The crystal and molecular structure of C.I.Pigment Yellow 155, a high performance bisacetoacetarylide disazo yellow pigment

Article abstract of DOI:10.1016/j.molstruc.2018.06.108

C.I.Pigment Yellow 155 (Y 155) is an important bisacetoacetarylide disazo yellow pigment with a unique structure, which has the potential to be an alternative for benzidine yellow pigments due to its superior solvent resistance and light fastness. It is essential to investigate the crystal structure of Y 155 to understand the relationship between the structure and technical performance. Y 155 crystallizes in the triclinic P1(—) space group. The molecule exists in the bisketohydrazone form which is consistent with that of disazoacetoacetanilide pigments (Diarylide Yellows). Different from the unsubstituted analogue (BADA), Y 155 molecules are approximately planar due to stronger intramolecular hydrogen bonding. In Y 155 crystals, each molecule is interleaved in two adjacent layers above and below. The color and the technical performance are discussed in relation to its crystal structure especially involving in the role of four methyl formate groups.

Full text of DOI:10.1016/j.molstruc.2018.06.108

Accepted Manuscript
The crystal and molecular structure of C.I.Pigment Yellow 155, a high
performance bisacetoacetarylide disazo yellow pigment
Zheng Li, Chong Liu, Shujun Wang, Dongjun Lv, Liwei Xiao
PII:
S0022-2860(18)30809-3
10.1016/j.molstruc.2018.06.108
MOLSTR 25395
DOI:
Reference:
To appear in:
Journal of Molecular Structure
Received Date:
Accepted Date:
09 April 2018
27 June 2018
Please cite this article as: Zheng Li, Chong Liu, Shujun Wang, Dongjun Lv, Liwei Xiao, The crystal
and molecular structure of C.I.Pigment Yellow 155, a high performance bisacetoacetarylide disazo
yellow pigment, Journal of Molecular Structure (2018), doi: 10.1016/j.molstruc.2018.06.108
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form.
Please note that during the production process errors may be discovered which could affect the
content, and all legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT
Graphical Abstract
The crystal and molecular structure of C.I.Pigment Yellow 155,
a high performance bisacetoacetarylide disazo yellow pigment
Zheng Li a, b*, Chong Liu a, Shujun Wang a, Dongjun Lv b, Liwei Xiao a
The crystal and molecular structure of C.I.Pigment Yellow 155 is disclosed and the
technical performance in relation to crystal structure is discussed.

ACCEPTED MANUSCRIPT
1
2
The crystal and molecular structure of C.I.Pigment Yellow 155, a high
performance bisacetoacetarylide disazo organic pigment
3
Zheng Li a, *, Chong Liu a, Shujun Wang a, Dongjun Lv b, Liwei Xiao a
4
5
a College of Chemistry and Materials Science, Langfang Normal University, Langfang 065000,
P.R. China;
6
b Shandong YuHong New Pigment Co., Ltd., Dezhou 253000, P.R. China.
7
* Corresponding author: E-mail: lizheng1105@tju.edu.cn (Z. Li). Tel: +86 316 2188370.
ABSTRACT: C.I.Pigment Yellow 155 (Y 155) is an important bisacetoacetarylide disazo
yellow pigment with a unique structure, which has the potential to be an alternative for benzidine
yellow pigments due to its superior solvent resistance and light fastness. It is essential to
investigate the crystal structure of Y 155 to understand the relationship between the structure and
8
9
10
11
12
technical performance. Y 155 crystallizes in the triclinic P— space group. The molecule exists in
1
13
14
15
16
17
18
the bisketohydrazone form which is consistent with that of disazoacetoacetanilide pigments
(Diarylide Yellows). Different from the unsubstituted analogue (BADA), Y 155 molecules are
approximately planar due to stronger intramolecular hydrogen bonding. In Y 155 crystals, each
molecule is interleaved in two adjacent layers above and below. The color and the technical
performance are discussed in relation to its crystal structure especially involving in the role of
four methyl formate groups.
19
20
Keywords: crystal structure; molecular structure; C. I. Pigment Yellow 155; bisacetoacetarylide
disazo; organic pigment
21
22
1. Introduction
In the range of yellow organic pigments, Diarylide Yellows (disazoacetoacetanilides)
1

