发明名称 单晶级[Cu<sub>2</sub>(L<sup>11</sup>)<sub>2</sub>]·(H<sub>2</sub>O)配合物的合成方法及作为抗癌药物应用
摘要 本发明公开了一种单晶级[Cu<sub>2</sub>(L<sup>11</sup>)<sub>2</sub>]·(H<sub>2</sub>O)配合物的合成方法及作为抗癌药物应用。[Cu<sub>2</sub>(L<sup>11</sup>)<sub>2</sub>]·(H<sub>2</sub>O)的分子式为:C<sub>68</sub>H<sub>56</sub>Cu<sub>2</sub>N<sub>18</sub>O<sub>21</sub>Br<sub>6</sub>,分子量为:2067.80,H<sub>2</sub>L<sup>11</sup> = (4S)-4-丁基3,6-二甲基1,8-二(6-溴吡啶)-4-(2-(6-溴吡啶)-5-(甲酯基)-3-氧-2,3-二氢-1-氢-吡唑)-9-氧-1,2,7,8-四氮杂螺 [4.4] 壬-6-烯-3,4,6-三甲酸甲酯。(1)将0.08-0.16克分析纯5-乙酸-1-(6-溴吡啶)-1-氢-吡唑-3-甲酸甲酯和0.05-0.15克分析纯三水硝酸铜溶于10-20毫升体积比为1:2的无水乙腈和分析纯正丁醇的混合溶液中。(2)转入反应釜中,在80-90°C下反应60-80小时,过滤,自然挥发结晶。[Cu<sub>2</sub>(L<sup>11</sup>)<sub>2</sub>]·(H<sub>2</sub>O)配合物能作为抗癌药物应用。本发明工艺简单、成本低廉、化学组分易于控制、重复性好并产量高。
申请公布号 CN104530098A 申请公布日期 2015.04.22
申请号 CN201410795878.9 申请日期 2014.12.19
申请人 桂林理工大学 发明人 肖瑜;黄秋萍;张淑华
分类号 C07F1/08(2006.01)I;A61P35/00(2006.01)I 主分类号 C07F1/08(2006.01)I
代理机构 代理人
主权项 一种单晶级[Cu<sub>2</sub>(L<sup>11</sup>)<sub>2</sub>]·(H<sub>2</sub>O)配合物,其特征在于单晶级[Cu<sub>2</sub>(L<sup>11</sup>)<sub>2</sub>]·(H<sub>2</sub>O)配合物的分子式为:C<sub>68</sub>H<sub>56</sub>Cu<sub>2</sub>N<sub>18</sub>O<sub>21</sub>Br<sub>6</sub>,分子量为:2067.80,H<sub>2</sub>L<sup>11</sup>=(4S)‑4‑丁基3,6‑二甲基1,8‑二(6‑溴吡啶)‑4‑(2‑(6‑溴吡啶)‑5‑(甲酯基)‑3‑氧‑2,3‑二氢‑1‑氢‑吡唑)‑9‑氧‑1,2,7,8‑四氮杂螺[4.4]壬‑6‑烯‑3,4,6‑三甲酸甲酯,晶体结构参数表见表一,键长键角数据见表二;具有良好的抗肿瘤活性;所述单晶级[Cu<sub>2</sub>(L<sup>11</sup>)<sub>2</sub>]·(H<sub>2</sub>O)配合物的原位合成方法具体步骤为:(1)将0.08‑0.16克分析纯5‑乙酸‑1‑(6‑溴吡啶)‑1‑氢‑吡唑‑3‑甲酸甲酯,0.05‑0.15克分析纯三水硝酸铜溶于10‑20毫升体积比为1:2的无水乙腈和分析纯正丁醇的混合溶液中;(2)将步骤(1)所制得的溶液转入聚四氟乙烯的反应釜中,在80‑90℃下反应60‑80小时,降温至室温,过滤,滤液置于室温下自然挥发结晶,8天后得到单晶级[Cu<sub>2</sub>(L<sup>11</sup>)<sub>2</sub>]·(H<sub>2</sub>O)配合物;表一:[Cu<sub>2</sub>(L<sup>11</sup>)<sub>2</sub>]·(H<sub>2</sub>O)的晶体学参数<img file="FDA0000639011710000011.GIF" wi="1341" he="1473" />表二:[Cu<sub>2</sub>(L<sup>11</sup>)<sub>2</sub>]·(H<sub>2</sub>O)的键长<img file="FDA0000639011710000012.GIF" wi="94" he="79" />和键角(°)<tables num="0001" id="ctbl0001"><table><tgroup cols="4"><colspec colname="c001" colwidth="21%" /><colspec colname="c002" colwidth="22%" /><colspec colname="c003" colwidth="34%" /><colspec colname="c004" colwidth="23%" /><tbody><row><entry morerows="1">Cu1‑N16</entry><entry morerows="1">2.009(6)</entry><entry morerows="1">N14‑N13</entry><entry morerows="1">1.364(9)</entry></row></tbody></tgroup></table></tables><tables num="0002" id="ctbl0002"><table><tgroup cols="4"><colspec colname="c001" colwidth="21%" /><colspec colname="c002" colwidth="22%" /><colspec colname="c003" colwidth="34%" /><colspec colname="c004" colwidth="23%" /><tbody><row><entry morerows="1">Cu1‑N1</entry><entry morerows="1">2.047(7)</entry><entry morerows="1">N14‑C59</entry><entry morerows="1">1.459(9)</entry></row><row><entry morerows="1">Cu1‑N18</entry><entry morerows="1">2.050(7)</entry><entry morerows="1">N14‑C54</entry><entry morerows="1">1.365(11)</entry></row><row><entry morerows="1">Cu1‑N3</entry><entry morerows="1">1.990(6)</entry><entry morerows="1">C40‑C44</entry><entry morerows="1">1.385(10)</entry></row><row><entry morerows="1">Cu2‑N12</entry><entry morerows="1">1.983(6)</entry><entry morerows="1">C40‑C41</entry><entry morerows="1">1.484(11)</entry></row><row><entry morerows="1">Cu2‑N10</entry><entry morerows="1">2.047(7)</entry><entry morerows="1">N13‑C45</entry><entry morerows="1">1.284(9)</entry></row><row><entry morerows="1">Cu2‑N7</entry><entry morerows="1">2.000(7)</entry><entry morerows="1">C60‑C61</entry><entry morerows="1">1.515(12)</entry></row><row><entry morerows="1">Cu2‑N9</entry><entry morerows="1">2.079(7)</entry><entry morerows="1">C60‑C59</entry><entry morerows="1">1.507(11)</entry></row><row><entry morerows="1">Br1‑C1</entry><entry morerows="1">1.880(9)</entry><entry