The synthesis and characterization of 4-isopropylanilino derivatives of cyclotriphosphazene

Article abstract of DOI:10.1016/j.ica.2013.05.031

Hexachlorocyclotriphosphazene N₃P₃Cl₆ and gem-disubstituted cyclotriphosphazene derivatives N₃P ₃Cl₄X₂ (X= Ph, PhS, PhNH) were reacted with 4-isopropylaniline to give geminal tet

Full text of DOI:10.1016/j.ica.2013.05.031

Inorganica Chimica Acta 405 (2013) 140–146
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Inorganica Chimica Acta
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The synthesis and characterization of 4-isopropylanilino derivatives
of cyclotriphosphazene
⇑
Aylin Uslu , Sßule Sßahin Ün, Adem Kılıç, Sßükriye Yılmaz, Fatma Yuksel, Ferda Hacıveliog˘lu
Department of Chemistry, Gebze Institute of Technology, PB. 141, 41400 Kocaeli, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
Hexachlorocyclotriphosphazene N3P3Cl6 and gem-disubstituted cyclotriphosphazene derivatives N3P3-
Cl4X2 (X = Ph, PhS, PhNH) were reacted with 4-isopropylaniline to give geminal tetra and hexa substi-
tuted compounds (1a–4a, 1b–4b). The compounds (1a–4a, 1b–4b) were separated by column
chromatography on silica gel and analyzed by elemental analysis, mass spectrometry, and 31P and 1H
NMR spectroscopies, and also crystal structures of 2a and 3b were determined by X-ray crystallography.
Compounds were prepared to cover the normal ranges of C-, S- and N-substituents in cyclophosphazene
(X = Cl, Ph, SPh, NHPh). Compounds (1a–4a, 1b–4b) were reported for the first time. We additionally
investigated the effect of substituent (Cl, Ph, SPh, NHPh) on 31P NMR chemical shifts of neighboring phos-
phorus atoms.
Received 22 November 2012
Received in revised form 17 May 2013
Accepted 24 May 2013
Available online 3 June 2013
Keywords:
Cyclotriphosphazene
31P NMR
X-ray
4-Isopropylaniline
Ó 2013 Elsevier B.V. All rights reserved.
1. Introduction
2. Experimental
Phosphazenes are cyclic or linear molecules that contain a
framework of alternating phosphorus and nitrogen atoms with
two substituent groups attached to each phosphorus atom [1]. Cyc-
lic phosphazenes are an important family of inorganic ring systems
[2,3] which have attracted the attention of inorganic chemists in
recent years because of their applications as flame retardants, anti-
microbial agents, lithium-ion batteries, liquid crystals, organic
light emitting diodes, membrane hydrogels, drug carriers, surfac-
tants and phase transfer catalysts [4–16]. Also the preparation of
new cyclophosphazene derivatives is very straightforward by a
substitution reaction of chlorine atoms on the phosphorus and
their physical and chemical properties can be tailored via appropri-
ate selection of substituted groups of phosphorus atoms [17–20].
In this work, we report the synthesis of the geminal 4-isopropy-
lanilino substituted derivatives of cyclotriphosphazenes N3P3Cl4X2
(X = Cl, Ph, PhS, PhNH). The structures of obtaining compounds
(1a–4a, 1b–4b) were characterized by elemental analysis, mass
spectrometry, and 31P and 1H NMR spectroscopies and crystal
structures of 2a and 3b were also confirmed by X-ray crystallogra-
phy. In addition, relationships between substituents effect (Cl, Ph,
SPh, NHPh) on phosphazene ring and 31P NMR chemical shifts of
4-isopropylanilino substituted phosphorus were obtained for com-
pounds (1a–4a) and (1b–4b).
