697 | 0.2138 | 0.029* | |
C11 | 0.4742 (5) | 0.8391 (3) | 0.0450 (3) | 0.0318 (9) | |
H11 | 0.5812 | 0.7988 | 0.0362 | 0.038* | |
C12 | 0.4249 (5) | 0.9165 (3) | −0.0472 (3) | 0.0302 (9) | |
H12 | 0.4989 | 0.9296 | −0.1194 | 0.036* | |
C13 | 0.2709 (5) | 0.9743 (3) | −0.0353 (3) | 0.0309 (9) | |
H13 | 0.2387 | 1.0275 | −0.099 | 0.037* | |
C14 | 0.1624 (4) | 0.9557 (3) | 0.0685 (3) | 0.0244 (8) | |
H14 | 0.0555 | 0.9957 | 0.0763 | 0.029* | |
C15 | 0.1567 (4) | 0.7414 (3) | 0.3975 (3) | 0.0198 (8) | |
C16 | 0.1466 (4) | 0.6276 (3) | 0.4163 (3) | 0.0264 (9) | |
H16 | 0.0899 | 0.6102 | 0.3767 | 0.032* | |
C17 | 0.2181 (5) | 0.5399 (3) | 0.4921 (3) | 0.0320 (9) | |
H17 | 0.2102 | 0.4627 | 0.5047 | 0.038* | |
C18 | 0.3018 (4) | 0.5651 (3) | 0.5497 (3) | 0.0290 (9) | |
H18 | 0.3519 | 0.5049 | 0.6014 | 0.035* | |
C19 | 0.3122 (5) | 0.6764 (3) | 0.5322 (3) | 0.0269 (9) | |
H19 | 0.3684 | 0.6931 | 0.5728 | 0.032* | |
C20 | 0.2417 (4) | 0.7656 (3) | 0.4559 (3) | 0.0251 (8) | |
H20 | 0.251 | 0.8423 | 0.4435 | 0.03* | |
C21 | −0.0684 (4) | 0.8008 (3) | 0.2692 (3) | 0.0225 (8) | |
C22 | −0.0205 (4) | 0.7420 (3) | 0.1738 (3) | 0.0287 (9) | |
H22 | 0.0792 | 0.736 | 0.1202 | 0.034* | |
C23 | −0.1217 (5) | 0.6925 (3) | 0.1590 (3) | 0.0352 (10) | |
H23 | −0.0903 | 0.6515 | 0.0955 | 0.042* | |
C24 | −0.2656 (5) | 0.7026 (3) | 0.2355 (3) | 0.0351 (10) | |
H24 | −0.3341 | 0.6695 | 0.2239 | 0.042* | |
C25 | −0.3130 (5) | 0.7606 (3) | 0.3295 (3) | 0.0348 (10) | |
H25 | −0.4137 | 0.7676 | 0.3817 | 0.042* | |
C26 | −0.2129 (4) | 0.8083 (3) | 0.3474 (3) | 0.0269 (9) | |
H26 | −0.2438 | 0.846 | 0.4131 | 0.032* | |
N1 | 0.1911 (5) | 0.4067 (4) | 0.0535 (4) | 0.0620 (12) | |
C27 | 0.1653 (5) | 0.3903 (4) | 0.1509 (4) | 0.0397 (11) | |
C28 | 0.1253 (6) | 0.3696 (4) | 0.2764 (4) | 0.0597 (14) | |
H28A | 0.0123 | 0.3888 | 0.3079 | 0.089* | |
H28B | 0.1638 | 0.419 | 0.3028 | 0.089* | |
H28C | 0.1726 | 0.2868 | 0.3037 | 0.089* | |
Br2 | 0.31729 (5) | 0.05853 (4) | 0.36399 (3) | 0.03526 (12) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0414 (3) | 0.0292 (3) | 0.0486 (3) | 0.0017 (2) | −0.0175 (2) | −0.0113 (2) |
P1 | 0.0172 (5) | 0.0218 (5) | 0.0185 (5) | −0.0050 (4) | −0.0032 (4) | −0.0050 (4) |
C1 | 0.039 (3) | 0.031 (2) | 0.024 (2) | −0.006 (2) | −0.0057 (18) | −0.0067 (17) |
C2 | 0.025 (2) | 0.022 (2) | 0.0220 (18) | −0.0026 (18) | −0.0049 (16) | −0.0094 (16) |
C3 | 0.038 (3) | 0.027 (2) | 0.025 (2) | −0.017 (2) | −0.0027 (18) | −0.0034 (17) |
C4 | 0.017 (2) | 0.030 (2) | 0.0236 (19) | −0.0083 (18) | 0.0004 (15) | −0.0063 (17) |
C5 | 0.023 (2) | 0.018 (2) | 0.0249 (19) | −0.0045 (17) | −0.0050 (16) | −0.0086 (15) |