morerows="1">C46‑C45</entry><entry morerows="1">1.494(11)</entry></row><row><entry morerows="1">Br4‑C35</entry><entry morerows="1">1.869(10)</entry><entry morerows="1">O7‑C18</entry><entry morerows="1">1.303(15)</entry></row><row><entry morerows="1">Br3‑C34</entry><entry morerows="1">1.868(9)</entry><entry morerows="1">O7‑C19</entry><entry morerows="1">1.485(16)</entry></row><row><entry morerows="1">Br6‑C68</entry><entry morerows="1">1.893(10)</entry><entry morerows="1">C44‑C48</entry><entry morerows="1">1.498(10)</entry></row><row><entry morerows="1">Br5‑C58</entry><entry morerows="1">1.861(12)</entry><entry morerows="1">C45‑C48</entry><entry morerows="1">1.525(10)</entry></row><row><entry morerows="1">Br2‑C20</entry><entry morerows="1">1.889(11)</entry><entry morerows="1">C6‑C7</entry><entry morerows="1">1.496(12)</entry></row><row><entry morerows="1">N12‑N11</entry><entry morerows="1">1.375(8)</entry><entry morerows="1">C6‑C10</entry><entry morerows="1">1.396(11)</entry></row><row><entry morerows="1">N12‑C40</entry><entry morerows="1">1.314(9)</entry><entry morerows="1">O8‑C27</entry><entry morerows="1">1.199(10)</entry></row><row><entry morerows="1">N16‑N17</entry><entry morerows="1">1.385(9)</entry><entry morerows="1">C29‑C25</entry><entry morerows="1">1.550(12)</entry></row><row><entry morerows="1">N16‑C60</entry><entry morerows="1">1.288(9)</entry><entry morerows="1">C31‑C30</entry><entry morerows="1">1.373(11)</entry></row><row><entry morerows="1">O11‑C41</entry><entry morerows="1">1.340(9)</entry><entry morerows="1">C31‑C32</entry><entry morerows="1">1.359(12)</entry></row><row><entry morerows="1">O11‑C42</entry><entry morerows="1">1.436(9)</entry><entry morerows="1">C25‑N5</entry><entry morerows="1">1.461(10)</entry></row><row><entry morerows="1">N1‑C5</entry><entry morerows="1">1.327(10)</entry><entry morerows="1">C25‑C26</entry><entry morerows="1">1.495(11)</entry></row><row><entry morerows="1">N1‑C1</entry><entry morerows="1">1.336(10)</entry><entry morerows="1">C25‑C11</entry><entry morerows="1">1.580(11)</entry></row><row><entry morerows="1">N18‑C64</entry><entry morerows="1">1.341(10)</entry><entry morerows="1">C63‑C59</entry><entry morerows="1">1.555(12)</entry></row><row><entry morerows="1">N18‑C68</entry><entry morerows="1">1.324(11)</entry><entry morerows="1">N5‑C24</entry><entry morerows="1">1.415(12)</entry></row><row><entry morerows="1">N3‑N2</entry><entry morerows="1">1.342(9)</entry><entry morerows="1">N5‑N4</entry><entry morerows="1">1.365(10)</entry></row><row><entry morerows="1">N3‑C6</entry><entry morerows="1">1.343(9)</entry><entry morerows="1">C49‑C48</entry><entry morerows="1">1.559(11)</entry></row><row><entry morerows="1">O17‑C46</entry><entry morerows="1">1.320(10)</entry><entry morerows="1">C5‑C4</entry><entry morerows="1">1.360(13)</entry></row><row><entry morerows="1">O17‑C47</entry><entry morerows="1">1.454(11)</entry><entry morerows="1">C34‑C33</entry><entry morerows="1">1.364(12)</entry></row><row><entry morerows="1">O18‑C61</entry><entry morerows="1">1.198(9)</entry><entry morerows="1">C48‑C59</entry><entry morerows="1">1.595(10)</entry></row><row><entry morerows="1">N17‑C64</entry><entry morerows="1">1.409(10)</entry><entry morerows="1">C35‑C36</entry><entry morerows="1">1.362(15)</entry></row><row><entry morerows="1">N17‑C63</entry><entry morerows="1">1.386(11)</entry><entry morerows="1">C9‑C10</entry><entry morerows="1">1.429(12)</entry></row><row><entry morerows="1">N11‑C43</entry><entry morerows="1">1.408(9)</entry><entry morerows="1">C39‑C38</entry><entry morerows="1">1.371(12)</entry></row><row><entry morerows="1">N11‑C39</entry><entry morerows="1">1.398(11)</entry><entry morerows="1">C26‑C27</entry><entry