2.1. Materials
Hexachlorocyclotriphosphazene (Otsuka Chemical Co., Ltd.)
was purified by fractional crystallization from hexane. The follow-
ing chemicals were obtained from Merck; triethylamine (>99%), n-
hexane (>96%), benzene (P99.5%), thiophenol (>98.0%), aniline
(>99%), tetrahydrofuran (THF) (P99.0%), dichloromethane
(P99.0%), diethyl ether (P99.0%), anhydrous sodium sulfate
(P99.0%) ethyl acetate (P99.0%) and chloroform-d1, from Alfa Ae-
sar; 4-isopropylaniline (>99%) and toluene (>99%). Column chro-
matography was performed on silica gel (Merck, Kieselgel 60,
230–400 mesh and, Kieselgel 60, 70–230 mesh; for 3 g crude mix-
ture, 100 g silica gel was used in a column of 3 cm in diameter and
60 cm in length).
2.2. Equipment
Elemental analyses were carried out using a Thermo Finnigan
Flash 1112 Instrument. Mass spectra were recorded on a Bruker
MicrOTOF LC–MS spectrometer with the electrospray ionization
method. 31P and 1H NMR spectra were recorded in CDCl3 solutions
on a Varian INOVA 500 MHz spectrometer using 85% H3PO4 as an
external reference for 31P and TMS as an internal reference for 1H.
2.2.1. X-ray crystallography
Intensity data were recorded on a Bruker APEX II QUAZAR dif-
fractometer. Absorption correction by multi-scan has been applied
[21] and space groups were determined using XPREP implemented
⇑
Corresponding author. Tel.: +90 262 6053129; fax: +90 262 6053101.
E-mail address: aylin@gyte.edu.tr (A. Uslu).
0020-1693/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.ica.2013.05.031

A. Uslu et al. / Inorganica Chimica Acta 405 (2013) 140–146
141
X
X
X
X
X
X
P
N
P
N
P
N
N
N
CH3
CH3
H3C
H3C
N
N
N
N
CH3
CH3
CH3
CH3
H
N
H
N
H
N
Cl
Cl
Cl
Cl
Cl
Cl
H2N
+
+
P
P
P
P
P
NH
P
NH
NH
X = Cl, Ph, SPh, NHPh
CH3
CH3
H3C
CH3
CH3
CH3
(1a-4a)
(1b-4b)
X = Cl
Ph
(1a)
(2a)
(3a)
(4a)
Cl
(1b)
(2b)
(3b)
(4b)
Ph
SPh
NHPh
SPh
NHPh
Scheme 1. The synthesis scheme of compounds (1a–4a, 1b–4b).
in APEX2 [22]. Structures were determined using the direct meth-
ods procedure in SHELXS-97 [23] and refined by full-matrix least
squares on F2 using SHELXL-97 [23]. All non-hydrogen atoms were
refined with anisotropic displacement parameters and C–H hydro-
gen atoms were placed in calculated positions and allowed to ride
on the parent atoms. The final geometrical calculations and the
molecular drawings were carried out with PLATON [24], and MERCURY
[25] programs. Structure determinations have been deposited with
the Cambridge Crystallographic Data Centre with references CCDC-
886526 for structure 2a and CCDC-886527 for structure 3b.
isolated by column chromatography using hexane:ethylacetate
(8:1) to give compounds 2a (0.23 g, 31.6%, mp. 155.0 °C) and 2b
(0.46 g, 48.1%, mp. 212.3 °C). Compound 2a was crystallized from
hexane-dichloromethane (1:4).
2.3.3. Reaction of N3P3Cl4(SPh)2 with 4-isopropylaniline to give
compounds 3a and 3b
Triethylamine (0.70 mL, 5.05 mmol) and 4-isopropylaniline
(0.68 mL, 5.05 mmol) in 10 mL dry THF were added to a stirred
solution of N3P3Cl4(SPh)2 (0.5 g, 1.01 mmol) dissolved in 10 mL
dry THF at room temperature under an argon atmosphere. The
reaction mixture was refluxed for 10 days and was followed by
TLC, which indicated product and no starting material remaining.
Triethylamine hydrochloride was then removed by filtration, and
the solvent removed under reduced pressure. The products were
isolated by column chromatography using hexane:THF (8:1) to
give compounds 3a (0.25 g, 35.8%, oily) and 3b (0.07 g, 7.8%, mp.