ACCEPTED MANUSCRIPT
1
2
is an important type. However, it has been reported that higher processing temperatures have led
to the thermal decomposition of the pigments leading to the release of aromatic amines including
dichlorobenzidine[1]. Environmental pressure and legislation have seen the decline in use of
diarylide yellows which may be subjected to high temperatures. In order to avoid potential
threats of diarylide yellows and meet the rapid developments of the plastic industry, further
improvements were sought by developing alternatives. Bisacetoacetarylide disazo yellow
pigments (as shown in Scheme 1 ), similar to Diarylide Yellows in structure, is a beneficial
3
4
5
6
7
8
exploration which provides important enhanced durability over traditional azo types[2~4]
.
9
Although these pigments are illustrated as disazo compound, the molecule exists in the
bisketohydrazone form and it is structurally analogous to the hydrazone form adopted by the
10
11
12
13
14
15
16
17
18
19
20
21
22
23
Diarylide Yellows[5~7]
.
Scheme 1 insert here
The pigment is a symmetrically-substituted compound, which is synthesized by a
tetrazotised aniline derivative (2 mol) with a bisacetoacetarylide derivative (1 mol) through azo
[8, 9].
coupling reaction
Bisacetoacetarylide disazo yellow pigments is divided into three types
according to the coupling component, namely N,N'-(4,4'-biphenyldiyl) bis(3-oxo-butanamide)
disazo pigments(C.I. PY16, C.I.PY 77)[10], N,N'-(1,4- phenylene) bis(cetoacetamide) disazo
pigments(C.I.PY 155, C.I.PY 198)[11,12], N,N'-(1,4-phenylene) bis(acetoacetamide) disazo
condensation pigments (C.I.PY 93, C.I.PY 95)[13, 14]. Y155 demonstrates a greenish-yellow hue
with superior solvent resistance and light fastness compared with its analogue C.I.PY 16, which
is suitable for extensive applications, such as low density PVC, polypropylene, polystyrene and
printing inks as well as in the baking paint[15~17]. The application performance of organic
pigments is determined by their molecular structure as well as by particle size, morphology and
2

ACCEPTED MANUSCRIPT
1
2
the crystal structure[18~20]
.
The crystal structure is vital to understand the relationship between the molecular structure
and physicochemical properties. A variety of crystal structures of Diarylide Yellows have been
revealed that they exist in the bisketohydrazone tautomeric form. As a result of the extremely
low solubility in organic solvent, the crystal structure of bisacetoacetarylide disazo yellow
pigments is rarely disclosed. In our previous studies, we have described the crystal structure of
the parent unsubstituted compound (BADA, CCDC 1437541) and its fluorinated analogue (F-
BADA, CCDC 1406682)[21]( as shown in Scheme 2). As a part of follow-up research, we
disclose the crystal and molecular structure of Y 155 and the color and technical performance in
relation to the crystal structure are discussed especially involving in the role of four methyl
formate groups.
3
4
5
6
7
8
9
10
11
12
Scheme 2 insert here
13
2. Experimental
14
15
16
17
18
19
20
21
2.1. Synthesis and crystallisation
C.I.Pigment Yellow 155 (Sandorin Yellow 4G), namely 2,2'-[1,4-phenylene-bis[imino-(1-
acetyl-2-oxo-2,1-ethanediyl-azo]]bis-1,4-benzenedicarboxylicacid,tertramethyl
ester,
was
prepared by tetrazotisation of 2-amino terephthalic acid dimethyl ester followed by azo coupling
of the tetrazonium salt with N,N'-(1,4-phenylene)bis(acetoacetamide) using the previous
procedures[22, 23]. The pigment is nearly insoluble that it is extremely difficult to crystallise in
organic solvent. Crystals suitable for X-ray single crystal diffraction were obtained by slow
cooling of solutions in 1,2,4-trichlorobenzene from 200℃.
22
23
2.2. Crystal data
The X-ray diffraction data for crystals were collected with MoKα radiation (0.7107 Å) at
3