morerows="1">1.521(12)</entry></row><row><entry morerows="1">O12‑C41</entry><entry morerows="1">1.183(9)</entry><entry morerows="1">C32‑C33</entry><entry morerows="1">1.336(12)</entry></row><row><entry morerows="1">O15‑C49</entry><entry morerows="1">1.320(9)</entry><entry morerows="1">N6‑C24</entry><entry morerows="1">1.299(12)</entry></row><row><entry morerows="1">O15‑C50</entry><entry morerows="1">1.423(11)</entry><entry morerows="1">N6‑C20</entry><entry morerows="1">1.309(11)</entry></row><row><entry morerows="1">O20‑C63</entry><entry morerows="1">1.180(10)</entry><entry morerows="1">N15‑C54</entry><entry morerows="1">1.313(11)</entry></row><row><entry morerows="1">N10‑C35</entry><entry morerows="1">1.324(11)</entry><entry morerows="1">N15‑C58</entry><entry morerows="1">1.361(12)</entry></row><row><entry morerows="1">N10‑C39</entry><entry morerows="1">1.335(10)</entry><entry morerows="1">C10‑C11</entry><entry morerows="1">1.493(10)</entry></row><row><entry morerows="1">O13‑C43</entry><entry morerows="1">1.247(9)</entry><entry morerows="1">C24‑C23</entry><entry morerows="1">1.370(14)</entry></row><row><entry morerows="1">O10‑C29</entry><entry morerows="1">1.204(10)</entry><entry morerows="1">C11‑C17</entry><entry morerows="1">1.512(12)</entry></row><row><entry morerows="1">O5‑C12</entry><entry morerows="1">1.324(10)</entry><entry morerows="1">C11‑C12</entry><entry morerows="1">1.543(12)</entry></row><row><entry morerows="1">O5‑C13</entry><entry morerows="1">1.437(12)</entry><entry morerows="1">N4‑C17</entry><entry morerows="1">1.288(11)</entry></row><row><entry morerows="1">N8‑N7</entry><entry morerows="1">1.391(8)</entry><entry morerows="1">C65‑C66</entry><entry morerows="1">1.377(14)</entry></row><row><entry morerows="1">N8‑C29</entry><entry morerows="1">1.394(10)</entry><entry morerows="1">C1‑C2</entry><entry morerows="1">1.370(13)</entry></row><row><entry morerows="1">N8‑C30</entry><entry morerows="1">1.392(10)</entry><entry morerows="1">C54‑C55</entry><entry morerows="1">1.402(14)</entry></row><row><entry morerows="1">N7‑C26</entry><entry morerows="1">1.276(10)</entry><entry morerows="1">C17‑C18</entry><entry morerows="1">1.480(15)</entry></row><row><entry morerows="1">O4‑C12</entry><entry morerows="1">1.190(11)</entry><entry morerows="1">C68‑C67</entry><entry morerows="1">1.304(15)</entry></row><row><entry morerows="1">O2‑C7</entry><entry morerows="1">1.318(9)</entry><entry morerows="1">C38‑C37</entry><entry morerows="1">1.356(14)</entry></row><row><entry morerows="1">O2‑C8</entry><entry morerows="1">1.434(10)</entry><entry morerows="1">C2‑C3</entry><entry morerows="1">1.342(13)</entry></row><row><entry morerows="1">O14‑C49</entry><entry morerows="1">1.178(9)</entry><entry morerows="1">C50‑C51</entry><entry morerows="1">1.519(17)</entry></row><row><entry morerows="1">O3‑C9</entry><entry morerows="1">1.252(11)</entry><entry morerows="1">C20‑C21</entry><entry morerows="1">1.337(17)</entry></row><row><entry morerows="1">C43‑C44</entry><entry morerows="1">1.405(11)</entry><entry morerows="1">C37‑C36</entry><entry morerows="1">1.348(14)</entry></row><row><entry morerows="1">N9‑C30</entry><entry morerows="1">1.322(9)</entry><entry morerows="1">C4‑C3</entry><entry morerows="1">1.380(13)</entry></row><row><entry morerows="1">N9‑C34</entry><entry morerows="1">1.342(11)</entry><entry morerows="1">C58‑C57</entry><entry morerows="1">1.315(16)</entry></row><row><entry morerows="1">N2‑C5</entry><entry morerows="1">1.406(10)</entry><entry morerows="1">C13‑C14</entry><entry morerows="1">1.476(15)</entry></row><row><entry morerows="1">N2‑C9</entry><entry morerows="1">1.424(10)</entry><entry morerows="1">C55‑C56</entry><entry morerows="1">1.490(18)</entry></row><row><entry