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

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.

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	F(000) = 344
Mr = 157.22	Dx = 1.237 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.2687 (6) Å	Cell parameters from 3399 reflections
b = 8.3690 (5) Å	θ = 3.0–30.3°
c = 8.9974 (5) Å	µ = 0.09 mm^−1
β = 95.724 (5)°	T = 200 K
V = 844.29 (8) Å^3	Bar, colorless
Z = 4	0.38 × 0.26 × 0.20 mm

Data collection

XtaLAB Synergy R, DW system, HyPix diffractometer	1640 reflections with I > 2σ(I)
Radiation source: Rotating-anode X-ray tube	Rint = 0.027
ω scans	θmax = 30.7°, θmin = 3.0°
Absorption correction: multi-scan (North et al., 1968)	h = −16→12
Tmin = 0.974, Tmax = 0.983	k = −12→9
8118 measured reflections	l = −12→11
2616 independent reflections

Refinement

Refinement on F^2	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F^2 > 2σ(F^2)] = 0.039	w = 1/[σ^2(Fo^2) + (0.0396P)^2 + 0.2373P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.097	(Δ/σ)max < 0.001
S = 1.05	Δρmax = 0.27 e Å^−3
2616 reflections	Δρmin = −0.16 e Å^−3
116 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2015b)
0 restraints	Extinction coefficient: 0.012 (3)

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 (Ų)

	x	y	z	Uiso*/Ueq
H2	0.5044 (16)	0.275 (2)	0.345 (2)	0.057 (5)*
H1	0.3994 (16)	0.275 (2)	0.4087 (19)	0.048 (5)*
H3A	0.4201 (14)	0.838 (2)	0.3883 (19)	0.040 (4)*
H3B	0.3984 (13)	0.994 (2)	0.3108 (17)	0.040 (4)*
C7	0.24509 (12)	0.36947 (17)	0.18145 (15)	0.0354 (3)
H7A	0.2078	0.2649	0.1747	0.042*
H7B	0.3218	0.3610	0.1419	0.042*
C6	0.14730 (11)	0.43570 (17)	0.39880 (15)	0.0331 (3)
H6A	0.1599	0.4674	0.5029	0.040*
H6B	0.1067	0.3334	0.3940	0.040*
C4	0.16618 (12)	0.48901 (17)	0.08594 (14)	0.0328 (3)
H4A	0.2082	0.5280	0.0042	0.039*
H4B	0.0934	0.4370	0.0442	0.039*
C5	0.06742 (11)	0.56098 (16)	0.31129 (15)	0.0318 (3)
H5A	−0.0061	0.5115	0.2686	0.038*
H5B	0.0475	0.6460	0.3777	0.038*
C3	0.13621 (10)	0.62896 (15)	0.18676 (13)	0.0265 (3)
H3	0.0893	0.7108	0.1293	0.032*
C2	0.25161 (10)	0.69677 (14)	0.25798 (12)	0.0227 (2)
C1	0.32424 (10)	0.57396 (14)	0.34956 (13)	0.0237 (3)
H1A	0.4022	0.5643	0.3135	0.028*
H1B	0.3353	0.6081	0.4530	0.028*
N3	0.39511 (10)	0.88691 (14)	0.30080 (13)	0.0291 (2)
N1	0.26369 (9)	0.41798 (12)	0.33943 (11)	0.0242 (2)
O1	0.46566 (9)	0.22272 (11)	0.40879 (11)	0.0315 (2)
N2	0.28043 (9)	0.84209 (12)	0.23735 (11)	0.0270 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C7	0.0380 (7)	0.0352 (8)	0.0314 (7)	0.0067 (5)	−0.0044 (5)	−0.0114 (5)
C6	0.0278 (7)	0.0388 (7)	0.0335 (7)	−0.0056 (5)	0.0066 (5)	0.0084 (5)
C4	0.0320 (7)	0.0428 (8)	0.0225 (6)	−0.0009 (5)	−0.0029 (5)	−0.0042 (5)
C5	0.0211 (6)	0.0397 (8)	0.0351 (7)	−0.0011 (5)	0.0053 (5)	0.0004 (5)
C3	0.0213 (6)	0.0317 (7)	0.0256 (6)	0.0030 (4)	−0.0018 (4)	0.0030 (5)
C2	0.0225 (6)	0.0261 (6)	0.0199 (6)	0.0016 (4)	0.0040 (4)	0.0011 (4)
C1	0.0208 (6)	0.0246 (6)	0.0249 (6)	−0.0024 (4)	−0.0011 (4)	0.0020 (4)
N3	0.0306 (6)	0.0242 (6)	0.0327 (6)	−0.0046 (4)	0.0046 (4)	0.0007 (4)
N1	0.0227 (5)	0.0245 (5)	0.0247 (5)	−0.0021 (4)	−0.0007 (4)	0.0002 (4)
O1	0.0310 (5)	0.0271 (5)	0.0360 (5)	0.0035 (4)	0.0020 (4)	0.0067 (4)
N2	0.0279 (5)	0.0275 (6)	0.0260 (5)	0.0010 (4)	0.0045 (4)	0.0026 (4)

