Structural studies of organoboron compounds LI. N-Methylhydroxylamine(O-B)2,5-diphenyl-1,3,2-dioxaborolan-4-one

1992 ◽  
Vol 70 (4) ◽  
pp. 1188-1194 ◽  
Author(s):  
Wolfgang Kliegel ◽  
Ute Schumacher ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Least Squares ◽  
Good Yield ◽  
Direct Methods ◽  
Synthetic Methods ◽  
Structural Studies ◽  
Open Chain ◽  
Full Matrix ◽  
Boron Complex ◽  
Independent Molecules ◽  
Average Bond

Three synthetic methods for the preparation of N-methylhydroxylamine(O-B)2,5-diphenyl-1,3,2-dioxaborolan-4-one (2-(1-oxa-2-azoniapropyl)-2,5-diphenyl-1,3-dioxa-2-boratacyclopentan-4-one), 9, in good yield are described. Crystals of this material are triclinic, a = 10.1073(7), b = 12.159(2), c = 14.116(2) Å, α = 65.079(8)°, β = 99.255(9)°, γ = 92.69(1)°, Z = 4, space group [Formula: see text]. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.039 and Rw = 0.045 for 2603 reflections with I ≥ 3σ(I). Compound 9 is the first structurally characterized example of an N-alkylhydroxylamine(O-B)boron complex having an open-chain B,N-betaine structure. Average bond lengths involving the tetrahedraily coordinated boron atoms in the two crystallographically independent molecules (corrected for thermal libration) are (N)O—B = 1.494, (carboxylate)O—B = 1.524, (alcoholic)O—B = 1.486, and(aryl)C—B = 1.594 Å.

Structural studies of organoboron compounds. LII. N-Ethylhydroxylamine- (O-B)1,7-diethyl-3,5-diphenyl-2,4,6-trioxa-7-aza-1-azonia-3-bora-5- boratabicyclo[3.3.0]octane

1992 ◽  
Vol 70 (7) ◽  
pp. 2015-2021 ◽  
Author(s):  
Wolfgang Kliegel ◽  
Gottfried Lubkowitz ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Least Squares ◽  
Good Yield ◽  
Direct Methods ◽  
Structural Studies ◽  
Asymmetric Unit ◽  
Open Chain ◽  
Full Matrix ◽  
Unit Space ◽  
Boron Complex ◽  
Ethanol Yields

The reaction of N,N′-diethyl- N,N′-dihydroxymethanediamine with oxybis(diphenylborane) in absolute ethanol yields N-ethylhydroxylamine(O-B)1,7-diethyl-3,5-diphenyl-2,4,6-trioxa-7-aza-1-azonia-3-bora-5-boratabicyclo[3.3.0]octane [3-(1-oxa-2-azoniabutyl)-1,7-diethyl-3,5-diphenyl-2,4,6-trioxa-7-aza-1-azonia-3,5-diboratabicyclo[3.3.0]octane], 7b, in good yield. Crystals of this material are monoclinic, a = 16.396(2), b = 11.303(2), c = 22.898(4) Å, β = 92.78(1)°, Z = 8 (two molecules per asymmetric unit), space group P21/a. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.041 and Rw = 0.050 for 3602 reflections with I ≥ 3σ(I). The product 7b is formed by O→B coordination between N-ethylhydroxylamine and the bicyclic bis-phenylboronate of N,N′-diethyl-N,N′-dihydroxymefhanediamine. Compound 7b is only the second structurally characterized example of an N-alkylhydroxylamine(O-B)boron complex having an open-chain B,N-betaine structure. Bond lengths about boron are: B—O(N) = 1.467(4)–1.527(4), B—O(B) = 1.433(4)–1.451(4), B—N = 1.688(4) and 1.707(4), B—C = 1.586(4)–1.606(5) Å.

