SOLID-STATE STRUCTURAL CHEMISTRY OF LARIAT ETHER AND BIBLE CATION COMPLEXES - METAL-ION IDENTITY AND COORDINATION-NUMBER DETERMINE CAVITY SIZE
SOLID-STATE STRUCTURAL CHEMISTRY OF LARIAT ETHER AND BIBLE CATION COMPLEXES - METAL-ION IDENTITY AND COORDINATION-NUMBER DETERMINE CAVITY SIZE
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DOI：
10.1021/ja00274a037
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发表时间：
1986-07-09
影响因子：
15
通讯作者：
GOKEL, GW
中科院分区：
文献类型：
--
作者：
GANDOUR, RD;FRONCZEK, FR;GOKEL, GW
本文报道了A ′-烯丙基单氮杂-18-冠-6（1）一水合物[K+ C5-烯丙基-H_（20）]、7V，7V ′-双（C5-烯丙基-H_（20）]、7V，7V ′-双（C5-烯丙基-H_（20）和7V，7V ′-双（C5-H_20）的K ~+配合物的X-射线晶体结构。（3-氧丁基）二氮杂-18-冠-6（2）[K+ C1-22-1]，7V-（3-氧杂丁基）单氮杂-15-冠-5（3）[K+ C4- 1]，7V-（3，6-二氧杂庚基）单氮杂-15-冠-5（4）[K+ C4-2]和7 N，N '-双（2-羟乙基）二氮杂-18-冠-6（5）[K+ CHl-22-lH]沿着与相关配合物一起报道！以初步形式：[Na+ CH 1 -22- 1H]和Ar-（3-氧杂丁基）单氮杂-18-冠-6（6）的K+络合物[K+ C5-1]（Am. 1983，105，6717-6718）以及（N-（乙氧基羰基甲基）单氮杂-15-冠-5（7）的Na+络合物[Na+ C4- 1 E Br-]（J.Am.Chem.Soc.1983，105，6717-6718）。1984，106，7244-7245）。K+ C5-烯丙基-H2O晶体属单斜晶系，空间群Cl/m，晶胞参数a= 13.254（3）k，B= 19.673（3）A，c= 9.111（1）A，ε = 112.72（2）。对于1416次反射，R= 0.052。K+ C1-22-1晶体属单斜晶系，空间群Cl/c，四个分子的晶胞参数为：a= 15.823（4）A，B= 9.076（4）A，c= 17.132（3）A，θ = 92.90（2）。对于2614个观察到的反射，R= 0.027。K+ C4- 1 Ⅰ为单斜晶系，空间群为P2 fn，晶胞参数为：a= 8.813（2）k，B= 13.283（2）A，c= 16.604（2）A，ε = 102.59（2）.对于2398个观察到的反射，R= 0.033。K+ C4-2晶体为单斜晶系，空间群为P2 fn，四个分子的晶胞参数为a= 11.199（2）A，B= 16.297（2）A，c- 12.047（2）A，ε = 104.48（2）。对于2899个观察到的反射，R= 0.025。K+ CH 1 -22- 1H晶体属单斜晶系，空间群Cl/c，四个分子的晶胞参数分别为a= 13.696（2）A，B= 16.441（2）A，c= 11.739（2）A，ε = 117.02（1）。对于2352个观察到的反射，R= 0.029。Na+ C1 -22-1晶体为单斜晶系，P2空间位，晶胞参数a= 8.027（5）k，B= 15.618（4）A，c= 9.228（4）A，ε = 107.61（4）。对于1820个观察到的反射，R= 0.028。K+ C5- 1晶体为正交晶系，空间群为P2 <$2t2 <$，四个分子的晶胞参数为a= 10.733（1）A，B= 12.806（2）A，c= 15.762（3）A。对于1530个观察到的反射，R= 0.020。Na+ C4- 1 EBr”晶体属单斜晶系，空间群P2 fc，晶胞参数a= 12.868（2）A，B= 9.037（1）A，c= 16.513（3）A，λ = 102.89（1）· R= 0.045。与弦和穴状配体的这些结构和复合物的比较表明，无论是“孔大小”还是“腔大小”的概念提供了令人满意的解释的数据。相反，实验确定的金属离子到施主的距离与香农定义的不同配位数的各种离子的有效离子半径相一致。对于这些柔性配体，客体阳离子组织主体的供体基团阵列。
X-ray crystal structure data are presented for K+ complexes of A'-allylmonoaza-18-crown-6 (1) monohydrate [K+ C 5-allyl-H20], 7V, 7V'-bis (3-oxabutyl) diaza-18-crown-6 (2)[K+ C1-22-1], 7V-(3-oxabutyl) monoaza-15-crown-5 (3)[K+ C4-l], 7V-(3, 6-dioxaheptyl) monoaza-15-crown-5 (4)[K+ C4-2], and 7V,/V'-bis (2-hydroxyethyl) diaza-18-crown-6 (5)[K+ CHl-22-lH] along with the related complexes reportó! in preliminary