劉 露 靳平寧 李 英 婁慧慧 王鍵吉 張裕平 侯紅衛 杜錦閣
(1河南科技學院化學化工學院,新鄉 453003)
(2新鄉醫學院,新鄉 453003)
(3河南師范大學化學化工學院,新鄉 453007)
(4鄭州大學化學與分子工程學院,鄭州 450052)
(5新鄉醫學院三全學院,新鄉 453003)
The design and construction of multifarious complexes has been a hot topic for all researchers owing to their intriguing structural motifs and potential applications in optics,magnetism,recognition,etc[1-8].Although the assembly of complexes is affected by varied factors,we haven′t stopped exploring them.In consideration of the superiority of the “mixed-ligand”synthetic strategies[9-12],which can lead to numerous graceful structures,we choose 1,4-bis(2-(4-thiazolyl)benzimidazole-1-ylmethyl)benzene(btbb)as the semirigid N-donor ligand and different multidentate O-donor carboxylates,m-phenylenediacetic acid(m-H2phda),1,3-adamantanedicarboxylic acid(H2adtda),5-tert-butylisophthalic acid (H2tbi),3-Nitro-1,2-benzenedicarboxylic acid(3-Nitro-o-H2bdc)as auxiliary ligands in the synthesis of metal-organic coordination polymer materials.Five diverse structural complexes,{[Zn(btbb)0.5(mphda)]·0.5H2O}n(1),{[Cd2(btbb)(adtda)2(H2O)]·H2O}n(2),[Mn2(btbb)(tbi)2]n(3),{[Cd(btbb)0.5(3-Nitro-o-bdc)(H2O)]·H2O}n(4)and[Cd2(btbb)(tbi)2]n(5)were prepared.The structures of 1~5 have been determined by single-crystal X-ray diffraction analyses and further characterized by infrared spectra,elemental analyses.
All reagents and solvents were commercially available without any further purification,except for ligand btbb,which was synthesized in accordance with the literature[13].The data of FT-IR spectra were recorded on a FTIR-7600 spectrophotometer with KBr pellets in a scale of 400~4 000 cm-1.Elemental analyses of C,H and N were performed introducing a FLASH EA 1112 analyzer.
A mixture of Zn(Ac)2·2H2O(0.2 mmol),btbb(0.1 mmol),m-H2phda(0.1 mmol),NaOH(0.2 mmol)and H2O (10 mL)was placed in a 25 mL Teflon-lined stainless steel container.The mixture was sealed and heated at 180℃for three days.After the mixture was cooled to ambient temperature at a rate of 5℃·h-1,colorless crystals of 1 were obtained with a yield of 10% (based on Zn).Anal.Calcd.for C24H20ZnN3O5S(%):C,54.60;H,3.81;N,7.95.Found(%):C,54.63;H,3.79;N,7.98.IR(KBr,cm-1):3 421(s),2 988(vw),1 615(s),1 481(w),1 448(w),1 395(m),1 364(m),1 314(vw),1 272(vw),1 174(w),1 079(w),1 001(w),937(m),887(w),828(w),784(w),750(w),622(w).
A mixture of Cd(NO3)2·4H2O(0.1 mmol),btbb(0.1 mmol),p-H2adtda(0.05 mmol),EtOH(5 mL)and H2O (5 mL)was placed in a 25 mL Teflon-lined stainless steel container.The mixture was sealed and heated at 170℃for three days.After the mixture was cooled to ambient temperature at a rate of 5℃·h-1,colorless crystals of 2 were obtained with a yield of 15%(based on Cd).Anal.Calcd.for C52H52Cd2N6O10S2(%):C,51.61;H,4.33;N,6.94.Found(%):C,51.59;H,4.30;N,6.97.IR(KBr,cm-1):3 440(s),2 908(m),2 946(m),1 616(w),1 562(s),1 479(w),1 448(s),1 386(s),1 307(s),1 241(w),1 124(w),1 041(w),931(m),889(m),823(m),744(s),713(m),622(w).
