Synthesis, crystal structures and anti-inflammatory activity of fluorine-substituted 1,4,5,6-tetra­hydro­benzo[h]quinazolin-2-amine derivatives

Two fluorine-substituted 1,4,5,6-tetra­hydro­benzo[h]quinazolin-2-amine (BQA) derivatives, namely 2-amino-4-(2-fluoro­phen­yl)-9-meth­oxy-1,4,5,6-tetra­hydro­benzo[h]quinazolin-3-ium chloride, (8), and 2-amino-4-(4-fluoro­phen­yl)-9-meth­oxy-1,4,5,6-tetra­hydro­benzo[h]quinazolin-3-ium chloride, (9), both C₁₉H₁₉FN₃O⁺·Cl⁻, were generated by Michael addition reactions between guanidine hydro­chloride and the α,β-unsaturated ketones (E)-2-(2-fluoro­benzyl­idene)-7-meth­oxy-3,4-di­hydro­naphthalen-1(2H)-one, C₁₈H₁₅FO₂, (6), and (E)-2-(4-fluoro­benzyl­idene)-7-meth­oxy-3,4-di­hydro­naphthalen-1(2H)-one, (7). Because both sides of α,β-unsaturated ketones (6) or (7) can be attacked by guanidine, we obtained a pair of isomers in (8) and (9). Single-crystal X-ray diffraction indicates that each isomer has a chiral C atom and both (8) and (9) crystallize in the achiral space group P2₁/c. The chloride ion, as a hydrogen-bond acceptor, plays an important role in the formation of multiple hydrogen bonds. Thus, adjacent mol­ecules are connected through inter­molecular hydrogen bonds to generate a banded structure. Furthermore, these bands are linked into an inter­esting 3D network via hydrogen bonds and π–π inter­actions. Fortunately, the solubilities of (8) and (9) were distinctly improved and can exceed 50 mg ml⁻¹ in water or PBS buffer system (pH 7.4) at room temperature. In addition, the results of an investigation of anti-inflammatory activity show that (8) and (9), with o- and p-fluoro substituents, respectively, display more potential for inhibitory effects on LPS-induced NO secretion than starting ketones (6) and (7).

Computing details

For all structures, data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015). Program(s) used to solve structure: SHELXS97 (Sheldrick, 2008) for 2-F; SHELXT2017 (Sheldrick, 2015a) for (2F), 4HF. For all structures, program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

(E)-2-(2-Fluorobenzylidene)-7-methoxy-3,4-dihydronaphthalen-1(2H)-one (2-F)

Crystal data

C18H15FO2	Z = 2
Mr = 282.30	F(000) = 296
Triclinic, P1	Dx = 1.407 Mg m^−3
a = 7.3336 (6) Å	Mo Kα radiation, λ = 0.71073 Å
b = 7.9301 (7) Å	Cell parameters from 3078 reflections
c = 12.5780 (12) Å	θ = 2.9–28.8°
α = 107.140 (8)°	µ = 0.10 mm^−1
β = 104.982 (7)°	T = 100 K
γ = 94.285 (7)°	Block, colourless
V = 666.16 (11) Å^3	0.14 × 0.13 × 0.11 mm

Data collection

Rigaku OD SuperNova Dual source diffractometer with an AtlasS2 detector	2483 independent reflections
Radiation source: micro-focus sealed X-ray tube	2111 reflections with I > 2σ(I)
Detector resolution: 5.2684 pixels mm^-1	Rint = 0.027
CCD plate scans	θmax = 25.5°, θmin = 2.7°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −8→8
Tmin = 0.434, Tmax = 1.000	k = −9→9
4966 measured reflections	l = −12→15

