Supplemental Material

Microwave, Raman, and infrared spectra, r0 structural parameters, conformational stability and ab initio calculations of cyclobutylisocyanate

Sarah Xiaohua Zhou,a[1] Gamil A. Guirgisb, Korreda K. Gause b Andrew R. Conradc[2], Michael J. Tubergenc,

James R. Durig,a[3]

aDepartment of Chemistry, University of MissouriKansas City, Kansas City, MO 64110 USA

bDepartment of Chemistry and Biochemistry, College of Charleston, Charleston, SC 29424 USA

c Department of Chemistry, Kent State University, Kent, OH 44242, US

Table 1S. Calculated and observed vibrational frequencies (cm-1) of cyclobutylisocyanate for the axial-trans conformer.

Vib.
No / Approx. description / MP2/6-31G(d) / MP2
scaleda / IR intb / Raman actc / dp
ratio / IR / Contour
solid / PEDd / A / B
A / 1 / β-CH2 antisymmetric str. / 3209 / 3010 / 37.6 / 51.8 / 0.67 / 50S1, 50S2 / 99 / 1
2 / γ-CH2 antisymmetric str. / 3192 / 2995 / 5.4 / 72.8 / 0.66 / 47S2, 49S1 / 1 / 99
3 / CH str. / 3168 / 2972 / 30.3 / 128.2 / 0.16 / 96S3 / 16 / 84
4 / γ-CH2 symmetric str. / 3139 / 2945 / 18.9 / 93.2 / 0.10 / 96S4 / 5 / 95
5 / β-CH2 symmetric str. / 3131 / 2937 / 6.1 / 148.9 / 0.21 / 93S5 / 68 / 32
6 / NCO antisymmetric str. / 2391 / 2268 / 771.6 / 0.9 / 0.00 / 98S6 / 79 / 21
7 / γ-CH2 scissors / 1572 / 1491 / 2.8 / 6.4 / 0.63 / 67S7, 31S8 / 0 / 100
8 / β-CH2 scissors / 1548 / 1468 / 2.4 / 15.9 / 0.70 / 66S8, 32S7 / 44 / 56
9 / NCO symmetric str. / 1483 / 1407 / 13.0 / 26.2 / 0.21 / 61S9, 25S17, 10S10 / 99 / 1
10 / CH in-plane-bend / 1417 / 1345 / 23.9 / 11.0 / 0.44 / 61S10, 17S20 / 92 / 8
11 / β-CH2 wag / 1326 / 1258 / 10.2 / 1.1 / 0.37 / 1260 / 83S11, 13S15 / 3 / 97
12 / β-CH2 twist / 1265 / 1200 / 2.7 / 15.6 / 0.71 / 66S12, 15S18 / 94 / 6
13 / β-CH2 rock / 1158 / 1098 / 25.8 / 7.1 / 0.23 / 41S13, 13S18, 11S10, 10S21 / 78 / 22
14 / Ring breathing / 1066 / 1011 / 4.8 / 16.3 / 0.20 / 83S14 / 78 / 22
15 / Ring deformation / 960 / 910 / 0.3 / 1.8 / 0.32 / 68S15, 15S11 / 84 / 16
16 / Ring deformation / 913 / 866 / 4.0 / 3.4 / 0.26 / 49S16, 24S18, 14S13 / 0 / 100
17 / Cα-Nstr. / 809 / 768 / 24.9 / 8.7 / 0.12 / 48S17, 18S9 / 91 / 9
18 / γ-CH2 rock / 707 / 674 / 12.9 / 0.7 / 0.19 / 32S18, 25S16, 11S19, 10S13 / 43 / 57
19 / NCO in-plane bend / 619 / 614 / 12.7 / 0.5 / 0.73 / 71S19 / 4 / 96
20 / Ring-N in-plane bend / 420 / 400 / 5.0 / 1.1 / 0.31 / 402 / 39S20, 11S16, 10S13 / 64 / 36
21 / Ring Puckering / 208 / 199 / 3.8 / 1.1 / 0.44 / 67S21, 19S22 / 58 / 42
22 / Cα–N=C in-plane bend / 93 / 92 / 1.8 / 2.2 / 0.64 / 71S22, 16S20 / 93 / 7
A / 23 / β-CH2 antisymmetric stretch / 3200 / 3002 / 8.3 / 60.1 / 0.75 / 98S23
24 / β-CH2 symmetric stretch / 3129 / 2935 / 29.8 / 4.8 / 0.75 / 98S24
25 / β-CH2 scissors / 1531 / 1452 / 4.7 / 8.2 / 0.75 / 100S25
26 / γ-CH2 wag / 1327 / 1259 / 0.7 / 1.0 / 0.75 / 50S26, 25S27, 11S32
27 / CH out-of-plane bend / 1295 / 1229 / 0.0 / 6.3 / 0.75 / 40S27, 25S26, 16S28, 11S29
28 / β-CH2 wag / 1288 / 1222 / 0.0 / 5.9 / 0.75 / 1221 / 48S28, 32S29
29 / γ-CH2 twist / 1206 / 1143 / 2.1 / 5.2 / 0.75 / 23S29, 22S28, 16S31, 15S27
30 / β-CH2 twist / 1107 / 1050 / 1.7 / 2.9 / 0.75 / 58S30, 13S33, 11S29
31 / Ring deformation / 982 / 932 / 0.1 / 13.5 / 0.75 / 943 / 72S31
32 / Ring deformation / 955 / 906 / 4.7 / 0.5 / 0.75 / 902 / 54S32, 12S30, 11S33
33 / β-CH2 rock / 787 / 748 / 0.1 / 0.3 / 0.75 / 61S33, 21S32, 12S29
34 / NCO out-of-plane bend / 565 / 565 / 17.1 / 0.3 / 0.75 / 552 / 98S34
35 / Ring-NC out-of-plane bend / 403 / 381 / 3.3 / 0.4 / 0.75 / 90S35
36 / Cα-N=C out-of-plane bend / 47 / 47 / 0.6 / 2.6 / 0.75 / 100S36

