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In the title compound, C
12H
16BNO
2, the B—N distance is 1.662 (4) Å. Molecules are linked through intermolecular N—H
O hydrogen bonds to form infinite chains with an N
O distance of 2.810 (2) Å.
Supporting information
CCDC reference: 182602
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.003 Å
- R factor = 0.030
- wR factor = 0.080
- Data-to-parameter ratio = 8.4
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
General Notes
REFLT_03
From the CIF: _diffrn_reflns_theta_max 26.36
From the CIF: _reflns_number_total 1259
Count of symmetry unique reflns 1267
Completeness (_total/calc) 99.37%
TEST3: Check Friedels for noncentro structure
Estimate of Friedel pairs measured 0
Fraction of Friedel pairs measured 0.000
Are heavy atom types Z>Si present no
Please check that the estimate of the number of Friedel pairs is
correct. If it is not, please give the correct count in the
_publ_section_exptl_refinement section of the submitted CIF.
Crystals of (I) were obtained by treatment of
(E)-2-phenyl-1-ethenylboronic acid dissolved in minimal amount of
2-propanol with diethanolamine (1 equiv.). The mixture was stirred for 2 h at
298 K prior to collection of the precipitate by filtration. Recrystallization
of the solid from acetonitrile gave (I) in 69% yield.
Hydrogen atoms were included in calculated positions with C—H distances
ranging from 0.95 to 0.99 Å, and the H atom to the N was refined with an
isotropic thermal parameter.
Data collection: COLLECT (Nonius, 1997–2001); cell refinement: DENZO SMN (Otwinowski & Minor, 1997); data reduction: DENZO SMN; program(s) used to solve structure: SHELXTL/PC (Sheldrick, 2001); program(s) used to refine structure: SHELXTL/PC; molecular graphics: SHELXTL/PC; software used to prepare material for publication: SHELXTL/PC.
(
E)-2-Styryl-[1,3,6,2]dioxazaborolane
top
Crystal data top
C12H16BNO2 | Dx = 1.246 Mg m−3 |
Mr = 217.07 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pca21 | Cell parameters from 8659 reflections |
a = 13.3725 (4) Å | θ = 4.2–26.4° |
b = 9.7045 (3) Å | µ = 0.08 mm−1 |
c = 8.9200 (2) Å | T = 150 K |
V = 1157.58 (6) Å3 | Needle, colourless |
Z = 4 | 0.43 × 0.25 × 0.15 mm |
F(000) = 464 | |
Data collection top
Nonius Kappa-CCD diffractometer | 1167 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.037 |
Graphite monochromator | θmax = 26.4°, θmin = 4.2° |
Detector resolution: 9 pixels mm-1 | h = −16→16 |
ϕ scans and ω scans with κ offsets | k = −12→12 |
8659 measured reflections | l = −11→11 |
1259 independent reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.030 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.080 | w = 1/[σ2(Fo2) + (0.0467P)2 + 0.1149P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
1259 reflections | Δρmax = 0.16 e Å−3 |
