Electronic Supplementary Material (ESI) for New Journal of Chemistry.

This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2019

Electronic Supplementary Information

Large-scale synthesize of azine-linked covalent organic frameworks in

water and promoted by water

Jian Lu,a,b Feng Lin,b Qiang Wen,b Qiao-Yan Qi,b Jia-Qiang Xu*a and Xin Zhao*b

a
NEST Laboratory, Department of Chemistry, College of Science, Shanghai
University, Shanghai 20044 , China

b
Key Laboratory of Synthetic and Self-Assembly Chemistry for Organic Functional
Molecules, Center for Excellence in Molecular Synthesis, Shanghai Institute of
Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai
200032, China

1
Fourier transform infrared spectroscopy (FT-IR)
Fourier transform infrared spectroscopy (FT-IR) was carried out with a Nicolet 380
FT-IR spectrometer. The samples for IR study were prepared as KBr pellets.

Solid-state nuclear magnetic resonance (NMR) spectroscopy

13
Solid-state C cross-polarization/magic angle spinning (CP/MAS) spectra were
collected on Agilent DD2 600 Solid system, equipped with a 3.2 mm HFXY MAS
probe. The Hartmann-Hahn conditions of the CP experiment were obtained at a 15
kHz MAS spinning speed with a contact time of 2.0 ms. Recycle delay times are 5 s.
The 13C chemical shifts were externally referenced to tetramethylsilane (δ = 0.0 ppm).

Scanning electron microscopy (SEM)

Scanning electron microscopy was carried out using a XL30 FEG scanning electron
microscope. The samples were dispersed over a slice of conductive adhesive adhered
to a flat copper platform sample holder and then coated with gold using a sputter 9
coater (ambient temperature, 85 torr pressure in a nitrogen atmosphere, sputtered for
80 s from a solid gold target at a current of 20 mA) before being submitted to SEM
characterization.

Transmission electron microscopy (TEM)

TEM was performed on a Philips CM 200/FEG transmission electron microscope.
The samples were prepared by carefully dropping suspending solutions of the COFs
in anhydrous EtOH onto the carbon coated copper grid followed by removal of the
solvent under vacuum.

Thermal gravimetric analysis (TGA)

Thermal gravimetric analyses were carried out on Waters TGA Q500 by heating the
samples from 35 to 900 oC under nitrogen atmosphere at a heating rate of 10 oC /min.

Powder X-ray diffraction experiment (PXRD)

Powder X-ray diffraction measurements were carried out with an X’Pert PROX
system using monochromated Cu/Kα (λ = 0.1542 nm). The samples were spread on
the square recess of XRD sample holder as a thin layer.
2
Nitrogen adsorption-desorption isotherm measurements
The measurements were carried out using a Micromeritics ASAP 2020 HD88
analyzer. Before gas adsorption measurements, the as-prepared samples (50 mg)
were activated by being immersed in anhydrous dioxane for 12 h. The solvent was
decanted and the samples were dried under dynamic vacuum at 160oC for 8 h. The
resulting samples were then used for gas adsorption measurements from 0 to 1 atm at
77 K. The Brunauer-Emmett-Teller (BET) method was utilized to calculate the
specific surface areas. By using the non-local density functional theory model, the
pore size distributions were derived from the sorption curves.

Structural simulation and powder X-ray diffraction analysis

The Pawley refinement of the experimental PXRD was conducted by the Reflux
module in the Materials Studio 7.0. The simulations of the possible structures were
carried out in Accelrys Materials Studio 7.0 software package. The stimulated PXRD
patterns were determined by the Reflex module. P6 space group was chosen for the
primitive models in the initial simulations.

Synthesis of 1,3,5-triformylphloroglucinol

A mixture of hexamethylenetetramine (22.3 g, 158.6 mmol) and phloroglucinol (10.0

g, 79.3 mmol) were dissolved in trifluoroacetic acid (60 mL) under an argon
atmosphere. The reaction mixture was heated at 100 oC for 2.5 h, then added HCl (3
M, 200 mL) and heated at 100 oC for another 1 h. After being cooled to room
temperature, the solution was filtered through Celite, extracted with dichloromethane
(3×150 mL), dried over sodium sulfate, and filtered. Rotary evaporation of the
solution afforded an organic powder (3.33g, 20%).The characterizations are consistent
with the literature reported.1 1
H NMR (500 MHz, CDCl3) δ 14.11 (s, 3H), 10.15 (s,
3H).