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.105	w = 1/[σ^2(Fo^2) + (0.046P)^2 + 0.1085P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
2483 reflections	Δρmax = 0.20 e Å^−3
191 parameters	Δρmin = −0.26 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
C1	0.7219 (2)	0.36064 (18)	0.51141 (12)	0.0160 (3)
H1	0.771228	0.397728	0.459412	0.019*
C2	0.8376 (2)	0.38741 (18)	0.62270 (12)	0.0159 (3)
C3	0.7621 (2)	0.3348 (2)	0.70103 (13)	0.0190 (3)
H3	0.838697	0.353096	0.776307	0.023*
C4	0.5723 (2)	0.25518 (19)	0.66611 (13)	0.0193 (3)
H4	0.522910	0.221566	0.719243	0.023*
C5	0.2523 (2)	0.12430 (19)	0.51545 (12)	0.0177 (3)
H5A	0.198841	0.156389	0.580286	0.021*
H5B	0.255855	−0.003073	0.494067	0.021*
C6	0.1213 (2)	0.1631 (2)	0.41247 (12)	0.0177 (3)
H6A	0.003819	0.077116	0.381316	0.021*
H6B	0.088339	0.281330	0.439371	0.021*
C7	0.2127 (2)	0.15410 (19)	0.31732 (12)	0.0166 (3)
C8	0.4169 (2)	0.24318 (19)	0.35363 (12)	0.0172 (3)
C9	0.5314 (2)	0.27827 (18)	0.47650 (12)	0.0149 (3)
C10	0.4534 (2)	0.22389 (18)	0.55411 (12)	0.0164 (3)
C11	0.1335 (2)	0.0673 (2)	0.20364 (13)	0.0187 (3)
H11	0.209750	0.074230	0.155901	0.022*
C12	−0.0593 (2)	−0.0379 (2)	0.14472 (12)	0.0185 (3)
C13	−0.0863 (2)	−0.1965 (2)	0.05371 (13)	0.0223 (4)
C14	−0.2605 (2)	−0.3018 (2)	−0.00726 (13)	0.0284 (4)
H14	−0.270830	−0.407259	−0.067319	0.034*
C15	−0.4207 (2)	−0.2480 (2)	0.02229 (13)	0.0288 (4)
H15	−0.540278	−0.318152	−0.017339	0.035*
C16	−0.4029 (2)	−0.0899 (2)	0.11074 (13)	0.0249 (4)
H16	−0.511128	−0.052936	0.129795	0.030*
C17	−0.2249 (2)	0.0139 (2)	0.17129 (13)	0.0215 (4)
H17	−0.215211	0.120052	0.230704	0.026*
C18	1.1507 (2)	0.4830 (2)	0.75923 (13)	0.0237 (4)
H18A	1.107737	0.560376	0.819054	0.036*
H18B	1.277251	0.533148	0.764463	0.036*
H18C	1.152546	0.367514	0.769061	0.036*
F1	0.07165 (13)	−0.25142 (13)	0.02496 (8)	0.0327 (3)
O1	1.02370 (14)	0.46497 (13)	0.64784 (8)	0.0189 (3)
O2	0.48946 (15)	0.27890 (15)	0.28387 (9)	0.0244 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0173 (8)	0.0128 (7)	0.0207 (7)	0.0034 (6)	0.0092 (6)	0.0061 (6)
C2	0.0139 (7)	0.0124 (7)	0.0215 (7)	0.0020 (6)	0.0072 (6)	0.0040 (6)
C3	0.0192 (8)	0.0199 (8)	0.0172 (7)	0.0036 (6)	0.0042 (6)	0.0058 (6)
C4	0.0222 (8)	0.0188 (8)	0.0217 (8)	0.0039 (6)	0.0124 (6)	0.0082 (6)
C5	0.0182 (8)	0.0165 (7)	0.0221 (8)	0.0027 (6)	0.0118 (6)	0.0067 (6)
C6	0.0130 (7)	0.0180 (8)	0.0214 (8)	−0.0002 (6)	0.0069 (6)	0.0047 (6)
C7	0.0151 (8)	0.0155 (7)	0.0218 (8)	0.0037 (6)	0.0067 (6)	0.0084 (6)
C8	0.0173 (8)	0.0151 (7)	0.0218 (8)	0.0048 (6)	0.0090 (6)	0.0065 (6)
C9	0.0151 (7)	0.0118 (7)	0.0197 (7)	0.0044 (6)	0.0083 (6)	0.0046 (6)
C10	0.0159 (8)	0.0132 (7)	0.0222 (7)	0.0047 (6)	0.0091 (6)	0.0055 (6)
C11	0.0164 (8)	0.0210 (8)	0.0224 (8)	0.0043 (6)	0.0081 (6)	0.0102 (6)
C12	0.0175 (8)	0.0216 (8)	0.0187 (7)	0.0031 (6)	0.0049 (6)	0.0102 (6)
C13	0.0219 (9)	0.0285 (9)	0.0189 (8)	0.0049 (7)	0.0076 (6)	0.0097 (7)
C14	0.0316 (10)	0.0290 (9)	0.0177 (8)	−0.0037 (7)	0.0032 (7)	0.0032 (7)
C15	0.0200 (9)	0.0374 (10)	0.0237 (8)	−0.0072 (7)	−0.0020 (7)	0.0127 (8)
C16	0.0154 (8)	0.0357 (10)	0.0258 (8)	0.0038 (7)	0.0046 (7)	0.0146 (7)
C17	0.0197 (8)	0.0224 (8)	0.0235 (8)	0.0038 (6)	0.0052 (7)	0.0099 (7)
C18	0.0159 (8)	0.0309 (9)	0.0201 (8)	−0.0015 (7)	0.0011 (6)	0.0072 (7)
F1	0.0287 (6)	0.0381 (6)	0.0277 (5)	0.0066 (4)	0.0133 (4)	0.0010 (4)
O1	0.0128 (5)	0.0234 (6)	0.0196 (5)	−0.0010 (4)	0.0032 (4)	0.0079 (4)
O2	0.0188 (6)	0.0348 (7)	0.0208 (6)	−0.0032 (5)	0.0071 (5)	0.0112 (5)

Geometric parameters (Å, º)