150 parameters | Δρmin = −0.14 e Å−3 |
1 restraint | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.026 (6) |
Crystal data top
C12H16BNO2 | V = 1157.58 (6) Å3 |
Mr = 217.07 | Z = 4 |
Orthorhombic, Pca21 | Mo Kα radiation |
a = 13.3725 (4) Å | µ = 0.08 mm−1 |
b = 9.7045 (3) Å | T = 150 K |
c = 8.9200 (2) Å | 0.43 × 0.25 × 0.15 mm |
Data collection top
Nonius Kappa-CCD diffractometer | 1167 reflections with I > 2σ(I) |
8659 measured reflections | Rint = 0.037 |
1259 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.030 | 1 restraint |
wR(F2) = 0.080 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | Δρmax = 0.16 e Å−3 |
1259 reflections | Δρmin = −0.14 e Å−3 |
150 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 | Uiso*/Ueq | |
O1 | 0.36568 (9) | 0.02575 (12) | 0.57885 (15) | 0.0287 (3) | |
O2 | 0.54825 (9) | 0.03601 (13) | 0.57204 (15) | 0.0280 (3) | |
N1 | 0.45858 (10) | −0.09011 (15) | 0.38133 (16) | 0.0222 (3) | |
C1 | 0.44798 (13) | 0.18667 (18) | 0.3898 (2) | 0.0250 (4) | |
H1A | 0.5097 | 0.2278 | 0.3620 | 0.030* | |
C2 | 0.36498 (13) | 0.24859 (19) | 0.3429 (2) | 0.0302 (4) | |
H2A | 0.3035 | 0.2098 | 0.3755 | 0.036* | |
C3 | 0.35828 (15) | 0.37126 (18) | 0.2457 (2) | 0.0303 (4) | |
C4 | 0.26994 (16) | 0.3983 (2) | 0.1683 (3) | 0.0415 (5) | |
H4A | 0.2141 | 0.3391 | 0.1817 | 0.050* | |
C5 | 0.26187 (18) | 0.5101 (2) | 0.0720 (3) | 0.0465 (5) | |
H5A | 0.2013 | 0.5261 | 0.0191 | 0.056* | |
C6 | 0.34207 (17) | 0.5978 (2) | 0.0531 (3) | 0.0416 (5) | |
H6A | 0.3366 | 0.6751 | −0.0118 | 0.050* | |
C7 | 0.43061 (17) | 0.57307 (19) | 0.1291 (2) | 0.0381 (5) | |
H7A | 0.4860 | 0.6332 | 0.1158 | 0.046* | |
C8 | 0.43859 (15) | 0.46087 (18) | 0.2244 (2) | 0.0321 (4) | |
H8A | 0.4996 | 0.4447 | 0.2759 | 0.039* | |
C9 | 0.34381 (13) | −0.11719 (19) | 0.5789 (2) | 0.0304 (4) | |
H9A | 0.2728 | −0.1334 | 0.6051 | 0.036* | |
H9B | 0.3866 | −0.1665 | 0.6519 | 0.036* | |
C10 | 0.36543 (13) | −0.16522 (19) | 0.4206 (2) | 0.0298 (4) | |
H10A | 0.3759 | −0.2662 | 0.4172 | 0.036* | |
H10B | 0.3102 | −0.1404 | 0.3519 | 0.036* | |
C11 | 0.61617 (13) | −0.0472 (2) | 0.4910 (2) | 0.0306 (4) | |
H11A | 0.6678 | −0.0859 | 0.5585 | 0.037* | |
H11B | 0.6496 | 0.0070 | 0.4114 | 0.037* | |
C12 | 0.55287 (13) | −0.16096 (19) | 0.4235 (2) | 0.0305 (4) | |
H12A | 0.5859 | −0.2014 | 0.3344 | 0.037* | |
H12B | 0.5401 | −0.2348 | 0.4976 | 0.037* | |
B1 | 0.45355 (13) | 0.05011 (19) | 0.4881 (2) | 0.0232 (4) | |
H1N | 0.4571 (17) | −0.069 (2) | 0.290 (3) | 0.037 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0308 (6) | 0.0325 (7) | 0.0227 (6) | 0.0010 (5) | 0.0059 (6) | −0.0003 (6) |
O2 | 0.0284 (6) | 0.0344 (7) | 0.0210 (7) | 0.0015 (5) | −0.0038 (5) | −0.0017 (5) |
N1 | 0.0246 (7) | 0.0261 (7) | 0.0160 (7) | 0.0005 (6) | 0.0000 (6) | 0.0010 (6) |
C1 | 0.0293 (8) | 0.0264 (8) | 0.0195 (8) | −0.0024 (6) | 0.0014 (7) | −0.0025 (7) |
