Matsuoka Shin-ichi

Matsushima Kazuo

Ogawa Kanji

小川 莞爾

松岡 慎一

Kanazawa University Repository for Academic Resources

SCl. ]1，epロ H~anaZ:P.('iNa U niv~ ， VoL 25， No. 1， p. 23-29 June 1980 'fheαg;"tm Posi.tiαn 1'in(H) Phosphate 沿tiむKazuo Shin-ichi MATSUOKA 01 MaUer (良忠仁日ivedApril 30， 1980) Al:I自traet The crystal structure of SnI-IPO'i has b在enstudied by Xプrayand neutr・01diffraction inclependentl:¥人 Reーゼxaminationof th巴hydrogen position by mecms of pro':on and phospho[ 1'lM夜間condmoments show~: that measur巴dsecond rnoments， 1.80土0.03and 2.Vl土0.05in 10-s'P. for prolのnanCi phosphor resp己c:tively，ar日 VJe!luncl白rstoodby assuB1Ing 1inear O-II-{) bond. introrl紋c1tiGID1Tlw crystal structure of tin(H) F. 日日rndtand R Larnbergl) has bεen studiαA. diffraction and bv L. lN. Schroeder eli1d E. Pri日C日2)using n日utrondifIraction. there are sonle diおじ instructure.s det巴rminedby these authors and the fOrUlfT did not rnention the of the atom， both stEdies ha'l日 8ho;;河江1ι that the unit cel which oJntains four rnolecular units is monoc1inic， the space group isP2，!C' and ions aa 1inked together to form dirneric ←I2 ion a 01 bonds. of the contents of the unit cell determined Schroeder and Prince2) 18 illustrated. in Fig. 1. TVl!o 反enbonds in ，，~ach dimer are related bv an. inver:sion symm日try.N eutro.n diffraction shovved that the a.tom lies 。口 theline わん bondecIoxygeηatoms and the 3horteγO-H durtance in the bond is L011 玖lbile0ーの distance and OHO angle are 2.560 A and 178園r"'fCil confirnl thi.:-; S色ιor口ldlT口1ω叫nl羽1ε臼n吠tsof Knρuじclea釘Tm白2g邸netlcreSOlη]e[汎nιζ主1ε2 (口:N守叫Iv、 ei.bコf日:;orpμti仁01主 l日inesof proコ;tonand pl〆山 上七h可刊!OI口u心k伝f工USof thヲ児1，:;PO'N 口m司eas乱ur記d means or Fou:rier lranslormation 01 f日einduction 氏 ay (FT-FIDi 9(Y Th母 F'r-FIDmethod vvhich has bθen. use.din the resolution I'HviR Kanji OGAWA， Kaz1Jo MATSUSl-IMA乳ndShin-ichi MATSUOKA @ 。 。、幅ト4 G P 5n 。d、" L--'一一」一一」 ???下、ig.1. Projection diagraru8 of o" unit c日Iof S:1HPO，2) (a) Projection dovin the a-axis. (b) Proj告ctlon批判.1 the c-axiso The dashed Jin巴silustrate t:lεhyd:rogen honds. the line free frorn elny distortions inεvitabIe in a NlvlR. ResuJts of NIVrR 臼コeεbvassumln反alinear state slow sweep bond. lPnmedm"es solutiO!1 added to extra which were v出 hed distiHec1 water and then dried at 80'12 for 2 Vlere testεd diffraction固 P、在日33ureddi:fraction of 16 1ines among 30 resolved diffraction lines 'cil!ith the estimated from the structure factors The to of 5 mm diameter and 7 mrn vvas used in NMR measurements勾Second rnoments of proton and nucleus vvεre obtained t1e Hyarof!i仰向'sitioniηSnHH九 25 cosine Fourier transformed FID signal園 FHJsignals a homemade pulse operating at 24 M!-Iz were recorded 3n 8 bi.t transient recorder， Kawasald Electronica TR-161G， with sョrnplingrate of }μS i:!l1d 1024 points. data wete transferred to a microcomputer， TEAC PS-30， via PIO inlerface. This car・riedOU1: the signal-to-noise enhancement FlD's und正;rthe control of programs written in BASIC for 。rfast Fourier same C0Il10uter。N umel'icai treatments were carried out bv the Theご)taticfL::ld '¥ivas stabilized 1.