Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801014866/om6050sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801014866/om6050Isup2.hkl |
CCDC reference: 175360
Key indicators
- Single-crystal X-ray study
- T = 173 K
- Mean (C-C) = 0.002 Å
- R factor = 0.037
- wR factor = 0.058
- Data-to-parameter ratio = 15.9
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
REFLT_03 From the CIF: _diffrn_reflns_theta_max 27.89 From the CIF: _reflns_number_total 2514 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 2733 Completeness (_total/calc) 91.99% Alert C: < 95% complete PLAT_420 Alert C D-H Without Acceptor N(1) - H(1) ?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
N-Methylhydroxylamine (0.19 g, 4 mmol) and oxybis(diphenylborane) (0.70 g, 2 mmol) were dissolved in 10 ml of ethanol and heated at boiling temperature for several minutes. Evaporation and cooling yielded 0.64 g (76%) of colorless crystals of (I) (m.p. 441–443 K). IR (KBr): 3145 cm-1 (N—H); 1H NMR (400 MHz, CDCl3/TMS), δ (p.p.m.): 1.40–1.90 (s, broad, exchangeable, 20% of 2 H), 2.78 (d, J = 6 Hz, 2 CH3), 6.33 (q, J = 6 Hz, partly exchangeable, 80% of 2 H), 7.23–7.99 (m, 10 aromatic H); EI mass spectrum (70 eV, 513 K), m/z: 422 (1%, M+), 211(51%, 1/2 M+), 165 (100%, Ph2B), 133 (28%, PhBONMe), 107 (21%), 105 (26%, PhBOH), 77 (52%, C6H5). Analysis calculated for C26H28B2N2O2: C 73.96, H 6.70, N 6.64, B 5.12; found: C 74.03, H 6.62, N 6.40, B 4.98. The compound gives a deep-blue color reaction with diphenylcarbazone in methanolic solution, indicating the presence of a diphenylboron moiety (Neu, 1960; Friese & Umland, 1978). Crystals suitable for X-ray analysis were obtained by very slow crystallization from ethanol.
The H1 atom was refined isotropically, while all other H atoms were refined as riding on their attached atoms.
Data collection: D*TREK (Molecular Structure Corporation, 1996-1998); cell refinement: D*TREK; data reduction: D*TREK; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: TEXSAN (Molecular Structure Corporation, 1992-1997); software used to prepare material for publication: TEXSAN.
C26H28B2N2O2 | F(000) = 448 |
Mr = 422.14 | Dx = 1.225 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.7107 Å |
a = 6.9184 (3) Å | Cell parameters from 6804 reflections |
b = 8.8703 (3) Å | θ = 3.2–27.9° |
c = 18.7337 (9) Å | µ = 0.08 mm−1 |
β = 95.444 (3)° | T = 173 K |
V = 1144.47 (8) Å3 | Block, colorless |
Z = 2 | 0.50 × 0.30 × 0.25 mm |
Rigaku/ADSC CCD diffractometer | 2514 independent reflections |
Radiation source: X-ray tube | 2059 reflections with I > 3σ(I) |
Graphite monochromator | Rint = 0.028 |
Detector resolution: 11.76 pixels mm-1 | θmax = 27.9°, θmin = 3.2° |
area detector scans | h = −8→7 |
