CH2Cl-C(OH)H-CH3




 






















 








 









Chlorine


Nuclear Quadrupole Coupling Constants

in 1-Chloropropan-2-ol  (m-ga)


 








 








 








Calculation of the chlorine nqcc's in 1-chloropropan-2-ol (m-ga) was made on structures derived ab initio by the methods of the Lille group, as described below.  These are compared with the experimental nqcc's of Goldstein et al. [1] in Tables 1 and 2.  Eigenvectors of the nqcc tensor are given in Table 3.  Structure parameters are given in Table 4.  Heavy atom coordinates and molecular rotational constants are given in Tables 5 and 6, respectively.


 








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.  z,CCl (degrees) is the angle between the z-axis of the nqcc tensor and the CCl bond axis.  ETA = (Xxx - Xyy)/Xzz.

 








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

 









 







 
   








Table 1.  35Cl nqcc's in 1-Chloropropan-2-ol (m-ga) (MHz).  Calculation was made on ab initio structures (1) MP2/6-311+G(d,p) and (2) MP2/6-311+G(2d,p) (see below).
   










Calc. (1)

Calc. (2)
Expt. [1]
   








Xaa - 44.98 - 45.38 - 45.0013(32)

Xbb
13.70
13.72
13.6805 **

Xcc
31.28
31.67
31.3208 **

Xab * - 38.89 - 38.98
39.05(55)

Xac *
20.48
19.47
20.2(12)

Xbc *
11.29
10.89
10.29(68)

 







RMS
0.03 (0.09 %) 0.30 (0.99 %)


RSD
0.49 (1.1 %)
0.49 (1.1 %)



 







Xxx
32.84
32.78
33.175 ***

Xyy
36.92
36.87
36.426

Xzz - 69.76 - 69.65 - 69.601

ETA
0.058
0.057
0.047

z,CCl
0.91
0.74



 








 








* Here and in Table 2, the algebraic signs of the off-diagonal nqcc's correspond to the atomic a,b,c coordinates given in Table 5.  The experimental off-diagonal nqcc's are absolute values.

** Calculated here from the experimental Xaa and Xbb - Xcc = - 17.6403(70) MHz.

*** Solution 2 ( - ) of Ref. [1].

 








 








   








Table 2.  37Cl nqcc's in 1-Chloropropan-2-ol (m-ga) (MHz).  Calculation was made on ab initio structures (1) MP2/6-311+G(d,p) and (2) MP2/6-311+G(2d,p) (see below).
   










Calc. (1)

Calc. (2)
Expt. [1]
   








Xaa - 35.47 - 35.79 - 35.4875(44)

Xbb
10.79
10.80
10.7718 **

Xcc
24.68
24.98
24.7157 **

Xab * - 30.66 - 30.74
31.37(81)

Xac *
16.08
15.29
16.1(20)

Xbc *
  8.87
  8.56
  8.3(12)

 







RMS
0.02 (0.09 %) 0.23 (0.99 %)


RSD
0.44 (1.1 %)
0.44 (1.1 %)



 








 








** Calculated here from the experimental Xaa and Xbb - Xcc = - 13.9439(89) MHz.

 








 









 









Table 3.  1-Chloropropan-2-ol-35Cl (m-ga).  Eigenvectors (direction cosines) of the nqcc tensor.  Ab initio (1) MP2/6-311+G(d,p) and (2) MP2/6-311+G(2d,p) structures.

 









 

   x
   y
   z


 









(1) a - 0.4831
0.0884
0.8711


  b
0.8440
0.3119
0.4364



c - 0.2331
0.9460 - 0.2253


   








(2) a - 0.4824
0.0638
0.8736



b
0.8350
0.3348
0.4366



c - 0.2646
0.9401 - 0.2148


 










 








 








Molecular Structure


 








Structures (1) and (2):  The molecular structure was optimized at the MP2/6-311+G(d,p) level of theory.  The optimized CC single bond length was then corrected using the equation obtained from linear regression analysis of the data given in Table IX of Ref. [2].  The CH bond lengths were corrected using r = 1.001 ropt, where ropt is obtained by MP2/6-31G(d,p) optimization [3].  

Structure (1):  The MP2/6-311+G(d,p) optimized CCl bond length was corrected by linear regression analysis of the data given in Table 4 of Ref. [4].  C-O-H geometry and all interatomic angles are those given by MP2/6-311+G(d,p) optimization.

Structure (2):  Same as (1) but with optimization made at the MP2/6-311+G(2d,p) level of theory.

 









 



Table 4.  1-Chloropropan-2-ol (m-ga).  Heavy atom and O-H structure parameters ( and degrees).  Complete structures are given here in Z-matrix format.

 






Struct. (1) Struct. (2)








ClC(1) 1.7880 1.7874


C(1)C(2) 1.5125 1.5125


C(2)C(3) 1.5110 1.5110


C(2)O 1.4201 1.4227


OH 0.9639 0.9679


ClC(1)C(2) 110.54 110.83


C(1)C(2)C(3) 110.54 110.19


C(1)C(2)O 111.10 111.18


C(2)OH 106.94 107.49


Cl - - - H 2.5794 2.6012



 








 
















Table 5.  1-Chloropropan-2-ol (m-ga).  35Cl species.  Heavy atom and O-H coordinates.
 









  a ()
  b ()
  c ()








Struct. (1) Cl
1.7555 - 0.0064 - 0.0629

C
0.1852 - 0.7706
0.3204

C - 0.9480 - 0.0110 - 0.3326

C - 2.2724 - 0.6747 - 0.0348

O - 1.0282
1.3162
0.1665

H - 0.1609
1.7170
0.0391
   





Struct. (2) Cl
1.7568 - 0.0052 - 0.0591

C
0.1850 - 0.7726
0.3088

C - 0.9501 - 0.0106 - 0.3381

C - 2.2698 - 0.6775 - 0.0272

O - 1.0316
1.3170
0.1667

H - 0.1726
1.7378
0.0185


 








 













Table 6.  1-Chloropropan-2-ol (m-ga).  35Cl species.  Rotational constants (MHz).







Struct. (1) Struct. (2)     Expt. [1]






A 8539.9 8519.2 8474.33677(99)

B 2215.9 2215.0 2199.9942(11)

C 1872.7 1870.0 1857.0413(12)


 








 








[1] T.Goldstein, M.S.Snow, and B.J.Howard, J.Mol.Spectrosc. 236,1(2006).

[2] J.Demaison, J.Coslou, R.Bocquet, and A.G.Lesarri, J.Mol.Spectrosc. 167,400(1994).

[3] J.Demaison and G.Wlodarczak, Structural Chem. 5,57(1994).

[4] I.Merke, L.Poteau, G.Wlodarczak, A.Bouddou, and J.Demaison, J.Mol.Spectrosc. 177,232(1996).

 








 








1-Chloropropan-2-ol (h-gg) 2-Chloropropan-1-ol (g-ga)



2-Chloroethanol 2-Chloropropan-1-ol (g'-gg)













 








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Last Modified 16 Feb 2006