A mixture of MnCl2·4H2O(0.1 mmol),btbb(0.05 mmol),H2tbi(0.05 mmol),CH3CN(4 mL)and H2O(6 mL)was placed in a 25 mL Teflon-lined stainless steel container.The mixture was sealed and heated at 160℃for three days.After the mixture was cooled to ambient temperature at a rate of 5℃·h-1,colorless crystals of 3 were obtained with a yield of 13%(based on Mn). Anal.Calcd.for C52H44Mn2N6O8S2(%):C,59.20;H,4.20;N,7.96.Found(%):C,59.23;H,4.22;N,7.92.IR(KBr,cm-1):3 409(m),3 091(m),2 962(s),2 865(w),1 604(s),1 554(s),1 436(s),1 371(s),1 307(s),1 268(s),1 108(s),1 014(m),923(s),850(s),819(s),725(s).
A mixture of Cd(NO3)2·4H2O(0.1 mmol),btbb(0.05 mmol),3-Nitro-o-H2bdc(0.05 mmol),EtOH(7 mL)and H2O (3 mL)was placed in a 25 mL Teflonlined stainless steel container.The mixture was sealed and heated at 120℃for three days.After the mixture was cooled to ambient temperature at a rate of 5℃·h-1,colorless crystals of 4 were obtained with a yield of 16%(based on Cd).Anal.Calcd.for C22H17CdN4O8S(%):C,43.32;H,2.80;N,9.18.Found(%):C,43.27;H,2.81;N,9.22.IR (KBr,cm-1):3 397(m),3 139(w),3 099(w),3 048(w),1 581(s),1 527(s),1 459(s),1 394(s),1 349(s),1 261(w),1 162(m),1 014(m),935(s),892(s),831(s),752(s),717(s).
A mixture of Cd(NO3)2·4H2O(0.05 mmol),btbb(0.05 mmol),H2tbi(0.05 mmol),EtOH(7 mL)and H2O(3 mL)was placed in a 25 mL Teflon-lined stainless steel container.The mixture was sealed and heated at 120℃for three days.After the mixture was cooled to ambient temperature at a rate of 5 ℃·h-1,colorless crystals of 5 were obtained with a yield of 20%(based on Cd).Anal.Calcd.for C52H44Cd2N6O8S2(%):C,53.38;H,3.79;N,7.18.Found(%):C,53.35;H,3.80;N,7.16.IR(KBr,cm-1):3 432(m),3 112(w),2 958(w),1 604(m),1 550(s),1 425(s),1 386(s),1 311(w),1 116(vw),927(s),854(vw),767(s),725(m).
The data of 1~5 were collected on a Rigaku Saturn 724 CCD diffractomer(Mo Kα,λ=0.071 073 nm)at temperature of 293(2)K.Absorption corrections were applied by using multi-scan program.The data were corrected for Lorentz and polarization effects.The structures were solved by direct methods and refined with a full-matrix least-squares technique based on F2with the SHELX-97 crystallographic software package[14].The hydrogen atoms were placed at calculated positions and refined as riding atoms with isotropic displacement parameters.Crystallographic crystal data and structure processing parameters for 1~5 are summarized in Table 1.Selected bond lengths and bond angles for 1~5 are listed in Table 2,respectively.
CCDC:1883643,1;1883644,2;1883645,3;1883646,4;1883647,5.
Table 1 Crystal data and structure refinement details for complexes 1~5
a R1=∑||F o|-|F c||/∑|F o|;b wR2=[∑w(F o2-F c2)2/∑w(F o2)2]1/2.
Table 2 Selected bond lengths(nm)and bond angles(°)for 1~5
Symmetry codes:#1:-x,-y,-z+1 for 1;#1:-x+1,-y+1,-z+1;#2:-x,-y+1,-z+1 for 2;#1:x+1,y,z for 3;#1:-x,-y+1,-z for 4;#1:x+1,y,z;#2:x-1,y,z for 5.
