Structure and Properties of 2,3,3,3-Tetrafluoropropene (HFO-1234yf)

Michael Feller, Karin Lux, Christian Hohenstein, and Andreas Kornath

Department of Chemistry, Ludwig-Maximilian University of Munich, Butenandtstr. 5 – 13,
Germany
Reprint requests to Prof. Dr. Andreas Kornath. Fax: +49-89-2180-77867.
E-mail: [email protected]

Z. Naturforsch. 2014, 69b, 379 – 387 / DOI: 10.5560/ZNB.2014-4017

Received February 4, 2014

The novel refrigerant 2,3,3,3-tetrafluoropropene (HFO-1234yf) is discussed as a replacement for

1,1,1,2-tetrafluoroethane (R-134a) due to its low global warming potential. Although it may therefore
have great potential for use on a large scale, no structural data and only a few vibrational data of the com-
pound are known. We describe low-temperature X-ray structure analysis, vibrational spectra and com-
bustion properties of 2,3,3,3-tetrafluoropropene. The experimental data are compared with the results of
theoretical calculations. Furthermore the basic combustion properties have been investigated.
Key words: X-Ray Diffraction, Vibrational Spectroscopy, Quantum Chemical Calculation,
Combustion Experiments

Introduction compound was only characterized on the basis of in-

frared, microwave and NMR spetra [9, 11, 37 – 41].
HFO-1234yf (2,3,3,3-tetrafluoropropene) is cur- This prompted us to investigate its structure and a de-
rently discussed as a novel replacement for the refrig- tailed vibrational analysis as well as its basic combus-
erant tetrafluoroethane in mobile air conditioners [1, tion properties, which have not been reported yet.
2]. Because the global warming potential (GWP) of
2,3,3,3-tetrafluoropropene (GWP100 = ca. 1) [3] is ap- Results and Discussion
proximately 1/1300 of the GWP of R-134a (1,1,1,2-
tetrafluoroethane) (GWP100 = 1300) [4], the substance
is discussed as an environmentally friendly alterna- Low-temperature single-crystal X-ray diffraction
tive. The compound was prepared for the first time by
Henne et al. in a five-step synthesis in 1946 [5]. Later, The solid state of HFO-1234yf has not been char-
only few studies have been reported until 2,3,3,3- acterized yet, since the growing of single crystals is
tetrafluoropropene has been patented as a heat trans- very difficult due to the low melting point. More-
fer reagent in 1992 and claimed as a refrigerant in over, hydrofluorocarbons (HFCs) show often a diffrac-
2004 [6 – 14]. Since then more than 600 patents have tion pattern of a distorted plastic phase below their
appeared. The studies of 2,3,3,3-tetrafluoropropene re- melting point [36]. Therefore several HFCs structures
ported in the literature were mainly restricted to its have been investigated by low-temperature powder X-
thermodynamic properties like vapor pressure, density ray diffraction. For our investigation we utilized both
or heat conductivity [15 – 35]. Thermodynamic and methods, powder and in situ grown single-crystal X-
heat-transporting properties are often controlled by in- ray diffraction.
termolecular forces of the refrigerant molecules [36]. Single crystals of 2,3,3,3-tetrafluoropropene were
The investigation of these interactions can therefore grown in situ in a glass capillary which was mounted
improve the potentials derived from physical mea- on a diffractometer and cooled by a nitrogen stream
surements and physicochemical modeling. Despite its at a controlled temperature. The focus of the gas
importance as a potential large-scale refrigerant, the stream was modified by moving the capillary in the

© 2014 Verlag der Zeitschrift für Naturforschung, Tübingen · http://znaturforsch.com

