Article
pubs.acs.org/JPCA
Solid-State 17O NMR of Oxygen−Nitrogen Singly Bonded
Compounds: Hydroxylammonium Chloride and Sodium
Trioxodinitrate (Angeli’s Salt)
Jiasheng Lu,† Xianqi Kong,† Victor Terskikh,†,‡ and Gang Wu*,†
†
Department of Chemistry, Queen’s University, 90 Bader Lane, Kingston, Ontario K7L 3N6, Canada
Department of Chemistry, University of Ottawa, 10 Marie Curie, Ottawa, Ontario K1N 6N5, Canada
‡
ABSTRACT: We report a solid-state NMR study of 17O-labeled
hydroxylammonium chloride ([H17O-NH3]Cl) and sodium trioxodinitrate monohydrate (Na2[17ONNO2]·H2O, Angeli’s salt). The common
feature in these two compounds is that they both contain oxygen atoms
that are singly bonded to nitrogen. For this class of oxygen-containing
functional groups, there is very limited solid-state 17O NMR data in the
literature. In this work, we experimentally measured the 17O chemical
shift and quadrupolar coupling tensors. With the aid of plane-wave DFT
computation, the 17O NMR tensor orientations were determined in the
molecular frame of reference. We found that the characteristic feature of
an O−N single bond is that the 17O nucleus exhibits a large quadrupolar coupling constant (13−15 MHz) but a rather small
chemical shift anisotropy (100−250 ppm), in sharp contrast with the nitroso (ON) functional group for which both quantities
are very large (e.g., 16 MHz and 3000 ppm, respectively).
1. INTRODUCTION
In a recent study, we demonstrated the utility of 17O (spin-5/2)
NMR spectroscopy in direct detection of iron(II)-bound
nitroxyl (HNO).1 HNO is among a small group of redoxrelated nitrogen oxides such as nitric oxide (NO·), nitrosonium
cation (NO+), nitrite (NO2−), and nitrate (NO3−) that have
significant biological functions.2−6 In HNO chemistry, 15N
(spin-1/2) has been used as a common NMR probe in the
structural characterization of some reaction products.7−12 While
15
N NMR experiments for solutions are usually straightforward,
15
N spin−lattice relaxation times in many cases can be rather
long (e.g., tens of seconds), making it time-consuming to
record high-quality 15N NMR spectra. Furthermore, when the
nitrogen of interest is not directly bonded to hydrogen, one
cannot use the more sensitive 1H NMR detection. As a result of
this relatively low sensitivity of 15N NMR, it is sometimes very
difficult to detect transient or short-lived reaction intermediates. Because unstable reaction species are ubiquitous in HNO
chemistry, it is thus important to develop an effective detection
technique for probing transient reaction intermediates.
As part of our recent effort to establish 17O NMR as a new
probe in HNO-related chemistry, we report herein a solid-state
17
O NMR study of two compounds, each containing an O−N
single bond: hydroxylammonium chloride ([H17O-NH3]Cl)
and Angeli’s salt (Na2[17ONNO2]·H2O); see Scheme 1. These
two compounds are of particular importance in HNO
chemistry. Hydroxylamine (HO-NH2 ) is an important
intermediate in the oxidation of NH3 to NO2−.13 Hydroxylamine-based compounds (HO-NHX, where X is a good leaving
group) are often used for HNO generation, the most notable
© 2015 American Chemical Society
Scheme 1. Molecular Structures of Hydroxylammonium
Chloride, Angeli’s Salt, and Hydrogen Peroxide
among which is perhaps Piloty’s acid (X = −SO2Ph). Piloty’s
acid decomposes spontaneously under basic conditions to
produce HNO. Hydroxylamine is also considered to be a
candidate for endogenous HNO production through its
oxidation by heme peroxidases. Similarly, Angeli’s salt is also
commonly used as a HNO donor because at pH 4−8 it
decomposes to HNO and NO2− with a half life of 17 min at 25
°C.6 The main goal of the present study is to experimentally
determine the 17O quadrupole coupling (QC) and chemical
shift (CS) tensors in these two compounds. In the literature,
very little has been reported on the 17O NMR tensors in
compounds containing O−N single bonds.14−16 To certain
Received: June 8, 2015
Revised: June 23, 2015
Published: June 24, 2015
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The Journal of Physical Chemistry A
the cell optimization. Following convergence tolerance
parameters were used in the geometry optimization process:
total energy 10−5 eV/atom, maximum displacement 0.001 Å,
maximum force 0.03 eV/Å, and maximum stress 0.05 GPa. It
should be noted that while the full geometry optimization did
change slightly the positions of the heavy atoms (≤0.02 Å), it
significantly reduced the average forces on all atoms from ∼1 to
<0.01 eV/Å.
extent, hydroxylammonium chloride and Angeli’s salt can also
be considered as an acid/base pair (i.e., H−O−N/−O−N).
