Structural studies of organoboron compounds LXII. Synthesis and structure of various N-alkylated 1,3-dioxa-4-aza-2-boracyclohexanes

1994 ◽  
Vol 72 (10) ◽  
pp. 2118-2130 ◽  
Author(s):  
Wolfgang Kliegel ◽  
Henning Amt ◽  
Harald Becker ◽  
Ute Lauterbach ◽  
Gottfried Lubkowitz ◽  
...  
Keyword(s):  
Least Squares ◽  
Phenylboronic Acid ◽  
Direct Methods ◽  
The Other ◽  
Structural Studies ◽  
Organoboron Compounds ◽  
Full Matrix ◽  
Space Group ◽  
Benzene Solvate

The synthesis of a number of variously substituted N-alkyl 2-hydroxyaminoalkanols 3 and their reactions with phenylboronic acid are detailed. The crystalline products proved to be 1:2 condensates 4 in a few cases and 1:1 condensates 5 in all the other cases studied. Crystals of 2-mesityl-6,6-pentamethylene-1,3-dioxa-4-aza-2-boracyclohexane, 5l, are triclinic, a = 11.540(2), b = 10.402(3), c = 8.440(2) Å, α = 108.86(2)°, β = 97.62(2)°, γ = 89.36(2)°, Z = 2, space group [Formula: see text] and those of 4,4′-methylenebis(6,6-pentamethylene-2-phenyl-1,3-dioxa-4-aza-2-boracyclohexane) benzene solvate, 15a•C6H6, are monoclinic, a = 22.690(1), b = 16.867(1), c = 8.4783(9) Å, β = 104.912(8)°, Z = 4, space group C2/c. The structures were solved by direct methods and refined by full-matrix least-squares procedures to R = 0.037 and 0.035 (Rw = 0.035 and 0.044) for 3190 and 2084 reflections with I ≥ 3σ(F2)• respectively.

Structural studies of organoboron compounds. LIV. 4-Cyclohexyl-2-methyl-3,6,8-triphenyl-5,7,9-trioxa-4-aza-1-azonia-8-bora-6-boratabicyclo[4.3.0]nonane

1992 ◽  
Vol 70 (7) ◽  
pp. 2027-2032 ◽  
Author(s):  
Wolfgang Kliegel ◽  
Gottfried Lubkowitz ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Least Squares ◽  
Phenylboronic Acid ◽  
Direct Methods ◽  
Structural Studies ◽  
Organoboron Compounds ◽  
Full Matrix ◽  
Space Group ◽  
Bond Lengths ◽  
Moderate Yield

The synthesis of N1-cyclohexyl-N1,N2-dihydroxy-1-phenyl-1,2-propanediamine and its reaction with phenylboronic acid to produce 4-cyclohexyl-2-methyl-3,6,8-triphenyl-5,7,9-trioxa-4-aza-1-azonia-8-bora-6-boratabicyclo[4.3.0]nonane, 5, in moderate yield are described. Crystals of the organoboron derivative 5 are triclinic, a = 11.4142(8), b = 12.4719(8), c = 10.2154(6) Å, α = 75.177(6), β = 112.306(5), γ = 105.000(6)°, 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 = 0.037 and Rw = 0.053 for 4232 reflections with I ≥ 3σ(I). The bicyclo[4.3.0]nonane system consists of a six-membered BONCNN ring and a five-membered BOBON ring cis-fused about the transannular N→B bond. Bond lengths involving boron are: (sp2)B—O(B) = 1.336(2), (sp2)B—O(N) = 1.411(2), (sp2)B—C(aryl) = 1.557(2), (sp3)B—O(B) = 1.457(2), (sp3)B—O(N) = 1.434(2), (sp3)B—N = 1.706(2), and (sp3)B—C(aryl) = 1.593(2) Å.

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. XV. Crystal and molecular structures of (3-aminopropanolato)diphenylboron, (2-N,N-dimethylaminoethanolato)diphenylboron, and (2-N,N-dimethylaminoethanolato)diphenylboron – diphenylborinic acid (1:1)

1983 ◽  
Vol 61 (10) ◽  
pp. 2334-2340 ◽  
Author(s):  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Least Squares ◽  
Boron Atom ◽  
Direct Methods ◽  
Molecular Structures ◽  
Structural Studies ◽  
Organoboron Compounds ◽  
Full Matrix ◽  
Space Group ◽  
Crystal And Molecular Structures

