N-Imidazole–boron trichloride adduct

Baber, R.A.; Bull, A.E.A.; Charmant, J.P.H.; Norman, N.C.; Orpen, A.G.

doi:10.1107/S1600536805002631

organic compounds

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Volume 61| Part 3| March 2005| Pages o553-o554

https://doi.org/10.1107/S1600536805002631

N-Imidazole–boron trichloride adduct

R. Angharad Baber,^a Andrew E. A. Bull,^a Jonathan P. H. Charmant,^a ^* Nicholas C. Norman ^a and A. Guy Orpen ^a

^aSchool of Chemistry, University of Bristol, Bristol BS8 1TS, England
^*Correspondence e-mail: jon.charmant@bris.ac.uk

(Received 18 January 2005; accepted 24 January 2005; online 5 February 2005)

The crystal structure of the title compound [alternatively called trichloro(1H-imidazole-κN³)boron], C₃H₄N₂–BCl₃ or C₃H₄BCl₃N₂, consists of a weakly hydrogen-bonded network of BCl₃–imidazole adducts. The network formed may be viewed as a cross-linked hydrogen-bonded ribbon polymer.

Comment

The title compound, (I), was obtained as a colourless powder during an attempt to synthesize a product of formula B₂S₃ from the reaction of BCl₃ with (Me₃Si)₂S (containing trace amounts of imidazole as a stabiliser). Recrystallization yielded crystals suitable for a diffraction study. The molecular structure of (I) is shown in Fig. 1, and selected bond lengths and angles are presented in Table 1.

A variety of nitrogen adducts of BCl₃ have previously been characterized crystallographically. These include amine (Minkwitz, Nass & Preest, 1987 ; Minkwitz, Nass, Rieland & Preest, 1987 ; Avent et al., 1995 , Hess, 1969 ; Anton et al., 1984 ; Abram et al., 1997 ; Voigt et al., 2000 ), pyridine (Töpel et al., 1981 ) and acetonitrile (Swanson et al., 1969 ) adducts. The B—N bond length in (I) is shorter than any previously reported, with the exception of adducts with rhenium nitride complexes (Dantona et al., 1984 ; Abram et al., 1997; Ritter & Abram, 1996 ).

The crystal structure of (I) may be viewed as a cross-linked hydrogen-bonded ribbon polymer (see Fig. 2). The N2—H2A donor of the imidazole makes a weak hydrogen bond with atom Cl1 in a neighbouring molecule. This interaction is supplemented by a weak interaction between C2—H2 and Cl3 of the same molecule. Although such an interaction might seem dubious, it is possible that C2 and N2 are disordered with respect to each other, leading to a disordered hydrogen bond between Cl1 or Cl3 and the two chemically feasible NH positions on the imidazole. Attempts to model this disorder were unsuccessful. A slightly stronger interaction between the N2—H2A donor and Cl2 of another neighbouring molecule cross-links the ribbons to give the overall structure.

Figure 1
The molecular structure of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

Figure 2
The crystal structure of the title compound, viewed as a series of cross-linked hydrogen-bonded ribbon polymers. [Symmetry codes: (i) x, y − 1, z; (ii) 1 + x, y − 1, z.]

Experimental

BCl₃ (1.0 M solution in heptane, 0.2 ml, 0.2 mmol) was added to a solution of (Me₃Si)₂S (0.57 ml, 0.3 mmol) in hexane (10 ml), resulting in the immediate formation of a colourless precipitate. The solution was stirred for 24 h, whereupon the solvent was removed by syringe and the resultant colourless solid was washed with hexane (3 × 10 ml) and dried. The solid was then redissolved in CH₂Cl₂ (10 ml), placed in a fresh Schlenk tube, layered with hexane (7 ml) and refrigerated at 243 K overnight, resulting in the formation of large colourless crystals (yield: 0.0056 g, 6%). NMR (CDCl₃): ¹¹B δ 3.1. Analysis calculated for C₃H₄BCl₃N₂: C 19.45, H 2.20, N 15.10%; found: C 19.60, H 1.65, N 14.85%.