morerows="1">C64‑C65</entry><entry morerows="1">1.378(13)</entry><entry morerows="1">C66‑C67</entry><entry morerows="1">1.380(16)</entry></row><row><entry morerows="1">O16‑C46</entry><entry morerows="1">1.189(10)</entry><entry morerows="1">C14‑C15</entry><entry morerows="1">1.48(2)</entry></row></tbody></tgroup></table></tables><tables num="0003" id="ctbl0003"><table><tgroup cols="4"><colspec colname="c001" colwidth="21%" /><colspec colname="c002" colwidth="22%" /><colspec colname="c003" colwidth="34%" /><colspec colname="c004" colwidth="23%" /><tbody><row><entry morerows="1">O19‑C61</entry><entry morerows="1">1.321(10)</entry><entry morerows="1">C56‑C57</entry><entry morerows="1">1.271(19)</entry></row><row><entry morerows="1">O19‑C62</entry><entry morerows="1">1.481(11)</entry><entry morerows="1">C23‑C22</entry><entry morerows="1">1.394(18)</entry></row><row><entry morerows="1">O1‑C7</entry><entry morerows="1">1.211(9)</entry><entry morerows="1">C51‑C52</entry><entry morerows="1">1.44(3)</entry></row><row><entry morerows="1">O6‑C18</entry><entry morerows="1">1.200(15)</entry><entry morerows="1">C21‑C22</entry><entry morerows="1">1.33(2)</entry></row><row><entry morerows="1">O9‑C27</entry><entry morerows="1">1.324(11)</entry><entry morerows="1">C15‑C16</entry><entry morerows="1">1.51(2)</entry></row><row><entry morerows="1">O9‑C28</entry><entry morerows="1">1.451(13)</entry><entry morerows="1">C52‑C53</entry><entry morerows="1">1.87(4)</entry></row><row><entry morerows="1">N16‑Cu1‑N1</entry><entry morerows="1">121.9(3)</entry><entry morerows="1">N4‑N5‑C24</entry><entry morerows="1">122.3(8)</entry></row><row><entry morerows="1">N16‑Cu1‑N18</entry><entry morerows="1">78.7(3)</entry><entry morerows="1">O15‑C49‑C48</entry><entry morerows="1">109.3(7)</entry></row><row><entry morerows="1">N1‑Cu1‑N18</entry><entry morerows="1">134.8(3)</entry><entry morerows="1">O14‑C49‑O15</entry><entry morerows="1">125.2(9)</entry></row><row><entry morerows="1">N3‑Cu1‑N16</entry><entry morerows="1">130.8(2)</entry><entry morerows="1">O14‑C49‑C48</entry><entry morerows="1">125.4(8)</entry></row><row><entry morerows="1">N3‑Cu1‑N1</entry><entry morerows="1">79.9(3)</entry><entry morerows="1">N9‑C30‑N8</entry><entry morerows="1">113.8(7)</entry></row><row><entry morerows="1">N3‑Cu1‑N18</entry><entry morerows="1">118.7(3)</entry><entry morerows="1">N9‑C30‑C31</entry><entry morerows="1">124.1(8)</entry></row><row><entry morerows="1">N12‑Cu2‑N10</entry><entry morerows="1">80.8(3)</entry><entry morerows="1">C31‑C30‑N8</entry><entry morerows="1">122.1(8)</entry></row><row><entry morerows="1">N12‑Cu2‑N7</entry><entry morerows="1">130.1(3)</entry><entry morerows="1">N1‑C5‑N2</entry><entry morerows="1">113.6(8)</entry></row><row><entry morerows="1">N12‑Cu2‑N9</entry><entry morerows="1">118.8(3)</entry><entry morerows="1">N1‑C5‑C4</entry><entry morerows="1">123.2(8)</entry></row><row><entry morerows="1">N10‑Cu2‑N9</entry><entry morerows="1">135.5(3)</entry><entry morerows="1">C4‑C5‑N2</entry><entry morerows="1">123.2(8)</entry></row><row><entry morerows="1">N7‑Cu2‑N10</entry><entry morerows="1">121.7(3)</entry><entry morerows="1">N9‑C34‑Br3</entry><entry morerows="1">115.7(6)</entry></row><row><entry morerows="1">N7‑Cu2‑N9</entry><entry morerows="1">77.9(3)</entry><entry morerows="1">N9‑C34‑C33</entry><entry morerows="1">122.6(9)</entry></row><row><entry morerows="1">N11‑N12‑Cu2</entry><entry morerows="1">112.2(5)</entry><entry morerows="1">C33‑C34‑Br3</entry><entry morerows="1">121.7(8)</entry></row><row><entry morerows="1">C40‑N12‑Cu2</entry><entry morerows="1">143.1(5)</entry><entry morerows="1">C44‑C48‑C45</entry><entry morerows="1">112.6(7)</entry></row><row><entry