Three new quinuclidine-based structures: Second harmonic generation response for 1,2-bis(1-azoniabicyclo[2.2.2]octan-3-ylidene)-hydrazine dichloride

Article abstract of DOI:10.1107/S2053229619005898

The crystal structures of three quinuclidine-based compounds, namely (1-azabicyclo[2.2.2]octan-3-ylidene)hydrazine monohydrate, C₇H₁₃N₃.H₂O(1), 1,2-bis(1-azabicyclo[2.2.2]octan-3-ylidene)hydrazine, C₁₄H₂₂N₄ (2), and 1,2-bis-(1-azoniabicyclo[2.2.2]octan-3-ylidene)hydrazine dichloride, C₁₄H₂₄N₄²⁺.2Cl (3), are reported. In the crystal structure of 1, the quinuclidine-substituted hydrazine and water molecules are linked through N—H…O and O—H…N hydrogen bonds, forming a two-dimensional array. The compound crystallizes in the centrosymmetric space group P2₁/c. Compound 2 was refined in the space group Pccn and exhibits no hydrogen bonding. However, its hydrochloride form 3 crystallizes in the noncentrosymmetric space group Pc. It shows a three-dimensional network structure via intermolecular hydrogen bonding (N—H…C and N/C—H…Cl). Compound 3, with its acentric structure, shows strong second harmonic activity.

Full text of DOI:10.1107/S2053229619005898

research papers
Three new quinuclidine-based structures:
second harmonic generation response for
1,2-bis(1-azoniabicyclo[2.2.2]octan-3-ylidene)-
hydrazine dichloride
ISSN 2053-2296
Liang Qiao,a Xiao-Gang Chen,a Ji-Xing Gaoa and Yong Aib*
Received 13 December 2018
Accepted 29 April 2019
aJiangsu Key Laboratory for Science and Applications of Molecular Ferroelectrics, Southeast University, Nanjing 211189,
People’s Republic of China, and bOrdered Matter Science Research Center, Nanchang University, Nanchang 330031,
People’s Republic of China. *Correspondence e-mail: yong.ai@ncu.edu.cn
Edited by B. D. Santarsiero, University of Illinois
at Chicago, USA
The crystal structures of three quinuclidine-based compounds, namely
(1-azabicyclo[2.2.2]octan-3-ylidene)hydrazine monohydrate, C7H13N3ꢀH2O (1),
1,2-bis(1-azabicyclo[2.2.2]octan-3-ylidene)hydrazine, C14H22N4 (2), and 1,2-bis-
Keywords: hydrogen bonding; crystal structure;
hydrazine; quinuclidine derivatives.
2+
(1-azoniabicyclo[2.2.2]octan-3-ylidene)hydrazine dichloride, C14H24N4 ꢀ2Clꢁ
CCDC references: 1884688; 1884689;
(3), are reported. In the crystal structure of 1, the quinuclidine-substituted
hydrazine and water molecules are linked through N—Hꢀ ꢀ ꢀO and O—Hꢀ ꢀ ꢀN
hydrogen bonds, forming a two-dimensional array. The compound crystallizes in
the centrosymmetric space group P21/c. Compound 2 was refined in the space
group Pccn and exhibits no hydrogen bonding. However, its hydrochloride form
3 crystallizes in the noncentrosymmetric space group Pc. It shows a three-
dimensional network structure via intermolecular hydrogen bonding (N—Hꢀ ꢀ ꢀC
and N/C—Hꢀ ꢀ ꢀCl). Compound 3, with its acentric structure, shows strong
second harmonic activity.
1884690
Supporting information: this article has
supporting information at journals.iucr.org/c
1. Introduction
Hydrogen bonding plays an important role in the crystal-
lization of molecules (Minkov et al., 2015; Zick & Geiger, 2018;
¨
Swinton Darious et al., 2018; Beko et al., 2014) and has a strong
influence on phase transitions (Fortes et al., 2014; Binns et al.,
2016). It is worth noting that not only strong N—Hꢀ ꢀ ꢀO and
O—Hꢀ ꢀ ꢀO hydrogen bonds, but also weak C—Hꢀ ꢀ ꢀO
hydrogen bonds, are important in the formation of structural
networks in crystals (Jelsch & Bibila Mayaya Bisseyou, 2017).
As early as 1982, Taylor & Kennard (1982) provided evidence
for the presence of dominant C—Hꢀ ꢀ ꢀO interactions in crys-
tals. Sarma & Desiraju (1986) pointed out that structures
could be modified by manipulation of the hydrogen bonds in
several planar aromatics. Not only hydrogen-bonding and
Coulombic interactions play a significant role (Taylor, 2016;
Gavezzotti & Lo Presti, 2016; Lo Presti, 2018), but weak
hydrogen bonding has also attracted widespread attention in
crystal packing or relative physicochemical properties
(Nogueira et al., 2015; Belkova et al., 2016). Nevertheless,
there is a debate on the importance of the interaction between
a C—Hꢀ ꢀ ꢀX-type (X = O, N and halogen) hydrogen bonds on
the crystal packing (Amamou et al., 2017; El Glaoui et al.,
2018; Ustabas¸ et al., 2018). Hence, particular attention is paid
to their roles when analyzing a crystal structure.
The well-known hydrazine-based molecules are of parti-
cular interest due to their ability to form both intra- and
intermolecular hydrogen bonds (Sonar et al., 2004; Duan et al.,
2005; Beckmann & Brooker, 2006). In this regard, we report
# 2019 International Union of Crystallography
728 https://doi.org/10.1107/S2053229619005898
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Table 1
Experimental details [see Note 5].
1
2
3
Crystal data
Chemical formula
Mr
C7H13N3ꢀH2O
C14H22N4
246.36
Orthorhombic, Pccn
288
19.7143 (13), 6.6047 (4), 9.9924 (6)
90, 90, 90
1301.08 (14)
4
Mo Kꢀ
0.08
C14H24N4 ꢀ2Clꢁ
2+
157.22
Monoclinic, P21/c
319.27
Monoclinic, Pc
Crystal system, space group
Temperature (K)
200
11.2687 (6), 8.3690 (5), 8.9974 (5)
90, 95.724 (5), 90
844.29 (8)
293
6.1699 (3), 12.5258 (7), 10.6570 (5)
90, 103.023 (5), 90
802.42 (7)
˚
a, b, c (A)
ꢀ, ꢁ, ꢂ (ꢂ)
3
˚
V (A )
Z
Radiation type
4
2
Mo Kꢀ
0.09
0.38 ꢃ 0.26 ꢃ 0.20
Mo Kꢀ
0.40
0.3 ꢃ 0.25 ꢃ 0.2
ꢃ (mmꢁ1
Crystal size (mm)
)
0.35 ꢃ 0.25 ꢃ 0.2
Data collection
Diffractometer
XtaLAB Synergy R, DW system,
HyPix
Multi-scan (North et al., 1968)
XtaLAB Synergy R, DW system,
HyPix
Multi-scan (CrysAlis PRO; Rigaku
OD, 2018)
0.977, 0.985
XtaLAB Synergy R, DW system,
HyPix
Multi-scan (CrystalClear; Rigaku,
2005)
0.887, 0.923
Absorption correction
Tmin, Tmax
0.974, 0.983
8118, 2616, 1640
No. of measured, independent and
observed [I > 2ꢄ(I)] reflections
Rint
6797, 2033, 1216
5076, 4949, 2820
0.027
0.718
0.026
0.719
0.019
0.717
ꢁ1
˚
(sin ꢅ/ꢆ)max (A
)
Refinement
R[F2 > 2ꢄ(F2)], wR(F2), S
No. of reflections
No. of parameters
No. of restraints
H-atom treatment
0.039, 0.097, 1.05
2616
116
0
H atoms treated by a mixture of
independent and constrained
0.041, 0.112, 1.07
2033
82
0
H-atom parameters constrained
0.038, 0.097, 1.00
4949
182
2
H-atom parameters constrained
refinement
0.27, ꢁ0.17
–
ꢁ3
˚
Áꢇmax, Áꢇmin (e A
Absolute structure
)
0.18, ꢁ0.16
0.28, ꢁ0.17
–
Flack x determined using 986
quotients [(I+) ꢁ (Iꢁ)]/
[(I+) + (Iꢁ)] (Parsons et al., 2013)
0.02 (4)
Absolute structure parameter
–
–
Computer programs: CrysAlis PRO (Rigaku OD, 2018), SHELXT (Sheldrick, 2015a), SHELXL2014 (Sheldrick, 2015b) and DIAMOND (Brandenburg & Putz, 2000).
herein the structures of the hydrazine-based compounds
(1-azabicyclo[2.2.2]octan-3-ylidene)hydrazine monohydrate (1),
(1-azabicyclo[2.2.2]octan-3-ylidene)hydrazine (2) and 1,2-bis(1-
azoniabicyclo[2.2.2]octan-3-ylidene)hydrazine dichloride (3).
The differences in the hydrogen-bond patterns and the types
of space groups are discussed. Second harmonic generation
(SHG) response was further examined for the crystal with a
noncentrosymmetric space group, i.e. 3.
the flask at 0 ꢂC, followed by Na2CO3 (6.56 g, 0.063 mol). The
reaction mixture was stirred for 0.5 h and the crude product
was extracted from the reaction mixture with dry dichloro-
methane (3 ꢃ 150 ml). The combined organic layers were
dried with Na2SO4, filtered and concentrated. The resulting
residue yielded 3-quinuclidone hydrochloride (77 g, yield
100%) as a white solid.
2.1.3. Synthesis of 1. 3-Quinuclidone (4.37 g, 0.035 mol)
and N2H4 (2.5 ml, 80%) in water were placed in a 100 ml flask
under a nitrogen atmosphere and heated at 120 ꢂC under
reflux overnight. The mixture was cooled in an ice bath for 3 h
to yield white crystals, which were separated and subsequently
washed with diethyl ether. The final compound, i.e. 1 (yield
3.9 g, 80%), was collected and further characterized by X-ray
diffraction.
2.1.4. Synthesis of 2 and 3. Compound 1 (2 g, 0.014 mol)
was dissolved in ethanol (20 ml) and the mixture was refluxed
at 80 ꢂC for 1 h. Crystals of 2 were obtained after the solvent
had been evaporated under ambient conditions (Barton et al.,
1983). Compound 3 was obtained by acidification of com-
pound 2 using a few drops of a 1 M HCl aqueous solution and
was recrystallized by solvent evaporation from an aqueous
solution.
2. Experimental
2.1. Synthesis and crystallization
2.1.1. Synthesis of 1,2-bis(1-azoniabicyclo[2.2.2]octan-3-
ylidene)hydrazine (BABYH) chloride. The synthesis of a Schiff
base is usually conducted by refluxing the solution of an amine
and a ketone or aldehyde (Vigato & Tamburini, 2004). We
began the synthesis of compounds 1, 2 and 3 with commer-
cially available 3-quinuclidone hydrochloride, as shown in
Fig. 1.
2.1.2. Synthesis of 3-quinuclidone. Commercially available
3-quinuclidone hydrochloride (100 g, 0.62 mol) was placed in a
1 l flask. NaOH (290 ml, 2 M in water) was added gradually to
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Three new quinuclidine-based structures 729

