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DIFFRACTION STUDIES OF

HYDRAZINIUM COMPOUNDS

J

..by

'.-'MARTIN ROUSSELANGE ANDERSON, B.Sc.,

..

.b

{.

Submitted to. the Faculty. of GraduatE;! St\)dies

. in Parti~ Fulfilment of t~e Requirement~'. ,-, .

-'

for the Degree. -

Doctor of Philosophy .v "

-McMaster Universi~y

..

\

; .

July; 1973" .

\

Martin RousselangeAn~erson

'." "' .,

" "

'.

../

DOCTOR 'OF Pi'!.ILOSOPHY(19,7~'(Physics)' _ {'

-t, r

McMASTER UNIVERSITY,.Hamilton, Ontario.

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•

, ,

TITLE:' "Diffraction Studies of Hydrazinium Compounds. ~~. ~

,AUTHOR: ",Martin Rou~selangeAndersOn,B.Sc. (Hull University)'

SUPER~OR: Dr. I. D. Brown ~

NUMBER OF PAGES:. xiii, 194 ~

SCOPE AND CONTENTS:,

o .

A neutron diffrac~~~eter has been designed and used.

to investigate the mechanisiri'O:f.,the supposed ferroelectric, . . .". ~ .

•sw~tch·ing in ~i (N2~S)S04' This w~~ done .by .studying the

ef!fect of the an.o~alous scattering. of~eutrons.from 6Li on,J

the $tructure factors of Bijvoet pairs., , The' absence of any

otiservable.change confirms tha~ Li}N2HS)S04 is not

, fe·rroelectric.'

The crystal structure,: ofLi (N2HS,> BeF4' Li (NH30H~SO4

and (N2H6)BeF4 have been determined, and anaccura~e

redetermination of the crystal structure o,f ':Li (N2HS)' SO4 has

been made:, all by X-ray diffraction. The s~ructure of. .. .' .

Li(N2HS)BeF4 hasal~o been:studied bYneutron~iffraction.

In the crystal structure determinations, all hydrogen' atoms... ~

6 . • ~.

were located and hydrogen bonding schemes,p,roposed; these

we're' verified by the method of bond-strength summations.

\ii

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,

Vi

"

- J. ACKNOWLEDGEHENTS

..c:J.A _.• .......... C' .

,I WOUl~i~eto thank mysuperyisor Dr. I. D. Brown

for his encouragement and many'val~ablediscussions'

. throughout this research. I am also indebted to the other~ " i

members of the crystallography grouPJespecially"

Dr"C. Calvo and'Dr. H. D.Grundy for'~heir fil.endly

assistance. '

Finally, I wish to thank Donna MacDonald for typi~g

this tl;lesis,.

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iii

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TABLE' OF' CONTENTS' .

1-

II

"

III

" .I

GENERAL INTRODUCTION

D~FRAC.TION.THEORY ANq ~TS APPLICAT~N TOC~YSTAL STRUCTURE AN~YSIS

•Diffractio~ by. a Crystal

X-ray Scattering:

Neutron Scattering

Crystal Structure betermination

-·Refinement of the Structure

Corrections to the Observed Intensities

METHODS OF- INTENSITY MEASUREHENT AND A. DESCRIPTION OF THE MCMASrER NEUTRON

DIFFRACTOMETER

pa9;e()

1 ,>L

9

9·

-, 13

15

20<

I26

29

34·

. ',-'. ---'--,---

The MCI-ias.ter Neutron Diffractometer·''/ ';-'I-~

The Mechanical Design

Detection andC?unting Electronics

Control Electronics

The Scan Control Paper Tape.~

IV ANOMALOUS NEUTRON SCATTERING AND THE QUESTIONOF FERROELECTRICITY IN LITHIUM HYDRAZ.INIUMSULPHATE,.

34

35L

39

. 43

45

.. 46

50 f

52

•. x-ray Methods.

Neutron Diffraction

• Experimentii'l" ..... ,, ';..J

iv

"

: 56..

61

'-.:;

)

•

/

VI

,",.'

VII

, VIII,'

•

" ..

"

~esults and Discussion

AN ACCU~TE REDETERHINATION OF'THE CRYSTALSTRUCTURJ;:OF LITHluH HYDRAZINIUH SULPHATEBy'X-RAY DIFFRACTION: •

'Exp'erijUental

Refinement of the Structure

Description of· the Structur'e". .. '. - .

~PE~mlIN~TION OF THE CRYSTAL STRUC~URE OF ' .LITH1UH HYDRAZINIUI~FLUOROBERYLLATE BY X-RAYAND NEjJTRON DIFFRASTION' ,.""\.

