Since a wide variety of materials either observed in nature or synthesized by chemists exhibit a marked preference to symmetry, it is quite difficult to find asymmetric substances. Nonetheless, discovering noncentrosymmetric (NCS) materials is a continuing challenge in inorganic solid-state materials chemistry field. This is mainly because acentric materials can reveal extremely important physical properties such as dielectric behavior, ferroelectricity, piezoelectricity, pyroelectricity, and

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... nlinear optical (NLO) properties. 1-5 On the basis of innumerable theoretical studies and synthetic approaches, it has been known that combining second-order Jahn-Teller (SOJT) cations would be an effective strategy to increase the incidence of asymmetric environments of materials with bond polarization. 6-15 With oxides, octahedrally coordinated d 0 transition metals and lone pair cations are two representative SOJT cations. Among them, many researchers have been paying special attention to the use of Bi 3+ cation in order to replace one of the best performing, yet very toxic lead-based NCS materials, e.g., lead zirconate titanate (PZT). In fact, several promising bismuth-based asymmetric oxide materials have been developed. [16] [17] [18] [19] Similarly, bismuth chloride materials have been also of great interest due to ferroelectric phase transitions, dielectric, and the related properties. 20-22 A variety of organic and inorganic template cations such as NH 4 + , CH 3 NH 3 + , (CH 3 ) 2 NH 2 + , C 5 H 5 NH + , K + , and Cs + have been introduced to prepare those asymmetric bismuth chlorides. [23] [24] [25] [26] [27] The versatility of the structure-directing agents definitely seems to affect local geometry as well as symmetry of the framework structure of the crystallized materials, which accordingly have influence upon the material properties. We have used a low-temperature (< 120°C ) reflux method to synthesize a new bismuth chloride. In this paper, we report the synthesis, structure, and characterization of a new organically templated zero-dimensional noncentrosymmetric bismuth chloride, [N(CH 3 Experimental Section Synthesis. Bi(NO 3 ) 3 ·5H 2 O (Fluka, 99%), aurintricarboxylic acid ammonium salt (C 22 H 14 O 9 ·3NH 3 ), N,N-dimethyl formamide, methanol, (CH 3 ) 2 N(CH 2 ) 2 N(CH 3 ) 2 , and HCl were used as received. Single crystals of compound 1 were prepared by using 0.485 g (1.00 mmol) of Bi(NO 3 ) 3 ·5H 2 O, 0.158 g (0.33 mmol) of aurintricarboxylic acid ammonium