2-Di­phenyl­phosphanyl-1-methyl-1H-benzimidazole

Jenkins, D.E.; Assefa, Z.

doi:10.1107/S1600536813020588

organic compounds

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Volume 69| Part 8| August 2013| Page o1364

doi:10.1107/S1600536813020588

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2-Diphenylphosphanyl-1-methyl-1H-benzimidazole

Darkus E. Jenkins ^a and Zerihun Assefa ^a ^*

^aNorth Carolina A&T State University, 1601 E Market St., Department of Chemistry, Greensboro, NC 27411, USA
^*Correspondence e-mail: zassefa@ncat.edu

(Received 8 July 2013; accepted 24 July 2013; online 31 July 2013)

In the title compound, C₂₀H₁₈N₂P, the P atom is bonded to the two phenyl and imidazole groups, with an average P—C bond length of 1.828 (2) Å. The three C—P—C bond angles have values consistent with a tetrahedral geometry around the P atom with the fourth site occupied by a H atom. Crystal packing is through van der Waals interactions.

Related literature

For the first synthesis of the title compound and related systems, see: Moore & Whitesides (1982 ). For multimode coordination of diphenylphosphine-substituted benzimidazoles featuring ethylene linkers, see: Hahn et al. (2010 ). For amino-group linkers, see: Braunstein et al. (1997 ). For the coordination of the N,P-type ligand (1-benzyl-2-imidazolyl)diphenylphosphine (BzimPh₂P) with several metal ions, see: Burini et al. (2000 ). For silver complexes with the same ligand, see: Bachechi et al. (2001 ).

Experimental

Crystal data

C₂₀H₁₈N₂P
M_r = 317.33
Triclinic, $[P \overline 1]$
a = 9.574 (2) Å
b = 9.904 (3) Å
c = 10.513 (3) Å
α = 74.215 (7)°
β = 67.172 (7)°
γ = 70.346 (7)°
V = 853.6 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.16 mm⁻¹
T = 200 K
0.50 × 0.50 × 0.05 mm

Data collection

Bruker SMART X2S diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.924, T_max = 0.992
8036 measured reflections
2973 independent reflections
2497 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.118
S = 1.06
2973 reflections
212 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: SMART (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: JMol (Hanson, 2010 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536813020588/kp2457sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813020588/kp2457Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813020588/kp2457Isup3.tif

Supporting information file. DOI: 10.1107/S1600536813020588/kp2457Isup4.tif

Supporting information file. DOI: 10.1107/S1600536813020588/kp2457Isup5.cml

checkCIF report

Comment top

Over the past four decades attention has been given to bi-functional ligands with regards to bringing two metal atoms in close proximity. In particular, interest has been given to the N, P-type ligands. These ligands follow the Lewis soft acid/base chemistry when coordinating with group 11 metals. Although N is to some extent a lesser soft base than P, (N is a stronger σ-donor and poorer π-acceptor than P) its ability to bind with the softer group 11 metals such as gold (I) is well documented. This multi-mode coordination has proven to bring homo- and heteronuclear atoms together with short distances. These ligands are thought to offer stability for metal – metal interactions. Diphenylphosphine-substituted benzimidazoles featuring ethylene or methylene linkers between the benzimidazole and the phosphine groups have been studied in few instances by Hahn et al. (2010) as are with amino linkers by Braunstein et al. (1997). Burini et al. (2000) have extensively studied the N, P type ligand, (1-benzyl-2-imidazolyl)diphenylphosphine (BzimPh2P) to understand the behaviour of coordination with various metal systems. The coordination of the ligand with gold (I), silver (I), copper (I), rhodium (I), iridium (I), mercury (II), zinc (II), and cadmium (II) metal ions has been studied utilizing the monodentate and bidentate features of the ligand. Through continued work Bachechi et al. (2001) have studied the X-ray crystal structures of the silver complexes with the same ligand. Although the synthesis of the title compound has been reported by Moore et al. (1982) surprisingly there has been no structural and coordination work of the this potentially bidentate system.

Related literature top

For the first synthesis of the compound and related systems, see: Moore & Whitesides (19826). For multimode coordination of diphenylphosphine-substituted benzimidazoles featuring ethylene linkers, see: Hahn et al. (20105). For amino-group linkers, see: Braunstein et al. (19972). For the coordination of the N,P-type ligand (1-benzyl-2-imidazolyl)diphenylphosphine (BzimPh₂P) with several metal ions, see: Burini et al. (2000). For silver complexes with the same ligand, see: Bachechi et al. (2001).

Experimental top

The compound was synthesized by reacting 1-methylbenzimidazole with chlorodiphenylphosphine in the presence of n-BuLi at 195 K. Single crystals were obtained from warm hexanes solution.