morerows="1">C40‑N12‑N11</entry><entry morerows="1">104.3(6)</entry><entry morerows="1">C44‑C48‑C49</entry><entry morerows="1">111.9(6)</entry></row><row><entry morerows="1">N17‑N16‑Cu1</entry><entry morerows="1">113.3(5)</entry><entry morerows="1">C44‑C48‑C59</entry><entry morerows="1">114.4(6)</entry></row><row><entry morerows="1">C60‑N16‑Cu1</entry><entry morerows="1">138.5(6)</entry><entry morerows="1">C45‑C48‑C49</entry><entry morerows="1">107.6(6)</entry></row><row><entry morerows="1">C60‑N16‑N17</entry><entry morerows="1">108.1(7)</entry><entry morerows="1">C45‑C48‑C59</entry><entry morerows="1">98.4(6)</entry></row><row><entry morerows="1">C41‑O11‑C42</entry><entry morerows="1">116.1(6)</entry><entry morerows="1">C49‑C48‑C59</entry><entry morerows="1">111.1(7)</entry></row><row><entry morerows="1">C5‑N1‑Cu1</entry><entry morerows="1">114.2(5)</entry><entry morerows="1">N10‑C35‑Br4</entry><entry morerows="1">114.2(8)</entry></row><row><entry morerows="1">C5‑N1‑C1</entry><entry morerows="1">116.8(8)</entry><entry morerows="1">N10‑C35‑C36</entry><entry morerows="1">123.7(10)</entry></row><row><entry morerows="1">C1‑N1‑Cu1</entry><entry morerows="1">128.5(6)</entry><entry morerows="1">C36‑C35‑Br4</entry><entry morerows="1">122.1(9)</entry></row><row><entry morerows="1">C64‑N18‑Cu1</entry><entry morerows="1">115.5(5)</entry><entry morerows="1">O3‑C9‑N2</entry><entry morerows="1">125.5(9)</entry></row><row><entry morerows="1">C68‑N18‑Cu1</entry><entry morerows="1">128.6(7)</entry><entry morerows="1">O3‑C9‑C10</entry><entry morerows="1">131.7(8)</entry></row><row><entry morerows="1">C68‑N18‑C64</entry><entry morerows="1">115.1(8)</entry><entry morerows="1">N2‑C9‑C10</entry><entry morerows="1">102.8(8)</entry></row><row><entry morerows="1">N2‑N3‑Cu1</entry><entry morerows="1">112.7(5)</entry><entry morerows="1">O2‑C7‑C6</entry><entry morerows="1">112.0(7)</entry></row><row><entry morerows="1">C6‑N3‑Cu1</entry><entry morerows="1">141.7(6)</entry><entry morerows="1">O1‑C7‑O2</entry><entry morerows="1">125.6(8)</entry></row><row><entry morerows="1">C6‑N3‑N2</entry><entry morerows="1">105.2(6)</entry><entry morerows="1">O1‑C7‑C6</entry><entry morerows="1">122.3(8)</entry></row><row><entry morerows="1">C46‑O17‑C47</entry><entry morerows="1">113.1(8)</entry><entry morerows="1">N10‑C39‑N11</entry><entry morerows="1">115.1(8)</entry></row><row><entry morerows="1">N16‑N17‑C64</entry><entry morerows="1">116.7(7)</entry><entry morerows="1">N10‑C39‑C38</entry><entry morerows="1">122.4(9)</entry></row><row><entry morerows="1">N16‑N17‑C63</entry><entry morerows="1">113.3(7)</entry><entry morerows="1">C38‑C39‑N11</entry><entry morerows="1">122.5(8)</entry></row><row><entry morerows="1">C63‑N17‑C64</entry><entry morerows="1">128.6(8)</entry><entry morerows="1">N14‑C59‑C60</entry><entry morerows="1">113.0(6)</entry></row><row><entry morerows="1">N12‑N11‑C43</entry><entry morerows="1">112.6(7)</entry><entry morerows="1">N14‑C59‑C63</entry><entry morerows="1">112.8(7)</entry></row><row><entry morerows="1">N12‑N11‑C39</entry><entry morerows="1">118.1(6)</entry><entry morerows="1">N14‑C59‑C48</entry><entry morerows="1">101.9(6)</entry></row><row><entry morerows="1">C39‑N11‑C43</entry><entry morerows="1">129.3(7)</entry><entry morerows="1">C60‑C59‑C63</entry><entry morerows="1">99.4(7)</entry></row><row><entry morerows="1">C49‑O15‑C50</entry><entry morerows="1">117.4(7)</entry><entry morerows="1">C60‑C59‑C48</entry><entry morerows="1">111.9(6)</entry></row><row><entry morerows="1">C35‑N10‑Cu2</entry><entry morerows="1">129.1(6)</entry><entry morerows="1">C63‑C59‑C48</entry><entry morerows="1">118.4(6)</entry></row><row><entry morerows="1">C35‑N10‑C39</entry><entry