Synthesis, crystal structure and Hirshfeld analysis of tri­phenyl­phosphine–(4-bromo­phen­yl)borane

Allen, C.J.; Olden, A.M.; Yates, J.L.; Wheeler, K.A.; Abbey, E.R.

doi:10.1107/S2053229622010002

Synthesis, crystal structure and Hirshfeld analysis of triphenylphosphine–(4-bromophenyl)borane

C. J. Allen, A. M. Olden, J. L. Yates, K. A. Wheeler and E. R. Abbey

The title compound, alternatively called (4-bromophenyl)dihydrido(triphenylphosphanyl)boron, C₂₄H₂₁BBrP, crystallizes in the space group P $\overline{1}$ with one symmetry-independent molecule in the asymmetric unit. The B and P atoms both adopt the expected tetrahedral geometry. A possible intramolecular B—H^δ−

^δ+H—C dihydrogen bond exists between an arene group on phosphorus and the borane center. In the solid state, the title molecule is connected to its neighbors by intermolecular C—H

π interactions, with the arene rings on the P atom acting as hydrogen-bond donors and the arene ring of the borane acting as the acceptor. Hirshfeld analysis supports the existence of these interactions, as well as weak Br

Br interactions between neighboring molecules.

Keywords: Lewis acid; Lewis base; phosphine-borane; NMR; crystal structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229622010002/zo3028sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229622010002/zo3028Isup2.hkl Contains datablock I

CCDC reference: 2212562

Computing details top

Data collection: APEX3 (Bruker, 2018); cell refinement: SAINT (Bruker, 2017); data reduction: SAINT (Bruker, 2017); program(s) used to solve structure: SHELXT2018 (Sheldrick, 2015b); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015a); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: X-SEED (Barbour, 2001).

(4-Bromophenyl)(triphenylphosphanyl)borane top

Crystal data top

C₂₄H₂₁BBrP	Z = 2
M_r = 431.10	F(000) = 440
Triclinic, P1	D_x = 1.403 Mg m⁻³
a = 9.4920 (6) Å	Cu Kα radiation, λ = 1.54178 Å
b = 10.0234 (7) Å	Cell parameters from 9941 reflections
c = 12.0606 (8) Å	θ = 3.8–72.1°
α = 81.515 (2)°	µ = 3.51 mm⁻¹
β = 74.038 (2)°	T = 100 K
γ = 67.798 (2)°	Plate, colourless
V = 1020.21 (12) Å³	0.24 × 0.21 × 0.03 mm

Data collection top

Bruker D8 Venture diffractometer	3986 independent reflections
Radiation source: Microsource IuS Incoatec 3.0	3904 reflections with I > 2σ(I)
Double Bounce Multilayer Mirrors monochromator	R_int = 0.022
Detector resolution: 7.9 pixels mm^-1	θ_max = 72.3°, θ_min = 3.8°
φ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −12→7
T_min = 0.644, T_max = 0.754	l = −14→14
6803 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.063	w = 1/[σ²(F_o²) + (0.0215P)² + 0.9841P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3986 reflections	Δρ_max = 0.41 e Å⁻³
250 parameters	Δρ_min = −0.53 e Å⁻³
0 restraints

Special details top

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

Refinement. All nonhydrogen atoms were located in a single difference Fourier electron density map and refined using anisotropic displacement parameters. All C-H hydrogen atoms were placed in calculated positions with Uiso = 1.2xUeqiv of the connected C atoms (1.5xUeqiv for methyl groups). Those H atoms attached to boron were located in Fourier diff maps and assigned Uiso = 1.2xUeqiv.

