Literature DB >> 21587929

Mesit-yl(2,4,6-trimeth-oxy-phen-yl)borinic acid.

Sergiusz Luliński1, Janusz Serwatowski.   

Abstract

In the title mol-ecule, C(18)H(23)BO(4), the dihedral angle between the least-squares planes of the aromatic rings is 84.88 (3)°. The B atom deviates by 0.202 (1) Å from the least-squares plane of the mesityl ring. All of the meth-oxy groups are approximately coplanar with the 2,4,6-trimeth-oxy-phenyl ring, whereas the BOH group is twisted with respect to it by 19.5°. The borinic OH group is engaged in an intra-molecular O-H⋯O hydrogen bond with one of ortho-meth-oxy groups. The mol-ecular structure is stabilized by weak C-H⋯O contacts. In the crystal, mol-ecules are linked by weak C-H⋯O and C-H⋯π inter-actions, generating a three-dimensional network.

Entities:  

Year:  2010        PMID： 21587929      PMCID： PMC3006901          DOI： 10.1107/S160053681002297X

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For background to ortho-alk­oxy­aryl­boronic acids, see: (Dąbrowski et al. 2008 ▶; Luliński (2008 ▶). For related structures, see: Beringhelli et al. (2003 ▶); Cornet et al. (2003 ▶); Entwistle et al. (2007 ▶); Kuhlmann et al. (2008 ▶); Weese et al. (1987 ▶).

Experimental

Crystal data

C18H23BO4 M = 314.17 Monoclinic, a = 6.7775 (2) Å b = 13.0005 (4) Å c = 19.6234 (7) Å β = 98.895 (3)° V = 1708.24 (10) Å3 Z = 4 Mo Kα radiation μ = 0.08 mm−1 T = 100 K 0.61 × 0.40 × 0.17 mm