morerows="1">117.2(8)</entry><entry morerows="1">N7‑C26‑C25</entry><entry morerows="1">115.3(7)</entry></row><row><entry morerows="1">C39‑N10‑Cu2</entry><entry morerows="1">113.1(6)</entry><entry morerows="1">N7‑C26‑C27</entry><entry morerows="1">117.9(8)</entry></row><row><entry morerows="1">C12‑O5‑C13</entry><entry morerows="1">116.8(8)</entry><entry morerows="1">C25‑C26‑C27</entry><entry morerows="1">126.7(8)</entry></row><row><entry morerows="1">N7‑N8‑C29</entry><entry morerows="1">111.3(7)</entry><entry morerows="1">C33‑C32‑C31</entry><entry morerows="1">120.4(9)</entry></row><row><entry morerows="1">N7‑N8‑C30</entry><entry morerows="1">117.3(6)</entry><entry morerows="1">C24‑N6‑C20</entry><entry morerows="1">117.0(10)</entry></row><row><entry morerows="1">C30‑N8‑C29</entry><entry morerows="1">130.2(7)</entry><entry morerows="1">C54‑N15‑C58</entry><entry morerows="1">118.7(9)</entry></row><row><entry morerows="1">N8‑N7‑Cu2</entry><entry morerows="1">113.5(5)</entry><entry morerows="1">C6‑C10‑C9</entry><entry morerows="1">106.1(7)</entry></row><row><entry morerows="1">C26‑N7‑Cu2</entry><entry morerows="1">137.8(6)</entry><entry morerows="1">C6‑C10‑C11</entry><entry morerows="1">131.2(8)</entry></row><row><entry morerows="1">C26‑N7‑N8</entry><entry morerows="1">108.6(7)</entry><entry morerows="1">C9‑C10‑C11</entry><entry morerows="1">122.6(8)</entry></row><row><entry morerows="1">C7‑O2‑C8</entry><entry morerows="1">116.0(6)</entry><entry morerows="1">N6‑C24‑N5</entry><entry morerows="1">115.0(9)</entry></row><row><entry morerows="1">O13‑C43‑N11</entry><entry morerows="1">124.4(8)</entry><entry morerows="1">N6‑C24‑C23</entry><entry morerows="1">124.4(11)</entry></row><row><entry morerows="1">O13‑C43‑C44</entry><entry morerows="1">132.8(8)</entry><entry morerows="1">C23‑C24‑N5</entry><entry morerows="1">120.5(12)</entry></row><row><entry morerows="1">C44‑C43‑N11</entry><entry morerows="1">102.9(7)</entry><entry morerows="1">C10‑C11‑C25</entry><entry morerows="1">112.7(7)</entry></row><row><entry morerows="1">C30‑N9‑Cu2</entry><entry morerows="1">115.2(5)</entry><entry morerows="1">C10‑C11‑C17</entry><entry morerows="1">114.8(7)</entry></row><row><entry morerows="1">C30‑N9‑C34</entry><entry morerows="1">116.4(7)</entry><entry morerows="1">C10‑C11‑C12</entry><entry morerows="1">112.6(8)</entry></row></tbody></tgroup></table></tables><tables num="0004" id="ctbl0004"><table><tgroup cols="4"><colspec colname="c001" colwidth="21%" /><colspec colname="c002" colwidth="22%" /><colspec colname="c003" colwidth="34%" /><colspec colname="c004" colwidth="23%" /><tbody><row><entry morerows="1">C34‑N9‑Cu2</entry><entry morerows="1">127.0(6)</entry><entry morerows="1">C17‑C11‑C25</entry><entry morerows="1">98.5(7)</entry></row><row><entry morerows="1">N3‑N2‑C5</entry><entry morerows="1">119.1(7)</entry><entry morerows="1">C17‑C11‑C12</entry><entry morerows="1">105.7(7)</entry></row><row><entry morerows="1">N3‑N2‑C9</entry><entry morerows="1">113.3(7)</entry><entry morerows="1">C12‑C11‑C25</entry><entry morerows="1">111.5(7)</entry></row><row><entry morerows="1">C5‑N2‑C9</entry><entry morerows="1">127.4(8)</entry><entry morerows="1">C32‑C33‑C34</entry><entry morerows="1">119.2(9)</entry></row><row><entry morerows="1">N18‑C64‑N17</entry><entry morerows="1">113.8(7)</entry><entry morerows="1">C17‑N4‑N5</entry><entry morerows="1">107.2(8)</entry></row><row><entry morerows="1">N18‑C64‑C65</entry><entry morerows="1">123.8(8)</entry><entry morerows="1">C64‑C65‑C66</entry><entry morerows="1">115.6(10)</entry></row><row><entry morerows="1">C65‑C64‑N17</entry><entry morerows="1">122.3(9)</entry><entry morerows="1">N1‑C1‑Br1</entry><entry morerows="1">115.1(7)</entry></row><row><entry