Geometric parameters (Å, º)

C7—N1	1.4730 (16)	C5—H5B	0.9700
C7—C4	1.5419 (18)	C3—C2	1.5025 (16)
C7—H7A	0.9700	C3—H3	0.9800
C7—H7B	0.9700	C2—N2	1.2771 (16)
C6—N1	1.4722 (16)	C2—C1	1.5068 (16)
C6—C5	1.5453 (18)	C1—N1	1.4716 (15)
C6—H6A	0.9700	C1—H1A	0.9700
C6—H6B	0.9700	C1—H1B	0.9700
C4—C3	1.5394 (18)	N3—N2	1.4106 (15)
C4—H4A	0.9700	N3—H3A	0.908 (17)
C4—H4B	0.9700	N3—H3B	0.898 (17)
C5—C3	1.5341 (17)	O1—H2	0.87 (2)
C5—H5A	0.9700	O1—H1	0.864 (18)
N1—C7—C4	112.18 (10)	C2—C3—C5	107.91 (10)
N1—C7—H7A	109.2	C2—C3—C4	107.89 (9)
C4—C7—H7A	109.2	C5—C3—C4	107.74 (10)
N1—C7—H7B	109.2	C2—C3—H3	111.0
C4—C7—H7B	109.2	C5—C3—H3	111.0
H7A—C7—H7B	107.9	C4—C3—H3	111.0
N1—C6—C5	112.22 (10)	N2—C2—C3	121.30 (11)
N1—C6—H6A	109.2	N2—C2—C1	126.65 (11)
C5—C6—H6A	109.2	C3—C2—C1	112.05 (10)
N1—C6—H6B	109.2	N1—C1—C2	110.36 (9)
C5—C6—H6B	109.2	N1—C1—H1A	109.6
H6A—C6—H6B	107.9	C2—C1—H1A	109.6
C3—C4—C7	108.27 (10)	N1—C1—H1B	109.6
C3—C4—H4A	110.0	C2—C1—H1B	109.6
C7—C4—H4A	110.0	H1A—C1—H1B	108.1
C3—C4—H4B	110.0	N2—N3—H3A	115.0 (10)
C7—C4—H4B	110.0	N2—N3—H3B	109.4 (10)
H4A—C4—H4B	108.4	H3A—N3—H3B	110.9 (14)
C3—C5—C6	108.22 (10)	C1—N1—C6	108.21 (9)
C3—C5—H5A	110.1	C1—N1—C7	108.95 (10)
C6—C5—H5A	110.1	C6—N1—C7	109.37 (10)
C3—C5—H5B	110.1	H2—O1—H1	103.7 (16)
C6—C5—H5B	110.1	C2—N2—N3	115.49 (10)
H5A—C5—H5B	108.4
N1—C7—C4—C3	2.85 (15)	N2—C2—C1—N1	−176.92 (11)
N1—C6—C5—C3	0.10 (15)	C3—C2—C1—N1	2.16 (13)
C6—C5—C3—C2	−56.98 (13)	C2—C1—N1—C6	−60.83 (12)
C6—C5—C3—C4	59.28 (13)	C2—C1—N1—C7	58.00 (12)
C7—C4—C3—C2	55.23 (13)	C5—C6—N1—C1	59.56 (13)
C7—C4—C3—C5	−61.04 (13)	C5—C6—N1—C7	−59.00 (14)
C5—C3—C2—N2	−123.94 (12)	C4—C7—N1—C1	−60.92 (13)
C4—C3—C2—N2	119.90 (12)	C4—C7—N1—C6	57.18 (14)
C5—C3—C2—C1	56.93 (13)	C3—C2—N2—N3	−175.16 (10)
C4—C3—C2—C1	−59.23 (12)	C1—C2—N2—N3	3.84 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	0.864 (18)	1.994 (19)	2.8207 (13)	159.9 (16)
O1—H2···N3^i	0.874 (2)	2.042 (2)	2.915 (2)	176.05 (2)
N3—H3A···O1^ii	0.908 (17)	2.186 (17)	3.0517 (15)	159.3 (14)
N3—H3B···O1^iii	0.898 (17)	2.212 (17)	3.0529 (15)	155.6 (13)

