High-Pressure Studies of 4-Acetamidobenzenesulfonyl Azide

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High Pressure Studies of 4-Acetamidobenzenesulfonyl Azide: Combined Raman Scattering, IR Absorption, and Synchrotron X-Ray Diffraction Measurements Junru Jiang, Peifen Zhu, Dongmei Li, Yanmei Chen, Miaoran Li, Xiao-li Wang, Bingbing Liu, Qiliang Cui, and Hongyang Zhu J. Phys. Chem. B, Just Accepted Manuscript • DOI: 10.1021/acs.jpcb.6b08745 • Publication Date (Web): 27 Oct 2016 Downloaded from http://pubs.acs.org on November 1, 2016

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The Journal of Physical Chemistry

High Pressure Studies of 4-Acetamidobenzenesulfonyl Azide: Combined Raman Scattering, IR Absorption, and Synchrotron X-ray Diffraction Measurements Junru Jiang,a Peifen Zhu,b Dongmei Li,a Yanmei Chen,a Miaoran Li,a Xiaoli Wang,c Bingbing Liu,a Qiliang Cuia and Hongyang Zhu*a

a

State Key Laboratory of Superhard Materials, Jilin University, Changchun, Jilin,

130012, China. b

Department of Physics and Engineering Physics, the University of Tulsa, Tulsa,

OK74104, USA c

Institute of Condensed Matter Physics, Linyi University, Linyi, 276005, China

*Corresponding author: Tel: +8643185168881; fax: +8643185168881. E-mail address: [email protected]

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Abstract We have reported the high-pressure behavior of 4-acetamidobenzenesulfonyl azide (C8H8N4O3S, 4-ABSA) by in situ Raman scattering, IR absorption, and synchrotron angle-dispersive X-ray diffraction (ADXRD) measurements in diamond anvil cells with the pressure up to ~ 13 GPa at room temperature. All the fundamental vibrational modes of 4-ABSA at ambient pressure were analyzed by combination of experimental measurements and theoretical calculations using DFT method. Detailed Raman and IR spectroscopic analyses reveal two phase transitions in the pressure region of 0.8 - 2 GPa and 4.2 GPa, respectively, which are confirmed by the changes of the ADXRD patterns. The first phase transition in the pressure region of 0.8 - 2 GPa is attributed to the ring distortion and the rotation of CH3 group, and the second phase transition at 4.2 GPa might be induced by the rearrangement of azide group and hydrogen bonds. The analyses of the N3 vibrational modes suggest that the bent azide group rotates progressively upon compression, which is ascribed to the compression of the unit cell along b-axis. This study is helpful to understand the behavior of azide group and structure evolution of 4-ABSA under high pressure.


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1. Introduction As a class of energetic materials, azides have been extensively studied for their vital

importance

in

nitrogen

sources,

initial explosives,

propellants,

and

combustibles.1-3 Particular recently, the application of pressure in the study of azides has aroused considerable interests, in part due to the relevant properties in such materials are usually very sensitive to pressure,4, 5 but also because the formation of polymeric nitrogen of these materials under high pressure and temperature.6 Since the firstly successful synthesis of polymeric nitrogen in nitrogen molecules, synthesis of stable polymeric nitrogen has become an attractive topic in experiment and theoretical study. Inorganic azides become attractive candidates ascribing to the unique structures and properties of the azide ions. As the bond energy of double nitrogen bond (418 KJ/mol) is lower than the bond energy of triple nitrogen bond (954 KJ/mol), azide ions have been expected more readily forming polymeric nitrogen than that of the triple-bonded molecular nitrogen (N≡N). Previous studies have found that the azide ion of NaN3 transformed into polymeric nitrogen form above 120 GPa in experiment.6 Moreover, several theoretical calculations on KN3, RbN3, CeN3, and LiN3 have predicted that the formation of polymeric nitrogen required extreme pressure.8-11 The extreme conditions of forming polymeric nitrogen confine the scientific study and the practical applications. Compared to inorganic azides, organic azides might readily form polymeric nitrogen due to the different electronic structure of the azide moieties. The azide group in organic azides is slightly bent and has a chain structure with two different