Absorption correction: multi-scan D*TREK (Molecular Structure Corporation, 1996-1998) | k = −10→10 |
Tmin = 0.96, Tmax = 0.98 | l = −23→21 |
9941 measured reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.058 | Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo2)] |
S = 1.91 | (Δ/σ)max = 0.005 |
2362 reflections | Δρmax = 0.32 e Å−3 |
149 parameters | Δρmin = −0.20 e Å−3 |
C26H28B2N2O2 | V = 1144.47 (8) Å3 |
Mr = 422.14 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 6.9184 (3) Å | µ = 0.08 mm−1 |
b = 8.8703 (3) Å | T = 173 K |
c = 18.7337 (9) Å | 0.50 × 0.30 × 0.25 mm |
β = 95.444 (3)° |
Rigaku/ADSC CCD diffractometer | 2514 independent reflections |
Absorption correction: multi-scan D*TREK (Molecular Structure Corporation, 1996-1998) | 2059 reflections with I > 3σ(I) |
Tmin = 0.96, Tmax = 0.98 | Rint = 0.028 |
9941 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.058 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.91 | Δρmax = 0.32 e Å−3 |
2362 reflections | Δρmin = −0.20 e Å−3 |
149 parameters |
Experimental. Data were collected in 0.50° oscillations with 35.0 s exposures. A sweep of data was done using ϕ oscillations from 0.0 to 190.0° at χ = -90° and a second sweep was performed using ω oscillations between -18.0 and 23.0° at χ = 90.0°. The crystal-to-detector distance was 39.80 mm. The detector swing angle was -5.0°. The absorption correction is based on a three-dimensional analysis of symmetry-equivalent data and is performed along with batch scaling in a single step. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.30565 (8) | 0.52581 (7) | 0.01485 (4) | 0.0189 (2) | |
N1 | 0.3988 (1) | 0.62161 (9) | −0.03335 (5) | 0.0177 (2) | |
C1 | 0.2742 (1) | 0.7565 (1) | −0.04507 (7) | 0.0288 (3) | |
C2 | 0.3175 (1) | 0.3004 (1) | −0.07083 (5) | 0.0203 (2) | |
C3 | 0.1584 (2) | 0.3628 (1) | −0.11227 (6) | 0.0317 (3) | |
C4 | 0.1030 (2) | 0.3134 (2) | −0.18177 (7) | 0.0442 (4) | |
C5 | 0.2011 (2) | 0.1980 (2) | −0.21108 (6) | 0.0462 (4) | |
C6 | 0.3545 (2) | 0.1297 (2) | −0.17050 (7) | 0.0436 (4) | |
C7 | 0.4121 (2) | 0.1815 (1) | −0.10167 (6) | 0.0315 (3) | |
C8 | 0.2759 (1) | 0.2759 (1) | 0.07272 (5) | 0.0189 (2) | |
C9 | 0.2614 (1) | 0.3455 (1) | 0.13907 (6) | 0.0257 (3) | |
C10 | 0.1824 (2) | 0.2706 (1) | 0.19474 (6) | 0.0319 (3) | |
C11 | 0.1167 (1) | 0.1238 (1) | 0.18547 (6) | 0.0309 (3) | |
C12 | 0.1303 (1) | 0.0520 (1) | 0.12055 (6) | 0.0282 (3) | |
C13 | 0.2089 (1) | 0.1277 (1) | 0.06504 (6) | 0.0228 (3) | |
B1 | 0.3677 (1) | 0.3656 (1) | 0.00934 (6) | 0.0174 (3) | |
H1 | 0.391 (2) | 0.571 (1) | −0.0767 (7) | 0.024 (3)* | |
H2 | 0.3439 | 0.8343 | −0.0695 | 0.035* | |
H3 | 0.1549 | 0.7294 | −0.0747 | 0.035* | |
H4 | 0.2413 | 0.7952 | 0.0013 | 0.035* | |
H5 | 0.0841 | 0.4435 | −0.0918 | 0.038* | |
H6 | −0.0069 | 0.3613 | −0.2099 | 0.053* | |