Crystals of (3-aminopropanolato)diphenylboron are monoclinic, a = 9.6717(13). b = 9.8867(6), c = 14.452(2) Å, β = 99.500(7)°, Z = 4, space group P21/n: those of (2-N,N-dimethylaminoethanolato)diphenylboron are monoclinic, a = 7.0721(4), b = 16.8829(4), c = 12.0975(8) Å, β = 97.875(3)°, Z = 4, space group Cc; and those of (2-N,N-dimethylaminoethanolato)diphenylboron – diphenylborinic acid (1:1) are monoclinic. a = 11.3231(10). b = 19.3190(12). c = 12.2451(11) Å, β = 109.321(4)°, Z = 4, space group P21/n. All three structures were solved by direct methods and were refined by full-matrix least-squares procedures to final R values of 0.038. 0.031, and 0.040 for 1522, 1649, and 2420 reflections with I ≥ 3σ(I) respectively. Each structure contains a tetrahedrally coordinated boron atom. The libration-corrected B—O, B—N, and mean B—C distances are: 1.481(2), 1.643(3), and 1.623(3) Å for (3-aminopropanolato)diphenylboron; 1.476(2), 1.691 (2), and 1.625(7) Å for (2-N,N-dimethylaminoethanolato)diphenylboron. The Ph2BOH molecule contains a trigonal-planar boron atom with B—O = 1.354(3) Å and mean B—C = 1.572(3) Å.

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. XII. Crystal and molecular structures of (acetylacetonato)diphenylboron and (tropolonato)diphenylboron

1982 ◽  
Vol 60 (23) ◽  
pp. 2957-2964 ◽  
Author(s):  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Least Squares ◽  
Chelate Ring ◽  
Direct Methods ◽  
Molecular Structures ◽  
Structural Studies ◽  
Organoboron Compounds ◽  
Full Matrix ◽  
Space Group ◽  
Crystal And Molecular Structures ◽  
The Mean

There are two crystalline modifications of (acetylacetonato)diphenylboron: triclinic, a = 8.3557(8), b = 9.3519(8), c = 9.6103(9) Å, α = 96.094(5), β = 94.904(6), γ = 93.489(6)°, Z = 2, space group [Formula: see text], and monoclinic, a = 11.6329(11), b = 17.1628, c = 7.6542(6) Å, β = 97.669(4)°, Z = 4, space group P21/c. Crystals of (tropolonato)diphenylboron are monoclinic, a = 12.1596(5), b = 10.2614(4), c = 12.4883(6) Å, β = 100.965(2)°, Z = 4, space group P21/c. All three structures were solved by direct methods and were refined by full-matrix least-squares procedures to R values of 0.046, 0.041, and 0.035 for 2465, 2124, and 1722 reflections with I ≥ 3σ(I) respectively. Each structure consists of discrete molecules containing tetrahedrally coordinated boron atoms, both the acetylacetonato and tropolonato moieties being delocalized and symmetric. The chelate rings in both forms of (acetylacetonato)-diphenylboron have distorted B-envelope conformations while the chelate ring in (tropolonato)diphenylboron is essentially planar. The mean B—O and B—C distances (corrected for libration) are: 1.543(4) and 1.605(4) Å in triclinic, 1.533(3) and 1.607(4) Å in monoclinic (acetylacetonato)diphenylboron, and 1.555(11) and 1.605(6) Å in (tropolonato)diphenylboron.

Structural studies of organoboron compounds. XIX. 1,7-Dimethyl-3,5-diphenyl-2,4,6-trioxa-7-aza-1-azonia-3-bora-5-boratabicyclo[3.3.0]octane

1984 ◽  
Vol 62 (3) ◽  
pp. 515-520 ◽  
Author(s):  
Wolfgang Kliegel ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Solid State ◽  
Least Squares ◽  
Variable Temperature ◽  
Direct Methods ◽  
Structural Studies ◽  
Organoboron Compounds ◽  
Full Matrix ◽  
Space Group ◽  
H Nmr ◽  
Valence Tautomers

Crystals of 1,7-dimethyl-3,5-diphenyl-2,4,6-trioxa-7-aza-1-azonia-3-bora-5-boratabicyclo[3.3.0]octane are triclinic, a = 10.559(2), b = 15.156(3), c = 10.338(2) Å, α = 99.14(1), β = 89.90(1), γ = 96.73(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 = 0.032 and Rw = 0.038 for 2396 reflections with I ≥ 3σ(I). The structure consists of two crystallographically independent, but virtually identical, molecules containing sterically lengthened N—B coordinative bonds (mean 1.740(3) Å). The structurally inequivalent (in the solid state) pairs of N-methyl and B-phenyl groups are observed by variable temperature 1H nmr to be magnetically equivalent in solution, implying a rapid interconversion of "valence tautomers" at temperatures down to −60 °C.