Data collection

Oxford Diffraction KM-4-CCD diffractometer Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2005 ▶) T min = 0.93, T max = 0.99 28861 measured reflections 4194 independent reflections 3326 reflections with I > 2σ(I) R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.038 wR(F 2) = 0.119 S = 1.15 4194 reflections 216 parameters H-atom parameters constrained Δρmax = 0.37 e Å−3 Δρmin = −0.25 e Å−3 Data collection: CrysAlis CCD (Oxford Diffraction, 2005 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2005 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXL97. Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681002297X/pv2296sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S160053681002297X/pv2296Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
C18H23BO4F(000) = 672
Mr = 314.17Dx = 1.222 Mg m−3
Monoclinic, P21/cMelting point: 411 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 6.7775 (2) ÅCell parameters from 19650 reflections
b = 13.0005 (4) Åθ = 2.2–28.9°
c = 19.6234 (7) ŵ = 0.08 mm−1
β = 98.895 (3)°T = 100 K
V = 1708.24 (10) Å3Prismatic, colourless
Z = 40.61 × 0.40 × 0.17 mm
Oxford Diffraction KM-4-CCD diffractometer4194 independent reflections
Radiation source: fine-focus sealed tube3326 reflections with I > 2σ(I)
graphiteRint = 0.016
Detector resolution: 8.6479 pixels mm-1θmax = 28.6°, θmin = 3.0°
ω scanh = −8→9
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2005)k = −17→17
Tmin = 0.93, Tmax = 0.99l = −26→26
28861 measured reflections
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.119w = 1/[σ2(Fo2) + (0.0686P)2 + 0.1911P] where P = (Fo2 + 2Fc2)/3
S = 1.15(Δ/σ)max = 0.004
4194 reflectionsΔρmax = 0.37 e Å−3
216 parametersΔρmin = −0.25 e Å−3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0075 (17)
Experimental. Yield of (I) 3.5 g, m.p. 410 K. 1H NMR (CDCl3): 8.62 (br, 1 H), 6.75 (s, 2 H), 6.10 (s, 1 H), 3.85 (s, 3 H), 3.64 (s, 6 H), 2.28 (s, 3 H), 2.22 (s, 6 H) p.p.m.; 13C NMR: 167.8, 164.5, 137.4, 135.5, 126.3, 90.8, 55.6, 55.2, 21.7, 21.1 p.p.m.; 11B NMR: 52.0 p.p.m..
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.
xyzUiso*/Ueq
B10.23386 (18)1.01129 (9)0.18572 (6)0.0181 (3)
O20.16799 (14)1.03300 (6)0.24658 (4)0.0299 (2)
H20.10600.98200.25890.045*
C30.20989 (15)0.89979 (8)0.15476 (5)0.0162 (2)
C40.06690 (16)0.83008 (8)0.17250 (5)0.0172 (2)
C50.03526 (16)0.73224 (8)0.14369 (5)0.0184 (2)
H5−0.06660.68860.15560.022*
C60.15707 (17)0.70085 (8)0.09724 (5)0.0188 (2)
C70.30614 (16)0.76388 (8)0.07894 (5)0.0183 (2)
H70.39050.74040.04780.022*
C80.32920 (15)0.86210 (8)0.10719 (5)0.0159 (2)
O9−0.04374 (12)0.86431 (6)0.22104 (4)0.0250 (2)
C10−0.20118 (18)0.80035 (9)0.23876 (7)0.0263 (3)
H10A−0.26400.83430.27450.039*
H10B−0.14570.73410.25610.039*
H10C−0.30120.78910.19770.039*
O110.14219 (13)0.60596 (6)0.06627 (4)0.0269 (2)
C120.0047 (2)0.53478 (10)0.08829 (7)0.0334 (3)
H12A0.01240.46920.06430.050*
H12B−0.13110.56240.07760.050*
H12C0.03840.52390.13820.050*
C140.59619 (17)0.89498 (9)0.04312 (6)0.0228 (3)
H14A0.69170.94940.03690.034*
H14B0.51250.8802−0.00110.034*
H14C0.66890.83270.06020.034*
O130.47269 (11)0.92799 (6)0.09198 (4)0.02081 (19)
C150.31889 (16)1.10878 (8)0.15189 (5)0.0163 (2)
