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六次甲基四胺(HMT)与氯化苄加成所得的Sommelet反应中间产物的单晶样品用SYNTEX R3型四圆衍射仪,以θ/2θ扫描方式收集了2677个衍射数据并进行了结构分析.晶体属空间群P2_12_12_1.晶胞参数α=7.692(1)A,b=18.405(3)A,c=19.059(3)A,晶胞中含八个G_6H_5CH_2Cl·N_4(CH_2)_6.经PL,K,B及吸收因子的校正得绝对强度。全部非氢原子坐标的初始参数由SHELXTL直接法程序所得的E图导出.对坐标及热参数经六轮块矩阵最小二乘法修正,再加入氢原子修正两轮后得一致性因子R_1=0.040,R_2=0.032(加权).结构分析证实,此Sommelet反应中间物由季胺盐阳离子与氯离子所组成.在晶体中观察到苄基与HMT中N~*直接键连,并导致HMT中N~*—C~*键有极显著的键长增长效应,而与N~*—C~*邻接的C~*—N键则有所增强.由此预期当此加合物水解时,N~*—C~*弱键首先瓦解是较合理的.
A single crystal sample of the Sommelet reaction intermediate obtained by the addition of hexamethylenetetramine (HMT) and benzyl chloride was collected using a SYNTEX R3 four-circle diffractometer and 2677 diffraction data were obtained by θ / 2θ scanning The crystal belongs to the space group P2_12_12_1. The unit cell parameters α = 7.692 (1) A, b = 18.405 (3) A, c = 19.059 (3) A and the unit cell contains eight G_6H_5CH_2Cl_N_4 (CH_2) _6 PL, K, B and absorption factor correction was absolute intensity. The initial parameters of all nonhydrogen atomic coordinates are derived from the E map obtained by the SHELXTL direct method program.The coordinate and thermal parameters are corrected by the least squares method of six-block matrix, and then the hydrogen atoms are modified two rounds to obtain the consistency factor R_1 = 0.040, R_2 = 0.032 (weight) .The structural analysis confirmed that this Sommelet reaction intermediate is composed of quaternary ammonium salt cation and chloride ion.It is observed in the crystal that the benzyl group is directly linked to N * in HMT and leads to the N * The C ~ * bond has a very significant effect on the bond length growth, while the C ~ * -N bond adjacent to N * * -C ~ * increases, and it is expected that when this adduct is hydrolyzed, the N ~ * - C ~ * weak key first collapse is more reasonable.