印ll1Sof NMR field lock system rεson.ated to 子~a23 nudeus in NaBr solution， Long term st日 ofthe field b剖:terthan 1 ppm vvas effective to aCCll日lulationofmany thnes over・T，Jl r¥fMR meaS1J，fi;cments ')モreruade at rOOlT1. l印刷H掛川1d.Di自1~U仰い羽.Proton 7V1J;R i.1Ji Fig 2 is 8hov"n i:he FID of proton whichwas obtained ε3ubコt仕rac:tIl日Igthe 口19 じai日1due to pr固esencε Oi 1p;コ)1'句1ひoton，j Lc立1f'丹空sidualfr凶'(巴::e¥い戸川r日aゐCCl山司]'汀mlぷμ叫t一句CI2[，てID's， 1n 必 2) thi巴 inlual of th臼 F'I) signal ¥NlCi!Ich <'I，]la.s due to a finiteinstrumental recovery time町 about4μS， was completed the hutial of a half solici echo， The peak of tl1日 solidecho recovery time "Ni12， 0'11;3" and it wmo recorded uno'er the same conditions aιFID5's lJut a t (，5) (a) Fig， 2. (a)むつゎctedFID s'lgnal (se 日xtj日ndG) th号 c;.oEineFO'lf.rie~~ tr&l1sfonnεd FB) 31広:i:)l日i千Pl'oto口.夜、 Tcb告をiubx刀it己delse'¥Nhe:rも26 Kanji OGAWA， Kazuo MATSUSHIMA and Shin-ichi MATSUOKA 900-，90090・sequencewas used. The half solid echo (HSE) is given by P. MansfieW> as follows : HSE(t) = FID(t) + M2e'τ(t+す十M'4e1♂(t+r)+ M'4e2t(t+ず+M'4e3r(t+が+…... (1) where M22e is Van Vleck's second moment-like term and M'4ei (i=1，2，3) are fourth moment-like terms. In the present measurements，τis equal to 10μS and t issmaller than 24μS， while M'2e and M'4ei's are estimated to be of the order of 108 HZ2 and 10'5 HZ4 respectively. Little algebra shows that the initial portion of the FID agrees with the initial portion of the HSE. Measured proton second moment is (1.80:10.03) x 10-8T2 where 1 T=104 gau田.Estimated error was introduced by ambiguous choice of cut-off of the wing in the transformed FID. To check the validity of the present FT -FID method， proton second moment and width of maximum slopes of absorption spectrum were measured by a steady state frequency sweep NMR. The steady state measurement gives second moment of (1.8:1・0.1) X 1O-8T2 and width of maximum slopes of (3.8土0.4)x 1O-4T. The present FT -FID also gives width of maximum slopes of (3.90:10.03) x 1O-4T. The agreement is quite well. PhosρhorNMR Fig. 3 shows the phosphor FID signal obtained by accumulating 100 FID's over about 2 hours. In this case， the initial portion of FID signal was not corrected， because -5 ?? ??『? ??????，?，?5 。120 240 t(μS) (a) 360 480 Fig. 3. (a) FID signal and (b) the cosine Fourier transformed FID signal of phosphor. Hydrcgen Position i対 SnHl:JOへ 27 the instrumental recovery time was not a significant fraction of the FID， not as in the case. FT-FID the phosphor second 1日01ηlentof 土 X1O-8T 2 • Estimated errOTWaS introduced the samεreason as in the proton cas色。Second j!;foment Considemtio附To determine the positiol1， measu:red second moments of proton and nucleus are COlTlpar町1with on四四lculated locE'tions in of a1 other magentic nuclei. lt has been shovvn5) many that tlぽ atOlTlin 0-H -0 bond s上;ho仇rt臼e臼町rt出hanabout 2 帽.5日5A lies nearly on t出h巴 st討凶z詳}hl沈t1仙i仕n児eJ刊oi包n位1ιjnbonded oxyg む1口~l a主此ton丘1ιS，剛 Since observed bond ar日 2.5，0 t，l) 01' Z 固:560 1.2)， it!s reasonable to assume that the atoms. The second moment of n"，"'-'-'.C'" atorn lies on the lin色 joining1λVり bondedoxygen ヱブ:ZAUeNm :L， r i.k' ¥ (2) 1) :(l jN) where I isv{hidl 1:0 of the resonant runs (J;'Ier aH non -resonant nuclccu of 's， and tbe uther are lH， 31p， <ire u日ualoγ1日80and. :.l~)Srt account of a stochastic distribution of tin a口仁 in10-81'2 are Proton secondmoment : foJJo市曲目 secondmOment2， uf where Yj，l' s are in A. くムFJ2 = 89.54 ):; 2: t'ji'-U十6.52Jキたト0.882，2:"，〆Y.it，fI'-6 ~一向where j runs c"Ver four al んover.