A dithiooxalato-bridged manganese(II)–nickel(II) one dimensional complex : synthesis, crystal structure and magnetic properties

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Pergamon PII ] S9166Ð4276"87#99908Ð8

Polyhedron Vol[ 06\ No[ 04\ pp[ 1406Ð1411\ 0887 Þ 0887 Elsevier Science Ltd All rights reserved[ Printed in Great Britain 9166Ð4276:87 ,08[99¦9[99

A dithiooxalato!bridged manganese"II#Ðnickel"II# one dimensional complex ] synthesis\ crystal structure and magnetic properties Jian!Zhong Cui\a Peng Cheng\a Dai!Zheng Liao\a Zong!Hui Jiang\a Shi!Ping Yan\a Geng!Lin Wanga and Xiao!Ying Huangb a b

Department of Chemistry\ Nankai University\ Tianjin\ 299960\ P[R[ China

State Key Laboratory of Structural Chemistry\ Fuzhou\ 249991\ P[R[ China "Received 09 November 0886 ^ accepted 5 January 0887#

Abstract*A dithiooxalato!bridged manganese"II#!nickel"II# bimetallic complex ] ðMnNi"C1O1S1#1"H1O#2Ł = 3H1O has been prepared and its crystal structure determined[ It consists of one!dimensional chains in which alternating Mn"II# and Ni"II# ions are bridged by C1O1S11− ligands[ The coordination environment is pentagonal bipyramidal for Mn"II# and square for Ni"II#[ The magnetic susceptibility of the complex in the range 0[4Ð299 K were _t by the axial zero _elds splitting e}ect[ That the experimental data depart from calculated values below 39 K may be due to the presence of a weak interchain antiferromagnetic interaction between the nearest Mn"II# ions and rhombic zero _eld splitting e}ect of the Mn"II# ions[ Þ 0887 Elsevier Science Ltd[ All rights reserved Keywords] dithiooxalato!bridged complex ^ one!dimensional chain complex ^ manganese complex ^ nickel complex ^ magnetism ———————————————————————————————————————————————

The synthesis and the study of polymetallic complexes\ including one!dimensional system\ has become one of the most active _elds since many homo! metallic binuclear complexes were widely studied[ The understanding of magnetic properties and the mag! neto!structural correlations in polymetallic complexes are of great importance[ Dithiooxalate is a special bridging ligand to obtain such polymetallic com! plexes[ This asymmetric ligand permits choosing coor! dinating atoms according to the nature of the metal ions[ The {{hard|| metal ions are coordinated with the {{hard|| oxygen atom of dithiooxalate\ and the {{soft|| metal ions with the {{soft|| sulfur atoms[ From this point of view\ dithiooxalate has a rich coordination chemistry with transition metal and rare earth ions ð0Ł[ However\ it is more di.cult to study the dithioox! alato!bridged polymetallic complexes due to the less stabile dithiooxalate and its complexes[ NiZn"S1C1O1#1"H1O#1[97 ð1Ł was described as an in_nite  Author to whom correspondence should be addressed[

parallel straight chain\ in which Ni\ Zn and dithioox! alate groups form planar ribbons\ the coordination of all Zn atoms and a few Ni atoms being octahedral completed with water molecules\ the molar magnetic moment me}  0[91 cm2 mol−0[ The complexes\ AMn"C1O1S1#1"H1O#2 = 3[4 H1O "A  Cu\ Ni\ Pd\ Pt# ð2\ 3Ł crystallize in monoclinic system ^ the crystal structure of the nickel complex was well solved under uncompleted data collection since crystal {{died out[|| In this paper\ we report a dithiooxalato!bridged manganese"II# and nickel"II# one!dimensional com! plex ðMnNi"C1O1S1#1"H1O#2Ł = 3H1O\ which is di}erent from the Ref[ 3\ it crystallizes in the orthorhombic system\ space group Ibca "(62#\ and has less crystal water molecules[ It is stable for crystal data collection and the structure was solved in a very good agreement factor "9[918#[ The magnetic susceptibilities of the complex in the range 0[4Ð299 K were _t by the axial zero _elds splitting e}ect ð4Ł\ giving the `  1[94 and D  0[91 cm−0[ That the experimental data depart from calculated values in low temperature area may be due to the presence of a weak interchains anti!

