organic compounds
(Furfurylamino)triphenylphosphonium bromide
aCentro de Investigaciones Químicas, Universidad Autónoma del Estado de Morelos. Av. Universidad 1001 Col., Chamilpa, CP 62100, Cuernavaca Mor., Mexico, and bDepartamento de Química, Cinvestav México, 07000 Mexico DF, Mexico
*Correspondence e-mail: jeanmichelg@gmail.com
In the title salt, C23H21NOP+·Br−, the dihedral angles between the phenyl rings are 70.41 (18), 73.6 (2) and 80.85 (19)°. In the crystal, neighboring molecules are linked through an N—H⋯Br hydrogen bond and four weak C—H⋯Br contacts, forming a three-dimensional network.
Related literature
For (amino)phosphonium bromides derived from primary et al. (2010); Boubekeur et al. (2006); Dyer et al. (2011); Horner & Oediger (1959). For C—H⋯X hydrogen bonds, see: Jeffrey (1997); Zhang et al. (2003). For graph-set motifs, see: Bernstein, et al. (1995).
see: CaoExperimental
Crystal data
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Refinement
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Data collection: XSCANS (Siemens, 1994); cell XSCANS; data reduction: SAINT-Plus NT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009), publCIF (Westrip, 2010) and DIAMOND (Brandenburg, 2006).
Supporting information
https://doi.org/10.1107/S1600536812050805/is5227sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812050805/is5227Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812050805/is5227Isup3.cml
A mixture of 630 mg of DABCO (5.65 mmol) and 1 ml of furfurylamine (11.31 mmol) in 10 ml of dry benzene was added dropwise through canula between 0 and 5 °C to a stirred suspension of Ph3PBr2 (11.31 mmol) in 20 ml of dry benzene. After 3 h of stirring at ambient temperature, 10 ml of distilled water were added to the medium and the compound extracted with 20 ml of methylene chloride. The organic phase was further washed with 10 ml of water, dried over MgSO4 and all volatiles were eliminated under vacuum. The off white powder obtained was suspended in Et2O and left under stirring overnight. After filtration of the suspension, the solid was crystallized from hot THF giving 4.05 g (81%) of colorless crystals of the title compound, which were suitable for X-ray
analysis and fully characterized by standard analytical methods. 31P NMR (CH2Cl2) 30.03 p.p.m.; m. p. 420 K.H atoms were positioned geometrically and constrained using the riding-model approximation [C—Haryl = 0.93 Å, Uiso(Haryl)= 1.2 Ueq(C); C—Hmethylene = 0.97 Å, Uiso(Hmethylene) = 1.2Ueq(C)]. The hydrogen atom bonded to N1 was located in a difference Fourier map. Its coordinates were refined with a distance restraint N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq(N).
Aminophosphonium salts are important species because of their reactivity and their role as intermediates in numerous organophosphorus reactions. For instance, aminophosphonium derived from primary amine are key intermediates in the preparation of iminophosphoranes through the Horner-Oediger reaction (Horner & Oediger, 1959). Apart from their use in the aza-Wittig reaction, this class of compounds became very important ligands during the past few years due to their good activity in various catalytic processes when coordinated to transition metals (Dyer et al., 2011). Here we report the structure of the (furfurylamino) triphenylphosphonium bromide obtained as an intermediate during the synthesis of the corresponding iminophosphorane.
