The high resolution infrared spectroscopy of cyanogen di-n-oxide [onccno]
The high resolution infrared spectroscopy of cyanogen di-N-oxide (ONCCNO)
Bujin GuoCentre for Molecular Beams and Laser Chemistry, Department of Chemistry, University of Waterloo,Waterloo, Ontario N2L 3G1, Canada
Tibor Pasinszki and Nicholas P. C. WestwoodGuelph-Waterloo Centre for Graduate Work in Chemistry, Department of Chemistry and Biochemistry,University of Guelph, Guelph, Ontario N1G 2W1, Canada
Peter F. BernathCentre for Molecular Beams and Laser Chemistry, Department of Chemistry, University of Waterloo,Waterloo, Ontario N2L 3G1, Canada and Department of Chemistry, University of Arizona,Tucson, Arizona 85721
͑Received 4 May 1995; accepted 16 May 1995͒
The high-resolution infrared absorption spectrum of the oxalodinitrile di-N-oxide ͑ONCCNO͒molecule has been recorded in the gas phase with a Fourier transform spectrometer at a resolutionof 0.003 cmϪ1. No previous high-resolution spectra have been recorded for this semistablepalindromic molecule. On the basis of the 2:1 intensity alternation in the rotational lines caused bynitrogen nuclear spin statistics, the ONCCNO molecule appears to be linear. A quasilinear structure,however, cannot be ruled out at this stage of the analysis. The 4 and 5 fundamental modes at2246.040 55͑23͒ cmϪ1 and 1258.475 30͑11͒ cmϪ1 have been analyzed to give ground staterotational constants of B ϭ
0.042 202 10͑96͒ cmϪ1 and D0 8.77͑70͒ϫ10Ϫ10 cmϪ1. By fixing the
CN and NO bond lengths to 1.1923 and 1.1730 Å, respectively, the C–C bond length wasdetermined to be 1.3329 Å using the B0 value. This short C–C bond length is thus similar to thatobserved for a carbon–carbon double bond. 1995 American Institute of Physics.INTRODUCTION
freshly prepared solution of ONCCNO in n-hexane beforepolymerization occurs to make polyfuroxan.3 Since dilute so-
The cyanogen di-N-oxide ͑oxalodinitrile di-N-oxide,
lutions are stable at 0 °C for several hours, ONCCNO has
ONCCNO͒ molecule was first prepared at the beginning of
been widely used in organic chemistry for 1,3-dipolar cy-
this century.1 However, its chemical formula and isolation
were not achieved until the early 1960s by Grundmann.2,3
The ONCCNO molecule is a candidate for astrophysical
The ONCCNO molecule was prepared in organic solutions
observation since it contains only the relatively abundant el-
by HCl elimination from the stable dichloroglyoxime͑
ements C, N, and O. The symmetric CNO dimer structure is
HONvC͑Cl͒–͑Cl͒CvNOH͒ precursor. Two strong infrared
also of spectroscopic and structural interest since there is the
absorption peaks at 2190 and 1235 cmϪ1 were observed in
possibility of quasilinear behavior as found in HCNO.5 The
CCl4 solution. The ultraviolet spectrum, which contains
symmetric linear CNO dimer ONCCNO has no dipole mo-
maxima at 312, 295, and 262 nm, can be obtained with a
ment so that pure rotational spectra will be very weak andinfrared or ultraviolet observations will be necessary. u CNO antisymmetric stretching mode of
the ONCCNO molecule. Note the lines due to the HNCO molecule near2270 cmϪ1. ͑b͒ An expanded portion of the R branch 2:1 intensity alterna-
FIG. 2. Portions of R and P branches of the 4 mode of the ONCCNO
tion caused by the nuclear spin statistics of two equivalent nitrogen nuclei in
molecule. The J quantum numbers are for the fundamental band and the
perturbed R͑96͒ and P͑98͒ lines are marked by arrows.
J. Chem. Phys. 103 (9), 1 September 1995
Guo et al.: Infrared spectroscopy of ONCCNO
TABLE I. The line list for the 4 vibrational mode of ONCCNO ͑cmϪ1͒.
J. Chem. Phys., Vol. 103, No. 9, 1 September 1995
Guo et al.: Infrared spectroscopy of ONCCNO
aObserved minus calculated line positions.