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NN bond lengths, which is different from the linear and centrosymmetric azide ion in inorganic azides.12 It is considered that the difference in stability of the azide moieties is derived from their differences in the chemical bonding. In the study of benzyl azide, the azide group transformed into an amorphous-like form above 25 GPa that the amorphization pressure is much lower than the azide ion of NaN3.13 We propose that the amorphous-like azide moieties are an important intermediate process in the formation of polymeric nitrogen. Investigation into the behavior of azide group addresses the fundamental search for the difference between azide group and azide ion, which provide valuable evidences for readily forming polymeric nitrogen. However, up to now, the high pressure studies of organic azides are mainly concentrated on azide-tetrazole transformation and azide-alkyne cycloaddition.5, 14-16 Accordingly, a detailed high pressure study on the behavior of azide group and structure offers a deep understanding of the microscopic properties and energetic behavior of organic azides. Under ambient conditions, 4-acetamidobenzenesulfonyl azide (4-ABSA) belongs to a monoclinic structure with P21 space group and cell parameters of a = 8.0529 Å, b = 22.988 Å, c = 8.3123 Å, β=93.534°, respectively.17 The structure of 4-ABSA is shown in Figure 1. The hydrogen-bonding interactions allow molecules to pair up and form π-stacked dimers.17 The studies of NH4N3 have reported that the hydrogen bonds are affected by the rotation of azide ions with increasing pressure.18,

19

The

cooperativity of hydrogen bonds and π-stacking interactions allow 4-ABSA to become an attractive candidate for studying the influence of noncovalent interactions


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within the organic azides in the process of compression. In addition, the bent azide groups of 4-ABSA are crucial for the process of electron orbit hybridization and the nitrogen polymerization.20 Thus, the peculiarity and the absence of high pressure study of 4-ABSA prompt our endeavor to explore its structure behavior under high pressure. High pressure investigations of 4-ABSA on the variation of the azide groups and phase transitions are conductive to expand the application of organic azides. Meanwhile, it is benefit for broadening the area of application and understanding the mechanism of nitrogen polymerization. We expect two questions to be answered. The first is the behavior of the azide group of 4-ABSA under pressure, the second is the relationship between structure and pressure.

Figure 1. Crystal structure of 4-ABSA under ambient conditions. The hydrogen bonds are marked as dashed lines. The grey, white, blue, yellow, and red spheres denote C, H, N, S, and O atoms, respectively.



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In this study, high-pressure in situ Raman scattering, IR absorption, and synchrotron angle-dispersive X-ray diffraction (ADXRD) study of 4-ABSA at pressure up to ~ 13 GPa have been performed at room temperature. The modifications of groups have been studied by analysis of the changes of the vibrational spectra, and the XRD data provide structural information. We have placed special emphasis on the vibrational assignments, the unique behavior of azide group under pressure, and the mechanism of the changes of 4-ABSA molecule. 2. Experimental and Computational Methods The 4-Acetamidobenzenesulfonyl azide (4-ABSA) powder sample was purchased from Sigma-Aldrich (purity of 97%) and used without further purification. The high pressure measurements were performed at room temperature using symmetric diamond anvil cells (DACs) with low fluorescence type-II diamonds and a culet of 300 µm in diameter. The sample was placed in the hole with a diameter of 100 µm of a T301 stainless steel gasket, which was preindented to about 60 µm in thickness. A ruby ball was loaded into the sample chamber for in situ pressure calibration according to the fluorescence of the ruby R1 line. A mixture of methanol and ethanol with a 4:1 volume ratio was chosen as the pressure transmitting medium in Raman and XRD experiments. For the IR experiment, KBr powder was selected as the pressure transmitting medium. The in situ high pressure Raman scattering measurements were recorded in a backscattering geometry using Acton SpectraPro 500i spectrometer with a liquid nitrogen-cooled CCD camera. The 532 nm excitation light was generated by a