3
Synthesis of 2-hydroxy-1,3,5-triformylbenzene

A mixture of phenol (7.27 g, 77 mmol) and hexamethylenetetramine (HMTA)

(23.52 g, 167 mmol) were dissolved in 70 mL trifluoroacetic acid (TFA) under an
argon atmosphere. The mixture was stirred at 130℃ for 16h, then heated to 150℃
for 3h. The mixture was treated with 100 mL of 4M HCl after cooled to 120℃, then
heated at 105℃ for 30min and cooled to room temperature overnight. The crude
products were filtered off, washed with water, ethol. Then powders were
recrystallized from DMF. Yield: 6.14g (44.6%). 1H NMR (400 MHz, DMSO-d6) δ
10.32 (s, 2H), 10.00 (s, 1H), 8.53 (s, 2H).

Synthesis of 2,4,6-triformylresorcinol

A mixture of resorcinol (7.16g, 65 mmol) and hexamethylenetetramine (HMTA) (20 g,

143 mmol) were dissolved in 70 mL trifluoroacetic acid (TFA) under an argon
atmosphere. The mixture was stirred at 120℃ for 24h, then heated to 150℃ for 3h.
The mixture was treated with 110 mL of 3N HCl after cooled to 120℃, then heated at
105℃ for 30min and cooled to room temperature overnight. The crude products were
filtered off, washed with water, ethol. Then powders were recrystallized from DMF.
Yield: 3.41g (27%). 1H NMR (400 MHz, DMSO-d6) δ 10.26 (s, 1H), 10.09 (s, 2H),
8.39 (s, 1H).

General procedure for the preparation of HCOF-1 under hydrothermal

condition
4
1,3,5-triformylphloroglucinol (21.0 mg, 0.1 mmol) and hydrazine hydrate (0.01 mL
80% weight in water, 0.15 mmol) were dissolved in deionized water(1mL) in a glass
ampoule. The ampoule was sealed after being degassed in a liquid nitrogen bath for
10 min, warmed to room temperature and then kept at 120oC without disturbance for
different times to yield a red solid at the bottom of the ampoule. After being cooled to
room temperature, the solvent was decanted and the solid was washed with anhydrous
1,4-dioxane for 3 times and then dried under dynamic vacuum at 120 oC for 2 h to
afford a red powder , which was insoluble in common organic solvents such as
acetone, ethanol, and N, N-dimethylformamide. Anal. Calcd. For chemical formula
C3H2NO: C, 52.95; H, 2.96; N, 20.58. Found: C, 52.88; H, 4.26; N, 19.27.

Representative procedure for the scale-up preparation of the COFs

To a 500 mL sealed glass tube, 1,3,5-triformylphloroglucinol (10.5 g, 0.05 mol),

deionized water (350 mL) and hydrazine hydrate (4.6 mL 80% weight in water, 0.076
mol) were added. The whole mixture was sealed after being degassed in a liquid
nitrogen bath for 30 min, warmed to room temperature and then kept at 120 oC
without disturbance for 12 h to yield a red solid at the bottom of the tube. After being
cooled to room temperature, the solvent was decanted and the solid was washed with
anhydrous 1,4-dioxane for 3 times and then dried under dynamic vacuum at 120 oC
for 2 h to afford a red powder (9.9 g, 97%).

To a 100 mL sealed glass tube, 2,4,6-triformylresorcinol (1 g, 0.00515 mol), deionized

water (50 mL) and hydrazine hydrate (0.44 mL 85% weight in water, 0.00773 mol)
5
were added. The whole mixture was sealed after being degassed in a liquid nitrogen
bath for 30 min, warmed to room temperature and then kept at 120 oC without
disturbance for 12 h or 3d to yield a yellow solid at the bottom of the tube. After being
cooled to room temperature, the solvent was decanted and the solid was washed with
THF for 3 times and then dried under dynamic vacuum at 120 oC for 2 h to afford a
red powder (0.98 g, 88% for an experiment of 3d). Anal. Calcd. For chemical formula
C18H12N6O4: C, 57.45; H, 3.21; N, 22.33. Found: C, 56.91; H, 4.34; N, 21.44.