morerows="1">C61‑O19‑C62</entry><entry morerows="1">115.9(7)</entry><entry morerows="1">N1‑C1‑C2</entry><entry morerows="1">125.3(9)</entry></row><row><entry morerows="1">C27‑O9‑C28</entry><entry morerows="1">114.6(9)</entry><entry morerows="1">C2‑C1‑Br1</entry><entry morerows="1">119.5(7)</entry></row><row><entry morerows="1">N13‑N14‑C59</entry><entry morerows="1">113.7(6)</entry><entry morerows="1">N14‑C54‑C55</entry><entry morerows="1">121.3(10)</entry></row><row><entry morerows="1">N13‑N14‑C54</entry><entry morerows="1">120.8(7)</entry><entry morerows="1">N15‑C54‑N14</entry><entry morerows="1">114.7(8)</entry></row><row><entry morerows="1">C54‑N14‑C59</entry><entry morerows="1">124.0(7)</entry><entry morerows="1">N15‑C54‑C55</entry><entry morerows="1">124.0(10)</entry></row><row><entry morerows="1">N12‑C40‑C44</entry><entry morerows="1">113.1(7)</entry><entry morerows="1">N4‑C17‑C11</entry><entry morerows="1">116.3(8)</entry></row><row><entry morerows="1">N12‑C40‑C41</entry><entry morerows="1">118.0(7)</entry><entry morerows="1">N4‑C17‑C18</entry><entry morerows="1">121.1(10)</entry></row><row><entry morerows="1">C44‑C40‑C41</entry><entry morerows="1">128.9(7)</entry><entry morerows="1">C18‑C17‑C11</entry><entry morerows="1">122.0(10)</entry></row><row><entry morerows="1">C45‑N13‑N14</entry><entry morerows="1">108.2(7)</entry><entry morerows="1">O5‑C12‑C11</entry><entry morerows="1">110.0(9)</entry></row><row><entry morerows="1">N16‑C60‑C61</entry><entry morerows="1">120.8(7)</entry><entry morerows="1">O4‑C12‑O5</entry><entry morerows="1">124.8(9)</entry></row><row><entry morerows="1">N16‑C60‑C59</entry><entry morerows="1">114.1(7)</entry><entry morerows="1">O4‑C12‑C11</entry><entry morerows="1">125.2(9)</entry></row><row><entry morerows="1">C59‑C60‑C61</entry><entry morerows="1">124.8(8)</entry><entry morerows="1">N18‑C68‑Br6</entry><entry morerows="1">113.7(8)</entry></row><row><entry morerows="1">O17‑C46‑C45</entry><entry morerows="1">110.3(8)</entry><entry morerows="1">C67‑C68‑Br6</entry><entry morerows="1">118.4(9)</entry></row><row><entry morerows="1">O16‑C46‑O17</entry><entry morerows="1">126.8(8)</entry><entry morerows="1">C67‑C68‑N18</entry><entry morerows="1">127.8(10)</entry></row><row><entry morerows="1">O16‑C46‑C45</entry><entry morerows="1">122.9(8)</entry><entry morerows="1">C37‑C38‑C39</entry><entry morerows="1">118.2(10)</entry></row><row><entry morerows="1">C18‑O7‑C19</entry><entry morerows="1">111.8(12)</entry><entry morerows="1">O9‑C27‑C26</entry><entry morerows="1">109.4(8)</entry></row><row><entry morerows="1">O18‑C61‑O19</entry><entry morerows="1">126.7(9)</entry><entry morerows="1">O8‑C27‑O9</entry><entry morerows="1">127.0(10)</entry></row><row><entry morerows="1">O18‑C61‑C60</entry><entry morerows="1">122.2(9)</entry><entry morerows="1">O8‑C27‑C26</entry><entry morerows="1">123.6(10)</entry></row><row><entry morerows="1">O19‑C61‑C60</entry><entry morerows="1">111.1(7)</entry><entry morerows="1">C3‑C2‑C1</entry><entry morerows="1">114.8(9)</entry></row><row><entry morerows="1">C43‑C44‑C48</entry><entry morerows="1">124.6(7)</entry><entry morerows="1">O15‑C50‑C51</entry><entry morerows="1">106.1(10)</entry></row><row><entry morerows="1">C40‑C44‑C43</entry><entry morerows="1">107.0(7)</entry><entry morerows="1">N6‑C20‑Br2</entry><entry morerows="1">116.5(9)</entry></row><row><entry morerows="1">C40‑C44‑C48</entry><entry morerows="1">128.4(7)</entry><entry morerows="1">N6‑C20‑C21</entry><entry morerows="1">124.6(12)</entry></row><row><entry morerows="1">O11‑C41‑C40</entry><entry morerows="1">111.4(7)</entry><entry morerows="1">C21‑C20‑Br2</entry><entry morerows="1">118.8(10)</entry></row><row><entry morerows="1">O12‑C41‑O11</entry><entry