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	Dx = 1.258 Mg m^−3
Mr = 246.36	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pccn	Cell parameters from 2940 reflections
a = 19.7143 (13) Å	θ = 3.2–30.6°
b = 6.6047 (4) Å	µ = 0.08 mm^−1
c = 9.9924 (6) Å	T = 288 K
V = 1301.08 (14) Å^3	Bar, colorless
Z = 4	0.35 × 0.25 × 0.2 mm
F(000) = 536

Data collection

XtaLAB Synergy R, DW system, HyPix diffractometer	1216 reflections with I > 2σ(I)
Radiation source: Rotating-anode X-ray tube	Rint = 0.026
ω scans	θmax = 30.7°, θmin = 3.3°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2018)	h = −28→23
Tmin = 0.977, Tmax = 0.985	k = −7→9
6797 measured reflections	l = −11→14
2033 independent reflections

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.041	H-atom parameters constrained
wR(F^2) = 0.112	w = 1/[σ^2(Fo^2) + (0.0482P)^2 + 0.2267P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
2033 reflections	Δρmax = 0.18 e Å^−3
82 parameters	Δρmin = −0.16 e Å^−3

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 (Ų)

	x	y	z	Uiso*/Ueq
N1	0.58882 (5)	0.18453 (15)	0.29148 (11)	0.0438 (3)
N2	0.73834 (5)	0.14848 (15)	0.07517 (10)	0.0431 (3)
C1	0.65099 (6)	0.27017 (19)	0.23467 (13)	0.0416 (3)
H1A	0.6811	0.3114	0.3064	0.050*
H1B	0.6399	0.3892	0.1822	0.050*
C2	0.68635 (6)	0.11736 (17)	0.14723 (11)	0.0363 (3)
C3	0.65173 (6)	−0.08475 (18)	0.15064 (13)	0.0420 (3)
H3	0.6763	−0.1850	0.0970	0.050*
C4	0.64643 (8)	−0.1510 (2)	0.29696 (15)	0.0524 (4)
H4A	0.6227	−0.2793	0.3028	0.063*
H4B	0.6914	−0.1682	0.3345	0.063*
C5	0.57970 (7)	−0.0515 (2)	0.09707 (14)	0.0498 (4)
H5A	0.5814	−0.0097	0.0041	0.060*
H5B	0.5540	−0.1764	0.1026	0.060*
C6	0.54573 (7)	0.1127 (2)	0.18161 (15)	0.0535 (4)
H6A	0.5342	0.2263	0.1244	0.064*
H6B	0.5039	0.0594	0.2185	0.064*
C7	0.60774 (7)	0.0112 (2)	0.37512 (13)	0.0509 (4)
H7A	0.5670	−0.0483	0.4128	0.061*
H7B	0.6357	0.0582	0.4487	0.061*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0405 (6)	0.0480 (6)	0.0428 (6)	0.0003 (4)	0.0046 (5)	−0.0086 (5)
N2	0.0359 (6)	0.0513 (6)	0.0420 (6)	−0.0056 (4)	0.0000 (4)	−0.0048 (5)
C1	0.0450 (7)	0.0392 (6)	0.0407 (7)	−0.0025 (5)	0.0029 (6)	−0.0052 (5)
C2	0.0344 (6)	0.0419 (6)	0.0326 (6)	−0.0019 (5)	−0.0029 (5)	−0.0044 (5)
C3	0.0397 (7)	0.0411 (6)	0.0452 (7)	−0.0032 (5)	0.0052 (5)	−0.0112 (5)
C4	0.0537 (8)	0.0466 (7)	0.0569 (9)	0.0003 (6)	−0.0019 (7)	0.0061 (6)
C5	0.0435 (8)	0.0616 (8)	0.0443 (7)	−0.0109 (6)	−0.0030 (6)	−0.0129 (6)
C6	0.0375 (7)	0.0637 (9)	0.0593 (9)	0.0055 (6)	−0.0071 (6)	−0.0082 (7)
C7	0.0587 (9)	0.0569 (8)	0.0369 (7)	−0.0109 (6)	0.0026 (6)	0.0003 (6)

