N-氧化吡啶类希夫碱配合物的合成、晶体结构及谱学表征
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摘要
通过N-氧化吡啶-2-甲醛与4-氨基安替比林在无水乙醇中按1：1摩尔比进行的反应，合成了希夫碱N—宰C,tL,比啶-2-甲醛缩安替比林，并获得其单晶。在此基础上使希夫碱与高氯酸铜在无水乙醇中按1：1摩尔比进一步反应，合成了配合物N-氧化吡啶-2-甲醛缩安替比林合铜(11)，并获得其单晶。二者均测定了单晶结构，用电子光谱、IR谱、HNMR谱对它们进行了研究。配体分子式为Ci?H1b吼(P~AAP)。晶体属正交晶系，空间群为Pbcn， 晶胞参数： a=l。3391(2)nm，b=1．0259(2)m，c=2．2242(4)旧，V=3．0556(9)nm3，Z=8，Lb二308．34，0c：1．341Ug扣’，ll二0．091mm-~，F(000)：1296，结构偏离因子R--0．0407，山R=0．0830。最佳吻合因子S=0．831。 配合物实验式为[Cu(PNOAAP)㈣~0t-1)：)C104)人。晶体属三斜晶系，空间群为Pi，晶胞参数a=1．12310(17)m，b=1．12728(17)nm，c=1．26820(19)，。=67．902(3)‘，p：73．530(3)‘，Y=73．290(3) ，V二1．3967(4)nm：l，Z=2，Mr=1325．82，Dc=1．576Mg，，／m’，皿’1．040nm-'，F(000)=682，结构偏离因子R=0．0653，山R=O．1678，最佳吻合因子S=0．986。晶体中Cu(11)与配体希夫碱中的N(-CH=N)，0(＼一0)，0(>C刁)原子，二分子乙醇的羟基氧，另一分子的0(N一0)原子配位形成拉长的八面体几何结构。Cu(1)与Cu(1A)间通过两个氧桥形成二聚体。
通过6-甲基-2-甲醛-N-氧化吡啶与氨基硫脲在无水乙醇中按1：1摩尔比进行的反应，合成了希夫碱6-甲基-2-甲醛-]'4-氧化吡啶缩氨基硫脲，并获得其单晶。测定了单晶结构，用电子光谱，m谱对其进行了研究。化合物分子式C8Hx州40S·H20。晶体属单斜晶系，空间群Cc，晶胞参数：a=1．3251(3)nm，b=2．4919(6)帅，c=1．3670(3)nm，p=101．334<5)’，V=4．4258(19)rh-n3，Z=16，Mr=-230．29，Dc=-1．382Mg／m3，ll=0．28lmm-1，F(000户1952，结构偏离因子R=0．0468， 山*二0．1128，最佳吻合因子S=0．692。存在六种分子间弱氢键，使之形成网状结构。
用一步法制备了N-氧化吡啶-2-甲醛缩纽氨酸席夫碱及其钼(Ⅵ)配合物。并用元素分析、m、差热-热重分析进行了表征，结果表明，钼(Ⅵ)通过与席夫碱的O(N-氧化吡啶)刘(席夫碱)，O(羧基)原子进行配位形成稳定的配合物，并据此推测出了配合物的可能的合理结构。生物活性试验表明：席夫碱对植物发芽有抑制作用，配合物则有促进作用，亦证明Mo(V1)为活性中心。
为比较N→0键与C=O键的差异，还合成了两颗单晶：
邻巯基-N-氧化吡啶与(n—Bu4X)+：M。，0：。]在无水甲醇中按2：l摩力；LL进行的反应，
l 合成了配84o，获得了单晶。测定了单晶结构，配合物分子式为 C，111．n－－－－xN．0；而。晶体
属单斜晶系，空间群为PZ；巾，晶胞参数：a＝＝l．09288（12）rm，b＝2．8777（3）urn，
C＝L32425（14）C，D二lbo．035（2）”，Vt．1011佃p‘，Z＝4，Mrl036．73，DC＝1．679Mg／nI3，
V＝1．llfor－‘，F（000）＝2096，结构偏离因子R＝（．0584，。ho．1691。最佳吻合因子
S＝1147。MO＃＆5种不同的配位环境。
通过水杨醛与乙醇胺与乙酞丙酮氧化铝在无水乙醇中按2：2：1摩尔比进行的反
应，合成了希夫碱水杨醛缩乙醇 钥（w），并获得其单晶，测定了单晶结构，配合
物实验式为【MO（0）（Wb」。。晶体属正交晶系，空间群为M，晶胞参数
a＝1．31007（16）urn，ho．89636（11）urn，c二1．6841（4）urn，V＝1．9777（4）nln，Z＝4，r582．22，
k司．95烈柏佃‘．p二1．31h可‘，F（000）＝1152，结构儡离因于R旬．肥93．oR刀．0819。最
佳吻合因子Sd．7听。通过配体的p原子与u。原子配位，配合物分子为二聚体。
－通过比较发现N—0键键长通常在0．131～0．135n之间，而水杨醛的CAI键长常
在0．133～0．137urn之间，这是由于N原子电负性大于C原子造成的。
The reaction of picolinaldehyde N-oxide and 4-aminoantipyrine in ethanol in the molar ratio of 1:1 gave the ligand. At the same time of yellow single crystal was obtained. The reaction of Schiff base and Cu(C104)2in absolute ethanol in the molar ratio of 1:1, coinplound ECu(PNOAAP) (c2H5CI1)2(Cl04)~]2 was further synthesized and its black single crystals was obtained. The crystal structure of ligand and compound had been determined by X-ray diffraction method, and its spectroscopic properties had been studied by electron spectrum, IR, 1HNMR. PNOAAP has the molecular formula C~7H1~~NO~, Mr308. 34, and crystalized in orthorhombic