morerows="1">124.0(8)</entry><entry morerows="1">C36‑C37‑C38</entry><entry morerows="1">120.5(11)</entry></row><row><entry morerows="1">O12‑C41‑C40</entry><entry morerows="1">124.6(7)</entry><entry morerows="1">C5‑C4‑C3</entry><entry morerows="1">116.7(10)</entry></row><row><entry morerows="1">N13‑C45‑C46</entry><entry morerows="1">121.7(8)</entry><entry morerows="1">N15‑C58‑Br5</entry><entry morerows="1">115.7(9)</entry></row><row><entry morerows="1">N13‑C45‑C48</entry><entry morerows="1">115.7(7)</entry><entry morerows="1">C57‑C58‑Br5</entry><entry morerows="1">121.7(11)</entry></row><row><entry morerows="1">C46‑C45‑C48</entry><entry morerows="1">121.1(7)</entry><entry morerows="1">C57‑C58‑N15</entry><entry morerows="1">122.5(12)</entry></row><row><entry morerows="1">N3‑C6‑C7</entry><entry morerows="1">116.1(7)</entry><entry morerows="1">O5‑C13‑C14</entry><entry morerows="1">109.1(10)</entry></row><row><entry morerows="1">N3‑C6‑C10</entry><entry morerows="1">112.5(7)</entry><entry morerows="1">C54‑C55‑C56</entry><entry morerows="1">111.1(12)</entry></row><row><entry morerows="1">C10‑C6‑C7</entry><entry morerows="1">131.4(7)</entry><entry morerows="1">C37‑C36‑C35</entry><entry morerows="1">118.0(11)</entry></row><row><entry morerows="1">O10‑C29‑N8</entry><entry morerows="1">125.3(9)</entry><entry morerows="1">C2‑C3‑C4</entry><entry morerows="1">123.2(11)</entry></row><row><entry morerows="1">O10‑C29‑C25</entry><entry morerows="1">128.3(8)</entry><entry morerows="1">O6‑C18‑O7</entry><entry morerows="1">128.1(12)</entry></row><row><entry morerows="1">N8‑C29‑C25</entry><entry morerows="1">106.3(7)</entry><entry morerows="1">O6‑C18‑C17</entry><entry morerows="1">118.1(13)</entry></row><row><entry morerows="1">C32‑C31‑C30</entry><entry morerows="1">117.2(9)</entry><entry morerows="1">O7‑C18‑C17</entry><entry morerows="1">113.7(13)</entry></row><row><entry morerows="1">C29‑C25‑C11</entry><entry morerows="1">116.4(7)</entry><entry morerows="1">C65‑C66‑C67</entry><entry morerows="1">121.7(11)</entry></row><row><entry morerows="1">N5‑C25‑C29</entry><entry morerows="1">111.5(6)</entry><entry morerows="1">C68‑C67‑C66</entry><entry morerows="1">115.8(11)</entry></row><row><entry morerows="1">N5‑C25‑C26</entry><entry morerows="1">114.7(7)</entry><entry morerows="1">C13‑C14‑C15</entry><entry morerows="1">113.6(14)</entry></row><row><entry morerows="1">N5‑C25‑C11</entry><entry morerows="1">101.8(7)</entry><entry morerows="1">C57‑C56‑C55</entry><entry morerows="1">123.0(13)</entry></row><row><entry morerows="1">C26‑C25‑C29</entry><entry morerows="1">98.4(7)</entry><entry morerows="1">C56‑C57‑C58</entry><entry morerows="1">120.3(14)</entry></row><row><entry morerows="1">C26‑C25‑C11</entry><entry morerows="1">114.6(6)</entry><entry morerows="1">C24‑C23‑C22</entry><entry morerows="1">115.3(13)</entry></row><row><entry morerows="1">N17‑C63‑C59</entry><entry morerows="1">105.0(8)</entry><entry morerows="1">C52‑C51‑C50</entry><entry morerows="1">132.6(19)</entry></row><row><entry morerows="1">O20‑C63‑N17</entry><entry morerows="1">127.0(9)</entry><entry morerows="1">C22‑C21‑C20</entry><entry morerows="1">117.8(13)</entry></row><row><entry morerows="1">O20‑C63‑C59</entry><entry morerows="1">128.0(8)</entry><entry morerows="1">C21‑C22‑C23</entry><entry morerows="1">120.7(14)</entry></row><row><entry morerows="1">C24‑N5‑C25</entry><entry morerows="1">121.7(8)</entry><entry morerows="1">C14‑C15‑C16</entry><entry morerows="1">114.5(18)</entry></row><row><entry morerows="1">N4‑N5‑C25</entry><entry morerows="1">113.4(7)</entry><entry morerows="1">C51‑C52‑C53</entry><entry morerows="1">85(2)</entry></row></tbody></tgroup></table></tables>
地址 541004 广西壮族自治区桂林市建干路12号