ACCEPTED MANUSCRIPT
1
2
113(2) K, using a Rigaku XtaLAB P200 diffractometer. The structure was solved by direct and
difference Fourier methods and refined by full-matrix least-square on F2. All non-hydrogen
atoms were refined anisotropically. Crystallographic computing was done with SHELXTL
programs. The hydrogen atoms H2N and H4N were located in the difference Fourier map and
freely refined.
3
4
5
6
The crystallographic data (excluding structure factors) have been deposited at the
Cambridge Crystallographic Data Centre as the supplementary materials. The CCDC number of
Y155 was 1429355 and it can be obtained free of charge from the Cambridge Crystallographic
Data Centre.
7
8
9
10
11
C.I.Pigment Yellow 155, C34H32N6O12, Mr=716.66; intense yellow crystals 0.72×0.48×0.18 mm3;
triclinic, a=5.6624(9)Å, b=9.2446(11)Å, c=16.125(2)Å; α= 74.967(6)°, β= 87.598(9)°, γ=
12
13
83.430(9)°; V= 809.8(2) Å3; space group P—; Z=1, Dc=1.470 g/cm3, T=113(2) K, F(000)=374;
1
λ=0.71073 Å, (MoKα radiation); R1= 0.0359, wR2= 0.1012 for I＞2σ(I ), R1= 0.0441, wR2=
14
15
16
17
18
19
20
21
22
23
0.1055 for all. Goodness-of-fit on F2=1.048.
2.3. Theoretical calculations
All the calculations were performed by using Gaussian 09 software[24] and GaussView 5.0.8
was used for visualization of the structure and simulated vibrational spectra. The ground state
geometries of BADA, F-BADA and Y155 were optimized by DFT methods with 6-31G(d,p)
basis sets. The frequency analyses indicate that the optimized geometries were in a minimum of
the potential surface with no imaginary frequencies. Time-dependent Density Functional Theory
(TDDFT) calculations were then performed with the same functional and basis set at the
optimized geometry to obtain the vertical excitation energies and oscillator strengths at the
optimized ground state equilibrium geometries. All the calculations in solvents were carried out
4

ACCEPTED MANUSCRIPT
1
2
3
4
5
using the Self-Consistent Reaction Field (SCRF) under the Polarizable Continuum Model (PCM).
3. Results and discussion
The molecular structure and atomic labelling scheme of Y 155 is shown in Fig. 1.
Compared with BADA and F-BADA, Y 155 molecules contain a complex substitution in the
terminal anilide ring with ortho- and meta-substituted methyl formate group. Y 155 crystallizes
6
in the triclinic system, space group P— with one molecule in the unit cell and therefore all
1
7
8
molecules have crystallographic Ci symmetry. The single crystal X-ray crystallographic reveals
that it adopts bisketohydrazone tautomeric form, which is in accordance with that of BADA and
F-BADA. In Y 155 crystals, the important relevant distances (as shown in Table 1) are N1-N2
[1.3160(14) Å] and C11-N1 [1.3157(14) Å], which appear to be normal according to the reported
9
10
11
12
13
14
15
16
17
literature[25, 26]
.
Fig. 1 insert here
Table 2 insert here
Compared to BADA, notable feature of Y155 molecules is that it is almost coplanar in
consideration of their similar structure. The average deviation from the plane defined by all non-
hydrogen atoms of Y155 is 0.0011Å, however, the deviation of the BADA molecule is 0.111(8)
Å. Further more, there exists bifurcated intramolecular hydrogen bonding involving N1…O4 and
18
19
20
N1…O5 which cause a decrease in charge density at the hydrazone chromophore and therefore
the light resistance is improved. The shorter N…O distance involving N1…O5 [2.5611(13) Å to
2.5791 Å ] and N3…O6 [2.6683(14) Å to 2.6704 Å ] (Table 2) indicate stronger intramolecular
21
22
23
interactions compared with that of BADA, which rationalize the better planarity of Y 155. O3
has the largest deviation at 0.6639Å, closely followed by O1 at 0.3537Å. Owing to the
intramolecular hydrogen bonding, O4(O4A) deviates from the plane only 0.0369Å. The bond
5