C160.50993 (16)1.14768 (9)0.17717 (6)0.0208 (2)
C170.57168 (17)1.24091 (9)0.15249 (6)0.0258 (3)
H170.70121.26630.16990.031*
C180.44838 (19)1.29785 (9)0.10304 (6)0.0262 (3)
C190.26153 (18)1.25828 (9)0.07763 (6)0.0236 (3)
H190.17611.29570.04340.028*
C200.19551 (16)1.16476 (8)0.10112 (5)0.0185 (2)
C210.64605 (19)1.08778 (10)0.23081 (7)0.0335 (3)
H21A0.65031.01580.21630.050*
H21B0.59571.09150.27490.050*
H21C0.78081.11710.23610.050*
C220.5173 (2)1.40011 (10)0.07841 (8)0.0414 (4)
H22A0.55471.44570.11810.062*
H22B0.40871.43160.04640.062*
H22C0.63291.38930.05490.062*
C23−0.00965 (18)1.12497 (10)0.07206 (6)0.0274 (3)
H23A−0.09081.18140.04960.041*
H23B−0.07371.09690.10950.041*
H23C0.00241.07080.03820.041*
U11U22U33U12U13U23
B10.0186 (6)0.0170 (6)0.0192 (6)0.0006 (4)0.0042 (4)−0.0005 (5)
O20.0484 (6)0.0182 (4)0.0279 (5)−0.0070 (4)0.0214 (4)−0.0055 (3)
C30.0181 (5)0.0140 (5)0.0167 (5)0.0005 (4)0.0034 (4)0.0006 (4)
C40.0193 (5)0.0158 (5)0.0173 (5)0.0027 (4)0.0053 (4)0.0020 (4)
C50.0206 (5)0.0146 (5)0.0204 (5)−0.0024 (4)0.0043 (4)0.0027 (4)
C60.0255 (6)0.0128 (5)0.0172 (5)−0.0004 (4)0.0009 (4)−0.0009 (4)
C70.0226 (5)0.0169 (5)0.0160 (5)0.0007 (4)0.0050 (4)−0.0011 (4)
C80.0170 (5)0.0154 (5)0.0154 (5)−0.0006 (4)0.0024 (4)0.0013 (4)
O90.0306 (5)0.0161 (4)0.0332 (5)−0.0025 (3)0.0208 (4)−0.0010 (3)
C100.0287 (6)0.0222 (6)0.0319 (6)−0.0031 (5)0.0169 (5)0.0047 (5)
O110.0402 (5)0.0156 (4)0.0275 (4)−0.0085 (3)0.0131 (4)−0.0071 (3)
C120.0508 (8)0.0184 (6)0.0341 (7)−0.0141 (5)0.0166 (6)−0.0074 (5)
C140.0221 (6)0.0228 (6)0.0262 (6)−0.0004 (4)0.0122 (5)−0.0025 (5)
O130.0226 (4)0.0178 (4)0.0248 (4)−0.0045 (3)0.0124 (3)−0.0048 (3)
C150.0184 (5)0.0136 (5)0.0179 (5)0.0002 (4)0.0061 (4)−0.0043 (4)
C160.0189 (5)0.0182 (5)0.0257 (5)0.0000 (4)0.0055 (4)−0.0069 (4)
C170.0207 (6)0.0213 (6)0.0377 (7)−0.0067 (4)0.0118 (5)−0.0114 (5)
C180.0361 (7)0.0157 (5)0.0314 (6)−0.0036 (5)0.0199 (5)−0.0033 (5)
C190.0339 (6)0.0176 (5)0.0212 (5)0.0032 (5)0.0107 (5)0.0014 (4)
C200.0219 (5)0.0171 (5)0.0176 (5)0.0008 (4)0.0066 (4)−0.0023 (4)
C210.0249 (6)0.0304 (7)0.0413 (7)0.0023 (5)−0.0073 (5)−0.0058 (6)
C220.0577 (9)0.0208 (6)0.0523 (9)−0.0102 (6)0.0295 (7)−0.0005 (6)
C230.0244 (6)0.0293 (6)0.0266 (6)−0.0003 (5)−0.0022 (5)0.0013 (5)
B1—O21.3675 (14)C14—H14A0.9800
B1—C31.5704 (15)C14—H14B0.9800
B1—C151.5803 (16)C14—H14C0.9800
O2—H20.8400C15—C201.4014 (15)
C3—C41.4093 (14)C15—C161.4070 (15)
C3—C81.4138 (14)C16—C171.3933 (17)
C4—O91.3742 (13)C16—C211.5051 (17)
C4—C51.3950 (15)C17—C181.3919 (18)
C5—C61.3827 (15)C17—H170.9500
C5—H50.9500C18—C191.3863 (17)
C6—O111.3719 (13)C18—C221.5128 (17)
C6—C71.3904 (15)C19—C201.3981 (16)
C7—C81.3911 (15)C19—H190.9500
C7—H70.9500C20—C231.5103 (16)
C8—O131.3633 (12)C21—H21A0.9800
O9—C101.4372 (13)C21—H21B0.9800
C10—H10A0.9800C21—H21C0.9800
C10—H10B0.9800C22—H22A0.9800
C10—H10C0.9800C22—H22B0.9800
O11—C121.4268 (14)C22—H22C0.9800
C12—H12A0.9800C23—H23A0.9800
C12—H12B0.9800C23—H23B0.9800
C12—H12C0.9800C23—H23C0.9800
C14—O131.4325 (13)
O2—B1—C3120.01 (10)H14A—C14—H14C109.5
O2—B1—C15113.00 (9)H14B—C14—H14C109.5
C3—B1—C15126.90 (9)C8—O13—C14117.95 (8)
B1—O2—H2109.5C20—C15—C16118.65 (10)
C4—C3—C8115.19 (9)C20—C15—B1119.92 (9)
C4—C3—B1122.13 (9)C16—C15—B1121.04 (10)
C8—C3—B1122.68 (9)C17—C16—C15119.98 (11)
