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. XXX. 1,9-Dimethyl-3,5,7-triphenyl-2,4,6,8-tetraoxa-1,9-diazonia-5-bora-3,7- diboratatricyclo[5.4.0.03,9]undecane

1988 ◽  
Vol 66 (5) ◽  
pp. 1117-1122 ◽  
Author(s):  
Henning Amt ◽  
Wolfgang Kliegel ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Physical Properties ◽  
Least Squares ◽  
Title Compound ◽  
Direct Methods ◽  
Ring System ◽  
Structural Studies ◽  
Organoboron Compounds ◽  
Full Matrix ◽  
Space Group ◽  
Bond Lengths

Details of the preparation and physical properties of the title compound are given. Crystals of 1,9-dimethyl-3,5,7- triphenyl-2,4,6,8-tetraoxa-1,9-diazonia-5-bora-3,7-diboratatricyclo[5.4.0.03,9]undecane are orthorhombic, a = 9.4026(3), b = 9.4663(2), c = 24.7462(9) Å, Z = 4, space group P212121. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.036 and Rw = 0.038 for 1536 reflections with I ≥ 3σ(I). The three six-membered and two seven-membered rings comprising the tricyclo[5.4.0.03,9]undecane ring system all have boat or boat-like conformations. Important bond lengths (corrected for libration) are: B(sp3)—N = 1.649(6) and 1.668(6), B(sp3)—O(N) = 1.492(5) and 1.497(6), B(sp3)—O[B(sp2)] = 1.444(6) and 1.438(5), B(sp3)—C = 1.600(6) and 1.594(7), B(sp2)—O = 1.357(6) and 1.370(6), B(sp2)—C = 1.574(6) Å.

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. XXIX. 6,6-Diethyl-2,2-diphenyl-1,3-dioxa-6-azonia-2-boratacyclooctane monohydrate

1988 ◽  
Vol 66 (5) ◽  
pp. 1091-1096 ◽  
Author(s):  
Wolfgang Kliegel ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Least Squares ◽  
Title Compound ◽  
Chelate Ring ◽  
Direct Methods ◽  
Structural Studies ◽  
Organoboron Compounds ◽  
Full Matrix ◽  
Space Group ◽  
Bond Lengths ◽  
Conformation Intermediate

Details of the preparation and structure of the title compound are given. Crystals of 6,6-diethyl-2,2-diphenvl-1,3-dioxa-6-azonia-2-boratacyclooctane monohydrate are orthorhombic, a = 7.0322(2), b = 16.3505(7), c = 16.8164(4) Å, Z = 4, space group P212121. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.045 and Rw = 0.050 for 2013 reflections with I ≥ 3σ(I). The monocyclic eight-membered B, N-betaine is the first to be structurally characterized. The eight-membered chelate ring has a conformation intermediate between the S4 and boat-boat forms which is probably stabilized by transannular [Formula: see text] interactions. The average libration-corrected O—B and B—C bond lengths of 1.500 and 1.639 Å are, respectively, the shortest and longest yet observed for an O,O-chelate of diphenylboron.

Structural studies of organoboron compounds. XXXIX.1 1,4-Bis(2,2-diethoxyethyl)-6,8-diphenyl-5,7,9-trioxa-4-aza-1-azonia-8- bora-6-boratabicyclo[4.3.0]nonane

1990 ◽  
Vol 68 (10) ◽  
pp. 1791-1796 ◽  
Author(s):  
Henning Amt ◽  
Wolfgang Kliegel ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Crystal Structure ◽  
Least Squares ◽  
Title Compound ◽  
Phenylboronic Acid ◽  
Direct Methods ◽  
Organoboron Compound ◽  
Structural Studies ◽  
Full Matrix ◽  
Space Group ◽  
Bond Lengths

Reaction of N,N′-1,2-ethanediylidenebis(2,2-diethoxyethanamine)- N,N′-dioxide and phenylboronic acid yields the title compound. Crystals of 1,4-bis(2,2-diethoxyethyl)-6,8-diphenyl-5,7,9-trioxa-4-aza-1-azonia-8-bora-6-boratabicyclo[4.3.0]-nonane are triclinic, a = 12.625(2), b = 13.962(2), c = 9.273(1) Å, α = 104.81(1), β = 98.61(1), γ = 106.52(1)°, Z = 2, space group [Formula: see text]. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.058 and Rw = 0.081 for 3677 reflections with I ≥ 3σ(I). The molecule has a bicyclo[4.3.0]nonane structure containing one transannular N—B bond. Important bond lengths are sp3-bomn, N—B = 1.759(3), O—B = 1.435(3) and 1.454(3), C—B = 1.579(4); sp2-boron, O—B = 1.335(3) and 1.404(3), C—B = 1.557(4) Å. The (sp3)B—C(phenyl) bond is the shortest yet reported for this type of compound.Keywords: crystal structure, boron compound, organoboron compound.

