1203

Acta Cryst. (1970). B26, 1203

The Crystal Structure of Cu(NO3)z.2"5 H20*
BY B. MOROSIN
Sandia Laboratories, Albuquerque, New Mexico 87115, U.S.A.

(Received 5 June 1969 and in revised form 28 August 1969)

The room temperature crystal structure of Cu(NO3)2.2"5 H 2 0 has been refined by the full-matrix
least-squares method using 2338 Mo K~ intensity data. The space group is I2/a with lattice constants
a0= 16.453, b0=4"936, co= 15.963/~ and fl=93.765 °. The copper ion is surrounded by four oxygen
atoms from two water molecules (1"959/~) and two NO;- oxygen atoms (,-, 1.99 tl,) in a near square-
planar arrangement, by two more distant oxygen atoms belonging to these same NO;- groups
( ~ 2.66/~) and by an oxygen atom (2.39/~) of an adjacent NO~- group. The copper ions are connected
via the oxygen atoms of the NO7 groups forming a crooked chain-like arrangement, and a network of
hydrogen bonds hold these chains and the water of hydration together. Differences in the nitrogen-
oxygen separations in NO3- groups appear to be correlated with chemical bonding in the structure.

This X-ray study on Cu(NO3)2.2-5H20 was initially
undertaken to provide detailed structural evidence to
support low-temperature thermal and magnetic meas-
urements (Berger, Friedberg & Schriempf, 1963;
Friedberg & Raquet, 1968; Wittekoek & Poulis, 1968;
Myers, Berger & Friedberg, 1969) which had been in-
terpreted to be those of a salt in which the cupric ions
were associated in pairs. A system of such pairs (or
binary clusters) is found in cupric acetate and other
cupric alkanoates. In cupric acetate (van Niekerk &
Schoening, 1953), the cupric ions are found to be
structurally paired by the acid groups forming a bi-
nuclear molecule, C u z ( C H 3 C O O ) 4 . 2 H 2 O, with a
C u - C u separation of 2.64 A. The earliest structural
study on Cu(NO3)2.2.5 H20 (Dornberger-Schiff & Le-
ciejewicz, 1958) contained several misprints, among
which were the chemical formula, the densities and the
location of a water molecule; hence Garaj (1968) did
not recognize this earlier work when he reported on
the crystal structure of this compound. Concurrent
with the appearance of Garaj's study, we had nearly
completed our more precise and detailed study; hence
in this note we summarize our structure results and
provide the details of the hydrogen bonding found in
C u ( N O 3 ) 2 . 2"5 H20.
The space group, 12/a, was selected on the basis of
systematic extinctions (h + k + l odd for hkl, and h odd
for hOI reflexions absent), absence of a piezoelectric
response, and statistics of the normalized structure
factors calculated from the intensity data. The lattice
constants a0 = 16.4539(4), b0 = 4-9384(3), Co= 15.9621 (3)
A, and ,8= 93.765(2) ° were obtained by a least-squares
fit of 60 high 20 values measured on films taken with
a 115 mm diameter Weissenberg camera utilizing
Straumanis film loading and Cu Ks radiation (2 for
K0q= 1.54050 A). With eight molecules per cell, the
observed and calculated densities are 2.35 and 2.38
* This work was supported by the U.S. Atomic Energy
Commission.
g.cm -3 respectively. The 2335 three-dimensional Mc Ks
intensity data were measured with a scintillation count-
er employing pulse-height discrimination using the
0-20 scan technique; of these data, 285 were con-
sidered to be unobserved.
No absorption corrections were included for the crys-
tal specimen of dimensions 0.23 x 0.08 x 0.12 mm moun-
ted along the longest direction (a) (PMoK~= 15"3 cm-1).
Lorentz and polarization factors were applied and
structure factors calculated using Cu 2÷, N, O and H
scattering factors from Table 3.3.1A (p. 202) and
dispersion corrections for copper from Table 3.3.2C
(p. 215) of International Tables for X-ray Crystal-
lography (1962). Positional parameters were obtained
from a Patterson synthesis and subsequent Fourier
syntheses. Atomic positional and thermal parameters
were refined by full-matrix least-squares refinement,
with. the function, ~ w(Fo-Fc) 2, minimized in which
weights were assigned from counting statistics or, for
unobserved reflections with. Ifol > Ifcl, set equal to
zero. On the basis of a three-dimensional difference
synthesis calculated with the refined parameters (the
reliability index, R = ~ [[Fol-lF_cll/S IFol, is 0.037 ex-
cluding unobserved and the 202, 602 and 020 reflec-
tions), the hydrogen positions were assigned and sub-
sequently refined using isotropic thermal parameters
along with the positional and anisotropic thermal par-
ameters for the heavy atoms. The final R value is
0.034; the final atomic positional and thermal param-
eters are given in Table 1. The observed and calculated
structure factors are listed on Table 2. Fig. 1 shows
the structural arrangement and hydrogen bonding
found in C u ( N O 3 ) 2 . 2 " 5 H 2 0 .
Although there are no gross structural differences
between Garaj's (R=0.109) and this refinement, many
of the y coordinates for various atoms differ signif-
icantly; this leads to interatomic separations involving
the copper environment which differ by almost 0.1 A.
Our interatomic separations and angles are given in
Table 3. As Garaj pointed out, the copper atom has