380 M. Feller et al. · 2,3,3,3-Tetrafluoropropene (HFO-1234yf)

vertical direction. Crystals were grown by decreas- contacts below the sum of the van der Waals radii
ing the temperature slowly from −145 to −170 ◦ C (2.46 Å). In similar hydrofluorocarbons C–H· · ·F con-
(m. p. −152.2 ◦ C) [42]. A single crystal of the size tacts are discussed for distances between 2.46 – 2.64 Å.
0.19 × 0.13 × 0.12 mm3 was obtained after repeating In our case we find only H· · ·F distances of 2.773 and
the procedure several times. The X-ray diffraction 2.733 Å.
was measured at 100(2) K. 2,3,3,3-Tetrafluoropropene
crystallizes in the monoclinic space group P21 /n with
4 molecules in the unit cell (Table 1). The asymmetric
unit is shown in Fig. 1.
The C=C bond length (C1–C2 1.304(7) Å) and the
C–C bond length (C2–C3 1.490(6) Å) are in the range
of regular carbon-carbon double and single bonds, re-
spectively [43]. The C–F bond lengths show also no
exceptions from regular C–F bonds. The carbon atoms
and F1 are arranged in a plane together with F4 of the
CF3 group. The bond lengths and bond angles are com-
pared with the results of theoretical calculations in Ta-
ble 2. Overall we find a satisfactory agreement between
experimental and calculated values.
The crystal packing of 2,3,3,3-tetrafluoropropene is Fig. 1. Molecular structure of C3 H2 F4 in the crystal (dis-
shown in Fig. 2. The molecules display no C–H· · ·F placement ellipsoids at the 50 % probability level).

Single-crystal diffraction data Powder diffraction data Table 1. Diffraction data

and parameters of C3 H2 F4 .
Formula mass, g mol−1 C3 H2 F4 114.05 Formula mass, g mol−1 C3 H2 F4 114.05
Crystal system monoclinic Crystal system monoclinic
Space group P21 /n Space group P21 /n
Z 4 Z 4
a, Å 6.4246(14) a, Å 6.4166(2)
b, Å 8.1536(14) b, Å 8.1466(3)
c, Å 8.913(3) c, Å 8.8799(2)
β , deg 110.80(3) β , deg 110.82(1)
V , Å3 436.46(17) V , Å3 433.86
ρcalcd. , g cm−3 1.74 ρcalcd. , g cm−3 1.73(4)
Crystal size, mm3 0.19 × 0.13 × 0.12 Monochromator Ge (111)
λMoKα , Å 0.71073 λCuKα , Å 1.54056
µ, mm−1 0.2 µ, mm−1 2.1
T, K 100(2) T, K 100(2)
F(000), e 224 2θ range, deg. 10 – 90
hkl range −6 : 7; −10 : 9;−10 : 10 Detector linear PSD
Refl. measured 2073 Data points 7920
Refl. unique 831 Rp 0.04234
Rint 0.0308 Rexp 0.04458
Parameters 64 Parameters 61
R1(F) / wR2(F 2 )a (all refl.) 0.1013 / 0.2253 Rwp 0.0604
Weighting schemeb 0.1007 / 0.9377 Program used T OPAS Academic
S (GooF)c 1.103 χ2 1.335
Residual density, e Å−3 0.37 / −0.30 Background function shifted Chebychev
Device type Oxford XCalibur Diffractometer Stoe StadiP
Solution/refinement S HELXS-97 / S HELXL-97 Structure refinement Rietveld method
a R1 = Σ||Fo | − |Fc ||/Σ|Fo |; b wR2 = [Σw(Fo2 − Fc2 )2 /Σw(Fo2 )2 ]1/2 , w = [σ 2 (Fo2 ) + (AP)2 + BP]−1 , where
P = (Max(Fo2 , 0) + 2Fc2 )/3 and A and B are constants adjusted by the program; c GoF = S = [Σw(Fo2 −
Fc2 )2 /(nobs − nparam )]1/2 , where nobs is the number of data and nparam the number of refined parameters.
Excluded region of the Rietvield refinement: 27.4 – 28◦ .
M. Feller et al. · 2,3,3,3-Tetrafluoropropene (HFO-1234yf) 381
Exp. Calcd.a Exp. Calcd.a Table 2. Selected bond
C1–C2 1.304(7) 1.312 C3–F2 1.350(6) 1.335 lengths (Å) and bond
C2–C3 1.490(6) 1.504 C3–F3 1.339(5) 1.335 angles (deg) of C3 H2 F4 .
C2–F1 1.343(5) 1.334 C3–F4 1.325(5) 1.332