a Force constant scaling factors: 0.88 for CH stretches; 0.9 for all other modes. b Infrared intensities in km/mol. c Raman activities in Å4/u. d PEDs from MP2 scaled calculation:values less than 10% are omitted.

Table 2S.Symmetry Coordinates for Cyclobutylisocyanate.

Symmetry Coordinate
A / 1 / β-CH2 antisymmetric str. / r1 – r2 + r3 – r4
2 / γ-CH2 antisymmetric str. / r5 – r6
3 / CH symmetric str. / r
4 / γ-CH2 symmetric str. / r5+ r6
5 / β-CH2 symmetric str. / r1+ r2 + r3+ r4
6 / NCO antisymmetric str. / R1 – R2
7 / γ-CH2 scissors / 4λ3– φ2– σ2– φ3– σ3
8 / β-CH2 scissors / 4λ1– α1– α2– ε1–ε2 + 4λ2– α3– α4– ε3– ε4
9 / NCO symmetric str. / R1+R2
10 / β-CH2 wag / α1 + α2– ε1– ε2 + α 3 + α4– ε3– ε4
11 / CH in-plane-bend / 4η1– η2– η3– φ1– σ1
12 / β-CH2 twist / α1– α2– ε1– ε2 + α 3– α4–ε3 + ε4
13 / β-CH2 rock / α1– α2 + ε1–ε2 + α 3– α4 + ε3 – ε4
14 / Ring breathing / δ1 + δ2 + δ3 + δ4
15 / γ-CH2 rock / φ2– φ3 + σ2– σ3
16 / Ring deformation / δ1 + δ2 – δ3 – δ4
17 / C-NCO stretch / R3
18 / Ring deformation / Δ1 + Δ2 – Δ3 – Δ4
19 / NCO in-plane-bend / π
20 / Ring-NCO in-plane-bend / η2 + η3– φ1– σ1
21 / C-NCO in-plane-bend / θ
22 / Ring puckering / Δ1 + Δ2 + Δ3 + Δ4
A / 23 / β-CH2 antisymmetric str. / r1 – r2 – r3 + r4
24 / β-CH2 symmetric str. / r1 + r2 – r3 – r4
25 / β-CH2 scissors / 4λ1– α1– α2– ε1–ε2– 4λ2 + α3 + α4+ ε3 + ε4
26 / γ-CH2 wag / φ2 + φ3– σ2– σ3
27 / CH out-of-plane bend / φ1 – σ1
28 / γ-CH2 twist / φ2– φ3– σ2 + σ3
29 / β-CH2 wag / α1 + α2– ε1– ε2– α 3– α4+ ε3 + ε4
30 / Ring deformation / δ1– δ2– δ3 + δ4
31 / Ring deformation / δ1– δ2 + δ3– δ4
32 / β-CH2 twist / α1– α2– ε1 + ε2– α 3 + α4 + ε3– ε4
33 / β-CH2 rock / α1– α2 + ε1– ε2– α 3 + α4–ε3 + ε4
34 / NCO out-of-plane-bend / Φ
35 / Ring-NC out-of-plane bend / η2– η3
36 / CαN out-of-plane bend / Σ

Table 3S. Comparison ofMP2/6-311+G(d,p) calculated structural parameters (Å and degree) with adjust r0 values for c-C4H7-X (X = NCO, OH, F, Cl, Br).