Preparation of the Crysta~s ~~ ~---, ..,

,Experimental (X~ray)

ExperijTIental (Neutron)

Solution and Refinement of the"Structure (X-ray) ,

, '

Refinement of the Stru<;:ture '(Neutron)-

Description of th1 Structu,re ..,·

THE CRYSTAL STRUCTu6x: OF HYDRAZONItJM. FLUOROBERYLLATE

, -

62 '

,- 65'

65

68, .

C. 69

80)

"'

, ,

Solution and Refinement of the Str~cture'. . '.

Description of'~e Structure. '

\Experimental

." ~ . . _,0"

" I'

I , '. •

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IX" 'ON~HE CRYSTAL STRbcTP~S OF ~i(N2H5)SO~

'VD Li(N2HS)B~F4 ,_ _, '

Comparison of X-ray and NeuttonDiffraction Results'

A Comparison 'of the Crystal Structure ofLi(N,H )S04 as Determined by X-rayDiff~a8ti~n ~ith that of Li(N2Ds)S04 as

,Determined by Neutron Dift'ract:ion .. (-Ross, 1970)

A Comparison of the Crystal Structures of 134Li(N,H~)BeF4Determinedby X~ray. andNeutron Diffr,action" "

,.. .

X ON THE CONFIGURATION AND HYDROGEN BONDING OFN2H62+, N 2HS+ AND NH

30H+ I-ONS,

139

I(

XI"

The Characterisation

The Configuration ,ofNH

30H+ .Ions

TheHydro~en Bondingand NHjOH Ions

SUMMARY

APPENDIX ATABLES OF OBSERVED ANDFACTORS AND GALcu.LATim

of a Hydrogen Bond

2+ +the N2~6 ' N2H~ and

CALCULATED SrRUCTUREPHASES'

;1.39

111.

, 146

158

161

. ,..

191

\

'.."

- .." '-. "

, .('" .'

vi - ,

r

5-1., ~Crystallographicdata, for Li(N2H5)SO4~.~ ,"'I.~ .

" Reflect"ions used in the least-squares', r~finement of the lattice parameters otLi (N2H5 ) SO.1

'73

Page

49

,'63

63

66

67 ...

" '70'finalX-ray d-ata for

, , '

BOnd distances and angles in Li(N2H5}SO asdetermineg by X-ray diffraction compare~ withtJ;1ose in. Li..u~2D5)so4 as determined by neutrond~ffrac,t::Lon (Ross, ~970)' , ,

Parameters derived from theleast~squares'refinement9fLi'~N2H5)S04" ,

Table otcharacters recognr~ed by thecontrol unit logic and their functions

The observed 'and calculated values of theratio'of the structure factors

2 .'The values of X and prob~ilityfor each

model'

5-2~

4-2.

3-1.

.4-1.

5-5.

:..,. 5-6.

• I

Hydrogen bond ~engths and angles' in, Li(N2H5 ) SJ'4'

Dihedral angles of thecomparedwith'thol;eof(neutron)

, 7S

7f>

5'-7.

5-8.

~nd-strengths in'Li,(N2H.'i)S04 calculatedtrombond lengths determined I5y' X:-ray: diffracti().Jl--

Bond-strengths.inLi(N2~5)sO~~~alculated·forthe'bondlengths ~etermined from the neutron'diffraction results of Ross, (1970l ,'"

77

79

"

6-]'.,

6:-2.

crystallographic data fot' Li (N2HS)BeF4Reflections used in the, least-squares'refinement of' the lattice parameters ofLi (NiHs) BeE'4 "

82

83

vii

, •

,,\ ....

f

.

/

89

96

9,3'

95

~19

120 .

115

I

Page

8'6

101

105

,,106

108

,109

c 112

113

"

-Pa~ameters derived from the finalleast-squares refinement of X-ray data for~i(N2HS)~eF4 .

Parametersde'rived'from the fi';lal - .least-squares refinement of neutrondiffrac~io~ d~ta fO~Li(N2H~)BeF4

Bond distan'ces~nd ~ngles forLi (~2H5)BeF4

Hydrogen bond lengths and angles inLi (N2HS ) BeF4

Dihedral angles of the (N2HS) ionf· . _.... .

Crystallographic data foQi(~30H)"S04

Bond'-strengths in Li(NH30H)S04

C~st.allOg~aPhiCd~0 for (N2H6 ).BeF~.

Reflections u ed i~theleast-squaresrefinement:' 0 the lat>ice.parameters of·(N2H6 ) BeF4 (..,.

b-'\.j· .Parameters derived from the finalleast-squares ref i:ilement··

Bond distances and angles for (N2H6 )BeF4Hydrogen bond lengths and angles· of ,the(N2H6) ion

~8-3.

8-4.