To a 500 mL sealed glass tube, 2-hydroxy-1,3,5-triformylbenzene (3.56 g, 0.02 mol),

deionized water (300 mL) and hydrazine hydrate (1.71 mL 85% weight in water, 0.03
mol) were added. The whole mixture was sealed after being degassed in a liquid
nitrogen bath for 30 min, warmed to room temperature and then kept at 120 oC
without disturbance for 5d to yield a yellow solid at the bottom of the tube. After
being cooled to room temperature, the solvent was decanted and the solid was washed
with THF for 3 times and then dried under dynamic vacuum at 120 oC for 2 h to
afford a yellow powder (3.6 g, 90%). Anal. Calcd. For chemical formula C18H12N6O2:
C, 62.79; H, 3.49; N, 24.42. Found: C, 60.81; H, 3.99; N, 23.05.

General Procedure for the screening of condensation conditions for the

hydrothermal synthesis of HCOF-1

1,3,5-triformylphloroglucinol (21.0 mg, 0.1 mmol) and hydrazine hydrate (0.01 mL

80% weight in water, 0.15 mmol) were dissolved in deionized water (1mL) and acetic
acid (aq., 0.1 mL, 0, 3 or 6 M ) in a glass ampoule. The ampoule was sealed after
being degassed in a liquid nitrogen bath for 10 min, warmed to room temperature and
then kept at 80, 120 or 150 oC without disturbance for different times to yield a red
solid at the bottom of the ampoule. After being cooled to room temperature, the
solvent was decanted and the solid was washed with anhydrous 1,4-dioxane for 3
times and then dried under dynamic vacuum at 120 oC for 2 h to afford a red powder.
6
 Table S1. Synthesis of HCOF-1 under different hydrothermal conditions.

Entry Solvent(1 Catalyst (0.1 Time (h) Temperature (oC)

mL) mL)
1 80
-1
2 Water 6.0 mol·L 72 120
3 AcOH 150

3
2
1

10 20 30
2-Theta (degree)

Figure S1. PXRD profiles of HCOF-1 synthesized under different temperatures.

7
 Table S2. Synthesis of HCOF-1 under different hydrothermal conditions.

Entry Solvent (1 Catalyst (0.1 Time (h) Temperature (oC)

mL) mL)
1 0 M AcOH
2 Water 3.0 M AcOH 72 120
3 6.0 M AcOH
1
2
3

10 20 30
2-Theta (degree)

Figure S2. PXRD profiles of HCOF-1 synthesized under different concentrations of

AcOH.

8
 Adsorption 0.0022
500 Desorption
0.0020
Quantity Adsorbed(cm3/g STP)

0.0018
400 -6
0.0016 y=0.00706x-9.51953*10
2
R =0.99878

1/[Q(P/P0-1)]
0.0014
300
0.0012

0.0010

200 0.0008
2
BET Surface Area: 617.3 m /g
0.0006

100 0.0004

0.0002
0.0 0.2 0.4 0.6 0.8 1.0 0.05 0.10 0.15 0.20 0.25 0.30
Relative Pressure(P/P0) Relative Pressure(P/P0)

Figure S3. N2 adsorption−desorption isotherms (77 K) (left) and BET surface area
plot (right) of HCOF-1 (1g-scale-synthesis).

450
Adsorption
0.0018
Desorption
Quantity Adsorbed(cm3/g STP)

400 0.0016

0.0014 -5
350 y=0.00577x-6.1174*10
2
0.0012 R =0.99699
1/[Q(P/P0-1)]

300 0.0010

0.0008
250
0.0006
2
BET Surface Area:763.0 m /g
200 0.0004

0.0002
150
0.0 0.2 0.4 0.6 0.8 1.0 0.05 0.10 0.15 0.20 0.25 0.30
Relative Pressure(P/P0) Relative Pressure(P/P0)

Figure S4. N2 adsorption−desorption isotherms (77 K) (left) and BET surface area
plot (right) of HCOF-1 (10g-scale-synthesis).

260 Adsorption
0.0030
Desorption
240
Quantity Absorbed(cm /g STP)

220 0.0025
-5
y=0.00957x-5.24283*10
200 2
R =0.9978
3

1/[Q(Po/P - 1)]

0.0020
180

160
0.0015
140

120 0.0010 2
BET Surface Area: 457.4 m /g
100
0.0005
80

0.0 0.2 0.4 0.6 0.8 1.0 0.05 0.10 0.15 0.20 0.25 0.30
Relative Pressure(P/P0) Relative Pressure(P/Po)

Figure S5. N2 adsorption−desorption isotherms (77 K) (left) and BET surface area
plot (right) of HCOF -1 (synthesized by running the hydrothermal reaction for 2 h).
9
a

1590 (C=C, C=N) 1277 (C-N)

1641 (C=O)

3500 3000 2500 2000 1500 1000 500

Wavenumber (cm-1)
Figure S6. FT-IR spectra of (a) HCOF-1 and (b) 1,3,5-triformylphloroglucinol.

