organic compounds
2-(p-Tolyl)-1,3,2-benzodioxaborole
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
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 ), 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)°].
comprises one molecule (Fig. 1Experimental
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
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Data collection
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Refinement
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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 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
https://doi.org/10.1107/S1600536806004089/bt6814sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536806004089/bt6814Isup2.hkl
Data collection: SMART (Bruker, 2001); cell
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.C13H11BO2 | F(000) = 440 |
Mr = 210.03 | Dx = 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 |
Bruker SMART 6000 CCD area-detector diffractometer | 1654 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.071 |
Graphite monochromator | θmax = 27.5°, θmin = 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 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(Fo2) + (0.0681P)2] where P = (Fo2 + 2Fc2)/3 |
2486 reflections | (Δ/σ)max < 0.001 |
189 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.19 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
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) |
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) |
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
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