C1—C2	1.381 (2)	C8—C9	1.487 (2)
C1—C9	1.396 (2)	C9—C10	1.402 (2)
C1—H1	0.9300	C11—C12	1.470 (2)
C2—O1	1.3704 (17)	C11—H11	0.9300
C2—C3	1.393 (2)	C12—C13	1.389 (2)
C3—C4	1.385 (2)	C12—C17	1.399 (2)
C3—H3	0.9300	C13—F1	1.3642 (18)
C4—C10	1.391 (2)	C13—C14	1.369 (2)
C4—H4	0.9300	C14—C15	1.381 (2)
C5—C10	1.5048 (19)	C14—H14	0.9300
C5—C6	1.527 (2)	C15—C16	1.380 (2)
C5—H5A	0.9700	C15—H15	0.9300
C5—H5B	0.9700	C16—C17	1.385 (2)
C6—C7	1.5030 (19)	C16—H16	0.9300
C6—H6A	0.9700	C17—H17	0.9300
C6—H6B	0.9700	C18—O1	1.4277 (17)
C7—C11	1.337 (2)	C18—H18A	0.9600
C7—C8	1.499 (2)	C18—H18B	0.9600
C8—O2	1.2243 (17)	C18—H18C	0.9600
C2—C1—C9	120.41 (13)	C10—C9—C8	121.19 (13)
C2—C1—H1	119.8	C4—C10—C9	117.60 (13)
C9—C1—H1	119.8	C4—C10—C5	121.03 (13)
O1—C2—C1	116.13 (12)	C9—C10—C5	121.24 (13)
O1—C2—C3	124.25 (13)	C7—C11—C12	128.04 (14)
C1—C2—C3	119.62 (13)	C7—C11—H11	116.0
C4—C3—C2	119.58 (13)	C12—C11—H11	116.0
C4—C3—H3	120.2	C13—C12—C17	115.84 (14)
C2—C3—H3	120.2	C13—C12—C11	119.95 (14)
C3—C4—C10	122.07 (14)	C17—C12—C11	124.17 (13)
C3—C4—H4	119.0	F1—C13—C14	118.31 (14)
C10—C4—H4	119.0	F1—C13—C12	117.63 (13)
C10—C5—C6	113.30 (12)	C14—C13—C12	124.05 (15)
C10—C5—H5A	108.9	C13—C14—C15	118.61 (15)
C6—C5—H5A	108.9	C13—C14—H14	120.7
C10—C5—H5B	108.9	C15—C14—H14	120.7
C6—C5—H5B	108.9	C16—C15—C14	119.87 (15)
H5A—C5—H5B	107.7	C16—C15—H15	120.1
C7—C6—C5	112.34 (12)	C14—C15—H15	120.1
C7—C6—H6A	109.1	C15—C16—C17	120.38 (15)
C5—C6—H6A	109.1	C15—C16—H16	119.8
C7—C6—H6B	109.1	C17—C16—H16	119.8
C5—C6—H6B	109.1	C16—C17—C12	121.22 (14)
H6A—C6—H6B	107.9	C16—C17—H17	119.4
C11—C7—C8	116.35 (13)	C12—C17—H17	119.4
C11—C7—C6	126.58 (13)	O1—C18—H18A	109.5
C8—C7—C6	116.99 (12)	O1—C18—H18B	109.5
O2—C8—C9	121.03 (13)	H18A—C18—H18B	109.5
O2—C8—C7	121.45 (13)	O1—C18—H18C	109.5
C9—C8—C7	117.45 (12)	H18A—C18—H18C	109.5
C1—C9—C10	120.70 (13)	H18B—C18—H18C	109.5
C1—C9—C8	118.05 (13)	C2—O1—C18	117.62 (11)
C9—C1—C2—O1	178.32 (12)	C1—C9—C10—C5	−175.98 (13)
C9—C1—C2—C3	−1.2 (2)	C8—C9—C10—C5	1.4 (2)
O1—C2—C3—C4	−179.08 (13)	C6—C5—C10—C4	157.80 (13)
C1—C2—C3—C4	0.5 (2)	C6—C5—C10—C9	−26.33 (19)
C2—C3—C4—C10	0.6 (2)	C8—C7—C11—C12	176.97 (14)
C10—C5—C6—C7	46.60 (17)	C6—C7—C11—C12	0.4 (3)
C5—C6—C7—C11	132.15 (15)	C7—C11—C12—C13	−140.31 (16)
C5—C6—C7—C8	−44.41 (17)	C7—C11—C12—C17	42.1 (2)
C11—C7—C8—O2	20.0 (2)	C17—C12—C13—F1	179.87 (13)
C6—C7—C8—O2	−163.05 (14)	C11—C12—C13—F1	2.1 (2)
C11—C7—C8—C9	−156.89 (13)	C17—C12—C13—C14	−1.2 (2)
C6—C7—C8—C9	20.02 (18)	C11—C12—C13—C14	−179.02 (14)
C2—C1—C9—C10	1.0 (2)	F1—C13—C14—C15	179.26 (14)
C2—C1—C9—C8	−176.44 (12)	C12—C13—C14—C15	0.3 (2)
O2—C8—C9—C1	2.9 (2)	C13—C14—C15—C16	0.8 (2)
C7—C8—C9—C1	179.80 (12)	C14—C15—C16—C17	−1.0 (2)
O2—C8—C9—C10	−174.57 (13)	C15—C16—C17—C12	0.0 (2)
C7—C8—C9—C10	2.4 (2)	C13—C12—C17—C16	1.0 (2)
C3—C4—C10—C9	−0.8 (2)	C11—C12—C17—C16	178.71 (13)
C3—C4—C10—C5	175.18 (13)	C1—C2—O1—C18	−175.63 (12)
C1—C9—C10—C4	0.0 (2)	C3—C2—O1—C18	3.9 (2)
C8—C9—C10—C4	177.40 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18B···O2^i	0.96	2.49	3.3795 (19)	154
C1—H1···O1^i	0.93	2.63	3.5475 (18)	168

Symmetry code: (i) −x+2, −y+1, −z+1.

2-Amino-4-(2-fluorophenyl)-9-methoxy-1,4,5,6-tetrahydrobenzo[h]quinazolin-3-ium chloride (2F)

Crystal data

C19H19FN3O^+·Cl^−	F(000) = 1504
Mr = 359.82	Dx = 1.390 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.1415 (7) Å	Cell parameters from 6100 reflections
b = 11.7917 (4) Å	θ = 2.5–29.3°
c = 17.3364 (7) Å	µ = 0.25 mm^−1
β = 101.165 (4)°	T = 100 K
V = 3437.8 (2) Å^3	Block, colourless
Z = 8	0.12 × 0.11 × 0.10 mm

Data collection

Rigaku OD SuperNova Dual source diffractometer with an AtlasS2 detector	6394 independent reflections
Radiation source: micro-focus sealed X-ray tube	5203 reflections with I > 2σ(I)
Detector resolution: 5.2684 pixels mm^-1	Rint = 0.032
CCD plate scans	θmax = 25.5°, θmin = 2.1°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −20→15
Tmin = 0.920, Tmax = 1.000	k = −14→12
16601 measured reflections	l = −21→20