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frequency-doubled diode-pumped neodymium: vanadate laser (Coherent Inc.). The laser output power on the sample was maintained at 2.8 mw and the acquisition time of each spectrum was 20 s. The in situ high pressure IR absorption measurements were performed by a Bruker Vertex80V infrared spectrometer. The range of the mid-IR spectra was within 670-3400 cm-1 and the spectral resolution for all measurements was 2 cm-1. The acquisition time of each spectrum was 10 min. The in situ high pressure synchrotron angle-dispersive XRD measurements were carried out at the 4W2 High-Pressure Station of Beijing Synchrotron Radiation Facility (BSRF) with use of beam wavelength of 0.6199 Å. The diffraction patterns were collected for 300 s at each pressure using a MAR345 image plate detector. The diffraction images were converted to intensity versus 2-theta using FIT2D software. Further analysis on the structural information was carried out using Pawley refinement method in Material Studio software. The calculations of the vibrational properties at ambient pressure were performed by using the DFT method with the local density approximation of Perdew-Wang (LDA/PWC) provided by DMol3 package. The optimized geometries of 4-ABSA at the ground state (in vacuo) were carried out without symmetry constraints. The frequencies of vibration modes were calculated, and ensured that the optimized geometry was a true minimum. 3. Results and Discussion 3.1 The assignment of vibrational modes at ambient pressure



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The IR spectra of 4-ABSA (as shown in Figure 2a) observed well match with the reported spectra.21 The Raman spectra of 4-ABSA can be assigned on the basis of the calculation and the vibrations of acetamido, benzenesulfonyl and other organic azdies because they have the same groups.12, 13, 22, 23 The vibrational modes of groups have approximate

charateristic

frequencies

in

different

chemical

environments.

Comparison of 4-ABSA with similar compounds containing acetamido and benzenesulfonyl is used to analyze the characteristic frequencies of the acetamido and benzenesulfonyl.24-27 The calculated results show quite similar feature to those of our experimental results. The experimental and calculated Raman spectra are collected as plotted in Figure 2b and 2c, respectively. The list of all the observed vibrational modes along with their corresponding frequencies and assignments are summarized in Table 1. Table 1. IR wavenumber, Raman shifts, and their corresponding assignments of 4-ABSA obtained from our experiments, calculations, and reference, respectively. IR wavenumber (cm-1) Exp.a

Ref.b

Raman shifts (cm-1)