X= / NCO / NCO / OH[28] / F[29] / Cl[30] / Br[31]
Parametera / Eqt-t / Eqt-g / Eqt-trans / Equatorial / Equatorial / Equatorial
MP2 / Adj. r0 / MP2 / Est. r0 / MP2 / Adj. r0 / MP2 / Adj. r0 / MP2 / Adj. r0 / MP2 / Adj. r0
rN=C / 1.216 / 1.208(5) / 1.216 / 1.208(5)
rC=O / 1.180 / 1.161(5) / 1.180 / 1.161(5)
rCα- X / 1.438 / 1.433(5) / 1.441 / 1.438(5) / 1.408 / 1.412(3) / 1.386 / 1.383(3) / 1.777 / 1.783(5) / 1.938 / 1.942(3)
rCα-Cβ,β" / 1.543 / 1.548(5) / 1.536/1.545 / 1.541/1.550(5) / 1.542 / 1.547(3) / 1.530 / 1.543(3) / 1.534 / 1.539(3) / 1.535 / 1.541(3)
rCγ-Cβ,β" / 1.549 / 1.557(5) / 1.551/1.547 / 1.559/1.555(5) / 1.548 / 1.556(3) / 1.551 / 1.554(3) / 1.551 / 1.558(3) / 1.551 / 1.552(3)
NCO / 172.7 / 172.0(5) / 172.8 / 172.1(5)
CαNC / 133.9 / 135.2(5) / 134.3 / 135.6(5)
C β,β"CαX / 119.8 / 119.8(5) / 118.2/118.6 / 118.0/118.3(5) / 120.6 / 120.2(5) / 117.3 / 117.4(5) / 118.7 / 118.1(5) / 118.9 / 118.4(5)
CβCαCβ" / 88.3 / 88.9(5) / 88.3 / 88.9(5) / 88.3 / 88.9(5) / 89.4 / 89.3(5) / 89.0 / 89.7(5) / 89.1 / 89.7(5)
CγC β,β"Cα / 86.9 / 87.2(5) / 87.1/87.0 / 87.4/87.3(5) / 86.8 / 87.1(5) / 86.4 / 85.0(5) / 86.6 / 86.9(5) / 86.4 / 86.8(5)
CβCγCβ" / 87.9 / 88.3(5) / 87.7 / 88.1(5) / 87.9 / 88.3(5) / 87.8 / 88.6(5) / 87.8 / 88.3(5) / 87.9 / 88.9(5)
 HCαC β,β" / 110.0 / 110.2(5) / 110.5/110.0 / 110.7/110.2(5) / 110.2 / 110.4(5) / 112.1 / 112.1(5) / 111.3 / 111.6(5) / 111.4 / 111.8(5)
 HCαX / 107.7 / 107.7(5) / 109.7 / 109.7 / 105.9 / 105.9(5) / 107.7 / 107.7(5) / 107.1 / 107.1(5) / 106.4 / 106.4(5)
A(MHz) / 6985 / 7128 / 9200 / 9157 / 10247 / 10120 / 10392 / 10250 / 10274 / 10095 / 10208 / 10003
B(MHz) / 1509 / 1503 / 1382 / 1397 / 4290 / 4283 / 4271 / 4275 / 2521 / 2522 / 1624 / 1630
C(MHz) / 1482 / 1470 / 1259 / 1271 / 3439 / 3421 / 3411 / 3403 / 2200 / 2196 / 1485 / 1488

Fig. 1SInfrared spectra (500-800 cm-1) of cyclobutylisocyanate: (A) Gas; (B) Amorphous solid; (C) First annealed solid; (D) Second annealed solid.

[1] Taken in part from the dissertation of S. X.Zhou which will be submitted to the Department of Chemistry in

partial fulfillment of the Ph.D. Degree.

[2]Taken in part from the thesis of A. R. Conrad, which will be submitted in partial fulfillment for the Ph.D. degree.

[3] Corresponding author, phone 01 (816) 235-6038, fax: 01 (816) 235-2290, email: .