Thus, a thorough characterization of 17O NMR tensors in these
two compounds would allow one to examine the effect of
protonation/deprotonation on the oxygen that is singly bonded
to nitrogen. Another reason to study [H17O-NH3]+ is that it is
electronically related to hydrogen peroxide (HO−OH).
Because the synthesis of 17O-labeled peroxides involves the
use of 17O2, which is more costly than the 17O-enriched H2O,
only a few scattered 17O NMR studies of peroxide compounds
can be found in the literature.17,18 Among them only two have
dealt with solid materials. In a previous 17O nuclear quadrupole
resonance (NQR) study, Lumpkin and Dixon19 reported that
the 17O quadrupolar coupling constant for a frozen solution of
hydrogen peroxide at 1.5 K is 16.31 MHz. Recently, Grey and
coworkers20,21 reported solid-state 17O NMR spectra of Li2O2
at natural abundance, which were then used to help interpret
the data obtained for discharge products in lithium−oxygen
batteries. In the present study, our main objective is to further
accumulate fundamental solid-state 17O NMR data for
peroxide-related compounds, which will help lay the foundation
for better understanding the 17O NMR properties in peroxide
compounds.
3. RESULTS AND DISCUSSION
Figure 1 shows the 17O MAS NMR spectra recorded for
[H17O-NH3]Cl and Na2[17ONNO2]·H2O at 21.1 T. In each
2. EXPERIMENTAL SECTION
17
O-labeled hydroxylammonium chloride and Angeli’s salt were
synthesized according to the literature methods.22,23 The 17O
enrichment level was ∼20% in both compounds. Solid-state
17
O NMR experiments were performed on Bruker Avance-600
(14.1 T) and Bruker Avance-II 900 (21.1 T) NMR
spectrometers. A Hahn-echo sequence was used for both static
and MAS experiments to eliminate the acoustic ringing from
the probe. Effective 90° pulses of 1.7 and 1.0 μs were used for
the 17O central transition (CT) experiments at 14.1 and 21.1 T,
respectively. The 17O static spectra at 14.1 T were recorded
using a 4 mm Bruker MAS probe without sample spinning. The
17
O MAS NMR spectra at 21.1 T were obtained with a 2.5 mm
Bruker HX MAS probe. To acquire static spectra at 21.1 T, we
used a home-built 5 mm H/X solenoid probe with solid
samples packed into a 5 mm Teflon tube to reduce the
background signal. High-power 1H decoupling (70 kHz) was
applied in all static experiments. A liquid H2O sample was used
for both RF power calibration and 17O chemical shift
referencing (δ = 0 ppm). All spectral simulations were
performed with DMfit.24
Plane-wave pseudopotential DFT calculations of the NMR
shielding and electric field gradient parameters were performed
using Materials Studio CASTEP software version 4.4
(Accelrys)25,26 on an HP xw4400 workstation with a single
Intel Dual-Core 2.67 GHz processor and 8 GB DDR RAM.
The Perdew, Burke, and Ernzerhof (PBE) functionals were
used in all calculations in the generalized gradient approximation (GGA) for the exchange correlation energy.27 On-thefly pseudopotentials were used as supplied in CASTEP with a
plane-wave basis set cutoff energy of 550 eV and the
Monkhorst−Pack k-space grid sizes of 4 × 4 × 4 (16 k-points
used), 4 × 3 × 4 (8 k-points used), and 6 × 6 × 3 (12 k-points
used) for hydroxylammonium chloride, Angeli’s salt, and
hydrogen peroxide, respectively. The reported crystal structures
of hydroxylammonium chloride,28 Angeli’s salt,29 and hydrogen
peroxide30 were used as starting structures; then, geometry
optimization was performed using the BFGS method31 without
Figure 1. Experimental (blue trace) and simulated (red trace) 17O
MAS NMR spectra of (a) [H17O-NH3]Cl and (b) Na2[17O-NNO2]·
H2O at 21.1 T. The sample spinning frequency was 31.25 kHz. In
panel a, the * marks an isotropic peak at 90 ppm, which arises from a
trace amount of liquid-like materials developed over time due to the
hygroscopic nature of the sample. Other data acquisition parameters
are (a) 1 s recycle delay, 26 000 transients and (b) 10 s recycle delay,
6000 transients.
