Orientated intercalation of tartrate as chiral ligand to impact asymmetric catalysis

► Interlayer orientation of tartrate affects its coordination modes to Ti (IV) centers. ► Perpendicular-standing tartrates hold both COTi and COTi coordination modes. ► Flat-lying tartrates hold only the COTi coordination mode. ► Complex in both COTi and COTi modes displays higher activity and ee value.