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RbNbB2O6 crystallizes in the monoclinic Pc space group. The structure is three-dimensional. there are five inequivalent Rb1+ sites. In the first Rb1+ site, Rb1+ is bonded in a 7-coordinate geometry to seven O2- atoms. There are a spread of Rb–O bond distances ranging from 3.00–3.30 Å. In the second Rb1+ site, Rb1+ is bonded in a 6-coordinate geometry to eight O2- atoms. There are a spread of Rb–O bond distances ranging from 3.02–3.46 Å. In the third Rb1+ site, Rb1+ is bonded in a 9-coordinate geometry to nine O2- atoms. There are a spread of Rb–O bond distances ranging from 3.03–3.40 Å. In the fourth Rb1+ site, Rb1+ is bonded in a 10-coordinate geometry to ten O2- atoms. There are a spread of Rb–O bond distances ranging from 3.01–3.52 Å. In the fifth Rb1+ site, Rb1+ is bonded in a 10-coordinate geometry to ten O2- atoms. There are a spread of Rb–O bond distances ranging from 3.03–3.50 Å. There are five inequivalent Nb5+ sites. In the first Nb5+ site, Nb5+ is bonded to six O2- atoms to form distorted corner-sharing NbO6 octahedra. The corner-sharing octahedra tilt angles range from 5–17°. There are a spread of Nb–O bond distances ranging from 1.82–2.26 Å. In the second Nb5+ site, Nb5+ is bonded to six O2- atoms to form distorted corner-sharing NbO6 octahedra. The corner-sharing octahedra tilt angles range from 19–21°. There are a spread of Nb–O bond distances ranging from 1.82–2.27 Å. In the third Nb5+ site, Nb5+ is bonded to six O2- atoms to form distorted corner-sharing NbO6 octahedra. The corner-sharing octahedra tilt angles range from 17–21°. There are a spread of Nb–O bond distances ranging from 1.82–2.26 Å. In the fourth Nb5+ site, Nb5+ is bonded to six O2- atoms to form distorted corner-sharing NbO6 octahedra. The corner-sharing octahedra tilt angles range from 10–19°. There are a spread of Nb–O bond distances ranging from 1.81–2.27 Å. In the fifth Nb5+ site, Nb5+ is bonded to six O2- atoms to form distorted corner-sharing NbO6 octahedra. The corner-sharing octahedra tilt angles range from 5–10°. There are a spread of Nb–O bond distances ranging from 1.81–2.27 Å. There are ten inequivalent B3+ sites. In the first B3+ site, B3+ is bonded in a trigonal planar geometry to three O2- atoms. There is two shorter (1.36 Å) and one longer (1.41 Å) B–O bond length. In the second B3+ site, B3+ is bonded in a trigonal planar geometry to three O2- atoms. There is two shorter (1.36 Å) and one longer (1.41 Å) B–O bond length. In the third B3+ site, B3+ is bonded in a trigonal planar geometry to three O2- atoms. There is two shorter (1.36 Å) and one longer (1.41 Å) B–O bond length. In the fourth B3+ site, B3+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of B–O bond distances ranging from 1.36–1.41 Å. In the fifth B3+ site, B3+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of B–O bond distances ranging from 1.36–1.41 Å. In the sixth B3+ site, B3+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of B–O bond distances ranging from 1.36–1.41 Å. In the seventh B3+ site, B3+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of B–O bond distances ranging from 1.36–1.41 Å. In the eighth B3+ site, B3+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of B–O bond distances ranging from 1.36–1.41 Å. In the ninth B3+ site, B3+ is bonded in a trigonal planar geometry to three O2- atoms. There is two shorter (1.36 Å) and one longer (1.41 Å) B–O bond length. In the tenth B3+ site, B3+ is bonded in a trigonal planar geometry to three O2- atoms. There is two shorter (1.36 Å) and one longer (1.41 Å) B–O bond length. There are thirty inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted bent 150 degrees geometry to two equivalent Rb1+, one Nb5+, and one B3+ atom. In the second O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Rb1+, one Nb5+, and one B3+ atom. In the third O2- site, O2- is bonded in a 2-coordinate geometry to two Rb1+, one Nb5+, and one B3+ atom. In the fourth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to two Rb1+, one Nb5+, and one B3+ atom. In the fifth O2- site, O2- is bonded in a 2-coordinate geometry to two Rb1+, one Nb5+, and one B3+ atom. In the sixth O2- site, O2- is bonded in a bent 120 degrees geometry to two Rb1+ and two B3+ atoms. In the seventh O2- site, O2- is bonded in a distorted linear geometry to one Rb1+, one Nb5+, and one B3+ atom. In the eighth O2- site, O2- is bonded in a 2-coordinate geometry to two Rb1+, one Nb5+, and one B3+ atom. In the ninth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two Rb1+ and two B3+ atoms. In the tenth O2- site, O2- is bonded in a bent 120 degrees geometry to two Rb1+ and two B3+ atoms. In the eleventh O2- site, O2- is bonded in a 2-coordinate geometry to two Rb1+, one Nb5+, and one B3+ atom. In the twelfth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Rb1+, one Nb5+, and one B3+ atom. In the thirteenth O2- site, O2- is bonded in a 2-coordinate geometry to one Rb1+, one Nb5+, and one B3+ atom. In the fourteenth O2- site, O2- is bonded in a 2-coordinate geometry to two Rb1+, one Nb5+, and one B3+ atom. In the fifteenth O2- site, O2- is bonded in a bent 120 degrees geometry to two Rb1+ and two B3+ atoms. In the sixteenth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Rb1+, one Nb5+, and one B3+ atom. In the seventeenth O2- site, O2- is bonded in a 2-coordinate geometry to two Rb1+, one Nb5+, and one B3+ atom. In the eighteenth O2- site, O2- is bonded in a 2-coordinate geometry to two Rb1+, one Nb5+, and one B3+ atom. In the nineteenth O2- site, O2- is bonded in a 2-coordinate geometry to one Rb1+ and two Nb5+ atoms. In the twentieth O2- site, O2- is bonded in a distorted linear geometry to two Nb5+ atoms. In the twenty-first O2- site, O2- is bonded in a distorted bent 150 degrees geometry to two Rb1+, one Nb5+, and one B3+ atom. In the twenty-second O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two Rb1+ and two B3+ atoms. In the twenty-third O2- site, O2- is bonded in a distorted linear geometry to two Rb1+, one Nb5+, and one B3+ atom. In the twenty-fourth O2- site, O2- is bonded in a 2-coordinate geometry to two Rb1+, one Nb5+, and one B3+ atom. In the twenty-fifth O2- site, O2- is bonded in a 2-coordinate geometry to one Rb1+, one Nb5+, and one B3+ atom. In the twenty-sixth O2- site, O2- is bonded in a 2-coordinate geometry to two Nb5+ atoms. In the twenty-seventh O2- site, O2- is bonded in a distorted linear geometry to one Rb1+, one Nb5+, and one B3+ atom. In the twenty-eighth O2- site, O2- is bonded in a 2-coordinate geometry to one Rb1+ and two Nb5+ atoms. In the twenty-ninth O2- site, O2- is bonded in a 2-coordinate geometry to one Rb1+, one Nb5+, and one B3+ atom. In the thirtieth O2- site, O2- is bonded in a distorted linear geometry to two Nb5+ atoms.

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