Pure samples of ONCCNO are difficult to handle. Crys-
The high-resolution absorption spectra were recorded
talline, monomeric ONCCNO is stable at Ϫ78 °C but begins
with a Bruker FTS 120 HR spectrometer at the University of
to visibly decompose near Ϫ45 °C and explodes a few min-
Waterloo with a resolution of 0.003 cmϪ1. The 4 mode, near
utes later at that temperature.6 Maier and Teles7 have re-
2250 cmϪ1, was recorded with an InSb detector and 46 scans
ported the formation of ONCCNO by flash vacuum pyrolysis
were coadded in the 1800–2900 cmϪ1 region. A redpass fil-
of dichloroglyoxime followed by condensation of the pyroly-
ter with a cutoff at 2900 cmϪ1 set the upper wave number
sis products diluted with argon on a cold ͑10 K͒ window,
limit while the lower wave number limit was set by the band
although they published no spectroscopic data. Until very
gap of the InSb detector. A HgCdTe detector was used to
recently no gas phase measurements have been made. Pasin-
record the 5 mode at 1260 cmϪ1 and the spectrum was
szki and Westwood8 have successfully studied gaseous ON-
obtained by coadding 55 scans. Another redpass filter ͑cutoff
CCNO by He I photoelectron spectroscopy, photoionization
at 1672 cmϪ1͒ set the high wave number limit and the
mass spectrometry, low-resolution midinfrared spectroscopy
HgCdTe detector response set the lower limit. A KBr beam-
as well as ab initio calculations. The strong IR absorption
bands at 2226 and 1260 cmϪ1 correspond to the antisymmet-ric ͑ ͒
vibrations, respectively, which were reported earlier at 2190
ANALYSIS
cmϪ1 and 1235 cmϪ1 in CCl4 solution.2 Unfortunately, the abinitio calculations did not provide a solid conclusion as to
The spectral analysis program PC-DECOMP, developed
whether the ONCCNO molecule was linear or bent although
by J. W. Brault, was used for the spectral line measurements.
a linear or quasilinear structure was preferred. High-
Using this program, the line profiles were fitted with Voigt
resolution gas phase spectroscopy can supply additional in-
lineshape functions. The signal-to-noise ratio for the stron-
formation on the molecular geometry.
gest lines in the spectrum was about 5:1 and the precision of
In this work, we report on our high-resolution Fourier
the line position measurement is better than Ϯ0.0006 cmϪ1
transform infrared spectra of the cyanogen di-N-oxide mol-ecule. The 4 and 5 vibrational modes have been recorded inthe gas phase and these two fundamental bands have beenrotationally analyzed. EXPERIMENT
The ONCCNO molecule was generated in situ using the
same method as described by Pasinszki and Westwood.8Briefly, the thermolysis of dichloroglyoxime in a quartz tube͑8 mm i.d. by 15 cm͒ heated to 550 °C gives a good yield ofONCCNO plus HCl with only trace amounts of the sideproducts, NO, CO, CO2, and HNCO. The experimental setupis typical for absorption spectroscopic work using a cell anda glower external to the spectrometer. The infrared glowerwas collimated by a parabolic mirror and passed through a20 cm long absorption cell equipped with KBr windows and
entered the spectrometer through the emission port. The ther-
FIG. 3. ͑a͒ An overview of the 5 u CNO symmetric stretching mode of theONCCNO molecule. ͑b͒ An expanded portion of the P branch of the
molysis products were pumped slowly through the gas cell at
mode. The marked lines are for the fundamental band and show the 2:1
intensity alternation caused by nuclear spin statistics.
J. Chem. Phys., Vol. 103, No. 9, 1 September 1995
Guo et al.: Infrared spectroscopy of ONCCNO
TABLE II. The line list for the 5 vibrational mode of ONCCNO ͑cmϪ1͒.
J. Chem. Phys., Vol. 103, No. 9, 1 September 1995
Guo et al.: Infrared spectroscopy of ONCCNO
aObserved minus calculated line positions.
for these lines. However, many of the weaker lines and the
ceeded in the same way as for 4. The 5 mode also had a
blended features were determined only to a precision of
high line density but no perturbations were present to help
the assignment. The rotational assignment of 5 was made by
An interactive color Loomis–Wood computer program
changing the relative assignment of the P and R branches
was used to pick out the branches and helped to assign the
until the ground state combination differences matched those
spectra. The CO molecule was present in the cell as a side
of 4. About 200 lines were assigned and the complete line
product of the thermolysis. The measured spectral lines of
the 4 vibrational mode were calibrated with the CO linesusing line positions taken from the literature.9 For the 5
The rotational constants
vibrational mode, we used the water absorption forcalibration.10
The line positions ͑Tables I and II͒ of the two fundamen-
tal bands were fitted together in a global least-squares fit. The 4 fundamental mode
Figure 1 shows the high-resolution spectrum of the CNO
F͑J͒ϭ ϩBJ͑Jϩ1͒ϪD͓J͑Jϩ1͔͒2ϩH͓J͑Jϩ1͔͒3
antisymmetric stretching mode ͑ ͒
HNCO molecule is present on the high wave number side of
was used in the fit and the resulting rotational constants are
the overview spectrum ͓Fig. 1͑a͔͒. Figure 1͑b͒ is an ex-
panded portion of the R branch of the 4 fundamental. The
0.042 202 10 cmϪ1 ͑1.265 187 GHz͒, is in good agreement
alternation in intensities is caused by the nuclear spin statis-
with the ab initio prediction8 of 1.24ϳ1.25 GHz. The cen-
tics of two equivalent ͑Iϭ1͒ nitrogen atoms. The symmetri-
trifugal distortion constants of the excited 4 vibrational level
cally located nitrogen atoms cause an intensity alternation of
may be perturbed by interaction with other modes.