O9—C4—C5120.66 (9)C17—C16—C21120.57 (11)
O9—C4—C3115.65 (9)C15—C16—C21119.45 (10)
C5—C4—C3123.69 (9)C18—C17—C16121.65 (11)
C6—C5—C4117.79 (10)C18—C17—H17119.2
C6—C5—H5121.1C16—C17—H17119.2
C4—C5—H5121.1C19—C18—C17118.03 (11)
O11—C6—C5123.15 (10)C19—C18—C22121.41 (12)
O11—C6—C7114.97 (10)C17—C18—C22120.56 (12)
C5—C6—C7121.87 (10)C18—C19—C20121.69 (11)
C6—C7—C8118.65 (10)C18—C19—H19119.2
C6—C7—H7120.7C20—C19—H19119.2
C8—C7—H7120.7C19—C20—C15119.98 (10)
O13—C8—C7121.98 (9)C19—C20—C23119.75 (10)
O13—C8—C3115.27 (9)C15—C20—C23120.26 (10)
C7—C8—C3122.73 (9)C16—C21—H21A109.5
C4—O9—C10119.04 (9)C16—C21—H21B109.5
O9—C10—H10A109.5H21A—C21—H21B109.5
O9—C10—H10B109.5C16—C21—H21C109.5
H10A—C10—H10B109.5H21A—C21—H21C109.5
O9—C10—H10C109.5H21B—C21—H21C109.5
H10A—C10—H10C109.5C18—C22—H22A109.5
H10B—C10—H10C109.5C18—C22—H22B109.5
C6—O11—C12117.12 (9)H22A—C22—H22B109.5
O11—C12—H12A109.5C18—C22—H22C109.5
O11—C12—H12B109.5H22A—C22—H22C109.5
H12A—C12—H12B109.5H22B—C22—H22C109.5
O11—C12—H12C109.5C20—C23—H23A109.5
H12A—C12—H12C109.5C20—C23—H23B109.5
H12B—C12—H12C109.5H23A—C23—H23B109.5
O13—C14—H14A109.5C20—C23—H23C109.5
O13—C14—H14B109.5H23A—C23—H23C109.5
H14A—C14—H14B109.5H23B—C23—H23C109.5
O13—C14—H14C109.5
O2—B1—C3—C422.19 (16)C7—C6—O11—C12174.12 (10)
C15—B1—C3—C4−154.17 (11)C7—C8—O13—C142.63 (15)
O2—B1—C3—C8−157.91 (10)C3—C8—O13—C14−178.89 (9)
C15—B1—C3—C825.73 (17)O2—B1—C15—C20−95.70 (12)
C8—C3—C4—O9177.19 (9)C3—B1—C15—C2080.87 (14)
B1—C3—C4—O9−2.90 (15)O2—B1—C15—C1677.06 (13)
C8—C3—C4—C5−2.93 (15)C3—B1—C15—C16−106.37 (13)
B1—C3—C4—C5176.97 (10)C20—C15—C16—C171.03 (15)
O9—C4—C5—C6−177.41 (10)B1—C15—C16—C17−171.82 (10)
C3—C4—C5—C62.72 (16)C20—C15—C16—C21−178.94 (10)
C4—C5—C6—O11179.07 (10)B1—C15—C16—C218.21 (16)
C4—C5—C6—C7−0.35 (16)C15—C16—C17—C180.20 (17)
O11—C6—C7—C8178.98 (9)C21—C16—C17—C18−179.83 (11)
C5—C6—C7—C8−1.55 (16)C16—C17—C18—C19−1.15 (17)
C6—C7—C8—O13179.63 (9)C16—C17—C18—C22178.50 (11)
C6—C7—C8—C31.26 (16)C17—C18—C19—C200.87 (17)
C4—C3—C8—O13−177.59 (9)C22—C18—C19—C20−178.77 (11)
B1—C3—C8—O132.50 (15)C18—C19—C20—C150.36 (16)
C4—C3—C8—C70.88 (15)C18—C19—C20—C23179.78 (10)
B1—C3—C8—C7−179.03 (10)C16—C15—C20—C19−1.30 (15)
C5—C4—O9—C10−3.75 (15)B1—C15—C20—C19171.63 (10)
C3—C4—O9—C10176.13 (10)C16—C15—C20—C23179.28 (10)
C5—C6—O11—C12−5.34 (16)B1—C15—C20—C23−7.79 (15)
Cg is the centroid of the C15–C20 ring.
D—H···AD—HH···AD···AD—H···A
O2—H2···O90.841.922.6262 (11)141
C21—H21A···O130.982.793.4825 (15)128
C10—H10B···O2i0.982.613.4920 (14)149
C12—H12A···O11ii0.982.793.5502 (15)135
C12—H12C···O2i0.982.843.6116 (17)136
C21—H21C···O2iii0.982.823.5746 (16)134
C21—H21A···O9iii0.982.853.6086 (15)135
C10—H10A···Cgiv0.982.793.3266 (14)115
C14—H14A···Cgv0.982.883.5988 (12)130
Table 1

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C15–C20 ring.

D—H⋯AD—HH⋯AD⋯AD—H⋯A
O2—H2⋯O90.841.922.6262 (11)141
C21—H21A⋯O130.982.793.4825 (15)128
C10—H10B⋯O2i0.982.613.4920 (14)149
C12—H12A⋯O11ii0.982.793.5502 (15)135
C12—H12C⋯O2i0.982.843.6116 (17)136
C21—H21C⋯O2iii0.982.823.5746 (16)134
C21—H21A⋯O9iii0.982.853.6086 (15)135
C10—H10A⋯Cgiv0.982.793.3266 (14)115
C14—H14A⋯Cgv0.982.883.5988 (12)130

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .

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