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.102	w = 1/[σ^2(Fo^2) + (0.0392P)^2 + 1.8116P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
6394 reflections	Δρmax = 0.60 e Å^−3
453 parameters	Δρmin = −0.28 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
C1	0.77318 (12)	0.68934 (17)	0.87615 (12)	0.0197 (5)
H1	0.822058	0.665648	0.866287	0.024*
C2	0.72156 (12)	0.61056 (17)	0.89837 (12)	0.0198 (5)
C3	0.64969 (13)	0.64515 (19)	0.91558 (12)	0.0236 (5)
H3	0.615754	0.593103	0.932339	0.028*
C4	0.62915 (13)	0.75944 (18)	0.90730 (12)	0.0232 (5)
H4	0.580599	0.782682	0.918238	0.028*
C5	0.65264 (13)	0.96060 (18)	0.86533 (13)	0.0252 (5)
H5A	0.613909	0.981150	0.896951	0.030*
H5B	0.626756	0.965871	0.810505	0.030*
C6	0.72072 (13)	1.04455 (18)	0.88095 (13)	0.0237 (5)
H6A	0.703336	1.116648	0.856616	0.028*
H6B	0.736690	1.056702	0.937131	0.028*
C7	0.79053 (12)	1.00131 (17)	0.84858 (11)	0.0175 (4)
C8	0.80470 (11)	0.89048 (17)	0.84464 (11)	0.0153 (4)
C9	0.75244 (12)	0.80355 (17)	0.86850 (11)	0.0163 (4)
C10	0.67840 (12)	0.83951 (17)	0.88340 (11)	0.0183 (5)
C11	0.84269 (12)	1.08906 (17)	0.82115 (12)	0.0188 (5)
H11	0.810265	1.131345	0.777813	0.023*
C12	0.92182 (12)	0.92333 (16)	0.79180 (11)	0.0152 (4)
C13	0.87880 (12)	1.17351 (17)	0.88404 (11)	0.0171 (4)
C14	0.88441 (13)	1.28725 (18)	0.86723 (12)	0.0205 (5)
C15	0.92037 (13)	1.36660 (18)	0.92082 (13)	0.0241 (5)
H15	0.922498	1.442551	0.906908	0.029*
C16	0.95314 (12)	1.33021 (19)	0.99574 (13)	0.0236 (5)
H16	0.978218	1.381891	1.032952	0.028*
C17	0.94881 (14)	1.21712 (19)	1.01567 (13)	0.0278 (5)
H17	0.970606	1.193086	1.066357	0.033*
C18	0.91214 (14)	1.13964 (18)	0.96039 (13)	0.0255 (5)
H18	0.909683	1.063769	0.974375	0.031*
C19	0.69762 (13)	0.41609 (18)	0.92465 (13)	0.0267 (5)
H19A	0.689195	0.433220	0.976552	0.040*
H19B	0.722416	0.343067	0.924789	0.040*
H19C	0.647455	0.415299	0.888629	0.040*
C1A	0.72808 (12)	0.87082 (16)	0.64295 (11)	0.0156 (4)
H1B	0.683683	0.892306	0.662887	0.019*
C2A	0.77900 (12)	0.95314 (16)	0.62342 (11)	0.0171 (4)
C3A	0.84551 (13)	0.92214 (17)	0.59422 (12)	0.0205 (5)
H3A	0.879949	0.977038	0.581655	0.025*
C4A	0.86009 (13)	0.80776 (18)	0.58395 (12)	0.0217 (5)
H4A	0.904591	0.786989	0.563925	0.026*
C5A	0.82410 (13)	0.60003 (17)	0.58813 (13)	0.0225 (5)
H5A1	0.880318	0.587741	0.589567	0.027*
H5A2	0.795591	0.579814	0.536021	0.027*
C6A	0.79705 (12)	0.52306 (17)	0.64831 (12)	0.0199 (5)
H6A1	0.794683	0.445421	0.629513	0.024*
H6A2	0.835513	0.526316	0.697308	0.024*
C7A	0.71688 (12)	0.55736 (16)	0.66291 (11)	0.0156 (4)
C8A	0.69295 (11)	0.66559 (16)	0.65483 (11)	0.0139 (4)
C9A	0.74323 (11)	0.75667 (16)	0.63281 (11)	0.0149 (4)
C10A	0.81041 (12)	0.72371 (17)	0.60261 (11)	0.0172 (4)
C11A	0.66786 (12)	0.46817 (16)	0.69303 (11)	0.0156 (4)
H11A	0.702632	0.427119	0.735434	0.019*
C12A	0.57782 (12)	0.62533 (17)	0.70959 (11)	0.0153 (4)
C13A	0.63176 (12)	0.38173 (16)	0.63043 (11)	0.0152 (4)
C14A	0.62156 (12)	0.26950 (17)	0.64953 (11)	0.0176 (4)
C15A	0.58783 (12)	0.18847 (17)	0.59644 (12)	0.0201 (5)
H15A	0.582958	0.113709	0.611933	0.024*
C16A	0.56140 (12)	0.22144 (18)	0.51938 (12)	0.0217 (5)
H16A	0.537891	0.168657	0.482179	0.026*
C17A	0.56983 (14)	0.33282 (19)	0.49746 (13)	0.0269 (5)
H17A	0.551799	0.354816	0.445549	0.032*
C18A	0.60494 (13)	0.41159 (18)	0.55236 (12)	0.0234 (5)
H18A	0.610722	0.486051	0.536698	0.028*
C19A	0.80734 (13)	1.15122 (17)	0.61430 (13)	0.0229 (5)
H19D	0.860523	1.143334	0.643874	0.034*
H19E	0.786463	1.223793	0.625118	0.034*
H19F	0.807905	1.145484	0.559170	0.034*
Cl1	0.96307 (3)	0.62076 (4)	0.80113 (3)	0.01843 (13)
Cl1A	0.51642 (3)	0.92160 (4)	0.67382 (3)	0.01800 (13)
F1	0.85466 (8)	1.32268 (10)	0.79223 (7)	0.0348 (3)
F1A	0.64645 (8)	0.23764 (10)	0.72615 (7)	0.0288 (3)
N1	0.87236 (10)	0.85180 (13)	0.81748 (10)	0.0169 (4)
H1A	0.881602	0.783543	0.812344	0.025*
N2	0.90769 (10)	1.03351 (14)	0.79089 (10)	0.0191 (4)
H2A	0.940904	1.073117	0.774138	0.029*
N3	0.98608 (10)	0.88383 (14)	0.76880 (10)	0.0191 (4)
H3B	0.990159	0.814864	0.765967	0.029*
H3C	1.012553	0.927153	0.745400	0.029*
N1A	0.61863 (10)	0.69642 (13)	0.67234 (9)	0.0164 (4)
H1AA	0.600447	0.759068	0.663802	0.025*