Figure S7. 13C NMR spectrum of 1,3,5-triformylphloroglucinol.

10
 C7

C2

C1,
C3

C8

C6

Figure S8. Solid-state 13C CP/MAS NMR spectrum of HCOF-1.

1.0 1,3,5-triformylphloroglucinol
HCOF-1

0.8
Absorbance(O.D.)

0.6

0.4

0.2

0.0

300 400 500 600 700 800

Wavelength(nm)

Figure S9. UV-vis spectra of (a) HCOF-1 and (b) 1,3,5-triformylphloroglucinol.

11
Figure S10. SEM image (left) and TEM image (right) of HCOF-1.

Adsorption Differential Pore Volume (cm3/g) 1.2

10.2Å
350 Desorption
Quantity Adsorbed(cm3/g STP)

1.0

300
0.8

250 0.6

0.4
200

0.2
150

0.0
0.0 0.2 0.4 0.6 0.8 1.0 10 100 1000
Relative Pressure(P/P0) Pore Width (Angstroms)

Figure S11. N2 adsorption−desorption isotherms (77 K) of HCOF-1 (left), and pore

size distribution profile of HCOF-1 (right) (the inserted photograph shows the
theoretical pore size).

100

80
Weight (%)

60

40

20

0
0 100 200 300 400 500 600 700 800
Temperature (oC)

Figure S12. TGA profile of HCOF-1 under nitrogen atmosphere.

12
Figure S13. Solid-state 13C CP/MAS NMR spectrum of HCOF-2.

Figure S14. Solid-state 13C CP/MAS NMR spectrum of HCOF-3.

13
 a

1595cm-1(C=N)

1683cm-1(C=O)

3500 3000 2500 2000 1500 1000 500

Wavenumber(cm-1)
Figure S15. FT-IR spectra of (a) HCOF-2 and (b) 2,4,6-triformylresorcinol.
a

1592cm-1(C=N)

1689cm-1(C=O)

3500 3000 2500 2000

1500 1000 500
Wavenumber(cm-1)
Figure S16. FT-IR spectra of (a) HCOF-3 and (b) 2-hydroxy-1,3,5-triformylbenzene.

14
 0.45
600
Adsorption
Desorption 0.40
500
0.35
Quantity Adsorbed(cm3/g STP)

y=3.90418x+0.00477
400 0.30
R2=0.99999

1/[Q(P0/P-1)]
0.25
300

0.20

200
0.15

100 0.10
BET Surface Area=890.9 m2/g
0.05
0
0.00
0.0 0.2 0.4 0.6 0.8 1.0 0.00 0.02 0.04 0.06 0.08 0.10
Relative Pressure(P/P0) Relative Pressure(P/P0)

Figure S17. N2 adsorption−desorption isotherms (77 K) (left) and BET surface area
plot (right) of HCOF-2 (1g-scale-synthesis).

250
Adsorption
Desorption 3.0

200
Quantity Adsorbed(cm3/g STP)

2.5

y=19.5461x+0.06144
150
1/[Q(P0/P-1)]

2.0 R2=0.9998

100 1.5

50
1.0
BET Surface Area:177.6 m2/g

0.5

0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16

Relative Pressure(P/P0) Relative Pressure(P/P0)

Figure S18. N2 adsorption−desorption isotherms (77 K) (left) and BET surface area
plot (right) of HCOF-3 (3g-scale-synthesis).

0.014
0.07
8.6Å 9.3Å
0.012
0.06
Differential Pore Volume (cm3/g)
Differential Pore Volume (cm3/g)

0.05 0.010

0.04 0.008

0.03 0.006

0.02 0.004

0.01 0.002

0.00 0.000
10 100 1000 10 100 1000
Pore Width(Angstroms) Proe Width(Angstroms)

Figure S19. Pore size distribution profile of HCOF-2 (left) and HCOF-3(right) (the
inserted photograph shows the theoretical pore size).