In the
neighboring molecules are linked through an N—H···Br hydrogen bond and four weak C—H···Br contacts (Jeffrey, 1997; Zhang, et al., 2003; Table 1), forming a three-dimensional network. In the hydrogen-bond pattern, the C—H···Br contacts form corrugated sheets. These sheets are composed of R24(12), R24(18), R24(22) and R24(24) graph set motifs (Bernstein, et al. 1995; Fig. 2). Neighboring sheets are further linked by N—H···Br hydrogen bonds, generating the three-dimensional network.For related literature with (amino)phosphonium bromides derived from primary
see: Cao et al. (2010); Boubekeur et al. (2006); Dyer et al. (2011); Horner & Oediger (1959). For C—H···X hydrogen bonds, see: Jeffrey (1997); Zhang et al. (2003). For graph-set motifs, see: Bernstein, et al. (1995).Data collection: XSCANS (Siemens, 1994); cell
XSCANS (Siemens, 1994); data reduction: SAINT-Plus NT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2009), publCIF (Westrip, 2010) and DIAMOND (Brandenburg, 2006).Fig. 1. The molecular structure of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radius. | |
Fig. 2. A view of the C—H···Br interactions (dashed lines), showing the R24(12), R24(18), R24(22) and R24(24) graph set motifs. The furfuryl group and hydrogen atoms not involved in hydrogen bonding have been omitted for clarity. |
C23H21NOP+·Br− | Z = 2 |
Mr = 438.29 | F(000) = 448 |
Triclinic, P1 | Dx = 1.388 Mg m−3 |
Hall symbol: -P 1 | Melting point: 420 K |
a = 9.5190 (19) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.812 (2) Å | Cell parameters from 3600 reflections |
c = 12.726 (3) Å | θ = 4.2–30° |
α = 110.30 (3)° | µ = 2.05 mm−1 |
β = 104.89 (3)° | T = 293 K |
γ = 96.81 (3)° | Plate, colourless |
V = 1048.7 (4) Å3 | 0.20 × 0.17 × 0.13 mm |
Siemens P4 diffractometer | 3673 independent reflections |
Radiation source: fine-focus sealed tube | 3213 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
Detector resolution: 8.3 pixels mm-1 | θmax = 25.0°, θmin = 4.2° |
ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −11→11 |
Tmin = 0.685, Tmax = 0.777 | l = −15→15 |
11498 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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.129 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.1P)2 + 0.001P] where P = (Fo2 + 2Fc2)/3 |
3673 reflections | (Δ/σ)max = 0.001 |
247 parameters | Δρmax = 0.32 e Å−3 |
1 restraint | Δρmin = −0.46 e Å−3 |
C23H21NOP+·Br− | γ = 96.81 (3)° |
Mr = 438.29 | V = 1048.7 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.5190 (19) Å | Mo Kα radiation |
b = 9.812 (2) Å | µ = 2.05 mm−1 |
c = 12.726 (3) Å | T = 293 K |
α = 110.30 (3)° | 0.20 × 0.17 × 0.13 mm |
β = 104.89 (3)° |
Siemens P4 diffractometer | 3673 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3213 reflections with I > 2σ(I) |