Computing details top

Data collection: SMART Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: JMol (Hanson, 2010); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. The molecular structure of the compound. Thermal ellipsoids for non- hydrogen atoms are drawn at 50% probability level.

2-Diphenylphosphanyl-1-methyl-1H-benzimidazole top

Crystal data top

C₂₀H₁₈N₂P	Z = 2
M_r = 317.33	F(000) = 334
Triclinic, P1	D_x = 1.235 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.574 (2) Å	Cell parameters from 3787 reflections
b = 9.904 (3) Å	θ = 2.2–24.0°
c = 10.513 (3) Å	µ = 0.16 mm⁻¹
α = 74.215 (7)°	T = 200 K
β = 67.172 (7)°	Plate, colourless
γ = 70.346 (7)°	0.50 × 0.50 × 0.05 mm
V = 853.6 (4) Å³

Data collection top

Bruker SMART X2S diffractometer	2973 independent reflections
Radiation source: fine-focus sealed tube	2497 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
automatic scans	θ_max = 25.1°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −11→11
T_min = 0.924, T_max = 0.992	k = −11→11
8036 measured reflections	l = −12→12

Refinement top

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0576P)² + 0.2237P] where P = (F_o² + 2F_c²)/3
2973 reflections	(Δ/σ)_max < 0.001
212 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₂₀H₁₈N₂P	γ = 70.346 (7)°
M_r = 317.33	V = 853.6 (4) Å³
Triclinic, P1	Z = 2
a = 9.574 (2) Å	Mo Kα radiation
b = 9.904 (3) Å	µ = 0.16 mm⁻¹
c = 10.513 (3) Å	T = 200 K
α = 74.215 (7)°	0.50 × 0.50 × 0.05 mm
β = 67.172 (7)°