C6 | 0.024 (2) | 0.019 (2) | 0.0227 (18) | −0.0099 (17) | −0.0035 (16) | −0.0041 (15) |
C7 | 0.022 (2) | 0.021 (2) | 0.032 (2) | −0.0027 (18) | −0.0074 (17) | −0.0092 (17) |
C8 | 0.025 (2) | 0.021 (2) | 0.0215 (18) | −0.0082 (18) | −0.0031 (16) | −0.0049 (16) |
C9 | 0.018 (2) | 0.023 (2) | 0.0218 (18) | −0.0050 (17) | −0.0056 (15) | −0.0085 (15) |
C10 | 0.021 (2) | 0.027 (2) | 0.0236 (19) | −0.0053 (17) | −0.0071 (16) | −0.0015 (16) |
C11 | 0.022 (2) | 0.038 (3) | 0.033 (2) | −0.0071 (19) | −0.0012 (17) | −0.0119 (19) |
C12 | 0.035 (3) | 0.036 (2) | 0.0193 (19) | −0.017 (2) | 0.0005 (17) | −0.0064 (17) |
C13 | 0.042 (3) | 0.030 (2) | 0.0192 (19) | −0.010 (2) | −0.0091 (18) | −0.0004 (17) |
C14 | 0.020 (2) | 0.030 (2) | 0.0204 (18) | −0.0045 (18) | −0.0034 (16) | −0.0068 (16) |
C15 | 0.017 (2) | 0.021 (2) | 0.0167 (17) | −0.0030 (16) | 0.0007 (14) | −0.0062 (14) |
C16 | 0.027 (2) | 0.030 (2) | 0.0215 (19) | −0.0077 (19) | −0.0064 (17) | −0.0056 (16) |
C17 | 0.037 (3) | 0.021 (2) | 0.035 (2) | −0.007 (2) | −0.0100 (19) | −0.0015 (18) |
C18 | 0.022 (2) | 0.028 (2) | 0.0245 (19) | 0.0061 (18) | −0.0072 (17) | −0.0014 (17) |
C19 | 0.022 (2) | 0.032 (2) | 0.024 (2) | −0.0021 (18) | −0.0066 (17) | −0.0071 (17) |
C20 | 0.026 (2) | 0.023 (2) | 0.0250 (19) | −0.0064 (18) | −0.0065 (16) | −0.0043 (16) |
C21 | 0.023 (2) | 0.023 (2) | 0.0210 (18) | −0.0058 (17) | −0.0085 (16) | −0.0008 (15) |
C22 | 0.029 (2) | 0.034 (2) | 0.0248 (19) | −0.0103 (19) | −0.0040 (17) | −0.0099 (17) |
C23 | 0.046 (3) | 0.037 (3) | 0.032 (2) | −0.017 (2) | −0.016 (2) | −0.0062 (19) |
C24 | 0.034 (3) | 0.031 (3) | 0.046 (3) | −0.013 (2) | −0.021 (2) | 0.002 (2) |
C25 | 0.025 (2) | 0.033 (2) | 0.046 (2) | −0.013 (2) | −0.0068 (19) | −0.004 (2) |
C26 | 0.024 (2) | 0.022 (2) | 0.031 (2) | −0.0029 (18) | −0.0049 (17) | −0.0075 (17) |
N1 | 0.060 (3) | 0.072 (3) | 0.065 (3) | −0.033 (3) | −0.010 (2) | −0.020 (2) |
C27 | 0.033 (3) | 0.039 (3) | 0.051 (3) | −0.016 (2) | −0.002 (2) | −0.020 (2) |
C28 | 0.065 (4) | 0.063 (4) | 0.053 (3) | −0.026 (3) | −0.003 (3) | −0.021 (3) |
Br2 | 0.0345 (3) | 0.0474 (3) | 0.0261 (2) | −0.0247 (2) | 0.00201 (18) | −0.0056 (2) |
Br1—C1 | 1.990 (4) | C13—H13 | 0.95 |
P1—C15 | 1.791 (3) | C14—H14 | 0.95 |
P1—C9 | 1.792 (3) | C15—C16 | 1.394 (4) |
P1—C21 | 1.800 (3) | C15—C20 | 1.401 (4) |
P1—C8 | 1.805 (3) | C16—C17 | 1.382 (5) |
C1—C2 | 1.480 (5) | C16—H16 | 0.95 |
C1—H1A | 0.99 | C17—C18 | 1.391 (5) |
C1—H1B | 0.99 | C17—H17 | 0.95 |
C2—C3 | 1.386 (5) | C18—C19 | 1.367 (5) |
C2—C7 | 1.400 (5) | C18—H18 | 0.95 |
C3—C4 | 1.392 (5) | C19—C20 | 1.390 (5) |
