CsHi2AgBF4N4, orthorhombic, Pna2\ (no. 33), a = 24.249(5) A , b = 8.608(2) A , c = 20.640(4) A , V = 4308.3 A 3 , Z = 12, Rgt(F) = 0.022, wR^F) = 0.055, r = 178 K. Source of material The title complex was formed during the reaction of 2-cyano-6methoxybenzothiazole with silver(I) tetrafluoroborate in a mixture of tetrahydrofuran and acetonitrile in the ratio of 3:1. On cooling the reaction mixture to 5 °C, colorless plate-shaped crystals were formed. Discussion Tetrakis(acetonitrile)silver(I) tetrafluoroborate can successfully be used as precursor for the synthesis of many hetero-metallic transition metal complexes which possess novel properties, for example, in material sciences. In addition, it can be applied in the synthesis of further silver(I) species comprising acetonitrile and tetrafluoroborate, respectively [1-3]. The structure of tetrakis(acetonitrile)silver(I) perchlorate has been determined at 240 K by Nilsson and Oskarsson [4] and re-determined by Jones and Bembenek [5] at 173 K in order to obtain more reliable dimensions. The crystallographic results of both groups showed large variations regarding Ag—N interatomic bond distances and N-Ag-N angles in the three independent [Ag(CH3CN)4] cations. Isotypic tetrakis(acetonitrile)copper(I) tetrafluoroborate [6] and perchlorate [7] compounds are described. The title complex is composed of discrete [Ag(CH3CN>4] and BF4" ions. The asymmetric unit comprises three [Ag(CH3CN>4] moieties and three BF4 anions. As in the case of the respective * Correspondence author (e-mail: heinrich.lang@chemie.tu-cheimiitz.de) silver(I) perchlorate complex there is a considerable range of equivalent dimensions in the tetrafluoroborate species regarding the interatomic bond distances Ag—N: 2.229(3) A 2.316 A , N—C: 1.117(4) A 1.142(4) A , C—C: 1.436(5) A 1.449(4) A and the N-Ag-N angles: 104.2(1)° 115.8(1)°, Ag-N-C: 165.4(3)° 178.9(3)°, N-C-C: 178.4(4)° 179.6(4)°. It seems that the silver-nitrogen bonds are rather weak and hence, the title complex eliminates acetonitrile by abstracting the crystals from the solution. It possesses almost the same crystallographic data as the silver(I) perchlorate species (vide supra) indicating that the tetra-fluoroborate anion is located at the same position as the perchlorate in the crystal lattice, probably, because both perchlorate and tetrafluoroborate have comparable ionic radii. Although the crystal structure analysis indicates no interaction between the tetrafluoroborate ion and the silver cation, the B—F bond distances are between 1.350(5) A 1.406(5) A . Therefore the cationic and the anionic building blocks exhibit a slightly distorted tetrahedral geometry. Table 1. Data collection and handling. Ciystal: colorless block, size 0.3 x 0.3 x 0.4 mm Wavelength: Mo Ka radiation (0.71073 Â) H1 4 . 