206.5 °C). Compound 3b was crystallized from hexane–dichloro-
methane (1:2).
2.3. Syntheses
The cyclotriphosphazene derivatives N3P3Cl4X2, (X = Ph, SPh,
NHPh), which we used as starting compounds were prepared as gi-
ven in the literature [26–28]. The reactions of cyclotriphosphazene
and gem-disubstituted derivatives of cyclotriphosphazene with 4-
isopropylaniline were done and compounds (1a–4a, 1b–4b)
(Scheme 1) were obtained.
2.3.4. Reaction of N3P3Cl4(NHPh)2 with 4-isopropylaniline to give
compounds 4a and 4b
2.3.1. Reaction of N3P3Cl6 with 4-isopropylaniline to give compounds
1a and 1b
Triethylamine (0.76 mL, 5.43 mmol) and 4-isopropylaniline
(0.74 mL, 5.43 mmol) in 10 mL dry toluene were added to a stirred
solution of N3P3Cl4(NHPh)2 (0.5 g, 1.09 mmol) dissolved in 10 mL
dry toluene at room temperature under an argon atmosphere.
The reaction mixture was refluxed for 5 days and was followed
by TLC, which indicated product and no starting material remain-
ing. Triethylamine hydrochloride was then removed by filtration,
and the solvent removed under reduced pressure. The products
were isolated by column chromatography using hexane:ethylace-
tate (3:1) to give compounds 4a (0.24 g, 15.3%, mp. 209.3 °C) and
4b (0.36 g, 16.8%, mp. 129 °C).
Triethylamine (1.60 mL,11.52 mmol) and 4-isopropylaniline
(1.58 mL, 11.52 mmol) in 20 mL dry THF were added to a stirred
solution of N3P3Cl6 (1 g, 2.88 mmol) dissolved in 20 mL dry THF
at room temperature under an argon atmosphere. The reaction
mixture was refluxed for 8 days and was followed by TLC, which
indicated product and no starting material remaining. Triethyl-
amine hydrochloride was then removed by filtration, and the sol-
vent removed under reduced pressure. The products were
isolated by column chromatography using hexane:ethylacetate
(3:1) to give compounds 1a (0.86 g, 54.9%, mp. 161.3 °C) and 1b
(0.08 g, 3.7%, mp. 212.3 °C).
2.3.2. Reaction of N3P3Cl4Ph2 with 4-isopropylaniline to give
compounds 2a and 2b
3. Results and discussion
Triethylamine (0.81 mL, 5.80 mmol) and 4-isopropylaniline
(0.79 mL, 5.80 mmol) in 10 mL dry toluene were added to a stirred
solution of N3P3Cl4(Ph)2 (0.5 g, 1.16 mmol) dissolved in 10 mL dry
toluene at room temperature under an argon atmosphere. The
reaction mixture was refluxed for 5 days and was followed by
TLC, which indicated product and no starting material remaining.
Triethylamine hydrochloride was then removed by filtration, and
the solvent removed under reduced pressure. The products were
3.1. Syntheses and characterizations of compounds 1a–4a, 1b–4b
Compounds 1a–4a and 1b–4b were obtained from the reactions
of hexachlorocyclotriphosphazene, N3P3Cl6 and gem-disubstituted
cyclotriphosphazene derivatives, N3P3Cl4X2 (X = Ph, PhS, PhNH)
with 4-isopropylaniline (Scheme 1). In present work, compounds
were prepared to cover the normal ranges of Cl-, C-, S- and N-sub-
stituents in di- or tetra- substituted 4-isopropylanilino derivatives

142
A. Uslu et al. / Inorganica Chimica Acta 405 (2013) 140–146
Table 1
31P NMR parameters of compounds (1a–4a, 1b–4b).a
Compound
Chemical shifts (ppm)
>PCl2 (1)
X
2J(PP)/Hz
>PX2 (2)
>P(NHR)2 (3)
1,2
1,3
2,3
1a
1b
2a
2b
3a
3b
4ab
4bc
21.76
24.35
21.14
À1.86
0.98
Cl
48.30
53.10
37.30
19.47
19.25
45.95
45.64
0.66
À0.77
Ph
18.40
6.60
2020
22.4
11.00
17.90
49.33
50.41
2.39
21.46
24.15
À1.47
1.57
0.99
SPh
NHPh
45.00
53.45
53.24
4.48
4.79
a
b
c
202, 38 MHz 31P NMR measurements in CDCl3 solutions at 293 K. Chemical shifts referenced to external H3PO4.
