144
Chapter 11 Pauling “3-Electron Bonds” and “Increased-Valence” Structures
Table 11-1: Bond lengths (Å) for some nitrosyl and nitro compounds.
r(N-O)
r(N-X)
r(N-O)
r(N-X)
NO
(a)
1.150
2
2
O NNO (j)
1.190
1.782
FNO
(b)
1.136
1.512
2
O NNO
(k)
1.142 (NO′)
1.864
ClNO
(c)
1.139
1.975
1.202, 1.217
(NO)
BrNO
(d)
1.146
2.140
2
FNO (1)
1.180
1.467
HNO
(e)
1.209
1.090
2
ClNO (m)
1.202
1.840
3
CH NO (f)
1.211
1.480
3
2
CF NO (n)
1.21
1.56
3
CF NO (g)
1.197
1.546
3
2
CCl NO (o)
1.21
1.59
2
NO
(h)
1.236
3
2
CH NO (p)
1.224
1.489
2
NO (i)
1.193
References: (a) K.P. Huber and G. Herzberg, Molecular Spectra and Molecular Structure, Vol. 4
(Van Nostrand Reinhold, 1979). (b) K.S. Buckton, A.C. Legon and D.J. Millen, Trans. Faraday
Soc., 65, 1975 (1969). (c) D.J. Millen and J. Pannell, J. Chem. Soc., 1322 (1961). (d) D.J. Millen
and D. Mitra, Trans. Faraday Soc., 66, 2408 (1970). (e) J.F. Ogilvie, J. Mol. Struct. 31, 407
(1976). (f) P.M. Turner and A.P. Cox, J. Chem. Soc., Faraday II, 74, 533 (1978). (g) S.H. Bauer
and A.L. Andreessen, J. Phys. Chem., 76, 3099 (1972). (h) G.B. Carpenter, Acta. Cryst., 8, 852
(1955). (I) G.R. Bird, J.C. Baird, A.W. Jache, J.A. Hodgeson, R.F. Curl, A.C. Kunkle, J.W.
Bransford, J. Rastrup-Andersen and J. Rosenthal, J. Chem. Phys., 40, 3378 (1964). (j) B.W.
McClelland, G. Gundersen and K. Hedberg, J. Chem. Phys. 56, 4541 (1972). (k) A.M. Brittain,
P.A. Cox and R.L. Kuczkowski, Trans. Faraday Soc., 65, 1963 (1969). (I) A.C. Legon and D.J.
Millen, J. Chem. Soc. A., 1736 (1968). (m) D.J. Millen and K.M. Sinnott, J. Chem. Soc., 350
(1958). (n) I.L. Karle and J. Karle, J. Chem. Phys., 36, 1969 (1962). (o) W.M. Barss, J. Chem.
Phys., 27, 1260 (1957). (p) A.P. Cox and S. Waring, J. Chem. Soc. Faraday II 68, 1060 (1972).
Table 11-2: Bond-lengths (Å) for some molecules with O-O linkages.
r(O-O) r(O-X)
r(O-O)
r(O-X)
2
O (a)
1.207
3
CF OOCl (f)
1.447
1.699 (O-Cl)
FOOF
(b)
1.217
1.575
1.372 (O-C
HOOH
(c, d)
1.475
0.950
3
CF OOF (f)
1.366
1.449 (O-F)
1.452
0.965
1.419 (O-C)
3
3
CF OOCF (e)
1.419
1.399
2
HO
(g, h)
1.335
0.977
3
CF OOH (f)
1.447
0.974 (O-H)
1.329
0.975
1.376 (O-C)
3
O (i)
1.272
References: (a) Ref. (a) of Table 11-1. (b) R.H. Jackson, J. Chem. Soc. 4585 (1962). (c) A.L.
Redington, W.B. Olson and P.C. Cross, J.Chem. Phys., 36, 1311 (1962). (d) G. Khachkuruzov
and I.W. Przherolskii, Opt. Spectrosk., 36, 172 (1974). (e) C.J. Marsden, L.S. Bartell and F.P.
Diodati, J. Mol. Struct. 39, 253 (1977). (f) C.J. Marsden, D.D. DesMarteau and L.S. Bartell,
Inorg. Chem., 16, 2359 (1977). (g) Y. Beers and C.J. Howard, J. Chem. Phys., 64, 1541 (1976).
(h) R.P. Uckett, P.A. Freedman and W.J. Jones, Mol. Phys., 37, 403 (1979). (I) J.-C. Depannemaecker and J. Bellet, J. Mol. Spectr., 66, 106 (1977).