H7 | 0.1631 | 0.1641 | −0.2602 | 0.055* | |
H8 | 0.4227 | 0.0449 | −0.1903 | 0.052* | |
H9 | 0.5223 | 0.1329 | −0.0740 | 0.038* | |
H10 | 0.3078 | 0.4492 | 0.1465 | 0.031* | |
H11 | 0.1733 | 0.3218 | 0.2406 | 0.038* | |
H12 | 0.0609 | 0.0711 | 0.2246 | 0.037* | |
H13 | 0.0846 | −0.0520 | 0.1137 | 0.034* | |
H14 | 0.2174 | 0.0756 | 0.0193 | 0.027* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0149 (3) | 0.0155 (4) | 0.0266 (4) | 0.0017 (2) | 0.0038 (2) | 0.0032 (3) |
N1 | 0.0160 (4) | 0.0133 (4) | 0.0235 (4) | 0.0016 (3) | 0.0003 (3) | 0.0029 (3) |
C1 | 0.0203 (5) | 0.0174 (5) | 0.0475 (7) | 0.0057 (4) | −0.0025 (4) | 0.0067 (5) |
C2 | 0.0195 (5) | 0.0192 (5) | 0.0221 (5) | −0.0052 (3) | 0.0012 (3) | 0.0030 (4) |
C3 | 0.0328 (6) | 0.0234 (6) | 0.0361 (6) | −0.0036 (4) | −0.0120 (4) | 0.0027 (5) |
C4 | 0.0534 (8) | 0.0383 (7) | 0.0361 (7) | −0.0174 (6) | −0.0210 (6) | 0.0107 (6) |
C5 | 0.0634 (8) | 0.0556 (9) | 0.0192 (6) | −0.0326 (7) | 0.0020 (5) | −0.0022 (6) |
C6 | 0.0451 (7) | 0.0529 (9) | 0.0352 (7) | −0.0138 (6) | 0.0159 (5) | −0.0179 (6) |
C7 | 0.0275 (5) | 0.0368 (7) | 0.0307 (6) | −0.0006 (4) | 0.0055 (4) | −0.0080 (5) |
C8 | 0.0134 (4) | 0.0194 (5) | 0.0236 (5) | 0.0030 (3) | −0.0004 (3) | 0.0026 (4) |
C9 | 0.0253 (5) | 0.0263 (5) | 0.0247 (5) | −0.0019 (4) | −0.0007 (4) | −0.0003 (4) |
C10 | 0.0325 (6) | 0.0410 (7) | 0.0220 (5) | 0.0007 (5) | 0.0016 (4) | 0.0007 (5) |
C11 | 0.0258 (5) | 0.0379 (7) | 0.0294 (6) | 0.0023 (4) | 0.0042 (4) | 0.0151 (5) |
C12 | 0.0243 (5) | 0.0215 (5) | 0.0390 (6) | 0.0015 (4) | 0.0045 (4) | 0.0095 (4) |
C13 | 0.0212 (5) | 0.0180 (5) | 0.0295 (6) | 0.0036 (3) | 0.0035 (4) | 0.0017 (4) |
B1 | 0.0127 (5) | 0.0147 (5) | 0.0242 (5) | 0.0016 (3) | −0.0008 (4) | 0.0006 (4) |
O1—N1 | 1.436 (1) | C5—H7 | 0.98 |
O1—B1 | 1.491 (1) | C6—C7 | 1.391 (2) |
N1—C1 | 1.479 (1) | C6—H8 | 0.98 |
N1—B1i | 1.640 (1) | C7—H9 | 0.98 |
N1—H1 | 0.93 (1) | C8—C9 | 1.400 (2) |
C1—H2 | 0.98 | C8—C13 | 1.397 (1) |
C1—H3 | 0.98 | C8—B1 | 1.609 (1) |
C1—H4 | 0.98 | C9—C10 | 1.391 (2) |
C2—C3 | 1.400 (1) | C9—H10 | 0.98 |
C2—C7 | 1.395 (2) | C10—C11 | 1.384 (2) |
C2—B1 | 1.616 (1) | C10—H11 | 0.98 |
C3—C4 | 1.393 (2) | C11—C12 | 1.384 (2) |
C3—H5 | 0.98 | C11—H12 | 0.98 |
C4—C5 | 1.372 (2) | C12—C13 | 1.391 (1) |
C4—H6 | 0.98 | C12—H13 | 0.98 |
C5—C6 | 1.385 (2) | C13—H14 | 0.98 |
C1···C12ii | 3.459 (1) | C1···C13ii | 3.483 (1) |
N1—O1—B1 | 111.78 (6) | C2—C7—C6 | 122.0 (1) |
O1—N1—C1 | 106.39 (7) | C2—C7—H9 | 119.1 |
O1—N1—B1i | 110.95 (7) | C6—C7—H9 | 119.0 |
O1—N1—H1 | 105.8 (8) | C9—C8—C13 | 117.08 (9) |
C1—N1—B1i | 122.01 (7) | C9—C8—B1 | 120.25 (9) |
C1—N1—H1 | 106.3 (8) | C13—C8—B1 | 122.68 (9) |
B1i—N1—H1 | 104.3 (7) | C8—C9—C10 | 121.4 (1) |
N1—C1—H2 | 109.4 | C8—C9—H10 | 119.3 |
N1—C1—H3 | 109.4 | C10—C9—H10 | 119.2 |