form:[Na+ CHl-22-lH] and the K+ complex of Ar-(3-oxabutyl) monoaza-18-crown-6 (6)[K+ C5-1](Am. Chem. Soc. 1983, 105, 6717-6718) as well as the Na+ complex of (V-(ethoxycarbonylmethyl) monoaza-15-crown-5 (7)[Na+ C4-1E Br~](J. Am. Chem. Soc. 1984, 106, 7244-7245). The crystals of K+ C5-allyl-H20 are monoclinic, space group Cl/m with four molecules in the unit cell dimensions a= 13.254 (3) k, b= 19.673 (3) A, c= 9.111 (1) A, andß= 112.72 (2). R= 0.052 for 1416 observedreflections. The crystals of K+ C1-22-1 are monoclinic, space group Cl/c with four molecules in the unit cell dimensions a= 15.823 (4) A, b= 9.076 (4) A, c= 17.132 (3) A, and 0= 92.90 (2). R= 0.027 for 2614 observed reflections. The crystals of K+ C4-l I are monoclinic, space group P2fn with four molecules in the unit celldimensions a= 8.813 (2) k, b= 13.283 (2) A, c= 16.604 (2) A, and ß= 102.59 (2). R= 0.033 for 2398 observed reflections. The crystals of K+ C4-2 are monoclinic, space group P2fn with four molecules in the unit cell dimensions a= 11.199 (2) A, b= 16.297 (2) A, c— 12.047 (2) A, and ß= 104.48 (2). R= 0.025 for 2899 observed reflections. The crystals of K+ CHl-22-lH are monoclinic, space group Cl/c with four molecules in the unit cell dimensions a= 13.696 (2) A, b= 16.441 (2) A, c= 11.739 (2) A, and ß= 117.02 (1). R= 0.029 for 2352 observed reflections. The crystals of Na+ C 1-22-1 are monoclinic, space P2¡ with twomolecules in the unit celldimensions a= 8.027 (5) k, b= 15.618 (4) A, c= 9.228 (4) A, andß= 107.61 (4). R= 0.028 for 1820 observed reflections. The crystals of K+ C5-l are orthorhombic, space group P2¡ 2t2¡ with four molecules in the unit cell dimensions a= 10.733 (1) A, b= 12.806 (2) A, and c= 15.762 (3) A. R= 0.020 for 1530 observed reflections. The crystals of Na+ C4-lEBr" are monoclinic, space group P2fc with four molecules in the unit celldimensions a= 12.868 (2) A, b= 9.037 (1) A, c= 16.513 (3) A, and ß= 102.89 (1)· R= 0.045 for 1757 observed reflections. Comparisons made with these structures and complexes of chorands and cryptands show that neither “hole-size” nor “cavity-size” concepts provide satisfactory explanations for the data. Instead, experimentally determined metal-ion-to-donor distances coincide with the effective ionic radius defined by Shannon for various ions of differing coordinationnumbers. For these flexible ligands, the guest cation organizes the host’s donor group array.