C3—H3 | 0.95 | C19—H19 | 0.95 |
C4—C5 | 1.392 (5) | C20—H20 | 0.95 |
C4—H4 | 0.95 | C21—C26 | 1.381 (5) |
C5—C6 | 1.393 (5) | C21—C22 | 1.405 (4) |
C5—C8 | 1.504 (5) | C22—C23 | 1.394 (5) |
C6—C7 | 1.373 (5) | C22—H22 | 0.95 |
C6—H6 | 0.95 | C23—C24 | 1.366 (5) |
C7—H7 | 0.95 | C23—H23 | 0.95 |
C8—H8A | 0.99 | C24—C25 | 1.384 (5) |
C8—H8B | 0.99 | C24—H24 | 0.95 |
C9—C10 | 1.389 (5) | C25—C26 | 1.388 (5) |
C9—C14 | 1.390 (4) | C25—H25 | 0.95 |
C10—C11 | 1.379 (5) | C26—H26 | 0.95 |
C10—H10 | 0.95 | N1—C27 | 1.123 (5) |
C11—C12 | 1.387 (5) | C27—C28 | 1.446 (6) |
C11—H11 | 0.95 | C28—H28A | 0.98 |
C12—C13 | 1.369 (5) | C28—H28B | 0.98 |
C12—H12 | 0.95 | C28—H28C | 0.98 |
C13—C14 | 1.375 (5) | ||
C15—P1—C9 | 110.46 (16) | C12—C13—H13 | 119.9 |
C15—P1—C21 | 107.13 (16) | C14—C13—H13 | 119.9 |
C9—P1—C21 | 108.45 (15) | C13—C14—C9 | 120.0 (4) |
C15—P1—C8 | 108.01 (14) | C13—C14—H14 | 120 |
C9—P1—C8 | 111.25 (16) | C9—C14—H14 | 120 |
C21—P1—C8 | 111.47 (17) | C16—C15—C20 | 119.0 (3) |
C2—C1—Br1 | 110.4 (2) | C16—C15—P1 | 120.2 (2) |
C2—C1—H1A | 109.6 | C20—C15—P1 | 120.7 (3) |
Br1—C1—H1A | 109.6 | C17—C16—C15 | 120.7 (3) |
C2—C1—H1B | 109.6 | C17—C16—H16 | 119.6 |
Br1—C1—H1B | 109.6 | C15—C16—H16 | 119.6 |
H1A—C1—H1B | 108.1 | C16—C17—C18 | 119.7 (3) |
C3—C2—C7 | 118.2 (3) | C16—C17—H17 | 120.2 |
C3—C2—C1 | 120.6 (3) | C18—C17—H17 | 120.2 |
C7—C2—C1 | 121.2 (3) | C19—C18—C17 | 120.1 (3) |
C2—C3—C4 | 121.1 (3) | C19—C18—H18 | 119.9 |
C2—C3—H3 | 119.5 | C17—C18—H18 | 119.9 |
C4—C3—H3 | 119.5 | C18—C19—C20 | 121.0 (3) |
C3—C4—C5 | 120.2 (3) | C18—C19—H19 | 119.5 |
C3—C4—H4 | 119.9 | C20—C19—H19 | 119.5 |
C5—C4—H4 | 119.9 | C19—C20—C15 | 119.5 (3) |
C4—C5—C6 | 118.6 (3) | C19—C20—H20 | 120.3 |
C4—C5—C8 | 120.5 (3) | C15—C20—H20 | 120.3 |
C6—C5—C8 | 120.9 (3) | C26—C21—C22 | 120.3 (3) |
C7—C6—C5 | 121.0 (3) | C26—C21—P1 | 120.1 (3) |
C7—C6—H6 | 119.5 | C22—C21—P1 | 119.3 (3) |
C5—C6—H6 | 119.5 | C23—C22—C21 | 118.9 (3) |
C6—C7—C2 | 120.8 (3) | C23—C22—H22 | 120.5 |
C6—C7—H7 | 119.6 | C21—C22—H22 | 120.5 |
C2—C7—H7 | 119.6 | C24—C23—C22 | 120.3 (3) |
C5—C8—P1 | 116.8 (2) | C24—C23—H23 | 119.9 |
C5—C8—H8A | 108.1 | C22—C23—H23 | 119.9 |
P1—C8—H8A | 108.1 | C23—C24—C25 | 120.9 (3) |
C5—C8—H8B | 108.1 | C23—C24—H24 | 119.6 |
P1—C8—H8B | 108.1 | C25—C24—H24 | 119.6 |
H8A—C8—H8B | 107.3 | C24—C25—C26 | 119.9 (4) |
C10—C9—C14 | 119.4 (3) | C24—C25—H25 | 120.1 |
C10—C9—P1 | 120.8 (3) | C26—C25—H25 | 120.1 |
C14—C9—P1 | 119.8 (3) | C21—C26—C25 | 119.7 (3) |
C11—C10—C9 | 120.4 (3) | C21—C26—H26 | 120.1 |
C11—C10—H10 | 119.8 | C25—C26—H26 | 120.1 |
