Ba5Ru3Na2O14 crystallizes in the monoclinic P2_1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(11), one O(14), one O(3), one O(5), and one O(9) atom to form distorted NaO6 octahedra that share corners with three equivalent Ru(1)O6 octahedra, corners with three equivalent Ru(3)O5 trigonal bipyramids, and  a faceface with one Ba(5)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 3-7°. In the second Na site, Na(2) is bonded to one O(10), one O(12), one O(2), one O(4), and one O(6) atom to form NaO5 square pyramids that share corners with three equivalent Ru(2)O6 octahedra, corners with two equivalent Ru(3)O5 trigonal bipyramids, and  a faceface with one Ba(5)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 4-7°. There are five inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to one O(11), one O(14), one O(4), one O(5), one O(9), two equivalent O(1), and two equivalent O(3) atoms. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to one O(10), one O(12), one O(14), one O(3), one O(6), two equivalent O(2), and two equivalent O(4) atoms. In the third Ba site, Ba(3) is bonded in a 10-coordinate geometry to one O(1), one O(13), one O(7), one O(8), two equivalent O(11), two equivalent O(5), and two equivalent O(9) atoms. In the fourth Ba site, Ba(4) is bonded in a 10-coordinate geometry to one O(13), one O(2), one O(7), one O(8), two equivalent O(10), two equivalent O(12), and two equivalent O(6) atoms. In the fifth Ba site, Ba(5) is bonded to one O(10), one O(11), one O(12), one O(5), one O(6), one O(9), two equivalent O(13), two equivalent O(7), and two equivalent O(8) atoms to form BaO12 cuboctahedra that share corners with six equivalent Ba(5)O12 cuboctahedra,  a faceface with one Na(1)O6 octahedra, faces with three equivalent Ru(1)O6 octahedra, faces with three equivalent Ru(2)O6 octahedra, and  a faceface with one Na(2)O5 square pyramid. There are three inequivalent Ru sites. In the first Ru site, Ru(1) is bonded to one O(11), one O(13), one O(5), one O(7), one O(8), and one O(9) atom to form RuO6 octahedra that share corners with three equivalent Na(1)O6 octahedra, faces with three equivalent Ba(5)O12 cuboctahedra, and  a faceface with one Ru(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. In the second Ru site, Ru(2) is bonded to one O(10), one O(12), one O(13), one O(6), one O(7), and one O(8) atom to form RuO6 octahedra that share corners with three equivalent Na(2)O5 square pyramids, faces with three equivalent Ba(5)O12 cuboctahedra, and  a faceface with one Ru(1)O6 octahedra. In the third Ru site, Ru(3) is bonded to one O(1), one O(14), one O(2), one O(3), and one O(4) atom to form RuO5 trigonal bipyramids that share corners with three equivalent Na(1)O6 octahedra and corners with two equivalent Na(2)O5 square pyramids. The corner-sharing octahedral tilt angles range from 16-57°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Na(1), one Ba(3), two equivalent Ba(1), and one Ru(3) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(2), one Ba(4), two equivalent Ba(2), and one Ru(3) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(1), one Ba(2), two equivalent Ba(1), and one Ru(3) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(2), one