Geometric parameters (Å, º)

N1—C1	1.4643 (15)	C3—H3	0.9800
N1—C7	1.4656 (17)	C4—C7	1.5294 (19)
N1—C6	1.4670 (17)	C4—H4A	0.9700
N2—C2	1.2693 (16)	C4—H4B	0.9700
N2—N2^i	1.418 (2)	C5—C6	1.5291 (19)
C1—C2	1.5060 (16)	C5—H5A	0.9700
C1—H1A	0.9700	C5—H5B	0.9700
C1—H1B	0.9700	C6—H6A	0.9700
C2—C3	1.4996 (16)	C6—H6B	0.9700
C3—C4	1.5296 (19)	C7—H7A	0.9700
C3—C5	1.5335 (18)	C7—H7B	0.9700
C1—N1—C7	108.05 (10)	C7—C4—H4B	109.9
C1—N1—C6	108.64 (10)	C3—C4—H4B	109.9
C7—N1—C6	108.75 (10)	H4A—C4—H4B	108.3
C2—N2—N2^i	114.53 (11)	C6—C5—C3	108.32 (10)
N1—C1—C2	110.70 (10)	C6—C5—H5A	110.0
N1—C1—H1A	109.5	C3—C5—H5A	110.0
C2—C1—H1A	109.5	C6—C5—H5B	110.0
N1—C1—H1B	109.5	C3—C5—H5B	110.0
C2—C1—H1B	109.5	H5A—C5—H5B	108.4
H1A—C1—H1B	108.1	N1—C6—C5	112.91 (11)
N2—C2—C3	121.63 (11)	N1—C6—H6A	109.0
N2—C2—C1	126.47 (11)	C5—C6—H6A	109.0
C3—C2—C1	111.88 (10)	N1—C6—H6B	109.0
C2—C3—C4	107.90 (10)	C5—C6—H6B	109.0
C2—C3—C5	106.63 (11)	H6A—C6—H6B	107.8
C4—C3—C5	108.14 (11)	N1—C7—C4	112.50 (10)
C2—C3—H3	111.3	N1—C7—H7A	109.1
C4—C3—H3	111.3	C4—C7—H7A	109.1
C5—C3—H3	111.3	N1—C7—H7B	109.1
C7—C4—C3	108.79 (11)	C4—C7—H7B	109.1
C7—C4—H4A	109.9	H7A—C7—H7B	107.8
C3—C4—H4A	109.9

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

C14H24N4^2+·2Cl^−	F(000) = 340
Mr = 319.27	Dx = 1.321 Mg m^−3
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
a = 6.1699 (3) Å	Cell parameters from 2739 reflections
b = 12.5258 (7) Å	θ = 3.3–28.9°
c = 10.6570 (5) Å	µ = 0.40 mm^−1
β = 103.023 (5)°	T = 293 K
V = 802.42 (7) Å^3	Bar, colorless
Z = 2	0.3 × 0.25 × 0.2 mm