Crystal data

C₃H₄BCl₃N₂
M_r = 185.24
Triclinic, $[P\overline 1]$
a = 6.0390 (12) Å
b = 7.2210 (14) Å
c = 8.5610 (17) Å
α = 84.48 (3)°
β = 81.33 (3)°
γ = 71.08 (3)°
V = 348.67 (14) Å³
Z = 2
D_x = 1.764 Mg m⁻³
Mo Kα radiation
Cell parameters from 1476 reflections
θ = 3.0–27.4°
μ = 1.21 mm⁻¹
T = 173 (2) K
Plate, colourless
0.15 × 0.15 × 0.05 mm

Data collection

Bruker SMART CCD area-detector diffractometer
ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ) T_min = 0.853, T_max = 0.940
4070 measured reflections
1597 independent reflections
1444 reflections with I > 2σ(I)
R_int = 0.023
θ_max = 27.5°
h = −7 → 7
k = −9 → 9
l = −11 → 11

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.070
S = 1.06
1597 reflections
82 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.037P)² + 0.0819P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

C1—N2	1.327 (3)
C1—N1	1.332 (2)
C2—C3	1.346 (3)
C2—N2	1.378 (3)
C3—N1	1.389 (2)
B1—N1	1.543 (3)
B1—Cl1	1.847 (2)
B1—Cl3	1.848 (2)
B1—Cl2	1.865 (2)

N2—C1—N1	108.82 (18)
C3—C2—N2	106.08 (17)
C2—C3—N1	108.22 (17)
N1—B1—Cl1	108.73 (13)
N1—B1—Cl3	109.43 (13)
Cl1—B1—Cl3	110.88 (11)
N1—B1—Cl2	109.32 (14)
Cl1—B1—Cl2	109.35 (11)
Cl3—B1—Cl2	109.11 (11)
C1—N1—C3	107.41 (16)
C1—N1—B1	126.94 (16)
C3—N1—B1	125.62 (16)
C1—N2—C2	109.46 (16)

Table 2
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯Cl2ⁱ	0.88	2.57	3.3696 (19)	152
N2—H2A⋯Cl1ⁱⁱ	0.88	2.86	3.429 (2)	124
C2—H2⋯Cl3ⁱⁱ	0.95	2.87	3.815 (2)	171
Symmetry codes: (i) x,y-1,z; (ii) 1+x,y-1,z.

H atoms were constrained to ideal geometries (C—H = 0.95 Å) and refined with displacement parameters equal to 1.2 times U_eq of their parent atom.

Data collection: SMART (Bruker, 2002 ); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT and SHELXTL (Bruker, 2002); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536805002631/ac6154sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805002631/ac6154Isup2.hkl

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT and SHELXTL (Bruker, 2002); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

(I) top

Crystal data top

C₃H₄BCl₃N₂	Z = 2
M_r = 185.24	F(000) = 184
Triclinic, P1	D_x = 1.764 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.0390 (12) Å	Cell parameters from 1476 reflections
b = 7.2210 (14) Å	θ = 3.0–27.4°
c = 8.5610 (17) Å	µ = 1.21 mm⁻¹
α = 84.48 (3)°	T = 173 K
β = 81.33 (3)°	Plate, colourless
γ = 71.08 (3)°	0.15 × 0.15 × 0.05 mm
V = 348.67 (14) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	1597 independent reflections
Radiation source: fine-focus sealed tube	1444 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
Detector resolution: 8.366 pixels mm^-1	θ_max = 27.5°, θ_min = 2.4°
frames, each covering 0.3° in ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	k = −9→9
T_min = 0.853, T_max = 0.940	l = −11→11
4070 measured reflections

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.070	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.037P)² + 0.0819P] where P = (F_o² + 2F_c²)/3
1597 reflections	(Δ/σ)_max < 0.001
82 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