Ba(1), two equivalent Ba(2), and one Ru(3) atom. In the fifth O site, O(5) is bonded to one Na(1), one Ba(1), one Ba(5), two equivalent Ba(3), and one Ru(1) atom to form distorted OBa4NaRu octahedra that share  a cornercorner with one O(6)Ba4NaRu octahedra,  a cornercorner with one O(7)Ba4Ru2 octahedra, corners with two equivalent O(11)Ba4NaRu octahedra, corners with two equivalent O(5)Ba4NaRu octahedra, corners with two equivalent O(13)Ba4Ru2 octahedra, corners with two equivalent O(8)Ba4Ru2 octahedra, edges with two equivalent O(7)Ba4Ru2 octahedra,  a faceface with one O(13)Ba4Ru2 octahedra,  a faceface with one O(8)Ba4Ru2 octahedra, and faces with two equivalent O(11)Ba4NaRu octahedra. The corner-sharing octahedral tilt angles range from 9-62°. In the sixth O site, O(6) is bonded to one Na(2), one Ba(2), one Ba(5), two equivalent Ba(4), and one Ru(2) atom to form distorted OBa4NaRu octahedra that share  a cornercorner with one O(11)Ba4NaRu octahedra,  a cornercorner with one O(5)Ba4NaRu octahedra,  a cornercorner with one O(8)Ba4Ru2 octahedra, corners with two equivalent O(6)Ba4NaRu octahedra, corners with two equivalent O(13)Ba4Ru2 octahedra, corners with two equivalent O(7)Ba4Ru2 octahedra, edges with two equivalent O(8)Ba4Ru2 octahedra,  a faceface with one O(13)Ba4Ru2 octahedra, and  a faceface with one O(7)Ba4Ru2 octahedra. The corner-sharing octahedral tilt angles range from 10-61°. In the seventh O site, O(7) is bonded to one Ba(3), one Ba(4), two equivalent Ba(5), one Ru(1), and one Ru(2) atom to form distorted OBa4Ru2 octahedra that share  a cornercorner with one O(5)Ba4NaRu octahedra, corners with two equivalent O(11)Ba4NaRu octahedra, corners with two equivalent O(6)Ba4NaRu octahedra, corners with two equivalent O(13)Ba4Ru2 octahedra, corners with two equivalent O(7)Ba4Ru2 octahedra, corners with two equivalent O(8)Ba4Ru2 octahedra, edges with two equivalent O(5)Ba4NaRu octahedra,  a faceface with one O(11)Ba4NaRu octahedra,  a faceface with one O(6)Ba4NaRu octahedra, faces with two equivalent O(13)Ba4Ru2 octahedra, and faces with two equivalent O(8)Ba4Ru2 octahedra. The corner-sharing octahedral tilt angles range from 6-61°. In the eighth O site, O(8) is bonded to one Ba(3), one Ba(4), two equivalent Ba(5), one Ru(1), and one Ru(2) atom to form distorted OBa4Ru2 octahedra that share  a cornercorner with one O(6)Ba4NaRu octahedra, corners with two equivalent O(11)Ba4NaRu octahedra, corners with two equivalent O(5)Ba4NaRu octahedra, corners with two equivalent O(13)Ba4Ru2 octahedra, corners with two equivalent O(7)Ba4Ru2 octahedra, corners with two equivalent O(8)Ba4Ru2 octahedra, edges with two equivalent O(6)Ba4NaRu octahedra,  a faceface with one O(11)Ba4NaRu octahedra,  a faceface with one O(5)Ba4NaRu octahedra, faces with two equivalent O(13)Ba4Ru2 octahedra, and faces with two equivalent O(7)Ba4Ru2 octahedra. The corner-sharing octahedral tilt angles range from 6-61°. In the ninth O site, O(9) is bonded in a distorted linear geometry to one Na(1), one Ba(1), one Ba(5), two equivalent Ba(3), and one Ru(1) atom. In the tenth O site, O(10) is bonded in a distorted linear geometry to one Na(2), one Ba(2), one Ba(5), two equivalent Ba(4), and one Ru(2) atom. In the