，Il ， andん O':;fersecond li1むrnentく，6，l-P> 14.G8 十0.83-6 -1-39.'("9 2:.i2 ，~f T .i I~r-6 wh日rほ JrUI18 0同 rfour nuclei in ??? ???? k 日raU phosphor nudei except J， Zlnd !z"-0τ河ra1 日andtin nuclei In actlI?J summaticns wer記 confinedup to iifth neare~;;t unit cciJs， Srn.aU (.:;，orrections due to G，uter nuclei ''lvere estirnωt杷dbv 円。ntinF'ig. 4: ShO><rVfS the calc¥Uatied sεcoηd rn，)ments of おxldVari()iJ.S h¥.i仁 nCIs1tlO18on th日assumedlinear目。 H-()bo口d. 'lhe NMR data areweH undl'.~rstood i:f the lati仁必 ofS，~:hroeder a，ld atom i03 located on the iinear bond iD th，:; in the 00nd i8 0.95土0.03A. Thi.s len:;<th is shortεr than the replJIt吃:dvalue oI UJl7 .A. Kanji OGAvVA， Kazuo !ViATSりSHIi¥I!Aand Shin-ichi MATSUOKA ?Q dらU?PROWi.1 o ~H dlstanc0'(.4) Fig. 4. Calcdatedτond moments of proton a円dphusphor nuc!日18for various J.ocations of tl1色 hydrogenatoms on the as呂umedO-H-O bonds in the c:rysはilin巴laticesof Berndt &nG l.，arnbergl} (Jas:b.ed 1ne8) 2J1d o:f Schroedeγ ;md Prince2) (solid Iines). ExpermentaI values obtained by th巴 presentNrv1R rneasurernents are ShO'Nn horizc.rit&l lin日 figり!res。For i:he Struct1じredetermined by Schroeder and PrlnC日， 2.21 X 10-8 T2 was calC1ユlatedfor the second moment. This value is much than the present mental value of 土 X10-ST2. Sincεthe second ¥TlOn1色ntof proton do尽snot il1crコeaseat temperature， th日pres.entE問。ndmoment is com，idered be the one of t1ぼ lattice.second moment is sensitive 1[0 the interval t削:V'leenthe nearest intεrval hetwθen two in a dimer is 2.531 A Schxoeder anc1 2.6n Ain the presεnt linear bond model. The determined Schroeder and Princε second moment oj' L76 x 1O-8'P固'I'hisvaiue is smaller than the preselYi value or (2，14こと)(1O-8T2o The interval between atorn and dimer i3 2.202 A bv Schroeder and while it 13 2園156A in the modeL It is conc1uded that careful1y mεasured second moments of criterion for the crvstai structure. ???????????? 、m a linear bond crystal present The authors express their sincerεthanks to Professor for dlffr吟actometerand toMr. S. Kawada for lending them the which V!aS U悶 din the Nl'v1R fieid lock system. are a180 T. rvJ[atsumoto for valuable discussions. them to Dr. to use Hア'drogenPosition in SnHPO 4 29 References 1) A. F. Berndt and R. Lamberg， Acta Cryst. B27 (1971) 1092. 2) L. W. Schroeder and E. Prince， Acta Cryst. B32 (1976) 3309. 3) R. R. Ernst and W. A. Anderson， Rev. Sci. Instr. 37 (1966) 93. 4) P. Mansfield， Phys. Rev. 137 (1965) A961. 5) A. F. Wells， Strucfurallnorganic Chemistη(Clarendon Press， Oxford， 1975) 4th edition， p.304. 6) C. P. Slichter， Principles 01 Magnetic Resonance (Springer Verlag， Berlin， 1978) 2nd Revised and Expanded Edition， p.62. 

The Hydrogen Position in Tin(II) Hydrogen Phosphate by Nuclear Magnetic Resonance

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The Hydrogen Position in Tin(II) Hydrogen Phosphate by Nuclear Magnetic Resonance

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