Assignment

Exp.a

Cal.a

86

84

Lattice mode

137

110

Lattice mode

166

146

Lattice mode

209

190

Lattice mode

227

205

Lattice mode

251

242

Lattice mode

335

304

τ SO2 + ω CH3

370

356

δ Ring C-C

382


δ Ring C-C

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413

393

ω CH3 + γ SO2

454

442

γ Ring + ω SO2 γ Ring + ω SO2

463 499

γ N3

512

522

γ N3

549

555

δ N-H

571

γ CH3

598

δ N-H

594

707

709

599

δ N-H

613

δ N-H

620

620

δ N-H

636

633

γ SO2

711

703

γ N3

724

728

γ Ring

730

γ Ring

752

764

755

827

839

826

840

844

839

834

δ Ring C-H

854

843

δ Ring C-H

859

788

δ Ring C-H

δ Ring C-H

862 958

ν S-N

968 1011

γ Ring

970

969

Ring breathing

1011

1016

1016

1041

1040

1086

1087

1168

1167

1182

1179

ν S-N

1014

Ring breathing ν C-N

1092

1166

1093

νas SO2

1104

νas SO2

1152

γ Ring C-H

1181

γ Ring C-H

1190

γ Ring C-H



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1196

γ Ring C-H 1231

1265

1316

1271

1284

γ N-H

1318

1322

νs N3

1325

1341

νs N3

1365 1370

γ CH3 γ CH3

1366 1374

1406

γ N-H νas SO2

1266

1315 1322

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1405

1409

1373

νas SO2

1389

νas SO2

1413

γ CH3

1427

γ CH3

1441

γ CH3

1470

ν Ring

1490

γ N-H

1499

1499

1530 1588

1588

1600

1493

γ N-H

1532

1531

γ N-H

1592

1616

ν Ring C-C

1601

1638

ν Ring C-C ν C=O

1650

1636

1678

1678

1681

ν C=O

1689

1696

1689

ν C=O

1697

1772

2121 2128

2121

3005 3057

3052

ν C=O νas N3

2136

2259

νas N3

2939

2970

ν CH3

3044

3045

ν CH3

3072

3090

ν CH3

3112

3113

3101

3108

ν Ring C-H

3134

3123

3134

3127

ν Ring C-H


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3187

3186

3265

3264

3304

3304

a

This study.

b

Reference.21

3185

3133

ν Ring C-H

3154

ν Ring C-H ν N-H

3441

ν N-H

τ, twisting; ω, wagging; δ, out-of-plane bending; γ, in-plane bending; ν, stretching; νas, asymmetric stretching; νs, symmetric stretching.

Figure 2. (a) Experimental IR spectra, (b) experimental Raman spectra, and (c) calculated Raman spectra of 4-ABSA at ambient conditions. The pink lines marked with ×5 means the spectra are at a magnification of 5 times. All the assignments of the vibrational modes are marked above each band. 3.2 High pressure vibrational spectra.



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High-pressure in situ Raman scattering and mid-IR absorption measurements of 4-ABSA have been performed at pressures up to 12.3 and 13 GPa, respectively. The selected Raman and IR spectra of 4-ABSA upon compression with their corresponding vibration modes as a function of pressure are shown in Figure 3 and 4, respectively. In Figure 3a, the vibrations are associated with the lattice modes which provide useful information on the structural changes. There are six lattice modes at ambient conditions. With increasing pressure to 0.8 GPa, two new lattice modes were observed as marked by arrows in Figure 3a, indicating the beginning of the first phase transition from phase I to phase II. The changes of internal vibration modes at 0.8 GPa are consistent with the proposed phase transition. As illustrated in Figure 3b-3f, the splitting of the existing modes and the appearance of new modes can be detected. New peaks at 738 and 1023 cm-1 are in the spectra range of ring in-plane bending and ring breathing modes, respectively. The ring C-H in-plane bending mode at 1166 cm-1 split into a doublet and a new peak showed up at 1197 cm-1 around this mode. Another new peak at 2949 cm-1 is identified as CH3 stretching mode. These changes of ring vibration modes are ascribed to the ring distortion, and the new CH3 vibration mode is due to the rotation of the CH3 group.28, 29 With further compression to 2.1 GPa, the appearance of peak for the N-H out-of-plane bending mode at 625 cm-1 suggests the rearrangement of hydrogen bond. The lattice mode marked by asterisk disappeared, implying the completion of the first phase transition. Importantly, the evolution of the N3 vibration modes in Raman and IR spectra provide details about the variations of azide group through the first phase transition.


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As shown in Figure 3b and 3f, new peaks emerge at 528 and 2140 cm-1 in the pressure region of 0.8 - 2.1 GPa are assigned to N3 in-plane bending and asymmetric stretching modes, respectively. Meanwhile, in the IR spectra of Figure 4b, new N3 symmetric stretching mode appears at 1305 cm-1 at 0.8 GPa. The changes of N3 vibration modes indicate that the azide groups rotate progressively with increasing pressure, which is ascribed to the compression of the unit cell along b-axis.18, 20 The behavior of N-H…O hydrogen bonds can be traced from the change of N-H stretching modes at ~ 3300 cm-1. In Figure 4c and 4f, the N-H stretching modes show red shifts, suggesting that the hydrogen bonds are weak and moderate.30 With increasing pressure, the contraction of the H…O distance leads to the increasing electrostatic attraction between H and O. Then the N-H distance is extended, resulting in the red shift of the N-H stretching modes. Similarly, the C=O stretching modes exhibit red shift with compression due to the extended C=O distance of N-H…O=C hydrogen bonds, as exhibited in Figure 3d. Other new peaks of IR spectra in the pressure region of 0.8 - 2 GPa result from the modification of the specific groups, which is in accordance with the Raman results.