MAS spectrum, a typical line shape due to the second-order
quadrupole interaction was observed with very weak spinning
sidebands. This spectral feature immediately suggests that in
these two compounds where the oxygen is singly bonded to
nitrogen the 17O chemical shift anisotropy must be rather small.
In sharp contrast, for C-nitroso compounds where the oxygen is
doubly bonded to nitrogen (17ON−C), a large number of
spinning sidebands were observed in 17O MAS spectra.32 The
experimental values of δiso, CQ, and ηQ determined for [H17ONH3]Cl and Na2[17ONNO2]·H2O are summarized in Table 1.
For both compounds, the absolute values of |CQ(17O)| (ca. 13−
15 MHz) are among the largest reported so far for oxygencontaining functional groups. As previously mentioned, hydrogen peroxide exhibits a |CQ(17O)| value of 16.31 MHz, as
determined from an early NQR study.19 Similarly, the O2
adduct of the Vaska’s compound and Pt(O2)(PPh3)2 have
CQ(17O) on the order of 16 MHz.33,34 Another related
compound studied by 17O NQR is γ-pyridine N-oxide.35 For
this compound, |CQ(17O)| is 15.63 MHz and ηQ is 0.328. These
parameters are very similar to those for O1 and O2 of the
Angeli’s salt, as seen from Table 1.
For [H17O-NH3]Cl, the isotropic 17O chemical shift is 90
ppm, which can be compared with that observed for H2O2 in
aqueous solution, 180 ppm.36 In Na2[17ONNO2]·H2O, the
oxygen in question can be considered to be the deprotonated
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Table 1. Experimental and Computed 17O CSa and QCb NMR Tensor Parametersc for Hydroxylammonium Chloride, Angeli’s
Salt, Hydrogen Peroxide, Lithium Peroxide, and Peroxide Dianiond
δiso/ppm
δ11/ppm
δ22/ppm
δ33/ppm
CQ/MHz
ηQ
exptl.
CASTEP
exptl.e
ADF
CASTEP
exptl.f
ADF
90(2)
83
180
182
221
227
221
125(5)
120
113(5)
114
32(5)
16
383
405
352
398
211
248
352
398
−48
10
−23
−133
−14.7(2)b
−15.86
−16.31b
−16.81
−17.06
−18.0(2)b
−18.66
0.71(2)
0.77
0.687
0.969
0.688
0.00(4)
0.000
exptl.
CASTEP
CASTEP
CASTEP
265(2)
307
295
244
395(5)
473
440
341
258(5)
322
275
237
142(5)
126
169
154
−13.5(2)b
−13.73
−14.21
−15.33
0.40(2)
0.46
0.29
0.20
compound
[H17O-NH3]Cl
H2O2
Li2O2
[O2]2−
Angeli’s salt
O3
O2
O1
a
Computed chemical shifts (δ) were obtained from computed shielding values (σ) by using δ = σref − σ where σref was chosen to be 295.7 ppm so
that the trend line relating the computed and experimental chemical shift data passes the origin. bSign of CQ was assumed to be negative on the basis
of computational results. cExperimental Euler angles are α = 90 ± 5, β = 0, and γ = 0° for [H17O-NH3]Cl and α = 0, β = 90 ± 5, and γ = −52 ± 10°
for O3 in Angeli’s salt. dEstimated errors in experimental data are shown in the parentheses. eFrom refs 19 (low-temperature 17O NQR) and 36
(solution 17O NMR). fFrom ref 20.
Figure 2. Experimental (blue trace) and simulated (red trace) 17O static NMR spectra of (a) [H17O-NH3]Cl and (b) Na2[17ONNO2]·H2O at two
magnetic fields. The * marks an isotropic peak at 90 ppm, which arises from a trace amount of liquid-like materials developed over time due to the
hygroscopic nature of the sample. The data acquisition parameters are (a) 14.1 T, 1 s recycle delay, 25 246 transients; 21.1 T, 1 s recycle delay, and
14 000 transients and (b) 14.1 T, 2 s recycle delay, 38160 transients; 21.1 T, 10 s recycle delay, and 6500 transients. For each compound, a single set
of parameters was used for simulating static and MAS spectra recorded at two magnetic fields. The simulation parameters are summarized in Table 1.
form of [H17O-NH3]+, and as such the isotropic 17O chemical
shift increases to 265 ppm. This trend is similar to what we
have previously observed for phenolic oxygens between
protonated and deprotonated states.37
To determine the full 17O CS tensor, we recorded the 17O
static spectra of [H17O-NH3]Cl and Na2[17ONNO2]·H2O at
two magnetic fields, 14.1 and 21.1 T; see Figure 2. Because for
both compounds the total spectral width is dominated by the
second-order quadrupole interaction, it is inversely scaled by
the applied magnetic field. For example, the total width of the
static spectrum of [H17O-NH3]Cl is ∼1800 ppm at 14.1 T (ca.
