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1.
Complex of podand 1,2-bis(2-(o-hydroxyphenoxy)ethyloxy)ethane (L) with potassium thiocyanate, [K2(NCS)2L2] (I) was synthesized and studied using X-ray diffraction analysis: space group P , a = 7.771 Å, b = 11.711 Å, c = 11.965 Å, = 72.22°, = 79.21°, = 89.07°, Z = 1. Structure I was solved by direct method and anisotropically refined by the full-matrix least-squares method to R = 0.040 for all 4370 independent reflections (CAD4 autodiffractometer, MoK ). Structure I contains [K(NCS)L] monomers of the host–guest type united into centrosymmetrical [K2(NCS)2L2] dimers via two bridging OH groups (one group from two L podands). In the monomer, the L podand appears as though to envelope the octacoordinated K+ cation, whose the coordination polyhedron is a strongly distorted hexagonal bipyramid with all six oxygen atoms of the L podand in its base and the N atom of the SCN ligand and the O atom of one of OH group of the neighboring (in dimer) L podand at its axial vertices. Molecules of I in crystal are joined through the O–H···N hydrogen bonds to form broad infinite chains along the x-axis.  相似文献   

2.
The aqua complex of podand 1,2-bis(2-(o-hydroxyphenoxy)ethyloxy)ethane (L) with strontium thiocyanate of the composition [Sr(NCS)L(H2O)2]+ · SCN (I), was synthesized and studied by X-ray diffraction analysis: space group P 21/c, a = 17.730 Å, b = 8.558 Å, c = 18.169 Å, = 116.15°, Z = 4. The structure was solved by direct method and anisotropically refined by the full-matrix least-squares method to R = 0.039 for 4333 independent reflections (CAD4 autodiffractometer, MoK ). Structure I contains complex cation [Sr(NCS)L(H2O)2]+ of the host–guest type. The coordination polyhedron of Sr2+ cation (coordination number 9) is a distorted pentagonal bipyramid with four oxygen atoms at the benzene rings of the L podand and the oxygen atom of one water molecule in its base, the N atom of the SCN ligand at its single vertex, and with the remaining two O atoms of the L podand and O atom of another water molecule at a triple vertex. In a crystal, the complex cations and SCN anions are joined through the hydrogen bonds to form bulky layers parallel to the xy plane.  相似文献   

3.
(2.2.2-Cryptand)lithium perchlorate [Li(2.2.2-Crypt)]+ClO 4 (I) is prepared and characterized by X-ray structural analysis. Structure I (space group P21212, a = 10.149 Å, b = 13.475 Å, c = 8.580 Å, Z = 2) is solved by the direct method and refined anisotropically by the full-matrix least-squares method to R = 0.056 for 2312 reflections (CAD4 automated diffractometer, MoK ). Crystal of complex I is built of [Li(2.2.2-Crypt)]+ complex cations of the host–guest type and randomly disordered ClO 4 anions. Both ions are located on the twofold crystallographic axes. The Li+ cation, which is also randomly disordered about the 2 axis, is coordinated by the N atom and five O atoms from eight heteroatoms (2N + 6O) of the cryptand. Two Li–O and one Li–N bonds are noticeably elongated. The Li+ cation forms irregular six-vertex coordination polyhedron.  相似文献   

4.
Absract—Diaqua(2.2.2-Cryptand)strontium dichloride trihydrate [Sr(2.2.2-Crypt)(H2O)2]2+ · 2Cl · 3H2O (I) was prepared and studied by X-ray diffraction. The triclinic structure of I (space group P , a = 9.152 Å, b = 10.140 Å, c = 15.219 Å, = 88.84°, = 88.19°, = 87.62°, Z = 2) was solved by the direct method and refined by full-matrix least-squares calculations in the anisotropic approximation to R = 0.050 for 4188 independent reflections (CAD4 automated diffractometer, CuK radiation). The structure contains the [Sr(2.2.2-Crypt)(H2O)2]2+ host–guest cation. The Sr2+ cation resides in the 2.2.2-cryptand cavity and is coordinated by all eight heteroatoms (6O + 2N) of the cryptand ligand and by two O atoms of water molecules. The Sr2+ coordination polyhedron (C.N. 10) is a highly distorted dibase-centered two-cap trigonal prism. The crystal structure of I contains a branched system of ion–ion (intermolecular) hydrogen bonds O(w)–H···Cl, which connect the complex cations, the Cl anions, and the crystal water molecules to form infinite thick layers parallel to the yz plane.  相似文献   