Structural studies of organoboron compounds. XXI. Crystal and molecular structures of 3-(phenylmethylidene)-4-methyl-1-phenyl-2,6,7-trioxa-3-azonia-1-boratabicyclo-[2.2.2]octane and N-(4-nitrophenylmethylidene)-5-methyl-2-phenyl-1,3-dioxa-2-bora-5-cyclohexaneamine N-oxide

1985 ◽  
Vol 63 (2) ◽  
pp. 509-515 ◽  
Author(s):  
W. Kliegel ◽  
L. Preu ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Least Squares ◽  
Phenylboronic Acid ◽  
Direct Methods ◽  
Molecular Structures ◽  
Structural Studies ◽  
Full Matrix ◽  
Space Group ◽  
Condensation Products ◽  
Crystal And Molecular Structures ◽  
Bicyclic Structure

Crystals of 3-(phenylmethylidene)-4-methyl-1-phenyl-2,6,7-trioxa-3-azonia-1-boratabicyclo[2.2.2]octane are orthorhombic, a = 8.0732(7), b = 11.8499(10), c = 31.679(2) Å, Z = 8, space group Pbca, and those of N-(4-nitrophenylmethylidene)-5-methyl-2-phenyl-1,3-dioxa-2-bora-5-cyclohexaneamine N-oxide are monoclinic, a = 6.1873(6), b = 23.206(2), c = 11.3081(11) Å, β = 92.326(5)°, Z = 4, space group P21/n. Both structures were solved by direct methods and were refined by full-matrix least-squares procedures to final R values of 0.041 and 0.036 for 943 and 1679 reflections with I ≥ 3σ(I), respectively. Both compounds are condensation products of bis(hydroxyalkyl)nitrones and phenylboronic acid. 3-(Phenyl-methylidene)-4-methyl-1-phenyl-2,6,7-trioxa-3-azonia-1-boratabicyclo[2.2.2]octane was found to possess a bicyclic structure resulting from intramolecular O → B coordination (O—B = 1.604(7) Å) and is the first such bicyclic boron compound to be structurally characterized. In N-(4-nitrophenylmethylidene)-5-methyl-2-phenyl-1,3-dioxa-2-bora-5-cyclohexaneamine N-oxide, which has weakened nitrone basicity, the O → B interaction does not occur, resulting in a monocyclic system incorporating a trigonal planar boron atom.

Structural studies of organoboron compounds. XXXVI. 2,2-Dimethyl-3,3-diphenyl-1,4-dioxa-2-azonia-3-boratacyclohexane

1989 ◽  
Vol 67 (12) ◽  
pp. 2218-2221 ◽  
Author(s):  
Klaus Drückler ◽  
Wolfgang Kliegel ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Crystal Structure ◽  
Least Squares ◽  
Title Compound ◽  
Direct Methods ◽  
Organoboron Compound ◽  
Boron Compound ◽  
Structural Studies ◽  
Organoboron Compounds ◽  
Full Matrix ◽  
Space Group

The synthesis of O-(2-hydroxyethyl)-N,N-dimethylhydroxylamine and its reaction with oxybis(diphenylborane) to yield the title compound are reported. Crystals of 2,2-dimethyl-3,3-diphenyl-1,4-dioxa-2-azonia-3-boratacyclohexane are orthorhombic, a = 7.0332(6), b = 9.2269(6), c = 22.967(2) Å, Z = 4, space group P212121. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to R = 0.051 and Rw = 0.047 for 1247 reflections with 1 ≥ 2σ(I). The molecule exhibits the longest N—B and the shortest O—B distances (1.723(6) and 1.468(5) Å, respectively, corrected for libration) yet reported for a six-membered N,O-chelate of diphenylboron. Keywords: crystal structure, boron compound, organoboron compound.

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. XXVII. (3-Hydroxy-2-methyl-4-pyridinonato)diphenylboron and (3-hydroxy-1,2-dimethyl-4-pyridinonato)diphenylboron

1988 ◽  
Vol 66 (1) ◽  
pp. 132-138 ◽  
Author(s):  
William O. Nelson ◽  
Chris Orvig ◽  
Steven J. Rettig ◽  
James Trotter
Keyword(s):  
Least Squares ◽  
Crystal Structures ◽  
Direct Methods ◽  
Structural Data ◽  
Structural Studies ◽  
Organoboron Compounds ◽  
Full Matrix ◽  
Space Group ◽  
Bond Lengths ◽  
Oxygen Atoms

Details of the preparation and crystal structures of the title compounds are given. Crystals of (3-hydroxy-2-methyl-4-pyridinonato)diphenylboron, 1, are orthorhombic, a = 13.4010(6), b = 15.005(1), c = 14.833(1) Å, Z = 8, space group Pbca, and those of (3-hydroxy-1,2-dimethyl-4-pyridinonato)diphenylboron, 2, are monoclinic, a = 8.2617(5), b = 12.374(1), c = 16.104(1) Å, β = 92.741(5)°, Z = 4, space group P21/n. Both structures were solved by direct methods and were refined by full-matrix least-squares procedures to R = 0.047 and 0.071 for 1654 and 1831 reflections with I ≥ 3σ(I), respectively. Both molecules contain five-membered C2O2B chelate rings, that in 2 being nearly planar. Structural data indicate weaker overall binding of the ligand oxygen atoms to boron in 1 than in 2. Bond lengths (corrected for libration) are O—B = 1.497(5) and 1.650(5), C—B = 1.600(5) and 1.599(5) Å for 1; O—B = 1.542(5) and 1.569(5), C—B = 1.607(6) and 1.609(6) Å for 2.

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