Structural studies of organoboron compounds. XLII. 4,6-Bis(1-cyano-1-methylethyl)-2-mesityl-1,3-dioxa-4,6-diaza-2-boracyclohexane

1991 ◽  
Vol 69 (2) ◽  
pp. 234-238 ◽  
Author(s):  
Wolfgang Kliegel ◽  
Gottfried Lubkowitz ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Least Squares ◽  
Key Words ◽  
Good Yield ◽  
Direct Methods ◽  
Organoboron Compound ◽  
Structural Studies ◽  
Full Matrix ◽  
Bond Lengths

The condensation of N,N′-bis(1-cyano-1-methylethyl)-N,N′-dihydroxymethanediamine and mesitylboronic acid gives 4,6-bis(1-cyano-1-methylethyl)-2-mesityl-1,3-dioxa-4,6-diaza-2-boracyclohexane in good yield. Crystals of the latter compound are orthorhombic, a = 15.825(1), b = 17.958(1), c = 14.014(1) Ǻ, Z = 8, space group Pbca. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.037 and Rw = 0.051 for 2844 reflections with 1 ≥ 3σ(I). The molecule has a six-membered cycloboronate structure featuring the first structurally characterized BONCNO ring. The ring was found to have a C-envelope conformation in the solid state. Bond lengths include: O—B(sp2) = 1.356(2) and 1.370(2), and C(aryl)—B = 1.560(2) Ǻ. Key words: organoboron compound, boron compound, crystal structure.

Structural studies of organoboron compounds. LV. N,N′-Di-tert-butyl-N,N′- dihydroxypropane-1,3-diamine(O-B)ethoxydiphenylborane and N1,N2-di-tert-butyl-N1,N2-dihydroxy-1-phenylpropane-1,3-diamine(N2-O-B)hydroxydiphenylborane

1992 ◽  
Vol 70 (7) ◽  
pp. 2033-2039 ◽  
Author(s):  
Wolfgang Kliegel ◽  
Gottfried Lubkowitz ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Hydrogen Bonds ◽  
Least Squares ◽  
Direct Methods ◽  
Structural Studies ◽  
Open Chain ◽  
Organoboron Compounds ◽  
Full Matrix ◽  
Bond Lengths ◽  
Tert Butyl ◽  
Intramolecular Hydrogen

The 1,3-propanediamine derivatives N,N′-di-tert-butyl-N,N′-dihydroxy-1,3-propanediamine and N,N′-di-tert-butyl-N,N′-dihydroxy-1-phenyl-1,3-propanediamine have been prepared and reacted with oxybis(diphenylborane) to yield, respectively, the crystalline organoboron compounds N,N′-di-tert-butyl-N,N′-dihydroxypropane-1,3-diamine(O-B)-ethoxydiphenylborane, 5a, and N1,N2-di-tert-butyl-N1,N2-dihydroxy-1-phenylpropane-1,3-diamine(N2-O-B)-hydroxydiphenylborane, 5b. Crystals of 5a are monoclinic, C2/c, a = 35.402(1), b = 9.212(2), c = 18.101(2) Å, β = 116.688(3)°, Z = 8, ρc = 1.079 g cm−3, and crystals of 5b are monoclinic, P21/c, a = 12.899(4), b = 12.571(4), c = 17.412(3) Å, β = 90.02(2)°, Z = 4, ρc = 1.121 g cm−3. The structures were solved by direct methods and were refined by full-matrix least-squares procedures to final R values of 0.047 and 0.041 for 2492 and 3334 reflections with I ≥ 3σ(I), respectively. Compounds 5a and 5b are open-chain hydroxylamine adducts of diphenylborinic acid and ethyl diphenylborinate, respectively. Both of these compounds are stabilized by a system of three intramolecular hydrogen bonds [Formula: see text]. Bond lengths involving the tetrahedrally coordinated boron atoms are: (C)O—B = 1.457(3), (N)O—B = 1.558(3), and C—B = 1.613(4) and 1.615(4) Å for 5a; (H)O—B = 1.475(3), (N)O—B = 1.562(2), and C—B = 1.618(3) and 1.619(3) Å for 5b.