Tmin = 0.685, Tmax = 0.777 | Rint = 0.046 |
11498 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 1 restraint |
wR(F2) = 0.129 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.32 e Å−3 |
3673 reflections | Δρmin = −0.46 e Å−3 |
247 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 | −0.09719 (3) | 0.34393 (3) | 0.15232 (3) | 0.05548 (17) | |
C1 | 0.3290 (6) | 0.1167 (5) | 0.0155 (5) | 0.0990 (16) | |
H1 | 0.3038 | 0.0160 | 0.0015 | 0.119* | |
C2 | 0.4595 (5) | 0.1890 (6) | 0.0228 (4) | 0.0888 (13) | |
H2 | 0.5425 | 0.1495 | 0.0163 | 0.107* | |
C3 | 0.4491 (4) | 0.3371 (4) | 0.0425 (3) | 0.0671 (9) | |
H3 | 0.5230 | 0.4131 | 0.0485 | 0.081* | |
C4 | 0.3156 (4) | 0.3483 (3) | 0.0509 (3) | 0.0562 (8) | |
C5 | 0.2489 (4) | 0.4800 (4) | 0.0737 (3) | 0.0582 (8) | |
H5A | 0.3108 | 0.5592 | 0.0654 | 0.070* | |
H5B | 0.1508 | 0.4539 | 0.0157 | 0.070* | |
C6 | 0.4994 (3) | 0.7451 (3) | 0.2917 (2) | 0.0435 (6) | |
C7 | 0.5865 (4) | 0.6410 (3) | 0.2895 (3) | 0.0564 (7) | |
H7 | 0.5496 | 0.5515 | 0.2936 | 0.068* | |
C8 | 0.7281 (4) | 0.6699 (4) | 0.2812 (4) | 0.0693 (9) | |
H8 | 0.7861 | 0.5996 | 0.2788 | 0.083* | |
C9 | 0.7826 (4) | 0.8027 (4) | 0.2765 (3) | 0.0690 (10) | |
H9 | 0.8779 | 0.8225 | 0.2711 | 0.083* | |
C10 | 0.6976 (4) | 0.9062 (4) | 0.2797 (3) | 0.0651 (9) | |
H10 | 0.7360 | 0.9963 | 0.2771 | 0.078* | |
C11 | 0.5550 (4) | 0.8782 (3) | 0.2867 (3) | 0.0523 (7) | |
H11 | 0.4973 | 0.9485 | 0.2880 | 0.063* | |
C12 | 0.3181 (3) | 0.6870 (3) | 0.4351 (3) | 0.0447 (6) | |
C13 | 0.1854 (4) | 0.6505 (4) | 0.4558 (3) | 0.0623 (8) | |
H13 | 0.0946 | 0.6267 | 0.3965 | 0.075* | |
C14 | 0.1884 (4) | 0.6497 (4) | 0.5642 (3) | 0.0690 (9) | |
H14 | 0.0992 | 0.6258 | 0.5781 | 0.083* | |
C15 | 0.3221 (4) | 0.6841 (4) | 0.6525 (3) | 0.0638 (9) | |
H15 | 0.3228 | 0.6832 | 0.7255 | 0.077* | |
C16 | 0.4526 (4) | 0.7190 (4) | 0.6332 (3) | 0.0659 (9) | |
H16 | 0.5427 | 0.7420 | 0.6930 | 0.079* | |
C17 | 0.4520 (4) | 0.7205 (4) | 0.5243 (3) | 0.0545 (7) | |
H17 | 0.5418 | 0.7440 | 0.5113 | 0.065* | |
C18 | 0.2227 (3) | 0.8445 (3) | 0.2856 (2) | 0.0443 (6) | |
C19 | 0.2166 (4) | 0.9579 (4) | 0.3855 (3) | 0.0545 (7) | |
H19 | 0.2557 | 0.9558 | 0.4597 | 0.065* | |
C20 | 0.1531 (4) | 1.0735 (4) | 0.3751 (4) | 0.0727 (10) | |
H20 | 0.1491 | 1.1490 | 0.4423 | 0.087* | |
C21 | 0.0956 (4) | 1.0780 (5) | 0.2661 (5) | 0.0790 (12) | |
H21 | 0.0534 | 1.1565 | 0.2591 | 0.095* | |
C22 | 0.1011 (5) | 0.9652 (6) | 0.1673 (4) | 0.0837 (12) | |
H22 | 0.0630 | 0.9685 | 0.0935 | 0.100* | |
C23 | 0.1620 (4) | 0.8474 (4) | 0.1758 (3) | 0.0660 (9) | |
H23 | 0.1621 | 0.7703 | 0.1080 | 0.079* | |
H1A | 0.157 (3) | 0.490 (4) | 0.193 (4) | 0.079* | |
N1 | 0.2354 (3) | 0.5341 (3) | 0.1936 (2) | 0.0576 (7) | |