eleventh O site, O(11) is bonded to one Na(1), one Ba(1), one Ba(5), two equivalent Ba(3), and one Ru(1) atom to form distorted OBa4NaRu octahedra that share  a cornercorner with one O(6)Ba4NaRu octahedra,  a cornercorner with one O(13)Ba4Ru2 octahedra, corners with two equivalent O(11)Ba4NaRu octahedra, corners with two equivalent O(5)Ba4NaRu octahedra, corners with two equivalent O(7)Ba4Ru2 octahedra, corners with two equivalent O(8)Ba4Ru2 octahedra, edges with two equivalent O(13)Ba4Ru2 octahedra,  a faceface with one O(7)Ba4Ru2 octahedra,  a faceface with one O(8)Ba4Ru2 octahedra, and faces with two equivalent O(5)Ba4NaRu octahedra. The corner-sharing octahedral tilt angles range from 9-62°. In the twelfth O site, O(12) is bonded in a 6-coordinate geometry to one Na(2), one Ba(2), one Ba(5), two equivalent Ba(4), and one Ru(2) atom. In the thirteenth O site, O(13) is bonded to one Ba(3), one Ba(4), two equivalent Ba(5), one Ru(1), and one Ru(2) atom to form distorted OBa4Ru2 octahedra that share  a cornercorner with one O(11)Ba4NaRu octahedra, corners with two equivalent O(5)Ba4NaRu octahedra, corners with two equivalent O(6)Ba4NaRu octahedra, corners with two equivalent O(13)Ba4Ru2 octahedra, corners with two equivalent O(7)Ba4Ru2 octahedra, corners with two equivalent O(8)Ba4Ru2 octahedra, edges with two equivalent O(11)Ba4NaRu octahedra,  a faceface with one O(5)Ba4NaRu octahedra,  a faceface with one O(6)Ba4NaRu octahedra, faces with two equivalent O(7)Ba4Ru2 octahedra, and faces with two equivalent O(8)Ba4Ru2 octahedra. The corner-sharing octahedral tilt angles range from 7-61°. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(1), one Ba(1), one Ba(2), and one Ru(3) atom.
Ba5Ru3Na2O14 crystallizes in the monoclinic P2_1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(11), one O(14), one O(3), one O(5), and one O(9) atom to form distorted NaO6 octahedra that share corners with three equivalent Ru(1)O6 octahedra, corners with three equivalent Ru(3)O5 trigonal bipyramids, and  a faceface with one Ba(5)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 3-7°. The Na(1)-O(1) bond length is 2.36 Å. The Na(1)-O(11) bond length is 2.32 Å. The Na(1)-O(14) bond length is 2.81 Å. The Na(1)-O(3) bond length is 2.39 Å. The Na(1)-O(5) bond length is 2.29 Å. The Na(1)-O(9) bond length is 2.25 Å. In the second Na site, Na(2) is bonded to one O(10), one O(12), one O(2), one O(4), and one O(6) atom to form NaO5 square pyramids that share corners with three equivalent Ru(2)O6 octahedra, corners with two equivalent Ru(3)O5 trigonal bipyramids, and  a faceface with one Ba(5)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 4-7°. The Na(2)-O(10) bond length is 2.19 Å. The Na(2)-O(12) bond length is 2.29 Å. The Na(2)-O(2) bond length is 2.50 Å. The Na(2)-O(4) bond length is 2.36 Å. The Na(2)-O(6) bond length is 2.29 Å. There are five inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 9-coordinate geometry to one O(11), one O(14), one O(4), one O(5), one O(9), two equivalent O(1), and two equivalent O(3) atoms. The Ba(1)-O(11) bond length is 2.85 Å. The Ba(1)-O(14) bond length is 2.67 Å. The Ba(1)-O(4) bond length is 2.72 Å. The Ba(1)-O(5) bond length is 2.79 Å. The Ba(1)-O(9) bond