C9—C10—H10 | 119.8 | N1—C27—C28 | 177.5 (5) |
C10—C11—C12 | 119.2 (4) | C27—C28—H28A | 109.5 |
C10—C11—H11 | 120.4 | C27—C28—H28B | 109.5 |
C12—C11—H11 | 120.4 | H28A—C28—H28B | 109.5 |
C13—C12—C11 | 120.7 (4) | C27—C28—H28C | 109.5 |
C13—C12—H12 | 119.6 | H28A—C28—H28C | 109.5 |
C11—C12—H12 | 119.6 | H28B—C28—H28C | 109.5 |
C12—C13—C14 | 120.3 (3) | ||
Br1—C1—C2—C3 | −104.0 (3) | P1—C9—C14—C13 | −179.5 (2) |
Br1—C1—C2—C7 | 74.5 (3) | C9—P1—C15—C16 | −101.6 (3) |
C7—C2—C3—C4 | 2.8 (5) | C21—P1—C15—C16 | 16.3 (3) |
C1—C2—C3—C4 | −178.6 (3) | C8—P1—C15—C16 | 136.5 (3) |
C2—C3—C4—C5 | −2.0 (5) | C9—P1—C15—C20 | 76.4 (3) |
C3—C4—C5—C6 | 0.1 (5) | C21—P1—C15—C20 | −165.6 (3) |
C3—C4—C5—C8 | −179.2 (3) | C8—P1—C15—C20 | −45.4 (3) |
C4—C5—C6—C7 | 1.0 (5) | C20—C15—C16—C17 | 0.5 (5) |
C8—C5—C6—C7 | −179.7 (3) | P1—C15—C16—C17 | 178.6 (3) |
C5—C6—C7—C2 | −0.1 (5) | C15—C16—C17—C18 | −0.3 (6) |
C3—C2—C7—C6 | −1.8 (5) | C16—C17—C18—C19 | 0.5 (6) |
C1—C2—C7—C6 | 179.7 (3) | C17—C18—C19—C20 | −0.9 (6) |
C4—C5—C8—P1 | −92.4 (3) | C18—C19—C20—C15 | 1.0 (6) |
C6—C5—C8—P1 | 88.4 (4) | C16—C15—C20—C19 | −0.8 (5) |
C15—P1—C8—C5 | −176.2 (3) | P1—C15—C20—C19 | −178.9 (3) |
C9—P1—C8—C5 | 62.4 (3) | C15—P1—C21—C26 | 80.5 (3) |
C21—P1—C8—C5 | −58.8 (3) | C9—P1—C21—C26 | −160.3 (3) |
C15—P1—C9—C10 | −5.0 (3) | C8—P1—C21—C26 | −37.5 (3) |
C21—P1—C9—C10 | −122.1 (3) | C15—P1—C21—C22 | −93.5 (3) |
C8—P1—C9—C10 | 114.9 (3) | C9—P1—C21—C22 | 25.8 (3) |
C15—P1—C9—C14 | 175.2 (3) | C8—P1—C21—C22 | 148.6 (3) |
C21—P1—C9—C14 | 58.1 (3) | C26—C21—C22—C23 | 0.6 (5) |
C8—P1—C9—C14 | −64.9 (3) | P1—C21—C22—C23 | 174.5 (3) |
C14—C9—C10—C11 | −1.5 (5) | C21—C22—C23—C24 | 0.9 (6) |
P1—C9—C10—C11 | 178.7 (2) | C22—C23—C24—C25 | −0.9 (6) |
C9—C10—C11—C12 | 1.4 (5) | C23—C24—C25—C26 | −0.5 (6) |
C10—C11—C12—C13 | −0.4 (5) | C22—C21—C26—C25 | −1.9 (6) |
C11—C12—C13—C14 | −0.4 (5) | P1—C21—C26—C25 | −175.8 (3) |
C12—C13—C14—C9 | 0.3 (5) | C24—C25—C26—C21 | 1.9 (6) |
C10—C9—C14—C13 | 0.7 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···N1i | 0.99 | 2.60 | 3.488 (6) | 150 |
C8—H8A···Br2ii | 0.99 | 2.64 | 3.625 (4) | 172 |
C8—H8B···Br2iii | 0.99 | 2.79 | 3.753 (3) | 166 |
C20—H20···Br2iii | 0.95 | 2.81 | 3.746 (4) | 169 |
C28—H28C···Br2 | 0.98 | 2.69 | 3.673 (5) | 176 |
Symmetry codes: (i) −x, −y+2, −z; (ii) −x, −y+1, −z+1; (iii) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C26H23BrP·Br·C2H3N |
Mr | 567.29 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 9.588 (2), 12.333 (3), 12.393 (3) |
α, β, γ (°) | 74.961 (19), 70.051 (18), 69.293 (19) |
V (Å3) | 1272.4 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.26 |
