High-silica ZSM-12 (MTW topology), synthesized with 6-azonia-spiro- (Rimer, 2018; Rimer, 2018) [5,5]-undecane as structure directing agent (SDA), was carefully characterized by using X-ray synchrotron powder diffraction. The structure refinement led to a monoclinic unit cell (space group Cc, Z = 4, a = 25.0814(13) Å, b = 15.0987(8) Å, c = 24.4419(17) Å, β = 107.844(6), V = 8810.8(8) ų) with a three times enlargement of the unit cell along the b axis with respect to the calcined starting ZSM-12 (space group C2/c, Z = 1, a = 24.8633(3) Å, b = 5.01238(7) Å, c = 24.3275(7) Å, β = 107.7215(6)°). The SDAs conformation and position in the framework structure did not maintain the twofold axes coinciding with the crystallographic twofold axis thus changing the space group symmetry from C2/c to Cc. The structure refinement gave an extraframework content 6.13 SDA molecules per unit cell (corresponding to ∼9.0 wt%) in good agreement with the weight loss given by the thermogravimetric analysis. The refined bond distances revealed the occurrence of non-bonding interactions of both azonia molecules with the MTW pore wall. AZO-1 and AZO-2 molecules are H-bonded between them thus forming clusters aligned along the b axis. This information is crucial to tailor the physicochemical properties of zeolites as well as to address their hydrophobicity, pore dimensions and cavities thus optimizing the selectivity of zeolite catalysts.

高硅酸ZSM-12（MTW拓扑结构）是由6-氮杂螺环-合成的（Rimer，2018； Rimer，2018）[5,5]-十一烷作为结构导向剂（SDA），通过使用X-射线同步加速器粉末衍射。结构的细化导致了单斜晶胞（空间群Cc，Z = 4，a = 25.0814（13）Å，b = 15.0987（8）Å，c = 24.4419（17）Å，β= 107.844（6），V = 8810.8（8）一种³）与三次肿大沿单元电池的b轴相对于所述煅烧起始的ZSM-12（空间群C2 / c ^，Z ＝ 1，a ＝ 24.8633（3），b ＝ 5.01238（7），c ＝ 24.3275（7），β＝ 107.7215（6）°）。SDA的构象和在框架结构中的位置不能保持双重轴与晶体学双重轴一致，从而将空间群对称性从C2 / c改变为Cc。结构上的改进使每单位晶胞的骨架含量为6.13 SDA分子（约9.0 wt％），与热重分析给出的重量损失非常吻合。精炼的键距揭示了氮杂分子与MTW孔壁之间非键相互作用的发生。AZO-1和AZO-2分子之间氢键结合，从而形成沿b排列的簇轴。该信息对于调整沸石的理化性质以及解决其疏水性，孔尺寸和孔洞从而优化沸石催化剂的选择性至关重要。