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Figure 1
The synthesis route for the preparation of 1, 2 and 3.
Table 2
Hydrogen-bond geometry (A, ) for 1.
2.2. Refinement
ꢂ
˚
Crystal data, data collection and structure refinement
details are summarized in Table 1. H atoms bonded to O and
most N atoms were located in difference Fourier maps and
refined freely. H atoms bonded to C atoms and to protonated
N atoms were placed in idealized positions and refined as
riders, with C—H = 0.97 (methylene) and 0.98 A (methine and
azonium). Uiso values for riding H atoms were set at
1.2Ueq(C,N).
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
O1—H1ꢀ ꢀ ꢀN1
0.864 (18)
0.874 (2)
0.908 (17)
0.898 (17)
1.994 (19)
2.042 (2)
2.186 (17)
2.212 (17)
2.8207 (13)
2.915 (2)
3.0517 (15)
3.0529 (15)
159.9 (16)
176.05 (2)
159.3 (14)
155.6 (13)
O1—H2ꢀ ꢀ ꢀN3ii
N3—H3Aꢀ ꢀ ꢀO1iv
N3—H3Bꢀ ꢀ ꢀO1v
˚
1
2
1
2
Symmetry codes: (ii) ꢁx þ 1; y ꢁ ; ꢁz þ ; (iv) ꢁx þ 1; ꢁy þ 1; ꢁz þ 1; (v) x; y þ 1; z.
unit of 1 include a (1-azabicyclo[2.2.2]octan-3-ylidene)-
hydrazine (ABYH) molecule and a water molecule. The
ABYH molecule has a quinuclidine structure with a hydrazine
group substituted at the meta position. The asymmetric unit of
2 is composed of one half of the BABYH molecule. The
complete molecule was generated by a twofold axis crossing
2.3. Second harmonic generation (SHG) measurement
The methods used for the SHG measurements have been
described elsewhere (Zhang et al., 2014). The SHG was
conducted with an unexpanded laser beam at low divergence
(pulsed Nd:YAG at a wavelength of 1064 nm, 5 ns pulse
duration, 1.6 MW peak power and 10 Hz repetition rate). The
instrument model was an Ins 1210058 (INSTEC Instruments),
while the laser was a Vibrant 355 II (OPOTEK). The
numerical values of the nonlinear optical coefficients for the
SHG were determined by comparison with a KDP reference.
the N2—N2vi bond [symmetry code: (vi) ꢁx + , ꢁy + , z].
3
1
2
2
Compound 3 consists of one protonated BABYH cation (i.e.
[BABYH2]+) and two independent Clꢁ anions (Fig. 2) in the
asymmetric unit. Full details of the bond lengths and angles
are listed in the supporting information (Tables S1–S3). The
hydrogen bonding has a significant influence on the molecular
packing. Specifically, compound 1 crystallizes in the centro-
symmetric space group P21/c through intermolecular N—
Hꢀ ꢀ ꢀO and O—Hꢀ ꢀ ꢀN hydrogen bonds, forming a two-
dimensional (2D) layer structure via the amine group and the
water network. Without the assistance of hydrogen bonding,
compound 2 crystallizes in the orthorhombic space group
Pccn. The presence of N—Hꢀ ꢀ ꢀC and N/C—Hꢀ ꢀ ꢀCl inter-
actions leads to compound 3, which crystallizes in the
3. Results and discussion
3.1. Crystal structure description
Compounds 1 and 2 crystallize in the centrosymmetric
space groups P21/c and Pccn, respectively, while compound 3
crystallizes in the noncentrosymmetric space group Pc
(Table 1). As shown in Fig. 2, the contents of the asymmetric
Figure 2
(a) The asymmetric unit of 1, (b) the molecular structure of 2 and (c) the asymmetric unit of 3, showing the atom-labelling schemes. Displacement
3
1
ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) ꢁx + , ꢁy + , z.]
2
2
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Table 3
Hydrogen-bond geometry (A, ) for 3.
ꢂ
˚
D—Hꢀ ꢀ ꢀA
D—H
Hꢀ ꢀ ꢀA
Dꢀ ꢀ ꢀA
D—Hꢀ ꢀ ꢀA
N1i—H1Aiꢀ ꢀ ꢀCl2
N4i—H4Ciꢀ ꢀ ꢀCl1
C2i—H2Biꢀ ꢀ ꢀCl2
C4ii—H4Biiꢀ ꢀ ꢀCl1
C7i—H7Aiꢀ ꢀ ꢀCl2
C12i—H12Aiꢀ ꢀ ꢀCl2
C13—H13Bꢀ ꢀ ꢀN3iii
0.98 (2)
0.98 (2)
0.97 (2)
0.97 (2)
0.97 (2)
0.97 (2)
0.97 (2)
2.027 (2)
2.069 (2)
2.852 (2)
2.888 (2)
2.893 (2)
2.906 (2)
2.626 (2)
3.007 (2)
3.043 (2)
3.657 (2)
3.737 (2)
3.697 (2)
3.684 (2)
3.356 (2)
177.90 (2)
172.42 (2)
141.00 (2)
146.75 (2)
140.87 (2)
137.92 (2)
132.3 (2)
Symmetry codes: (i) x, ꢁy + 1, z ꢁ 12; (ii) x, ꢁy + 1, z + 21; (iii) x, ꢁy + 2, z + 21.
3.1.1. Crystal structure of (1-azabicyclo[2.2.2]octan-3-
ylidene)hydrazine monohydrate, 1. In the crystal structure
of 1, the ABYH and H2O molecules are linked through N—
Hꢀ ꢀ ꢀO and O—Hꢀ ꢀ ꢀN hydrogen bonds into a 2D array along
the bc plane (Figs. 3a and 3b, and Table 2). As shown in
Fig. 3(c), the water molecule interacts with the ABYH mol-
ecule through two types of hydrogen bonds and is embedded
between the ABYH layers. Firstly, the amino N3 atoms act as
donors and the water O atoms as acceptors in N—Hꢀ ꢀ ꢀO
hydrogen bonds (red dashed lines). The average hydrogen-
˚
bond length (N—Hꢀ ꢀ ꢀO) is 3.0517 (15) A. Secondly, the O
atoms act as donors and form hydrogen bonds with N1 and
N3ii, as depicted in Fig. 3(c). It is worth noting that since the
acceptors are derived from different sites on the ABYH
molecule, the hydrogen-bond lengths are 2.8207 (13) and
ii
˚
2.915 (2) A for O1—H1ꢀ ꢀ ꢀN1 and O1—H2ꢀ ꢀ ꢀN3 , respec-
tively. The asymmetry of the ABYH molecule itself and the
two different types of hydrogen bonds leads to compound 3,
which crystallizes in a monoclinic system with relatively low
symmetry. The hydrogen-bond interactions in the regular
sandwiched ABYH/water/ABYH structure seems to play a
key role in achieving the packing characteristics and the
higher stability of the structure (Etter et al., 1990; Etter, 1990;
Steiner, 2002).
3.1.2. Crystal structure of (1-azabicyclo[2.2.2]octan-3-
ylidene)hydrazine, 2. As shown in Fig. 4, compound 2 exhi-
bits the typical s-trans E,E configuration (Sanz et al., 1999;
Figure 3
The 2D layer formed through intermolecular hydrogen bonds in 1,
viewed (a) along the b axis and (b) along the a axis. (c) The detailed
hydrogen bonding, with intermolecular N—Hꢀ ꢀ ꢀO and O—Hꢀ ꢀ ꢀN
hydrogen bonds indicated by red and blue dashed lines, respectively.
1
2
1
2
1
2
[Symmetry codes: (i) ꢁx, y + , ꢁz + ; (ii) ꢁx, ꢁy, ꢁz; (iii) x, ꢁy ꢁ ,
1
z ꢁ .]
2
noncentrosymmetric space group Pc. The crystal structures
are described below.
Figure 4
A packing view of 2 on the ac plane.
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Three new quinuclidine-based structures 731