N1—C1—H4 | 109.4 | C9—C10—C11 | 120.2 (1) |
H2—C1—H3 | 109.6 | C9—C10—H11 | 119.9 |
H2—C1—H4 | 109.5 | C11—C10—H11 | 119.9 |
H3—C1—H4 | 109.5 | C10—C11—C12 | 119.6 (1) |
C3—C2—C7 | 116.4 (1) | C10—C11—H12 | 120.3 |
C3—C2—B1 | 117.52 (9) | C12—C11—H12 | 120.1 |
C7—C2—B1 | 126.01 (9) | C11—C12—C13 | 119.9 (1) |
C2—C3—C4 | 121.8 (1) | C11—C12—H13 | 120.1 |
C2—C3—H5 | 119.1 | C13—C12—H13 | 119.9 |
C4—C3—H5 | 119.2 | C8—C13—C12 | 121.8 (1) |
C3—C4—C5 | 120.4 (1) | C8—C13—H14 | 119.1 |
C3—C4—H6 | 119.8 | C12—C13—H14 | 119.1 |
C5—C4—H6 | 119.8 | O1—B1—N1i | 101.40 (7) |
C4—C5—C6 | 119.3 (1) | O1—B1—C2 | 111.58 (8) |
C4—C5—H7 | 120.4 | O1—B1—C8 | 106.50 (7) |
C6—C5—H7 | 120.4 | N1i—B1—C2 | 113.50 (8) |
C5—C6—C7 | 120.1 (1) | N1i—B1—C8 | 106.21 (7) |
C5—C6—H8 | 119.8 | C2—B1—C8 | 116.34 (8) |
C7—C6—H8 | 120.0 | ||
O1—N1—B1i—C2i | −58.7 (1) | C2—B1—C8—C9 | −161.06 (9) |
O1—N1—B1i—C8i | 172.27 (7) | C2—B1—C8—C13 | 19.3 (1) |
O1—N1—B1i—O1i | 61.14 (9) | C3—C2—C7—C6 | 1.5 (2) |
O1—B1—N1i—C1i | 172.29 (8) | C3—C2—B1—C8 | 94.0 (1) |
O1—B1—C2—C3 | −28.5 (1) | C3—C4—C5—C6 | 0.8 (2) |
O1—B1—C2—C7 | 155.16 (9) | C4—C3—C2—C7 | −2.8 (2) |
O1—B1—C8—C9 | −36.0 (1) | C4—C3—C2—B1 | −179.5 (1) |
O1—B1—C8—C13 | 144.35 (8) | C4—C5—C6—C7 | −2.1 (2) |
N1—O1—B1—C2 | −59.41 (9) | C6—C7—C2—B1 | 177.9 (1) |
N1—O1—B1—C8 | 172.64 (7) | C7—C2—B1—C8 | −82.4 (1) |
N1—O1—B1—N1i | 61.73 (9) | C8—C9—C10—C11 | 0.3 (2) |
N1—B1i—C2i—C3i | 142.28 (9) | C8—C13—C12—C11 | 0.1 (1) |
N1—B1i—C2i—C7i | −41.3 (1) | C9—C8—C13—C12 | 0.2 (1) |
N1—B1i—C8i—C9i | −71.5 (1) | C9—C10—C11—C12 | 0.1 (2) |
N1—B1i—C8i—C13i | 108.14 (9) | C10—C9—C8—C13 | −0.4 (1) |
C1—N1—O1—B1 | 157.63 (8) | C10—C9—C8—B1 | 179.90 (8) |
C1—N1—B1i—C2i | 67.9 (1) | C10—C11—C12—C13 | −0.3 (2) |
C1—N1—B1i—C8i | −61.2 (1) | C12—C13—C8—B1 | 179.90 (8) |
C2—C3—C4—C5 | 1.7 (2) | B1—O1—N1—B1i | −67.60 (9) |
C2—C7—C6—C5 | 1.0 (2) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C26H28B2N2O2 |
Mr | 422.14 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 173 |
a, b, c (Å) | 6.9184 (3), 8.8703 (3), 18.7337 (9) |
β (°) | 95.444 (3) |
V (Å3) | 1144.47 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.50 × 0.30 × 0.25 |
Data collection | |
Diffractometer | Rigaku/ADSC CCD diffractometer |
Absorption correction | Multi-scan D*TREK (Molecular Structure Corporation, 1996-1998) |
Tmin, Tmax | 0.96, 0.98 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 9941, 2514, 2059 |
Rint | 0.028 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.058, 1.91 |
No. of reflections | 2362 |
No. of parameters | 149 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.32, −0.20 |
Computer programs: D*TREK (Molecular Structure Corporation, 1996-1998), D*TREK, SIR97 (Altomare et al., 1999), TEXSAN (Molecular Structure Corporation, 1992-1997), TEXSAN.