N2A	0.60446 (10)	0.52113 (13)	0.72611 (9)	0.0168 (4)
H2AA	0.578269	0.481653	0.751346	0.025*
N3A	0.51041 (10)	0.65949 (14)	0.72898 (10)	0.0191 (4)
H3AC	0.486887	0.612044	0.758321	0.029*
H3AB	0.499668	0.725795	0.722589	0.029*
O1	0.74783 (9)	0.50027 (12)	0.90086 (9)	0.0257 (4)
O1A	0.75840 (8)	1.06343 (11)	0.63623 (8)	0.0204 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0142 (11)	0.0231 (11)	0.0225 (11)	0.0005 (9)	0.0049 (9)	0.0014 (9)
C2	0.0193 (11)	0.0180 (11)	0.0206 (11)	−0.0005 (9)	0.0003 (9)	0.0006 (9)
C3	0.0187 (12)	0.0300 (13)	0.0230 (11)	−0.0075 (10)	0.0062 (9)	0.0003 (10)
C4	0.0160 (11)	0.0293 (12)	0.0257 (12)	−0.0033 (9)	0.0074 (9)	−0.0085 (10)
C5	0.0195 (12)	0.0259 (12)	0.0303 (12)	0.0034 (10)	0.0054 (10)	−0.0066 (10)
C6	0.0261 (13)	0.0198 (11)	0.0260 (12)	0.0059 (9)	0.0070 (10)	0.0005 (9)
C7	0.0184 (11)	0.0179 (10)	0.0163 (10)	0.0042 (9)	0.0037 (8)	0.0018 (9)
C8	0.0133 (10)	0.0199 (11)	0.0119 (9)	0.0016 (8)	0.0005 (8)	−0.0008 (8)
C9	0.0160 (11)	0.0188 (11)	0.0137 (10)	−0.0006 (8)	0.0015 (8)	−0.0008 (8)
C10	0.0161 (11)	0.0226 (11)	0.0156 (10)	−0.0015 (9)	0.0016 (8)	−0.0048 (9)
C11	0.0212 (12)	0.0166 (10)	0.0191 (10)	0.0054 (9)	0.0054 (9)	0.0032 (9)
C12	0.0187 (11)	0.0153 (10)	0.0114 (9)	−0.0001 (8)	0.0024 (8)	0.0003 (8)
C13	0.0182 (11)	0.0170 (11)	0.0180 (10)	0.0045 (9)	0.0082 (9)	0.0009 (9)
C14	0.0225 (12)	0.0223 (11)	0.0178 (11)	0.0046 (9)	0.0067 (9)	0.0061 (9)
C15	0.0249 (12)	0.0191 (11)	0.0302 (12)	−0.0005 (9)	0.0103 (10)	−0.0028 (10)
C16	0.0180 (12)	0.0288 (12)	0.0256 (12)	−0.0014 (9)	0.0082 (9)	−0.0094 (10)
C17	0.0326 (14)	0.0318 (13)	0.0184 (11)	0.0055 (11)	0.0035 (10)	−0.0007 (10)
C18	0.0326 (13)	0.0193 (11)	0.0242 (12)	0.0057 (10)	0.0046 (10)	0.0046 (10)
C19	0.0241 (12)	0.0232 (12)	0.0311 (12)	−0.0080 (10)	0.0010 (10)	0.0079 (10)
C1A	0.0128 (10)	0.0187 (10)	0.0153 (10)	0.0010 (8)	0.0031 (8)	0.0002 (8)
C2A	0.0199 (11)	0.0151 (10)	0.0145 (10)	0.0000 (9)	−0.0009 (8)	−0.0006 (8)
C3A	0.0198 (11)	0.0204 (11)	0.0222 (11)	−0.0080 (9)	0.0064 (9)	−0.0004 (9)
C4A	0.0178 (11)	0.0250 (12)	0.0244 (11)	−0.0015 (9)	0.0088 (9)	−0.0038 (10)
C5A	0.0185 (12)	0.0217 (11)	0.0282 (12)	−0.0019 (9)	0.0068 (9)	−0.0067 (10)
C6A	0.0172 (11)	0.0144 (10)	0.0270 (11)	0.0003 (9)	0.0018 (9)	−0.0044 (9)
C7A	0.0160 (11)	0.0156 (10)	0.0138 (10)	−0.0010 (8)	−0.0006 (8)	−0.0023 (8)
C8A	0.0127 (10)	0.0164 (10)	0.0117 (9)	0.0008 (8)	−0.0002 (8)	−0.0012 (8)
C9A	0.0136 (10)	0.0164 (10)	0.0126 (10)	−0.0025 (8)	−0.0025 (8)	−0.0003 (8)
C10A	0.0147 (11)	0.0194 (11)	0.0177 (10)	−0.0004 (9)	0.0031 (8)	−0.0030 (9)
C11A	0.0181 (11)	0.0123 (10)	0.0159 (10)	0.0034 (8)	0.0019 (8)	0.0005 (8)
C12A	0.0167 (11)	0.0164 (10)	0.0115 (9)	−0.0014 (8)	−0.0002 (8)	−0.0020 (8)
C13A	0.0139 (10)	0.0131 (10)	0.0183 (10)	0.0003 (8)	0.0026 (8)	−0.0006 (8)
C14A	0.0180 (11)	0.0190 (11)	0.0165 (10)	0.0031 (9)	0.0048 (8)	0.0017 (9)
C15A	0.0203 (12)	0.0111 (10)	0.0317 (12)	−0.0002 (9)	0.0118 (9)	−0.0029 (9)
C16A	0.0172 (11)	0.0240 (12)	0.0257 (12)	−0.0061 (9)	0.0088 (9)	−0.0109 (10)
C17A	0.0335 (14)	0.0291 (13)	0.0173 (11)	−0.0069 (10)	0.0029 (10)	−0.0005 (10)
C18A	0.0308 (13)	0.0166 (11)	0.0217 (11)	−0.0061 (9)	0.0020 (10)	0.0017 (9)
C19A	0.0223 (12)	0.0147 (11)	0.0319 (12)	−0.0042 (9)	0.0057 (10)	0.0047 (9)
Cl1	0.0190 (3)	0.0133 (2)	0.0242 (3)	0.0006 (2)	0.0072 (2)	−0.0026 (2)
Cl1A	0.0175 (3)	0.0140 (2)	0.0232 (3)	0.0014 (2)	0.0055 (2)	−0.0020 (2)
F1	0.0510 (9)	0.0230 (7)	0.0269 (7)	−0.0016 (6)	−0.0008 (6)	0.0078 (6)
F1A	0.0418 (8)	0.0191 (6)	0.0231 (7)	−0.0035 (6)	0.0005 (6)	0.0069 (5)
N1	0.0159 (9)	0.0107 (8)	0.0256 (9)	0.0010 (7)	0.0082 (7)	−0.0018 (7)
N2	0.0232 (10)	0.0138 (9)	0.0238 (9)	0.0012 (7)	0.0135 (8)	0.0034 (7)
N3	0.0196 (10)	0.0118 (8)	0.0293 (10)	0.0007 (7)	0.0132 (8)	0.0023 (7)
N1A	0.0159 (9)	0.0106 (8)	0.0233 (9)	0.0009 (7)	0.0051 (7)	0.0031 (7)
N2A	0.0227 (10)	0.0131 (9)	0.0162 (9)	0.0001 (7)	0.0076 (7)	0.0029 (7)
N3A	0.0197 (10)	0.0135 (9)	0.0261 (10)	−0.0006 (7)	0.0091 (8)	0.0018 (7)
O1	0.0208 (8)	0.0184 (8)	0.0397 (9)	−0.0029 (6)	0.0101 (7)	0.0052 (7)
O1A	0.0191 (8)	0.0128 (7)	0.0306 (8)	−0.0023 (6)	0.0080 (6)	0.0012 (6)