146 kHz), and it is reduced to 800 ppm at 21.1 T (ca. 98 kHz).
Therefore, the observed scaling factor (in Hz) of 0.67 is
approximately equal to the magnetic field ratio (14.1 vs 21.1
T). This situation is quite different from those often seen for
compounds containing either NO or CO double bonds
where large 17O chemical shift anisotropies also exist. For these
latter compounds, higher magnetic fields do not always produce
narrower static 17O NMR spectra. As also seen in Figure 2, the
general agreement between experimental and simulated static
spectra at two magnetic fields is satisfactory. All experimental
17
O CS tensor components are listed in Table 1, together with
the computational results obtained from the CASTEP program.
In general, the computational results are in good agreement
with the experimental data. The computations also suggest that
the sign of CQ is negative in both compounds. In comparison,
the large CQ values found in NO and CO compounds are
all positive. Although the experimental solid-state 17O NMR
spectra are invariant of the sign of CQ, the sign of CQ is
intrinsically tied to the orientation of the QC tensor (vide
infra). For completeness, we also listed in Table 1 the CASTEP
computed results for the other two oxygen atoms in Angeli’s
salt that are not labeled by 17O in this study. In addition, we
also performed CASTEP and ADF38 calculations for hydrogen
peroxide and peroxide dianion.
As seen from Table 1, the 17O CS tensor in [H17O-NH3]Cl is
nearly axially symmetric (δ11 ≈ δ22), with a very small chemical
shift anisotropy (span Ω = δ11 − δ33 = 93 ppm). In
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Na2[17ONNO2]·H2O, the aforementioned increase in δiso is
accompanied by a considerable increase in chemical shift
anisotropy (Ω = 253 ppm). The same trend is seen for the 17O
CS tensors between hydrogen peroxide and peroxide dianion.
This trend in the 17O CS tensor components is also parallel to
that reported for phenolic oxygens between different ionization
states;37 however, we should caution that because the 17O CSA
is rather small for H2O2 one should avoid overinterpretation of
the data. For example, we also used the crystal structure of
hydrogen peroxide determined from a neutron diffraction
study30 to perform CASTEP calculations. As seen in Table 1,
δiso(17O) is increased by ∼40 ppm for H2O2 in the crystal lattice
as compared with that calculated for an isolated H2O2 by ADF.
This discrepancy is most likely due to the strong hydrogen
bonding around the H2O2 molecule in the crystal lattice, where
each H2O2 molecule serves simultaneously as hydrogen
bonding donor and acceptor (rO···O = 2.761 Å).30 We also
note that the experimental 17O NMR parameters reported for
Li2O2 obtained electrochemically20 are in reasonable agreement
with those calculated for an isolated peroxide dianion by ADF.
Another benefit from the CASTEP calculations is that the
17
O CS and QC tensor orientations can be unambiguously
determined in the molecular frame of reference. As we have
shown in several studies,37,39−42 careful examination of the 17O
NMR tensor orientations often allows one to gain more
insights into the relationship between NMR tensor components
and molecular structures. In addition, information about the
17
O NMR tensor orientation in the molecular frame is critical in
the analysis of solid-state 17O NMR spectra obtained for
systems where molecular motion is significant.43,44 The
CASTEP results for the 17O NMR tensor orientations in
[H17O-NH3]Cl and Na2[17ONNO2]·H2O are depicted in
Figure 3. For comparison, the computed 17O NMR tensor
orientations in hydrogen peroxide are also shown. For the 17O
QC tensors, one common feature among the three compounds
is that the largest tensor component, χzz, is always along the
O−N (or O−O) single bond; however, the orientations of the
other two QC tensor components can be different. For the two
protonated compounds ([H17O-NH3]Cl and HOOH), the
smallest QC tensor component, χxx, lies in the plane
perpendicular to the O−N (or O−O) bond, whereas for the
deprotonated compound (Angeli’s salt), the in-plane component is the intermediate QC tensor component, χyy.