Data collection

XtaLAB Synergy R, DW system, HyPix diffractometer	2820 reflections with I > 2σ(I)
Radiation source: Rotating-anode X-ray tube	Rint = 0.019
ω scans	θmax = 30.6°, θmin = 2.6°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −7→8
Tmin = 0.887, Tmax = 0.923	k = −17→13
5076 measured reflections	l = −14→15
4949 independent reflections

Refinement

Refinement on F^2	H-atom parameters constrained
Least-squares matrix: full	w = 1/[σ^2(Fo^2) + (0.0517P)^2] where P = (Fo^2 + 2Fc^2)/3
R[F^2 > 2σ(F^2)] = 0.038	(Δ/σ)max < 0.001
wR(F^2) = 0.097	Δρmax = 0.28 e Å^−3
S = 1.00	Δρmin = −0.17 e Å^−3
4949 reflections	Extinction correction: SHELXL2014 (Sheldrick, 2015b), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
182 parameters	Extinction coefficient: 0.012 (3)
2 restraints	Absolute structure: Flack x determined using 986 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013)
Hydrogen site location: inferred from neighbouring sites	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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.8805 (5)	0.8659 (2)	1.0231 (3)	0.0406 (7)
H1A	0.8086	0.8278	1.0817	0.049*
H1B	0.9687	0.9231	1.0706	0.049*
C2	1.0310 (4)	0.7901 (3)	0.9705 (2)	0.0418 (7)
H2A	1.0183	0.7186	1.0031	0.050*
H2B	1.1847	0.8128	0.9985	0.050*
C3	0.8185 (5)	0.9758 (2)	0.8280 (3)	0.0435 (7)
H3A	0.9037	1.0336	0.8760	0.052*
H3B	0.7064	1.0066	0.7588	0.052*
C4	0.9719 (4)	0.9037 (3)	0.7722 (3)	0.0448 (7)
H4A	1.1231	0.9305	0.7964	0.054*
H4B	0.9262	0.9038	0.6789	0.054*
C5	0.5723 (4)	0.8252 (2)	0.8403 (2)	0.0347 (6)
H5A	0.4583	0.8556	0.7719	0.042*
H5B	0.5001	0.7837	0.8960	0.042*
C6	0.7243 (4)	0.7553 (2)	0.7845 (2)	0.0289 (5)
C7	0.9630 (4)	0.7898 (2)	0.8229 (2)	0.0332 (6)
H7A	1.0586	0.7419	0.7865	0.040*
C8	0.0225 (4)	0.7195 (2)	0.4151 (3)	0.0416 (7)
H8A	−0.1350	0.7125	0.3767	0.050*
H8B	0.0465	0.7882	0.4581	0.050*
C9	0.1537 (5)	0.7139 (3)	0.3112 (3)	0.0539 (9)
H9A	0.0527	0.7047	0.2279	0.065*
H9B	0.2347	0.7800	0.3095	0.065*
C10	0.0605 (4)	0.5227 (2)	0.4428 (3)	0.0413 (7)
H10A	0.1124	0.4652	0.5030	0.050*
H10B	−0.0969	0.5120	0.4066	0.050*
C11	0.1869 (5)	0.5209 (3)	0.3358 (3)	0.0561 (9)
H11A	0.2893	0.4610	0.3483	0.067*