Data collection top

Bruker SMART X2S diffractometer	2973 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	2497 reflections with I > 2σ(I)
T_min = 0.924, T_max = 0.992	R_int = 0.027
8036 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.30 e Å⁻³
2973 reflections	Δρ_min = −0.18 e Å⁻³
212 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
P1	0.78385 (6)	0.78051 (5)	0.17374 (6)	0.05124 (19)
N1	0.70104 (17)	0.53236 (16)	0.18024 (16)	0.0448 (4)
N2	0.73242 (17)	0.53550 (18)	0.37950 (16)	0.0511 (4)
C1	0.73869 (19)	0.6038 (2)	0.24516 (19)	0.0449 (4)
C2	0.6711 (2)	0.4084 (2)	0.27610 (19)	0.0461 (4)
C3	0.6890 (2)	0.4095 (2)	0.4008 (2)	0.0489 (5)
C4	0.6339 (3)	0.2909 (2)	0.2604 (2)	0.0617 (5)
H4	0.6225	0.2878	0.1755	0.074*
C5	0.6143 (3)	0.1788 (3)	0.3722 (3)	0.0731 (6)
H5	0.5911	0.0965	0.3631	0.088*
C6	0.6276 (3)	0.1836 (3)	0.4966 (3)	0.0754 (7)
H6	0.6099	0.1060	0.5721	0.090*
C7	0.6658 (3)	0.2977 (3)	0.5147 (2)	0.0668 (6)
H7	0.6759	0.3001	0.6003	0.080*
C9	0.9911 (2)	0.73075 (19)	0.1591 (2)	0.0454 (4)
C10	1.0919 (2)	0.5953 (2)	0.1370 (2)	0.0503 (5)
H10	1.0539	0.5222	0.1285	0.060*
C11	1.2477 (2)	0.5647 (2)	0.1273 (2)	0.0516 (5)
H11	1.3154	0.4708	0.1129	0.062*
C12	1.3044 (2)	0.6700 (2)	0.1383 (2)	0.0513 (5)
H12	1.4110	0.6491	0.1320	0.062*
C13	1.2059 (2)	0.8058 (2)	0.1585 (2)	0.0613 (6)
H13	1.2453	0.8791	0.1646	0.074*
C14	1.0496 (2)	0.8365 (2)	0.1700 (2)	0.0568 (5)
H14	0.9821	0.9302	0.1855	0.068*
C15	0.7894 (2)	0.79884 (18)	−0.0053 (2)	0.0468 (4)
C16	0.9256 (2)	0.7847 (2)	−0.1200 (2)	0.0578 (5)
H16	1.0245	0.7596	−0.1067	0.069*
C17	0.9192 (3)	0.8067 (2)	−0.2525 (3)	0.0740 (7)
H17	1.0133	0.7977	−0.3303	0.089*
C18	0.7758 (3)	0.8418 (2)	−0.2731 (3)	0.0763 (7)
H18	0.7716	0.8549	−0.3646	0.092*
C19	0.6397 (3)	0.8576 (2)	−0.1605 (3)	0.0718 (7)
H19	0.5410	0.8827	−0.1742	0.086*
C20	0.6462 (2)	0.8373 (2)	−0.0282 (2)	0.0578 (5)
H20	0.5516	0.8497	0.0488	0.069*
H1	0.6977 (18)	0.8932 (17)	0.2303 (16)	0.034 (4)*
C8	0.7688 (3)	0.5830 (3)	0.4799 (2)	0.0778 (7)
H8A	0.7544	0.5131	0.5671	0.117*
H8B	0.6986	0.6788	0.4988	0.117*
H8C	0.8779	0.5893	0.4413	0.117*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.0393 (3)	0.0487 (3)	0.0715 (4)	−0.0111 (2)	−0.0183 (2)	−0.0191 (2)
N1	0.0434 (8)	0.0496 (9)	0.0467 (8)	−0.0197 (7)	−0.0167 (7)	−0.0035 (7)
N2	0.0408 (9)	0.0710 (11)	0.0437 (9)	−0.0111 (8)	−0.0152 (7)	−0.0154 (8)
C1	0.0306 (9)	0.0546 (11)	0.0493 (11)	−0.0093 (8)	−0.0109 (8)	−0.0138 (8)
C2	0.0373 (10)	0.0504 (10)	0.0470 (10)	−0.0125 (8)	−0.0125 (8)	−0.0030 (8)
C3	0.0342 (9)	0.0585 (11)	0.0471 (11)	−0.0068 (8)	−0.0116 (8)	−0.0071 (9)
C4	0.0679 (14)	0.0596 (12)	0.0630 (13)	−0.0293 (11)	−0.0232 (11)	0.0004 (10)
C5	0.0784 (16)	0.0574 (13)	0.0799 (17)	−0.0289 (11)	−0.0242 (13)	0.0062 (11)
C6	0.0694 (15)	0.0636 (14)	0.0727 (17)	−0.0180 (12)	−0.0197 (13)	0.0160 (12)
C7	0.0553 (13)	0.0822 (16)	0.0469 (12)	−0.0070 (11)	−0.0174 (10)	0.0013 (11)
C9	0.0422 (10)	0.0453 (10)	0.0560 (11)	−0.0147 (8)	−0.0185 (8)	−0.0119 (8)
C10	0.0459 (11)	0.0459 (10)	0.0682 (13)	−0.0160 (8)	−0.0203 (9)	−0.0158 (9)
C11	0.0473 (11)	0.0486 (10)	0.0603 (12)	−0.0091 (8)	−0.0214 (9)	−0.0096 (9)
C12	0.0430 (10)	0.0607 (12)	0.0564 (12)	−0.0194 (9)	−0.0237 (9)	−0.0007 (9)
C13	0.0604 (13)	0.0569 (12)	0.0865 (16)	−0.0288 (10)	−0.0359 (12)	−0.0077 (11)
C14	0.0539 (12)	0.0441 (10)	0.0845 (15)	−0.0140 (9)	−0.0312 (11)	−0.0148 (10)
C15	0.0397 (10)	0.0321 (9)	0.0700 (13)	−0.0100 (7)	−0.0214 (9)	−0.0045 (8)
C16	0.0466 (11)	0.0498 (11)	0.0705 (14)	−0.0014 (9)	−0.0218 (10)	−0.0098 (10)
C17	0.0731 (16)	0.0611 (13)	0.0688 (15)	0.0051 (11)	−0.0226 (12)	−0.0104 (11)
C18	0.107 (2)	0.0487 (12)	0.0802 (17)	−0.0059 (13)	−0.0538 (17)	−0.0058 (11)
C19	0.0771 (17)	0.0552 (13)	0.102 (2)	−0.0204 (12)	−0.0572 (16)	0.0038 (12)
C20	0.0460 (11)	0.0485 (11)	0.0820 (15)	−0.0189 (9)	−0.0268 (11)	0.0018 (10)
C8	0.0765 (16)	0.111 (2)	0.0616 (14)	−0.0232 (14)	−0.0293 (12)	−0.0298 (14)