For complex 1,it consists of one crystallographically independent Znギion,half a btbb ligand,onem-phda2-ligand,and half a lattice water molecule.As illustrated in Fig.1a,Zn1ギion is six-coordinated by four O atoms of carboxylate groups (O1,O2,O3#1,O4#1)provided by two differentm-phda2-ligands,and two nitrogen atoms (N1,N2)deriving from one btbb ligand to give a octahedral coordination geometry.The distances of Zn1-N1/N2 is 0.205 1(3)/0.213 4(3)nm,while the Zn1-O bond lengths range from 0.197 8(3)to 0.242 9(3)nm.Ligand btbb exhibit asymmetricaltrans-conformation.Ndonor…N-Csp3…Csp3torsion angles of btbb is 143.613°and 143.614°,respectively.Ligandm-phda2-adopts asymmetriccis-conformation,and the angles of two-CH2-are 112.478°and 116.908°.In 1,two carboxylic groups of the “V” shape ligandmphda2-take a chelating bidentate coordination modes.The m-phda2-anions connect two adjacent Znギions using its two carboxylate groups resulting in a 22-membered rings alonga-axis (Fig.1b).The 22-membered rings are linked by btbb leading to a 1D chain along thea-axis(Fig.1c).The Zn…Zn distances across btbb ligands are 1.322 17 nm.
Fig.1 (a)Coordination environments of Znギin complex 1;(b)View of 22-membered rings constructed by two m-phda2-ligands and two Znギions along the a-axis;(c)1D chain structure containing 22-membered rings along the a-axis
Single crystal X-ray diffraction analysis reveals that 2 crystallizes in monoclinic space group P21/c.The asymmetric unit of 2 consists of two Cdギions,one btbb ligand,two adtda2-anions,one coordinated water molecule and one lattice water molecule.As shown in Fig.2a,the Cd1ギion adopts a distorted octahedral geometry via coordinating with four oxygen atoms (O1,O2,O8#1)from two adtda2-anions,one oxygen atom(O3)from one coordinated water molecule and two nitrogen atoms (N1 and N3)from one btbb ligand.The Cd1-O bond distances vary from 0.216 4(7)to 0.258 3(5)nm,while the Cd1-N1/N3 bond length is 0.227 9(6)/0.243 7(6)nm,separately.While the octahedral coordination geometry of the central Cd2ギion is completed by two N atoms(N4 and N5)of one btbb ligand,and four O atoms(O4,O5,O6,O7#2)of three adtda2-anions.The Cd2-O bond distances vary from 0.219 8(6)to 0.253 8(6)nm,while the Cd2-N4/N5 bond length is 0.240 2(7)/0.232 4(6)nm.The btbb ligand adopts asymmetric trans-conformation with two different Ndonor…N-Csp3…Csp3torsion angles of 71.150°and 93.156°.The ligand adtda2-takes two different coordination modes.The first type (adtda2--Ⅰ)is that one carboxylate group of adtda2-ligand is in a bridging bidentate mode,and the other adopts a monodentate mode,whereas the two carboxylate groups of the second type(adtda2--Ⅱ)both adopt chelating bidentate modes.The adtda2--Ⅰ and adtda2--Ⅱ anions link Cdギ ions to produce a one-dimensional (1D)chain structure having a dinuclear units[Cd2(OCO)2]with a Cd…Cd separation of 0.424 84 nm (Fig.2b).Interestingly,1D Cdギ/adtda2-chain is further embellished by btbb giving rise to a more complex and beautiful 1D chain structure,and the Cd…Cd separation across btbb bridge is 1.013 00 nm(Fig.2c).
Fig.2 (a)Perspective view of the coordination environment of Cdギion in 2;(b)1D chain constructed by Cdギions and adtda2-anions having a 8-membered rings;(c)1D chain embellished by btbb
Fig.3 (a)Coordination environments of Mnギin complex 3;(b)View of 1D Mnギ/tbi2-chain;(c)1D double chain structure of 3
The asymmetric unit of complex 3 contains two Mnギions,one btbb ligand and two tbi2-ligands in the monoclinic space group P21/c.As shown in Fig.3a,the Mn1 center is six-coordinated by four oxygen atoms(O1,O2,O3 and O6)belonging to three separated tbi2-ligands as well as two nitrogen atoms(N1 and N2)from one btbb ligand to generate a distorted octahedral coordination geometry.The Mn1-O bond distances lie in a range of 0.213 2(4)~0.234 4(4)nm,and Mn1-N1/N2 bond distances are 0.234 3(4)/0.225 4(5)nm,respectively.The Mn2 center also adopts a distorted octahedral coordination environment,which is provided by two nitrogen atoms(N4,N5)from one separate btbb and four oxygen atoms(O4,O5,O7,O8)from three tbi2-.The Mn2-O bond distances lie in a range of 0.212 0(4)~0.244 9(4)nm, and Mn2-N4/N5 bond distances are 0.233 2(6)/0.224 5(5)nm.As shown in Fig.3b,both carboxylate groups of rigid tbi2-anions adopt the mono-bidentate-bridging coordination fashion and chelating bidentate mode,separately,linking Mnギions to a 1D chain,which contains a dual-core unit[Mn2(OCO)2]with the Mn…Mn distance of 0.413 54 nm.The ligand btbb adopts asymmetric transconformation with two differenttorsion angles of 44.822°and 78.136°,and it connects two adjacent 1D Mnギ/tbi2-chain by sharing the Mnギions resulting in a 1D double chain(Fig.3c).