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J[!Z[ Cui et al[

ferromagnetic interaction between the nearest Mn"II# ions and rhombic zero _eld splitting e}ect of the Mn"II# ions[ EXPERIMENTAL Materials K1C1S1O1 was prepared according to the literature method ð5Ł[ Nickel nitrate hydrates and 49) aqueous solution of Mn"NO2#1 were reagent grade[

Synthesis of ðMnNi"C1O1S1#1"H1O#2Ł = 3H1O To an aqueous solution of K1C1S1O1\ solutions of Mn"NO2#1 and Ni"NO2#1 were added in aqueous! ethanol in a Mn"NO2#1 ] Ni"NO2#1 ] K1C1O1S1 molar ratio of 0 ] 0 ] 1[ The mixed solution was stirred for a few minutes\ then _ltered[ The _ltrate was stood for a week to evaporate solvent[ Black microcrystals obtained were recrystallized in ethanol!water solution[ Crystals obtained were suitable for X!ray analysis[ Elemental analyses found ] C\ 09[21 ^ H\ 1[82 ^ S\ 15[88 ^ Mn\ 00[24 ^ Ni\ 01[19[ Calcd for C3H03O00S3MnNi ] C\ 09[90 ^ H\ 1[83 ^ S\ 15[61 ^ Mn\ 00[34 ^ Ni\ 01[12)[

Physical measurements Elemental analyses of carbon\ hydrogen and sulfur were carried out on a PerkinÐElmer analyzer\ model 139C[ Metal contents were determined by EDTA titration[ Density of the complex was determined by using the ~otation method "carbontetrachloride and 0\2!dibromopropane#[ Magnetic susceptibility measurements of crystal samples were carried out in the temperature range of 0[4Ð299 K on an extracting sample magnetometer\ model CF!0[ The experimental susceptibilities were corrected by Pascal|s constants for the diamagnetism of the constituent atoms[

Crystallo`raphic data collection and structure deter! mination

Table 0[ Crystallographic data and data!collection par! ameters for the compound Empirical formula Formula weight Crystal system Space group a "_# b "_# c "_# V "_2# Z Dc "Mg m−2# Dm "Mg m−2# h\ k\ l Limits F"999# No[ variables Largest shift:e[s[d[ in _nal cycle Ra Rb Goodness of _tc

C3H03MnNiO00S3 379[92 Orthorhombic Ibca "No[ 62# 6[915"0# 19[610"2# 11[159"1# 2139[8"6# 7 0[856 0[86 9 to 7\ −14 to 9\ 9 to 16 0833 86 9[31 9[918 9[939 0[09

a

S>Fo=−=Fc>:S=Fo=[ ðS"w=Fo=−=Fc=#1:Sw=Fo=1Ł0:1 ^ w  0:"s1"F#¦88[9999F1[ c ðSw"=Fo−Fc=#1:"Nobs−Npara#Ł0:1[ b

nique was employed\ the v!scan width equal to "9[49¦9[24 tanu#>\ and the scan speed 9[81Ð4[38> min−0[ A total of 0716 independent re~ections was measured giving 0156 observed re~ections "I × 2s"I## used in the re_nement[ Three standard re~ections monitored every 59 min showed no intensity variation during the data collection[ No absorption correction was made during processing[ The structure was solved by direct method "MUL! TAN 71# using SDP!PLUS program ð6Ł and re_ned by the full!matrix least!squares method using the SHELXL!82 package of program[ Atomic scattering factors were taken from Ref[ 7[ The _nal R and R? values were 9[918 and 9[939\ respectively[ All cal! culations were performed on a MICRO!VAX2099 computer[ Atom coordinates and equivalent isotropic displacement coe.cients are listed in Table 1[ Selected interatomic bond distances and bond angles are given in Table 2[ The molecular structure is shown in Fig[ 0[ RESULTS AND DISCUSSION