C2 | 0.0305 (8) | 0.0294 (9) | 0.0306 (9) | −0.0011 (7) | 0.0008 (8) | 0.0034 (8) |
C3 | 0.0341 (9) | 0.0291 (9) | 0.0277 (9) | 0.0018 (7) | 0.0008 (7) | 0.0007 (8) |
C4 | 0.0367 (10) | 0.0395 (10) | 0.0485 (13) | 0.0003 (8) | −0.0041 (9) | 0.0114 (10) |
C5 | 0.0428 (11) | 0.0464 (11) | 0.0503 (13) | 0.0072 (9) | −0.0081 (12) | 0.0135 (11) |
C6 | 0.0556 (13) | 0.0304 (9) | 0.0387 (11) | 0.0073 (9) | 0.0034 (10) | 0.0099 (9) |
C7 | 0.0469 (11) | 0.0303 (10) | 0.0372 (12) | −0.0030 (8) | 0.0030 (9) | 0.0037 (8) |
C8 | 0.0377 (10) | 0.0299 (9) | 0.0287 (9) | −0.0011 (7) | −0.0008 (8) | 0.0010 (7) |
C9 | 0.0291 (9) | 0.0369 (10) | 0.0250 (9) | −0.0037 (7) | 0.0017 (8) | 0.0044 (8) |
C10 | 0.0293 (9) | 0.0346 (10) | 0.0255 (9) | −0.0069 (8) | 0.0001 (8) | 0.0005 (8) |
C11 | 0.0233 (8) | 0.0424 (11) | 0.0262 (9) | 0.0018 (7) | 0.0014 (8) | 0.0014 (8) |
C12 | 0.0294 (9) | 0.0322 (9) | 0.0297 (10) | 0.0072 (7) | −0.0003 (8) | −0.0005 (8) |
B1 | 0.0264 (9) | 0.0270 (10) | 0.0161 (9) | 0.0006 (7) | −0.0008 (8) | −0.0029 (8) |
Geometric parameters (Å, º) top
O1—C9 | 1.418 (2) | C5—C6 | 1.380 (3) |
O1—B1 | 1.446 (2) | C5—H5A | 0.9500 |
O2—C11 | 1.414 (2) | C6—C7 | 1.385 (3) |
O2—B1 | 1.477 (2) | C6—H6A | 0.9500 |
N1—C12 | 1.485 (2) | C7—C8 | 1.385 (3) |
N1—C10 | 1.485 (2) | C7—H7A | 0.9500 |
N1—B1 | 1.663 (2) | C8—H8A | 0.9500 |
N1—H1N | 0.84 (3) | C9—C10 | 1.515 (3) |
C1—C2 | 1.330 (2) | C9—H9A | 0.9900 |
C1—B1 | 1.591 (3) | C9—H9B | 0.9900 |
C1—H1A | 0.9500 | C10—H10A | 0.9900 |
C2—C3 | 1.476 (3) | C10—H10B | 0.9900 |
C2—H2A | 0.9500 | C11—C12 | 1.516 (3) |
C3—C4 | 1.393 (3) | C11—H11A | 0.9900 |
C3—C8 | 1.395 (3) | C11—H11B | 0.9900 |
C4—C5 | 1.387 (3) | C12—H12A | 0.9900 |
C4—H4A | 0.9500 | C12—H12B | 0.9900 |
| | | |
C9—O1—B1 | 109.14 (13) | C3—C8—H8A | 119.5 |
C11—O2—B1 | 110.16 (14) | O1—C9—C10 | 105.15 (15) |
C12—N1—C10 | 115.16 (14) | O1—C9—H9A | 110.7 |
C12—N1—B1 | 105.55 (13) | C10—C9—H9A | 110.7 |
C10—N1—B1 | 103.44 (13) | O1—C9—H9B | 110.7 |
C12—N1—H1N | 112.3 (16) | C10—C9—H9B | 110.7 |
C10—N1—H1N | 109.3 (16) | H9A—C9—H9B | 108.8 |
B1—N1—H1N | 110.5 (15) | N1—C10—C9 | 103.24 (14) |
C2—C1—B1 | 126.08 (16) | N1—C10—H10A | 111.1 |
C2—C1—H1A | 117.0 | C9—C10—H10A | 111.1 |
B1—C1—H1A | 117.0 | N1—C10—H10B | 111.1 |
C1—C2—C3 | 126.88 (17) | C9—C10—H10B | 111.1 |
C1—C2—H2A | 116.6 | H10A—C10—H10B | 109.1 |
C3—C2—H2A | 116.6 | O2—C11—C12 | 105.08 (13) |
C4—C3—C8 | 117.87 (17) | O2—C11—H11A | 110.7 |
C4—C3—C2 | 119.67 (17) | C12—C11—H11A | 110.7 |
C8—C3—C2 | 122.44 (18) | O2—C11—H11B | 110.7 |
C5—C4—C3 | 121.35 (19) | C12—C11—H11B | 110.7 |
C5—C4—H4A | 119.3 | H11A—C11—H11B | 108.8 |
C3—C4—H4A | 119.3 | N1—C12—C11 | 103.74 (14) |
C6—C5—C4 | 119.8 (2) | N1—C12—H12A | 111.0 |
C6—C5—H5A | 120.1 | C11—C12—H12A | 111.0 |
C4—C5—H5A | 120.1 | N1—C12—H12B | 111.0 |