space group Pbcn, with unit cell parameters :a=1.3391(2)nm,b1.0259(2)nm, c=2. 2242(4) nm, V=3. 0556(9) nm3, Z8, Dc=l. 341Mg/rn3, ii 0. O9lmrrf', F (000) 1296, final R=0. 0407 and wR=0. 0830, S0. 831. compound crystals belongs to triclinic
system, space group PT, with unit cell parameters: a1. 12310(17)nm, b=l. 12728 (17)
nm, c1. 26820 (19), a =67. 902(3) , P =73. 530(3) , i' 73. 290(3) 0 , V1. 3967(4)
~ Z=2, Mr1325. 82, Dc=1. 576Mg/m~, ~ 4 040nm1, F(000)682, final R=0. 0653 and w R~0. 1678, S=0. 986. The structure of the compound is a dimer with oxide bridges(Py-N--0). The Cu(II) is in a distorted octahedral environment whose plane is constructed by 01,N3 and 02 of ligand and 0k3 of the ethanol. One of the apical positions is occupied by oxygen atom(04) of another ethanol group. Another site is linked to 0(2A) of ligand belonging to synmietry unit.
By the reaction of 6-methyl-2-picolinaldehyde N-oxide and thiosemicarbazone in absolute ethanol in the molecular ratio of 1:1 ,6-methyl-2-picolinaldehyde N-oxide thiosemica was synthesized and its yellow single crystals was obtained. The crystal structure had been determined by X-ray diffl~acdon method and its spectroscopic properties had studied by electron spectrum, IR. Compound has the molecular formula C8H 10N40S H20 art] its crystal belongs to monoclinic system, space group Cc with unit cell parameters: a=13251(3)nm, b=2.4919(6)nm, c~12670(3)nrn, P =101.334(5) 0 ,V=4.4258(19)nm3,Z=16,Mr23029,Dc= I .382Mg/rn3, ~i 28Irnm1,F(000)=1952,final R=O.O468,wR~).1 128,F2=O.692. Six weak hydrogen bonds exit in the crystal of the compound which make net structure.
Molybdenum(VI) complex with Schiff base derived from 2-picolinaldehyde N-oxide and Histidine was synthesized by one step method and characterized by elemental analysis, IR spectra and thermal analysis. The results showed that molvbdenum(VI) coordinated to the Schiff bases via 0(N-oxide pyridine), N(Schiff
3
base) and O(-COCF) donors and formed stable complex. Based on these results, the possibly reasonable structure of complexes was suggested. Biological activity tests of the Schiff base and complex evidenced that Schiff base could inhibit the sprout of green bean, while molybdenum(VI) complexes could promote it. These facts confirmed that Mo(Vl)was active centre.
In order to compare N-0 bond with HCO bond , two single crystals were obtained. For the N atom is more electronegative than C atom, N-0 bond lengths are 0. 131- 0. 135nm,while C0 bond lengths are 0. 133-'O. l37nm.