5.
Palladium clusters Pd4(SEt)4(OAc)4(I) and Pd6(SEt)12(II) were synthesized and studied. Their structure was determined by X-ray diffraction analysis. For I, a= 9.774(2) Å, b= 10.821(2) Å, c= 13.061(3) Å, = 92.88(3)°, V= 1379.6(5) Å3, (calcd.) = 2.182 g/cm3, space group P21/n, Z= 4, N ref= 1558, and R= 0.031; for II, a= 10.581(1) Å, b= 10.584(2) Å, c= 11.478(2) Å, = 101.62(1)°, = 104.95(1)°, = 106.74(1)°, V= 1135.2(4) Å3, (calcd) = 2.007 g/cm3, space group P1, Z= 1, N ref= 2828, and R= 0.022. In cluster I, four Pd atoms form a planar cycle. The neighboring palladium atoms are bound by two acetate or by two mercaptide bridges, the Pd···Pd distances being 3.036–3.195 Å. In cluster II, Pd atoms form a planar six-membered cycle with Pd···Pd distances of 3.083–3.127 Å. The neighboring palladium atoms are bound by two mercaptide bridges. The formation of analogous clusters in solution was confirmed by IR spectroscopy.  相似文献   

6.
Twinned and disordered crystals of solvated bis[aqua(2.2.2-cryptand)calcium] hexa(isothiocyanato)calcium 2[Ca(2.2.2-Crypt)(H2O)]2+ · [Ca(NCS)6]4– · Sol (I), where Sol is acetone and/or ethanol and may be water, were synthesized and studied by X-ray diffraction analysis. Structure I (space group P21/n, a = 11.841 Å, b = 21.787 Å, c = 12.377 Å, = 90.90°) was solved by the direct method and refined by the full-matrix least squares method in anisotropic approximation to R = 0.079 from 4168 independent reflections (CAD4 automated diffractometer, MoK ). In crystal form, complex I exists as the two aforesaid complex ions [I1]2+ and [I2]4– in the molar ratio 2 : 1 united through hydrogen bonds. Complex cation I1 is of the guest–host type. Its Ca2+ cation is coordinated by all eight heteroatoms (6O + 2N) of the cryptand ligand and by the O atom of the water molecule; the coordination polyhedron of this Ca2+ cation (CN 9) is irregular. The Ca2+ cation of complex anion I2 (in the crystallographic center of inversion) is coordinated by six N atoms of six neighboring SCN anionic ligands; the coordination polyhedron of this Ca2+ cation (CN 6) is a slightly distorted octahedron.  相似文献   

7.
The salt tetrakis(isothiocyanato)zinc(II) 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane, [H2(Crypt-222)]2+ · [Zn(NCS)4]2– (I), was synthesized and its structure was determined using X-ray diffraction analysis: space group P21/n, a = 13.734 Å, b = 11.627 Å, c = 20.816 Å, = 91.51°, Z = 4. The structure was solved by direct methods and anisotropically refined by the full-matrix least-squares method to R =0.093 for 4920 independent reflections (CAD4 autodiffractometer, CuK radiation). The structural units of crystal I are 2.2.2-cryptand dications (with two protonated nitrogen atoms) and complex anions [Zn(NCS)4]2–. The coordination polyhedron of the Zn2+ cation is a distorted tetrahedron. The 2.2.2-cryptand dication contains trifurcate N–H(...O)3 hydrogen bonds.  相似文献   

8.
Crystal structures of [Co(MH)2(Thio)2][BF4] · H2O (I) and [Co(DH)2(NH3)2][BF4] (II), where MH is H3C–C(NOH)–C(NO)–H and DH is H3C–C(NOH)–C(NO)–CH3, were determined by X-ray diffraction. The crystals are monoclinic, space group C2/c, unit cell parameters (for I and II, respectively): a = 22.018(2) Å, b = 7.943(1) Å, c = 11.681(1) Å, = 92.68(1)° and a = 21.436(2) Å, b = 6.400(2) Å, c = 12.389(2) Å, = 113.13(1)°. In both cases, the Co(III) coordination polyhedron is a centrosymmetrical trans-octahedron, N4S2 for I and N6 for II. In the crystals of I and II, the complex cations and the outer-sphere [BF4] anions (and the crystal water molecules in I) form elaborate hydrogen bonding system.  相似文献   