ABX spin system, the parameters were obtained from simulation analysis.
AB2 spin system, the parameters were obtained from simulation analysis.
Table 2
1H NMR chemical shifts (ppm) of compounds (1a–4a, 1b–4b).a
Compound
Aromatic peaks of 4-isopropylaniline
CH3
CH
NH
Aromatic peaks of substituent
Cl
1a
d; 7.11
d; 7.00
m; 6.96
m; 6.91
d; 7.02
d; 6.99
d; 1.21
m; 2.85
4.99
1b
2a
m; 1.13
d; 1.20
m; 2.75
m; 2.82
4.89
5.03
Cl
Ph
m; 7.74
m; 7.46
m; 7.37
m; 7.62
m; 7.36
m; 7.22
m; 7.46
m; 7.29
m; 7.19
m; 7.40
m; 7.31
m; 7.13
m; 7.17
m; 7.04
m; 6.93
m; 7.10
m; 7.00
m; 6.87
2b
3a
3b
4a
4b
m; 6.98
m; 6.93
m; 1.19
d; 1.11
m; 1.20
d; 1.19
m; 1.20
m; 2.80
m; 2.73
m; 2.82
m; 2.82
m; 2.80
5.31
4.42
5.30
Ph
d; 6.95
d; 6.76
SPh
SPh
NHPh
NHPh
m; 6.99
m; 6.90
d; 6.99
d; 7.03
5.14
5.06
m; 6.97
m; 6.97
5.07
4.99
a
1H NMR measurements at 499,95 MHz in CDCl3 solution with chemical shifts referenced to internal TMS.
Table 3
Microanalysis and MS of compounds (1a–4a, 1b–4b).
Compound
MH+(m/z)(calc)
C(%) (calc)
H(%)(calc)
N(%) (calc)
Empirical formula
18H24Cl4N5P3
C36H48Cl2N7P3
C30H34Cl2N5P3
C48H58N7P3
C30H34Cl2N5P3S2
C48H58N7P3S2
C30H36Cl2N7P3
C48H60N9P3
1a
1b
2a
2b
3a
3b
4a
4b
546.68 (543)
745.15 (741)
626.12 (627)
824.39 (825)
692.60 (691)
890.79 (889)
658.65 (657)
857.29 (855)
39.48(39.66)
57.98(58.22)
57.28(57.34)
69.75(69.80)
51.87(52.03)
64.58(64.77)
54.67(54.72)
67.33(67.35)
4.23(4.44)
6.28(6.51)
5.38(5.45)
7.05(7.08)
4.79(4.95)
6.43(6.57)
5.44(5.51)
7.05(7.07)
12.58(12.85)
12.96(13.20)
11.08(11.14)
11.79(11.87)
09.87(10.11)
10.89(11.02)
14.76(14.89)
14.62(14.73)
C
of cyclophosphazenes to investigate substituent effects on phos-
phorus chemical shifts. Although a mixture of mono-, di-, tri-
and tetra-4-isopropylanilino substituted derivatives was formed,
only di- and tetra-substituted products were isolated to provide
a related set of compounds for comparison. The yields of the
isolated compounds were low because of forming mixed substitu-
tion. All compounds were characterized by elemental analysis,
mass spectrometry, and 31P and 1H NMR spectroscopies. In
addition, the crystal structure of 2a and 3b were also confirmed
by X-ray crystallography. The phosphorus chemical shifts,
phosphorus–phosphorus coupling constants and 1H NMR spectros-
copy results were summarized in Tables 1 and 2, respectively, and
the other analytical information was given in Table 3.
