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SO2Cl-N=C=O
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Nitrogen and Chlorine
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Nuclear
Quadrupole Coupling Constants |
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in Sulfonyl Chloride Isocyanate |
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The microwave spectrum of sulfonyl chloride isocyanate was observed by Jo et al. [1], a mixed ro- ra (microwave + electron diffraction) structure was derived. N and Cl nqcc'c were determined.
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Calculation of the chlorine nqcc
tensors was made here on this ro, ra structure and on a structure given by MP2/6-311+G(3df) optimization (ropt). Calculated and experimental nqcc's are compared in Tables 1 - 3. Structure parameters are given in Table 4,
rotational constants in Table 5.
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In Tables 1 -3, subscripts a,b,c refer to
the principal axes of the inertia tensor, subscripts x,y,z to the
principal axes of the nqcc tensor. ETA = (Xxx - Xyy)/Xzz. Ø (degrees) is the angle between its subscript parameters.
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RMS is the root mean square difference between calculated and experimental nqcc's. RSD is the residual standard
deviation
of calibration of the B3PW91/6-311+G(df,pd) model for calculation of the N efg's/nqcc's; and of the B1LYP/TZV(3df,2p) model for calculation of
the Cl efg's/nqcc's. |
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Table 1. 14N nqcc's in SO235Cl-N=C=O
(MHz). Calculation was made
on ro- ra and ropt molecular structures.
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Calc /ro- ra
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Calc /ropt
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Expt [1]
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Xaa |
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2.254
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3.002
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2.905(8)
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Xbb |
-
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1.194
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1.844
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1.709(12)
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Xcc |
-
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1.059
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-
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1.158
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-
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1.196
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Xab |
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0.940
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1.081
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Xac |
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1.202
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-
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0.628
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Xbc |
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0.210
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0.321
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RMS
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0.485 (25. %)
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0.098 (5.1 %)
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RSD |
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0.030 (1.3 %) |
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0.030 (1.3 %) |
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Xxx |
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1.346
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1.037
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Xyy |
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1.524
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-
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2.262
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Xzz |
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2.870
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3.300
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ETA |
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0.0618
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0.371
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Øz,SN |
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13.49
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23.2
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Table 2. 35Cl nqcc's in SO235Cl-N=C=O
(MHz). Calculation was made
on ro- ra and ropt molecular structures.
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Calc /ro- ra
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Calc /ropt
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Expt [1]
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Xaa |
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16.98
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23.16
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15.768(9)
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Xbb |
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55.65
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61.45
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-
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53.641(10)
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Xcc |
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38.67
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38.29
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37.873
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Xab |
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42.33
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34.16
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Xac |
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0.95
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0.41
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Xbc |
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1.80
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3.25
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RMS
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1.43 (4.0 %)
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6.22 (17. %)
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RSD |
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0.49 (1.1 %) |
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0.49 (1.1 %) |
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Xxx |
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35.59
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34.65
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Xyy |
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39.53
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38.95
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Xzz |
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75.12
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-
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73.60
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ETA |
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0.0524
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0.0584
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Øz,SCl |
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0.59
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0.58
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Table 3. 14N and 37Cl nqcc's in SO237Cl-N=C=O
(MHz). Calculation was made
on ro- ra and ropt molecular structures.
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Calc /ro- ra
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Calc /ropt
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Expt [1]
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Xaa(14N) |
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2.218
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2.959
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2.875(19)
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Xbb |
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1.158
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1.801
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1.652(14)
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Xcc |
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1.060
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1.158
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1.223
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Xab |
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1.004
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1.173
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Xac |
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1.198
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0.634
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Xbc |
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0.233
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0.308
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RMS
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0.484 (25. %)
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0.106 (5.5 %)
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RSD |
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0.030 (1.3 %) |
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0.030 (1.3 %) |
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Xaa(37Cl) |
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12.11
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17.20
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11.186(20)
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Xbb |
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42.58
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47.38
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41.049(14)
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Xcc |
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30.47
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30.18
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29.863
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Xab |
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34.42
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28.19
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Xac |
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0.70
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0.29
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Xbc
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1.48
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2.54
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RMS
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1.09 (4.0 %)
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5.05 (18. %)
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RSD
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0.44 (1.1 %)
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0.44 (1.1 %) |
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| Table 4. Sulfonyl Chloride Isocyanate. Molecular structure parameters, ro- ra and ropt (Å and degrees). Bond lengths are ra values [2], angles are ro [1].
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ro- ra
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ropt
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SCl
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2.0185
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2.0196
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SO(6)
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1.4177
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1.4164
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SO(7)
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1.4177
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1.4228
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SN
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1.6584
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1.6472
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NC
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1.146
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1.2329
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CO
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1.233
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1.1590
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SN=C
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124.00(1)
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123.94
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NS=O(6)
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109.22(1)
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106.59
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109.22(1)
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106.92
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NSCl
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97.86(3)
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100.00
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N=C=O
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175.63(2)
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173.56
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ClSN=C
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94.12(3)
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81.43
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O(6)=SN=C
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206.02(3)
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193.15
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O(7)=SN=C
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342.21(3)
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328.96
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Table 5. Sulfonyl Chloride Isocyanate, 35Cl species.
Rotational Constants (MHz).
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Calc /ro- ra
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Calc /ropt
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Expt [1]
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A |
3078.6
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2985
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3078.396(7)
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B |
1471.9
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1493
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1471.985(3)
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C |
1240.3
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1244
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1240.364(2)
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[1] O.L.Jo, J.D.Graybeal, F.J.Lovas, and R.D.Suenram, J.Mol.Spectrosc. 153,261(1992).
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[2] J.Brunvoll and I.Hargittal, J.Chem.Soc. Dalton Trans, 299-302(1978).
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Methane Sulphonyl Chloride
| Benzene Sulphonyl Chloride |
SO2ClF
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HN=C=O
| ClN=C=O
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Table of Contents |
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Molecules/Chlorine |
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SO2ClNCO.html |
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Last
Modified 26 May 2014 |
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