9.
The crystals of N-allylisoquinolinium chlorides of the compositions [C9H7N(C3H5)]2CuIICl4 (I), [C9H7N(C3H5)]CuICl2 · H2O (II), and [C9H7N(C3H5)]CuICl1.43Br0.57 · H2O (III) were prepared by alternating-current electrosynthesis. X-ray diffraction analysis (using diffractometer models DARCH1 for I, STOE for II, and KUMA/CCD for III, MoK radiation) showed that the crystals of I are monoclinic, space group P21/n, a = 14.91(1) Å, b = 10.41(1) Å, c = 16.90(1) Å, = 109.73(8)°, V = 2470(8) Å3, Z = 4. The crystals of isostructural compounds II and III are triclinic, space group P, Z = 2; crystals II: a = 7.2446(6) Å, b = 7.4379(6) Å, c = 12.110(1) Å, = 80.95(1)°, = 85.55(1)°, = 86.60(1)°, V = 641.8(2) Å3; crystals III: a = 7.253(2) Å, b = 7.459(4) Å, c = 12.151(5) Å, = 80.82(4)°, = 83.73(3)°, = 86.81(4)°, V = 644.6(9) Å3. The structure of I is composed of CuIICl4 2– tetrahedra and N-allylisoquinolinium cations united by C–H···Cl hydrogen bonds in corrugated layers. The crystal structures of -complexesII and III are built of [C9H7(C3H5)]2Cu2 IX4 dimers, which form layers along the c axis due to the C–H···X hydrogen bonds. An important role in the structure formation is played by water molecules, which crosslink the organometallic layers to form a three-dimensional framework through the O–H···X contacts.  相似文献   

10.
Crystalline bis(dibenzo-18-crown-6)rubidium triiodide complex [Rb(DB18C6)2]+ · I3 (I) is synthesized and its structure is studied by X-ray diffraction analysis. The structure of I (space group Pnma, a = 23.854 Å, b = 23.612 Å, c = 7.863 Å, Z = 4) is solved by the direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.079 against 3990 independent reflections (CAD4 automated diffractometer, MoK ). Structural units of crystal I are the I3 anions and [Rb(DB18C6)2]+ cations. The crystal has the structure intermediate between that of a standard host–guest complex and a sandwich complex. In the structure of complex I, the crystallographic plane with symmetry m passes through the I3 anion (perpendicularly to its axis) and complex cation. The coordination polyhedron of the Rb+ cation is a strongly distorted hexagonal pyramid with the O atom of one crown ligand at the axial vertex and a base of six O atoms of another DB18C6 crown ligand.  相似文献   

11.
Paramagnetic copper(II) complexes with N-(3-hydroximino-2-methylbutan-2-yl)methylamine (HL), namely, Cu(HL)Cl2(I), Cu(HL)(SO4) · 2H2O (II), and Cu(HL)(NO3)2(III), were obtained. The crystal structures of I and II were determined. The blue crystals of these compounds are monoclinic. For I(C6H14Cl2CuN2O): a = 8.820(1) Å, b = 6.511(1) Å, c = 18.255(2) Å, = 92.86(1)° V = 1047.0(2) Å3, space group P21/c, calcd = 1.679 g/cm3, Z = 4 for R 1 = 0.0250; for II(C6H18CuN2O7S): a = 9.999(2) Å, b = 9.927(2) Å, c = 12.963(3) Å, = 106.37(3)°, V = 1234.5(4) Å3, space group P21/c, calcd = 1.753 g/cm3, Z = 4 for R 1 = 0.0324. Crystals of I have a molecular structure. The Cu coordination polyhedron is a square bipyramid (2N + 2Cl + Cl + Cl) due to additional contacts with two Cl atoms from the neighboring molecules. Structure II is built from polymeric chains. The environment of the Cu atom is a distorted cis-octahedron (2N + 2O(H2O) + 2O(SO4)). Complexes IIIIare characterized by IR and EPR spectroscopy.  相似文献   