The reaction of N-oxide o-mercaptopyridine and (n-Bu4N)4[Mo~O~j in absolute methanol in the molar ratio of 2:1 gave the complex. At the same time of its colorless single crystal was obtained. The crystal structure had been determined by X-ray diffraction. Complex has the molecular formula C31l-L~Mo3N4O11S3, Mr= 1036. 73,and crystalized in monoclinic ,space group P21/n , with unit cell parameters :a1. 09288(l2)nm, b2. 8777 (3) nm, cl. 32425(14)nm, P =100. 035 ,
4. 1011 (8)r&, Z-4, Dc=l. 679Mg/rn3, ii Z1. ll4nmf1, F(000)2096, final R0. 0508 and wRO. 1691, S1. 147. Molybdenum atoms exit three complex environments.
By the reaction of salicylal, aminoethanol and Mo02(acac)2 in absolute ethanol in the molecular ratio of 22:1, [Mo (0) (CqH~~NO:i) 1, was synthesized and its single ciystals was obtained. The crystai stnicture has been determined by X-ray diffiaction method and its crystai belongs to
通过6-甲基-2-甲醛-N-氧化吡啶与氨基硫脲在无水乙醇中按1：1摩尔比进行的反应，合成了希夫碱6-甲基-2-甲醛-]'4-氧化吡啶缩氨基硫脲，并获得其单晶。测定了单晶结构，用电子光谱，m谱对其进行了研究。化合物分子式C8Hx州40S·H20。晶体属单斜晶系，空间群Cc，晶胞参数：a=1．3251(3)nm，b=2．4919(6)帅，c=1．3670(3)nm，p=101．334<5)’，V=4．4258(19)rh-n3，Z=16，Mr=-230．29，Dc=-1．382Mg／m3，ll=0．28lmm-1，F(000户1952，结构偏离因子R=0．0468， 山*二0．1128，最佳吻合因子S=0．692。存在六种分子间弱氢键，使之形成网状结构。
用一步法制备了N-氧化吡啶-2-甲醛缩纽氨酸席夫碱及其钼(Ⅵ)配合物。并用元素分析、m、差热-热重分析进行了表征，结果表明，钼(Ⅵ)通过与席夫碱的O(N-氧化吡啶)刘(席夫碱)，O(羧基)原子进行配位形成稳定的配合物，并据此推测出了配合物的可能的合理结构。生物活性试验表明：席夫碱对植物发芽有抑制作用，配合物则有促进作用，亦证明Mo(V1)为活性中心。
为比较N→0键与C=O键的差异，还合成了两颗单晶：
邻巯基-N-氧化吡啶与(n—Bu4X)+：M。，0：。]在无水甲醇中按2：l摩力；LL进行的反应，
l 合成了配84o，获得了单晶。测定了单晶结构，配合物分子式为 C，111．n－－－－xN．0；而。晶体
属单斜晶系，空间群为PZ；巾，晶胞参数：a＝＝l．09288（12）rm，b＝2．8777（3）urn，
C＝L32425（14）C，D二lbo．035（2）”，Vt．1011佃p‘，Z＝4，Mrl036．73，DC＝1．679Mg／nI3，
V＝1．llfor－‘，F（000）＝2096，结构偏离因子R＝（．0584，。ho．1691。最佳吻合因子
S＝1147。MO＃＆5种不同的配位环境。
通过水杨醛与乙醇胺与乙酞丙酮氧化铝在无水乙醇中按2：2：1摩尔比进行的反
应，合成了希夫碱水杨醛缩乙醇 钥（w），并获得其单晶，测定了单晶结构，配合
物实验式为【MO（0）（Wb」。。晶体属正交晶系，空间群为M，晶胞参数
a＝1．31007（16）urn，ho．89636（11）urn，c二1．6841（4）urn，V＝1．9777（4）nln，Z＝4，r582．22，
k司．95烈柏佃‘．p二1．31h可‘，F（000）＝1152，结构儡离因于R旬．肥93．oR刀．0819。最
佳吻合因子Sd．7听。通过配体的p原子与u。原子配位，配合物分子为二聚体。
－通过比较发现N—0键键长通常在0．131～0．135n之间，而水杨醛的CAI键长常
在0．133～0．137urn之间，这是由于N原子电负性大于C原子造成的。
The reaction of picolinaldehyde N-oxide and 4-aminoantipyrine in ethanol in the molar ratio of 1:1 gave the ligand. At the same time of yellow single crystal was obtained. The reaction of Schiff base and Cu(C104)2in absolute ethanol in the molar ratio of 1:1, coinplound ECu(PNOAAP) (c2H5CI1)2(Cl04)~]2 was further synthesized and its black single crystals was obtained. The crystal structure of ligand and compound had been determined by X-ray diffraction method, and its spectroscopic properties had been studied by electron spectrum, IR, 1HNMR. PNOAAP has the molecular formula C~7H1~~NO~, Mr308. 34, and crystalized in orthorhombic
space group Pbcn, with unit cell parameters :a=1.3391(2)nm,b1.0259(2)nm, c=2. 2242(4) nm, V=3. 0556(9) nm3, Z8, Dc=l. 341Mg/rn3, ii 0. O9lmrrf', F (000) 1296, final R=0. 0407 and wR=0. 0830, S0. 831. compound crystals belongs to triclinic
system, space group PT, with unit cell parameters: a1. 12310(17)nm, b=l. 12728 (17)
nm, c1. 26820 (19), a =67. 902(3) , P =73. 530(3) , i' 73. 290(3) 0 , V1. 3967(4)