Structural studies of organoboron compounds. XXXI. (3-Benzoyl-(+)-camphorato)diphenylboron

1988 ◽  
Vol 66 (8) ◽  
pp. 2007-2013 ◽  
Author(s):  
William R. Cullen ◽  
Steven J. Rettig ◽  
James Trotter ◽  
Eugene B. Wickenheiser
Keyword(s):  
Physical Properties ◽  
Crystal Lattice ◽  
Least Squares ◽  
Structure Analysis ◽  
Title Compound ◽  
Direct Methods ◽  
Structural Studies ◽  
Full Matrix ◽  
Bond Lengths ◽  
Independent Molecules

Details of the synthesis and physical properties of the title compound are reported along with a new preparation of 3-benzoyl-(+)-camphor. Crystals of (3-benzoyl-(+)-camphorato)diphenylboron are triclinic, a = 9.0362(3), b = 9.4679(3), c = 14.2731(7) Å, α = 101.920(3), β = 100.086(3), γ = 93.251(3)°, Z = 2, space group P1. The structure was solved by non-routine application of direct methods and was refined by full-matrix least-squares procedures to R = 0.036 and Rw = 0.039 for 4094 reflections with I ≥ 3σ(I). The unit-cell contains two crystallographically independent molecules, related to one another in the crystal lattice by a pseudo-inversion centre, and having the same configuration but different conformations. The structure analysis shows that the chiral, anionic, 1,3-diketonate ligand derived from 3-benzoyl-(+)-camphor is not symmetrically delocalized like most related ligands, resulting in significantly different O—B bond lengths. Bond lengths (corrected for libration) include: O—B = 1.514(4), 1.522(4); 1.568(4) and 1.567(4) Å; C—B = 1.594(5)−1.616(5) Å.

Structural studies of organoboron compounds. XLI. (3-Hydroxy-2-methyl-1-(p-tolyl)-4-pyridinonato)diphenylboron

1990 ◽  
Vol 68 (10) ◽  
pp. 1803-1807 ◽  
Author(s):  
Chris Orvig ◽  
Steven J. Rettig ◽  
James Trotter ◽  
Zaihui Zhang
Keyword(s):  
Crystal Structure ◽  
Least Squares ◽  
Direct Methods ◽  
Organoboron Compound ◽  
High Yield ◽  
Structural Studies ◽  
Full Matrix ◽  
Bond Lengths ◽  
The Mean ◽  
Independent Molecules

(3-Hydroxy-2-methyl-1-(p-tolyl)-4-pyridinonato)diphenylboron has been prepared in high yield by the reaction of 3-hydroxy-2-methyl-1-(p-tolyl)-4-pyridinone with diphenylborinic acid. Crystals of the hemi-acetone solvate are triclinic, a = 15.119(2), b = 16.528(1), c = 9.5802(9) Å, α = 98.721(6), β = 93.344(8), γ = 102.443(6)°, Z = 4, space group [Formula: see text]. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.050 and Rw = 0.065 for 4330 reflections with I ≥ 3σ(I). The five-membered chelate rings in both of the two crystallographically independent molecules have flattened B-envelope conformations (maximum deviations from the mean planes = 0.114(4) and 0.065(5) Å). Mean bond lengths O—B = 1.553 and C—B = 1.599 Å are consistent with intermediate strength binding of the diphenylboron moiety by the O,O-chelating ligand. Keywords: crystal structure, organoboron compound.

Structural studies of organoboron compounds. XX.(Salicylaldoximato-O,N)diphenylboron

1984 ◽  
Vol 62 (7) ◽  
pp. 1363-1368 ◽  
Author(s):  
Wolfgang Kliegel ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Hydrogen Bonds ◽  
Least Squares ◽  
Chelate Ring ◽  
Direct Methods ◽  
Structural Studies ◽  
Organoboron Compounds ◽  
Full Matrix ◽  
Space Group ◽  
Bond Lengths ◽  
Phenolic Oxygen

Crystals of (salicylaldoximato-O,N)diphenylboron are triclinic, a = 10.125(2), b = 10.797(1), c = 14.760(2) Å, α = 89.05(1), β = 86.98(1), γ = 83.18(1)°, Z = 4, space group [Formula: see text]. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.040 and Rw = 0.048 for4145 reflections with I ≥ 3σ(I). The structure consists of two crystallographically independent, but essentially identical, molecules linked by strong [Formula: see text] hydrogen bonds to form continuous spirals along the a axis. The Ph2B moiety is chelated by the phenolic oxygen and oxime nitrogen atoms of the ligand resulting in the formation of a non-planar six-membered chelate ring. Important libration-corrected mean bond lengths are O—B = 1.516(1), N—B = 1.609(2), and C—B = 1.613(2) Å.