Structural analysis indicates that complex 4 is a 1D chain structure and crystallizes in the monoclinic P21/c space group.The asymmetric unit of 4 is composed of one crystallographically independent Cdギion,half a btbb ligand,and one 3-Nitro-o-bdc2-ligand,a coordination water molecule and a free water molecule.As shown in Fig.4a,the Cdギion adopts a seven-coordinated environment,which is provided by two nitrogen atoms (N1,N2)from one btbb ligand,four oxygen atoms(O1,O2,O3#1,O4#1)from two 3-Nitro-o-bdc2-anions and one oxygen atom(O7)from a coordination water molecule.The Cd-O distances are in a range of 0.234 8(5)~0.256 8(7)nm,while the Cd-N1/N2 bond length are 0.234 5(6)/2.298(5)nm,separately.The ligand btbb shows the symmetric transconformation with thetorsion angle of 162.223°.The carboxylic groups of each 3-Nitro-obdc2-anion both adopt chelating bidentate coordination modes.By this way,two 3-Nitro-o-bdc2-anions bridge two adjacent Cdギions to form a 14-membered ring along c-axis (Fig.4b).Interestingly,the neighboring 14-membered rings are connected by the transconformational btbb ligands generating the 1D chain of 4(Fig.4c),with a Cd…Cd distance of 1.334 02 nm.
Fig.4 (a)Coordination environments of Cdギin complex 4;(b)View of 14-membered rings constructed by two 3-Nitro-o-bdc2-anions and two Cdギions along the c-axis;(c)1D chain structure containing 14-membered rings along the c-axis
Fig.5 (a)Perspective view of the coordination environment of Cdギ ion in 5;(b)1D chain constructed by Cdギions and tbi2-anions;(c)1D double chain of 5
Single crystal X-ray diffraction analysis shows that 5 crystallizes in the space group P21/c.As shown in Fig.5a,Cd1ギion adopts a distorted octahedral coordination environment,defined by four oxygen atoms(O1#1,O2#1,O3,O5)deriving from three different tbi2-anions and two nitrogen atoms(N1,N3)originating from one btbb ligand.The distances of Cd1-N1/N3 are 0.233 7(10)/0.240 9(9)nm,while the Cd1-O bond lengths range from 0.228 7(7)to 0.248 4(7)nm.It can be clearly seen that the Cd2ギion also sits in a distorted octahedral coordination geometry defined by four oxygen atoms(O4,O6,O7#2,O8#2)from three different tbi2-anions and two nitrogen atoms(N4,N6)from one btbb ligand.The distances of Cd2-N4/N6 are 0.231 1(11)/0.243 5(13)nm,while the Cd2-O bond lengths range from 0.224 7(7)to 0.253 9(7)nm.Interestingly,there are one kind of independent tbi2-,in which one carboxylate group adopts a bisdentate chelated coordination mode and the other adopts a bridging bidentate mode.The tbi2-anions connect two Cdギ ions resulting in a Cd2(OCO)2,and Cd…Cd distance is 0.403 32 nm.The dual-core Cd2(OCO)2units are further linked and extended by tbi2-anions leading to the production of a 1D Cdギ/tbi2-chain(Fig.5b).While the btbb ligand adopts asymmetrictransconformation with two differenttorsion angles of 78.334°and 43.989°,and the bridged Cd…Cd distances along μ-btbb are 1.099 83 nm.Finally,the Cd1ギ ion and Cd2ギ ion are connected by btbb to afford a 1D double chain taking on stairstep(Fig.5c).
In short,the synergistic effect of the btbb and various carboxylates to react with Znギ/Cdギ/Mnギions gains five different complexes.Complexes 1~5 exhibit captivating structural motifs.