C1–C2–C3 126.5(4) 126.0 F2–C3–F4 107.6(4) 108.2

C1–C2–F1 123.6(4) 123.3 F4–C3–C2 112.1(4) 111.1
F1–C2–C3 109.9(4) 110.7 F3–C3–C2 111.8(4) 110.9
F2–C3–F3 105.9(4) 107.4 F2–C3–C2 111.3(4) 110.9
F3–C3–F4 107.9(4) 108.2
Torsion angles (deg)
C1–C2–C3–F4 −0.5(7) 0 F1–C2–C3–F2 58.2(5) 59.6
F1–C2–C3–F4 178.7(4) 180 F1–C2–C3–F3 60.0(5) 59.6
a Calculated at the M062X/aug-cc-pVTZ level of theory with the program package G AUSSIAN 09 [59].

Fig. 2. Molecular packing

of HFO-1234yf as seen
down the crystallographic b
axis.

Low-temperature powder X-ray diffraction Rietvield method [44]. The observed, calculated and
difference diffraction patterns are shown in Fig. 3.
For powder X-ray diffraction the compound was During the low-temperature measurement ice was
transferred to a glass capillary (d = 0.48 mm) which formed at the capillary. Therefore 5 % of ice was con-
was then mounted on a diffractometer and cooled by sidered in the Rietvield refinement. Below their melt-
a nitrogen stream to 100 K. The diffraction pattern was ing points several HFCs show a diffraction pattern typ-
recorded in Debye-Scherrer geometry. Refinement of ical for disordered plastic phases with a body-centered
the structural data was carried out by employing the cubic lattice [36]. The reflection at 27.72◦ appears to
382 M. Feller et al. · 2,3,3,3-Tetrafluoropropene (HFO-1234yf)

Fig. 3. Observed (crossed)

and calculated (black line)
powder diffraction patterns
of 2,3,3,3-tetrafluoroprope-
ne, the position of Bragg
reflections (vertical lines)
and the difference profile
(bright gray line). Excluded
region 27.4 – 28◦ .

represent a disordered plastic phase and was excluded combination modes. The Raman line at 1700 cm−1 is
from the refinement. The cell parameters of the powder assigned to the stretching vibration of the C=C dou-
diffraction data correspond well to the single-crystal ble bond. The C–F stretching vibrations appear in their
X-ray measurement, as listed in Table 1. typical region between 1135 and 1340 cm−1 . The C–
C stretching vibration occurs at 790 cm−1 as an in-
Raman and IR spectra of 2,3,3,3-tetrafluoropropene tense Raman line. This is a rather low frequency for
a C–C single bond which typically appears in the re-
The Raman spectra of all three aggregation gion between 850 and 1150 cm−1 [45]. The low C–C
states, and the IR spectrum of gaseous 2,3,3,3- vibrational frequency does not indicate a weak C–C
tetrafluoropropene, are shown in Fig. 4. The vibra- bond, since the X-ray structure analyses yield a reg-
tional data together with quantum chemically calcu- ular C–C single bond. It is therefore caused by cou-
lated frequencies are listed in Table 3. The assign- pling effects which occur when a double bond is adja-
ments were made by comparison with previously re- cent to a C–C single bond [46]. The deformation vibra-
ported IR spectra [11, 38, 39], quantum chemically tions of the CH2 group are detected at 1390 (δ CH2 ),
calculated frequencies and consideration of the carte- 940 (ρ CH2 ), 910 (ω CH2 ), and 751 cm−1 (τ CH2 ).
sian displacement coordinates. According to Cs sym- The remaining deformation modes are observed below
metry, 21 fundamentals (14 A0 + 7 A00 ) are expected 670 cm−1 . Their assignment is listed in Table 3.
for HFO-1234yf.
For the molecule 8 stretching vibrations are Combustion of 2,3,3,3-tetrafluoropropene
expected. The symmetric and antisymmetric C–
H stretching vibrations are assigned at 3037 and Several combustion experiments report an igni-
3160 cm−1 , respectively. It should be noted that in this tion temperature of HFO-1234yf in the region of
region, typical for C–H vibrations, more Raman lines 405 ◦ C [47 – 50]. Flammability, burning velocity and
are observed than expected. Since these additional heat of combustion were determined [51], but the com-
lines persist in all three aggregation states, we do not position of the combustion products has not been in-
think that they arise from intermolecular interactions vestigated yet. Therefore we performed combustion
or crystal field splitting. The additional lines are rather experiments with different HFO-1234yf/oxygen mix-
M. Feller et al. · 2,3,3,3-Tetrafluoropropene (HFO-1234yf) 383