3 5 cm" Diffractometer, scan mode: Bruker SMART CCD lk, <0 2ßmax'. 5 2 . 9 ° N(hkl)masmá, N(hkl)unique: 4 9 0 8 5 , 9 6 4 6 Criterion for /obs, N(hkl)gc. /obs > 2 o(Iobs), 8 4 0 8 N(param)nfuxA5 0 0 Programs: SHELXS-97 [8], SHELXL-97 [9] Table 2. Atomic coordinates and displacement parameters (in Á). Atom Site X y z U'iso H(2A) 4a 0.1325 0.5464 0.6146 0.093 H(2B) 4a 0.1557 0.4146 0.5672 0.093 H(2C) 4a 0.0944 0.4018 0.5955 0.093 H(4A) 4a 0.1696 0.5586 0.2068 0.091 H(4B) 4a 0.1158 0.4924 0.1715 0.091 H(4C) 4a 0.1469 0.3895 0.2247 0.091 H(6A) 4a -0.1416 0.4621 0.4804 0.098 H(6B) 4a -0.1434 0.3903 0.4089 0.098 H(6C) 4a -0.1719 0.5544 0.4232 0.098 H(8A) 4a 0.0773 1.3142 0.4172 0.082 H(8B) 4a 0.0166 1.3065 0.4475 0.082 H(8C) 4a 0.0245 1.3204 0.3707 0.082 H(10A) 4a 0.2809 0.0679 0.2991 0.102 H(10B) 4a 0.3043 0.2417 0.3014 0.102 H(10C) 4a 0.3397 0.1070 0.2678 0.102 H(12A) 4a 0.3187 0.0700 -0.1250 0.100 490 [Ag(C2H3N)4][BF4] Table 1. Continued. Table 2. Continued. Atom Site x y z ÌA» Atom Site H(12B) 4a 0.3262 0.2537 -0.1332 0.100 H(12C) 4a 0.2707 0.1716 -0.1573 0.100 H(14A) 4a 0.1753 0.9013 0.0816 0.077 H(14B) 4a 0.2271 0.9032 0.0335 0.077 H(14C) 4a 0.2366 0.9044 0.1102 0.077 H(16A) 4a 0.0036 0.2813 0.0694 0.100 H(16B) 4a 0.0094 0.1100 0.0988 0.100 H(16C) 4a 0.0134 0.1365 0.0222 0.100 H(18A) 4a 0.3512 0.6194 0.3922 0.091 H(18B) 4a 0.3788 0.5309 0.4522 0.091 H(18C) 4a 0.3241 0.4627 0.4194 0.091 H(20A) 4a 0.4710 -0.3388 0.1936 0.075 H(20B) 4a 0.4161 -0.3462 0.2365 0.075 H(20C) 4a 0.4751 -0.3426 0.2710 0.075 H(22A) 4a 0.6297 0.6110 0.2347 0.083 H(22B) 4a 0.6625 0.4568 0.2149 0.083 H(22C) 4a 0.6500 0.4928 0.2895 0.083 H(24A) 4a 0.3899 0.5749 0.0432 0.099 H(24B) 4a 0.3310 0.5707 0.0781 0.099 H(24C) 4a 0.3478 0.4362 0.0283 0.099 Table 3. Atomic coordinates and displacement parameters (in A). Atom Site X y z Uu Un t/33 Un U13 i /23 Ag(l) 4a 0.03805(1) 0.71676(3) 0.39249(1) 0.0510(1) 0.0445(1) 0.0415(1) 0.00755(9) 0.0035(1) 0.0011(1) N(l) 4a 0.0857(1) 0.6248(3) 0.4819(1) 0.050(1) 0.047(1) 0.039(1) 0.007(1) -0.005(1) 0.001(1) C(l) 4a 0.1022(1) 0.5589(3) 0.5248(1) 0.040(1) 0.037(1) 0.038(1) 0.003(1) 0.002(1) -0.005(1) C(2) 4a 0.1229(2) 0.4736(4) 0.5800(2) 0.091(2) 0.056(2) 0.039(2) 0.017(2) -0.012(2) 0.004(2) N(2) 4a 0.0763(1) 0.6157(3) 0.3021(1) 0.044(1) 0.059(2) 0.040(1) -0.001(1) 0.000(1) -0.008(1) C(3) 4a 0.1024(1) 0.5621(3) 0.2623(1) 0.042(1) 