2:1 with the even JЉ values being stronger.
The main problem in the analysis was the presence of a
DISCUSSION AND CONCLUSION
large number of hot bands which causes a line density ashigh as 100 lines/cmϪ1. It was impossible to locate the band
The semistable cyanogen di-N-oxide ͑ONCCNO͒ mol-
origin because of the overlapping hot bands. The final J as-
ecule can be generated in situ with a good yield in the gas
signments were achieved with the help of a small local per-
phase from the precursor molecule dichloroglyoxime by
turbation at JЈϭ97 in the upper level. Figure 2 shows the
thermolysis. The high-resolution spectra of the ONCCNO
perturbed R͑96͒ and P͑98͒ lines. The R͑96͒ line was shifted
molecule have been obtained for the two strongest vibra-
by 0.005 cmϪ1 to higher wave numbers while the P͑98͒ line
tional modes 4 and 5. The rotational analysis of these two
was shifted by the same amount. There are several other
modes and the intensity alternation of the lines indicates that
small local perturbations in this band which also confirm the
assignments. In total, 230 rotational lines were assigned forthe 4 band and they are listed in Table I.
TABLE III. The rotational constants for ONCCNO ͑in cmϪ1͒. One standard
The 5 fundamental mode
The high-resolution spectrum of the CNO symmetric
portion of the P branch is shown in Fig. 3͑b͒, again demon-
strating the 2:1 intensity alternation due to nitrogen nuclear
spin statistics. The measurement and assignment of 5 pro-
J. Chem. Phys., Vol. 103, No. 9, 1 September 1995
Guo et al.: Infrared spectroscopy of ONCCNO
TABLE V. The C–C bond lengths ͑r ͒
brS bond lengths from HCNO, Ref. 11.
cSee text for details. dBond length calculated using experimental rotational constant.
Indications from the ab initio calculations, and compari-
sons with similar molecules, suggest that the important CC
achieved. For example, the possibility of quasilinear behav-
bond is quite short.8 The single B value obtained in this work
ior cannot be ruled out at this stage of the analysis. We plan
is insufficient to provide this parameter without some as-
additional experiments to record spectra of the much weaker
sumptions about the CN and NO bond lengths. One approach
bending vibrational modes as well as combination bands.
to this problem is to use the known CN and NO bond lengths
This work will help assign the numerous hot bands that we
in the parent HCNO molecule,11 and assuming a linear struc-
have measured and will provide information on the missing
ture, extract the CC value from the rotational constant ͑B ͒
determined in this work. Table IV, structure I, shows thestructure of ONCCNO, predicted by this method. This, of
ACKNOWLEDGMENTS
course, assumes that the CN and NO bond lengths are trans-
We thank the Natural Science and Engineering Research
Council of Canada ͑NSERC͒ for the support of this research.
A possible improvement on this method is to see how a
T.P. thanks NSERC for the award of a NATO Science Fel-
computational method ͓MP3͑full͒/6-31G*͔8 performs for
lowship. Partial support was provided by the Petroleum Re-
both HCNO and ONCCNO, and then ‘‘correct’’ the CN and
search Fund and the NASA laboratory astrophysics program.
NO values and apply them to ONCCNO. With these ‘‘re-fined’’ CN and NO bond lengths, the mutual effect of back-
1 W. Steinkopf and B. Ju¨rgens, J. Prakt. Chem. 83, 453 ͑1911͒.
to-back CNO groups should be taken into account, and, us-
2 Ch. Grundmann, Angew. Chem. 75, 450 ͑1963͒; Angew. Chem. Int. Ed.
ing the experimental rotational constant, a value for the CC
Engl. 2, 260 ͑1963͒.
bond length is obtained. This assumes that the differences
Ch. Grundmann, V. Mini, J. M. Dean, and H.-D. Frommeld, Justus Liebigs Ann. Chem. 687, 191 ͑1965͒.
between the CN and NO bond lengths in HCNO and ONC-
4 ͑a͒ N. E. Alexandrou and D. N. Nicolaides, J. Chem. Soc. C, 2319 ͑1969͒;
CNO are predicted correctly by the MP3 method. Table IV,
͑b͒ D. N. Nicolaides and T. A. Kouimtzis, Chem. Chron. 3, 63 ͑1974͒; ͑c͒
structure II, shows the revised values for ONCCNO. This
A. Gu¨l, A. I. Okur, A. Cihan, N. Tan, and O
structure which takes into account the interaction of the two
¨ . Bekaroglu, Z. Anorg. Allg. Chem. 496, 197
͑1983͒; ͑e͒ Y. Go¨k and O¨. Bekaroglu, Synth. React. Inorg. Met.-Org.