Fig. 4. Vibrational spectra of solid (IIc, 100 K), liquid (IIb, 130 K) and gaseous (IIa and I, 298 K) 2,3,3,3-tetrafluoropropene.
384 M. Feller et al. · 2,3,3,3-Tetrafluoropropene (HFO-1234yf)

Table 3. Experimental and calculated frequencies of HFO-1234yf.

Raman IR Calcd.a Assignment
gaseous liquid solid (Raman / IR)
3161 (4) 3158 (9) 3160 (26) 3146 (38 / 3) νas (CH2 ) ν1 (A0 )
3099 (6) 3098 (5) 3107 (5)
3094 (5)
3062 (6)
3056 (12)
3069(6) 3050 (13) 3050 (16) ν3 + ν5
3055 (13) 3036 (19) 3037 (23) 3055 (vw) 3049 (91 / 6) νs (CH2 ) ν2 (A0 )
1701(52) 1698 (53) 1700 (67) 1700 (w) 1710 (39 / 51) ν (C=C) ν3 (A0 )
1408 (3) 1408 (4)
1393(5) 1388 (9) 1390 (8) 1391 (m) 1370 (7 / 130) δ (CH2 ) ν4 (A0 )
1363 (2) 1352 (2) 1347 (10) 1357 (m) 1340 (4 / 60) v (CF) ν5 (A0 )
1211 (2) 1208 (2) 1192 (5) 1210 (vs) 1202 (2 / 294) vas (CF3 ) ν6 (A0 )
1190 (vs)
1162 (2) 1161 (6) 1181 (vs) 1170 (3 / 299) vas (CF3 ) ν15 (A00 )
1160 (vs)
1134 (6) 1152 (s) 1135 (0.3 / 179) vs (CF3 ) ν7 (A0 )
949 (11) 942 (3) 938 (29) 945 (w) 927 (4 / 23) ρ (CH2 ) ν8 (A0 )
902 (3) 910 (20) 889 (w) 909 (3 / 47) ω (CH2 ) ν16 (A00 )
793 (100) 790 (100) 790 (100) 793 (vw) 778 (10 / 2) v (C–C) ν9 (A0 )
736 (2) 741 (10) 736 (0.2 / 0.5) τ (CH2 ) ν17 (A00 )
666 (0.2 / 1) δ (CCC) o.o.p. ν18 (A00 )
617 (7) 616 (10) 614 (21) 615 (w) 594 (2 / 21) δ (CCF) i.p. ν10 (A0 )
578 (4) 576 (4) 576 (15) 579 (vw) 556 (1 / 11) δs (CF3 ) ν11 (A0 )
497 (4) 497 (20) 482 (1 / 1) δas (CF3 ) ν19 (A00 )
421 (7) 423 (27) 405 (1 / 1) δ (CCC) i.p. ν12 (A0 )
366 (20) 367 (21) 370 (40) 351 (2 / 0.5) δ (C=C–F) i.p. ν13 (A0 )
236 (6) 239 (16) 237 (31) 228 (1 / 0.1) δ (CF3 ) ν20 (A00 )
225 (0.2 / 1) δ (H2 CFC/CF3 ) ν14 (A0 )
60 (1 / 1) τ (C–C) ν21 (A00 )
aCalculated at the M062X/aug-cc-pVTZ level of theory with the program package G AUSSIAN 09 [59]. Raman activity is stated on a scale
of 1 to 100. Raman intensities in Å4 µ −1 and IR intensities in km mol−1 .