0.042(1) 0.037(1) -0.008(1) 0.001(1) -0.003(1) C(4) 4a 0.1364(2) 0.4953(4) 0.2123(2) 0.070(2) 0.059(2) 0.053(2) -0.002(2) 0.021(2) -0.013(2) N(3) 4a -0.0494(1) 0.6267(3) 0.4067(1) 0.044(1) 0.068(2) 0.051(2) 0.002(1) 0.004(1) -0.001(1) C(5) 4a -0.0898(1) 0.5648(3) 0.4186(1) 0.048(2) 0.047(2) 0.039(1) 0.006(1) -0.001(1) -0.007(1) C(6) 4a -0.1408(2) 0.4866(4) 0.4340(2) 0.059(2) 0.060(2) 0.079(2) -0.012(2) 0.014(2) -0.012(2) N(4) 4a 0.0407(1) 0.9772(3) 0.4008(2) 0.073(2) 0.042(1) 0.057(2) 0.005(1) -0.005(1) 0.005(1) C(7) 4a 0.0405(1) 1.1082(4) 0.4055(1) 0.049(2) 0.043(2) 0.042(2) 0.003(1) -0.005(1) 0.001(1) C(8) 4a 0.0397(2) 1.2758(4) 0.4107(2) 0.064(2) 0.038(2) 0.062(3) -0.002(1) -0.002(2) -0.010(1) Ag(2) 4a 0.216343(9) 0.30482(3) 0.07845(1) 0.0546(1) 0.0398(1) 0.0529(1) 0.00036(9) 0.0098(1) -0.0009(1) N(5) 4a 0.2559(1) 0.2036(3) 0.1664(2) 0.071(2) 0.051(2) 0.056(2) -0.005(1) -0.008(1) 0.002(1) C(9) 4a 0.2761(1) 0.1789(4) 0.2147(2) 0.039(2) 0.049(2) 0.058(2) -0.011(1) 0.006(1) -0.012(1) C(10) 4a 0.3023(2) 0.1463(5) 0.2756(2) 0.051(2) 0.102(3) 0.050(2) -0.008(2) -0.007(2) -0.014(2) N(6) 4a 0.2562(1) 0.2126(3) -0.0129(2) 0.067(2) 0.051(2) 0.059(2) -0.003(1) 0.024(1) -0.006(1) C( l l ) 4a 0.2755(1) 0.1944(4) -0.0614(2) 0.041(2) 0.049(2) 0.044(2) 0.004(1) 0.008(1) 0.002(1) C(12) 4a 0.2997(2) 0.1705(6) -0.1242(2) 0.057(2) 0.103(3) 0.040(2) 0.015(2) 0.009(1) 0.007(2) N(7) 4a 0.21549(9) 0.5655(3) 0.0768(2) 0.057(1) 0.035(1) 0.045(1) -0.0010(9) 0.002(1) -0.002(1) C(13) 4a 0.2142(1) 0.6969(3) 0.0755(2) 0.039(1) 0.038(2) 0.033(1) 0.001(1) -0.003(1) -0.004(1) C(14) 4a 0.2132(1) 0.8650(3) 0.0752(2) 0.068(2) 0.036(1) 0.051(2) -0.000(1) -0.006(2) 0.001(2) N(8) 4a 0.12694(9) 0.2181(3) 0.0741(2) 0.047(1) 0.053(1) 0.065(2) -0.003(1) 0.005(1) -0.004(1) C(15) 4a 0.0812(1) 0.2020(3) 0.0703(1) 0.045(1) 0.051(2) 0.039(1) 0.005(1) 0.006(1) 0.003(1) C(16) 4a 0.0221(1) 0.1807(5) 0.0647(2) 0.040(1) 0.106(3) 0.054(2) 0.004(2) -0.005(2) 0.015(2) Ag(3) 4a 0.456291(9) 0.25321(3) 0.23977(2) 0.0527(1) 0.0394(1) 0.0518(1) -0.00260(9) 0.0033(1) -0.0015(1) N(9) 4a 0.4176(1) 0.3587(3) 0.3314(1) 0.049(1) 0.059(2) 0.045(1) -0.002(1) 0.005(1) -0.008(1) C(17) 4a 0.3923(1) 0.4277(3) 0.3671(1) 0.044(1) 0.044(2) 0.040(1) -0.011(1) -0.000(1) -0.001(1) C(18) 4a 0.3589(2) 0.5174(4) 0.4113(2) 0.071(2) 0.053(2) 0.057(2) -0.008(2) 0.018(2) -0.011(1) N(10) 4a 0.4504(1) -0.0051(3) 0.2371(2) 0.062(2) 0.038(1) 0.066(2) -0.000(1) -0.013(1) -0.001(2) C(19) 4a 0.4517(1) -0.1375(3) 0.2356(2) 0.041(1) 0.038(2) 0.047(2) -0.000(1) -0.011(1) 0.004(2) C(20) 4a 0.4536(1) -0.3046(3) 0.2341(2) 0.059(2) 0.031(1) 