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Figure 3. Selected high-pressure Raman spectra of 4-ABSA in the spectra region of (a) 60-320 cm-1 (b) 320-700 cm-1 (c) 700-1250 cm-1 (d) 1360-1800 cm-1 (e) 2050-2250 cm-1 (f) 2800-3200 cm-1 with the corresponding modes as a function of pressure, respectively. The arrows and asterisks denote the appearance of new peaks and the disappearance of peaks, respectively. The vertical dashed lines mean the proposed phase boundaries.



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Figure 4. Selected high-pressure IR spectra of 4-ABSA in the spectral region of (a) 680-1300 cm-1 (b) 1300-1750 cm-1 (c) 2950-3400 cm-1, respectively. The corresponding modes as a function of pressure are shown in (d, e, f), respectively. The arrows and asterisks represent the appearance of new peaks and the disappearance of peaks, respectively. The vertical dashed lines imply the proposed phase boundaries. With the pressure increased to 4.2 GPa, the lattice modes marked by asterisks disappeared accompanied with the emergence of new lattice modes labeled with arrows, implying the second phase transition from phase II to phase III. In Figure 3b and 4b, new peaks at 539 and 1316 cm-1 are assigned to N3 in-plane bending and symmetric stretching modes, respectively. The intensity of the new peaks is significantly increased accompanied with the intensity of the original N3 in-plane bending and symmetric stretching modes significantly decreased, demonstrating the rearrangement of the azide groups during the second phase transition. In Figure 4c


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and 4f, one N-H stretching mode vanishes and another one turns to blue shift suggesting the rearrangement of hydrogen bond.31 This is consistent with the splitting of the N-H in-plane bending mode in Figure 3d. Above 4.2 GPa, there is a dramatic weakness in the intensities of the C-H stretching vibrations in Figure 3f, revealing that CH3 groups undergo significant modifications in the second phase transition. The lattice modes vanished at 8 GPa, implying the distortion of the unit cell upon compression. All the Raman internal modes disappeared at 12.3 GPa. Concurrently, the IR bands broad and diffuse at 13 GPa, the highest pressure in the experiments, signifying 4-ABSA in the completely amorphous phase. 3.3 High pressure XRD experiment. Synchrotron angle-dispersive XRD measurements were carried out up to 12.6 GPa to confirm the phase transitions and monitor structural properties of 4-ABSA at high pressures. The evolution of the XRD patterns is depicted in Figure 5. As illustrated in Figure 5, the peaks (111) and (

), (151) and (

), and (160) and (122) merged

each other at 0.8 GPa accompanied with the disappearance of peaks labeled with green arrows. When increasing pressure to 1.7 GPa, the peaks (060) and (220), (042) and (

1), (240) and (132), and (161) and (2 1) merged together. The pressure range

of the changes observed in XRD patterns is consistent with the first phase transition from phase I to phase II in Raman and IR measurements. To obtain more information on phase II, the Pawley refinement of the diffraction pattern at 1.7 GPa was conducted, as illustrated in Figure 6. The refinement result shows that phase II belongs to monoclinic structure with space group P2. With pressure increasing to 4.3 GPa,



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4-ABSA undergoes the second phase transition, as demonstrated by the red shift of the

Bragg peak labeled with pink dashed line in Figure 5. The

Bragg

peak shifts to lower angle that attributes to the increase in the interplanar distance, which might be caused by the rearrangement of the azide groups and hydrogen bond drawn from the vibrational anaylses. Besides this Bragg peak, all the Bragg peaks shift to higher angles with increasing pressure due to the decrease in d-spacings. Upon subsequent compression, the Bragg peaks became broad and the intensity was decreased, signifying the accelerated distortion of the unit cell which is in agreement with the evolution of the lattice mode in Figure 3a. At 12.6 GPa, all the Bragg peaks vanished, meaning 4-ABSA transformed into an amorphous phase. When pressure is released to ambient conditions, the amorphous phase is retained, which is supported by the decompression spectra of Bragg peaks (Figure 5) and the Raman lattice mode (Figure 3a). Part of the internal vibration modes of 4-ABSA can be recovered as exhibited in Figure 3 and 4. This is because the groups of single molecule are preserved, although the crystal structure has been destroyed.