8-5;

. '

Reflections used in the least-squaresrefinement of the.iattice parameters ofLi(NH30H)S04

Parameters derived from the finalle~st-squares refinement

~nd distances 'and angles for Li(NH30H)~04

Hydrogen bond lengths and angles of ,the '(NHjOH) ion

7-6. Dihedral~ngles of, the (NH30H) ion

8-l.

8-2.

-"

7-7 •.

6-6.

7-4.

7'-1­

i-2.

6-3·•.

7-3;

6-5.

6-7.

·7-5 •.

_6-4.

• •• I

.V:Ll.l.

, ..

..'c

.. ,

• \,:,(,:-'" " Page,

8-6.

9-1.

Dihedral angles of, the (N2H6) ion

Bond ang'le distortions from the idea'!values in the space group Icmm

121

123

",'

"i

"',ii," ,"€

.. \~

'.

p3

168

152

137

1:47

151

132

125

153

162

Space groups, ,.cell vc;>lumes and cation, ionic radii of stuffed tetrahedralframework compou~ds and.Li(~H30H)S04 "

A comparison bet~een'thex-~aY~d'neutron',root-mean-square ,displacements along the,,principal axes of the.therma1 ellipsoidsin L~,(N2HS)S04 ,.

Ac6mpa:r:ison between 'the X-ray' and'n"eutionropt-mean-square displacements a1ong,theprincfl5al axes of the thermal ellipsoids"in Li(N2HS)BeF4 ',_

!

J

A-I.

A-2.

9-2.

'Therobt~mean-squa~edisplacements along theprincipal axes of ,the thermal ellipsoids ofthe ~ydrogen ~toms in Li~N/.Hs)BeF4,and the'an~les these, axes make~~tfi Ehe Cell axes

Bond-strengths~~Li(N2Hs )BeFAcalculated'from bond lengths,det~rm~ned,oyX-rqy ,diffraction/

,/ ~., '-.:;- .Bond-strengths ~n Li(N2Hs)BefA ;ca1cula:tedfronr bond, /lengths deteJ:nU..ned oy.neutron"diffract7bJl ' , " '

Bond-S~iengths in, (N2H6)BeF4,

Observ~d and'calculated structure facto'rsand cilculated phases, for the X-ray

, meas,)irements '~~ Li (N2JIS) S04 ','. ".~ :"".

, Obs~rved and calculated" structure factorsand calculated phases for the x":;ray"mfasurements on Li(N2Hs)BeF4 ,~

/ . '--"-

A-3. , 6bserved and calculated, structure' factors...-J land calculated :Phases'.. for the 'neutron/'< me,;,-sureinents on Li w2::) BeF4 1

10-4.

10-1.

9-3.

9-4.,

, 10-2~

"...-

A-4.

A-5.

, ,

J,

Observed" and calculated structure factorsand calculate~phases for the, X-raymeasu~ements on Li(NH 30H)S04' r

Observed and'c~lculated structure facto~sand calculatecl phas,es for the. X-raymeasurements on (N2H6 )BeF4

'f)

Page

1.77

.·185

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~.'. :,-\

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oJ.,

x

......

,, .

o •....

.''.

, ~,

I

"

t•. "

.. ', 1.'..

.. ' ~

g

3-1. Tne four-circlediffrac,tometer •.. "

gon;i.ostat of the neutron''. ~ . ~, ,

,,'

,. -.4.1 .

.'

. ,3-2. ~ general view.of theneutron~iffractomet~r.·

P•.

\'-,

F;igures' •

. ," .~;:~._ ...

A b1'oc)c diagram of the counting . electronics.>and the control electronic81.: " '~ , ..\

L

- ,

38~

,

47' "

55,

.;: ;:-'

36

19

18:

..72~

.. :

,, .-, ,

on

-.

r' ..,r./,_•...-~

•~~ :~. ><._,·':i

~!.. ..

the'six-memb~red, ringstriaymite~d~rivative

• .. .,"

, ,

A possible 'ferroelectric switching meChanismin ,Li (N2H5 l"SO4' .. ',', ,.,.' -':. -5':';'. \, (N.;~;;._. • •

~al .s~:z::uct';ll'e of-'·r;i(N2H5 l.SOlI' viewed"along the a d~rect~on. .' '-' - ,-.. - '.,--;...T~e cry:sta'l .s~r.uct~re of ,Li (N2H5)S~4' viewedalong the c duedt;~on. . ....':

-.' '. ", ~.. "

~ ~i .. ::...,. ..".

'1" '.A comparison of th~_X':'ray and neutronscattering lengths "as a fUnction of.scattering angle.

'\). . . .

"

The two possible configurations of hydroge.n,~bonded chains of hydrazin'iUm ions; .'