The spin systems of the compounds were interpreted as A2X,
AMX and ABX from the 1H-decoupled 31P NMR spectra of 1a,
2–3a and 4a, respectively. The 31P NMR spectrum of compound
4a showed the ABX pattern due to the similar chemical environ-
ment of anilino substituted phosphorus atoms. 31P NMR spectra
showed the AX2 and AB2 spin systems for compounds 1–3b and
4b, respectively. The proton-decoupled 31P NMR spectra of the

A. Uslu et al. / Inorganica Chimica Acta 405 (2013) 140–146
143
Fig. 1. Proton decoupled 31P NMR spectra of (a) reaction mixture of 1a and 1b (b) compound 1a (c) compound 1b.
(a)
X
X
X
X
(b)
P
N
P
H
N
H
N
H
N
N
N
N
N
Cl
P
P
P
P
N
O
N
CH3
N
CH3
Cl
I
II
Fig. 3. Variations of the substituent constants – 31P chemical shifts of P(Y)(Z) (ppm)
for compounds and II (trans) [29c]. (P(Y)(Z) chemical shift value is for
I
>P(NH)(NMe) on compound I. P(Y)(Z) are >P(NH)(NMe) and >P(NH)(O) for
compound II. X groups on PX2 are Cl, SPh, Ph, NHPh groups).
reaction mixture showed the predominance of A2X spin system
due to the formation of the di-substituted 4-isopropylanilino phos-
phazene derivative 1a and the minor product 1b in AX2 spin sys-
tem. The remaining multiple small peaks can be attributed to the
mono-, tri- and penta-4-isopropylanilino substituted compounds
(Fig. 1a).
The electron withdrawing or releasing nature of the substituent
on the cyclophosphazene ring can effect the 31P chemical shift of
neighboring phosphorus atoms and electron withdrawing or
releasing behavior of the substituted group can be compared in
geminal substituted cyclophosphazenes [29–30]. This substituent
effect on neighboring phosphorus chemical shifts can be attributed
Fig. 2. Variations of the substituent constants – 31P chemical shifts of >P(NHR)2
(ppm) for (a) compounds (1a–4a); (b) compounds (1b–4b).
reaction mixture of N3P3Cl6 with 4-isopropylaniline and the spec-
tra of the isolated compounds 1a and 1b from the reaction mixture
were given as an example in Fig. 1. The spectra of the resulting

144
A. Uslu et al. / Inorganica Chimica Acta 405 (2013) 140–146
Fig. 4. Mass spectra of compound 2a.
Hammett substituent constants (r) values of groups on neighbor-
ing phosphorus atom and variations between them were shown in
Fig. 2 [32]. The substituent effects on the neighboring phosphorus
chemical shifts for similar compounds reported in the literature
were plotted as an example and the same trend in Fig. 3 was ob-
served for these compounds [29c].
The mass spectrum of compound 2a was given as an example in
Fig. 4. It showed a molecular ion peak at m/z 626.12 and contained
an isotope pattern indicating the presence of two chlorine atoms in
the structure of 2a (Fig. 4).
3.2. X-ray crystallographic characterizations of 2a and 3b
The molecular structures of compounds 2a, and 3b have been
established by single crystal X-ray diffraction and their molecular
structures are presented in Figs. 5 and 6, respectively. The com-
pound 2a gives monoclinic crystals, space group C2/c, while com-
ꢀ
pound 3b gives triclinic crystals, space group P1. Other
appropriate crystallographic data are summarized in Table 4. Fur-
thermore, the molecular structure of compound 2b was confirmed
by X-ray. However, the crystal structure did not give a good refine-
ment presumable due to poor crystal quality.
Compound 2a contains the six-membered (N3P3) cyclophospha-
zene ring whose phosphorus atoms are gem-substituted with two
phenyl, two chlorine and two 4-isopropylanilino-moieties (Fig. 5).