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Figure 5. Representative XRD patterns of 4-ABSA at high pressures. The asterisks denote the noise peaks. The green arrows mean the disappearance of the diffraction peaks.



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Figure 6. Pawley refinement result of the ADXRD pattern of 4-ABSA at 1.7 GPa with monoclinic structure (P2) and cell parameters of a=14.2790 Å, b=13.2514 Å, c=12.7201 Å, β=127.822°. 4. Conclusion In the present study, the high-pressure characterization of 4-ABSA using Raman and IR spectroscopy, and synchrotron ADXRD techniques was achieved in diamond anvil cells up to 12.3, 13, and 12.6 GPa, respectively. Observed with all three measurements, two phase transitions were determined to occur in the pressure region of 0.8 - 2 GPa and 4.2 GPa, respectively. The first phase transition in the pressure region of 0.8 - 2 GPa was induced by the ring distortion and the rotation of CH3 group. Further XRD experiment confirmed the structure transformation from P21 to P2 space group. The second phase transition at 4.2 GPa might be caused by the rearrangement of the azide groups and hydeogen bond. The analyses of N3 vibration modes reveal that the bent azide group rotates progressively with increasing pressure. Upon elevation pressure to 13 GPa, 4-ABSA transforms into amorphous state, which is irreversible when pressure decomposition to 0GPa. Generally, our detailed spectroscopic and XRD analyses provide more insight into the behavior of azide group and the structure evolution of 4-ABSA.

Acknowledgements This work is supported by the National Natural Science Foundation of China (11304111, 11304139), and the Natural Science Foundation of Shandong Province