A C 26B - 1
1204 THE CRYSTAL STRUCTURE OF Cu(NO3)2.2"5H20

a n u n u s u a l coordination. Fig. 2 shows this copper en-
v i r o n m e n t as well as the crooked chain-like arrange-
m e n t by w h i c h the copper atoms are connected. As in
Cu(NO3)E.CH3NO2 (Duffin & W a l l w o r k , 1966) a n d
C u ( N H 3 ) 4 S O 4 . H 2 0 (Morosin, 1969), the closer five
n e i g h b o r s a r o u n d the copper a t o m f o r m a slightly
distorted [ 4 + 1] tetragonal p y r a m i d in w h i c h the base
o f the p y r a m i d is f o r m e d b y 4 atoms at a p p r o x i m a t e l y
2 . 0 / ~ a n d the apex by an oxygen a t o m at a b o u t 2.3/~.
H o w e v e r in those c o m p o u n d s the copper a t o m is lo-
cated a b o u t 0 - 2 / ~ above the p l a n e o f the base o f the
p y r a m i d , while in C u ( N O 3 ) 2 . 2 - 5 H 2 0 the copper lies
in the plane.
The spread (1.22-1.31 /~) f o u n d in the n i t r o g e n -
oxygen separations o f the N O j - ions m u s t be con-
sidered real. Similar spreads in N - O values have been

T a b l e 1. Final atomic coordinates and thermal factors for Cu(NO3). 2 " 5 H 2 0

X Y Z Bll or B B22 B33 BI2 BI3 B23
Cu 0"12613(2) 0"01352 (6) 0"11376 (2) 1"915 (9) 1"755 (9) 1"804 (9) -0"023 (7) -0"272 (5) -0"142 (7)
N(1) 0"1683 (1) -0"0243 (4) 0"2797 (1) 1"74 (5) 1"83 (6) 1"96 (7) -0"06 (5) -0"08 (4) --0"25 (5)
N(2) 0"4016 (1) 0"0765 (4) 0"9888(1) 1"73 (6) 1"84 (6) 2"12 (7) 0"06 (5) -0"10 (4) 0"13 (5)
O(1) 0"1914 (1) 0"0299 (4) 0'3534 (1) 3'12 (6) 2"74 (7) 1"77 (5) -0"19 (6) -0"34 (5) -0"19 (5)
0(2) 0"1580 (1) 0"1685 (4) 0"2264 (1) 2"71 (6) 1"79 (5) 1"96 (6) 0"09 (5) -0"60 (5) -0"04 (5)
0(3) 0"1557 (1) -0"2597 (4) 0"2556 (1) 3"45 (7) 1"88 (6) 2"92 (7) -0"46 (6) -0"33 (6) -0"41 (6)
0(4) 0"4235 (1) -0"0602 (4) 0"0500 (1) 3"24 (7) 2"49 (7) 2"66 (7) -0-02 (6) -0"31 (5) 0"99 (6)
0(5) 0"3725 (1) -0"0160 (4) -0"0785 (1) 3"40 (7) 1"95 (6) 2"57 (6) 0"00 (6) -0"76 (5) -0"43 (5)
0(6) 0"4096 (1) 0"3393 (4) 0"9941 (1) 2"63 (6) 1"57 (5) 1'99 (6) 0"01 (5) -0"47 (5) 0"01 (4)
0(7) 0.2407 (1) -0.0172 (4) 0.0883 (1) 2.13 (5) 2.35 (6) 2.72 (6) 0.05 (6) -0.20 (5) -0.16 (5)
0(8) 0.0119 (1) 0.0457 (4) 0.1399 (1) 2.01 (5) 2.12 (7) 2.20 (6) -0.03 (5) -0.29 (4) -0-28 (5)
0(9) ½ 0.0458 (6) ¼ 2.51 (9) 2.12 (9) 3.11 (10) 0.31 (7)
H(1) 0.267 (3) 0.11 (1) 0-120 (3) 2.4 (10)
H(2) 0.265 (3) -0.18 (1) 0.099 (3) 2.5 (10)
H(3) -0"025 (3) 0"05 (1) 0"091 (3) 2"6 (11)
H(4) 0-000 (3) 0"20 (1) 0"175 (3) 1"5 (8)
H(5) 0.452 (4) -0.05 (1) 0.247 (4) 4.8 (15)
3 3
The temperature factor is of the form exp ( - ¼ ~ ~ B~sh~hsa~*aj*).
i=lj=l

,, ° ..... C> .... -O.* ,.

". l/ y yo, , ..
\\ a/ / I \\
% J \

• Ol51 N(I)

0171 \
N

I
/
I

Fig. 1. A representation of the crystal structure of Cu(NO3)2.2"5H20 viewed along the b axis. Solid and dashed lines indicate
chemical and hydrogen bonding respectively.
 B. MOROSIN 1205

reported in several other carefully determined struc- Ce2Mg3(NO3)~2.24H20, by Garner & Wallwork
tures containing NO~- ions. Among these are the (1966) on Ti(NO3)4, by Gallezot, Weigel & Prettre
studies by Zalkin, Forrester & Templeton (1963) on (1967) on Ni(NO3)2.4H20, by Britton & Dunitz

Table 2. Observed and calculated structure factors for Cu(NO3)2.2"5H20

* Denotes 'less than'.

.. o ~ o z 561 SZ9 :~,0 Z~Z ZO ,60 -1.so z~'9 ,,~s -1.. ,.,o -,.z; -; ~J.. -,~s .. 1:, =~ z ~:• :9° -,91

8 2,81 aa.o ~ ,oo -b,~z -8 87~ -SO, "' ,0 ~ ~ 1.0 1.81. -,~e -ze a29 z J9 -~ 31.o 3,Z 3 ,~8 1~o e ~ -~.~ |~. ~,o 6 -o 11o -,,.

~. ,Bb -llo -& 590 ~e5 12 1.25 351 3 61. *)9 -12" 60 $8 2,re I$ ,~ ,5 e 'J 1" 7 Ob -1" -,0 20, Elb -13 8e -;? io 3b~ -.~b
~6 a~ z~.s ,o ,,z ,~o -zz ~1.,~ no -~ ,o.. -1.o3 ,~, ~a za -,~a. ;; -.I -|s. sJ -~ -~ ,~o -~. ~2 ~a ,68 ,~ ,ol -*, -~o. .s -z

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I; ........................ I; %' ...........

. . . . . . . . . . . . 1. . . . . i . . . . , o. , . . . . . . . ".2 . . -.. , . . . . .• . . i.. . . -. s . . . . . I:I I;;-.. .... ;I I "'; "IS" ,t' ~:-I: ~:I -,,,'~-I:. ~l -o." 4: :t ::~
o"' d, t',o.° -I: ~'~' ";h' -lo` ............ -.,Io ' "' II. "-',4 II . . . . 2[~ ....... o"' ~'~'. %9.'
~ %;, .,:, :l, . . . . . .
I,*: l h ~ ....
1.. . . . .
. . . . .
.
., ,o,
ii. . :ii .
%o', -,,. 21, -.,
!i .......... :i: i! *" -°"

-~. 136~ ,.be 15* bo ~0 se e~ -,tl 9 9z -sz • 2.3 -zzo H~ ,s Ko 2 • 502 .95 -7. ,2 -~
2090 2200 el lo KD 0 N| • ~# , -15 tg, -~80 -S ;o ., -? J)l -)}o -. oz2 0~$ o 65 -gz HI ~ m° 3 -" 19S 17. e* B| -~Z
-e ,zq -oq9 o o~2 o'*o , e$ st 1~ 85 -61 ; 1.7 -15.~ 11* ~o .o o °~) 889 • 66~ -~oz i '*o -i~ 6 ~,~, ~z -9. ~; 9
e 1.~oo sz°/ a ~ ~,~ -z ..,....o -zx* ~o to -~, z2., -,o,~ -,s 9. -o. -6 *o. -~,98 -z ~,1~, ~,z; -, z;r, *.1,. *~, lz~ -z~,z -,, |,o -,~z
-8 8e5 -87o -2 t87 |~) 3 .Z. .). 19 tZ' ,i) 9" 09 -.~5 1} ib~ 1o0 8 8SO 8(~, ~ 29 -. 3 2eo 300 ° 190 -,91

z.z

. 1. . 1. . . . . , 1. 8 . . 8. . 3 .o , . . 3 , .7 . .- 1 . . 8.. . . a s. . . . 8. .11 . KJ , -13" ~2S ; 2[ - l ,. . . . .~,I8 ;gl -I 2 .2.9. .; 2~:; -~ 2. 1.. . .- 2 ;. , . . :~ -:I~ -122e .~I 22~ ": ';l -1;,

,b 669 600 ,0 7S $o -9 8~s 8o~ 2 100 -65. -1S • 17 -.9 -89~ 60 -.b -it il) -llZ -10 281 Z}3 -9 .2:~ ~,}1 -l'* 2~ 2,2 e |~$ -~

zo '*n -'*.o z,, 1.,~ -~zo -1~ ~,o )~,, o ~1,~. 1879 o .sz -.~ -,0. X3 -z.~ -z. o~ -°s -z~ ,~ -~,• -za .,0 -1~ .. zv .. ,

2~. ~. ~9 1~ Is °6 -zs 60 -zz • ~01. -a~. -2 ~z zoo 0 9)~ -91,, -20 ~ao 38. -~ zo,~ 218 .. ,a ,,~ 1. -

-. a , .. . a.a . . -.a , s. . - ,.8 . . , . o. . .z ~ o. .- s ~. . z,~o

. . . 8 8. o . . s o. .z0a'~
. . - '.~ g 8. . -,,
. . .. o ~. . . ,. ~ . . - a. . ~.n . -.~ 6 1. . . . ~. .11 . ~ o z | ~o . . . zo - I ° : ~: ;0; - , zoo.
~ zo~ - I: I; ;;

-z 31, -~zo -z ~1~ s~ z~. o~ -s -1,, z,e z~9 ,o '.90 -,,.s e 5o,, - . o o s •1. 2~o ~, oo 72
. 79b 75~ 4,4. ~., ,o -25" i], ]o Z6 o, ez -1o ~ ;o -is -~ 371 - $ o l -$ 12o 1~o 7 -7~ .o )
.: ,~o., ;;o. -: ,o, .zs -~, .,z -,~ ~a. Ig -~,, to :oos -1o91 ; so, -)~. '~ -z. o'* ;, 3° -; ,?~ -so'; .~ ,o'~[ .;'2:
,~z ~9~ .~ ~ K* ~ ,o .z. -.~1 -la z:~ ,do -,o ~9. -~:. -~. a8 ~ ,~. ~,, -~. a ~. ~o,, -9 ~s q.. • ~b: -~.~
-, 89', aO', -* olo -:oz 0 .,~.z ,.,z -,e s~.~ -208 -s,,. :1. .: |2 910 0~5 9. ..8 -,~ -,,. ~: -~a -a 0 -. ,i 2~? aol 8 ~ ~o

-8 0)~ -81.1 -o ~oo -~oo -2 2° .9 -ZO ~Z~ ~aO I" ..z ~:~ ,, 1o .s -z,, x~ 1., -. .18 ~90 1. ~1. -~ 82 a.~ -2.~

-83 609 -05~ - 0 3b $6 - OZO 637 , Ob -b. ,6 Jo$ -ST. ,$ 820 281 -|~ 88 68 -b lf~,# 13~V ,~* $$ -7 ,o |2, 81~
........ :~ 12o-So: : soo ""~9 .o tz u ~ -s 89 -so -~o ,-, -o~ -t) ~ o~ ........
,. ~la no 1. z.~.. z.z e ,zoo-,oi. -, ,ss SZ8 -J. ox -),~ -,8 ~,9'~ -*'~'~-,~ ;. ~o o ..~2 -..~ ,o o,~ ~>1 -~ 1~,. ,2'.
-~'* ~; ;., -,~ ~io -so° -o ~oa -.98 ~ zss 81, ~ ,oo -o~ zo z~ z:o ,~ oz -:. 2. ;2 3q -,u ~u. -6~ -1~* ~ -~o .o : .o •
- : 6~ ~I: . . . . . . . . . . . . . . - I o ° e , . 5.o . - 1. , ..5 5. ~ a:l 2. 9. , . . 1 4° .- .o. . zo 37,'°'s ~7o~-:4ee ~2 Iz~ -z ,,~: . ~ : s¢ ol2'2 lz.~,~ -. z. .,.o .o ,3 K, 1. _:. z~7 -28oo
i, ~oo -~, . , ao ,~, o ,z qs, 9.z -s :,, 1.,o -~. os z.. -az s.~ ~2 -,9 ~1~ -~ -" a~ zo8 ,. ,90 ,07 0 ~0'~ - ~ | Z 3 OZ6 -o~e
-,e 090 -O~ 0 ~'~ -~5'~ -18 1.,~a - , s o ~* .o -z, 9 t,s -.9 -28. ;o -.s o zoo ~o. -,. ,.~ ,~s a ..o9 .o~ -) ~ ,**.
~o ~02 s,o 2" 09 -~1. s. .oo ,,,. -; o. 3o -9 ,,~ -eo .. s .. z -o ,o. ,:6 ~o ,,~2 -.~,o -z ,)~: -~.z ~, 2~ zl,~

:~ !!! !ii :i ~i~-~!i :!i '}ii :~ii ~!. :!i'ii :!i" :!~ .:!! ! :!! :~ {'~!4"':~ ~!" :i~ 2~] :ii !i! :i!i "}i!-~!i :! i!~ !!!!
........................................
-o 12. ~o~ -|o s~o -~o) is aa) :~zo 1 2; .....
2, ~, ,,,
..............
ooo -. ,°0 :~t _~ ~:~ _;o~ -~ :IS-Y.I -; [o; :,'l:
o"',h %.o _,,. ';t ":-P I~:-;4 I;. :" 4: o"'~;.':M ~ ~.~: :~;" : ,& ,'4 . . . . . . . . . . . o.,
. . . , . . ,o. . ,..
. . . .,. . -,,
. . . ,.o ,.
-z . O l a -,.82~ -zo ~os -,,~o -zz 2o. 21S ,: ,~ ,20 -2 ,.9 -~oz ,~ aoa z.r ,, I.,, -~1 1. oo -1 -~ ~.~ ~ao ,a .~s *~8 -,~ :~ ,~
• o.8 o', :z s~.. ,9.. -,r. o,~ ~.~ • ~,, ,e. -9 •,,o ~.2 -0 .e, -'*~. -~ ,,~ -oo ~ ~o -.98 -:a" .. -~ z~. o~ ~,,
698 -720 -,2 17) [80 HO O £0 [ ,ge 7S Z'b -.e 7. -SZ ,S 8b e'* I0 .99 -.99 3o ~= -JO -) 1). -|Z6 |.e IZ 39 -lb 9~. -7=
0 |OZ', -loS,* -,. '.~O S"~' I 2J" -2~'~ -~.9" 'O -Z • ,~ ",~Z "1' Z~ "Z*O -10 ~.0 "~O -~ ZOO -09 ~ ~0' -~ -'" ~; ~OZ ~; ~ "~'~
-o s,J .94, -1. ,~ ,9, -2Ae ]8 -*[ -6 28* ~05 11. °9 ~ ,,~ •I. Z1) ~ 71 -07 ..~ 1.7 -Lt7 ~.O ~eo -.$o -,? 120 -~V

-o' ,,:I ,,.2-" g'ff,",1 -,.' 'I.' '-%' ....... : ~ . . . . . . . . . .,,. . . . . .2,.
-,.o . . . -,oo ,. .. .~II I '4,~ -:o: j. ~; -o," :I:., .........
-2,, -,9. ~,'--*:;

-,2
'° ,:':.,::o,.o
.
181. - I O J
. -L :ii'-:~-~
-.
. .
~,,
. .
-,,2
. .
-:"
. ,.,
.......
o:~
-~,~,o . ! :::,o, .,o,::: -:o''.,, ':~" :i~ :F: ,~i , ~! :ii ::2[ .2oo
~,~,. ~)5
.... .,.:: ,,:: :i
,9 ''0 '.~J ze
.
S,,*
. .
-.~',S
.
-I,*
. .
,~0
.
23 -,1
~! i!i
,~s -,~: -s
,:":,",: 2.~, z~,.
0"'2:9".',,:
z ,~,,,* -93S

" * .~,0 .28 102 L02 b Z95 -217 1 I] ~, 81 • 11 .2 *ZO 9, oS HI 2l Ko • *,) ~*) ~,* -Je .? *S/ . SO* -°is
,o o ~,* a~, ,~,. 6O -z~ s ,~ -ts/ -,, .ao .~1.

,, ,o I . . .... . . . . '"
~,.! .' - ! a,o6
. . . ~'. .
e~ !~ h"-4
:I. . .:i! . ....
. . .. . . . . . o',' ....
. -,o,
] i ~:; !!!
&o ......
.........., .. o -I; %'-2,'I-I~ .,.. I;;
. . I: . ~ . ;: . J . ,8,9-,..
. . -I . '~': . _%o. -: . ,oo
. ... . . -.o. 4.'.. ';I -~;; 2,. .o ;~" ,,, ....
.;g: ,o -;t o ';; -....... -,,. :: ':-I.' ,:~ ;:: ";: It I: . . . '22
. . .-''0
. . . -'" :0-2'' :: i:l lh' ........................-,, ,.8 ,,9 ,2 .o -0'0
H, e ,~, 0 ,, 28~ -2.z -89 ~,, ~; ,o ~90 -58r -iz* 00 -1. -o ,,*oe z..oz -x ,s,> ,28 0 ~ o1.2 -83. 5~ ,, ~,* ~os ~

-,~ o[; o.'° ......... :~I" 4.' ";;-I: 2[;I :2['I o"Io'.",o; ~[ ~o' . 9,'I 'Wo-I;. '."~-,o; "I: l[I I~;
1o~,~,-t~ob - ~ .. ~ ,~, • -18 9~,
.: ..........
. . . . . . . . . !.,;,,1..;
Ize 6','9' • ........ .......... " ~-:;: :: ~': ::: :'" ~:-:!! ii !! '~ -.,. :~! ,o, o . . . . . . . . . . . . zz; I

d ,2, ~!i !::~ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1.c.el - , o . 9 -J 2os 2oo -8 212 zz~ -,* ~o .~. -,1 6~ le 1 o~o -68~ -,o ,o~ -,o~ -.~

. . . . :'5. . . e.2 . . , ~. , . . ~,~. . .- , ,. . . - o. . .6 . ~.. . .0 2.8 . . - ~." . . ~ . . .- s .~ . . . . o. 2. . . .,~o. .~ . -., 8

,2 ~.~ .:1.~ ~ ~ :~ ~ :' - I,~ I:: :~: - : 211[ . .2.. .U. . . . . . .:~. . a~. zso
-,z .~ -.,o. ,; 1..~ t~9 o ,o8 ,s,~ ~ zo9 aoe 1.. 8~ ~o zo ~o s:o .~ ,. ~, z : 6~ .9, z. .o~ -..zr e soo ,~9 -3 2.~, -aa9
-,,,'l Z2~1 ,21S -20 59 -zo 9 6,,e osz 5
'" ,,.::o'-!;i !i: ,I: ,o: ,: ...... -,o ,81 -180
-4 ':~ '!;-:: ia -s*
~[ }! -28*
2,. 'i~ ": 2 ;:' _,,,"1. ',' :!i-!i~ :i! ~.::::::4,,, .,o.;: ";~ _,,
-,:
..... ,,o":: :::.,,,
-1.'": I:~
,o. ':;
;:.
:::
;'::~ I :!!I; -........................
4:
s,,, -,,,0 -,,
,~; ....
-,o, 41
2..•
I~ :,o o.,2,o..I,/o '
"''':2,:
~,'~ ......
:i "'I;,~ 4;: "14 'il ",'~ '" . ~! . I~.........
-;~; ......................
. -,.,2oo
,2o. "','.. .':
. . ..'~'
. . . . . . . ;:' ....
t;: -.o

. .. . .. .- , , ~.I . . . . . . .. . . . . . . l e o. . .. . . . . . . .. .
1. . . . . . . . . . . . . .
;oOZ . . .. . . . . . . . "I I, ~: *; -Iz°~ 1.o,

................ o.,, ~ '.:; .'11 I: ,;~ "~ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . :~

.................................................
.:. ,,o~ 1.,oI -,/. I;:"4~,,, .I . . . . . . . . . . . . . . . . . . . . - -~.o - ,~:; :I: :I ::: ,; :i" :ii : :]i ' ii - ;;i ':: , " ,99 -,,.

607 s - -~, -i.... ~o |o ~. oo ..s 1.z .~o -,zo2

....
-.~so : ~'It !X
-lz 2.0 ]2 . . . . . -3|$'1" s[l ° . . . . . . . . . . . . . . . -3.029 - 1 9 ,0~ ,~: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ~17 .X22
1.. OOS oo~ -zo 887 ,°3 38' -)as Z2 836 szo -5 1.~ -ZO. ZZ. ro -2Z -, ,,~ -sas -so ~,s -,)z.
-1., 1.o~ -zzo 28 z., -zoo ,z. zes -28. 7~ -.z 1 68 ~s 88 z~s 161 -,~. ~ -z. .~ ,: ,u, 3 -6 *~3 -~oo

-,6 zsz -a,)o t~ -,so -z~s 6,0 .. -~i - ~,o,,

,8 ~o., -s,2 .. a ~. ,
- S o~ " s 12[ - z. , 6. . .-1.. . ,.~1
. . . ,,.,2 - It . o. . .- s o. . .- s.o . . 1.89
~ . . . ~.os - II . . z..~
. . . z.. . . - z. . .'**~. . ...o~
. . - , ., . . ,1.z
. . . | z. ~ . . . . . . .~
. . . . . . . . . . . . . . . . . . . . . . . . . . . I' ............. -II' ,:o -,,,-" 1..... -',4
3*6 -,o -sz~ ~89 -,.~ - "~,6 -,o -z•o

. . . . . . . . . . . . "IS: ;.' :I -: %oo .....

,., I;" ,~,'° ;~, -I ,q~ Ill -:
.z 1..) -1..s -, ,~a~ ~,)~ -a|. ~:, -z,~ ) °6 ,,s -z; :.~ -,e,. -~ ~:ol 1oe~ -,i* ;. • s ~eo ~98 o
., 2.. . . . ,. , , _Iz z~l -a~a8 . . . . . .
".5. 8
. . . . 1.s3a
. . . 1.1.. . ,~a,.. . . . . . . . II I: . . z. .z 1.8
.............
....... % h' o"',:,'.l -,
61 -¢,2 -'1. ::'
2)e
o"'
' ;':-: ,::-ii -:o
&lo -o5o -1.3 ~,g -Z s 7.3 1.7,)6 1..4~ JL~T -23 65 ~l 1.~
1.~z 1.6 zoo a81. ,,5* -.~s -,~ zsz zza -zz

- i~ ":; .....
............ .............
:~ ::: _,,,
.~o,~ ~ .o..
............
,., ::. ~ ..'o" o" :,",~-::
-~oo ,,.
........, : .......-,~ _:: ;:: .,'-_::
,,. ,)8° -,)9',
. ;i
. . . -~s
. . . -~
. . . 7z
. . . . lJ 4 , 1 0z ,Z~:

- , ,.~. . . . . ,.~.s.a .~,J ;,: ~l . .3.~. . . . .1.O

... ",1.', "*Z~ l,'t 8. 8. . . . -~,~ 2 ........~ z ; ;
1.83,) - I .z . . . . .O.9. . . .-1.,~z
..... lO ~,z s,J - ll . .o .s . . . . -. s.~ -1.a
z.,~ s,,e 1.so -28. -zs 2u~ -zu6
-1.o 1.86 -1.z.i 83., ~,~ 18 ~s -76o -1.~. ~ ~ - ~.',6-~'~,', .~ • ~ • ~Z S0S -,0S -1.9 1.aO -,ZS -9 9'~ -9~ ,JW o~ -hi

..........
......................
-I." ....... lh "..I
;i
. . . . . .
. . . .., , . . . . . . . . . . . . . . . . . . . , .,
~. . . . . . . . . .
.,.
9~ s;~
:i"
I° ! *',o:
-., " ii* '"-:;
" -:~ ~::
,, -,. o8 :~iI
......
zao a.~1 ,t: ,.
o 1.~$ &&,~ /. 580 561, -1.| 21.9 226 --4~ 239 -,i~o lb 219 2SZ ; iS6 -1.6'~ - ;oo - •. . z~ z

A C 26B - I*
1206 THE CRYSTAL STRUCTURE OF Cu(NO3)~.2"5H~O

Table 2 ( c o n t . ) that thellength of the N - O separation tends to in-

crease with shortening of the A g - O separation in a
z,,~ -a~ at6 -2.]~ -z~,~ s *z 62 nearly linear relationship. In Fig. 3 we have plotted
1 7o9 7ox 365 369 27~ 2/C the metal-oxygen separation vs. the adjacent N - O
• g5 ~,~, - z o .],.s ~.t -zz z~ -t** -, ~; zo/ -o zoo ,og
separation for the previously mentioned studies. The
,o
. ,s

z,,,
- s * -1'~

zn
71
longer metal-oxygen separation for any particular'ion
-lz z .2 0. . . . -.z . ~ -I .......
z,. ~ 0"'~9 x _. , ,.2 . . - t z. z~ t~l -,z ~*s,s' -3",Z~' always appears to be associated with the shorter N - O
.........
1~. ~z* ~z~ -
l"
tz
6: -ts
-zzz -
: . . . . .
za~ in,
o
ze*
.......
zo~
: ......
zt, zzo
separation. If we assume the 'effective' ionic radii of
. . . . . . .
-so soz -~
-I"
o
z::
it
-,,at'
ez
.:
a
~. .,.z.
~sg
los
-,.is
- ~ . . .~.z . . .- 2 ~ ,
--,. ~t -)8o
7o~
-,o
l:~
z~s
I::
a~
Shannon & Prewitt (1969) in order to subtract the
-*
1 322
......
316 ~.1
-sz. ~I
1o 12.~ 110 "-6 ).19
zss . . . . . . . . . . . . . . . . . . . . .
metal ion contribution and, hence, normalize the sep-
aration, we find the iron group members to be situated
9 318 .]21 2.
. . . . . .
IS? L~O
-i: :zs: . . . . .
3
X,~
94
....
-69
_ss.
71
,,
67
a::
--1S
on a line with a slope identical to that obtained by the
-*z z~a ZSS 200 -$ 61 -.]$
A g - O separations. Unfortunately 'effective' ionic radii
. I~
-i~
~
. . ..~o. . -L.~
,s
. . . -6
. . . 114
~z
. . . -zsz
.
8 .]52 ~*;
-)
~
Xl
t*5
. .**~
..
-**~
-I
-0
. . . . . . .-zz5
zz~
*aa
........
,~,, o"' zo '~-a"o
of 1"15 and 1.25 A rather than values of 1.30 and 1.29A
-zs *oe -~. -e Z6L ~,s -s 3,0 -,.o~ *o~
,x
.**
z~)
**
1)~ zo
-ao
LZS
.]z~
laO
-7
? ee -so
tzo
.~ 17
s~
zlz
~ S
zee
-2S~
Z 39)
.])~
-~11
~s2
-8~
for Ag + and Ce 3+ respectively, as well as a 1-13 A
.8 • ~,
-12
,.-*'~ z~x
-1~
-;;~ tz
1o~.
u8
~06
zz,. ~
18)
z~a
l~&
-z,.s
-~,
6
130
.]~*
12)
~., 'radius' for the UO~ + ion would be required to place
o aoo ~ix -~6 )oa -)oz 2s6 235
- z. . . z s. s . . z. ~.o . . 1 . :o'U' : - 2.3. . . . ,5, -z,z ~ . . . . . . . : ....... all these data on a c o m m o n straight line. [The 1-13 A
:i 3/.0
.......- 3 1 2 :i ........ -17
:ii *'
11~* |
.4 KI-- 6
: HI
. . . . . . .
11 r~ o
UO~ + ion 'radius' is reasonable considering Shannon
-IX . . . . . . 3~,4,
3~9 - '9 ,:: - 1-0' °1 -I .
.501 . - 5 1 .0 . H.I 0. KII. 6. - . 1• 146 [30
& Prewitt's 1.36 A oxygen radius and the 2.49 A U - O
(equatorial) separation in sodium uranyl acetate and
.~
iz
P,I-~
o 70
~:~'-;:I
-a~
?.
.,s
:~
,so
:b' L" '~I-111
271 ze,
o"'IL"-.~
uranyl carbonate (Zachariasen & Plettinger, 1959).] In
-se

..
zoz
s ~.
zo~
•
-,
'."
6
2IS
~ob
ze
26~
3s~
-~ -to

-*z
SZ"
az
;~
,.~o
-*~
-~q
-~52
z*

.o
70
z ~o
-so
6
z.
-Z
',
7o
Zb7
~so
-ZS9
z,

3sL
Fig. 4 w e have plotted values of the N - O separation
vs. the O - H . • • O separation for N - O bonds which are
' t'..' -' q .........
influenced only by hydrogen bond interactions. In
..... Lq-; ......... ;~ ...................
cases where more than one interaction is involved, we
111 SJ IS9 144 $4 11 1,21 -12s S l~.S -lo$
have simply averaged the values. We find in sulfate
I. -I . . . . 1,~ --ql - " I~'~
-~9 • "1 t" u 6

)7 ,~ zo ~ • it lz, -zzs o zz~ -zz7 z z~ Z8*

-I Ill "l~ -" If: . . . . . . . . . . . . . ~z e . . . . . . . . . . .

-: ,:: 6o'I , , . . ,.. . . - , , o zez

...... -~,, 7oo z:o .- z ., , . . . . . . . . .
o
~o -)ez lzs
i~ .,,.
. . -s,t
. . . . .,*. . .6,. . .-,,
.
. . . . . . . . . . . . . . . . . . . . . . . . . . . ., , .7 . . . • . . . .
: g~°e "I~: -l~z ':I t:: -z. . . . .a~,
.:.
...
21S01 " 2 0 )
25,
I~0(8)
-lZ lo~ llo ts* o
1~ z~ z~z 27* az -~ -tot°.,

;r ,X ;Io' "&".~ I~. 2~; 2 1 f ';1 *'~: . . . . . . . .

. . . . . . _z ., .o. ,. . . . ., -lr z~o~ -29,''" -I * ,.0 . . .a ' ' *"''
2 X~
..... I 89o
, " , , o. . . . . . . o -: . ., . . . .-. . ,. . . . . . . . . -,. -"~ . . . . *, l~,~ " l ~
"I ~:: . ._. .
' ~I "0
-: I ; ~ - . ,. . . . . . .,. . . -%1 -: 2"6; .-...,. . . , l~.~ ,,,"'
: ........... ll~ ...............
89° 98° 0

i:
~4~
. . . .158
1¢6
--Z~.6-1l
. . .-1*
. . . 251
. . . .-25a
. . . . . 9 . . 216
7)
-Z68
15
o*
Hd
. 67
4 KII
. . . -3g
.
6
-I
o 287
.......
16) 166
/
-l~e

-15
~9

XgZ
41

1~ -*S]
-ll

-15" 77
-82

62
-*

-)~
39t 115 221
015 ~ N
3 t~) 11~ -e 20~, -zxo H~ • U *

-Z3l -$ 286 1*3 2 1e6 -lgX 2ZZ 3 t85 18&

~ 0
......... -I l:~ -z51
.... ~ Ill Iz~ -z,-*z IX: ..6
... I u,
.....
6

......... II '" l:l .............. I .....

0(2)../^ 80o~;/
........ -. . . . . . . . : d: -,00'*
-16 11~' -t77 HI 3 If 5 nd 12 ~ f $ -q 189 17g -6 ~.12 106
o S60 -~6 Z lSt ~* st *~ z~9

z. 1 11 6 . . z~z
. . .- z . . . ~ 7 ; Ill . ). . . .1 ~. . . . z. l o. . . ..;*
. . . . ,6
. ..~z *: J :?u 7
-1 ao9 - 2 6 ~ * )s~, ~ss -~ 89 - z z ) z) zoz -ins -z z~z aes
azs - 2 2 ~ * ~ 30~ ~oo ~,. ~ 7'. ) 11~ - z z ~
-) 80 -~Z 6 *6Z ,75 -S ~t -~o ., 6 ~ 6 -3 ,zs -o,

-
I "I.S9
'-"
-233
-" " " 23'
8 319 -);~* -
I I -I .119. . .
t 0 2
do4 .0
393 -
, .244
.....
-U)
-- 7 130 125 |0 S~I -Stlg .g~t 7S U8 120 N* 7 KIP 7

- 1' l g : .- z. z. ~. . l:" d : ,I: o"'l:, ,' ......

is 13o -,~z-16 zto -zoo z za~ ZZ7 =*0 Z~ -z~z ,, * u *
-IS zo~ -96 -z Z~6 -2~1 120 )~ zz z ztz -ao6
.J ,, ,~ s ~. z,-. a,.o -zz z*z -zse -t ~o ~o
HO 1 &l 6

-z . . . -¢,31
. . . "117
8 - I lul ~ 1:: . . . . . l. . . . :
-* *is -tl.i -s z61 ~e 1. 1~ -1 soz |

(1965) on A g C N . 2AgNO3, by Taylor & Mueller (1965)

Fig. 2. A schematic drawing of the crooked chains which link
on UO2(H20)6(NO3)2, and by Sass, Vidale & Dono- the copper ions in Cu(NO3)2.2.SH20. The two water
hue (1957) on NaNO3; all will hereafter be denoted oxygen atoms about the lower copper atom have not been
by their initials. It has been previously noted by BD included.
 B. M O R O S I N 1207

compounds, where a much larger number of reliable n u m b e r of carefully determined structures containing
bond separations are available, that this averaging nitrate ions is limited, we are unable to m a k e a more
procedure may be questionable. In such. sulfate com- detailed comparison in this case. However, we find a
pounds, the average O - H . . . O separations appear to reasonably linear relationship for N - O separation vs.
be consistently longer whenever three, rather than two, O - H . • • O separation in these nitrate compounds. (The
hydrogen-bond interactions are involved. Since the average N - O separation of 1-185(6) found in Ti(NO3)4
(GW) involves no hydrogen bond interactions and the
1.218(4) value in NaNO3 (SVD) involved in the Na
I i I polyhedra are the only accurate NO~- ion non-hydro-
gen bonded separations available for comparison with
' I
those given in Fig. 4.) It appears the ionic interactions
and bonding associated with the hydrogen atoms in
the lattice have a well characterized influence upon in-
2.6 teratomic separation in anions. Our results on sulfate
A
~II I ions will be reported elsewhere.
Since our room-temperature structure results on
Z
0 Cu(NO3)z.2-5H20 indicate a chain-like arrangement
rather than isolated binary clusters as suggested by the
<2.4
a_
low-temperature thermal and magnetic data, we have
also examined crystals at liquid nitrogen temperatures.
z
k~ No gross changes in the intensity data, recorded by
(_9
m- precession photographs, were found, suggesting that
R
0 there is no structural phase transition upon cooling.
i
Evidently long-range magnetic ordering requires fa-
~2.2 vorable chain geometry (more linear as found in the
=E copper tetrammine compound; Morosin, 1969) and,
hence, the crooked chain system in Cu(NO3)2.2"5 H20
is favorable only to short-range exchange. The latter
would yield properties very similar to binary clusters.
2.0 l-ll-I
References
I I I
1. 20 1. 25 1.30 BERGER, L., FRIEDBERG, S. A. & SCHRIEMPF, J. T. (1963).
Phys. Rev. 132, 1057.
N-0 SEPARATION(~,) BRITTON, D. (~ DUNITZ, J. O. (1965). Acta Cryst. 19, 815.
Fig.3. The N-O bond lengths vs. metal-oxygen separations. DORNBERGER-SCHIFF, K. (~ LECIEJEWICZ, J. (1958). Acta
The values shown are for the following ions: Ti (open Cryst. 11,825.
circle, GW), U (solid diamond, TM), Ce (solid circle, ZFT), DUFFIN, B. & WALLWORI<,S. C. (1966). Acta Cryst. 20, 210.
Ni (open square, GWP), Ag (crosses, BD), and Cu (solid FRIEDBERG,S. A. & RAQUET,C. A. (1968). J. Appl. Phys. 39,
squares, this work). (Initials are defined in the text.) 1132.

Table 3. Interatomic separations and angles in Cu(NO3) 2 . 2.5 H20

(a) Those which involve the copper environment
Cu-O(8) 1.959 (2) ~ 0(8) -Cu-O(6) 91.20 (8) o
Cu-O(7) 1-959 0(8) -Cu-O(5') 81-91
Cu-O(6) 1.978 0(8) -Cu-O(3) 90.72
Cu-O(2) 1.992 0(8) -Cu-O(2) 90.99
Cu-O(5) 2.391 0(8) -Cu-O(5) 90.14
Cu-O(3) 2.653 0(6) -Cu-O(5) 102.99
Cu-O(5") 2.675 0(6) -Cu-O(7) 89.18
O(5')-Cu-O(7) 98-37
0(3) -Cu-O(7) 89-11
0(2) -Cu-O(5) 80.40
0(2) -Cu-O(7) 88.63
0(5) -Cu-O(7) 89-73
(b) Those which involve nitrate ions
N(1)-O(3) 1.238 (3) .~ O(3)-N(1)-O(1) 122.1 (1) °
N(1)-O(1) 1"241 O(3)-N(1)-O(2) 118.6
N(1)-O(2) 1.281 O(1)-N(1)-O(2) 119.2
N(2)-O(4) 1.222 O(4)-N(2)-O(5) 124.6
N(2)-O(5) 1.235 O(4)-N(2)-O(6) 118.3
N(2)-O(6) 1.306 O(5)-N(2)-O(6) 117.0
1208 THE CRYSTAL STRUCTURE O F Cu(NO3)2.2"5H20

Table 3 (cont.)
(c) Those which involve hydrogen-bond interactions
0(9)-0(3) 2.922 (3) A 0(3)-0(9)-0(3') 122.2 (1) °
O(7)-O(1) 2.787 O(1)-O(7)-O(1) 120-7
O(7)-O(1) 2.896
0(8)-0(6) 2.838 0(6)-0(8)-0(9) 108.7
0(8)-0(9) 2.692
(d) Those which involve hydrogen atoms
O(7)-H(1) 0.91 (8) A O(1)-H(1) 1.94 (8) .~,
O(9)-H(5) 0.92 O(3)-H(5) 2.00
O(7)-H(2) 0.92 O(1)-H(2) 1.99
O(8)-H(3) 0.96 O(6)-H(3) 1-90
O(8)-H(4) 0.98 O(9)-H(4) 1.73
H(1)-O(7)-H(2) 108 ° O(7)-H(1)-O(1) 155 °
H(3)-O(8)-H(4) 107 O(7)-H(2)-O(1) 168
H(5)O(9)-H(5) 119 O(8)-H(3)-O(6) 166
O(8)-H(4)-O(9) 166
O(9)-H(5)-O(3) 177

3.1 GALLEZOT, P., WEIGEL,D. & PRETrRE, M. (1967). Acta

' I ' I ' ' I ' ' ' ' i
Cryst. 22, 699.
GARAJ, J. (1968). Acta Chem. Scand. 22, 1710.
~ 3.0 GARNER, G. D. & WALLWORK,S. C. (1966). J. Chem. Soc.
z p. 1496.
O
I--
International Tables for X-ray Crystallography (1962). Vol.
<2.9 III. Birmingham: Kynoch Press.
MOROSIN, B. (1969). Acta Cryst. B25, 19.
I.i..1
m MYER, B. E., BERGER, L. & FRIEDBERG, S. A. (1969). J. Appl.
o2.8 Phys. 40, 1149.
Nn~KERK, J. N. VAN & SCnOENINO, F. R. L. (1953). ,4cta
Cryst. 6, 227.
=:2.7
!
SASS, R. L., VIDALE, R. & DONOHLrE, J. (1957). Acta Cryst.
0 10, 567.
SHANNON, R. D. & PREWlTr, C. T. (1969). Acta Cryst. B25,
2.6 925.
I I I I I t I I I I I 1--
I. 20 I. 25 I. 30 TAYLOR, J. C. & MtrELLER, M. H. (1965). Acta Cryst. 19, 536.
N- O SEPARATION (~,) WITTEHOEK, S. & POULIS, N. J. (1968). J. Appl. Phys. 39,
1017.
Fig.4. The N-O bond lengths vs. O - H ' . . O separation. The ZACHARIASEN, W. H. & PLEa~rINOER, H. A. (1959). Acta
values shown are from GWP (open circles), TM (triangles), Cryst. 12, 5260.
FBLT (squares), ZFT (solid squares), and this work (solid ZALrdN, A., FORRESTER, J. D. & TEMPLETON, D. H. (1963).
circles). (Initials are defined in the text.) J. Chem. Phys. 39, 2881.