~ Z=2, Mr1325. 82, Dc=1. 576Mg/m~, ~ 4 040nm1, F(000)682, final R=0. 0653 and w R~0. 1678, S=0. 986. The structure of the compound is a dimer with oxide bridges(Py-N--0). The Cu(II) is in a distorted octahedral environment whose plane is constructed by 01,N3 and 02 of ligand and 0k3 of the ethanol. One of the apical positions is occupied by oxygen atom(04) of another ethanol group. Another site is linked to 0(2A) of ligand belonging to synmietry unit.
By the reaction of 6-methyl-2-picolinaldehyde N-oxide and thiosemicarbazone in absolute ethanol in the molecular ratio of 1:1 ,6-methyl-2-picolinaldehyde N-oxide thiosemica was synthesized and its yellow single crystals was obtained. The crystal structure had been determined by X-ray diffl~acdon method and its spectroscopic properties had studied by electron spectrum, IR. Compound has the molecular formula C8H 10N40S H20 art] its crystal belongs to monoclinic system, space group Cc with unit cell parameters: a=13251(3)nm, b=2.4919(6)nm, c~12670(3)nrn, P =101.334(5) 0 ,V=4.4258(19)nm3,Z=16,Mr23029,Dc= I .382Mg/rn3, ~i 28Irnm1,F(000)=1952,final R=O.O468,wR~).1 128,F2=O.692. Six weak hydrogen bonds exit in the crystal of the compound which make net structure.
Molybdenum(VI) complex with Schiff base derived from 2-picolinaldehyde N-oxide and Histidine was synthesized by one step method and characterized by elemental analysis, IR spectra and thermal analysis. The results showed that molvbdenum(VI) coordinated to the Schiff bases via 0(N-oxide pyridine), N(Schiff
3
base) and O(-COCF) donors and formed stable complex. Based on these results, the possibly reasonable structure of complexes was suggested. Biological activity tests of the Schiff base and complex evidenced that Schiff base could inhibit the sprout of green bean, while molybdenum(VI) complexes could promote it. These facts confirmed that Mo(Vl)was active centre.
In order to compare N-0 bond with HCO bond , two single crystals were obtained. For the N atom is more electronegative than C atom, N-0 bond lengths are 0. 131- 0. 135nm,while C0 bond lengths are 0. 133-'O. l37nm.
The reaction of N-oxide o-mercaptopyridine and (n-Bu4N)4[Mo~O~j in absolute methanol in the molar ratio of 2:1 gave the complex. At the same time of its colorless single crystal was obtained. The crystal structure had been determined by X-ray diffraction. Complex has the molecular formula C31l-L~Mo3N4O11S3, Mr= 1036. 73,and crystalized in monoclinic ,space group P21/n , with unit cell parameters :a1. 09288(l2)nm, b2. 8777 (3) nm, cl. 32425(14)nm, P =100. 035 ,
4. 1011 (8)r&, Z-4, Dc=l. 679Mg/rn3, ii Z1. ll4nmf1, F(000)2096, final R0. 0508 and wRO. 1691, S1. 147. Molybdenum atoms exit three complex environments.
By the reaction of salicylal, aminoethanol and Mo02(acac)2 in absolute ethanol in the molecular ratio of 22:1, [Mo (0) (CqH~~NO:i) 1, was synthesized and its single ciystals was obtained. The crystai stnicture has been determined by X-ray diffiaction method and its crystai belongs to
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