ACCEPTED MANUSCRIPT
1
N2-C11 makes N1-H1…O5 very little bent(136.0(15)°). The angle between planes C1-N1 and
2
3
4
5
N2-C7 is 179.65(9)°. And the angle between planes N2-C7 and C10-N3 is -179.82(10) (Table 3).
Table 2 insert here
Table 3 insert here
The crystallographic arrangement of Y155 crystals is illustrated in Fig. 2-3. Y155
6
crystallizes in the triclinic system, space group P—. The molecular packing of Y 155 differs from
1
7
8
that observed in the BADA and F-BADA crystals, which may be explained by the electron
withdrawing group in the terminal aniline ring. The molecule forms an inclined, interleaved
stacking arrangement. One fifth of each molecule lies sandwiched between adjacent layers and
the molecules are parallel to each other viewed down the b direction as shown in Fig. 2. For
BADA solvates crystals, there is only C9-H9A…O3 hydrogen bonding involving intermolecular
forces, while in the case of Y 155, there exists C-H…O hydrogen bonding involving C1…O1
hydrogen bonding between adjacent molecules of the same layer viewed down the c direction as
shown in Fig. 3. Further more, there also exists C-X…π interaction [C14-O5…Cg1, 3.2552(10)
Å and C14-O5…Cg2, 3.3417(11)Å] (Cg1 refers to C3-C8 and Cg2 refers to C15-C16-C17a-
C15a-C16a-C17). It's not surprising that Y 155 possesses a significantly better solvent resistance
than BADA.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
Fig. 2 insert here
Fig. 3 insert here
The UV-vis spectra in solutions for BADA, F-BADA and Y155 in DMSO is listed in Table
4. Compared with BADA, F-BADA and Y155 show 2 nm and 19 nm hypsochromic shift
separately, which is due to the electron-withdrawing effect of fluorine and methyl formate group.
The molar extinction coefficient for BADA, F-BADA and Y155 is 1.46, 1.47 and 2.12×104 mol-
6

ACCEPTED MANUSCRIPT
1
2
1cm-1 respectively. However, BADA shows significantly lower color strength than that of F-
BADA and Y155, which can be attributed to the greater deviation from planarity of BADA
3
molecules[27, 28]
.
4
Table 4 insert here
5
In order to gain the insight of electric properties of BADA, F-BADA and Y155, TDDFT
calculation was performed. The representative calculated optical transitions are listed in Table 5
The long-wavelength transition for these three compounds at 439.04 nm, 437.89 nm and 415.96
nm which involve mainly the HOMO and LUMO responding to 389, 387 and 370 nm
respectively as observed in Uv-vis absorption spectra. The calculated value of the maximum
absorption wavelength exceeds the experimental value, however, TDDFT calculations was
consistent with the trend of experimental results influenced by substituents. HOMO-LUMO
transition could be from π-π* transitions, which exhibits transitions from bonding and
antibonding orbitals of the central phenyl to antibonding orbitals of the carbonyl group and
hydrazine. Deviations from planarity are obviously caused by the presence of large substituents,
such as a dihedral angle of 26.85° of N1-N2-C7-C8 in Y155 while the angle is 0.05° and 0.38°
in BADA and F-BADA, is likely to cause a hypsochromic shift of the visible absorption band in
solution. Table 6 presents HOMO and LUMO and the orbits near to them calculated with
TDDFT. It can be seen that HOMO has a majority of bonding orbitals while LUMO has
antibonding orbitals. The excited state corresponding to the main absorption band at 291 nm
observed in UV-Vis absorption measurement exhibits transitions from bonding and antibonding
orbitals of the central phenyl to antibonding orbitals of the carbonyl group and hydrazine. The
transition takes place in 355.15 nm, 351.95 nm and 349.4 nm is described as a combination of
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
7