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Figure 7
SHG response of 3 relative to KDP.
cause deviations from close packing and hence affect the
crystal structures and properties at a subtle level (Prokopchuk
et al., 2019; Paufler, 2012). The absence of H atoms on the N
atoms and no potential for hydrogen-bond interactions in the
molecular stacking of 2 (Fig. 4) leads to a symmetrical
arrangement during the molecular packing process. (ii) The
centrosymmetric feature of 2 originates mainly from the
molecular shape and van der Waals forces.
Figure 5
Part of the crystal structure of 3, showing the hydrogen-bond information
for N/C—Hꢀ ꢀ ꢀCl (red dashed lines) and C—Hꢀ ꢀ ꢀN (blue dashed lines).
1
[Symmetry codes: (i) x, ꢁy + 1, z ꢁ ; (ii) x, ꢁy + 1, z + 12; (iii) x, ꢁy + 2,
2
z + 12.]
3.1.3. Crystal structure of 1,2-bis(1-azoniabicyclo[2.2.2]-
octan-3-ylidene)hydrazine dichloride, 3. Fig. 5 displays the
hydrogen-bond information for N/C—Hꢀ ꢀ ꢀCl and C—Hꢀ ꢀ ꢀN.
Fig. 6 shows the crystal packing of 3. The [BABYH2]+ cations
connect with each other through intermolecular hydrogen
bonds (N—Hꢀ ꢀ ꢀC and N/C—Hꢀ ꢀ ꢀCl) and form a regularly
arranged three-dimensional (3D) network structure. There are
three types of hydrogen bonds in the crystal structure; detailed
information is given in Table 3. Firstly, the Cl1 atom bridges
two quinine units through N/C—Hꢀ ꢀ ꢀCl hydrogen bonds,
where Cl1 acts as an acceptor and N4 and C4 act as donors.
The hydrogen-bond lengths are 3.043 (2) (N4i—H4Ciꢀ ꢀ ꢀCl1)
Saeed et al., 2012; Ali et al., 2011; Li & Han, 2016; Hsu et al.,
1993). Each molecular unit of compound 2 is related by a
crystallographic twofold axis parallel to the c axis and a
crystallographic glide plane perpendicular to the a axis
between the N2 and N2i atoms. Compound 2 crystallizes in the
orthorhombic space group Pccn, which is higher in symmetry
than 1 (space group P21/c). This could be explained by two
facts: (i) the intermolecular interactions (hydrogen bonding)
ii
ii
˚
and 3.737 (2) A (C4 —H4B ꢀ ꢀ ꢀCl1). Secondly, the Cl2 atom
acts as an acceptor and forms hydrogen bonds with H1A,
H7A, H2B and H12A. The third type of hydrogen bond is N—
Hꢀ ꢀ ꢀC involving atom C13; the H13Bꢀ ꢀ ꢀN3iii bond distance is
˚
2.626 (2) A. Compound 3 crystallizes in the noncentrosym-
metric space group Pc, which is lower in symmetry than 1 and
2. The hydrogen-bond stacking of 3 is obviously different from
that of 1. The asymmetry of 3 could be attributed to the
diversity of hydrogen bonds. The Clꢁ anions bridge the cations
and form the 3D structure, resulting in significant polarization.
The asymmetry properties of these compounds were further
investigated by the measurement of second harmonic
generation (SHG) response. To measure the relative value of
the SHG efficiencies, potassium dihydrogen phosphate
(KH2PO4, KDP) powder was chosen as the reference sample.
KDP is famous for its excellent nonlinear optical properties,
showing strong SHG properties (Shkir et al., 2013). It has been
widely developed for powerful laser systems (De Yoreo et al.,
2002). Since the nonlinear optical properties result from the
dipole moment, the SHG signal is a sign of the polarity of the
material. Here, the sample powders were placed under a
pulsed laser at 1064 nm. As shown in Fig. 7, the measured
Figure 6
The 3D structure of 3 mediated by the intermolecular hydrogen bonding
(dashed lines).
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at room temperature. Unsurprisingly, 1 and 2 show no signif-
icant SHG signal.
`
´
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4. Conclusion
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In summary, the title compounds have been synthesized
through a catalyst-free route. Hydrogen bonding plays a
crucial role in the molecular packing. Compound 1 crystallized
in the centrosymmetric space group P21/c via robust hydrogen
bonding (N—Hꢀ ꢀ ꢀO and O—Hꢀ ꢀ ꢀN) and formed a 2D sand-
wich structure. Compound 2 crystallizes in the space group
Pccn without hydrogen-bonding assistance. Compound 3
shows a 3D network structure via intermolecular hydrogen
bonds (N—Hꢀ ꢀ ꢀC and N/C—Hꢀ ꢀ ꢀCl) and crystallizes in the
noncentrosymmetric space group Pc. Analysis of the hydro-
gen-bond interactions allows us to understand the symmetry
properties of the crystal structures.
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Acknowledgements
The authors thank Nanchang University and Southeast
University, China, for financial support.
Saeed, A., Bolte, M. & Arshad, M. (2012). Acta Cryst. E68, o255.
´
´
Sanz, D., Alejandra Ponce, M., Marıa Claramunt, R., Fernandez-
Castan˜o, C., Foces-Foces, C. & Elguero, J. (1999). J. Phys. Org.
Chem. 12, 455–469.
Funding information
Funding for this research was provided by: National Natural
Science Foundation of China (grant No. 2190011311).
Sarma, J. A. R. P. & Desiraju, G. R. (1986). Acc. Chem. Res. 19, 222–
228.
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8.
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8.
Shkir, M., Ganesh, V., Vijayan, N., Riscob, B., Kumar, A., Rana, D. K.,
Shoeb Khan, M., Hasmuddin, M., Wahab, M. A., Ramesh Babu, R.
& Bhagavannarayana, G. (2013). Spectrochim. Acta A Mol. Biomol.
Spectrosc. 103, 199–204.
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Brandenburg, K. & Putz, H. (2000). DIAMOND. Crystal Impact
GbR, Bonn, Germany.
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ꢄ
Acta Cryst. (2019). C75, 728–733
Qiao et al.
Three new quinuclidine-based structures 733