A black crystal with dimensions 9[07×9[07×9[964 mm2 was mounted on a glass _ber in a random orien! tation[ The determination of the unit cell and data collection were performed on a computer!controlled Enraf!Nonius CAD3 di}ractometer with a graphite! monochromatized MoÐKa radiation "9[60962 _#[ Lat! tice parameters were calculated by a least!squares re_nement based on the setting angles of 14 re~ections with u angles ranging from 02 to 03[89> at 185 K[ Lattice dimensions and additional crystal data are listed in Table 0[ The intensities of the 2hkl re~ections were measured up to umax  15> ^ the v!1u scan tech!

Description of the crystal structure The complex crystallizes in the orthorhombic system\ space group Ibca "62#\ with a  6[915"0# _\ b  19[610"2# _\ c  11[159"1# _\ and z  7[ The structure consists of chains in which alternating Mn"II# and Ni entities are bridged by dithiooxalate ligands\ oxygen atoms and sulfur atoms of bridged! dithiooxalate are coordinate to Mn"II# and Ni"II# respectively\ as shown in Fig[ 0[ The Mn coordination environment is a bipentagonal pyramidal with four

A dithiooxalato!bridged Mn"II#!Ni"II# complex

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Table 1[ Atom coordinates "_# and B"eq# of the complex atom Ni Mn S"0# S"1# O"0# O"1# O"2# O"3# C"0# C"1# O"4# O"5# H"0# H"1# H"2# H"3# H"4# H"5# H"6#

x 9[23193"09# 0:3 9[23319"05# 9[22559"03# 9[2077"3# 9[2946"2# 0:3 −9[9333"3# 9[2145"4# 9[2199"4# 9[1675"4# 9[0818"04# 9[1437 −9[0937 −9[9701 9[2395 9[0252 9[1968 9[0693

y

z

9 9[09472"2# 9[98651"3# −9[93162"3# 9[02238"00# 9[90439"00# 9[19801"05# 9[09309"00# 9[97731"05# 9[91946"05# 9[29572"04# 9[1377"3# 9[1217 9[0211 9[9645 9[1789 9[1785 9[1181 9[1803

0:3 9 9[10263"3# 9[05957"2# 9[09066"09# 9[94652"8# 9 9[91059"01# 9[02700"03# 9[00182"02# 9[97283"04# 9[0829"2# 9[9175 9[9286 9[9292 9[0060 9[9880 9[0328 9[1937

B"eq# 1[30"2# 1[03"2# 2[05"3# 1[52"3# 2[9"0# 1[6"0# 3[9"1# 2[1"0# 1[2"0# 1[1"0# 4[2"1# 12[1"6# 4[2 5[5 5[9 5[3 5[3 12[9 12[9

Table 2[ Selected interatomic bond distances "_# and angles "># Ni0S"0# Ni0S"1# Mn0O"0# Mn0O"1# Mn0O"2# Mn0O"3#

1[0679"8# 1[0656"7# 1[275"1# 1[294"1# 1[039"2# 1[013"2#

S"1#0Ni0S"1# S"1#0Ni0S"0# S"1#0Ni0S"0# S"0#0Ni0S"0# O"3#0Mn0O"3# O"3#0Mn0O"2# O"3#0Mn0O"1# O"3#0Mn0O"1# O"3#0Mn0O"0# O"3#0Mn0O"0# O"2#0Mn0O"1# O"2#0Mn0O"0# O"1#0Mn0O"1#

066[88"6# 81[14"2# 76[65"2# 068[19"7# 067[0"0# 89[86"6# 76[9"0# 80[36"8# 78[1"0# 80[1"0# 033[39"5# 65[00"5# 60[1"0#

oxygen atoms of two dithiooxalates and one oxygen atom of water in basal plane\ and two oxygen atoms of water occupying the axial positions[ Ni"II# was coordinated with four sulfur atoms of two dithiox! alates in planar square[ The Mn"II# and Ni"II# ion are almost lying in its coordination basal plane "see Fig[ 1#[ Dihedral angles between the basal plane of manga! nese"II# ion and coordination planes of nickel"II# ions are 09[80> and 04[86>[ The chain arrangement within the lattice cell is shown in Fig[ 1[ The shortest inter!