tures. The combustion products were analyzed by FT- ric ratio of oxygen the formation of COF2 increases
IR spectroscopy. The recorded IR spectra of a typical while a part of HFO-1234yf remains unchanged. At
experiment are shown in Fig. 5. first sight the formation of COF2 is unusual for hy-
Carbon dioxide, carbonyl fluoride and hydrogen flu- drofluorocarbon combustion. The reason for the COF2
oride were found as typical combustion products. It formation is the F to H ratio in the molecule. The H and
should be noted that the quantitative analysis of HF F atoms combine during combustion preferentially to
by infrared spectroscopy is difficult since HF forms HF which is thermodynamically favored. The remain-
oligomers, with the equilibrium depending on the pres- ing F atoms remain bonded to the carbon atoms and
sure, and leading to a larger variation of the band therefore COF2 is formed as one combustion product.
shape. Therefore, HF was detected indirectly as SiF4 The COF2 formation is not observed in case of sat-
which was formed in a subsequent reaction with the urated fluorohydrocarbons, because these compounds
glass wall of the reaction vessel. Furthermore minor show usually no flammability when the F to H ratio is
amounts of CF4 (around 5 %) were observed. 1 or larger. At F to H ratios below 1, all fluorine atoms
At a stoichiometric ratio of oxygen and HFO- form HF as the combustion product.
1234yf the combustion proceeds according to Eq. (1). The flammability of HFO-1234yf is unusual for a hy-
drofluorocarbon with an F to H ratio larger than 1. It has
2CF3 CFCH2 + 5O2 → 4CO4 + 4HF + 2COF2 (1)
been discussed controversially, because it is an impor-
An excess of oxygen does not change the composi- tant safety issue for a mobile air conditioner. The reason
tion of the combustion products. At a substoichiomet- for the flammability or with other words, instability to-
M. Feller et al. · 2,3,3,3-Tetrafluoropropene (HFO-1234yf) 385

Fig. 5. FT-IR spectra of neat 2,3,3,3-tetrafluoropropene (black) and combustion products of HFO-1234yf at a stoichiometric
oxygen level (white grid) and substoichiometric oxygen ratio of 1 : 2 (grey).