length is 2.86 Å. There is one shorter (2.88 Å) and one longer (3.16 Å) Ba(1)-O(1) bond length. There is one shorter (2.94 Å) and one longer (3.09 Å) Ba(1)-O(3) bond length. In the second Ba site, Ba(2) is bonded in a 9-coordinate geometry to one O(10), one O(12), one O(14), one O(3), one O(6), two equivalent O(2), and two equivalent O(4) atoms. The Ba(2)-O(10) bond length is 2.90 Å. The Ba(2)-O(12) bond length is 2.87 Å. The Ba(2)-O(14) bond length is 2.66 Å. The Ba(2)-O(3) bond length is 2.76 Å. The Ba(2)-O(6) bond length is 2.80 Å. There is one shorter (2.76 Å) and one longer (3.34 Å) Ba(2)-O(2) bond length. There is one shorter (2.92 Å) and one longer (3.11 Å) Ba(2)-O(4) bond length. In the third Ba site, Ba(3) is bonded in a 10-coordinate geometry to one O(1), one O(13), one O(7), one O(8), two equivalent O(11), two equivalent O(5), and two equivalent O(9) atoms. The Ba(3)-O(1) bond length is 2.95 Å. The Ba(3)-O(13) bond length is 2.86 Å. The Ba(3)-O(7) bond length is 2.85 Å. The Ba(3)-O(8) bond length is 2.79 Å. There is one shorter (2.96 Å) and one longer (2.99 Å) Ba(3)-O(11) bond length. There is one shorter (2.97 Å) and one longer (3.04 Å) Ba(3)-O(5) bond length. There is one shorter (3.00 Å) and one longer (3.04 Å) Ba(3)-O(9) bond length. In the fourth Ba site, Ba(4) is bonded in a 10-coordinate geometry to one O(13), one O(2), one O(7), one O(8), two equivalent O(10), two equivalent O(12), and two equivalent O(6) atoms. The Ba(4)-O(13) bond length is 2.86 Å. The Ba(4)-O(2) bond length is 2.87 Å. The Ba(4)-O(7) bond length is 2.78 Å. The Ba(4)-O(8) bond length is 2.81 Å. There is one shorter (2.99 Å) and one longer (3.02 Å) Ba(4)-O(10) bond length. There is one shorter (2.95 Å) and one longer (3.01 Å) Ba(4)-O(12) bond length. There is one shorter (3.00 Å) and one longer (3.03 Å) Ba(4)-O(6) bond length. In the fifth Ba site, Ba(5) is bonded to one O(10), one O(11), one O(12), one O(5), one O(6), one O(9), two equivalent O(13), two equivalent O(7), and two equivalent O(8) atoms to form BaO12 cuboctahedra that share corners with six equivalent Ba(5)O12 cuboctahedra,  a faceface with one Na(1)O6 octahedra, faces with three equivalent Ru(1)O6 octahedra, faces with three equivalent Ru(2)O6 octahedra, and  a faceface with one Na(2)O5 square pyramid. The Ba(5)-O(10) bond length is 3.01 Å. The Ba(5)-O(11) bond length is 3.02 Å. The Ba(5)-O(12) bond length is 3.10 Å. The Ba(5)-O(5) bond length is 3.03 Å. The Ba(5)-O(6) bond length is 3.03 Å. The Ba(5)-O(9) bond length is 2.97 Å. There is one shorter (2.95 Å) and one longer (2.97 Å) Ba(5)-O(13) bond length. There is one shorter (2.99 Å) and one longer (3.00 Å) Ba(5)-O(7) bond length. There is one shorter (3.00 Å) and one longer (3.01 Å) Ba(5)-O(8) bond length. There are three inequivalent Ru sites. In the first Ru site, Ru(1) is bonded to one O(11), one O(13), one O(5), one O(7), one O(8), and one O(9) atom to form RuO6 octahedra that share corners with three equivalent Na(1)O6 octahedra, faces with three equivalent Ba(5)O12 cuboctahedra, and  a faceface with one Ru(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. The Ru(1)-O(11) bond length is 1.92 Å. The Ru(1)-O(13) bond length is 2.09 Å. The Ru(1)-O(5) bond length