Transformation of ammonium dicyanamide into dicyandiamide in the solid

被引:39
作者
Jurgens, B [1 ]
Höppe, HA [1 ]
Irran, E [1 ]
Schnick, W [1 ]
机构
[1] Univ Munich, Dept Chem, D-81377 Munich, Germany
关键词
D O I
10.1021/ic025800k
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Ammonium dicyanamide NH4[N(CN)21 was synthesized through aqueous ion exchange. The crystal structure was investigated by single-crystal X-ray diffraction (P2(1)/c, a = 378.67(6) pm, b = 1240.9(3) pm, c = 911.84(14) pm, beta = 91.488(18)degrees, Z = 4). It derives from the CsCl structure type. Medium strong hydrogen bonds between NH4+ and [N(CN)(2)](-) ions are indicative of the observed formation of dicyandiamide H4C2N4 during heating. According to DSC and temperature-dependent X-ray powder diffractometry, this isomerization is exothermic and occurs between 102 and 106 degreesC in the solid. The reaction represents the isolobal analogue to the classical synthesis of urea by heating NH4OCN. While other alkali and alkaline earth dicyanamides undergo trimerization or polymerization of their anions during heating, ammonium dicyanamide thus shows a different reactivity.
引用
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页码:4849 / 4851
页数:3
相关论文
共 32 条
[1]  
BIELING H, 1965, J PRAKT CHEM, V28, P325, DOI 10.1002/prac.19650280509
[2]   CRYSTAL-STRUCTURE OF SILVER DICYANAMIDE, AGN(CN)2 [J].
BRITTON, D ;
CHOW, YM .
ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE, 1977, 33 (MAR15) :697-699
[4]   Wohler's synthesis of urea: How do the textbooks report it? [J].
Cohen, PS ;
Cohen, SM .
JOURNAL OF CHEMICAL EDUCATION, 1996, 73 (09) :883-886
[5]   New light on an old story: The solid-state transformation of ammonium cyanate into urea [J].
Dunitz, JD ;
Harris, KDM ;
Johnston, RL ;
Kariuki, BM ;
MacLean, EJ ;
Psallidas, K ;
Schweizer, WB ;
Tykwinski, RR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (50) :13274-13275
[6]   X-RAY DETERMINATION OF THE CHARGE DEFORMATION DENSITY IN 2-CYANOGUANIDINE [J].
HIRSHFELD, FL ;
HOPE, H .
ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE, 1980, 36 (FEB) :406-415
[7]  
Hoffmann R., 1982, Angew. Chem., V94, P725
[8]  
Irran E, 2001, CHEM-EUR J, V7, P5372, DOI 10.1002/1521-3765(20011217)7:24<5372::AID-CHEM5372>3.0.CO
[9]  
2-#
[10]   PSEUDOHALOGEN COMPOUNDS - SYNTHESIS AND REACTIVITY OF ALKYLAMMONIUM AND ARYLAMMONIUM DICYANAMIDES, TRICYANMETHANIDES, AND DICYANMETHANIDOACETATES [RNH3]X (X = N(CN)2, C(CN)3, C(CN)2C(O)CH3) [J].
JAGER, L ;
KRETSCHMANN, M ;
KOHLER, H .
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE, 1992, 611 (05) :68-72