The structure was solved by direct methods and refined by full-matrix least-squares analysis onF²using X-Seed (ref) equipped with SHELXT (ref). All non-hydrogen atoms were refined anisotropically by full-matrix least-squares onF²using the SHELXL (ref) program.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.32328 (2)	0.48490 (2)	0.10590 (2)	0.02829 (7)
P1	0.33317 (4)	0.25085 (4)	0.71649 (3)	0.01089 (9)
C1	0.27423 (18)	0.26888 (16)	0.48269 (13)	0.0138 (3)
C2	0.14369 (18)	0.34670 (17)	0.43727 (14)	0.0159 (3)
H2	0.042212	0.357635	0.484672	0.019*
C3	0.15653 (19)	0.40865 (17)	0.32563 (14)	0.0184 (3)
H3	0.065679	0.459834	0.297054	0.022*
C4	0.3039 (2)	0.39432 (17)	0.25703 (14)	0.0183 (3)
C5	0.43797 (19)	0.31845 (17)	0.29691 (14)	0.0185 (3)
H5	0.538792	0.308835	0.248898	0.022*
C6	0.42157 (18)	0.25669 (17)	0.40878 (14)	0.0170 (3)
H6	0.513121	0.204428	0.436253	0.020*
C7	0.24868 (17)	0.44382 (16)	0.73670 (13)	0.0130 (3)
C8	0.26936 (18)	0.53691 (17)	0.63964 (13)	0.0159 (3)
H8	0.329205	0.498154	0.566921	0.019*
C9	0.20268 (19)	0.68562 (17)	0.64938 (14)	0.0180 (3)
H9	0.217521	0.748213	0.583525	0.022*
C10	0.11435 (19)	0.74256 (17)	0.75545 (15)	0.0199 (3)
H10	0.068703	0.844141	0.762101	0.024*
C11	0.09272 (19)	0.65123 (18)	0.85174 (15)	0.0207 (3)
H11	0.032144	0.690538	0.924145	0.025*
C12	0.15934 (18)	0.50237 (17)	0.84270 (14)	0.0169 (3)
H12	0.143978	0.440397	0.908890	0.020*
C13	0.54478 (17)	0.20455 (16)	0.67799 (12)	0.0116 (3)
C14	0.63650 (18)	0.06484 (16)	0.64157 (13)	0.0140 (3)
H14	0.587565	0.001074	0.633363	0.017*
C15	0.79873 (18)	0.01938 (16)	0.61745 (13)	0.0149 (3)
H15	0.860611	−0.075613	0.593161	0.018*
C16	0.87093 (17)	0.11267 (17)	0.62878 (13)	0.0140 (3)
H16	0.981988	0.081366	0.612318	0.017*
C17	0.78068 (18)	0.25123 (17)	0.66410 (13)	0.0152 (3)
H17	0.830186	0.314913	0.671449	0.018*
C18	0.61755 (18)	0.29778 (16)	0.68893 (13)	0.0141 (3)
H18	0.556163	0.392851	0.713263	0.017*
C19	0.29636 (17)	0.15859 (16)	0.85681 (13)	0.0146 (3)
C20	0.2256 (2)	0.0560 (2)	0.87270 (15)	0.0240 (4)
H20	0.190504	0.038696	0.811541	0.029*
C21	0.2063 (2)	−0.0213 (2)	0.97838 (17)	0.0290 (4)
H21	0.160281	−0.092902	0.988478	0.035*
C22	0.2540 (2)	0.0060 (2)	1.06842 (15)	0.0261 (4)
H22	0.240089	−0.046403	1.140437	0.031*
C23	0.3218 (2)	0.10963 (19)	1.05379 (14)	0.0228 (4)