Chapter 11 Pauling “3-Electron Bonds” and “Increased-Valence” Structures
Table 11-1: Bond lengths (Å) for some nitrosyl and nitro compounds.
r(N-O)
r(N-X)
r(N-O)
r(N-X)
NO
(a)
1.150
2
2
O NNO (j)
1.190
1.782
FNO
(b)
1.136
1.512
2
O NNO
(k)
1.142 (NO′)
1.864
ClNO
(c)
1.139
1.975
1.202, 1.217
(NO)
BrNO
(d)
1.146
2.140
2
FNO (1)
1.180
1.467
HNO
(e)
1.209
1.090
2
ClNO (m)
1.202
1.840
3
CH NO (f)
1.211
1.480
3
2
CF NO (n)
1.21
1.56
3
CF NO (g)
1.197
1.546
3
2
CCl NO (o)
1.21
1.59
2
NO
(h)
1.236
3
2
CH NO (p)
1.224
1.489
2
NO (i)
1.193
References: (a) K.P. Huber and G. Herzberg, Molecular Spectra and Molecular Structure, Vol. 4
(Van Nostrand Reinhold, 1979). (b) K.S. Buckton, A.C. Legon and D.J. Millen, Trans. Faraday
Soc., 65, 1975 (1969). (c) D.J. Millen and J. Pannell, J. Chem. Soc., 1322 (1961). (d) D.J. Millen
and D. Mitra, Trans. Faraday Soc., 66, 2408 (1970). (e) J.F. Ogilvie, J. Mol. Struct. 31, 407
(1976). (f) P.M. Turner and A.P. Cox, J. Chem. Soc., Faraday II, 74, 533 (1978). (g) S.H. Bauer
and A.L. Andreessen, J. Phys. Chem., 76, 3099 (1972). (h) G.B. Carpenter, Acta. Cryst., 8, 852
(1955). (I) G.R. Bird, J.C. Baird, A.W. Jache, J.A. Hodgeson, R.F. Curl, A.C. Kunkle, J.W.
Bransford, J. Rastrup-Andersen and J. Rosenthal, J. Chem. Phys., 40, 3378 (1964). (j) B.W.
McClelland, G. Gundersen and K. Hedberg, J. Chem. Phys. 56, 4541 (1972). (k) A.M. Brittain,
P.A. Cox and R.L. Kuczkowski, Trans. Faraday Soc., 65, 1963 (1969). (I) A.C. Legon and D.J.
Millen, J. Chem. Soc. A., 1736 (1968). (m) D.J. Millen and K.M. Sinnott, J. Chem. Soc., 350
(1958). (n) I.L. Karle and J. Karle, J. Chem. Phys., 36, 1969 (1962). (o) W.M. Barss, J. Chem.
Phys., 27, 1260 (1957). (p) A.P. Cox and S. Waring, J. Chem. Soc. Faraday II 68, 1060 (1972).
Table 11-2: Bond-lengths (Å) for some molecules with O-O linkages.
r(O-O) r(O-X)
r(O-O)
r(O-X)
2
O (a)
1.207
3
CF OOCl (f)
1.447
1.699 (O-Cl)
FOOF
(b)
1.217
1.575
1.372 (O-C
HOOH
(c, d)
1.475
0.950
3
CF OOF (f)
1.366
1.449 (O-F)
1.452
0.965
1.419 (O-C)
3
3
CF OOCF (e)
1.419
1.399
2
HO
(g, h)
1.335
0.977
3
CF OOH (f)
1.447
0.974 (O-H)
1.329
0.975
1.376 (O-C)
3
O (i)
1.272
References: (a) Ref. (a) of Table 11-1. (b) R.H. Jackson, J. Chem. Soc. 4585 (1962). (c) A.L.
Redington, W.B. Olson and P.C. Cross, J.Chem. Phys., 36, 1311 (1962). (d) G. Khachkuruzov
and I.W. Przherolskii, Opt. Spectrosk., 36, 172 (1974). (e) C.J. Marsden, L.S. Bartell and F.P.
Diodati, J. Mol. Struct. 39, 253 (1977). (f) C.J. Marsden, D.D. DesMarteau and L.S. Bartell,
Inorg. Chem., 16, 2359 (1977). (g) Y. Beers and C.J. Howard, J. Chem. Phys., 64, 1541 (1976).
(h) R.P. Uckett, P.A. Freedman and W.J. Jones, Mol. Phys., 37, 403 (1979). (I) J.-C. Depannemaecker and J. Bellet, J. Mol. Spectr., 66, 106 (1977).