Structural studies of organoboron compounds. XXXIV. 4-(N-Methoxymethylimino)-2,2-diphenyl-1,3-dioxa-2-borata-1,2,3,4-tetrahydronaphthalene and 4-diethylimino-2,2-diphenyl-1,3-dioxa-2-borata-1,2,3,4-tetrahydronaphthalene

1989 ◽  
Vol 67 (10) ◽  
pp. 1636-1643 ◽  
Author(s):  
Wolfgang Kliegel ◽  
Mahmood Tajerbashi ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Physical Properties ◽  
Least Squares ◽  
Crystal Structures ◽  
Direct Methods ◽  
Structural Studies ◽  
Boron Compounds ◽  
Organoboron Compounds ◽  
Full Matrix ◽  
Space Group ◽  
Bond Lengths

Details of the syntheses, physical properties, and crystal structures of the title compounds are reported. Crystals of 4-(N-methoxymethylimino)-2,2-diphenyl-1,3-dioxa-2-borata-1,2,3,4-tetrahydronaphthalene, 4, are monoclinic, a = 9.8072(5), b = 9.6217(7), c = 19.6793(12) Å, β = 94.871(5)°, Z = 4, space group P21/c, and those of 4-diethylimino-2,2-diphenyl-1,3-dioxa-2-borata-1,2,3,4-tetrahydronaphthalene, 9, are orthorhombic, a = 17.0593(7), b = 16.1372(6), c = 14.3753(5) Å, Z = 8, space group Pbca. Both structures were solved by direct methods and were refined by full-matrix least-squares procedures to R = 0.046 and 0.038 for 2198 and 2969 reflections with I ≥ 3σ(I), respectively. In both structures the N,N-dialkylsalicylamidate ligands coordinate the diphenylboron moieties via the phenolate oxygen and amide oxygen atoms, forming six-membered O—B—O chelate rings. The O(ar)—B, O(amide)—B, and mean C—B bond lengths (corrected for libration) are as follows: 1.490(3), 1.549(4), and 1.612 Å for 4 and 1.494(2), 1.550(2), and 1.612 Å for 9. Keywords: crystal structures, boron compounds, organoboron compounds.

Structural studies of organoboron compounds. XXXVII. 8,8-Pentamethylene-6-phenyl-6,9-epoxy-5,7-dioxa-8-azonia-6-borata-6,7,8,9-tetrahydro-5H-benzocycloheptene

1990 ◽  
Vol 68 (1) ◽  
pp. 64-68 ◽  
Author(s):  
Wolfgang Kliegel ◽  
Hans-Walter Motzkus ◽  
Klaus Drückler ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Crystal Structure ◽  
Least Squares ◽  
Title Compound ◽  
Phenylboronic Acid ◽  
Direct Methods ◽  
Structural Studies ◽  
Boron Compounds ◽  
Full Matrix ◽  
Space Group ◽  
Bond Lengths

Condensation of equimolar amounts of salicylaldehyde, N-hydroxypiperidine, and phenylboronic acid yields the title compound. Crystals of 8,8-pentamethylene-6-phenyl-6,9-epoxy-5,7-dioxa-8-azonia-6-borata-6,7,8,9-tetrahydro-5H-benzocycloheptene are monoclinic, a = 12.773(1), b = 11.9600(7), c = 10.6411(6) Å, β = 103.786(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 = 0.039 and Rw = 0.047 for 2420 reflections with I ≥ 3σ(I). The compound has a bridged heterocyclic B,N-betaine structure with a PhB(OR)3 anionic centre. Bond lengths (corrected for libration) include: B—O(aryl C) = 1.481(2), B—O(alkyl C) = 1.488(2), B—O(N) = 1.539(2), and B—C = 1.591(2) Å. Keywords: organoboron, boron compounds, crystal structure.

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.

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