2-(p-Tol­yl)-1,3,2-benzodioxaborole

Bramham, G.; Batsanov, A.S.; Marder, T.B.; Norman, N.C.

doi:10.1107/S1600536806004089

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 62| Part 3| March 2006| Pages o972-o973

https://doi.org/10.1107/S1600536806004089

2-(p-Tolyl)-1,3,2-benzodioxaborole

George Bramham,^a Andrei S. Batsanov,^b ^* Todd B. Marder ^b and Nicholas C. Norman ^a

^aSchool of Chemistry, University of Bristol, Bristol BS8 1TS, England, and ^bDepartment of Chemistry, University of Durham, South Road, Durham DH1 3LE, England
^*Correspondence e-mail: a.s.batsanov@durham.ac.uk

(Received 31 January 2006; accepted 2 February 2006; online 8 February 2006)

The title molecule, C₁₃H₁₁BO₂, adopts a planar conformation and a stack/herringbone packing motif in the solid state.

Comment

Compound (I) was obtained via cobalt-mediated borylation of 4-iodotoluene, observed during our studies of the synthesis and reactivity of cobalt boryl complexes (Dai et al., 1996 ; Adams et al., 2006 ).

The asymmetric unit comprises one molecule (Fig. 1), which is nearly planar (r.m.s. deviation for all non-H atoms 0.057 Å), like its prototype 2-phenyl-1,3,2-benzodioxaborole (Zettler et al., 1974 ). The B atom is trigonal-planar; its coordination plane is inclined by 2.9 (1)° to the catechol arene ring (i) and by 3.7 (1)° to the tolyl arene ring (ii). Molecules related via the b translation form a stack with a mean interplanar separation of 3.52 (5) Å. Stacks are packed in a herringbone motif, in which planes of adjacent molecules are nearly perpendicular [dihedral angle 89.7 (1)°].

Figure 1
Molecular structure of (I)

. Atomic displacement ellipsoids are drawn at the 50% probability level.

Experimental

To a stirred light-yellow solution of [Co(PMe₃)₃(BO₂C₆H₄)₂] (Dai et al., 1996) (0.110 g, 0.21 mmol) in hexane (2.0 ml), 4-iodotoluene (0.054 g, 0.25 mmol) was added at room temperature, resulting in a brown solution. After heating at 343 K overnight, the mixture became pink in colour. The solvent was then removed in vacuo and the residues were redissolved in THF (10 ml) to which was added excess CoCl₂. The mixture was stirred for a further 15 min before being reduced to dryness in vacuo. The residues were then extracted with hexane and the resulting solution was concentrated in vacuo, during which a colourless solid appeared. This was redissolved by gentle heating, after which the solution was cooled slowly to give colourless crystals of (I) (0.015 g). ¹¹B NMR: δ 31.9. EI–MS m/z 210 (M⁺).

Crystal data

C₁₃H₁₁BO₂
M_r = 210.03
Monoclinic, P 2₁ /c
a = 17.7405 (10) Å
b = 4.9935 (4) Å
c = 12.3989 (16) Å
β = 100.80 (1)°
V = 1078.93 (17) Å³
Z = 4
D_x = 1.293 Mg m⁻³
Mo Kα radiation
Cell parameters from 687 reflections
θ = 10.3–24.0°
μ = 0.09 mm⁻¹
T = 120 (2) K
Plate, colourless
0.22 × 0.15 × 0.05 mm

Data collection

Bruker SMART 6000 CCD area-detector diffractometer
ω scans
Absorption correction: none
9171 measured reflections
2486 independent reflections
1654 reflections with I > 2σ(I)
R_int = 0.071
θ_max = 27.5°
h = −23 → 17
k = −6 → 6
l = −16 → 16

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.128
S = 1.02
2486 reflections
189 parameters
All H-atom parameters refined
w = 1/[σ²(F_o²) + (0.0681P)²] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.25 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

O1—C1	1.384 (2)
O1—B	1.389 (2)
O2—C2	1.384 (2)
O2—B	1.393 (2)
C7—B	1.533 (2)

O1—B—O2	111.00 (14)
O1—B—C7	124.33 (14)
O2—B—C7	124.66 (13)

O1—B—C7—C8	−3.0 (2)
O2—B—C7—C12	−3.4 (2)

All H atoms were refined isotropically, yielding the following distances: Csp³—H = 0.98 (2) to 1.01 (2) Å and Csp²—H = 0.95 (2) to 1.00 (2) Å.

