The vanadium analog of MIL-69, V(OH)ndc·H₂O (ndc = 2,6-naphthalenedicarboxylate) was prepared solvothermally and the structure determined by single crystal X-ray diffraction (Space Group P2₁/c (#14), a = 6.7936(2) Å, b = 14.6816(4) Å, c = 23.9156(6) Å, β = 91.734(2)°, V = 2394.3(1) ų). Anhydrous V(OH)ndc was obtained from V(OH)ndc·H₂O by heating under nitrogen flow at 378 K in situ the crystal used to determine the structure of the as synthesized hydrated compound. The water molecules are removed on heating in a crystal to crystal transformation. Minor changes in the structure occur with no change in the V³⁺ oxidation state though the space group symmetry changes from P2₁/c to C2/c. (Space Group C2/c (#15), a = 24.684(4) Å, b = 7.079(2) Å, c = 6.853(1) Å, β = 104.35(1)°, V = 1160.2(4) ų). The structure of VOndc (Space Group C2/c (#15), a = 24.628 (2) Å, b = 7.1434(5)Å, c = 6.7428(4) Å, β = 104.637(3)°, V = 1147.8 ų) obtained by heating V(OH)ndc·H₂O in air at 573 K, in contrast shows a change in oxidation state from V³⁺ to V⁴⁺ evidenced by bond valence sum calculations and by the appearance of a characteristic distorted VO₆ octahedron and an O⋯V(IV) = O chain.

溶剂热制备MIL-69的钒类似物V（OH）ndc·H ₂ O（ndc = 2,6-萘二甲酸二甲酯），并通过单晶X射线衍射（空间群P2 ₁ / c（＃14 ），一个 = 6.7936（2）埃，b  = 14.6816（4），C ^  = 23.9156（6）A，β= 91.734（2）°，V = 2394.3（1）埃³）。无水V（OH）NDC从V（OH）NDC获得·H ₂通过在氮气流下在378 K加热Ó原位用于确定作为合成水合化合物的结构的晶体。加热至结晶至结晶相变时除去水分子。在V ³⁺不变的情况下发生了结构上的微小变化尽管空间基团对称性从P2 ₁ / c改变为C2 / c，但氧化态仍然存在。（空间组C2 / c（＃15），a  = 24.684（4）Å，b  = 7.079（2）Å，c  = 6.853（1）Å，β= 104.35（1）°，V = 1160.2（4）Å ³）。VOndc（空间群C2 / c（＃15），a  = 24.628（2）Å，b  = 7.1434（5）Å，c  = 6.7428（4）Å，β= 104.637（3）°，V = 1147.8的结构埃³）通过加热V（OH）NDC获得·H ₂ ö在空气中在573 K，与此相反示出了在从V氧化态变化³⁺到V ⁴⁺通过键价总和计算和通过特性的外观证实失真的VO₆八面体和O⋯V（IV）= O链。