C3H5-C(=O)Cl



 


























 








 









Chlorine


Nuclear Quadrupole Coupling Constants

in cis-Cyclopropyl Carbonyl Chloride

 








 








Chlorine nqcc's in cis-cyclopropyl carbonyl chloride (C3H5-C(=O)Cl) were determined by Heldmann et al. [1].

 








Calculation was made here of the Cl nqcc tensors in C3H5-C(=O)Cl on molecular structures given by MP2/6-311+G(3df,3pd) and MP2/aug-cc-pVTZ optimization, and on these same structures but with empirically corrected approximate equilibrium C-C(=O)Cl bond lengths.   These calculated nqcc's are compared with experimental values in Tables 1 and 2.  Structure parameters are given in Table 3, rotational constants in Table 4.

 








In Tables 1 and 2, subscripts a,b,c refer to the principal axes of the inertia tensor; x,y,z to the principal axes of the nqcc tensor.  ETA = (Xxx - Xyy)/Xzz.  Ø (degrees) is the angle between its suscripted parameters.

RMS is the root mean square difference between calculated and experimental diagonal nqcc's (percent of average experimental diagonal nqcc).  RSD is the calibration residual standard deviation of the B1LYP/TZV(3df,2p) model for calculation of the efg's/nqcc's.

 








 







 
   







Table 1.  Chlorine nqcc tensors in C3H5-C(=O)Cl (MHz).  Calculation was made on (1) MP2/6-311+G(3df,3pd) optimized structure and on (2) this same structure but with approximate equilibrium bond lengths for C-C(=O)Cl.
   









Calc (1)
Calc (2)
Expt [1]
   







Xaa (35Cl) -
 43.44
 -
 43.51
 -
 43.2413(91)

Xbb
22.15
22.15
21.202(11)

Xcc
21.29
21.35
22.039(11)

|Xab|
37.98
37.78
37.301(18)

 







RMS
0.71 (2.4 %)
0.69 (2.4 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
39.54
39.37
38.271(21)

Xyy
21.29
21.35
22.039(18)

Xzz -
 60.82
 -
 60.73
 -
 60.311(19)

ETA -
 0.300
 -
 0.297



Øz,a
24.60
24.50
24.589(8)

Øa,CCl
24.82
24.78



Øz,CCl
  0.22
  0.27



 







 







Xaa (37Cl) -
 34.64
 -
 34.69



Xbb
17.86
17.86



Xcc
16.78
16.83



|Xab|
29.59
29.42



 







RMS







RSD
0.44 (1.1 %)
0.44 (1.1 %)



 








 








 








   







Table 2.  Chlorine nqcc tensors in C3H5-C(=O)Cl (MHz).  Calculation was made on (1) MP2/aug-cc-pVTZ optimized structure and on (2) this same structure but with approximate equilibrium bond lengths for C-C(=O)Cl.
   









Calc (1)
Calc (2)
Expt [1]
   







Xaa (35Cl) -
 43.50
 -
 43.23
 -
 43.2413(91)

Xbb
21.95
21.90
21.202(11)

Xcc
21.55
21.33
22.039(11)

|Xab|
38.14
37.86
37.301(18)

 







RMS
0.54 (1.8 %)
0.57 (2.0 %)



RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
39.48
39.27
38.271(21)

Xyy
21.55
21.33
22.039(18)

Xzz -
 61.03
 -
 60.60
 -
 60.311(19)

ETA -
 0.294
 -
 0.296



Øz,a
24.69
24.65
24.589(8)

Øa,CCl
24.85
24.89



Øz,CCl
  0.16
  0.25



 







 







Xaa (37Cl) -
 34.69
 -
 34.48



Xbb
17.71
17.66



Xcc
16.98
16.82



|Xab|
29.70
29.48



 







RMS







RSD
0.44 (1.1 %)
0.44 (1.1 %)



 








 








 











Table 3.  C3H5-C(=O)Cl.  MP2/6-311+G(3df,3pd) and MP2/aug-cc-pVTZ optimized molecular structure parameters (Å and degrees).  Corrected approximate equilibrium bond lengths are given in parentheses.
 


 C
 C,1,B1
 C,1,B2,2,A1
 H,1,B3,3,A2,2,D1,0
 H,1,B4,3,A3,2,D2,0
 H,2,B5,1,A4,3,D3,0
 H,2,B6,1,A5,3,D4,0
 H,3,B7,1,A6,2,D5,0
 C,3,B8,1,A7,2,D6,0
 O,9,B9,3,A8,1,D7,0
 Cl,9,B10,3,A9,1,D8,0

 

 MP2/6-311+G(3df,3pd) MP2/aug-cc-pVTZ

 

 B1=1.48423695
 B2=1.51828308
 B3=1.07918696
 B4=1.07856297
 B5=1.07918696
 B6=1.07856297
 B7=1.07648067
 B8=1.46911764     (1.4695)
 B9=1.19445375     (1.1898)
 B10=1.78248814   (1.7870)
 A1=60.73905171
 A2=115.42292151
 A3=115.88374778
 A4=117.37784156
 A5=118.75819868
 A6=118.52748764
 A7=115.62240571
 A8=126.67548821
 A9=112.65988195
 D1=-108.50076913
 D2=109.94478759
 D3=-105.30805245
 D4=105.26691686
 D5=-107.73134734
 D6=105.58749848
 D7=-32.82642045
 D8=147.17357955
 B1=1.48531808
 B2=1.52042269
 B3=1.07940623
 B4=1.0786972
 B5=1.07940623
 B6=1.0786972
 B7=1.07637999
 B8=1.46718305       (1.4675)
 B9=1.19685005       (1.1891)
 B10=1.79386378     (1.7906)
 A1=60.76087422
 A2=115.31802544
 A3=115.85591414
 A4=117.39962026
 A5=118.82395912
 A6=118.65995478
 A7=115.58149219
 A8=127.10233147
 A9=112.35775181
 D1=-108.5787354
 D2=110.04139631
 D3=-105.18006789
 D4=105.21374584
 D5=-107.81598806
 D6=105.54399348
 D7=-32.78866309
 D8=147.21133691



 














Table 3.  C3H5-C(=O)35Cl  Rotational Constants (MHz).   r(1) = Optimized structure and r(2) = Optimized structure with approximate equilibrium bond lengths for C-C(=O)Cl.







MP2/6-311+G(3df,3pd)
   MP2/aug-cc-pVTZ

  r(1)   r(2)   r(1)
   r(2)
      Expt [1]






     A  6586.
  6601.
  6544.
  6580.
 6542.01009(60)
     B  1814.
  1810.
  1808.
  1810.
 1796.68887(18)
     C  1598.
  1596.
  1591.
  1595.
 1583.89270(17)






















[1] C.Heldmann, H.Dreizler, and R.Schwarz, Z.Naturforsch. 45a, 1169(1990).

 








K.P.R.Nair and J.E.Boggs, J.Mol.Struct, 33,45(1976).

K.P.R.Nair and J.E.Boggs, Abstract, OSU International Symposium on Molecular Spectroscopy, 1975.











 








HC(=O)Cl
 FC(=O)Cl CH3C(=O)Cl
 CH2CHC(=O)Cl

Cyclobutyl Carbonyl Chloride (CH3)3C-C(=O)Cl


 








 








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Molecules/Chlorine




 








 













cycC3H5COCl.html






Last Modified 15 Dec 2015