Fig. 5. Crystal structure of compound 2a with the atom-numbering scheme. The
hydrogen atoms have been omitted for clarity.
to negative hyperconjugative interactions [31]. The 31P chemical
shifts of 4-isopropylanilino substituted phosphorus (>P(NHR)2)
data for compounds 1a–4a and 1b–4b were evaluated with the
Fig. 6. Crystal structure of compound 3b with the atom-numbering scheme. The hydrogen atoms have been omitted for clarity.

A. Uslu et al. / Inorganica Chimica Acta 405 (2013) 140–146
145
Table 4
structures [29c,37–39] and which was attributed to negative
hyperconjugation [31a,b,e].
Crystalographic data of compounds (2a and 3b).
The crystal structure investigations of compound 2a showed
that weak inter-molecular hydrogen bonds and CHÁ Á ÁCg interac-
tions between aromatic rings probably improve the stabilization
of crystal packing (Table 5). The crystal structure of compound
3b confirms that molecule contains the six-membered (N3P3)
cyclophosphazene ring whose phosphorus atoms are gem-substi-
tuted with two thiophenyl-, and four 4-isopropylanilino- moieties
(Fig. 6). The six-membered (N3P3) phosphazene ring is nearly pla-
nar in compound 3b with maximum deviation from the plane of
the cyclophosphazene ring being only 0.0693(12) Å (P3). In the
N3P3 ring, The P–N bond lengths [1.585(3)–1.600(3) Å], P–N–P
bond angles [122.97(16)–121.46(16)°] and N–P–N bond angles
[116.48(13)–118.50(13)°] of are found in the normal ranges for
many cyclotriphosphazenes [29c,33,37–40]. The variation in these
values is not large compared to those in compound 2a and there is
no significant difference between those P(SPh)2 and P(4-isopropy-
lanilino)2 moieties on the contrary of 2a. This observation probably
caused by similar steric and electron releasing or withdrawing ef-
fect of thiophenyl-, and 4-isopropylanilino-substituents on cyclo-
triphosphazene ring. Furthermore, the crystal packing of
compound 3b is stabilized by weak inter-molecular hydrogen
bonds and CHÁ Á ÁCg interactions between aromatic rings as given
in Table 5.
Compound
2a
3b
Empirical formula
Formula weight
T (K)
Crystal system
Space group
a (Å)
C
30H34Cl2N5P3
C48H58N7P3S2
890.04
120(2)
628.43
120(2)
monoclinic
C2/c
18.9842(9)
29.5057(14)
11.6680(6)
triclinic
ꢀ
P1
12.2067(7)
13.4508(8)
16.3160(10)
70.953(4)
76.783(4)
72.268(4)
2387.0(2)
2
b (Å)
c (Å)
a
(°)
b(°)
100.851(2)
c
(°)
V (Å3)
6418.9(5)
8
1.301
0.380
2624
Z
Dcalc (Mg/m3)
Absorption coefficient (mmÀ1
F (000)
1.238
0.253
944
)
Crystal size (mm3)
hmax (°)
0.21 Â 0.27 Â 0.43
0.08 Â 0.11 Â 0.62
28.31
25.03
Reflections collected
Independent reflections
Rint (merging R value)
Parameter
29890
7978
27132
8429
0.0660
561
0.0501
0.1265
1.031
0.471/À0.578
0.0261
371
0.0361
0.0985
1.029
R (F2 > 2
r
F2)
wR (all data)
Goodness-of-fit (GOF) on F2
D
q
Maximum/minimum (e ÅÀ3
)
1.342/À0.549
The six-membered (N3P3) phosphazene ring is nearly planar with
maximum deviation from the plane of the ring being only 0.0543