ACCEPTED MANUSCRIPT
1
many orbital pairs (HOMO-2→LUMO, HOMO-1→LUMO+1 and HOMO→LUMO+2), which
2
3
might be responsible for the main absorption band at about 291 nm.
Table 5 insert here
4
5
Table 6 insert here
The solvent resistance of organic pigments is related to the efficiency of the molecular
6
7
packing in crystals as well as intermolecular interactions. Y 155 molecules possess a complex
substitution in the terminal anilide ring with ortho- and meta-substituted methyl formate group,
which is essential to determine the application performance. Compared with Hansa Yellows,
bisacetoacetarylide disazo pigments possess better resistance to solvent due to their larger
molecular dimension and enhanced interactions strength[29, 30]. There is a C-H…O hydrogen
8
9
10
11
bonding involving C1 and O1 in Y 155 crystals where the C…O distance is 3.489(2) Å and the
12
13
14
15
16
17
18
19
20
21
22
23
angle at H1B is 152°, which is involving in meta- methyl formate group and may contribute
greatly to the enhanced solvent resistance of Y155 compared with that of BADA and F-BADA.
There are inversion centres between adjacent molecules above or below which are at about one
fifth and four-fifths of the way along the length of a molecule, which results in that each
molecule is interleaved in two adjacent layers above and below. The distance between two
adjacent molecules in the stacks of Y155 crystals is 3.27 Å, which is estimated by the
perpendicular distance between the molecule in the plane of Cg1(C3-C8) and the other molecule
in the plane defined by N3-C14-C11-C12. It indicates the existence of π-π interactions between
the two adjacent molecules. A comparison of the intermolecular face to face distances shows that
Y155 packs more efficiently than BADA and F-BADA, which may rationalize the better solvent
resistance of Y155 than that of BADA and F-BADA.
Y155 provides superior application performance compared with that of other disazo
8

ACCEPTED MANUSCRIPT
1
2
3
4
5
6
7
pigments, especially in terms of light fastness. It is generally accepted that light fastness is
improved by introducing electron-withdrawing substituents in diazo components (anilide
derivatives) or electron-releasing substituents in coupling components (bisacetoacetarylide)[31, 32]
.
In the case of Y155, there is four methyl formate groups in the terminal anilide ring with ortho-
and meta-substituted and the photooxidation process of chromophores is inhibited by a decrease
of charge density, which rationalizes the superior lightness compared with Y16. Furthermore,
there exists bifurcated intramolecular hydrogen bonding between N1…O4 and N1…O5
8
9
involving ortho-substituted methyl formate group and it may provide electronic and
stereochemical protection of the chromophore towards photochemical degradation. It is
conceivable that the four methyl formate groups contribute towards the good light fastness of
Y155. As the closest intermolecular centroidecentroid distance is more than 3.6 Å between the
ring Cg1 and ring Cg2, there appears no π-π interactions. A comparison of the crystal structure
and application performance shed light on the factor that influences application properties.
4. Conclusion
10
11
12
13
14
15
16
17
18
19
20
21
22
23
The X-ray single crystal structure of C.I. Pigment Yellow 155 manifests that it exists in the
bisketohydrazone form which is structurally analogous to the hydrazone form adopted by
Diarylide Yellows. The molecule is almost planar due to intramolecular hydrogen bonding. The
unique structure of four methyl formate groups plays a crucial role in determining the higher
color strength and superior solvent resistance and light fastness. The crystal structure provides
enhanced understanding of the technical performance and offers some guidance for the design of
new organic pigments with desirable application properties.
Acknowledgements
This work was supported by a grant from the Natural Science Foundation Research Project
9

ACCEPTED MANUSCRIPT
1
2
3
of Hebei Province (B2016408037, B2014408009), Science Research Program plan of Hebei
Institution of Higher Learning (ZD2016046, QN2017129) and Self-raised Project of Technology
Bureau of Langfang City, Hebei Province, China ( 2017011007).
4
Reference
5
6
[1] Christie R M, Howie B D., Dyes Pigm., 80 (2009) 245.
[2] Hao Z, Iqbal A., Chem. Soc. Rev., 26 (1997) 203.
7
[3] Lomax S Q, Learner T., J. Amer. Inst. Conserv., 45 (2006) 107.
[4] Herbst W, Hunger K., John Wiley & Sons, 2006.
8
9
[5] Barrow M J, Christie R M, Lough A J, et al., Dyes Pigm., 45 (2000) 153.
[6] Christie R M, Standring P N. Dyes Pigm., 11(1989) 109.
[7] Nakpathom M, Hinks D, Freeman H S. Dyes Pigm., 48(2001) 93.
[8] Liedek E, Ruff W, Berger G, et al., US4602960 (1986).
[9] Hinks D, Freeman H S, Nakpathom M, et al., Dyes Pigm., 44 (2000) 199.
[10] Rieper W, Baier E., US5266110 (1993).
10
11
12
13
14
15
16
17
18
19
20
21
22
23
[11] Schweikart K H, Lerch J P, US7384472 (2008).
[12] Macholdt H T, Baur R, Ritter J., US6117606 (2000).
[13] Nickel U, Kund K, Alfter F., US6437104 (2002).
[14] Ronco K., US4689403 (1987).
[15] Erdtmann D, Grady B L, Oldfield D J, et al., US6152999 (2000).
[16] House G, Wang X, Wyand A, et al., US10/891334 (2004).
[17] Walker N A, Rose P E., US6530986 (2003).
[18] Thetford D, Chorlton A P, Hardman J., Dyes Pigm., 59 (2003) 185.
[19] Nagao Y., Prog. Org. Coat., 31 (1997) 43.
10