Data collection: SMART (Bruker, 2001 ); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Bruker, 2001); 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/S1600536806004089/bt6814sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806004089/bt6814Isup2.hkl

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Bruker, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

2-(p-tolyl)-1,3,2-benzodioxaborole top

Crystal data top

C₁₃H₁₁BO₂	F(000) = 440
M_r = 210.03	D_x = 1.293 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.7405 (10) Å	Cell parameters from 687 reflections
b = 4.9935 (4) Å	θ = 10.3–24.0°
c = 12.3989 (16) Å	µ = 0.09 mm⁻¹
β = 100.80 (1)°	T = 120 K
V = 1078.93 (17) Å³	Plate, colourless
Z = 4	0.22 × 0.15 × 0.05 mm

Data collection top

Bruker SMART 6000 CCD area-detector diffractometer	1654 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.071
Graphite monochromator	θ_max = 27.5°, θ_min = 1.2°
Detector resolution: 5.6 pixels mm^-1	h = −23→17
ω scans	k = −6→6
9171 measured reflections	l = −16→16
2486 independent 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)] = 0.040	Hydrogen site location: difference Fourier map
wR(F²) = 0.128	All H-atom parameters refined
S = 1.02	w = 1/[σ²(F_o²) + (0.0681P)²] where P = (F_o² + 2F_c²)/3
2486 reflections	(Δ/σ)_max < 0.001
189 parameters	Δρ_max = 0.25 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Special details top

Experimental. The data collection nominally covered over 3/4 of the full sphere of reciprocal space, by a combination of 3 sets of ω scans; each set at different φ angles and each scan (20 sec exposure) covering 0.3° in ω. Crystal to detector distance 4.84 cm.

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.

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

	x	y	z	U_iso*/U_eq
O1	0.26370 (6)	0.5110 (2)	0.65710 (8)	0.0304 (3)
O2	0.32209 (6)	0.5032 (2)	0.50706 (8)	0.0317 (3)
C1	0.32220 (9)	0.6985 (3)	0.67077 (12)	0.0287 (4)
C2	0.35703 (9)	0.6944 (3)	0.58054 (12)	0.0297 (4)
C3	0.41590 (10)	0.8648 (4)	0.57084 (15)	0.0408 (4)
H3	0.4396 (11)	0.861 (4)	0.5035 (15)	0.047 (5)*
C4	0.43888 (11)	1.0432 (4)	0.65723 (16)	0.0436 (5)
H4	0.4779 (11)	1.172 (4)	0.6538 (14)	0.048 (5)*
C5	0.40358 (11)	1.0468 (3)	0.74747 (15)	0.0421 (5)
H5	0.4171 (11)	1.172 (4)	0.8068 (15)	0.049 (5)*
C6	0.34387 (10)	0.8728 (3)	0.75651 (13)	0.0367 (4)
H6	0.3182 (10)	0.877 (3)	0.8214 (15)	0.041 (5)*
C7	0.20757 (9)	0.1786 (3)	0.50309 (11)	0.0273 (3)
C8	0.15251 (9)	0.0748 (3)	0.55850 (13)	0.0316 (4)
H8	0.1495 (9)	0.140 (3)	0.6324 (14)	0.035 (4)*
C9	0.10013 (10)	−0.1151 (3)	0.51049 (13)	0.0341 (4)
H9	0.0606 (11)	−0.190 (4)	0.5502 (14)	0.049 (5)*
C10	0.10028 (9)	−0.2085 (3)	0.40431 (13)	0.0311 (4)
C11	0.15523 (9)	−0.1058 (3)	0.34862 (13)	0.0322 (4)
H11	0.1546 (10)	−0.172 (3)	0.2721 (14)	0.043 (5)*
C12	0.20784 (9)	0.0831 (3)	0.39697 (12)	0.0309 (4)
H12	0.2439 (10)	0.159 (3)	0.3550 (14)	0.041 (5)*
C13	0.04401 (11)	−0.4166 (3)	0.35259 (16)	0.0393 (4)
H131	0.0568 (12)	−0.597 (4)	0.3802 (17)	0.058 (6)*
H132	−0.0076 (13)	−0.384 (4)	0.3710 (18)	0.065 (7)*
H133	0.0387 (14)	−0.416 (4)	0.270 (2)	0.074 (7)*
B	0.26424 (10)	0.3944 (3)	0.55553 (13)	0.0274 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0311 (6)	0.0353 (6)	0.0255 (5)	0.0005 (5)	0.0074 (4)	−0.0008 (4)
O2	0.0331 (6)	0.0381 (6)	0.0247 (5)	−0.0070 (5)	0.0076 (4)	−0.0030 (4)
C1	0.0278 (8)	0.0291 (8)	0.0278 (7)	0.0047 (6)	0.0017 (6)	0.0018 (6)
C2	0.0295 (9)	0.0309 (8)	0.0269 (7)	0.0000 (7)	0.0006 (6)	−0.0005 (6)
C3	0.0367 (10)	0.0450 (10)	0.0404 (10)	−0.0074 (8)	0.0067 (8)	0.0005 (8)
C4	0.0366 (11)	0.0353 (9)	0.0545 (11)	−0.0063 (8)	−0.0023 (8)	−0.0005 (8)
C5	0.0430 (11)	0.0340 (9)	0.0428 (10)	0.0069 (8)	−0.0082 (8)	−0.0098 (8)
C6	0.0380 (10)	0.0383 (9)	0.0311 (8)	0.0077 (7)	0.0000 (7)	−0.0048 (7)
C7	0.0262 (8)	0.0295 (8)	0.0262 (7)	0.0036 (6)	0.0045 (6)	0.0035 (6)
C8	0.0330 (9)	0.0360 (8)	0.0269 (8)	0.0006 (7)	0.0080 (7)	0.0042 (6)
C9	0.0309 (9)	0.0363 (8)	0.0362 (9)	−0.0024 (7)	0.0086 (7)	0.0080 (7)
C10	0.0274 (9)	0.0268 (7)	0.0376 (8)	0.0020 (6)	0.0019 (6)	0.0051 (6)
C11	0.0321 (9)	0.0330 (8)	0.0317 (8)	0.0003 (7)	0.0060 (7)	−0.0033 (6)
C12	0.0298 (9)	0.0345 (8)	0.0296 (8)	−0.0008 (7)	0.0084 (7)	−0.0007 (6)
C13	0.0361 (11)	0.0322 (9)	0.0473 (11)	−0.0042 (8)	0.0021 (8)	0.0040 (7)
B	0.0290 (10)	0.0306 (9)	0.0232 (8)	0.0037 (7)	0.0063 (7)	0.0034 (6)