As seen from Figure 3, the 17O CS tensor orientations exhibit
more variations among the three compounds. For [H17ONH3]Cl and HOOH, one common feature is that δ33 is along
the O−N (or O−O) bond. For O3 of Angeli’s salt, δ11 lies close
to the O−N bond. In contrast, δ11 components for O2 and O1
of Angeli’s salt are perpendicular to the O−N bond. Overall, it
seems difficult to observe any clear trend among the 17O CS
tensor components. Closer examination of the CS tensor
orientations for [H17O-NH3]Cl and O3 of Angeli’s salt,
however, reveals an interesting pattern. As illustrated in Figure
4, if one looks only at the individual tensor components, the
only feature is that all three components for O3 of the Angeli’s
salt are shifted toward the higher frequency end, leading to an
increase in δiso, as previously noted. Now if one links the tensor
components between the two compounds according to their
orientations within the respective molecular frame of reference
one immediately sees that the tensor component perpendicular
to the molecular plane changes very little. That is, δ11 for
[HONH3]Cl is nearly the same as δ33 in O3 of Angeli’s salt;
also see Figure 3. In sharp contrast, the tensor component
Figure 3. Depiction of the 17O CS and QC tensor orientations in the
molecular frames of reference. (a) [H17O-NH3]Cl, (b) hydrogen
peroxide, and (c) Na2[17ONNO2]·H2O. For convenience, computed
values of the tensor components are shown in parentheses (megahertz
for QC and ppm for CS). Selected bond distances are also listed.
Tensor components that are perpendicular to the paper plane are not
shown for clarity.
Figure 4. Illustration of the “crossover” effect between the 17O CS
tensor components in (a) [H17O-NH3]Cl and (b) O3 of Angeli’s salt.
along or close to the O−N bond changes by 363 ppm between
the two compounds. The in-plane tensor component
perpendicular to the O−N bond changes by 145 ppm. This
is a similar “crossover” effect, as we discussed recently for
phenolic oxygens37 and for Pt−carboxylate complexes.42 After
observing this “crossover” effect, it becomes easier to
understand the magnetic shielding changes observed in these
two compounds. The largest magnetic shielding change along
the O−N bond is clearly due to the fact that the O3−N2 bond
(rON = 1.338 Å) in Angeli’s salt has a partial double-bond
character, as compared with the O−N bond in [HO-NH3]Cl
(rON = 1.374 Å). This would lower the energy of the π*
molecular orbital in Angeli’s salt, making it possible to have the
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n(O) → π* type of mixing when the magnetic field is along the
O−N bond. This results in an increase in the paramagnetic
contribution to the total magnetic shielding. This situation is
nearly identical to that seen in phenolic oxygens.37 Once again,
the present case is another example to illustrate the importance
of examining both the magnitude and orientation of individual
CS tensor components rather than the isotropic chemical shift
only.
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4. CONCLUSIONS
We have carried out solid-state 17O NMR experiments to
determine the 17O CS and QC tensors in 17O-labled
hydroxylammonium chloride and Angeli’s salt. One common
feature found in these compounds containing O−N single
bonds is that the oxygen exhibits a large 17O quadrupolar
coupling constant (13−15 MHz) but a rather small chemical
shift anisotropy (100−250 ppm). Similar 17O NMR properties
are also expected for peroxides. This particular combination of
the 17O NMR tensors makes it advantageous to perform solidstate NMR experiments at ultrahigh magnetic fields. The
experimental solid-state 17O NMR results were reasonably well
reproduced by plane-wave DFT calculations. Such plane-wave
DFT calculations also produced the 17O NMR tensor
orientations in the molecular frame of reference. We showed
that it is important to compare tensor components with the
same orientation within the molecular frame of reference to
gain insight into the relationship between nuclear magnetic
shielding and chemical bonding. This work continues our effort
to accumulate solid-state 17O NMR data for important oxygencontaining functional groups. Further investigation of solidstate 17O NMR in peroxides is under way in our laboratory.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: [email protected].
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the Natural Sciences and
Engineering Research Council (NSERC) of Canada. We
thank Abouzar Toubaei for performing ADF calculations for
hydrogen peroxide and peroxide dianion. Access to the 900
MHz NMR spectrometer and CASTEP software was provided
by the National Ultrahigh Field NMR Facility for Solids
(Ottawa, Canada), a national research facility funded by a
consortium of Canadian universities, National Research
Council Canada and Bruker BioSpin and managed by the
University of Ottawa (http://nmr900.ca).
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