CNO groups, indicates that the NO bond length has slightly
Chem. 11, 621 ͑1981͒; ͑f͒ V. Ahsen, E. Musluoglu, A. Gu¨rek, A. Gu¨l, O
decreased, while the CN bond length has slightly increased,
Bekaroglu, and M. Zehnder, Helv. Chim. Acta 73, 174 ͑1990͒; ͑g͒ Y. Go¨k
in accord with expectations based on a more delocalized
and S. Serin, Synth. React. Inorg. Met.-Org. Chem. 18, 975 ͑1988͒; ͑h͒ Y. Go¨k and A. Demirbas, ibid. 19, 681 ͑1989͒.
5 B. P. Winnewisser, Molecular Spectroscopy: Modern Research, edited by
Both the directly transferred CN and NO lengths, and the
K. N. Rao ͑Academic, New York, 1985͒, Vol. 3.
corrected values, lead to the result that the CC bond length is
6 Ch. Grundmann and P. Gru¨nanger, The Nitrile Oxides ͑Springer-Verlag,
about 1.333 Å, approximately the same as that in ethylene,
7 G. Maier and J. H. Teles, Angew. Chem. 99, 152 ͑1987͒; Angew. Chem.
H2CCH2, a molecule of known double bond character. Table
Int. Ed. Engl. 26, 155 ͑1987͒.
V shows CC bond lengths for a range of molecules. An im-
8 T. Pasinszki and N. P. C. Westwood, J. Am. Chem. Soc. ͑to be published͒.
portant observation is that the experimental CC bond length
9 A. G. Maki and J. S. Wells, Wavenumber Calibration Tables from Hetero-
in cyanogen, NC-CN is 1.389 Å,12 already much shorter than
dyne Frequency Measurements ͑NIST Special Publication 821, Washing-ton DC, 1991͒.
a typical CC single bond and we anticipate that this will
10 R. A. Toth, J. Opt. Soc. Am. B 8, 2236 ͑1991͒.
decrease upon adding terminal oxygen atoms ͑compare
11 ͑a͒ H. K. Bodenseh and M. F. Winnewisser, Z. Naturforsch. A 24, 1973
͑1969͒; ͑b͒ B. P. Winnewisser, M. F. Winnewisser, and F. Winther, J. Mol.
MP3͑full͒/6-31G* calculations for NCCN predict CC to be
Spectrosc. 51, 65 ͑1974͒.
12 A. G. Maki, J. Chem. Phys. 3, 3193 ͑1965͒.
1.393 Å, with similar calculations for ONCCNO predicting
13 W. J. Lafferty and E. K. Plyler, J. Chem. Phys. 37, 2688 ͑1962͒.
CC to be 1.361 Å.8 The inference from this is that the CC
14 C. C. Costain, J. Chem. Phys. 29, 864 ͑1958͒.
length in ONCCNO is at least 0.03 Å less than that in
15 H. K. Bodensen and K. Morgenstern, Z. Naturforsch 25a, 150 ͑1970͒.
A. A. Westenberg and E. B. Wilson, Jr., J. Am. Chem. Soc. 72, 199 ͑1950͒.
17 H. C. Allen, Jr. and E. K. Plyler, J. Am. Chem. Soc. 80, 2673 ͑1958͒.
Clearly, experimental and theoretical studies on this mol-
18 A. Baldacci, S. Ghersetti, S. C. Hurlock, and K. N. Rao, J. Mol. Spectrosc.
ecule have a long way to go before a full characterization is
59, 116 ͑1976͒.
J. Chem. Phys., Vol. 103, No. 9, 1 September 1995
Pallidotomy Thalamotomy This booklet will provide information about the following Preparing for Surgey surgical procedures: Pallidotomy and Thalamotomy. Before Admission to Hospital What is a Pallidotomy? 1) Anticoagulants (e.g. coumadin) and other medications A pallidotomy is an operation for Parkinson’s disease where that thin your blood, e.g. Aspirin, Ticlid, Plavix, Ginkgo
ProGlutamine Product Categorie proGlutaminen Glutamine Glutamine behoort tot de aminozuren. Dit zijn moleculen die de bouwstenen vormen van alle weefsels waaronder het spierweefsel. Glutamine komt voor in alle eiwitbronnen zoals vlees, vis, graan, bonen etc. Tegenwoordig is het mogelijk L-Glutamine in zuivere vorm als voedingssupplement in te nemen. Glutamine is voldoende aanwezig