supporting information
supporting information
Acta Cryst. (2019). C75, 728-733 [https://doi.org/10.1107/S2053229619005898]
Three new quinuclidine-based structures: second harmonic generation response
for 1,2-bis(1-azoniabicyclo[2.2.2]octan-3-ylidene)hydrazine dichloride
Liang Qiao, Xiao-Gang Chen, Ji-Xing Gao and Yong Ai
Computing details
For all structures, data collection: CrysAlis PRO (Rigaku OD, 2018); cell refinement: CrysAlis PRO (Rigaku OD, 2018);
data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXT (Sheldrick, 2015a);
program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg &
Putz, 2000); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).
(1-Azabicyclo[2.2.2]oct-3-ylidene)hydrazine monohydrate (P21C)
Crystal data
C7H13N3·H2O
Mr = 157.22
F(000) = 344
Dx = 1.237 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 3399 reflections
θ = 3.0–30.3°
Monoclinic, P21/c
a = 11.2687 (6) Å
b = 8.3690 (5) Å
c = 8.9974 (5) Å
β = 95.724 (5)°
V = 844.29 (8) Å3
Z = 4
µ = 0.09 mm−1
T = 200 K
Bar, colorless
0.38 × 0.26 × 0.20 mm
Data collection
XtaLAB Synergy R, DW system, HyPix
diffractometer
Radiation source: Rotating-anode X-ray tube
ω scans
2616 independent reflections
1640 reflections with I > 2σ(I)
Rint = 0.027
θ
max = 30.7°, θmin = 3.0°
Absorption correction: multi-scan
(North et al., 1968)
h = −16→12
k = −12→9
l = −12→11
T
min = 0.974, Tmax = 0.983
8118 measured reflections
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.039
wR(F2) = 0.097
H atoms treated by a mixture of independent
and constrained refinement
w = 1/[σ2(Fo2) + (0.0396P)2 + 0.2373P]
where P = (Fo2 + 2Fc2)/3
S = 1.05
2616 reflections
116 parameters
(Δ/σ)max < 0.001
Δρmax = 0.27 e Å−3
Δρmin = −0.16 e Å−3
0 restraints
Hydrogen site location: mixed
Extinction correction: SHELXL2014
(Sheldrick, 2015b)
Extinction coefficient: 0.012 (3)
Acta Cryst. (2019). C75, 728-733
sup-1