is 1.92 Å. The Ru(1)-O(7) bond length is 2.10 Å. The Ru(1)-O(8) bond length is 2.09 Å. The Ru(1)-O(9) bond length is 1.89 Å. In the second Ru site, Ru(2) is bonded to one O(10), one O(12), one O(13), one O(6), one O(7), and one O(8) atom to form RuO6 octahedra that share corners with three equivalent Na(2)O5 square pyramids, faces with three equivalent Ba(5)O12 cuboctahedra, and  a faceface with one Ru(1)O6 octahedra. The Ru(2)-O(10) bond length is 1.89 Å. The Ru(2)-O(12) bond length is 1.92 Å. The Ru(2)-O(13) bond length is 2.10 Å. The Ru(2)-O(6) bond length is 1.91 Å. The Ru(2)-O(7) bond length is 2.09 Å. The Ru(2)-O(8) bond length is 2.11 Å. In the third Ru site, Ru(3) is bonded to one O(1), one O(14), one O(2), one O(3), and one O(4) atom to form RuO5 trigonal bipyramids that share corners with three equivalent Na(1)O6 octahedra and corners with two equivalent Na(2)O5 square pyramids. The corner-sharing octahedral tilt angles range from 16-57°. The Ru(3)-O(1) bond length is 1.82 Å. The Ru(3)-O(14) bond length is 1.84 Å. The Ru(3)-O(2) bond length is 1.84 Å. The Ru(3)-O(3) bond length is 1.96 Å. The Ru(3)-O(4) bond length is 1.98 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Na(1), one Ba(3), two equivalent Ba(1), and one Ru(3) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(2), one Ba(4), two equivalent Ba(2), and one Ru(3) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(1), one Ba(2), two equivalent Ba(1), and one Ru(3) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(2), one Ba(1), two equivalent Ba(2), and one Ru(3) atom. In the fifth O site, O(5) is bonded to one Na(1), one Ba(1), one Ba(5), two equivalent Ba(3), and one Ru(1) atom to form distorted OBa4NaRu octahedra that share  a cornercorner with one O(6)Ba4NaRu octahedra,  a cornercorner with one O(7)Ba4Ru2 octahedra, corners with two equivalent O(11)Ba4NaRu octahedra, corners with two equivalent O(5)Ba4NaRu octahedra, corners with two equivalent O(13)Ba4Ru2 octahedra, corners with two equivalent O(8)Ba4Ru2 octahedra, edges with two equivalent O(7)Ba4Ru2 octahedra,  a faceface with one O(13)Ba4Ru2 octahedra,  a faceface with one O(8)Ba4Ru2 octahedra, and faces with two equivalent O(11)Ba4NaRu octahedra. The corner-sharing octahedral tilt angles range from 9-62°. In the sixth O site, O(6) is bonded to one Na(2), one Ba(2), one Ba(5), two equivalent Ba(4), and one Ru(2) atom to form distorted OBa4NaRu octahedra that share  a cornercorner with one O(11)Ba4NaRu octahedra,  a cornercorner with one O(5)Ba4NaRu octahedra,  a cornercorner with one O(8)Ba4Ru2 octahedra, corners with two equivalent O(6)Ba4NaRu octahedra, corners with two equivalent O(13)Ba4Ru2 octahedra, corners with two equivalent O(7)Ba4Ru2 octahedra, edges with two equivalent O(8)Ba4Ru2 octahedra,  a faceface with one O(13)Ba4Ru2 octahedra, and  a faceface with one O(7)Ba4Ru2 octahedra. The corner-sharing octahedral tilt angles range from 10-61°. In the seventh O site, O(7) is bonded to one Ba(3), one Ba(4), two equivalent Ba(5), one Ru(1), and one Ru(2) atom to form distorted OBa4Ru2 octahedra that share  a cornercorner with one O(5)Ba4NaRu octahedra, corners with two equivalent O(11)Ba4NaRu octahedra, corners with two equivalent O(6)Ba4NaRu