C5—C6—C7 | 119.85 (19) | C11—C12—H12B | 111.0 |
C5—C6—H6A | 120.1 | H12A—C12—H12B | 109.0 |
C7—C6—H6A | 120.1 | O1—B1—O2 | 113.45 (16) |
C6—C7—C8 | 120.15 (19) | O1—B1—C1 | 113.99 (14) |
C6—C7—H7A | 119.9 | O2—B1—C1 | 113.36 (14) |
C8—C7—H7A | 119.9 | O1—B1—N1 | 102.69 (13) |
C7—C8—C3 | 120.96 (19) | O2—B1—N1 | 100.36 (12) |
C7—C8—H8A | 119.5 | C1—B1—N1 | 111.57 (15) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2i | 0.84 (3) | 1.97 (3) | 2.810 (2) | 175 (2) |
Symmetry code: (i) −x+1, −y, z−1/2. |
Experimental details
Crystal data |
Chemical formula | C12H16BNO2 |
Mr | 217.07 |
Crystal system, space group | Orthorhombic, Pca21 |
Temperature (K) | 150 |
a, b, c (Å) | 13.3725 (4), 9.7045 (3), 8.9200 (2) |
V (Å3) | 1157.58 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.43 × 0.25 × 0.15 |
|
Data collection |
Diffractometer | Nonius Kappa-CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 8659, 1259, 1167 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.625 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.080, 1.08 |
No. of reflections | 1259 |
No. of parameters | 150 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.16, −0.14 |
Selected geometric parameters (Å, º) topO1—B1 | 1.446 (2) | N1—B1 | 1.663 (2) |
O2—B1 | 1.477 (2) | C1—B1 | 1.591 (3) |
| | | |
O1—B1—O2 | 113.45 (16) | O2—B1—C1 | 113.36 (14) |
O1—B1—C1 | 113.99 (14) | C1—B1—N1 | 111.57 (15) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O2i | 0.84 (3) | 1.97 (3) | 2.810 (2) | 175 (2) |
Symmetry code: (i) −x+1, −y, z−1/2. |
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The title compound (I) shows high reactivity in rhodium(I)-catalysed 1,4-additions to α,β-unsaturated carbonyl compounds and additions to aldehydes (see Scheme below) (Batey & Smil, 2001). Use of (E)-2-phenyl-1-ethenylboronic acid, along with other aryl- and alkenylboronic acids, in 1,4-additions to α,β-unsaturated carbonyl compounds (Sakai et al., 1997) and additions to aldehydes (Sakai et al., 1998) has been reported, but the additional stability of diethanolamine boronate (I) to air and water makes its preparation, isolation, storage and handling more facile.
The structure of (I) is similar to that of the compounds 4,5,7,8-tetrahydro-2-(2-propenyl)-6H-[1,3,6,2]-dioxazaborocine (II) (Thadani et al., 2001a) and 2-(2-cyclohex-1-enylvinyl)-[1,3,6,2] dioxazaborocane (III) (Thadani et al., 2001b) which we have already determined. Molecules of (I) are linked by hydrogen bonds to form infinite chains through 21 screw axes in the y direction. The N···O distance in (I) is 2.810 (2) Å for N1.·O1 (see Fig. 2 and Table 2). The B1—N1 distance is 1.662 (4) Å in (I), 1.6720 (17) Å in (II) and 1.659 (4) Å in (III). A list of references for other dioxazaborocine compounds is included in our earlier paper (Thadani et al., 2001a).