Packing considerations of 10-oxa-9-boraphenanthrene derivatives

The crystal structures of three products of the reaction of 2-phenylphenol and BCl3 have been determined. The structures show intriguing packing patterns and an interesting case of pseudosymmetry. In addition, one of the two polymorphs has a primitive monoclinic crystal system, but it is twinned and emulates an orthorhombic C-centred structure. Tris(biphenyl-2-yl) borate, C36H27BO3, (III), crystallizes with only one molecule in the asymmetric unit. The dihedral angles between the planes of the aromatic rings in the biphenyl moieties are 50.47 (13), 44.95 (13) and 42.60 (13)°. The boron centre is in a trigonal planar coordination with two of the biphenyl residues on one side of the BO3 plane and the remaining biphenyl residue on the other side. One polymorph of 10-oxa-9-boraphenanthren-9-ol, C12H9BO2, (Va), crystallizes with two almost identical molecules (r.m.s. deviation of all non-H atoms = 0.039 Å) in the asymmetric unit. All non-H atoms lie in a common plane (r.m.s. deviation = 0.015 Å for both molecules in the asymmetric unit). The two molecules in the asymmetric unit are connected into dimers via O-H···O hydrogen bonds. A second polymorph of 10-oxa-9-boraphenanthren-9-ol, (Vb), crystallizes as a pseudo-merohedral twin with two almost identical molecules (r.m.s. deviation of all non-H atoms = 0.035 Å) in the asymmetric unit. All non-H atoms lie in a common plane (r.m.s. deviation = 0.012 Å for molecule 1 and 0.014 Å for molecule A). Each of the two molecules in the asymmetric unit is connected into a centrosymmetric dimer via O-H···O hydrogen bonds. The main difference between the two polymorphic structures is that in (Va) the two molecules in the asymmetric unit are hydrogen bonded to each other, whereas in (Vb), each molecule in the asymmetric unit forms a hydrogen-bonded dimer with its centrosymmetric equivalent. 9-[(Biphenyl-2-yl)oxy]-10-oxa-9-boraphenanthrene, C24H17BO2, (VI), crystallizes with four molecules in the asymmetric unit. The main differences between them are the dihedral angles between the ring planes. Apart from the biphenyl moiety, all non-H atoms lie in a common plane (r.m.s. deviations = 0.026, 0.0231, 0.019 and 0.033 Å for molecules 1, A, B and C, respectively). This structure shows pseudosymmetry; molecules 1 and A, as well as molecules B and C, are related by a pseudo-translation of about 1/2 in the direction of the b axis. Molecules 1 and B, as well as molecules A and C, are related by a pseudo-inversion centre at 1/4,1/8,1/2. Neither between molecules 1 and C nor between molecules A and B can pseudosymmetry be found.