supporting information
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
H2
H1
0.5044 (16)
0.3994 (16)
0.4201 (14)
0.3984 (13)
0.24509 (12)
0.2078
0.3218
0.14730 (11)
0.1599
0.1067
0.16618 (12)
0.2082
0.0934
0.06742 (11)
−0.0061
0.275 (2)
0.275 (2)
0.838 (2)
0.994 (2)
0.36947 (17)
0.2649
0.3610
0.43570 (17)
0.4674
0.3334
0.48901 (17)
0.5280
0.4370
0.56098 (16)
0.5115
0.345 (2)
0.4087 (19)
0.3883 (19)
0.3108 (17)
0.18145 (15)
0.1747
0.1419
0.39880 (15)
0.5029
0.3940
0.08594 (14)
0.0042
0.0442
0.31129 (15)
0.2686
0.057 (5)*
0.048 (5)*
0.040 (4)*
0.040 (4)*
0.0354 (3)
0.042*
0.042*
0.0331 (3)
0.040*
0.040*
0.0328 (3)
0.039*
0.039*
0.0318 (3)
0.038*
H3A
H3B
C7
H7A
H7B
C6
H6A
H6B
C4
H4A
H4B
C5
H5A
H5B
C3
0.0475
0.13621 (10)
0.0893
0.6460
0.62896 (15)
0.7108
0.3777
0.18676 (13)
0.1293
0.038*
0.0265 (3)
0.032*
H3
C2
C1
H1A
H1B
N3
N1
O1
N2
0.25161 (10)
0.32424 (10)
0.4022
0.69677 (14)
0.57396 (14)
0.5643
0.25798 (12)
0.34956 (13)
0.3135
0.0227 (2)
0.0237 (3)
0.028*
0.3353
0.6081
0.4530
0.028*
0.39511 (10)
0.26369 (9)
0.46566 (9)
0.28043 (9)
0.88691 (14)
0.41798 (12)
0.22272 (11)
0.84209 (12)
0.30080 (13)
0.33943 (11)
0.40879 (11)
0.23735 (11)
0.0291 (2)
0.0242 (2)
0.0315 (2)
0.0270 (2)
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
C7
C6
C4
C5
C3
C2
C1
N3
N1
0.0380 (7)
0.0278 (7)
0.0320 (7)
0.0211 (6)
0.0213 (6)
0.0225 (6)
0.0208 (6)
0.0306 (6)
0.0227 (5)
0.0352 (8)
0.0388 (7)
0.0428 (8)
0.0397 (8)
0.0317 (7)
0.0261 (6)
0.0246 (6)
0.0242 (6)
0.0245 (5)
0.0314 (7)
0.0067 (5)
−0.0056 (5)
−0.0009 (5)
−0.0011 (5)
0.0030 (4)
0.0016 (4)
−0.0024 (4)
−0.0046 (4)
−0.0021 (4)
−0.0044 (5)
0.0066 (5)
−0.0029 (5)
0.0053 (5)
−0.0018 (4)
0.0040 (4)
−0.0011 (4)
0.0046 (4)
−0.0007 (4)
−0.0114 (5)
0.0084 (5)
−0.0042 (5)
0.0004 (5)
0.0030 (5)
0.0011 (4)
0.0020 (4)
0.0007 (4)
0.0002 (4)
0.0335 (7)
0.0225 (6)
0.0351 (7)
0.0256 (6)
0.0199 (6)
0.0249 (6)
0.0327 (6)
0.0247 (5)
Acta Cryst. (2019). C75, 728-733
sup-2

supporting information
O1
N2
0.0310 (5)
0.0279 (5)
0.0271 (5)
0.0275 (6)
0.0360 (5)
0.0260 (5)
0.0035 (4)
0.0010 (4)
0.0020 (4)
0.0045 (4)
0.0067 (4)
0.0026 (4)
Geometric parameters (Å, º)
C7—N1
1.4730 (16)
C5—H5B
0.9700
C7—C4
1.5419 (18)
0.9700
0.9700
1.4722 (16)
1.5453 (18)
0.9700
0.9700
1.5394 (18)
0.9700
0.9700
1.5341 (17)
0.9700
C3—C2
C3—H3
C2—N2
C2—C1
C1—N1
C1—H1A
C1—H1B
N3—N2
N3—H3A
N3—H3B
O1—H2
O1—H1
1.5025 (16)
0.9800
1.2771 (16)
1.5068 (16)
1.4716 (15)
0.9700
C7—H7A
C7—H7B
C6—N1
C6—C5
C6—H6A
C6—H6B
C4—C3
C4—H4A
C4—H4B
C5—C3
0.9700
1.4106 (15)
0.908 (17)
0.898 (17)
0.87 (2)
C5—H5A
0.864 (18)
N1—C7—C4
112.18 (10)
109.2
109.2
109.2
109.2
107.9
112.22 (10)
109.2
109.2
109.2
109.2
107.9
108.27 (10)
110.0
110.0
110.0
110.0
108.4
108.22 (10)
110.1
C2—C3—C5
C2—C3—C4
C5—C3—C4
C2—C3—H3
C5—C3—H3
C4—C3—H3
N2—C2—C3
N2—C2—C1
C3—C2—C1
N1—C1—C2
N1—C1—H1A
C2—C1—H1A
N1—C1—H1B
C2—C1—H1B
H1A—C1—H1B
N2—N3—H3A
N2—N3—H3B
H3A—N3—H3B
C1—N1—C6
C1—N1—C7
C6—N1—C7
H2—O1—H1
C2—N2—N3
107.91 (10)
107.89 (9)
107.74 (10)
111.0
111.0
111.0
121.30 (11)
126.65 (11)
112.05 (10)
110.36 (9)
109.6
109.6
109.6
109.6
108.1
115.0 (10)
109.4 (10)
110.9 (14)
108.21 (9)
108.95 (10)
109.37 (10)
103.7 (16)
115.49 (10)
N1—C7—H7A
C4—C7—H7A
N1—C7—H7B
C4—C7—H7B
H7A—C7—H7B
N1—C6—C5
N1—C6—H6A
C5—C6—H6A
N1—C6—H6B
C5—C6—H6B
H6A—C6—H6B
C3—C4—C7
C3—C4—H4A
C7—C4—H4A
C3—C4—H4B
C7—C4—H4B
H4A—C4—H4B
C3—C5—C6
C3—C5—H5A
C6—C5—H5A
C3—C5—H5B
C6—C5—H5B
H5A—C5—H5B
110.1
110.1
110.1
108.4
N1—C7—C4—C3
N1—C6—C5—C3
C6—C5—C3—C2
C6—C5—C3—C4
2.85 (15)
0.10 (15)
−56.98 (13)
59.28 (13)
N2—C2—C1—N1
C3—C2—C1—N1
C2—C1—N1—C6
C2—C1—N1—C7
−176.92 (11)
2.16 (13)
−60.83 (12)
58.00 (12)
Acta Cryst. (2019). C75, 728-733
sup-3