0.061(2) -0.002(1) -0.003(2) -0.002(2) N(l l ) 4a 0.54332(9) 0.3526(3) 0.2370(1) 0.043(1) 0.055(1) 0.052(1) -0.002(1) 0.003(1) -0.003(1) C(21) 4a 0.5835(1) 0.4167(3) 0.2403(1) 0.041(1) 0.040(1) 0.042(1) 0.005(1) 0.001(1) -0.003(1) C(22) 4a 0.6358(1) 0.5014(4) 0.2453(2) 0.040(1) 0.054(2) 0.073(2) -0.006(1) -0.004(2) 0.003(2) N(12) 4a 0.4046(1) 0.3496(3) 0.1555(1) 0.045(1) 0.045(1) 0.050(1) 0.003(1) -0.000(1) -0.002(1) C(23) 4a 0.3849(1) 0.4184(3) 0.1145(1) 0.030(1) 0.035(1) 0.053(2) 0.001(1) 0.002(1) -0.006(1) C(24) 4a 0.3615(1) 0.5072(4) 0.0618(2) 0.061(2) 0.057(2) 0.079(3) 0.010(2) -0.015(2) 0.006(2) B(l) 4a 0.2064(1) 0.2162(4) 0.7352(2) 0.044(2) 0.052(2) 0.040(2) -0.002(1) -0.008(2) -0.002(2) F(l) 4a 0.1789(1) 0.2635(3) 0.7918(1) 0.080(2) 0.110(2) 0.056(1) 0.005(1) 0.018(1) 0.004(1) F(2) 4a 0.2112(1) 0.0594(3) 0.7388(2) 0.138(2) 0.059(1) 0.148(3) -0.004(1) -0.001(2) 0.009(2) F(3) 4a 0.1752(1) 0.2592(4) 0.6827(1) 0.060(1) 0.162(3) 0.056(1) 0.009(1) -0.016(1) 0.031(1) F(4) 4a 0.25681(8) 0.2827(3) 0.7319(1) 0.054(1) 0.102(2) 0.056(1) -0.024(1) 0.001(1) 0.007(1) B(2) 4a 0.2996(2) 0.7214(5) 0.9088(2) 0.046(2) 0.044(2) 0.046(2) -0.003(2) -0.000(1) -0.004(1) F(5) 4a 0.2969(1) 0.5648(3) 0.9070(2) 0.158(3) 0.045(1) 0.115(2) 0.001(1) -0.006(2) -0.003(1) F(6) 4a 0.2461(1) 0.7797(3) 0.9150(1) 0.061(1) 0.120(2) 0.071(2) 0.022(1) -0.001(1) -0.014(1) F(7) 4a 0.3225(1) 0.7769(3) 0.8525(1) 0.090(2) 0.095(2) 0.058(1) -0.002(1) 0.016(1) 0.008(1) F(8) 4a 0.3292(1) 0.7723(3) 0.9619(1) 0.082(2) 0.104(2) 0.059(1) -0.017(1) -0.022(1) -0.010(1) B(3) 4a 0.5440(2) 0.7590(5) 0.0720(3) 0.062(2) 0.061(3) 0.049(2) 0.001(2) 0.006(2) 0.008(2) F(9) 4a 0.5700(1) 0.7038(4) 0.1282(1) 0.085(2) 0.123(2) 0.073(2) 0.001(2) -0.020(1) 0.022(1) [ A g ( C 2 H 3 N ) 4 ] [ B F 4 ] 4 9 1

中文翻译：

---

四（乙腈）四氟硼酸银（I）的晶体结构，[Ag(C2H3N)4][BF4]

CsHi2AgBF4N4, 正交, Pna2\ (no. 33), a = 24.249(5) A , b = 8.608(2) A , c = 20.640(4) A , V = 4308.3 A 3 , Z = 12, Rgt(F) = 0.022, wR^F) = 0.055, r = 178 K. 材料来源 标题配合物是在 2-氰基-6 甲氧基苯并噻唑与四氟硼酸银 (I) 在四氢呋喃和乙腈的混合物中以 3 的比例反应形成的：1。将反应混合物冷却至5°C，形成无色板状晶体。讨论 四（乙腈）四氟硼酸银 (I) 可成功地用作合成许多具有新特性的杂金属过渡金属配合物的前体，例如在材料科学中。此外，它还可用于合成其他银 (I) 物质，分别包含乙腈和四氟硼酸盐 [1-3]。Nilsson 和 Oskarsson [4] 在 240 K 时测定了四（乙腈）高氯酸银 (I) 的结构，Jones 和 Bembenek [5] 在 173 K 时重新测定了结构，以获得更可靠的尺寸。两组的晶体学结果表明，在三个独立的 [Ag(CH3CN)4] 阳离子中，Ag-N 原子间键距离和 N-Ag-N 角存在很大差异。描述了同型四（乙腈）铜 (I) 四氟硼酸盐 [6] 和高氯酸盐 [7] 化合物。标题复合物由离散的 [Ag(CH3CN>4] 和 BF4" 离子组成。不对称单元包含三个 [Ag(CH3CN>4] 部分和三个 BF4 阴离子。与各自的 * 通讯作者 (e-邮件：heinrich.lang@chemie.tu-cheimiitz。