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
C1	0.6954 (4)	0.2644 (3)	0.2045 (2)	0.0152 (4)
H1	0.5650	0.2734	0.1512	0.018*
C2	1.0222 (4)	0.1432 (3)	0.3170 (2)	0.0162 (4)
H2	1.1585	0.0529	0.3554	0.019*
C3	0.9453 (3)	0.3391 (3)	0.3283 (2)	0.0142 (4)
H3	1.0189	0.4129	0.3765	0.017*
B1	0.5971 (4)	0.6339 (3)	0.2389 (3)	0.0125 (4)
Cl1	0.29565 (8)	0.65479 (7)	0.20312 (6)	0.01703 (13)
Cl2	0.74130 (8)	0.74987 (6)	0.06673 (5)	0.01543 (13)
Cl3	0.59006 (8)	0.75682 (6)	0.42002 (5)	0.01600 (13)
N1	0.7401 (3)	0.4147 (2)	0.25726 (18)	0.0123 (3)
N2	0.8631 (3)	0.1002 (2)	0.23866 (19)	0.0167 (4)
H2A	0.8713	−0.0180	0.2149	0.020*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0168 (10)	0.0137 (9)	0.0155 (10)	−0.0052 (8)	−0.0020 (8)	−0.0020 (7)
C2	0.0149 (10)	0.0153 (9)	0.0174 (10)	−0.0036 (8)	−0.0036 (8)	0.0018 (7)
C3	0.0124 (9)	0.0151 (9)	0.0150 (9)	−0.0039 (7)	−0.0036 (7)	0.0006 (7)
B1	0.0111 (10)	0.0138 (10)	0.0137 (10)	−0.0050 (8)	−0.0024 (8)	−0.0013 (8)
Cl1	0.0119 (2)	0.0155 (2)	0.0243 (3)	−0.00375 (17)	−0.00505 (18)	−0.00161 (18)
Cl2	0.0175 (3)	0.0151 (2)	0.0151 (2)	−0.00724 (18)	−0.00290 (18)	0.00153 (17)
Cl3	0.0188 (3)	0.0140 (2)	0.0154 (2)	−0.00417 (18)	−0.00315 (18)	−0.00375 (17)
N1	0.0129 (8)	0.0125 (7)	0.0118 (8)	−0.0042 (6)	−0.0023 (6)	−0.0003 (6)
N2	0.0203 (9)	0.0106 (8)	0.0194 (9)	−0.0050 (6)	−0.0022 (7)	−0.0024 (6)

Geometric parameters (Å, º) top

C1—N2	1.327 (3)	C3—H3	0.9500
C1—N1	1.332 (2)	B1—N1	1.543 (3)
C1—H1	0.9500	B1—Cl1	1.847 (2)
C2—C3	1.346 (3)	B1—Cl3	1.848 (2)
C2—N2	1.378 (3)	B1—Cl2	1.865 (2)
C2—H2	0.9500	N2—H2A	0.8800
C3—N1	1.389 (2)

N2—C1—N1	108.82 (18)	Cl1—B1—Cl3	110.88 (11)
N2—C1—H1	125.6	N1—B1—Cl2	109.32 (14)
N1—C1—H1	125.6	Cl1—B1—Cl2	109.35 (11)
C3—C2—N2	106.08 (17)	Cl3—B1—Cl2	109.11 (11)
C3—C2—H2	127.0	C1—N1—C3	107.41 (16)
N2—C2—H2	127.0	C1—N1—B1	126.94 (16)
C2—C3—N1	108.22 (17)	C3—N1—B1	125.62 (16)
C2—C3—H3	125.9	C1—N2—C2	109.46 (16)
N1—C3—H3	125.9	C1—N2—H2A	125.3
N1—B1—Cl1	108.73 (13)	C2—N2—H2A	125.3
N1—B1—Cl3	109.43 (13)

N2—C2—C3—N1	0.1 (2)	Cl2—B1—N1—C1	−97.5 (2)
N2—C1—N1—C3	−0.3 (2)	Cl1—B1—N1—C3	−160.49 (15)
N2—C1—N1—B1	177.77 (17)	Cl3—B1—N1—C3	−39.2 (2)
C2—C3—N1—C1	0.1 (2)	Cl2—B1—N1—C3	80.2 (2)
C2—C3—N1—B1	−177.98 (17)	N1—C1—N2—C2	0.4 (2)
Cl1—B1—N1—C1	21.8 (2)	C3—C2—N2—C1	−0.3 (2)
Cl3—B1—N1—C1	143.04 (17)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl2ⁱ	0.88	2.57	3.3696 (19)	152
N2—H2A···Cl1ⁱⁱ	0.88	2.86	3.429 (2)	124
C2—H2···Cl3ⁱⁱ	0.95	2.87	3.815 (2)	171

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

Acknowledgements

We thank the EPSRC for financial support.

References

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 61| Part 3| March 2005| Pages o553-o554

https://doi.org/10.1107/S1600536805002631

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

N-Imidazole–boron trichloride adduct

Comment

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds