Chem. SOC.: Single-Crystal Raman and Far-Infrared Spectra Tetrakis (Thiourea) - Nickel (Ii) Dichloride
Chem. SOC.: Single-Crystal Raman and Far-Infrared Spectra Tetrakis (Thiourea) - Nickel (Ii) Dichloride
Chem. SOC.: Single-Crystal Raman and Far-Infrared Spectra Tetrakis (Thiourea) - Nickel (Ii) Dichloride
Raman and far-i.r. spectra for single crystals of tetrakis(thiourea)nickel(ii) dichloride have been obtained at ca.
120 K and at ambient temperature. The results allow unambiguous assignment to A , 6, and E species (in C4
symmetry). Descriptions of many of the internal modes are also offered.
WE have previously reported the far-i.r. spectra of modes are of the rotatory type. Since we are not
several series of thiourea (tu) complexes and made concerned with the internal modes of thiourea, we
assignments which at the time appeared to be internally consider the ligand only as C=S for purposes of factor-
consistent. In view of the complexity of the spectra, group analysis; we then subtract the v(C=S) modes
and because part of our argument was based upon + +
( A B E ) which occur above 600 cm-l and add the
recently discredited X-ray structural data: we have torsional modes ( A B + +E ) which are not included
studied the low-frequency vibrational spectrum of one when this approximation is used.
of the more important compounds by single-crystal
techniques, viz, trarts-[Ni(tu),Cl,]. EXPERIMENTAL
Theory.-trarts-[Ni (tu),Cld cryst allises in the tetragonal Crystals of [Ni(tu),ClJ were obtained as golden-yellow
system, space group 14 = C4 (No. 79) with 2 = 2.4 rods by slow evaporation of an aqueous solution of NiCl,,-
This is an exceptionally favourable crystal for our 6H,O and thiourea. They showed well-developed { 100)
and { 001) faces.
TABLE1 Raman spectra were obtained with a Coderg PH 1
spectrometer with 632.8 nm excitation. A ‘ Cryocirc ’
Factor-group analysis of [Ni(tu),Cl,] cold cell was employed for work at liquid nitrogen tem-
C45 Total TA R N# Activity perature. The crystal space group allows optical rotation,
A 9 1 1 +
7 I.r.(z); Raman (atzz a’vv,a’J in principle, although we found no evidence of rotatory
B 6 0 0 6 Raman (dm-
E 9 1 1 7 I.r.(%,y); Raman (aW,a’=) power under the polarising microscope. Nevertheless, we
TA= acoustic modes; R = rotatory lattice modes; N f = restricted incident and outgoing beams to the x- and y-
internal modes, excluding v(C=S) but including torsions. axial directions in which optical rotation is much less
likely to occur. The excellent extinction between different
purposes since factor group, site symmetry, and molecular orientations confirms this.
symmetry are all C4, and there is only one formula unit Far-i.r. spectra were obtained as described e l s e ~ h e r e . ~ ~ ~
in the primitive cell. Hence, as shown by the factor- 3 M. Nardelli, L. Cavalca, and A. Braibanti, Guzzetta, 1956,
group analysis (Table l),the only optical branch lattice 86, 867.
4 A. Lopez-Castro and M. R. Truter, J. Chem. SOL, 1963,
1 D. M. Adams and J. B. Cornell, J. Chem. SOC.( A ) , 1967, 884. 1309.
2 J. E. O’Connor and E. L. Amma, Chem. Comm., 1968, 892: 5 D. M. Adams and R. R. Smardzewski, preceding paper.
Inorg. Chem., 1969, 8, 2367. D. M. Adams and R. R. Smardzewski, to be published.
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radiation. .-c
0
VI
Y)
.-
. l h /. . TABLE3
250 ZOO 150 100 50 16 250 ZOO 150 100 50 16
Bands in the far4.r. spectrum of [Ni(tu),C1,]
Symmetry Polaris- Temp.
species ationa (K) v(cm-l)
a z 298’ 236sh, 204s, 169s, 126s, llOs, 84sh
77 232sh, 212s, 172s. 132s, 118s, 96s
e x 298 232s, 202sh,b 166sh,b 142s, 94s, 49s
L .
77 224s, 192sh,b l68sh,b 150s, 102s, 59s,
250 200 150 100 50 16250 200 150 fD0 50 16 48s
1 Raman spectra of [Ni(tu),Cl,] at ambient
FIGURE a C,-axis E crystal z-axis. b Estimated.
temperature
TABLE4
TABLE2 Correlation of internal modes of [Ni(tu),Cl,j between
Relative peak heights in the Raman spectrum of groups
[Ni(tu)&Id Symmetry Molecule
co- Molecule and Factor
slit- ordinates * (C*J Site (C,) Group (C,3
Symmetry Orient- Temp. width
species ation (K) (cm-l) Av(cm-l)
u x(zz)y 298’ 4 216(8)br,a128(43), 109(100),
87(31)
77 2 215(8)br,a131(43), 112(100), 7A b
-
, 7A
b x(yx)y 298 4
93(31)
181(2),a 131(12), 75(91),
(Tz
; a’, + a’w,a’z,)
50( 100)
77 2 188(2),a 137(8),= 76(64),
51(100)
e x(yz)y 27978 4 96(18), 61(69), 52(100)
2 216(3),a 205(3),0 164(8),=
146(8),a 96(22), 62(60), (a‘Z.2 - a’w)
50(100) t---------B
6- 6B
e x(zx)y 298
77
4
2
96(18), 61(67), 50(100)
215(2),a 205(2),“ 163(7),a
148(6),0 98(18), 61(67),
k}
SU
3B,
(a’*)
2 (a’= - a’,,&-)
50(100)
a = slit-width 8 cm-1.