Single crystals of type I Na-Si clathrate, Na8Si46, were synthesized by heating Na, Na4Si4, and Na15Sn4 at 723 K under an Ar gas pressure of 10(4) Pa for 12 h. The single crystals having {110} habit planes grew up to 1.5 mm in size due to Na evaporation from a Na-Si-Sn melt with a starting compositional molar ratio of Na/Si/Sn=5.75:2:1. (C) 2016 Elsevier B.V. All rights reserved.