wards oxidative media is the presence of a C=C double theoretical calculations. Combustion experiments of
bond. This instability is reflected in the short half life of 2,3,3,3-tetrafluoropropene show carbon dioxide, hy-
the molecule in the atmosphere (ca. 10 days), where it is drogen fluoride and carbonyl fluoride as combustion
slowly attacked by OH radicals [39, 51, 52]. products. The formation of carbonyl fluoride as a com-
The combustion products of HFO-1234yf are an im- bustion product is rarely observed, because a fluorohy-
portant safety issue for mobile air conditioner, espe- drocarbon usually has to have an F to H ratio smaller
cially for the case of fire. To our knowledge risk assess- than one to be flammable. 2,3,3,3-Tetrafluoropropene
ment studies for HFO-1234yf only consider the forma- is flammable despite an F to H ratio larger than one
tion of HF. If COF2 is mentioned as a potential combus- because of the C=C double bond. The higly toxic
tion product, it is assumed that it undergoes a rapid hy- carbonylfluoride has to be considered in safety risk
drolysis with formation of CO2 and HF. Therefore it is analyses.
claimed to be irrelevant for safety issues. To our knowl-
edge the hydrolysis kinetics of COF2 have not been in- Experimental Section
vestigated yet, but from laboratory practice it is known
that COF2 does not undergo an immediate hydrolysis Vibrational spectra of HFO-1234yf
under contact with water. Since the toxicity of COF2 is
much larger than that of HF, and our studies have shown 2,3,3,3-Tetrafluoropropene (99.8 % from ABCR) was
that COF2 is formed as one major combustion product, used without further purification. The purity of the com-
it should be considered in safety risk analyses. pound was determined by 1 H, 13 C and 19 F NMR spec-
troscopy and a GC-MS analysis. The Raman spectra of liq-
Conclusion uid, solid and gaseous HFO-1234yf were recorded using the
regular lateral entrance slit of a Jobin Yvon ISA T64000
spectrometer and an argon ion laser (Stabilite 2017, Spectra
The crystal structure of 2,3,3,3-tetrafluoropropene
Physics, λ = 514.5 nm) as irradiation source.
was investigated by in situ single-crystal and pow-
der X-ray diffraction. Raman spectra were recorded X-Ray structure determination
also for all three aggregation states. The struc-
tural parameters and vibrational modes of 2,3,3,3- The low-temperature single-crystal X-ray diffraction of
tetrafluoropropene are compared with the results of HFO-1234yf was performed on an Oxford XCalibur3
386 M. Feller et al. · 2,3,3,3-Tetrafluoropropene (HFO-1234yf)

diffractometer equipped with a Spellman generator (volt- ferred through a stainless-steel line into the vessel. The com-
age 50 kV, current 40 mA) and a KappaCCD detector op- bustion was initiated by rapid electrical heating of the fil-
erating with MoKα radiation (λ = 0.7107 Å). Data collec- ament. The combustion products were transferred to an IR
tion at 100 K was performed using the C RYS A LIS CCD cell and analyzed with an FT-IR spectrometer (Bruker Ver-
software [53]. The data reduction was carried out using tex 80 v).
the C RYS A LIS RED software [54]. The solution and re-
finement of the structure was performed with the programs Theoretical calculations
S HELXS [55, 56] and S HELXL-97 [55, 56] implemented in
the W IN GX software package [57] and finally checked with Quantum-chemical calculations were performed with the
the P LATON software [58]. Selected data and parameters of G AUSSIAN 09 program package [59], using the restricted
the X-ray structure analysis are given in Table 1. hybrid density functional M06-2X [60] and the aug-cc-
CCDC 984019 contains the supplementary crystallo- pVTZ [61] basis set. Structure optimization was performed
graphic data for this paper. These data can be obtained free by employing the GDIIS algorithm with very tight con-
of charge from The Cambridge Crystallographic Data Centre vergence criteria, corresponding to maximum deviations of
via www.ccdc.cam.ac.uk/data_request/cif. 10−6 in the density matrix elements, of 10−6 Hartree in the
Low-temperature powder X-ray diffraction was per- energies, of 0.000002 Hartree per Bohr in the forces and of
formed on a Stoe Stadi P powder diffractometer (Stoe & Cie, 0.000006 Bohr in the atomic cartesian displacements [62].
Darmstadt, Germany) in Debye-Scherrer geometry using Ge Vibrational analysis was performed at the fully optimized
(111)-monochromated CuKα1 radiation (λ = 154.056 pm). structure. Frequencies are scaled by a factor of 0.9553.
A linear PSD was used to obtain the energy-dispersive X-ray
spectra. Acknowledgement

Combustion experiments Financial support of this work by the Ludwig-Maximilian

University of Munich (LMU) and the Deutsche Forschungs-
Combustion experiments were performed in a glass ves- gemeinschaft (DFG) is gratefully aknowledged. Thanks go
sel. The glass vessel contained a tantalum filament attached also to Dominik Baumann for help with the powder diffrac-
to an electrical feedthrough. The reacting agents were trans- tion data.

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