supporting information
C7—C4—C3—C2
C7—C4—C3—C5
C5—C3—C2—N2
C4—C3—C2—N2
C5—C3—C2—C1
C4—C3—C2—C1
55.23 (13)
C5—C6—N1—C1
C5—C6—N1—C7
C4—C7—N1—C1
C4—C7—N1—C6
C3—C2—N2—N3
C1—C2—N2—N3
59.56 (13)
−59.00 (14)
−60.92 (13)
57.18 (14)
−175.16 (10)
3.84 (17)
−61.04 (13)
−123.94 (12)
119.90 (12)
56.93 (13)
−59.23 (12)
Hydrogen-bond geometry (Å, º)
D—H···A
D—H
H···A
D···A
D—H···A
O1—H1···N1
0.864 (18)
0.874 (2)
0.908 (17)
0.898 (17)
1.994 (19)
2.042 (2)
2.186 (17)
2.212 (17)
2.8207 (13)
2.915 (2)
3.0517 (15)
3.0529 (15)
159.9 (16)
176.05 (2)
159.3 (14)
155.6 (13)
O1—H2···N3i
N3—H3A···O1ii
N3—H3B···O1iii
Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) x, y+1, z.
1,2-Bis(1-azabicyclo[2.2.2]oct-3-ylidene)hydrazine (PCCN)
Crystal data
C14H22N4
Mr = 246.36
Dx = 1.258 Mg m−3
Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pccn
a = 19.7143 (13) Å
b = 6.6047 (4) Å
c = 9.9924 (6) Å
V = 1301.08 (14) Å3
Z = 4
Cell parameters from 2940 reflections
θ = 3.2–30.6°
µ = 0.08 mm−1
T = 288 K
Bar, colorless
0.35 × 0.25 × 0.2 mm
F(000) = 536
Data collection
XtaLAB Synergy R, DW system, HyPix
diffractometer
Radiation source: Rotating-anode X-ray tube
ω scans
2033 independent reflections
1216 reflections with I > 2σ(I)
Rint = 0.026
θ
max = 30.7°, θmin = 3.3°
Absorption correction: multi-scan
(CrysAlis PRO; Rigaku OD, 2018)
h = −28→23
k = −7→9
T
min = 0.977, Tmax = 0.985
l = −11→14
6797 measured reflections
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.041
wR(F2) = 0.112
S = 1.07
2033 reflections
82 parameters
0 restraints
Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
w = 1/[σ2(Fo2) + (0.0482P)2 + 0.2267P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.18 e Å−3
Δρmin = −0.16 e Å−3
Acta Cryst. (2019). C75, 728-733
sup-4

supporting information
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
N1
N2
C1
H1A
H1B
C2
C3
H3
0.58882 (5)
0.73834 (5)
0.65099 (6)
0.6811
0.18453 (15)
0.14848 (15)
0.27017 (19)
0.3114
0.29148 (11)
0.07517 (10)
0.23467 (13)
0.3064
0.0438 (3)
0.0431 (3)
0.0416 (3)
0.050*
0.6399
0.3892
0.1822
0.050*
0.68635 (6)
0.65173 (6)
0.6763
0.11736 (17)
−0.08475 (18)
−0.1850
0.14723 (11)
0.15064 (13)
0.0970
0.0363 (3)
0.0420 (3)
0.050*
C4
0.64643 (8)
0.6227
0.6914
0.57970 (7)
0.5814
0.5540
0.54573 (7)
0.5342
0.5039
0.60774 (7)
0.5670
0.6357
−0.1510 (2)
−0.2793
−0.1682
−0.0515 (2)
−0.0097
−0.1764
0.1127 (2)
0.2263
0.0594
0.0112 (2)
−0.0483
0.0582
0.29696 (15)
0.3028
0.3345
0.09707 (14)
0.0041
0.1026
0.18161 (15)
0.1244
0.2185
0.37512 (13)
0.4128
0.4487
0.0524 (4)
0.063*
0.063*
0.0498 (4)
0.060*
0.060*
0.0535 (4)
0.064*
0.064*
0.0509 (4)
0.061*
0.061*
H4A
H4B
C5
H5A
H5B
C6
H6A
H6B
C7
H7A
H7B
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
N1
N2
C1
C2
C3
C4
C5
C6
C7
0.0405 (6)
0.0359 (6)
0.0450 (7)
0.0344 (6)
0.0397 (7)
0.0537 (8)
0.0435 (8)
0.0375 (7)
0.0587 (9)
0.0480 (6)
0.0513 (6)
0.0392 (6)
0.0419 (6)
0.0411 (6)
0.0466 (7)
0.0616 (8)
0.0637 (9)
0.0569 (8)
0.0428 (6)
0.0003 (4)
−0.0056 (4)
−0.0025 (5)
−0.0019 (5)
−0.0032 (5)
0.0003 (6)
−0.0109 (6)
0.0055 (6)
−0.0109 (6)
0.0046 (5)
0.0000 (4)
0.0029 (6)
−0.0029 (5)
0.0052 (5)
−0.0019 (7)
−0.0030 (6)
−0.0071 (6)
0.0026 (6)
−0.0086 (5)
−0.0048 (5)
−0.0052 (5)
−0.0044 (5)
−0.0112 (5)
0.0061 (6)
−0.0129 (6)
−0.0082 (7)
0.0003 (6)
0.0420 (6)
0.0407 (7)
0.0326 (6)
0.0452 (7)
0.0569 (9)
0.0443 (7)
0.0593 (9)
0.0369 (7)
Geometric parameters (Å, º)
N1—C1
N1—C7
N1—C6
1.4643 (15)
1.4656 (17)
1.4670 (17)
C3—H3
C4—C7
C4—H4A
0.9800
1.5294 (19)
0.9700
Acta Cryst. (2019). C75, 728-733
sup-5

supporting information
N2—C2
N2—N2i
C1—C2
C1—H1A
C1—H1B
C2—C3
C3—C4
C3—C5
1.2693 (16)
1.418 (2)
1.5060 (16)
0.9700
C4—H4B
C5—C6
0.9700
1.5291 (19)
0.9700
0.9700
0.9700
0.9700
0.9700
0.9700
C5—H5A
C5—H5B
C6—H6A
C6—H6B
C7—H7A
C7—H7B
0.9700
1.4996 (16)
1.5296 (19)
1.5335 (18)
C1—N1—C7
C1—N1—C6
C7—N1—C6
C2—N2—N2i
N1—C1—C2
N1—C1—H1A
C2—C1—H1A
N1—C1—H1B
C2—C1—H1B
H1A—C1—H1B
N2—C2—C3
N2—C2—C1
C3—C2—C1
C2—C3—C4
C2—C3—C5
C4—C3—C5
C2—C3—H3
C4—C3—H3
C5—C3—H3
C7—C4—C3
C7—C4—H4A
C3—C4—H4A
108.05 (10)
108.64 (10)
108.75 (10)
114.53 (11)
110.70 (10)
109.5
109.5
109.5
109.5
108.1
121.63 (11)
126.47 (11)
111.88 (10)
107.90 (10)
106.63 (11)
108.14 (11)
111.3
111.3
111.3
108.79 (11)
109.9
109.9
C7—C4—H4B
C3—C4—H4B
H4A—C4—H4B
C6—C5—C3
C6—C5—H5A
C3—C5—H5A
C6—C5—H5B
C3—C5—H5B
H5A—C5—H5B
N1—C6—C5
N1—C6—H6A
C5—C6—H6A
N1—C6—H6B
C5—C6—H6B
H6A—C6—H6B
N1—C7—C4
N1—C7—H7A
C4—C7—H7A
N1—C7—H7B
C4—C7—H7B
H7A—C7—H7B
109.9
109.9
108.3
108.32 (10)
110.0
110.0
110.0
110.0
108.4
112.91 (11)
109.0
109.0
109.0
109.0
107.8
112.50 (10)
109.1
109.1
109.1
109.1
107.8
Symmetry code: (i) −x+3/2, −y+1/2, z.
1,2-Bis(1-azoniabicyclo[2.2.2]oct-3-ylidene)hydrazine dichloride (PC)
Crystal data
C14H24N42+·2Cl−
Mr = 319.27
F(000) = 340
Dx = 1.321 Mg m−3
Monoclinic, Pc
a = 6.1699 (3) Å
b = 12.5258 (7) Å
c = 10.6570 (5) Å
β = 103.023 (5)°
V = 802.42 (7) Å3
Z = 2
Mo Kα radiation, λ = 0.71073 Å
Cell parameters from 2739 reflections
θ = 3.3–28.9°
µ = 0.40 mm−1
T = 293 K
Bar, colorless
0.3 × 0.25 × 0.2 mm
Acta Cryst. (2019). C75, 728-733
sup-6