Structural studies of organoboron compounds. XLIII. 4-[(1-Hydroxycyclohexyl)methyl]-2,2,5-triphenyl-1,3-dioxa-4-azonia-2-borata-4-cyclopentene

1991 ◽  
Vol 69 (3) ◽  
pp. 545-549 ◽  
Author(s):  
Wolfgang Kliegel ◽  
Ute Schumacher ◽  
Mahmood Tajerbashi ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Crystal Structure ◽  
Least Squares ◽  
Key Words ◽  
Hydroxamic Acid ◽  
Direct Methods ◽  
Organoboron Compound ◽  
Structural Studies ◽  
Full Matrix ◽  
Bond Lengths ◽  
Acid Chelate

The reaction of N′-hydroxy-N-[(1-hydroxycyclohexyl)methyl]benzamide and diphenylborinic anhydride gives 4-[(1-hydroxycyclohexyl)methyl]-2,2,5-triphenyl-1,3-dioxa-4-azonia-2-borata-4-cyclopentene in nearly quantitative yield. Crystals of the product are monoclinic, a = 9.9117(6), b = 13.308(1), c = 17.339(2) Ǻ, β = 99.420(7)°, Z = 4, space group P21/c. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.040 and Rw = 0.047 for 2423 reflections with I > 3σ(I). The molecule has a normal five-membered hydroxamic acid chelate structure, the BONCO ring having a B-envelope conformation. Bond lengths (corrected for libration) (N)O—B = 1.535(3), (C)O—B = 1.569(3), C—B = 1.603(3) and 1.601(3) Ǻ are normal for this type of complex. Key words: organoboron compound, boron compound, crystal structure.

Structural studies of organoboron compounds. LIII. N,N-Diethylhydroxylamine-(O-B)1,7-dimethyl-3,5-diphenyl-2,4,6-trioxa-7-aza-1-azonia-3-bora-5- boratabicyclo[3.3.0]octane

1992 ◽  
Vol 70 (7) ◽  
pp. 2022-2026 ◽  
Author(s):  
Wolfgang Kliegel ◽  
Gottfried Lubkowitz ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Hydrogen Bond ◽  
Least Squares ◽  
Title Compound ◽  
Condensation Product ◽  
Phenylboronic Acid ◽  
Direct Methods ◽  
High Yield ◽  
Structural Studies ◽  
Full Matrix ◽  
Bond Lengths

Reaction of the condensation product of N,N′-dimethyl-N,N′-dihydroxymethanediamine and phenylboronic acid with N,N-diethylhydroxylamine gives N,N-diethylhydroxylamine(O-B)1,7-dimethyl-3,5-diphenyl-2,4,6-trioxa-7-aza-1-azonia-3-bora-5-boratabicyclo[3.3.0]octane [3-(2-ethyl-1-oxa-2-azoniabutyl)-1,7-dimethyl-3,5-diphenyl-2,4,6-trioxa-7-aza-1-azonia-3,5-diboratabicyclo[3.3.0]octane, 3] in high yield. Crystals of 3 are orthorhombic, a = 11.8132(11), b = 15.4768(11), c = 11.7325(16) Å, Z = 4, space group P212121. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.039 and Rw = 0.044 for 1729 reflections with I ≥ 2σ(I). The title compound is the second example of this recently characterized class of O-B coordinated hydroxylamine complexes, stabilized by an intramolecular [Formula: see text] hydrogen bond [Formula: see text]. Bond lengths about boron are: B—O(N) = 1.482(4)–1.526(4), B—O(B) = 1.412(4) and 1.420(4), B—N = 1.712(4), B—C = 1.591(5) and 1.602(5) Å.