de) 高氯酸银 (I) 配合物 在四氟硼酸盐种类中，关于原子间键距 Ag-N：2.229(3) A 2.316 A，NC：1.117(4) A 1.142(4) 存在相当大范围的等效尺寸A , C—C: 1.436(5) A 1.449(4) A 和 N-Ag-N 角度: 104.2(1)° 115.8(1)°, Ag-NC: 165.4(3)° 178.9(3)° , NCC: 178.4(4)° 179.6(4)°。似乎银-氮键相当弱，因此，标题络合物通过从溶液中提取晶体来消除乙腈。它具有与高氯酸银 (I) 物种几乎相同的晶体学数据（见上文），表明四氟硼酸根阴离子与晶格中的高氯酸根位于相同的位置，可能是因为高氯酸根和四氟硼酸根具有相当的离子半径。虽然晶体结构分析表明四氟硼酸根离子和银阳离子之间没有相互作用，但BF键距离在1.350(5) A 1.406(5) A 之间。因此，阳离子和阴离子结构单元呈现出略微扭曲的四面体几何形状。表 1. 数据收集和处理。晶体：无色块状，尺寸0.3×0.3×0.4毫米波长：莫卡辐射（0.71073°）H1 4 。3 5 cm" 衍射仪，扫描模式：Bruker SMART CCD lk, <0 2ßmax'。5 2 . 9 ° N(hkl)masmá, N(hkl)unique: 4 9 0 8 5 , 9 6 4 6 /obs 标准, N(hkl)gc. /obs > 2 o(Iobs), 8 4 0 8 N(param)nfuxA5 0 0 程序：SHELXS-97 [8], SHELXL-97 [9] 表 2. 原子坐标和位移参数(在 Á). Atom Site X yz U'iso H(2A) 4a 0.1325 0.5464 0.6146 0.093 H(2B) 4a 0.1557 0.4146 0.5672 0.093 H(2C) 4a 0.0944 0. 4018 0.5955 0.093 H（4A）4A 0.1696 0.5586 0.2068 0.091 H（4B）4A 0.1158 0.1158 0.4924 0.1715 0.091 H（4C）4A 0.1469 0.1469 0.3895 0.2247 0.2240 0.091 H（6A）4A -0.14414414414141414244.144.144.144.144.144.144.144.141444.144.144.144.144.144b an H（6C）4A -0.1719 0.5544 0.4232 0.098 H（8A）4A 0.0773 1.3142 1.3142 0.4172 0.082 H（8B）4A 0.0166 1.3065 1.3065 0.4475 0.475 0.082 0.0082 H（8C）4A 0.0245 1.320 0.320 0.320 0.320 0.320 0.320 0.320 0.320 0.320 0.320 0.320 0.320 0.06（ 4a 0.3043 0.2417 0.3014 0.102 H(10C) 4a 0.3397 0.1070 0.2678 0.102 H(12A) 4a 0.3187 0.0700 -0.1250 0.100 490 [Ag(C2H3N)4][BF4] 表 1. 续 表 2. 续。原子网站xyz´a»atom网站h（12b）4A 0.3262 0.2537 -0.1332 0.100 H（12C）4A 0.2707 0.2707 0.1716 -0.1573 0.100 H（14A）4A 0A 0A 0A 0A 0.1753 0.1753 0.9013 0.0816 0.0816 0.016 0.0B（14B）0.03.224.22222.222222222.22222.22222.22222.2222222.22222.2222222.2222.2222222.222222.2222222.222222.222222.222222.222222.222222.222222.222222.2222 0.2366 0.9044 0.1102 0.077 H(16A) 4a 0.0036 0.2813 0.0694 0.100 H(16B) 4a 0.0094 0.1100 0.0988 0.100 H(16C) 4a 0. 0134 0.1365 0.0222 0.100 H（18A）4A 0.3512 0.6194 0.3922 0.091 H（18B）4A 0.3788 0.3788 0.5309 0.4522 0.091 0.091 H（18C）4A 0.3241 0.3241 0.3241 0.4627 0.4627 0.4194 0.034 0.094 0.194 0.191 H（20A） 0.075 h（20C）4A 0.4751 -0.3426 0.2710 0.075 h（22a）4A 0.6297 0.6110 0.6110 0.2347 0.083 H（22b）4A 0.6625 0.6625 0.4568 0.2149 0.2149 0.2149 0.083 H（22C）4A 0.6500 0.6500 0.2500 0.2500 0.49.495.49.495.495.495.495.495.495.495.49.49.49.495 a（ ) 4a 0.3310 0.5707 0.0781 0.099 H(24C) 4a 0.3478 0.4362 0.0283 0.099 表 3. 原子坐标和位移参数（以 A 为单位）。原子位点 X yz Uu Un t/33 Un U13 i /23 Ag(l) 4a 0.03805(1) 0.71676(3) 0.39249(1) 0.0510(1) 0.0445(1) 0.0415(1) 0.00755(9) 0.0035(1) ) 0.0011(1) N(l) 4a 0.0857(1) 0.6248(3) 0.4819(1) 0.050(1) 0.047(1) 0.039(1) 0.007(1) -0.005(1) 0.001(1) C(l) ) 4a 0.1022(1) 0.5589(3) 0.5248(1) 0.040(1) 0.037(1) 0.038(1) 0.003(1) 0.002(1) -0。