ACCEPTED MANUSCRIPT
1
2
[20] Christie R M, Hill J M, Rosair G., Dyes Pigm., 71 (2006) 194.
[21] Li Z, Lv D, Li X, et al., Dyes Pigm., 128 (2016) 246.
[22] Jung R, Weide J, Metz H J., US5428136 (1995).
3
4
[23] Jung R, Weide J, Metz H J., US5559216 (1996).
5
[24] Frisch, M. J. T., G. W., Schlegel, H. B., et al. Gaussian 09, Rev. D. 0.1, 2013.
[25] Whitaker A., Z. Krist-Cryst. Mater., 163 (1983) 139.
[26] Whitaker A., Z. Krist-Cryst. Mater., 167 (1984) 225.
[27] Barrow M J, Christie R M, Monteith J E., Dyes Pigm., 55 (2002) 79.
[28] Hunger K. Color. Technol., 29 (1999) 71.
6
7
8
9
10
11
12
13
14
15
[29] Barrow M J, Christie R M, Badcock T D., Dyes Pigm., 57 (2003) 99.
[30] Christie R M, Howie B D. Dyes Pigm., 80 (2009) 245.
[31] Chang C H, Christie R M, Rosair G M. Dyes Pigm., 82(2009) 147.
[32] Christie R M, Chang C H, Huang H Y, et al. Surf. Coat. Int. Part B: Coat. Transact., 89
(2006) 77.
11

ACCEPTED MANUSCRIPT
1
Scheme captions:
2
3
4
Scheme 1 The general formula of bisacetoacetarylide disazo yellow pigment.
Scheme 2 Molecular structure of BADA and F-BADA.
12

ACCEPTED MANUSCRIPT
1
2
Scheme 1 The general formula of bisacetoacetarylide disazo yellow pigment
3
4
5
6
7
Scheme 2 Molecular structure of BADA and F-BADA
13

ACCEPTED MANUSCRIPT
1
Figure captions:
2
3
4
5
6
Fig. 1. Molecular structure of Y155 with 30% probability displacement ellipsoids (with C1’H3
and C1A’H3A 36% occupancy at O2 and O2A respectively) intramolecular hydrogen bonds
indicated.
Fig. 2. Part of the packing of Y155 crystals, viewed down the b direction.
Fig. 3. Part of the packing of Y155 crystals involving C-H…O intermolecular hydrogen bond-
7
8
ing, viewed down the c direction.
14

ACCEPTED MANUSCRIPT
1
2
Fig. 1. Molecular structure of Y155 with 30% probability displacement ellipsoids (with C1’H3
and C1A’H3A 36% occupancy at O2 and O2A respectively) intramolecular hydrogen bonds
indicated.
3
4
5
15

ACCEPTED MANUSCRIPT
1
2
Fig. 2. Part of the packing of Y155 crystals, viewed down the b direction.
3
16

ACCEPTED MANUSCRIPT
1
2
Fig. 3. Part of the packing of Y155 crystals involving C-H…O intermolecular hydrogen bond-
ing, viewed down the c direction.
3
4
5
17

ACCEPTED MANUSCRIPT
1
Table captions:
2
3
4
5
6
7
8
9
Table 1. Selected bond length of BADA, F-BADA and Y155.
Table 2. Intramolecular hydrogen bonds for Y155.
Table 3. Selected torsion angles of BADA, F-BADA and Y155.
Table 4. UV-vis spectra in solutions for BADA, F-BADA and Y155 in DMSO.
Table 5. The theoretical electronic absorption spectra of BADA, F-BADA and Y155 and
experimental results in DMSO solution.
Table 6. HOMO and LUMO and the orbits near to them calculated with TDDFT.
18