O1—N1 | 1.436 (1) | C5—C6 | 1.385 (2) |
O1—B1 | 1.491 (1) | C6—C7 | 1.391 (2) |
N1—C1 | 1.479 (1) | C8—C9 | 1.400 (2) |
N1—B1i | 1.640 (1) | C8—C13 | 1.397 (1) |
C2—C3 | 1.400 (1) | C8—B1 | 1.609 (1) |
C2—C7 | 1.395 (2) | C9—C10 | 1.391 (2) |
C2—B1 | 1.616 (1) | C10—C11 | 1.384 (2) |
C3—C4 | 1.393 (2) | C11—C12 | 1.384 (2) |
C4—C5 | 1.372 (2) | C12—C13 | 1.391 (1) |
N1—O1—B1 | 111.78 (6) | C9—C8—B1 | 120.25 (9) |
O1—N1—C1 | 106.39 (7) | C13—C8—B1 | 122.68 (9) |
O1—N1—B1i | 110.95 (7) | C8—C9—C10 | 121.4 (1) |
C1—N1—B1i | 122.01 (7) | C9—C10—C11 | 120.2 (1) |
C3—C2—C7 | 116.4 (1) | C10—C11—C12 | 119.6 (1) |
C3—C2—B1 | 117.52 (9) | C11—C12—C13 | 119.9 (1) |
C7—C2—B1 | 126.01 (9) | C8—C13—C12 | 121.8 (1) |
C2—C3—C4 | 121.8 (1) | O1—B1—N1i | 101.40 (7) |
C3—C4—C5 | 120.4 (1) | O1—B1—C2 | 111.58 (8) |
C4—C5—C6 | 119.3 (1) | O1—B1—C8 | 106.50 (7) |
C5—C6—C7 | 120.1 (1) | N1i—B1—C2 | 113.50 (8) |
C2—C7—C6 | 122.0 (1) | N1i—B1—C8 | 106.21 (7) |
C9—C8—C13 | 117.08 (9) | C2—B1—C8 | 116.34 (8) |
Symmetry code: (i) −x+1, −y+1, −z. |
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The BONBON heterocycle (I), a condensation product of N-methylhydroxylamine and diphenylborinic acid, is an example of substituted aminoxyboranes, the dimeric nature of which has often been postulated for aminoxy- or iminoxyboranes [references cited in Kliegel et al. (1992, 1994)]. A monocyclic BONBON ring was first established by an X-ray analysis of an oxime diarylborinate (Kliegel et al., 1994). The same ring system is also present in several polycyclic compounds, which have been analysed by X-ray crystallography (Rettig & Trotter, 1983; Amt et al., 1988; Kliegel et al., 1991, 1992). Whereas in solution (1H NMR) and gas phase (mass spectrum) of (I) the presence of the monomer Ph2BONHMe is indicated, the crystals contain exclusively the BONBON dimer (I).
The molecule of (I) contains a centrosymmetric six-membered BONBON ring system, with a chair conformation [ring dihedral angles in a B—O—N—B section being 61.7 (1), -67.6 (1) and 61.1 (1)°], similar to that in related materials [e.g. Kliegel et al. (1994)]. The methyl substituents of the N atoms are in equatorial sites. The dative B—N bond is (typically) fairly long [1.640 (1) Å]. There is no N—H···O hydrogen bond, presumably as a result of the steric influence of the bulky phenyl substituents, the shortest intermolecular non-hydrogen contacts being C1···C12 and C13 = 3.46 and 3.48 Å.