H11B	0.0833	0.5120	0.2533	0.067*
C12	0.3415 (4)	0.6441 (2)	0.5650 (2)	0.0290 (6)
C13	0.4718 (4)	0.6380 (3)	0.4621 (2)	0.0421 (7)
H13A	0.5560	0.7032	0.4609	0.051*
H13B	0.5755	0.5787	0.4790	0.051*
C14	0.0964 (4)	0.6299 (2)	0.5133 (2)	0.0310 (6)
H14A	0.0155	0.6329	0.5825	0.037*
N1	0.7083 (3)	0.91179 (18)	0.9153 (2)	0.0331 (5)
H1C	0.6105	0.9588	0.9511	0.040*
N4	0.3130 (3)	0.6228 (2)	0.33635 (19)	0.0408 (6)
H4C	0.3959	0.6201	0.2681	0.049*
N2	0.6605 (3)	0.67783 (19)	0.70772 (19)	0.0336 (5)
N3	0.4259 (3)	0.66326 (18)	0.68247 (19)	0.0329 (5)
Cl1	0.57596 (10)	0.63584 (7)	0.12698 (7)	0.05067 (19)
Cl2	0.39849 (11)	0.05252 (7)	0.02162 (8)	0.0565 (2)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0421 (13)	0.0470 (17)	0.0306 (12)	0.0046 (13)	0.0036 (10)	−0.0034 (12)
C2	0.0383 (13)	0.0460 (18)	0.0362 (13)	0.0112 (12)	−0.0020 (11)	−0.0062 (12)
C3	0.0434 (14)	0.0315 (15)	0.0535 (15)	−0.0041 (12)	0.0065 (12)	0.0052 (13)
C4	0.0400 (14)	0.0500 (18)	0.0471 (14)	−0.0119 (12)	0.0155 (11)	−0.0021 (13)
C5	0.0276 (11)	0.0365 (14)	0.0401 (12)	−0.0016 (10)	0.0077 (9)	−0.0059 (11)
C6	0.0308 (11)	0.0319 (13)	0.0238 (9)	0.0017 (10)	0.0054 (8)	0.0012 (10)
C7	0.0250 (11)	0.0392 (14)	0.0346 (11)	−0.0003 (10)	0.0049 (9)	−0.0104 (10)
C8	0.0325 (12)	0.0429 (17)	0.0473 (14)	0.0025 (11)	0.0050 (11)	0.0019 (13)
C9	0.0484 (15)	0.070 (2)	0.0439 (14)	0.0022 (14)	0.0123 (12)	0.0215 (14)
C10	0.0423 (14)	0.0378 (16)	0.0424 (13)	−0.0092 (12)	0.0069 (11)	−0.0051 (13)
C11	0.0610 (17)	0.058 (2)	0.0529 (15)	−0.0045 (15)	0.0201 (13)	−0.0237 (14)
C12	0.0316 (11)	0.0280 (13)	0.0286 (10)	−0.0022 (9)	0.0095 (9)	−0.0016 (9)
C13	0.0295 (12)	0.069 (2)	0.0278 (11)	0.0014 (12)	0.0066 (10)	−0.0017 (12)
C14	0.0282 (11)	0.0377 (15)	0.0283 (11)	−0.0048 (10)	0.0091 (9)	−0.0034 (10)
N1	0.0347 (10)	0.0277 (11)	0.0368 (10)	0.0020 (9)	0.0081 (8)	−0.0063 (9)
N4	0.0351 (10)	0.0651 (16)	0.0244 (9)	−0.0006 (10)	0.0116 (8)	−0.0037 (10)
N2	0.0297 (10)	0.0379 (13)	0.0330 (10)	−0.0034 (9)	0.0064 (8)	−0.0038 (9)
N3	0.0323 (9)	0.0351 (12)	0.0316 (9)	−0.0069 (9)	0.0081 (8)	−0.0034 (9)
Cl1	0.0489 (3)	0.0668 (5)	0.0401 (3)	−0.0099 (3)	0.0179 (2)	0.0007 (3)
Cl2	0.0476 (3)	0.0573 (4)	0.0599 (4)	0.0158 (3)	0.0020 (3)	−0.0226 (4)