12.
A new copper carboxylate polymer with cyanoacetate anion as a ligand was synthesized and studied using X-ray diffraction, IR, and EPR spectroscopy. The crystal is tetragonal: a= 14.702(2) Å, c= 13.470(3) Å, Z= 8, space group I41/a, and R= 0.0634. The copper atoms in the centrosymmetric dimeric fragment have a square-pyramidal surrounding with the CuO4N coordination core and are joined through four bidentate bridging anions of cyanoacetic acid Cu(1)"–O(1A) 1.931(4) Å, Cu(1)"–O(1B) 1.926(4) Å, Cu(1)–O(2B) 2.018(3) Å, Cu(1)–O(2A) 2.036(4) Å, and Cu(1)–N(1A)" 2.206(5) Å). The Cu···Cu" distance in the dimer is 2.709 Å. The copper atom is extended from the mean equatorial plane toward the axial nitrogen atom by 0.23 Å. EPR data confirm strong antiferromagnetic interaction (2J –275 cm–1) between the copper(II) ions of the dimeric fragment, whereas the interaction between the dimers is significantly weaker (J< 0.3 cm–1).  相似文献   

13.
Crystals of anionic complexes of the composition M[CuCl2(HOCH2CCCH2OH)], where M = NH4 + (I), K+ (II), were isolated from concentrated aqueous solutions of CuCl and MCl (M = NH4 +, K+) in the presence of 2-butyne-1,4-diol. Their structures were studied by X-ray diffraction analysis. Isostructural crystals I and II are orthorhombic; Z = 8, space group Ibam; a = 6.735(1) and 6.666(2) Å, b = 17.206(3) and 16.874(6) Å, c = 15.172(3) and 15.032(4) Å, V = 1758(1) and 1691(1) Å3, respectively. The compounds are built of individual [CuCl2(HOCH2CCCH2OH)] anions; the NH4 + (I) or K+ (II) cations are arranged in the voids between the anions. The -coordinated Cu(I) atoms have trigonal-planar environment of two chlorine atoms and CC bond of the 2-butyne-1,4-diol molecule. The Cu–(CC) distances in the -core are 1.892(4) and 1.887(6) Å, CC are 1.233(5) and 1.228(5) Å in I and II, respectively. In complex I, additional hydrogen bonds Cl···H–NH3 (Cl···H 2.43(4) Å) and O···H–NH3 (O···H 1.97(3) Å) stabilize the structure.  相似文献   

14.
A new coordination compound [Co(Pht)(2-MeIm)2] (I), where Pht2–is the deprotonated radical of o-phthalic acid (H2Pht) and 2-MeIm is 2-methylimidazole, was synthesized. Its structure was established using X-ray diffraction analysis. The crystal is orthorhombic: space group Pca21, a= 15.350(3), b= 7.957(2), c= 13.997(3) Å, (calcd.) = 1.505 g/cm3, and Z= 4. The tetrahedral coordination of the Co(II) atom includes two N atoms of two 2-methylimidazole molecules and two oxygen atoms of two carboxyl groups from different acid radicals. The Co–N distances are equal to 2.022(2) and 2.031(2) Å, while the Co–O distances are 1.972(2) and 2.000(2) Å. The carboxyl groups of the Pht2–radical and the aromatic nucleus form angles of 47.2° and 35.9°, whereas the angle formed by the carboxyl groups themselves is 50.3°. Compound Iis a polymer, which is confirmed by the 1,6-bridging function of the o-phthalic acid radical. The Co···Co distance in a chain is equal to 7.367 Å. Separate chains are united in the crystal into a framework via N–H···O hydrogen bonds.  相似文献   

15.
The crystal adduct (1 :1) 4,7,13,16,21,24-hexaoxa-1,10-diazoniabicyclo[8.8.8]hexacosane triaquachlorolithium dichloride, [H2(Crypt-222)]2+ · 2Cl · [LiCl(H2O)3] (I), was synthesized and studied using X-ray diffraction analysis. Structure I (space group R3, a = 7.922 Å, c = 37.207 Å, Z = 3) was solved by direct methods and anisotropically refined by the full-matrix least-squares method to R = 0.034 for 1363 independent reflections (CAD4 autodiffractometer, MoK ). Crystal I consists of disordered 2.2.2-cryptand dications, chloride anions, and tetrahedral [LiCl(H2O)3] complexes. All of them lie on threefold axes. There are tridentate +N–H (···O)3 hydrogen bonds in the [H2(Crypt-222)]2+ dication. The crystal structure of adduct I contains a complex interionic hydrogen bonding system.  相似文献   