ACCEPTED MANUSCRIPT
1
Table 1 Selected bond length of BADA, F-BADA and Y155
F-BADA
Bond
BADA
Y155
C1-N1(C7-N1)
N1-N2
1.4106(15)
1.3046(14)
1.3190(14)
1.4950(15)
1.3510(14)
1.4145(14)
1.2406(13)
1.2330(14)
1.400(5)
1.305(4)
1.317(4)
1.491(5)
1.342(5)
1.406(4)
1.240(5)
1.225(4)
1.4010(14)
1.3160(14)
1.3157(14)
1.5017(16)
1.3546(15)
1.4153(14)
1.2347(14)
1.2309(15)
C7-N2(C11-N2)
C7-C10(C11-C14)
C10-N3(C14-N3)
N3-C11(C15-N3)
C10-O2(C14-O5)
C8-O1(C12-O6)
2
3
Table 2 Intramolecular hydrogen bonds for Y155
D-H…A
d (H…A)
1.832(16)
1.996(17)
1.872(12)
d (D…A)
2.5611(13)
2.6235(14)
2.6683(14)
d (D–H)
0.905(16)
0.905(16)
0.912(12)
<(DHA)
136.0(15)
125.1(14)
144.6(11)
N1-H1…O5
N1-H1…O4
N3-H3…O6
4
5
Table 3 Selected torsion angles of BADA, F-BADA and Y155
Angle
BADA
F-BADA
Y155
C1-N1-N2-C7(C7-N1-N2-C11)
N2-C7-C10-N3(N2-C11-C14-N3)
176.07(9)
-177.94(9)
177.7(3)
-175.9(3)
177.7(3)
-178.2(3)
5.2(5)
179.65(9)
-179.82(10)
177.66(10)
179.52(10)
-2.87(18)
C10-N3-C11-C13(C14-N3-C15-C16) 163.62(10)
C8-C7-C10-O2(C12-C11-C14-O5)
C10-C7-C8-O1(C14-C11-C12-O6)
C10-C7-C8-C9(C14-C11-C12-C13)
N3-C11-C13-C12( N3-C15-C16-C17)
-178.48(9)
-0.77(16)
177.72(9)
177.25
-174.6(3)
179.8(3)
177.23(10)
-179.78(10)
6
7
19

ACCEPTED MANUSCRIPT
1
2
Table 4 UV-vis spectra in solutions for BADA, F-BADA and Y155 in DMSO
λmax(nm)
389
ε×10-4 (mol-1cm-1)
Compound
BADA
1.46
1.47
2.12
F-BADA
Y155
387
370
3
4
Table. 5 The theoretical electronic absorption spectra of BADA, F-BADA and Y155 and
experimental results in DMSO solution
Compound
Exp. (nm)
Theor.(nm)
Composition
Eg（ev）
HOMO-2→LUMO
HOMO-1→LUMO+1
HOMO→LUMO+2
HOMO→LUMO
291
389
292
387
292
370
355.15
439.04
351.95
437.89
349.4
BADA
3.25
HOMO-2→LUMO
HOMO-1→LUMO+1
HOMO→LUMO+2
HOMO→LUMO
F-BADA
Y155
3.26
3.48
HOMO-2→LUMO
HOMO-1→LUMO+1
HOMO→LUMO+2
HOMO→LUMO
415.96
5
6
Table. 6 HOMO and LUMO and the orbits near to them calculated with TDDFT
BADA F-BADA Y155
LUMO+2
LUMO+1
20

ACCEPTED MANUSCRIPT
LUMO
HOMO
HOMO-1
HOMO-2
1
21

ACCEPTED MANUSCRIPT
Highlights
●
●
The crystal and molecular structure of C.I.Pigment Yellow 155 is disclosed.
Different from the unsubstituted analogue (BADA), Y 155 molecules are
approximately planar due to stronger intramolecular hydrogen bonding.
The technical performance in relation to crystal structure especially with regard to
the role of four methyl formate groups is discussed.
●