Geometric parameters (Å, º)

C1—C2	1.388 (3)	C2A—C3A	1.383 (3)
C1—C9	1.393 (3)	C3A—C4A	1.389 (3)
C1—H1	0.9300	C3A—H3A	0.9300
C2—O1	1.374 (2)	C4A—C10A	1.385 (3)
C2—C3	1.384 (3)	C4A—H4A	0.9300
C3—C4	1.393 (3)	C5A—C10A	1.506 (3)
C3—H3	0.9300	C5A—C6A	1.521 (3)
C4—C10	1.383 (3)	C5A—H5A1	0.9700
C4—H4	0.9300	C5A—H5A2	0.9700
C5—C10	1.509 (3)	C6A—C7A	1.500 (3)
C5—C6	1.514 (3)	C6A—H6A1	0.9700
C5—H5A	0.9700	C6A—H6A2	0.9700
C5—H5B	0.9700	C7A—C8A	1.340 (3)
C6—C7	1.506 (3)	C7A—C11A	1.502 (3)
C6—H6A	0.9700	C8A—N1A	1.413 (2)
C6—H6B	0.9700	C8A—C9A	1.473 (3)
C7—C8	1.333 (3)	C9A—C10A	1.409 (3)
C7—C11	1.504 (3)	C11A—N2A	1.463 (2)
C8—N1	1.409 (2)	C11A—C13A	1.530 (3)
C8—C9	1.472 (3)	C11A—H11A	0.9800
C9—C10	1.409 (3)	C12A—N2A	1.323 (3)
C11—N2	1.474 (2)	C12A—N3A	1.327 (3)
C11—C13	1.517 (3)	C12A—N1A	1.336 (2)
C11—H11	0.9800	C13A—C14A	1.383 (3)
C12—N2	1.321 (2)	C13A—C18A	1.388 (3)
C12—N3	1.327 (2)	C14A—F1A	1.367 (2)
C12—N1	1.332 (2)	C14A—C15A	1.374 (3)
C13—C14	1.380 (3)	C15A—C16A	1.381 (3)
C13—C18	1.395 (3)	C15A—H15A	0.9300
C14—F1	1.367 (2)	C16A—C17A	1.383 (3)
C14—C15	1.377 (3)	C16A—H16A	0.9300
C15—C16	1.380 (3)	C17A—C18A	1.382 (3)
C15—H15	0.9300	C17A—H17A	0.9300
C16—C17	1.383 (3)	C18A—H18A	0.9300
C16—H16	0.9300	C19A—O1A	1.430 (2)
C17—C18	1.384 (3)	C19A—H19D	0.9600
C17—H17	0.9300	C19A—H19E	0.9600
C18—H18	0.9300	C19A—H19F	0.9600
C19—O1	1.426 (2)	N1—H1A	0.8285
C19—H19A	0.9600	N2—H2A	0.8310
C19—H19B	0.9600	N3—H3B	0.8185
C19—H19C	0.9600	N3—H3C	0.8383
C1A—C9A	1.388 (3)	N1A—H1AA	0.8043
C1A—C2A	1.390 (3)	N2A—H2AA	0.8280
C1A—H1B	0.9300	N3A—H3AC	0.9021
C2A—O1A	1.377 (2)	N3A—H3AB	0.8059
C2—C1—C9	120.61 (19)	C10A—C4A—H4A	119.0
C2—C1—H1	119.7	C3A—C4A—H4A	119.0
C9—C1—H1	119.7	C10A—C5A—C6A	112.67 (17)
O1—C2—C3	124.89 (19)	C10A—C5A—H5A1	109.1
O1—C2—C1	114.81 (18)	C6A—C5A—H5A1	109.1
C3—C2—C1	120.30 (19)	C10A—C5A—H5A2	109.1
C2—C3—C4	118.7 (2)	C6A—C5A—H5A2	109.1
C2—C3—H3	120.6	H5A1—C5A—H5A2	107.8
C4—C3—H3	120.6	C7A—C6A—C5A	111.45 (17)
C10—C4—C3	122.3 (2)	C7A—C6A—H6A1	109.3
C10—C4—H4	118.8	C5A—C6A—H6A1	109.3
C3—C4—H4	118.8	C7A—C6A—H6A2	109.3
C10—C5—C6	113.39 (18)	C5A—C6A—H6A2	109.3
C10—C5—H5A	108.9	H6A1—C6A—H6A2	108.0
C6—C5—H5A	108.9	C8A—C7A—C6A	120.74 (18)
C10—C5—H5B	108.9	C8A—C7A—C11A	121.53 (18)
C6—C5—H5B	108.9	C6A—C7A—C11A	117.55 (17)
H5A—C5—H5B	107.7	C7A—C8A—N1A	119.55 (18)
C7—C6—C5	110.65 (17)	C7A—C8A—C9A	122.62 (18)
C7—C6—H6A	109.5	N1A—C8A—C9A	117.72 (16)
C5—C6—H6A	109.5	C1A—C9A—C10A	120.06 (18)
C7—C6—H6B	109.5	C1A—C9A—C8A	122.75 (18)
C5—C6—H6B	109.5	C10A—C9A—C8A	117.16 (17)
H6A—C6—H6B	108.1	C4A—C10A—C9A	118.23 (18)
C8—C7—C11	122.20 (18)	C4A—C10A—C5A	122.09 (18)
C8—C7—C6	121.12 (19)	C9A—C10A—C5A	119.62 (18)
C11—C7—C6	116.68 (17)	N2A—C11A—C7A	110.22 (15)
C7—C8—N1	120.28 (18)	N2A—C11A—C13A	109.47 (16)
C7—C8—C9	122.77 (18)	C7A—C11A—C13A	113.38 (16)
N1—C8—C9	116.95 (17)	N2A—C11A—H11A	107.9
C1—C9—C10	119.73 (19)	C7A—C11A—H11A	107.9
C1—C9—C8	122.83 (18)	C13A—C11A—H11A	107.9