O1 | 0.2369 (3) | 0.2133 (3) | 0.0317 (3) | 0.0935 (9) | |
P1 | 0.31407 (8) | 0.69765 (8) | 0.29668 (6) | 0.0415 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0476 (2) | 0.0683 (2) | 0.0579 (2) | 0.01512 (15) | 0.02311 (15) | 0.02845 (17) |
C1 | 0.118 (4) | 0.070 (2) | 0.147 (4) | 0.049 (3) | 0.080 (4) | 0.049 (3) |
C2 | 0.078 (3) | 0.106 (3) | 0.085 (3) | 0.041 (3) | 0.038 (2) | 0.026 (2) |
C3 | 0.058 (2) | 0.064 (2) | 0.068 (2) | −0.0066 (16) | 0.0343 (16) | 0.0094 (16) |
C4 | 0.071 (2) | 0.0468 (15) | 0.0448 (16) | 0.0052 (14) | 0.0174 (14) | 0.0147 (13) |
C5 | 0.071 (2) | 0.0541 (17) | 0.0449 (16) | 0.0118 (15) | 0.0177 (14) | 0.0151 (13) |
C6 | 0.0419 (14) | 0.0445 (14) | 0.0417 (14) | 0.0072 (11) | 0.0166 (11) | 0.0128 (11) |
C7 | 0.0508 (17) | 0.0490 (15) | 0.072 (2) | 0.0138 (13) | 0.0261 (14) | 0.0223 (14) |
C8 | 0.0502 (18) | 0.069 (2) | 0.088 (2) | 0.0212 (16) | 0.0285 (17) | 0.0226 (19) |
C9 | 0.0449 (17) | 0.075 (2) | 0.075 (2) | −0.0001 (16) | 0.0280 (16) | 0.0140 (18) |
C10 | 0.058 (2) | 0.0620 (19) | 0.070 (2) | −0.0046 (15) | 0.0287 (17) | 0.0207 (17) |
C11 | 0.0536 (17) | 0.0487 (15) | 0.0551 (17) | 0.0071 (13) | 0.0227 (14) | 0.0187 (13) |
C12 | 0.0485 (16) | 0.0439 (14) | 0.0486 (15) | 0.0119 (11) | 0.0203 (12) | 0.0223 (12) |
C13 | 0.0513 (18) | 0.085 (2) | 0.0552 (18) | 0.0065 (16) | 0.0207 (14) | 0.0328 (17) |
C14 | 0.069 (2) | 0.082 (2) | 0.071 (2) | 0.0107 (18) | 0.0389 (18) | 0.0381 (19) |
C15 | 0.084 (2) | 0.0650 (19) | 0.0555 (18) | 0.0161 (17) | 0.0283 (17) | 0.0353 (16) |
C16 | 0.064 (2) | 0.079 (2) | 0.058 (2) | 0.0146 (17) | 0.0115 (16) | 0.0368 (18) |
C17 | 0.0498 (17) | 0.0644 (18) | 0.0545 (17) | 0.0096 (14) | 0.0173 (13) | 0.0303 (15) |
C18 | 0.0375 (14) | 0.0532 (15) | 0.0461 (15) | 0.0113 (12) | 0.0138 (11) | 0.0234 (13) |
C19 | 0.0508 (17) | 0.0547 (16) | 0.0538 (17) | 0.0143 (13) | 0.0115 (13) | 0.0196 (14) |
C20 | 0.061 (2) | 0.0589 (19) | 0.092 (3) | 0.0228 (16) | 0.0202 (19) | 0.0232 (19) |
C21 | 0.058 (2) | 0.080 (2) | 0.117 (4) | 0.0233 (19) | 0.022 (2) | 0.063 (3) |
C22 | 0.074 (3) | 0.121 (3) | 0.086 (3) | 0.034 (2) | 0.023 (2) | 0.075 (3) |
C23 | 0.064 (2) | 0.092 (2) | 0.0545 (19) | 0.0258 (18) | 0.0226 (16) | 0.0379 (18) |
N1 | 0.0556 (16) | 0.0542 (14) | 0.0539 (15) | −0.0049 (12) | 0.0266 (12) | 0.0099 (12) |
O1 | 0.0757 (18) | 0.0658 (15) | 0.141 (3) | 0.0168 (13) | 0.0499 (18) | 0.0326 (17) |
P1 | 0.0393 (4) | 0.0451 (4) | 0.0424 (4) | 0.0081 (3) | 0.0177 (3) | 0.0171 (3) |
Br1—H1A | 2.49 (2) | C12—C13 | 1.387 (4) |
C1—C2 | 1.319 (7) | C12—P1 | 1.791 (3) |
C1—O1 | 1.365 (5) | C13—C14 | 1.376 (5) |
C1—H1 | 0.9300 | C13—H13 | 0.9300 |
C2—C3 | 1.407 (6) | C14—C15 | 1.377 (6) |
C2—H2 | 0.9300 | C14—H14 | 0.9300 |
C3—C4 | 1.317 (5) | C15—C16 | 1.354 (5) |