H23	0.352238	0.129765	1.116371	0.027*
C24	0.34567 (18)	0.18436 (17)	0.94789 (14)	0.0174 (3)
H24	0.395575	0.253059	0.937423	0.021*
B1	0.2510 (2)	0.19065 (19)	0.60936 (16)	0.0159 (3)
H1A	0.315 (2)	0.071 (2)	0.6110 (17)	0.019*
H1B	0.123 (2)	0.219 (2)	0.6589 (17)	0.019*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.04593 (13)	0.03054 (12)	0.01421 (10)	−0.02059 (9)	−0.00767 (8)	0.00151 (7)
P1	0.01051 (17)	0.01121 (17)	0.01213 (18)	−0.00479 (13)	−0.00335 (13)	−0.00028 (13)
C1	0.0168 (7)	0.0119 (7)	0.0162 (7)	−0.0067 (6)	−0.0053 (6)	−0.0039 (6)
C2	0.0155 (7)	0.0151 (7)	0.0194 (8)	−0.0066 (6)	−0.0048 (6)	−0.0037 (6)
C3	0.0216 (8)	0.0168 (8)	0.0214 (8)	−0.0077 (6)	−0.0113 (6)	0.0000 (6)
C4	0.0295 (9)	0.0163 (7)	0.0140 (7)	−0.0120 (7)	−0.0069 (6)	−0.0014 (6)
C5	0.0195 (8)	0.0189 (8)	0.0185 (8)	−0.0095 (6)	−0.0007 (6)	−0.0057 (6)
C6	0.0157 (7)	0.0160 (7)	0.0204 (8)	−0.0049 (6)	−0.0061 (6)	−0.0034 (6)
C7	0.0106 (6)	0.0128 (7)	0.0171 (7)	−0.0039 (5)	−0.0062 (6)	−0.0001 (6)
C8	0.0159 (7)	0.0184 (8)	0.0147 (7)	−0.0066 (6)	−0.0050 (6)	−0.0004 (6)
C9	0.0204 (8)	0.0167 (8)	0.0200 (8)	−0.0086 (6)	−0.0097 (6)	0.0046 (6)
C10	0.0188 (8)	0.0130 (7)	0.0268 (9)	−0.0014 (6)	−0.0096 (7)	−0.0011 (6)
C11	0.0187 (8)	0.0189 (8)	0.0192 (8)	−0.0002 (6)	−0.0035 (6)	−0.0044 (6)
C12	0.0154 (7)	0.0168 (8)	0.0162 (8)	−0.0032 (6)	−0.0050 (6)	0.0014 (6)
C13	0.0119 (7)	0.0130 (7)	0.0107 (7)	−0.0050 (5)	−0.0035 (5)	0.0000 (5)
C14	0.0162 (7)	0.0127 (7)	0.0155 (7)	−0.0068 (6)	−0.0048 (6)	−0.0011 (6)
C15	0.0151 (7)	0.0119 (7)	0.0157 (7)	−0.0029 (6)	−0.0027 (6)	−0.0022 (6)
C16	0.0117 (7)	0.0169 (7)	0.0128 (7)	−0.0051 (6)	−0.0025 (5)	0.0006 (6)
C17	0.0157 (7)	0.0162 (7)	0.0167 (7)	−0.0098 (6)	−0.0034 (6)	−0.0003 (6)
C18	0.0144 (7)	0.0116 (7)	0.0163 (7)	−0.0045 (6)	−0.0034 (6)	−0.0020 (6)
C19	0.0120 (7)	0.0141 (7)	0.0145 (7)	−0.0023 (6)	−0.0025 (6)	0.0013 (6)
C20	0.0267 (9)	0.0271 (9)	0.0227 (9)	−0.0158 (7)	−0.0071 (7)	0.0046 (7)
C21	0.0293 (9)	0.0282 (9)	0.0294 (10)	−0.0165 (8)	−0.0040 (8)	0.0105 (8)
C22	0.0224 (8)	0.0249 (9)	0.0185 (8)	−0.0016 (7)	0.0002 (7)	0.0082 (7)
C23	0.0217 (8)	0.0217 (8)	0.0158 (8)	0.0020 (7)	−0.0044 (6)	−0.0001 (6)
C24	0.0162 (7)	0.0149 (7)	0.0171 (8)	−0.0010 (6)	−0.0041 (6)	−0.0010 (6)
B1	0.0170 (8)	0.0174 (8)	0.0180 (8)	−0.0091 (7)	−0.0073 (7)	−0.0011 (7)