S"0#0C"0# S"1#0C"1# O"0#0C"0# O"1#0C"1# C"0#0C"1#

0[588"2# 0[581"2# 0[126"3# 0[139"3# 0[403"4#

O"1#0Mn0O"0# O"1#0Mn0O"0# O"0#0Mn0O"0# C"0#0S"0#0Ni C"1#0S"1#0Ni C"0#0O"0#0Mn C"1#0O"1#0Mn O"0#0C"0#0C"1# C"0#0C"0#0S"0# C"1#0C"0#0S"0# O"1#0C"1#0C"0# O"1#0C"1#0S"1# C"0#0C"1#0S"1#

028[29"7# 57[33"7# 041[1"0# 094[1"0# 094[0"0# 005[5"1# 008[7"1# 006[2"2# 013[4"2# 007[1"1# 005[6"2# 013[1"2# 008[9"1#

chain separations are 5[9056 _ for Mn = = = Ni\ and 01[922 _ for Mn = = = Mn within chain and 4[508 _ for Mn = = = Mn between chains along the c and a direc! tions\ respectively[

Ma`netic properties The magnetic behavior of the compound is rep! −0 resented in Fig[ 2 in the forms of xm vs T and xm vs

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Fig[ 0[ The ORTEP drawing of ðMnNi"C1O1S1#1"H1O#2Ł = 3H1O\ showing thermal ellipsoids drawn at the 29) probability level[

Fig[ 1[ View of the crystal cell of the compound[

T\ and in Fig[ 3 in the form of xmT vs T[ At room temperature\ the xmT value is 3[44 cm2 mol−0 K\ close to expected value for isolated S  4:1 spins for manganese"II# and S  9 for square coordinated nick! el"II# "3[27 cm2 mol−0 K#[ When the temperature is lowered\ xmT remains constant until 19 K and then decreases sharply to 0[84 cm2 mol−0 K at 2[8 K[ The

−0 plot of xm vs T gives a Curie constant\ C  3[48 cm2 −0 mol K\ and the CurieÐWeiss constant u of −2[17 K[ These results suggest the operation of an interchain antiferromagnetic interaction between the nearest Mn"II# ions and the presence of the zero _elds splitting e}ect of the single Mn"II# ions[ We attempted to interpret the magnetic properties

A dithiooxalato!bridged Mn"II#!Ni"II# complex

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Fig[ 2[ Plots of xm "# vs T and x−0 m "žžžžžž# vs T for ðMnNi"C1O1S1#1"H1O#2Ł = 3H1O[

Fig[ 3[ Plots of xmT vs T and for ðMnNi"C1O1S1#1"H1O#2Ł = 3H1O ^ circles "# represent experimental data\ solid line "**# represents the theoretical values based on the eqn "0#[

employing the axial zero!_eld splitting e}ect within the S  4:1 local ground states of the Mn"II# ions[ The theoretical expression of xzfs ð4Ł is then xzfs 

N`1b1 0¦8 exp "1x#¦14 exp "5x# 3kT 0¦exp "1x#¦exp "5x#

$

%

"0#

where x  D:kT\ D is the axial zero!_eld splitting parameter for Mn"II# ions[ Least!squares _tting gave rise to `  1[94 and D  0[91 cm−0\ and the agreement calcd 1 factor F\ de_ned as F  S"xobs # :S"xobs i −xi i #\ is

equal to 0[64×09−2 for all of the 89 observations "see Fig[ 3#[ Derivation of the calculated value from the experimental data below 39 K may be due to the presence of a weak interchain antiferromagnetic inter! action between the nearest Mn"II# ions and rhombic zero _eld splitting e}ect of Mn"II# ions[ Acknowled`ment*This work was supported by the National Natural Science Foundation of China\ State Key Laboratory of Structural Chemistry and a Doctoral Special Grant of Chinese University[

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J[!Z[ Cui et al[ REFERENCES

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