(11)B MAS NMR and First-Principles Study of the [OBO3] Pyramids in Borates.

Borates are built from the [Bϕ3] planar triangles and the [Bϕ4] tetrahedral groups, where ϕ denotes O or OH. However, the [Bϕ4] groups in some borates are highly distorted to include three normal B-O bonds and one anomalously long B-O bond and, therefore, are best described as the [OBO3] pyramids. Four synthetic borates of the boracite-type structures (Mg3B7O13Br, Cu3B7O13Br, Zn3B7O13Cl, and Mg3B7O13Cl) containing a range of [OBO3] pyramids were investigated by multifield (7.05, 14.1, and 21.1 T) (11)B magic-angle spinning nuclear magnetic resonance (MAS NMR), triple quantum (3Q) MAS NMR experiments, as well as density functional theory calculations. The high-resolution (11)B MAS NMR spectra supported by theoretical predictions show that the [OBO3] pyramids are characterized by isotropic chemical shifts δiso((11)B) from 1.4(1) to 4.9(1) ppm and nuclear quadrupole parameters CQ((11)B) up to 1.3(1) MHz, both significantly different from those of the [BO4] and [BO3] groups in borates. These δiso((11)B) and CQ((11)B) values indicate that the [OBO3] pyramids represent an intermediate state between the [BO4] tetrahedra and [BO3] triangles and demonstrate that the (11)B NMR parameters of four-coordinate boron oxyanions are sensitive to local structural environments. The orientation of the calculated unique electronic field gradient tensor element Vzz of the [OBO3] pyramids is aligned approximately along the direction of the anomalously long B-O bond, corresponding to B-2pz with the lowest electron density.

Cerium(III) dihydroxidohexa-oxidotetra-borate chloride.

The crystal structure of the title compound, Ce[B(4)O(6)(OH)(2)]Cl, is built from polyborate sheets parallel to the (001) plane. These sheets stack along the [001] direction and are linked by Ce atoms exhibiting an CeO(8)Cl(2) coordination sphere. O-H⋯O and O-H⋯Cl hydrogen bonds additionally stabilize the structural set-up. The polyborate sheet is made up of zigzag borate chains running along the [[Formula: see text]10] direction. These zigzag chains are inter-connected by shared O-vertices, resulting in a two-dimensional layer with nine-membered rings. All B and O atoms (except for the terminal OH atoms) lie in the nearly planar sheets of polyborates, leading to their isotropic atomic displacement parameters being significantly smaller than usual. This may be attributed to the fact that the atomic displacement parameters correlate not only with their atomic masses but with their coordination environments also.

Redetermination of Ce[B(5)O(8)(OH)(H(2)O)]NO(3)·2H(2)O.

The crystal structure of Ce[B(5)O(8)(OH)(H(2)O)]NO(3)·2H(2)O, cerium(III) aqua-hydroxidoocta-oxidopenta-borate nitrate dihydrate, has been redetermined from single-crystal X-ray diffraction data. In contrast to the previous determination [Li et al. (2003 ▶). Chem. Mater.15, 2253-2260], the present study reveals the location of all H atoms, slightly different fundamental building blocks (FBBs) of the polyborate anions, more reasonable displacement ellipsoids for all non-H atoms, as well as a model without disorder of the nitrate anion. The crystal structure is built from corrugated polyborate layers parallel to (010). These layers, consisting of [B(5)O(8)(OH)(H(2)O)](2-) anions as FBBs, stack along [010] and are linked by Ce(3+) ions, which exhibit a distorted CeO(10) coordination sphere. The layers are additionally stabilized via O-H⋯O hydrogen bonds between water mol-ecules and nitrate anions, located at the inter-layer space. The [BO(3)(H(2)O)]-group shows a [3 + 1] coordination and is considerably distorted from a tetra-hedral configuration. Bond-valence-sum calculation shows that the valence sum of boron is only 2.63 valence units (v.u.) when the contribution of the water mol-ecule (0.49 v.u.) is neglected.

MnBa(2)(HPO(4))(2)(H(2)PO(4))(2).

Crystals of manganese(II) dibarium bis-(hydrogenphosphate) bis-(dihydrogenphosphate), MnBa(2)(HPO(4))(2)(H(2)PO(4))(2), were obtained by hydro-thermal synthesis. The title compound is isotypic with its Cd(II) and Ca(II) analogues. The structure is built up of an infinite {[Mn(HPO(4))(2)(H(2)PO(4))(2)](4-)}(n) chain running along [100], which consists of alternate MnO(6) octa-hedra and [PO(4)] tetra-hedra, in which the centrosymmetric MnO(6) octa-hedra share their four equatorial O-atom corners with tetra-hedral [PO(3)(OH)] groups and their two axial apices with tetra-hedral [PO(2)(OH)(2)] groups. These chains are held together by BaO(9) coordination polyhedra, developing into a three-dimensional structure. The O-H⋯O hydrogen bonds additionally stabilize the structural set-up. Due to the ionic radius of Mn(2+) being much smaller than those of Ca(2+) and Cd(2+), this may imply that their adopted structure type has a great tolerance for incorporating various ions and the exploitation of more diverse compounds in the future is encouraged.