Geometric parameters (Å, º) top

Br1—C4	1.9062 (16)	C12—H12	0.9500
P1—C19	1.8161 (16)	C13—C18	1.394 (2)
P1—C7	1.8175 (15)	C13—C14	1.401 (2)
P1—C13	1.8198 (15)	C14—C15	1.388 (2)
P1—B1	1.9444 (18)	C14—H14	0.9500
C1—C2	1.400 (2)	C15—C16	1.391 (2)
C1—C6	1.408 (2)	C15—H15	0.9500
C1—B1	1.609 (2)	C16—C17	1.385 (2)
C2—C3	1.391 (2)	C16—H16	0.9500
C2—H2	0.9500	C17—C18	1.395 (2)
C3—C4	1.382 (2)	C17—H17	0.9500
C3—H3	0.9500	C18—H18	0.9500
C4—C5	1.388 (2)	C19—C20	1.392 (2)
C5—C6	1.392 (2)	C19—C24	1.397 (2)
C5—H5	0.9500	C20—C21	1.395 (2)
C6—H6	0.9500	C20—H20	0.9500
C7—C12	1.395 (2)	C21—C22	1.382 (3)
C7—C8	1.403 (2)	C21—H21	0.9500
C8—C9	1.391 (2)	C22—C23	1.383 (3)
C8—H8	0.9500	C22—H22	0.9500
C9—C10	1.389 (2)	C23—C24	1.389 (2)
C9—H9	0.9500	C23—H23	0.9500
C10—C11	1.388 (2)	C24—H24	0.9500
C10—H10	0.9500	B1—H1A	1.12 (2)
C11—C12	1.391 (2)	B1—H1B	1.14 (2)
C11—H11	0.9500

C19—P1—C7	107.96 (7)	C18—C13—C14	119.56 (13)
C19—P1—C13	103.51 (7)	C18—C13—P1	123.29 (11)
C7—P1—C13	106.24 (7)	C14—C13—P1	117.06 (11)
C19—P1—B1	110.16 (8)	C15—C14—C13	120.13 (14)
C7—P1—B1	113.37 (7)	C15—C14—H14	119.9
C13—P1—B1	114.93 (7)	C13—C14—H14	119.9
C2—C1—C6	116.19 (14)	C14—C15—C16	120.13 (14)
C2—C1—B1	119.85 (14)	C14—C15—H15	119.9
C6—C1—B1	123.81 (14)	C16—C15—H15	119.9
C3—C2—C1	122.68 (15)	C17—C16—C15	119.93 (14)
C3—C2—H2	118.7	C17—C16—H16	120.0
C1—C2—H2	118.7	C15—C16—H16	120.0
C4—C3—C2	118.74 (15)	C16—C17—C18	120.38 (14)
C4—C3—H3	120.6	C16—C17—H17	119.8
C2—C3—H3	120.6	C18—C17—H17	119.8
C3—C4—C5	121.38 (15)	C13—C18—C17	119.86 (14)
C3—C4—Br1	119.30 (13)	C13—C18—H18	120.1
C5—C4—Br1	119.30 (13)	C17—C18—H18	120.1
C4—C5—C6	118.60 (15)	C20—C19—C24	119.39 (15)
C4—C5—H5	120.7	C20—C19—P1	120.06 (12)
C6—C5—H5	120.7	C24—C19—P1	120.46 (12)
C5—C6—C1	122.40 (15)	C19—C20—C21	120.05 (17)
C5—C6—H6	118.8	C19—C20—H20	120.0
C1—C6—H6	118.8	C21—C20—H20	120.0
C12—C7—C8	119.17 (14)	C22—C21—C20	120.14 (17)
C12—C7—P1	122.87 (12)	C22—C21—H21	119.9
C8—C7—P1	117.90 (12)	C20—C21—H21	119.9
C9—C8—C7	120.32 (14)	C21—C22—C23	120.07 (16)
C9—C8—H8	119.8	C21—C22—H22	120.0
C7—C8—H8	119.8	C23—C22—H22	120.0
C10—C9—C8	119.95 (15)	C22—C23—C24	120.23 (17)
C10—C9—H9	120.0	C22—C23—H23	119.9
C8—C9—H9	120.0	C24—C23—H23	119.9
C11—C10—C9	120.08 (15)	C23—C24—C19	120.08 (16)
C11—C10—H10	120.0	C23—C24—H24	120.0
C9—C10—H10	120.0	C19—C24—H24	120.0
C10—C11—C12	120.29 (15)	C1—B1—P1	114.22 (11)
C10—C11—H11	119.9	C1—B1—H1A	114.2 (10)
C12—C11—H11	119.9	P1—B1—H1A	102.0 (10)
C11—C12—C7	120.19 (15)	C1—B1—H1B	113.8 (10)
C11—C12—H12	119.9	P1—B1—H1B	100.0 (10)
C7—C12—H12	119.9	H1A—B1—H1B	111.2 (14)

