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Na7Li4Yb5C12O37 crystallizes in the monoclinic Cm space group. The structure is three-dimensional. there are five inequivalent Na1+ sites. In the first Na1+ site, Na1+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Na–O bond distances ranging from 2.32–2.62 Å. In the second Na1+ site, Na1+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Na–O bond distances ranging from 2.47–2.54 Å. In the third Na1+ site, Na1+ is bonded in a 8-coordinate geometry to eight O2- atoms. There are a spread of Na–O bond distances ranging from 2.41–2.65 Å. In the fourth Na1+ site, Na1+ is bonded in a distorted q6 geometry to ten O2- atoms. There are a spread of Na–O bond distances ranging from 2.60–2.80 Å. In the fifth Na1+ site, Na1+ is bonded in a distorted q6 geometry to ten O2- atoms. There are a spread of Na–O bond distances ranging from 2.56–2.76 Å. There are three inequivalent Li1+ sites. In the first Li1+ site, Li1+ is bonded in an octahedral geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 2.05–2.26 Å. In the second Li1+ site, Li1+ is bonded in an octahedral geometry to six O2- atoms. There are a spread of Li–O bond distances ranging from 1.99–2.15 Å. In the third Li1+ site, Li1+ is bonded in a 1-coordinate geometry to one O2- atom. The Li–O bond length is 2.51 Å. There are three inequivalent Yb3+ sites. In the first Yb3+ site, Yb3+ is bonded in a 10-coordinate geometry to ten O2- atoms. There are a spread of Yb–O bond distances ranging from 2.50–2.79 Å. In the second Yb3+ site, Yb3+ is bonded in a 9-coordinate geometry to nine O2- atoms. There are a spread of Yb–O bond distances ranging from 2.31–2.86 Å. In the third Yb3+ site, Yb3+ is bonded in a distorted q6 geometry to ten O2- atoms. There are a spread of Yb–O bond distances ranging from 2.50–2.65 Å. There are nine inequivalent C4+ sites. In the first C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. All C–O bond lengths are 1.30 Å. In the second C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. All C–O bond lengths are 1.29 Å. In the third C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of C–O bond distances ranging from 1.28–1.31 Å. In the fourth C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. There is one shorter (1.28 Å) and two longer (1.29 Å) C–O bond length. In the fifth C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. There is one shorter (1.28 Å) and two longer (1.29 Å) C–O bond length. In the sixth C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. There is one shorter (1.28 Å) and two longer (1.30 Å) C–O bond length. In the seventh C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. There is one shorter (1.27 Å) and two longer (1.31 Å) C–O bond length. In the eighth C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. There are a spread of C–O bond distances ranging from 1.28–1.30 Å. In the ninth C4+ site, C4+ is bonded in a trigonal planar geometry to three O2- atoms. All C–O bond lengths are 1.29 Å. There are twenty-two inequivalent O2- sites. In the first O2- site, O2- is bonded in a 5-coordinate geometry to one Na1+, one Li1+, two Yb3+, and one C4+ atom. In the second O2- site, O2- is bonded in a 4-coordinate geometry to one Na1+, two equivalent Yb3+, and one C4+ atom. In the third O2- site, O2- is bonded in a 5-coordinate geometry to three Na1+, one Li1+, and one C4+ atom. In the fourth O2- site, O2- is bonded in a 5-coordinate geometry to two Na1+, one Li1+, one Yb3+, and one C4+ atom. In the fifth O2- site, O2- is bonded in a 1-coordinate geometry to one Na1+, two Yb3+, and one C4+ atom. In the sixth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to two Na1+, one Li1+, one Yb3+, and one C4+ atom. In the seventh O2- site, O2- is bonded in a distorted bent 120 degrees geometry to two equivalent Yb3+ atoms. In the eighth O2- site, O2- is bonded in a 5-coordinate geometry to three Na1+, one Li1+, and one C4+ atom. In the ninth O2- site, O2- is bonded in a 2-coordinate geometry to three Na1+, one Li1+, and one C4+ atom. In the tenth O2- site, O2- is bonded in a distorted single-bond geometry to one Na1+, two equivalent Yb3+, and one C4+ atom. In the eleventh O2- site, O2- is bonded in a 5-coordinate geometry to one Na1+, one Li1+, two Yb3+, and one C4+ atom. In the twelfth O2- site, O2- is bonded in a distorted single-bond geometry to three Yb3+ and one C4+ atom. In the thirteenth O2- site, O2- is bonded in a distorted single-bond geometry to one Na1+, two Yb3+, and one C4+ atom. In the fourteenth O2- site, O2- is bonded in a 1-coordinate geometry to two Na1+, one Yb3+, and one C4+ atom. In the fifteenth O2- site, O2- is bonded in a 2-coordinate geometry to one Na1+, one Li1+, two Yb3+, and one C4+ atom. In the sixteenth O2- site, O2- is bonded in a 1-coordinate geometry to two Na1+, one Yb3+, and one C4+ atom. In the seventeenth O2- site, O2- is bonded in a 1-coordinate geometry to two Na1+, one Yb3+, and one C4+ atom. In the eighteenth O2- site, O2- is bonded in a 2-coordinate geometry to three Na1+, one Li1+, and one C4+ atom. In the nineteenth O2- site, O2- is bonded in a 1-coordinate geometry to two Na1+, one Yb3+, and one C4+ atom. In the twentieth O2- site, O2- is bonded in a distorted single-bond geometry to three Na1+, one Li1+, and one C4+ atom. In the twenty-first O2- site, O2- is bonded in a distorted single-bond geometry to one Na1+, two equivalent Yb3+, and one C4+ atom. In the twenty-second O2- site, O2- is bonded in a distorted bent 150 degrees geometry to two Na1+, one Li1+, one Yb3+, and one C4+ atom.

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