Structural studies of organoboron compounds. XXXII. 5,5-Difluoro-2,2-pentamethylene-1,4,6-trioxa-3a-azonia-5-borata-1,2,3,4,5,6-hexahydrobenzo[h]azulene and 2,2-pentamethylene-5,5-diphenyl-1,4,6-trioxa-3a-azonia-5-borata-1,2,3,4,5,6-hexahydrobenzo[h]azulene

1988 ◽  
Vol 66 (10) ◽  
pp. 2621-2630 ◽  
Author(s):  
Wolfgang Kliegel ◽  
Mahmood Tajerbashi ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Solid State ◽  
Physical Properties ◽  
Least Squares ◽  
Crystal Structures ◽  
Direct Methods ◽  
Structural Studies ◽  
Full Matrix ◽  
Space Group ◽  
Bond Lengths ◽  
Conformational Isomers

Details of the syntheses, physical properties, and crystal structures of the title compounds are reported. Crystals of 5,5-difluoro-2,2-pentamethylene-1,4,6-trioxa-3a-azonia-5-borata-1,2,3,4,5,6-hexahydrobenzo[h]azulene are triclinic, a = 6.1576(3), b = 11.2651(3), c = 10.8118(3) Å, α = 109.747(3), β = 105.807(4), γ = 92.976(4)°, Z = 2, space group [Formula: see text], and those of 2,2-pentamethylene-5,5-diphenyl-1,4,6-trioxa-3a-azonia-5-borata-1,2,3,4,5,6-hexahydrobenzo[h]azulene are monoclinic, a = 9.8549(6), b = 10.9242(6), c = 41.263(2) Å, β = 92.717(6)°, Z = 8, space group P21/n. Both structures were solved by direct methods and were refined by full-matrix least-squares procedures to R = 0.045 and 0.042 for 2344 and 4248 reflections with I ≥ 3σ(I), respectively. The molecules were both found to possess a seven-membered chelate structure, the O,O-chelatїng ligand being strongly bound to the X2B moiety. Two conformational isomers of the X = Ph compound were found in the solid state. The 2-oxazoline N-oxide moieties present in both compounds are the first to be structurally characterized. Important mean libration-corrected bond lengths are: O—B = 1.491 and F—B = 1.387 Å for X = F; O—B = 1.511 and C—B = 1.620 Å for X = Ph.

Structural studies of organoboron compounds. XXXV. 4,8-Diethyl-2,2,6,6-tetraphenyl-1,3,5,7-tetraoxa-4,8-diazonia- 2,6-diborata-1,2,3,5,6,7-hexahydronaphthalene

1989 ◽  
Vol 67 (10) ◽  
pp. 1644-1649 ◽  
Author(s):  
Wolfgang Kliegel ◽  
Mahmood Tajerbashi ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Crystal Structure ◽  
Least Squares ◽  
Title Compound ◽  
Direct Methods ◽  
Organoboron Compound ◽  
Boron Compound ◽  
Structural Studies ◽  
Full Matrix ◽  
Binding Strength ◽  
The Mean

The reaction of Ν,Ν′-diethyloxalohydroxamic acid with oxybis(diphenylborane) yields the title compound. Crystals of 4,8-diethyl-2,2,6,6-tetraphenyl-1,3,5,7-tetraoxa-4,8-diazonia-2,6-diborata-1,2,3,5,6,7-hexahydronaphthalene are monoclinic, a = 14.3405(9), b = 14.3053(5), c = 14.9301(8) Å, β = 116.136(4)°, Z = 4, space groupP21/n. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.038 and Rw = 0.038 for 3501 reflections with I ≥ 3σ(I). The molecule has a novel bis-six-membered binuclear chelate structure, the Ph2B moieties each being coordinated by (N)O and (C=)O oxygen atoms from different hydroxamate groups. The mean libration-corrected bond distances (C=)O—B, 1.587 Å, (N)O—B, 1.511 Å, and B—C, 1.602 Å, represent the weakest overall binding strength of an O,O-chelating ligand with respect to the Ph2B moiety yet observed for a six-membered O—B—O chelate. Keywords: crystal structure, boron compound, organoboron compound.

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