C3—H3 | 0.9300 | C15—H15 | 0.9300 |
C4—O1 | 1.350 (4) | C16—C17 | 1.390 (5) |
C4—C5 | 1.479 (5) | C16—H16 | 0.9300 |
C5—N1 | 1.477 (4) | C17—H17 | 0.9300 |
C5—H5A | 0.9700 | C18—C23 | 1.380 (4) |
C5—H5B | 0.9700 | C18—C19 | 1.389 (4) |
C6—C11 | 1.379 (4) | C18—P1 | 1.796 (3) |
C6—C7 | 1.387 (4) | C19—C20 | 1.377 (5) |
C6—P1 | 1.794 (3) | C19—H19 | 0.9300 |
C7—C8 | 1.383 (5) | C20—C21 | 1.372 (6) |
C7—H7 | 0.9300 | C20—H20 | 0.9300 |
C8—C9 | 1.371 (6) | C21—C22 | 1.375 (7) |
C8—H8 | 0.9300 | C21—H21 | 0.9300 |
C9—C10 | 1.368 (6) | C22—C23 | 1.378 (6) |
C9—H9 | 0.9300 | C22—H22 | 0.9300 |
C10—C11 | 1.384 (5) | C23—H23 | 0.9300 |
C10—H10 | 0.9300 | N1—P1 | 1.614 (3) |
C11—H11 | 0.9300 | N1—H1A | 0.817 (19) |
C12—C17 | 1.386 (4) | ||
C2—C1—O1 | 109.1 (4) | C12—C13—H13 | 120.1 |
C2—C1—H1 | 125.4 | C13—C14—C15 | 120.7 (3) |
O1—C1—H1 | 125.4 | C13—C14—H14 | 119.7 |
C1—C2—C3 | 106.9 (4) | C15—C14—H14 | 119.7 |
C1—C2—H2 | 126.5 | C16—C15—C14 | 120.2 (3) |
C3—C2—H2 | 126.5 | C16—C15—H15 | 119.9 |
C4—C3—C2 | 107.4 (3) | C14—C15—H15 | 119.9 |
C4—C3—H3 | 126.3 | C15—C16—C17 | 120.1 (3) |
C2—C3—H3 | 126.3 | C15—C16—H16 | 120.0 |
C3—C4—O1 | 109.4 (3) | C17—C16—H16 | 120.0 |
C3—C4—C5 | 129.4 (3) | C12—C17—C16 | 120.3 (3) |
O1—C4—C5 | 121.2 (3) | C12—C17—H17 | 119.9 |
N1—C5—C4 | 111.2 (3) | C16—C17—H17 | 119.9 |
N1—C5—H5A | 109.4 | C23—C18—C19 | 119.3 (3) |
C4—C5—H5A | 109.4 | C23—C18—P1 | 119.2 (2) |
N1—C5—H5B | 109.4 | C19—C18—P1 | 121.4 (2) |
C4—C5—H5B | 109.4 | C20—C19—C18 | 120.2 (3) |
H5A—C5—H5B | 108.0 | C20—C19—H19 | 119.9 |
C11—C6—C7 | 119.8 (3) | C18—C19—H19 | 119.9 |
C11—C6—P1 | 122.2 (2) | C21—C20—C19 | 120.4 (4) |
C7—C6—P1 | 117.9 (2) | C21—C20—H20 | 119.8 |
C8—C7—C6 | 120.2 (3) | C19—C20—H20 | 119.8 |
C8—C7—H7 | 119.9 | C20—C21—C22 | 119.3 (4) |
C6—C7—H7 | 119.9 | C20—C21—H21 | 120.4 |
C9—C8—C7 | 119.6 (3) | C22—C21—H21 | 120.4 |
C9—C8—H8 | 120.2 | C21—C22—C23 | 121.2 (4) |
C7—C8—H8 | 120.2 | C21—C22—H22 | 119.4 |
C10—C9—C8 | 120.4 (3) | C23—C22—H22 | 119.4 |
C10—C9—H9 | 119.8 | C22—C23—C18 | 119.5 (4) |
C8—C9—H9 | 119.8 | C22—C23—H23 | 120.2 |
C9—C10—C11 | 120.6 (3) | C18—C23—H23 | 120.2 |
C9—C10—H10 | 119.7 | C5—N1—P1 | 125.8 (2) |
C11—C10—H10 | 119.7 | C5—N1—H1A | 110 (3) |
C6—C11—C10 | 119.4 (3) | P1—N1—H1A | 119 (3) |
C6—C11—H11 | 120.3 | C4—O1—C1 | 107.1 (3) |
C10—C11—H11 | 120.3 | N1—P1—C12 | 107.89 (14) |
C17—C12—C13 | 119.0 (3) | N1—P1—C6 | 107.03 (14) |
C17—C12—P1 | 121.1 (2) | C12—P1—C6 | 111.12 (14) |
C13—C12—P1 | 119.9 (2) | N1—P1—C18 | 115.68 (15) |
C14—C13—C12 | 119.8 (3) | C12—P1—C18 | 106.98 (13) |
C14—C13—H13 | 120.1 | C6—P1—C18 | 108.18 (13) |
O1—C1—C2—C3 | −1.0 (6) | C19—C18—C23—C22 | 2.2 (5) |
C1—C2—C3—C4 | 2.6 (5) | P1—C18—C23—C22 | −175.4 (3) |
C2—C3—C4—O1 | −3.1 (5) | C4—C5—N1—P1 | 119.5 (3) |