C6—C1—C2—C3	0.3 (2)	C19—P1—C13—C14	75.38 (13)
B1—C1—C2—C3	−175.62 (14)	C7—P1—C13—C14	−171.02 (11)
C1—C2—C3—C4	−0.8 (2)	B1—P1—C13—C14	−44.80 (14)
C2—C3—C4—C5	0.8 (2)	C18—C13—C14—C15	0.5 (2)
C2—C3—C4—Br1	−177.57 (11)	P1—C13—C14—C15	−176.17 (12)
C3—C4—C5—C6	−0.3 (2)	C13—C14—C15—C16	−0.3 (2)
Br1—C4—C5—C6	178.03 (11)	C14—C15—C16—C17	−0.1 (2)
C4—C5—C6—C1	−0.2 (2)	C15—C16—C17—C18	0.3 (2)
C2—C1—C6—C5	0.2 (2)	C14—C13—C18—C17	−0.3 (2)
B1—C1—C6—C5	175.92 (14)	P1—C13—C18—C17	176.18 (12)
C19—P1—C7—C12	−5.66 (15)	C16—C17—C18—C13	−0.1 (2)
C13—P1—C7—C12	−116.17 (13)	C7—P1—C19—C20	127.27 (13)
B1—P1—C7—C12	116.67 (13)	C13—P1—C19—C20	−120.37 (14)
C19—P1—C7—C8	177.19 (11)	B1—P1—C19—C20	2.99 (16)
C13—P1—C7—C8	66.69 (13)	C7—P1—C19—C24	−55.97 (14)
B1—P1—C7—C8	−60.48 (14)	C13—P1—C19—C24	56.38 (14)
C12—C7—C8—C9	0.5 (2)	B1—P1—C19—C24	179.75 (12)
P1—C7—C8—C9	177.80 (12)	C24—C19—C20—C21	−0.8 (3)
C7—C8—C9—C10	−0.4 (2)	P1—C19—C20—C21	175.98 (14)
C8—C9—C10—C11	0.1 (2)	C19—C20—C21—C22	1.5 (3)
C9—C10—C11—C12	0.1 (2)	C20—C21—C22—C23	−0.4 (3)
C10—C11—C12—C7	0.1 (2)	C21—C22—C23—C24	−1.5 (3)
C8—C7—C12—C11	−0.4 (2)	C22—C23—C24—C19	2.2 (2)
P1—C7—C12—C11	−177.52 (12)	C20—C19—C24—C23	−1.0 (2)
C19—P1—C13—C18	−101.16 (13)	P1—C19—C24—C23	−177.78 (12)
C7—P1—C13—C18	12.44 (15)	C2—C1—B1—P1	−122.51 (13)
B1—P1—C13—C18	138.67 (13)	C6—C1—B1—P1	61.93 (18)

Hydrogen-bond geometry (Å, º) top

Cg1 is the centroid of the C1–C6 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C14—H14···Cg1ⁱ	0.95	3.10	3.786	131
C15—H15···Cg1ⁱ	0.95	3.31	3.890	122
C17—H17···Cg1ⁱⁱ	0.95	3.28	3.947	129
C18—H18···Cg1ⁱⁱ	0.95	3.49	4.047	120

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y+1, −z+1.

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Synthesis, crystal structure and Hirshfeld analysis of tri­phenyl­phosphine–(4-bromo­phen­yl)borane

Supporting information

Synthesis, crystal structure and Hirshfeld analysis of triphenylphosphine–(4-bromophenyl)borane