Geometric parameters (Å, º) top

P1—C15	1.823 (2)	C10—H10	0.9500
P1—C9	1.8304 (19)	C11—C12	1.376 (3)
P1—C1	1.8321 (19)	C11—H11	0.9500
P1—H1	1.281 (15)	C12—C13	1.374 (3)
N1—C1	1.312 (2)	C12—H12	0.9500
N1—C2	1.394 (2)	C13—C14	1.386 (3)
N2—C1	1.378 (2)	C13—H13	0.9500
N2—C3	1.381 (3)	C14—H14	0.9500
N2—C8	1.457 (3)	C15—C16	1.387 (3)
C2—C3	1.389 (3)	C15—C20	1.392 (3)
C2—C4	1.392 (3)	C16—C17	1.373 (3)
C3—C7	1.395 (3)	C16—H16	0.9500
C4—C5	1.381 (3)	C17—C18	1.386 (3)
C4—H4	0.9500	C17—H17	0.9500
C5—C6	1.377 (4)	C18—C19	1.375 (4)
C5—H5	0.9500	C18—H18	0.9500
C6—C7	1.376 (3)	C19—C20	1.373 (3)
C6—H6	0.9500	C19—H19	0.9500
C7—H7	0.9500	C20—H20	0.9500
C9—C10	1.382 (3)	C8—H8A	0.9800
C9—C14	1.390 (2)	C8—H8B	0.9800
C10—C11	1.386 (3)	C8—H8C	0.9800

C15—P1—C9	103.70 (8)	C12—C11—C10	120.12 (18)
C15—P1—C1	99.42 (8)	C12—C11—H11	119.9
C9—P1—C1	100.85 (8)	C10—C11—H11	119.9
C15—P1—H1	113.2 (7)	C13—C12—C11	119.64 (17)
C9—P1—H1	115.7 (7)	C13—C12—H12	120.2
C1—P1—H1	121.4 (7)	C11—C12—H12	120.2
C1—N1—C2	104.89 (16)	C12—C13—C14	120.51 (17)
C1—N2—C3	106.83 (15)	C12—C13—H13	119.7
C1—N2—C8	127.27 (19)	C14—C13—H13	119.7
C3—N2—C8	125.87 (18)	C13—C14—C9	120.28 (18)
N1—C1—N2	112.64 (17)	C13—C14—H14	119.9
N1—C1—P1	125.23 (15)	C9—C14—H14	119.9
N2—C1—P1	122.03 (14)	C16—C15—C20	118.3 (2)
C3—C2—C4	119.95 (18)	C16—C15—P1	124.29 (15)
C3—C2—N1	110.33 (16)	C20—C15—P1	117.29 (16)
C4—C2—N1	129.68 (18)	C17—C16—C15	120.7 (2)
N2—C3—C2	105.29 (16)	C17—C16—H16	119.7
N2—C3—C7	132.60 (19)	C15—C16—H16	119.7
C2—C3—C7	122.1 (2)	C16—C17—C18	120.2 (2)
C5—C4—C2	117.9 (2)	C16—C17—H17	119.9
C5—C4—H4	121.1	C18—C17—H17	119.9
C2—C4—H4	121.1	C19—C18—C17	119.7 (2)
C6—C5—C4	121.4 (2)	C19—C18—H18	120.2
C6—C5—H5	119.3	C17—C18—H18	120.2
C4—C5—H5	119.3	C20—C19—C18	120.0 (2)
C7—C6—C5	122.0 (2)	C20—C19—H19	120.0
C7—C6—H6	119.0	C18—C19—H19	120.0
C5—C6—H6	119.0	C19—C20—C15	121.0 (2)
C6—C7—C3	116.6 (2)	C19—C20—H20	119.5
C6—C7—H7	121.7	C15—C20—H20	119.5
C3—C7—H7	121.7	N2—C8—H8A	109.5
C10—C9—C14	118.61 (17)	N2—C8—H8B	109.5
C10—C9—P1	123.80 (13)	H8A—C8—H8B	109.5
C14—C9—P1	117.59 (14)	N2—C8—H8C	109.5
C9—C10—C11	120.84 (17)	H8A—C8—H8C	109.5
C9—C10—H10	119.6	H8B—C8—H8C	109.5
C11—C10—H10	119.6

Experimental details

Crystal data
Chemical formula	C₂₀H₁₈N₂P
M_r	317.33
Crystal system, space group	Triclinic, P1
Temperature (K)	200
a, b, c (Å)	9.574 (2), 9.904 (3), 10.513 (3)
α, β, γ (°)	74.215 (7), 67.172 (7), 70.346 (7)
V (Å³)	853.6 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.16
Crystal size (mm)	0.50 × 0.50 × 0.05

Data collection
Diffractometer	Bruker SMART X2S diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.924, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	8036, 2973, 2497
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.118, 1.06
No. of reflections	2973
No. of parameters	212
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.18

Computer programs: SMART Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), JMol (Hanson, 2010), publCIF (Westrip, 2010).

Acknowledgements

Support for this research from National Science Foundation (CHE-0959406) and the NOAA Educational Partnership Program award number NA06OAR4810187 to NCAT State University as well as support from the donors of the Petroleum Research Fund (ACS–PRF) are kindly acknowledged.

References

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