Geometric parameters (Å, º) top

O1—C1	1.384 (2)	C7—C12	1.400 (2)
O1—B	1.389 (2)	C7—B	1.533 (2)
O2—C2	1.384 (2)	C8—C9	1.382 (2)
O2—B	1.393 (2)	C8—H8	0.983 (16)
C1—C6	1.372 (2)	C9—C10	1.397 (2)
C1—C2	1.376 (2)	C9—H9	1.001 (18)
C2—C3	1.370 (2)	C10—C11	1.394 (2)
C3—C4	1.394 (3)	C10—C13	1.499 (2)
C3—H3	1.003 (18)	C11—C12	1.382 (2)
C4—C5	1.381 (3)	C11—H11	1.002 (17)
C4—H4	0.95 (2)	C12—H12	0.974 (18)
C5—C6	1.391 (3)	C13—H131	0.98 (2)
C5—H5	0.962 (19)	C13—H132	1.00 (2)
C6—H6	0.996 (18)	C13—H133	1.01 (2)
C7—C8	1.395 (2)

C1—O1—B	105.19 (12)	C9—C8—H8	118.5 (10)
C2—O2—B	105.09 (11)	C7—C8—H8	120.2 (10)
C6—C1—C2	122.41 (15)	C8—C9—C10	121.00 (15)
C6—C1—O1	128.22 (14)	C8—C9—H9	121.3 (10)
C2—C1—O1	109.34 (13)	C10—C9—H9	117.7 (10)
C3—C2—C1	121.89 (15)	C11—C10—C9	117.99 (15)
C3—C2—O2	128.74 (14)	C11—C10—C13	120.96 (15)
C1—C2—O2	109.36 (13)	C9—C10—C13	121.04 (15)
C2—C3—C4	116.59 (16)	C12—C11—C10	120.95 (15)
C2—C3—H3	120.5 (11)	C12—C11—H11	121.4 (10)
C4—C3—H3	122.9 (11)	C10—C11—H11	117.7 (10)
C5—C4—C3	121.26 (17)	C11—C12—C7	121.26 (15)
C5—C4—H4	118.1 (11)	C11—C12—H12	119.4 (10)
C3—C4—H4	120.6 (11)	C7—C12—H12	119.2 (10)
C4—C5—C6	121.68 (16)	C10—C13—H131	113.5 (12)
C4—C5—H5	122.8 (11)	C10—C13—H132	110.8 (12)
C6—C5—H5	115.5 (11)	H131—C13—H132	103.4 (17)
C1—C6—C5	116.17 (16)	C10—C13—H133	111.1 (13)
C1—C6—H6	122.5 (11)	H131—C13—H133	109.2 (17)
C5—C6—H6	121.4 (10)	H132—C13—H133	108.3 (19)
C8—C7—C12	117.52 (15)	O1—B—O2	111.00 (14)
C8—C7—B	121.09 (13)	O1—B—C7	124.33 (14)
C12—C7—B	121.37 (13)	O2—B—C7	124.66 (13)
C9—C8—C7	121.28 (15)

O1—B—C7—C8	−3.0 (2)	O2—B—C7—C12	−3.4 (2)

Acknowledgements

The authors thank the EPSRC for financial support and Frontier Scientific Inc. for generous gifts of diborane(4) compounds.

References

Adams, C. J., Baber, R. A., Batsanov, A. S., Bramham, G., Charmant, J. P. H., Haddow, M. F., Howard, J. A. K., Lam, W. H., Lin, Z. Y., Marder, T. B., Norman, N. C. & Orpen, A. G. (2006). Dalton Trans. In the press (DOI 10 1039/b516594f). Google Scholar
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