C10—C9—C8	117.43 (18)	N2A—C12A—N3A	120.54 (18)
C4—C10—C9	118.27 (19)	N2A—C12A—N1A	119.77 (18)
C4—C10—C5	122.49 (19)	N3A—C12A—N1A	119.68 (18)
C9—C10—C5	118.98 (18)	C14A—C13A—C18A	116.28 (18)
N2—C11—C7	110.10 (16)	C14A—C13A—C11A	121.35 (17)
N2—C11—C13	108.43 (17)	C18A—C13A—C11A	122.34 (17)
C7—C11—C13	114.15 (16)	F1A—C14A—C15A	118.13 (17)
N2—C11—H11	108.0	F1A—C14A—C13A	117.73 (17)
C7—C11—H11	108.0	C15A—C14A—C13A	124.13 (19)
C13—C11—H11	108.0	C14A—C15A—C16A	117.97 (19)
N2—C12—N3	120.18 (18)	C14A—C15A—H15A	121.0
N2—C12—N1	119.97 (18)	C16A—C15A—H15A	121.0
N3—C12—N1	119.83 (17)	C15A—C16A—C17A	120.1 (2)
C14—C13—C18	116.50 (19)	C15A—C16A—H16A	120.0
C14—C13—C11	121.44 (18)	C17A—C16A—H16A	120.0
C18—C13—C11	121.95 (18)	C18A—C17A—C16A	120.3 (2)
F1—C14—C15	118.03 (18)	C18A—C17A—H17A	119.9
F1—C14—C13	118.00 (18)	C16A—C17A—H17A	119.9
C15—C14—C13	123.94 (19)	C17A—C18A—C13A	121.27 (19)
C14—C15—C16	118.1 (2)	C17A—C18A—H18A	119.4
C14—C15—H15	120.9	C13A—C18A—H18A	119.4
C16—C15—H15	120.9	O1A—C19A—H19D	109.5
C15—C16—C17	120.2 (2)	O1A—C19A—H19E	109.5
C15—C16—H16	119.9	H19D—C19A—H19E	109.5
C17—C16—H16	119.9	O1A—C19A—H19F	109.5
C16—C17—C18	120.2 (2)	H19D—C19A—H19F	109.5
C16—C17—H17	119.9	H19E—C19A—H19F	109.5
C18—C17—H17	119.9	C12—N1—C8	121.66 (17)
C17—C18—C13	121.1 (2)	C12—N1—H1A	115.6
C17—C18—H18	119.5	C8—N1—H1A	122.5
C13—C18—H18	119.5	C12—N2—C11	125.61 (17)
O1—C19—H19A	109.5	C12—N2—H2A	114.9
O1—C19—H19B	109.5	C11—N2—H2A	119.4
H19A—C19—H19B	109.5	C12—N3—H3B	116.9
O1—C19—H19C	109.5	C12—N3—H3C	119.4
H19A—C19—H19C	109.5	H3B—N3—H3C	121.1
H19B—C19—H19C	109.5	C12A—N1A—C8A	121.38 (16)
C9A—C1A—C2A	120.30 (18)	C12A—N1A—H1AA	116.4
C9A—C1A—H1B	119.9	C8A—N1A—H1AA	122.0
C2A—C1A—H1B	119.9	C12A—N2A—C11A	124.26 (16)
O1A—C2A—C3A	124.33 (18)	C12A—N2A—H2AA	115.9
O1A—C2A—C1A	115.31 (18)	C11A—N2A—H2AA	119.1
C3A—C2A—C1A	120.35 (18)	C12A—N3A—H3AC	117.4
C2A—C3A—C4A	119.01 (19)	C12A—N3A—H3AB	116.5
C2A—C3A—H3A	120.5	H3AC—N3A—H3AB	124.3
C4A—C3A—H3A	120.5	C2—O1—C19	117.09 (17)
C10A—C4A—C3A	122.04 (19)	C2A—O1A—C19A	117.32 (16)
C9—C1—C2—O1	177.65 (18)	C6A—C7A—C8A—C9A	−1.0 (3)
C9—C1—C2—C3	−2.0 (3)	C11A—C7A—C8A—C9A	173.92 (17)
O1—C2—C3—C4	−177.24 (19)	C2A—C1A—C9A—C10A	0.0 (3)
C1—C2—C3—C4	2.4 (3)	C2A—C1A—C9A—C8A	177.95 (18)
C2—C3—C4—C10	−0.7 (3)	C7A—C8A—C9A—C1A	−163.65 (19)
C10—C5—C6—C7	45.2 (2)	N1A—C8A—C9A—C1A	12.6 (3)
C5—C6—C7—C8	−30.5 (3)	C7A—C8A—C9A—C10A	14.4 (3)
C5—C6—C7—C11	149.43 (19)	N1A—C8A—C9A—C10A	−169.42 (17)
C11—C7—C8—N1	3.0 (3)	C3A—C4A—C10A—C9A	0.1 (3)
C6—C7—C8—N1	−177.12 (18)	C3A—C4A—C10A—C5A	177.21 (19)
C11—C7—C8—C9	−177.63 (18)	C1A—C9A—C10A—C4A	0.2 (3)
C6—C7—C8—C9	2.3 (3)	C8A—C9A—C10A—C4A	−177.87 (18)
C2—C1—C9—C10	0.0 (3)	C1A—C9A—C10A—C5A	−177.02 (18)
C2—C1—C9—C8	−179.60 (19)	C8A—C9A—C10A—C5A	4.9 (3)
C7—C8—C9—C1	−169.7 (2)	C6A—C5A—C10A—C4A	148.3 (2)
N1—C8—C9—C1	9.7 (3)	C6A—C5A—C10A—C9A	−34.6 (3)
C7—C8—C9—C10	10.7 (3)	C8A—C7A—C11A—N2A	−12.2 (3)