Geometric parameters (Å, º)

C1—N1	1.493 (3)	C8—H8A	0.9700
C1—C2	1.521 (4)	C8—H8B	0.9700
C1—H1A	0.9700	C9—N4	1.490 (4)
C1—H1B	0.9700	C9—H9A	0.9700
C2—C7	1.534 (3)	C9—H9B	0.9700
C2—H2A	0.9700	C10—C11	1.519 (4)
C2—H2B	0.9700	C10—C14	1.530 (4)
C3—N1	1.502 (4)	C10—H10A	0.9700
C3—C4	1.522 (4)	C10—H10B	0.9700
C3—H3A	0.9700	C11—N4	1.494 (4)
C3—H3B	0.9700	C11—H11A	0.9700
C4—C7	1.532 (4)	C11—H11B	0.9700
C4—H4A	0.9700	C12—N3	1.266 (3)
C4—H4B	0.9700	C12—C14	1.499 (3)
C5—N1	1.488 (3)	C12—C13	1.500 (3)
C5—C6	1.501 (4)	C13—N4	1.484 (3)
C5—H5A	0.9700	C13—H13A	0.9700
C5—H5B	0.9700	C13—H13B	0.9700
C6—N2	1.273 (3)	C14—H14A	0.9800
C6—C7	1.501 (3)	N1—H1C	0.9800
C7—H7A	0.9800	N4—H4C	0.9800
C8—C9	1.514 (4)	N2—N3	1.423 (3)
C8—C14	1.532 (4)
N1—C1—C2	110.2 (2)	N4—C9—H9A	109.6
N1—C1—H1A	109.6	C8—C9—H9A	109.6
C2—C1—H1A	109.6	N4—C9—H9B	109.6
N1—C1—H1B	109.6	C8—C9—H9B	109.6
C2—C1—H1B	109.6	H9A—C9—H9B	108.2
H1A—C1—H1B	108.1	C11—C10—C14	109.8 (2)
C1—C2—C7	109.3 (2)	C11—C10—H10A	109.7
C1—C2—H2A	109.8	C14—C10—H10A	109.7
C7—C2—H2A	109.8	C11—C10—H10B	109.7
C1—C2—H2B	109.8	C14—C10—H10B	109.7
C7—C2—H2B	109.8	H10A—C10—H10B	108.2
H2A—C2—H2B	108.3	N4—C11—C10	109.8 (2)
N1—C3—C4	109.5 (2)	N4—C11—H11A	109.7
N1—C3—H3A	109.8	C10—C11—H11A	109.7
C4—C3—H3A	109.8	N4—C11—H11B	109.7
N1—C3—H3B	109.8	C10—C11—H11B	109.7
C4—C3—H3B	109.8	H11A—C11—H11B	108.2
H3A—C3—H3B	108.2	N3—C12—C14	122.8 (2)
C3—C4—C7	109.9 (2)	N3—C12—C13	124.3 (2)
C3—C4—H4A	109.7	C14—C12—C13	112.83 (19)
C7—C4—H4A	109.7	N4—C13—C12	108.2 (2)
C3—C4—H4B	109.7	N4—C13—H13A	110.1
C7—C4—H4B	109.7	C12—C13—H13A	110.1
H4A—C4—H4B	108.2	N4—C13—H13B	110.1
N1—C5—C6	108.1 (2)	C12—C13—H13B	110.1
N1—C5—H5A	110.1	H13A—C13—H13B	108.4
C6—C5—H5A	110.1	C12—C14—C8	106.5 (2)
N1—C5—H5B	110.1	C12—C14—C10	107.9 (2)
C6—C5—H5B	110.1	C8—C14—C10	108.7 (2)
H5A—C5—H5B	108.4	C12—C14—H14A	111.2
N2—C6—C5	124.7 (2)	C8—C14—H14A	111.2
N2—C6—C7	122.5 (2)	C10—C14—H14A	111.2
C5—C6—C7	112.7 (2)	C5—N1—C1	110.5 (2)
C6—C7—C4	106.5 (2)	C5—N1—C3	109.6 (2)
C6—C7—C2	107.8 (2)	C1—N1—C3	109.8 (2)
C4—C7—C2	109.6 (2)	C5—N1—H1C	109.0
C6—C7—H7A	110.9	C1—N1—H1C	109.0
C4—C7—H7A	110.9	C3—N1—H1C	109.0
C2—C7—H7A	110.9	C13—N4—C9	109.8 (2)
C9—C8—C14	109.8 (2)	C13—N4—C11	110.5 (2)
C9—C8—H8A	109.7	C9—N4—C11	109.4 (2)
C14—C8—H8A	109.7	C13—N4—H4C	109.0
C9—C8—H8B	109.7	C9—N4—H4C	109.0
C14—C8—H8B	109.7	C11—N4—H4C	109.0
H8A—C8—H8B	108.2	C6—N2—N3	111.9 (2)
N4—C9—C8	110.1 (2)	C12—N3—N2	112.7 (2)