15
 100

110 001

5 10 15 20 25 30

2 Theta
Figure S20. (a) Experimental (black) and refined (red) PXRD patterns of HCOF-2,
(b) difference plot between the experimental and refined PXRD patterns, and
simulated PXRD patterns of (c) HCOF-2 with AA stacking, (d) HCOF-2 with AB
stacking.

5 10 15 20 25 30
2-Theta(degree)

Figure S21. Experimental PXRD patterns of HCOF-2 (synthesized by running the

hydrothermal reaction for 12 h).

16
 a 100

001
110

d
5 10 15 20 25 30

2-Theta

Figure S22. (a) Experimental (black) and refined (red) PXRD patterns of HCOF-3,
(b) difference plot between the experimental and refined PXRD patterns, and
simulated PXRD patterns of (c) HCOF-3 with AA stacking, (d) HCOF-3 with AB
stacking.

100
100

351℃,93%
379oC,83%
80 90
Weight(%)

Weight(%)

80
60

70

40

60

20
50

0 40
200 400 600 800 0 200 400 600 800

Temperature(oC) Temperature(oC)

Figure S23. TGA profile of HCOF-2 (left) and HCOF-3 (right) under nitrogen
atmosphere.

17
Figure S24. SEM image (left) and TEM image (right) of HCOF-2.

Figure S25. SEM image (left) and TEM image (right) of HCOF-3.

18
 a 2.5
0min b 2.0
0min
1.8 10min
10min
1h
2.0 30min 1.6 2h
1h
3h
2h 1.4
4h
3h
1.5 1.2 5h
4h
5h
Abs

Abs
1.0

1.0 0.8

0.6

0.5 0.4

0.2

0.0 0.0
350 400 450 500 550 600 400 450 500 550 600
Wavelength (nm)
Wavelength (nm)
1.0 1.0
c 0min d 0min
1min 1min
10min 10min
0.8 0.8
30min 30min
60min 60min

0.6 0.6
Abs

0.4 Abs 0.4

0.2 0.2

0.0 0.0
350 400 450 500 550 600 650 700 750 450 500 550 600 650 700 750

Wavelength (nm) Wavelength (nm)

Figure S26. Time-dependent UV-vis absorption spectra of (a) MO, (b) AR1, (c)
MB/MO, and (d) MB/AR1 in the presence of HCOF-1. The inserted photographs
show the color change during the processes of dyes uptakes.

Table S3. The space groups and cell parameters of the HCOF-1 structures.
Structure Space Group Cell Parameters
AA P6 a = b = 15.41Å, c = 3.34 Å, α = β = 90.00° and γ = 120.00°
AB P3 a = b = 15.41 Å, c = 6.68 Å, α = β = 90.00° and γ = 120.00°

Table S4. Fractional atomic coordinates for the unit cell of HCOF-1 with AA
stacking.
P6
A = b = 15.41 Å, c = 3.34 Å, α = β = 90.00° and γ = 120.00°
Element Number u v w
N 1 0.04958 0.53953 -0.01066
C 2 0.12955 0.51955 0.05933
C 3 0.2252 0.59061 0.13572
C 4 0.25848 0.69842 0.18496
O 5 0.1995 0.72455 0.29095
H 6 0.06292 0.61119 -0.07383
H 7 0.11114 0.44213 0.04468

19
Table S5. The space groups and cell parameters of the HCOF-2 structures.
Structure Space Group Cell Parameters
AA P1 a =14.70Å b = 15.44Å, c = 3.20Å, α = β = 90.00° and γ =
120.00°
AB P1 a =14.70Å b = 15.44 Å, c = 6.40Å, α = β = 90.00° and γ =
120.00°

Table S6. Fractional atomic coordinates for the unit cell of HCOF-2 with AA
stacking.