Crystal size (mm) | 0.2 × 0.2 × 0.1 |
Data collection | |
Diffractometer | Stoe IPDSII diffractometer |
Absorption correction | Integration (X-AREA; Stoe & Cie, 2002) |
Tmin, Tmax | 0.336, 0.661 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9761, 4473, 2659 |
Rint | 0.069 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.051, 0.68 |
No. of reflections | 4473 |
No. of parameters | 290 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.41, −0.36 |
Computer programs: X-AREA (Stoe & Cie, 2002), X-RED (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and WinGX (Farrugia, 1999).
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···N1i | 0.99 | 2.60 | 3.488 (6) | 149.6 |
C8—H8A···Br2ii | 0.99 | 2.64 | 3.625 (4) | 171.9 |
C8—H8B···Br2iii | 0.99 | 2.79 | 3.753 (3) | 165.8 |
C20—H20···Br2iii | 0.95 | 2.81 | 3.746 (4) | 168.7 |
C28—H28C···Br2 | 0.98 | 2.69 | 3.673 (5) | 176.0 |
Symmetry codes: (i) −x, −y+2, −z; (ii) −x, −y+1, −z+1; (iii) x, y+1, z. |
Acknowledgements
We acknowledge the EPSRC for funds which enabled the purchase of the Stoe IPDSII diffractometer. We thank the University of Hull for the provision of a scholarship for BPB and the Nuffield Foundation for sponsorship of PG via the CREST programme. We acknowledge the use of the EPSRC's Chemical Database Service at Daresbury (Fletcher et al., 1996).
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Triphenylphosphonium cations are known to accumulate in cancer cell mitochondria due to a significant increase in mitochondrial transmembrane potential between normal epithelial cells and carcinoma cells, causing a potential tenfold higher accumulation of cationic compounds in carcinoma cells (Modica-Napolitano et al., 2001; Modica-Napolitano et al., 2002). Increase in uptake in myocardial cells also gives the potential for use as heart targeting agents (Kim et al., 2012). (4-Bromomethylbenzyl)triphenylphosphonium bromide has been used as a precursor to synthesize a 64Cu radiolabelled molecule for potential cancer detection by positron emission tomography (Wang et al., 2007). Related compounds have also been radiolabelled with the 18F isotope (Kim et al., 2012; Madar et al., 2007).
In the cation of the title compound (Fig. 1), the dihedral angles formed by the C2–C7 benzene ring with the C9–C14, C15–C20 and C21–C26 phenyl rings are 34.04 (12), 45.48 (13) and 87.18 (9)°, respectively. In the crystal (Fig. 2), centrosymmetric pairs of ions are linked through C—H···Br hydrogen bonds (Table 1). The dimeric aggregates interact with the acetonitrile solvent molecules by C—H···N hydrogen bonds.