The dependence of the' ,scat't~ring leng.ths'atomic number. .

'The configuration ofin .~hetridymite.~ndframewor)cs.

.... " .. ~,

A perspective drawing' ~f a tour--C'ircle , :'0 "g?niost~t in th~ .equatorial' geometry.

. . .'. ,,'- '~:,." . -," .The exp~rimerital·configuration.ofthe,neutron

to diffr,actometer at- beam-port #6 of ~ the'.,'MeMa~er nuclear ,reactor . ,'. . "

. , .

5,..2.•.

,4-1.

5-1.

3-3.

1-1.

.~

1-2 •.?

/'2-1.

~-2.I

3-1:

3-2.

-.

.....-~~~;.~ ... '-.-

~-- --:::--:.~ .,',

, =

"

,6-1~" The crystal structure of Li(N2HS)BeF4:viewed along the a ·direction. " ..

- '-,-

page,

90

&.

8-1. .

'The cry~tal M;ruetureo-fLi. (N2HS

)BeF4: viewed 'along the C. direction. "

.. ' " -. ~ "!,.

TJ;e crystal. struQt\lr7 of ~i:(NH30H)sb4v:j.ewed 'along the a d~rect~on. . ... '. \.,'-

.TJ;e·crysta'ls~rlfctur7of~i:(NH30H)SO~· v~~wed along; the c d~rect~on. ,j4 ...

The'crystal structure.of {N2H6)~~F4viewedalong the ~ direction.

.91

102

103

116

..

,:'

, .

'. I ...150

.14,3

148

136

131',

133

-117

t·g

, .

H-P

.The crystal ~tructure of (N2H6)BeF4 viewed ','"alon~ th~bdirec~on. ;

. '-~'

The plane containing the nitr6~en atoms ofan X-N difference synthesis for Li{N2HS)S04;

~Th: plane co~tai~?g'the lithiJrn and· ;~~Eh~r.atoms of <In X-N -difference synthesis for '~_:..

· Li{N2

HS)s04' . ""~,~< .

The plane containing the~nitrogen atoms ofan X-N diffe.rence syntge~is for Li (N2HS)~eF4•

'-. . . ..' ."

The plane ~ontaining thelit~um .andbel'.';yllium atoms.of.anX-N differencesynthesis lor Li(N2H?)BeF4' .

• ~e~an proj,7c;:tions of' the N'~H5""" N1I30H+and "N2H62+' ~ons. ' " .

'A thermal ellipsoid drawing of theN2HS+iqn ,frQnitheri~utrondiffractionifvestiga1;.ion of J,i (N2HS). BeF4"

10-:3•. "~Bond""strength. - bond-length cu~es for.... .bonds determined by X-ray or 'neutrqn,

diffraction•.•

..'10-2.

9-1,.

8-2..

9-3.

.

", . . ~

. '9-2 •.

.10-4.' . A diagram,showing the.correlation betweenthe hydrogen. bond angle and 'thedorior-accep~ordistance.. '

'155"

'. "

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xii

10-5.

•

, .

•

.\ ....

A diagram showing the cbrrela~ion betweenthe hydrQgen bond angle and thehydrogen=acceptor distance.

• . .

..

156

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II

/ xiii

': .

CHAPTER I

GENERAL INTRODUCTION

This work is an investigation by X-ray and neutron

~iffraction of the crystal structures of sulphate and

fluoroberyllate compounds containing: hydrazinium,

hy~roXYlammoni~, NH30H+~ andhYdrazonium,;N2H6~+'r/ '

many reasons Why these compounds are of interest to,

+'N'2HS ;

There are

crystallographers, solid state physicists and chemists.

The compound lithium 'hydrazinium sulphate, Li(N2HS)S04'

was first prepared ,by Sommer and Weise (1916). Pepinsky"

Vedam, Okaya & Hoshino(l9S8) reporte'd that it was. a .room. .-'t! .

temperatu~e ferroelectric, likening it to.theother

ferroelectric sUlphat~: . ammonium hydrogen sulphate,

..,.

(NH4) HS04

(NH4 )2S04

(Pepinsky et al., 19S8a) and ammonium' sulphate,

(Matthias and Remeika, 19S6). They also correctly

reported the space group'ana lattice parameters.

Subsequently, Li(N2HS)S04 was extensively inve~tigated, .

crystallographically,. spectroscopically and d;electrically. , - " ,

(cf. Chapter IV); but.no further evidence was found of

,ferroelectricity, nor of the existence of a ferroelectric to

paraelectric phase change, nor as to what the possible

switching mechanism would. be. Neutron diffraction has

''"''. played an important part in the understanding of hydrogen

1

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