(14) Å (N3). The P–N bond lengths of N3P3 ring of 2a are in the
range of 1.5664(14)–1.6256(14) Å. Although these values are found
within the normal range for those similar cyclophosphazene deriv-
atives [29c,33–36], there is significant difference in P–N bond
lengths for bonds involving PPh2 [1.5932(14), and 1.6218(14) Å],
and P(4-isopropylanilino)2 [1.5906(14), and 1.6256(14) Å], com-
pared to those involving PCl2 groups [1.5744(13), and
1.5664(14) Å]. Similarly, the P(R1)2–N1–P(R2)2 [124.47(9)°; where
R1: Ph, R2: 4-isopropylanilino] bond angle is slightly greater than
those involving PCl2 groups, P(R1)2–N3–PCl2 [120.52(9)°] and
P(R2)2–N2–PCl2 [120.32(8)°]. Additionally, N–P–N bond angle
belonging to PCl2 phosphorus atom [121.52(7)°] is greater than
other N–P–N bond angles [116.34(7)°, and 116.21(7)°] of cyclotri-
phosphazene ring. These behaviors were observed in previous
4. Conclusion
In this paper we report the synthesis and characterization of a
series of 4-isopropylanilino derivatives of cyclotriphosphazene
(1a–4a, 1b–4b). All compounds have been fully characterized by
standard spectroscopic techniques. The compounds 2a and 3b have
been also determined by X-ray crystallography. It was seen that 31
P
chemical shifts of >P(isopropylanilino)2 nuclei of compounds (1a–
4a, 1b–4b) moved downfield with the substituents of neighboring
phosphorus atom in the order Cl < SPh < Ph < NHPh.
Acknowledgement
We thank to Gebze Institute of Technology (GIT) for providing
financial support (Grant No: BAP 2011-A-16).
Table 5
Selected inter-molecular interactions for compound 2a, and 3b.
D–HÁ Á ÁA
D–H
HÁ Á ÁA
DÁ Á ÁA
DHA
Symmetry code
2a
N4–H1Á Á ÁN2
C2–H3Á Á ÁN3
C12–H12Á Á ÁN1
C18–H18cÁ Á ÁCg1a
C20–H20Á Á ÁCg2b
C30–H30Á Á ÁCg1a
0.864(15)
0.95
0.95
2.308(15)
2.61
2.60
2.74
2.85
3.1628(19)
3.034(2)
3.036(2)
3.696(2)
3.6104(17)
3.6970(19)
170.2(16)
107
108
167
138
1 À x, y, 3/2 À z
1 À x, y, 1/2 À z
1/2 À x, 1/2 À y, 1 À z
1/2 À x, 1/2 À y, 1 À z
2.77
165
3b
N4–H1Á Á ÁN2
C39–H39Á Á ÁN7
C14–H15Á Á ÁCg3c
C21–H21Á Á ÁCg4d
C30–H30Á Á ÁCg5e
C33–H33Á Á ÁCg6f
0.86 (2)
0.95
2.35(3)
2.57
2.60
2.66
2.79
3.155(4)
3.261(4)
3.337(3)
3.382(4)
3.652(4)
3.713(4)
157(3)
130
135
132
152
1 À x, 2 À y, Àz
x, y, z
1 À x, 2 À y, Àz
1 À x, 2 À y, Àz
1 À x, 1 À y, 1 À z
2.81
160
a
b
c
d
e
f
Centroid of ring C13/C14/C15/C16/C20/C21 in compound 2a.
Centroid of ring C1/C2/C3/C4/C5/C6 in compound 2a.
Centroid of ring P1/N1/P2/N2/P3/N3 in compound 3b.
Centroid of ring C40/C41/C42/C43/C47/C48 in compound 3b.
Centroid of ring C13/C14/C15/C16/C20/C21 in compound 3b.
Centroid of ring C1/C2/C3/C4/C5/C6 in compound 3b.

146
A. Uslu et al. / Inorganica Chimica Acta 405 (2013) 140–146
[21] Bruker, SADABS, Bruker AXS Inc, Madison, Wisconsin, USA, 2005.
Appendix A. Supplementary material
[22] Bruker APEX2 (Version 2011.4-1). Bruker AXS Inc., Madison, Wisconsin, USA,
2008.
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.ica.2013.05.031.
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