supporting information
Data collection
XtaLAB Synergy R, DW system, HyPix
diffractometer
Radiation source: Rotating-anode X-ray tube
ω scans
4949 independent reflections
2820 reflections with I > 2σ(I)
Rint = 0.019
θ
max = 30.6°, θmin = 2.6°
Absorption correction: multi-scan
(CrystalClear; Rigaku, 2005)
h = −7→8
k = −17→13
l = −14→15
T
min = 0.887, Tmax = 0.923
5076 measured reflections
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.038
wR(F2) = 0.097
w = 1/[σ2(Fo2) + (0.0517P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.28 e Å−3
S = 1.00
Δρmin = −0.17 e Å−3
4949 reflections
182 parameters
Extinction correction: SHELXL2014
(Sheldrick, 2015b),
2 restraints
Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Extinction coefficient: 0.012 (3)
Absolute structure: Flack x determined using
986 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et
al., 2013)
Hydrogen site location: inferred from
neighbouring sites
H-atom parameters constrained
Absolute structure parameter: 0.02 (4)
Special details
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance
matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles;
correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate
(isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
z
Uiso*/Ueq
C1
0.8805 (5)
0.8086
0.9687
1.0310 (4)
1.0183
1.1847
0.8185 (5)
0.9037
0.7064
0.9719 (4)
1.1231
0.9262
0.5723 (4)
0.4583
0.5001
0.7243 (4)
0.9630 (4)
1.0586
0.8659 (2)
0.8278
0.9231
0.7901 (3)
0.7186
0.8128
0.9758 (2)
1.0336
1.0066
0.9037 (3)
0.9305
0.9038
0.8252 (2)
0.8556
0.7837
0.7553 (2)
0.7898 (2)
0.7419
1.0231 (3)
1.0817
1.0706
0.9705 (2)
1.0031
0.9985
0.8280 (3)
0.8760
0.7588
0.7722 (3)
0.7964
0.6789
0.8403 (2)
0.7719
0.8960
0.7845 (2)
0.8229 (2)
0.7865
0.0406 (7)
0.049*
0.049*
0.0418 (7)
0.050*
0.050*
0.0435 (7)
0.052*
0.052*
0.0448 (7)
0.054*
0.054*
0.0347 (6)
0.042*
0.042*
0.0289 (5)
0.0332 (6)
0.040*
H1A
H1B
C2
H2A
H2B
C3
H3A
H3B
C4
H4A
H4B
C5
H5A
H5B
C6
C7
H7A
Acta Cryst. (2019). C75, 728-733
sup-7

supporting information
C8
0.0225 (4)
−0.1350
0.0465
0.1537 (5)
0.0527
0.2347
0.0605 (4)
0.1124
0.7195 (2)
0.7125
0.7882
0.7139 (3)
0.7047
0.7800
0.5227 (2)
0.4652
0.5120
0.5209 (3)
0.4610
0.5120
0.6441 (2)
0.6380 (3)
0.7032
0.5787
0.6299 (2)
0.6329
0.91179 (18)
0.9588
0.6228 (2)
0.6201
0.67783 (19)
0.66326 (18)
0.63584 (7)
0.05252 (7)
0.4151 (3)
0.3767
0.4581
0.3112 (3)
0.2279
0.3095
0.4428 (3)
0.5030
0.4066
0.3358 (3)
0.3483
0.2533
0.5650 (2)
0.4621 (2)
0.4609
0.4790
0.5133 (2)
0.5825
0.9153 (2)
0.9511
0.33635 (19)
0.2681
0.70772 (19)
0.68247 (19)
0.12698 (7)
0.02162 (8)
0.0416 (7)
0.050*
0.050*
0.0539 (9)
0.065*
0.065*
0.0413 (7)
0.050*
0.050*
0.0561 (9)
0.067*
0.067*
0.0290 (6)
0.0421 (7)
0.051*
0.051*
0.0310 (6)
0.037*
0.0331 (5)
0.040*
0.0408 (6)
0.049*
0.0336 (5)
0.0329 (5)
0.05067 (19)
0.0565 (2)
H8A
H8B
C9
H9A
H9B
C10
H10A
H10B
C11
H11A
H11B
C12
C13
H13A
H13B
C14
H14A
N1
−0.0969
0.1869 (5)
0.2893
0.0833
0.3415 (4)
0.4718 (4)
0.5560
0.5755
0.0964 (4)
0.0155
0.7083 (3)
0.6105
0.3130 (3)
0.3959
0.6605 (3)
0.4259 (3)
0.57596 (10)
0.39849 (11)
H1C
N4
H4C
N2
N3
Cl1
Cl2
Atomic displacement parameters (Å2)
U11
U22
U33
U12
U13
U23
C1
C2
C3
C4
C5
C6
C7
C8
0.0421 (13)
0.0383 (13)
0.0434 (14)
0.0400 (14)
0.0276 (11)
0.0308 (11)
0.0250 (11)
0.0325 (12)
0.0484 (15)
0.0423 (14)
0.0610 (17)
0.0316 (11)
0.0295 (12)
0.0282 (11)
0.0347 (10)
0.0351 (10)
0.0297 (10)
0.0323 (9)
0.0470 (17)
0.0460 (18)
0.0315 (15)
0.0500 (18)
0.0365 (14)
0.0319 (13)
0.0392 (14)
0.0429 (17)
0.070 (2)
0.0378 (16)
0.058 (2)
0.0280 (13)
0.069 (2)
0.0306 (12)
0.0046 (13)
0.0112 (12)
−0.0041 (12)
−0.0119 (12)
−0.0016 (10)
0.0017 (10)
−0.0003 (10)
0.0025 (11)
0.0022 (14)
−0.0092 (12)
−0.0045 (15)
−0.0022 (9)
0.0014 (12)
−0.0048 (10)
0.0020 (9)
0.0036 (10)
−0.0020 (11)
0.0065 (12)
0.0155 (11)
0.0077 (9)
0.0054 (8)
0.0049 (9)
0.0050 (11)
0.0123 (12)
0.0069 (11)
0.0201 (13)
0.0095 (9)
0.0066 (10)
0.0091 (9)
0.0081 (8)
0.0116 (8)
0.0064 (8)
0.0081 (8)
−0.0034 (12)
−0.0062 (12)
0.0052 (13)
−0.0021 (13)
−0.0059 (11)
0.0012 (10)
−0.0104 (10)
0.0019 (13)
0.0215 (14)
−0.0051 (13)
−0.0237 (14)
−0.0016 (9)
−0.0017 (12)
−0.0034 (10)
−0.0063 (9)
−0.0037 (10)
−0.0038 (9)
−0.0034 (9)
0.0362 (13)
0.0535 (15)
0.0471 (14)
0.0401 (12)
0.0238 (9)
0.0346 (11)
0.0473 (14)
0.0439 (14)
0.0424 (13)
0.0529 (15)
0.0286 (10)
0.0278 (11)
0.0283 (11)
0.0368 (10)
0.0244 (9)
0.0330 (10)
0.0316 (9)
C9
C10
C11
C12
C13
C14
N1
N4
N2
N3
0.0377 (15)
0.0277 (11)
0.0651 (16)
0.0379 (13)
0.0351 (12)
−0.0006 (10)
−0.0034 (9)
−0.0069 (9)
Acta Cryst. (2019). C75, 728-733
sup-8