16.
The crystal and molecular structure of bis(O,O"-diisopropyldithiophosphato-S,S")(dimethylglyoximato-N,N")rhodium(III) (I) was studied using X-ray diffraction analysis: space group P21/c, a = 13.644 Å, b = 10.350 Å, c = 20.906 Å, = 109.02°, Z = 4. The structure was solved by the direct method and anisotropically refined by the full-matrix least-squares method to R = 0.029 using 5447 independent reflections (CAD-4 autodiffractometer, MoK ). Compound I is a mononuclear tris-chelate complex whose three ligands are singly charge anions. The individual molecule of the complex has a noncrystallographic two-fold axis; its Rh atom is coordinated by four S atoms and two N atoms, forming a distorted octahedron. The average coordination bond lengths are Rh–S 2.402 and Rh–N 2.023 Å. The molecules in structureI are joined into infinite chains via weak intramolecular C–H···S hydrogen bonds and intermolecular N–O–H···O–N hydrogen bonds.  相似文献   

17.
The processes of complexation and solvation in the Tb(ClO4)3 · nH2O –adamantylideneadamantane-1,2-dioxetane (I)–benzophenone (II) system in acetonitrile solutions were studied at 280–320 K. The complexation of Tb(ClO4)3 · nH2O in ground and electronically excited states with I and II was found out. An anomalous increase in the lifetime of Tb(ClO4)* 3 · nH2O with temperature was observed; this anomalous increase is indicative of a structural change in the environment of the terbium ion in solution. It was found that of Tb(III)* increased because of rearrangement of the inner sphere of solvation aqua complexes toward the replacement of H2O molecules by solvent molecules that exhibit a lower quenching ability.  相似文献   

18.
The crystal structure of thallium fluoroantimonate(III) complex TlSb4F13 (I), which is isostructural to KSb4F13 (II), is determined. Crystals I are tetragonal: a = 9.634(2) Å, c = 6.590(2) Å, V = 611.7(2) Å3, Z = 2, (calcd) = 5.094 g/cm3, F(000) = 804.0, space group I4¯. The structure consists of tetrameric [Sb4F13] anions formed by SbF3 groups connected by the fluoride ion and the l+ cations.  相似文献   

19.
Two novel heterometallic cubane-like and double cubane-like clusters, {MoCu3S3(S2COEt)}(O)(Ph3P)3 I and {Mo2Cu6S6(SCMe3)2}(O)2(Ph3P)4 II, were synthesized by reaction of {MoCu2S3}(O)(Ph3P)3 with CuS2COEt and CuSCMe3, respectively. ClusterI crystallized in the triclinic space group (2) witha=12.766(6) Å,b=22.904(5) Å,c=10.522(3) Å, =99.86(2)°, =109.68(2)°, =86.84(3)°,V=2854(2) Å3,Z=2,R=0.049 for 6622 observed reflections (I>5(I)) and 410 variables. ClusterII crystallized in the triclinic space group (2) with dimensionsa=14.212(4) Å,b=14.725(5) Å,c=12.396(8) Å, =110.32(4)°, =90.40(5)°, =62.88(2)°,V=2129(2) Å3,Z=1,R=0.039 for 6020 observed reflections (I>3(I)) and 461 variables. ClusterI consists of a neutral cubane-like molecule with the core {MoCu3S3(S2COEt)}2+, in which one corner of the cubane-like core is a novel triply bridging bidentate 1,1-dithiolato (xanthate, S2COEt) ligand. ClusterII is a double cubane-like one, in which two cubane-like cores {MoCu3S3(SCMe3)}2+ are connected by two Cu-S bonds of the triply bridging monothiolato (SCMe 3 ) ligand. Two different pathways of unit construction from a small heterometallic cluster {MoCu2S3}(O)(Ph3P)3 have been outlined. Comparisons of the selected bond lengths and bond angles for the cubane-like core {MoCu3S3 X} (X=Cl, Br, S2COEt, SCMe 3 ) are given. Spectroscopic properties of the title clusters are also reported.  相似文献   

20.
A new complex, hexadimethylsulfoxidenickel(II) tetraisothiocyanatozincate [Ni(DMSO)6][Zn(NCS)4](I), is synthesized. Its crystal structure is determined by X-ray diffraction analysis. Compound I forms light green, monoclinic crystals shaped like plates: a = 8.4358(8) Å ,b = 21.655(2) Å, c = 10.8351(8) Å = 105.162(7)°, V = 1910.4(3) Å3, space group P21/m, Z = 2, (calcd) = 1.434 g/cm 3 , µ= 1.699mm –1. The Zn atom has a tetrahedral environment, while the Ni atom has an octahedral environment.Translated from Koordinatsionnaya Khimiya, Vol. 30, No. 12, 2004, pp. 939–942.Original Russian Text Copyright © 2004 by Cherkasova, Tsalko.  相似文献   

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