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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
ꢄ
Acta Cryst. (2019). C75, 728–733
Qiao et al.
Three new quinuclidine-based structures 729