octahedra, corners with two equivalent O(13)Ba4Ru2 octahedra, corners with two equivalent O(7)Ba4Ru2 octahedra, corners with two equivalent O(8)Ba4Ru2 octahedra, edges with two equivalent O(5)Ba4NaRu octahedra,  a faceface with one O(11)Ba4NaRu octahedra,  a faceface with one O(6)Ba4NaRu octahedra, faces with two equivalent O(13)Ba4Ru2 octahedra, and faces with two equivalent O(8)Ba4Ru2 octahedra. The corner-sharing octahedral tilt angles range from 6-61°. In the eighth O site, O(8) is bonded to one Ba(3), one Ba(4), two equivalent Ba(5), one Ru(1), and one Ru(2) atom to form distorted OBa4Ru2 octahedra that share  a cornercorner with one O(6)Ba4NaRu octahedra, corners with two equivalent O(11)Ba4NaRu octahedra, corners with two equivalent O(5)Ba4NaRu octahedra, corners with two equivalent O(13)Ba4Ru2 octahedra, corners with two equivalent O(7)Ba4Ru2 octahedra, corners with two equivalent O(8)Ba4Ru2 octahedra, edges with two equivalent O(6)Ba4NaRu octahedra,  a faceface with one O(11)Ba4NaRu octahedra,  a faceface with one O(5)Ba4NaRu octahedra, faces with two equivalent O(13)Ba4Ru2 octahedra, and faces with two equivalent O(7)Ba4Ru2 octahedra. The corner-sharing octahedral tilt angles range from 6-61°. In the ninth O site, O(9) is bonded in a distorted linear geometry to one Na(1), one Ba(1), one Ba(5), two equivalent Ba(3), and one Ru(1) atom. In the tenth O site, O(10) is bonded in a distorted linear geometry to one Na(2), one Ba(2), one Ba(5), two equivalent Ba(4), and one Ru(2) atom. In the eleventh O site, O(11) is bonded to one Na(1), one Ba(1), one Ba(5), two equivalent Ba(3), and one Ru(1) atom to form distorted OBa4NaRu octahedra that share  a cornercorner with one O(6)Ba4NaRu octahedra,  a cornercorner with one O(13)Ba4Ru2 octahedra, corners with two equivalent O(11)Ba4NaRu octahedra, corners with two equivalent O(5)Ba4NaRu octahedra, corners with two equivalent O(7)Ba4Ru2 octahedra, corners with two equivalent O(8)Ba4Ru2 octahedra, edges with two equivalent O(13)Ba4Ru2 octahedra,  a faceface with one O(7)Ba4Ru2 octahedra,  a faceface with one O(8)Ba4Ru2 octahedra, and faces with two equivalent O(5)Ba4NaRu octahedra. The corner-sharing octahedral tilt angles range from 9-62°. In the twelfth O site, O(12) is bonded in a 6-coordinate geometry to one Na(2), one Ba(2), one Ba(5), two equivalent Ba(4), and one Ru(2) atom. In the thirteenth O site, O(13) is bonded to one Ba(3), one Ba(4), two equivalent Ba(5), one Ru(1), and one Ru(2) atom to form distorted OBa4Ru2 octahedra that share  a cornercorner with one O(11)Ba4NaRu octahedra, corners with two equivalent O(5)Ba4NaRu octahedra, corners with two equivalent O(6)Ba4NaRu octahedra, corners with two equivalent O(13)Ba4Ru2 octahedra, corners with two equivalent O(7)Ba4Ru2 octahedra, corners with two equivalent O(8)Ba4Ru2 octahedra, edges with two equivalent O(11)Ba4NaRu octahedra,  a faceface with one O(5)Ba4NaRu octahedra,  a faceface with one O(6)Ba4NaRu octahedra, faces with two equivalent O(7)Ba4Ru2 octahedra, and faces with two equivalent O(8)Ba4Ru2 octahedra. The corner-sharing octahedral tilt angles range from 7-61°. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(1), one Ba(1), one Ba(2), and one Ru(3) atom.