C2—C3—C4—C5 | 178.7 (4) | C3—C4—O1—C1 | 2.5 (5) |
C3—C4—C5—N1 | −108.5 (4) | C5—C4—O1—C1 | −179.1 (4) |
O1—C4—C5—N1 | 73.5 (4) | C2—C1—O1—C4 | −0.8 (6) |
C11—C6—C7—C8 | −0.6 (5) | C5—N1—P1—C12 | −160.2 (3) |
P1—C6—C7—C8 | 177.6 (3) | C5—N1—P1—C6 | −40.5 (3) |
C6—C7—C8—C9 | 0.7 (6) | C5—N1—P1—C18 | 80.1 (3) |
C7—C8—C9—C10 | −0.2 (6) | C17—C12—P1—N1 | 120.1 (3) |
C8—C9—C10—C11 | −0.5 (6) | C13—C12—P1—N1 | −62.5 (3) |
C7—C6—C11—C10 | −0.1 (5) | C17—C12—P1—C6 | 3.1 (3) |
P1—C6—C11—C10 | −178.2 (2) | C13—C12—P1—C6 | −179.5 (2) |
C9—C10—C11—C6 | 0.7 (5) | C17—C12—P1—C18 | −114.8 (3) |
C17—C12—C13—C14 | 0.7 (5) | C13—C12—P1—C18 | 62.6 (3) |
P1—C12—C13—C14 | −176.7 (3) | C11—C6—P1—N1 | 128.4 (3) |
C12—C13—C14—C15 | −0.4 (6) | C7—C6—P1—N1 | −49.7 (3) |
C13—C14—C15—C16 | 0.0 (6) | C11—C6—P1—C12 | −114.0 (3) |
C14—C15—C16—C17 | 0.1 (6) | C7—C6—P1—C12 | 67.8 (3) |
C13—C12—C17—C16 | −0.7 (5) | C11—C6—P1—C18 | 3.2 (3) |
P1—C12—C17—C16 | 176.7 (3) | C7—C6—P1—C18 | −175.0 (2) |
C15—C16—C17—C12 | 0.3 (5) | C23—C18—P1—N1 | −39.4 (3) |
C23—C18—C19—C20 | −1.2 (5) | C19—C18—P1—N1 | 143.0 (3) |
P1—C18—C19—C20 | 176.4 (3) | C23—C18—P1—C12 | −159.6 (3) |
C18—C19—C20—C21 | −0.2 (6) | C19—C18—P1—C12 | 22.8 (3) |
C19—C20—C21—C22 | 0.5 (7) | C23—C18—P1—C6 | 80.6 (3) |
C20—C21—C22—C23 | 0.6 (7) | C19—C18—P1—C6 | −97.0 (3) |
C21—C22—C23—C18 | −2.0 (6) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Br1 | 0.81 (3) | 2.49 (3) | 3.293 (3) | 170 (4) |
C8—H8···Br1i | 0.93 | 2.98 | 3.835 (4) | 153 |
C15—H15···Br1ii | 0.93 | 3.00 | 3.728 (4) | 137 |
C21—H21···Br1iii | 0.93 | 2.94 | 3.829 (6) | 161 |
C23—H23···Br1iv | 0.93 | 2.97 | 3.782 (4) | 147 |
Symmetry codes: (i) x+1, y, z; (ii) −x, −y+1, −z+1; (iii) x, y+1, z; (iv) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C23H21NOP+·Br− |
Mr | 438.29 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 9.5190 (19), 9.812 (2), 12.726 (3) |
α, β, γ (°) | 110.30 (3), 104.89 (3), 96.81 (3) |
V (Å3) | 1048.7 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.05 |
Crystal size (mm) | 0.20 × 0.17 × 0.13 |
Data collection | |
Diffractometer | Siemens P4 |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.685, 0.777 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11498, 3673, 3213 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.129, 1.02 |
No. of reflections | 3673 |
No. of parameters | 247 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.46 |
Computer programs: XSCANS (Siemens, 1994), SAINT-Plus NT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009), publCIF (Westrip, 2010) and DIAMOND (Brandenburg, 2006).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···Br1 | 0.81 (3) | 2.49 (3) | 3.293 (3) | 170 (4) |
C8—H8···Br1i | 0.93 | 2.98 | 3.835 (4) | 153 |
C15—H15···Br1ii | 0.93 | 3.00 | 3.728 (4) | 137 |