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(ZR2014JL005). ADXRD measurements were performed at Beijing Synchrotron Radiation Facility (BSRF). References 1. Pereira, C. M.; Chaudhri, M. M. Optical and Raman Studies of Explosives under Varying Pressure and Temperature. J. Energ. Mater., 1989, 7, 297-322. 2. Yoffe, A. D. Thermal Decomposition and Explosion of Azides. Proc. R. Soc. Lond. A, 1951, 208, 188-199. 3. Evans, B. L.; Yoffe, A. D. Physics and Chemistry of the Inorganic Azides. Chem. Rev. , 1959, 59, 515-568. 4. Schneider, S. B.; Frankovsky, R.; Schnick, W. Synthesis of Alkaline Earth Diazenides MAEN2 (MAE = Ca, Sr, Ba) by Controlled Thermal Decomposition of Azides under High Pressure. Inorg. Chem., 2012, 51, 2366-2373. 5. Borukhova, S.; Seeger, A. D.; Noel, T.; Wang, Q.; Busch, M.; Hessel, V. Pressure-Accelerated Azide-Alkyne Cycloaddition: Micro Capillary versus Autoclave Reactor Performance. ChemSusChem, 2015, 8, 504-512. 6. Eremets, M. I.; Popov, M. Y.; Trojan, I. A.; Denisov, V. N.; Boehler, R.; Hemley, R. J. Polymerization of Nitrogen in Sodium Azide. J. Chem. Phys, 2004, 120, 10618-10623. 7. Eremets, M. I.; Gavriliuk, A. G.; Trojan, I. A.; Dzivenko, D. A.; Boehler, R. Single-Bonded Cubic Form of Nitrogen. Nat. Mate., 2004, 3, 558-563. 8. Li, J.; Wang, X.; Xu, N.; Li, D.; Wang, D.; Chen, L. Pressure-Induced Polymerization of Nitrogen in Potassium Azides. Europhys. Lett., 2013, 104, 16005. 9. Wang, X.; Li, J.; Xu, N.; Zhu, H.; Hu, Z.; Chen, L. Layered Polymeric Nitrogen in RbN3 at High Pressures. Scientific reports, 2015, 5, 16677. 10. Wang, X.; Li, J.; Zhu, H.; Chen, L.; Lin, H. Polymerization of Nitrogen in Cesium Azide under Modest Pressure. J. Chem. Phys., 2014, 141, 044717. 11. Medvedev, S. A.; Trojan, I. A.; Eremets, M. I.; Palasyuk, T.; Klapotke, T. M.; Evers, J. Phase Stability of Lithium Azide at Pressures up to 60 GPa. J. Phys. Condens. Matter, 2009, 21, 195404. 12. Sklenak, S.; Gatial, A.; Biskupic, S. Ab Initio Study of Small Organic Azides. J. Mol. Struct., 1997, 397, 249-262. 13. Jiang, J.; Wu, X.; Li, D.; Ma, B.; Liu, R.; Wang, X.; Zhang, J.; Zhu, H.; Cui, Q. High Pressure Raman Scattering and Synchrotron X-ray Diffraction Studies of Benzyl Azide. J. Phys. Chem. B, 2015, 119, 513-518. 14. Cantillo, D.; Gutmann, B.; Kappe, C. O. Mechanistic Insights on Azide-Nitrile Cycloadditions: on the Dialkyltin Oxide-Trimethylsilyl Azide Route and a New Vilsmeier-Haack-Type Organocatalyst. J. Am. Chem. Soc., 2011, 133, 4465-4475. 15. Wang, F.; Du, H.; Zhang, J.; Gong, X. First-Principle Study on High-Pressure Behavior of Crystalline Polyazido-1,3,5-triazine. J. Phys. Chem. C, 2012, 116, 6745-6753. 16. Liu, Y.; Zhang, L.; Wang, G.; Wang, L.; Gong, X. First-Principle Studies on the Pressure-Induced Structural Changes in Energetic Ionic Salt 3-Azido-1,2,4-Triazolium Nitrate Crystal. J. Phys. Chem. C, 2012, 116, 16144-16153.