P1
a =15.45 b = 15.05 Å, c = 3.45 Å, α = β = 90.00° and γ = 120.00°
Element Number u v w
H 1 4.686746 -3.957565 0.295478
H 2 4.757805 -4.302301 -0.035101
H 3 4.481584 -4.413417 0.239185
H 4 4.933108 -4.170492 -0.153755
H 5 4.488538 -4.193731 0.420488
H 6 4.816885 -3.92317 -0.077581
H 7 4.589001 -4.604203 -0.280924
H 8 4.315891 -4.716394 -0.020075
H 9 4.140912 -4.847964 0.125036
H 10 4.383296 -5.066227 -0.203277
H 11 4.630279 -4.710655 -0.072775
H 12 4.181107 -5.062432 0.253967
C 13 4.638016 -4.028948 0.154812
C 14 4.671135 -4.104324 0.11628
C 15 4.600647 -4.208947 0.158832
C 16 4.631123 -4.280389 0.087334
C 17 4.733498 -4.2473 0.006086
C 18 4.805679 -4.143947 -0.01144
C 19 4.773945 -4.071996 0.028253
C 20 4.555326 -4.389662 0.113955
C 21 4.913851 -4.113533 -0.074261
C 22 4.518437 -4.628625 -0.129726
C 23 4.444923 -4.737995 -0.083191
C 24 4.341192 -4.771281 -0.029365
C 25 4.268973 -4.874561 -0.000451
C 26 4.302044 -4.946214 -0.012688
C 27 4.404986 -4.914107 -0.078234
C 28 4.477021 -4.810224 -0.107225
C 29 4.160293 -4.903978 0.033004
20
 C 30 4.436447 -4.991156 -0.098965
N 31 4.553521 -4.045262 0.004731
N 32 4.574103 -4.457866 -0.016227
N 33 4.501123 -4.560641 0.013351
N 34 4.088278 -4.994125 -0.053886
N 35 4.524561 -4.971845 0.023051
N 36 4.986017 -4.021602 -0.013126
O 37 4.500314 -4.244393 0.277762
O 38 4.84511 -3.969914 -0.038194
O 39 4.579526 -4.781657 -0.155618
O 40 4.236399 -5.048877 0.063539

Table S7. The space groups and cell parameters of the HCOF-3 structures.
Structure Space Group Cell Parameters
AA P1 a =15.42Å b = 14.96Å, c = 3.51Å, α = β = 90.00° and γ =
120.00°
AB P1 a =15.42Å b = 14.96 Å, c = 7.02Å, α = β = 90.00° and γ =
120.00°

Table S8. Fractional atomic coordinates for the unit cell of HCOF-3 with AA
stacking.

P1
a =15.45 b = 15.05 Å, c = 3.45 Å, α = β = 90.00° and γ = 120.00°
Element Number u v w
H 1 4.873489 -3.193579 0.060414
H 2 4.593068 -3.295044 -0.044866
H 3 4.824309 -3.372184 0.056277
H 4 4.417847 -3.425892 -0.150001
H 5 4.651418 -3.659135 0.015615
H 6 4.450274 -3.647463 -0.333061
H 7 4.212639 -3.752867 0.133706
H 8 3.806521 -3.801985 0.00119
H 9 4.036204 -3.882272 0.042685
H 10 3.978709 -3.516588 -0.023039
H 11 3.755762 -3.981151 -0.024713
H 12 4.108303 -3.497802 0.276335
C 13 4.79637 -3.212478 0.024259
C 14 4.717653 -3.321541 -0.0027
C 15 4.615945 -3.352361 -0.042538
C 16 4.543101 -3.45692 -0.071587
C 17 4.573925 -3.531403 -0.077019

21
 C 18 4.675187 -3.500712 -0.017858
C 19 4.746062 -3.396123 0.016222
C 20 4.436522 -3.484518 -0.079367
C 21 4.706977 -3.578288 0.003484
C 22 4.194348 -3.693042 0.082879
C 23 4.087916 -3.720221 0.072659
C 24 4.059213 -3.644613 0.090406
C 25 3.956982 -3.673923 0.053417
C 26 3.884987 -3.778567 0.027421
C 27 3.912427 -3.853999 0.029988
C 28 4.014123 -3.82436 0.04912
C 29 3.924626 -3.596673 0.024017
C 30 3.832851 -3.962801 0.005742
N 31 4.77597 -3.139086 0.001845
N 32 4.365809 -3.575495 0.015366
N 33 4.265561 -3.600267 0.014052
N 34 3.830894 -3.624018 0.039577
N 35 3.852825 -4.036547 0.023746
N 36 4.800774 -3.550826 0.010298
O 37 4.50735 -3.635052 -0.155792
O 38 4.132957 -3.54246 0.157726

Reference
1. Z.-D. Ding, Y.-X. Wang, S.-F. Xi, Y. Li, Z. Li, X. Ren and Z.-G. Gu,
Chemistry, 2016, 22, 17029-17036.

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