supporting information
Cl1
Cl2
0.0489 (3)
0.0476 (3)
0.0668 (5)
0.0573 (4)
0.0401 (3)
0.0599 (4)
−0.0099 (3)
0.0158 (3)
0.0179 (2)
0.0020 (3)
0.0007 (3)
−0.0226 (4)
Geometric parameters (Å, º)
C1—N1
1.493 (3)
C8—H8A
0.9700
C1—C2
1.521 (4)
0.9700
0.9700
1.534 (3)
0.9700
0.9700
1.502 (4)
1.522 (4)
0.9700
0.9700
1.532 (4)
0.9700
C8—H8B
C9—N4
0.9700
1.490 (4)
0.9700
C1—H1A
C1—H1B
C2—C7
C2—H2A
C2—H2B
C3—N1
C3—C4
C3—H3A
C3—H3B
C4—C7
C4—H4A
C4—H4B
C5—N1
C5—C6
C5—H5A
C5—H5B
C6—N2
C6—C7
C7—H7A
C8—C9
C9—H9A
C9—H9B
C10—C11
C10—C14
C10—H10A
C10—H10B
C11—N4
C11—H11A
C11—H11B
C12—N3
C12—C14
C12—C13
C13—N4
C13—H13A
C13—H13B
C14—H14A
N1—H1C
N4—H4C
N2—N3
0.9700
1.519 (4)
1.530 (4)
0.9700
0.9700
1.494 (4)
0.9700
0.9700
1.266 (3)
1.499 (3)
1.500 (3)
1.484 (3)
0.9700
0.9700
0.9800
0.9800
0.9800
0.9700
1.488 (3)
1.501 (4)
0.9700
0.9700
1.273 (3)
1.501 (3)
0.9800
1.514 (4)
1.532 (4)
1.423 (3)
C8—C14
N1—C1—C2
110.2 (2)
109.6
109.6
109.6
109.6
108.1
109.3 (2)
109.8
109.8
109.8
109.8
108.3
109.5 (2)
109.8
109.8
109.8
109.8
108.2
109.9 (2)
N4—C9—H9A
C8—C9—H9A
N4—C9—H9B
C8—C9—H9B
109.6
109.6
109.6
109.6
108.2
109.8 (2)
109.7
109.7
109.7
109.7
108.2
109.8 (2)
109.7
109.7
109.7
109.7
108.2
122.8 (2)
124.3 (2)
N1—C1—H1A
C2—C1—H1A
N1—C1—H1B
C2—C1—H1B
H1A—C1—H1B
C1—C2—C7
C1—C2—H2A
C7—C2—H2A
C1—C2—H2B
C7—C2—H2B
H2A—C2—H2B
N1—C3—C4
N1—C3—H3A
C4—C3—H3A
N1—C3—H3B
C4—C3—H3B
H3A—C3—H3B
C3—C4—C7
H9A—C9—H9B
C11—C10—C14
C11—C10—H10A
C14—C10—H10A
C11—C10—H10B
C14—C10—H10B
H10A—C10—H10B
N4—C11—C10
N4—C11—H11A
C10—C11—H11A
N4—C11—H11B
C10—C11—H11B
H11A—C11—H11B
N3—C12—C14
N3—C12—C13
Acta Cryst. (2019). C75, 728-733
sup-9

supporting information
C3—C4—H4A
C7—C4—H4A
C3—C4—H4B
C7—C4—H4B
H4A—C4—H4B
N1—C5—C6
N1—C5—H5A
C6—C5—H5A
N1—C5—H5B
C6—C5—H5B
H5A—C5—H5B
N2—C6—C5
109.7
109.7
109.7
109.7
108.2
108.1 (2)
110.1
110.1
110.1
C14—C12—C13
N4—C13—C12
N4—C13—H13A
C12—C13—H13A
N4—C13—H13B
C12—C13—H13B
H13A—C13—H13B
C12—C14—C8
C12—C14—C10
C8—C14—C10
C12—C14—H14A
C8—C14—H14A
C10—C14—H14A
C5—N1—C1
112.83 (19)
108.2 (2)
110.1
110.1
110.1
110.1
108.4
106.5 (2)
107.9 (2)
108.7 (2)
111.2
111.2
111.2
110.5 (2)
109.6 (2)
109.8 (2)
109.0
109.0
109.0
109.8 (2)
110.5 (2)
109.4 (2)
109.0
110.1
108.4
124.7 (2)
122.5 (2)
112.7 (2)
106.5 (2)
107.8 (2)
109.6 (2)
110.9
110.9
110.9
109.8 (2)
109.7
109.7
N2—C6—C7
C5—C6—C7
C6—C7—C4
C6—C7—C2
C5—N1—C3
C1—N1—C3
C4—C7—C2
C5—N1—H1C
C1—N1—H1C
C3—N1—H1C
C13—N4—C9
C13—N4—C11
C9—N4—C11
C13—N4—H4C
C9—N4—H4C
C11—N4—H4C
C6—N2—N3
C6—C7—H7A
C4—C7—H7A
C2—C7—H7A
C9—C8—C14
C9—C8—H8A
C14—C8—H8A
C9—C8—H8B
C14—C8—H8B
H8A—C8—H8B
N4—C9—C8
109.7
109.7
108.2
110.1 (2)
109.0
109.0
111.9 (2)
112.7 (2)
C12—N3—N2
Acta Cryst. (2019). C75, 728-733
sup-10