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17. Vicarel, M. L.; Norris, P.; Zeller, M. 4-Acetamidobenzenesulfonyl Azide. Acta Crystallogr. Sect. E: Struct. Rep. Online, 2006, 62, 1751-1753. 18. Wu, X.; Cui, H.; Zhang, J.; Cong, R.; Zhu, H.; Cui, Q. High Pressure Synchrotron X-ray Diffraction and Raman Scattering Studies of Ammonium Azide. Appl. Phys. Lett., 2013, 102, 121902. 19. Wu, X.; Ma, F.; Ma, C.; Cui, H.; Liu, Z.; Zhu, H.; Wang, X.; Cui, Q. Pressure-Driven Variations of Hydrogen Bonding Energy in Ammonium Azide (NH4N3): IR Absorption and Raman Scattering Studies. J. Chem. Phys., 2014, 141, 024703. 20. Zhu, H.; Han, X.; Zhu, P.; Wu, X.; Chen, Y.; Li, M.; Li, X.; Cui, Q. Pressure-Induced Amorphization of Strontium Azide. J. Phys. Chem. C, 2016, 120 12423-12428. 21. Spectral Database for Organic Compounds, SDBS. http://sdbs.db.aist.go.jp. (accessed Sept 30, 2004). 22. Durig, D. T.; Durig, M. S.; Durig, J. R. On the Vibrational Spectra and Structural Parameters of Methyl, Silyl, and Germyl Azide from Theoretical Predictions and Experimental Data. Spectrochim. Acta, Part A 2005, 61, 1287-1306. 23. Lieber, E.; Rao, C. N. R.; Thomas, A. E.; Oftedahl, E.; Minnis, R.; Nambury, C. V. N. Infrared Spectra of Acid Azides, Carbamyl Azides and Other Azido Derivatives.* Anomalous Splittings of the N3 Stretching Bands. Spectrochim. Acta, 1963, 19, 1135-1144. 24. Dabbagha, H. A.; Teimouri, A. Insertion Reaction of Azidosulfonyl Azo Dye with Model Alicyclic and Heterocyclic Compounds. Russ. J. Org. Chem., 2006, 48, 1464-1470. 25. Teimouri, A.; Chermahini, A. N.; Emamic, M. Synthesis, Spectroscopic Characterization and DFT Calculations on [4-(Sulfonylazide)phenyl]-1-Azide. Arkivoc, 2008, 12, 172-187. 26. Spinner, E. The Vibration Spectra and Structures of the Hydrochlotides of Urea, Thiourea and Acetamide. The Basic Properties of Amides and Thioamides. Spectrochim. Acta, 1959, 15, 95-109. 27. Dabbagh, H. A.; Teimouri, A.; Chermahini, A. N.; Shiasi, R. DFT and Ab Initio Calculations of the Vibrational Frequencies and Visible Spectra of Triazenes Derived from Cyclic Amines. Spectrochim. Acta. Part A: Mol Biomol Spectrosc, 2007, 67, 437-443. 28. Zhang, D.; Dou, S.; Weiss, A. Molecular Motions in (CH3)3XC1, X=Sn and Pb. NMR Investigations and Crystal Structure Study of (CH3)3PbCl and CH3SnBr3. Z. Naturforsch., 1991, 46a, 337-343. 29. Jiang, J.; Zhu, P.; Li, D.; Li, M.; Wang, X.; Liu, B.; Cui, Q.; Zhu, H. High Pressure Studies of Trimethyltin Azide by Raman Scattering, IR Absorption, and Synchrotron X-ray Diffraction. RSC Adv., 2016, 6, 98921-98926. 30. Hamann, S. D.; Linton, M. The Influence of Pressure on the Infrared Spectra of Hydrogen-Bonded Solids. III* Compounds with N-H…X Bonds. Aust. J. Chem., 1976, 29, 1641-1647. 31. Li, S.; Wang, K.; Zhou, M.; Li, Q.; Liu, B.; Zou, G.; Zou, B. Pressure-Induced Phase Transitions in Ammonium Squarate: a Supramolecular Structure Based on Hydrogen-Bonding and π-Stacking Interactions. J. Phys. Chem. B, 2011, 115, 8981-8988.

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Figure 1. Crystal structure of 4-ABSA under ambient conditions. The hydrogen bonds are marked as dashed lines. The grey, white, blue, yellow, and red spheres denote C, H, N, S, and O atoms, respectively. 300x183mm (72 x 72 DPI)


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Figure 2. (a) Experimental IR spectra, (b) experimental Raman spectra, and (c) calculated Raman spectra of 4-ABSA at ambient conditions. The pink lines marked with ×5 means the spectra are at a magnification of 5 times. All the assignments of the vibrational modes are marked above each band. 287x201mm (300 x 300 DPI)



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Figure 3a 190x201mm (300 x 300 DPI)


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Figure 3b 190x201mm (300 x 300 DPI)



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Figure 3c 190x201mm (300 x 300 DPI)


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Figure 3d 190x201mm (300 x 300 DPI)



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Figure 3e 190x202mm (300 x 300 DPI)


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Figure 3f 190x200mm (72 x 72 DPI)



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Figure 4abc 228x201mm (300 x 300 DPI)


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Figure 4def 254x201mm (300 x 300 DPI)



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Figure 5. Representative XRD patterns of 4-ABSA at high pressures. The asterisks denote the noise peaks. The green arrows mean the disappearance of the diffraction peaks. 152x201mm (300 x 300 DPI)


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Figure 6. Pawley refinement result of the ADXRD pattern of 4-ABSA at 1.7 GPa with monoclinic structure (P2) and cell parameters of a=14.2790 Å, b=13.2514 Å, c=12.7201 Å, β=127.822°. 190x127mm (300 x 300 DPI)



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High-Pressure Studies of 4-Acetamidobenzenesulfonyl Azide

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