C21—H21···Br1iii | 0.93 | 2.94 | 3.829 (6) | 161 |
C23—H23···Br1iv | 0.93 | 2.97 | 3.782 (4) | 147 |
Symmetry codes: (i) x+1, y, z; (ii) −x, −y+1, −z+1; (iii) x, y+1, z; (iv) −x, −y+1, −z. |
Acknowledgements
This work was supported by the Consejo Nacional de Ciencia y Tecnología (proyecto No. 134528, CB 2009–01)
References
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Boubekeur, L., Ulmer, S., Ricard, L., Mézailles, N. & Le Floch, P. (2006). Organometallics, 25, 315–317. Web of Science CSD CrossRef CAS Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact, Bonn, Germany. Google Scholar
Bruker (2001). SAINT-Plus NT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cao, T. P. A., Payet, E., Auffrant, A., Le Goff, X. F. & Le Floch, P. (2010). Organometallics, 29, 3991–3996. Web of Science CSD CrossRef CAS Google Scholar
Dyer, H., Picot, A., Vendier, L., Auffrant, A., Le Floch, P. & Sabo-Etienne, S. (2011). Organometallics, 30, 1478–1486. Web of Science CSD CrossRef CAS Google Scholar
Horner, L. & Oediger, H. (1959). Liebigs Ann. Chem. 627, 142–162. CrossRef Google Scholar
Jeffrey, G. A. (1997). An Introduction to Hydrogen Bonding, ch. 5. New York: Oxford University Press Inc. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1994). XSCANS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zhang, F., Lerner, H.-W. & Bolte, M. (2003). Acta Cryst. E59, o1181–o1182. Web of Science CSD CrossRef IUCr Journals Google Scholar
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.
Aminophosphonium salts are important species because of their reactivity and their role as intermediates in numerous organophosphorus reactions. For instance, aminophosphonium derived from primary amine are key intermediates in the preparation of iminophosphoranes through the Horner-Oediger reaction (Horner & Oediger, 1959). Apart from their use in the aza-Wittig reaction, this class of compounds became very important ligands during the past few years due to their good activity in various catalytic processes when coordinated to transition metals (Dyer et al., 2011). Here we report the structure of the (furfurylamino) triphenylphosphonium bromide obtained as an intermediate during the synthesis of the corresponding iminophosphorane.
In the crystal structure, neighboring molecules are linked through an N—H···Br hydrogen bond and four weak C—H···Br contacts (Jeffrey, 1997; Zhang, et al., 2003; Table 1), forming a three-dimensional network. In the hydrogen-bond pattern, the C—H···Br contacts form corrugated sheets. These sheets are composed of R24(12), R24(18), R24(22) and R24(24) graph set motifs (Bernstein, et al. 1995; Fig. 2). Neighboring sheets are further linked by N—H···Br hydrogen bonds, generating the three-dimensional network.