N1—C8—C9—C10	−169.86 (17)	C6A—C7A—C11A—N2A	162.94 (16)
C3—C4—C10—C9	−1.2 (3)	C8A—C7A—C11A—C13A	110.9 (2)
C3—C4—C10—C5	172.8 (2)	C6A—C7A—C11A—C13A	−74.0 (2)
C1—C9—C10—C4	1.6 (3)	N2A—C11A—C13A—C14A	−90.2 (2)
C8—C9—C10—C4	−178.80 (18)	C7A—C11A—C13A—C14A	146.27 (19)
C1—C9—C10—C5	−172.61 (19)	N2A—C11A—C13A—C18A	87.5 (2)
C8—C9—C10—C5	7.0 (3)	C7A—C11A—C13A—C18A	−36.0 (3)
C6—C5—C10—C4	150.5 (2)	C18A—C13A—C14A—F1A	−179.22 (18)
C6—C5—C10—C9	−35.5 (3)	C11A—C13A—C14A—F1A	−1.4 (3)
C8—C7—C11—N2	0.2 (3)	C18A—C13A—C14A—C15A	0.6 (3)
C6—C7—C11—N2	−179.68 (17)	C11A—C13A—C14A—C15A	178.40 (19)
C8—C7—C11—C13	−122.0 (2)	F1A—C14A—C15A—C16A	178.81 (17)
C6—C7—C11—C13	58.1 (2)	C13A—C14A—C15A—C16A	−1.0 (3)
N2—C11—C13—C14	97.3 (2)	C14A—C15A—C16A—C17A	0.6 (3)
C7—C11—C13—C14	−139.5 (2)	C15A—C16A—C17A—C18A	0.2 (3)
N2—C11—C13—C18	−78.8 (2)	C16A—C17A—C18A—C13A	−0.6 (3)
C7—C11—C13—C18	44.3 (3)	C14A—C13A—C18A—C17A	0.3 (3)
C18—C13—C14—F1	177.89 (18)	C11A—C13A—C18A—C17A	−177.5 (2)
C11—C13—C14—F1	1.5 (3)	N2—C12—N1—C8	−0.4 (3)
C18—C13—C14—C15	0.0 (3)	N3—C12—N1—C8	178.09 (17)
C11—C13—C14—C15	−176.4 (2)	C7—C8—N1—C12	−3.1 (3)
F1—C14—C15—C16	−177.56 (18)	C9—C8—N1—C12	177.50 (17)
C13—C14—C15—C16	0.4 (3)	N3—C12—N2—C11	−174.38 (18)
C14—C15—C16—C17	−0.6 (3)	N1—C12—N2—C11	4.1 (3)
C15—C16—C17—C18	0.5 (3)	C7—C11—N2—C12	−3.9 (3)
C16—C17—C18—C13	−0.2 (3)	C13—C11—N2—C12	121.6 (2)
C14—C13—C18—C17	−0.1 (3)	N2A—C12A—N1A—C8A	−4.5 (3)
C11—C13—C18—C17	176.3 (2)	N3A—C12A—N1A—C8A	176.21 (17)
C9A—C1A—C2A—O1A	−179.72 (17)	C7A—C8A—N1A—C12A	11.9 (3)
C9A—C1A—C2A—C3A	−0.4 (3)	C9A—C8A—N1A—C12A	−164.50 (17)
O1A—C2A—C3A—C4A	179.90 (18)	N3A—C12A—N2A—C11A	166.43 (18)
C1A—C2A—C3A—C4A	0.7 (3)	N1A—C12A—N2A—C11A	−12.8 (3)
C2A—C3A—C4A—C10A	−0.5 (3)	C7A—C11A—N2A—C12A	20.3 (3)
C10A—C5A—C6A—C7A	45.0 (2)	C13A—C11A—N2A—C12A	−105.1 (2)
C5A—C6A—C7A—C8A	−29.1 (3)	C3—C2—O1—C19	−1.4 (3)
C5A—C6A—C7A—C11A	155.78 (17)	C1—C2—O1—C19	178.97 (18)
C6A—C7A—C8A—N1A	−177.20 (17)	C3A—C2A—O1A—C19A	3.0 (3)
C11A—C7A—C8A—N1A	−2.2 (3)	C1A—C2A—O1A—C19A	−177.73 (17)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3A—H3AB···Cl1A	0.81	2.49	3.2427 (17)	155
N3A—H3AC···Cl1A^i	0.90	2.54	3.3496 (17)	150
N2A—H2AA···Cl1A^i	0.83	2.37	3.1736 (17)	163
N1A—H1AA···Cl1A	0.80	2.42	3.1841 (17)	158
N3—H3C···Cl1^ii	0.84	2.48	3.2318 (17)	149
N3—H3B···Cl1	0.82	2.44	3.1903 (17)	154
N2—H2A···Cl1^ii	0.83	2.36	3.1433 (17)	158
N1—H1A···Cl1	0.83	2.40	3.1766 (16)	156
C15A—H15A···Cl1A^iii	0.93	2.84	3.720 (2)	159
C1A—H1B···Cl1A	0.93	2.93	3.816 (2)	160
C19—H19C···Cl1A^i	0.96	2.81	3.736 (2)	162
C15—H15···Cl1^iv	0.93	2.96	3.796 (2)	151
C11—H11···O1A	0.98	2.57	3.265 (3)	128
C1—H1···Cl1	0.93	2.91	3.818 (2)	167

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+2, y+1/2, −z+3/2; (iii) x, y−1, z; (iv) x, y+1, z.

2-Amino-4-(4-fluorophenyl)-9-methoxy-1,4,5,6-tetrahydrobenzo[h]quinazolin-3-ium chloride (4HF)

Crystal data

C19H19FN3O^+·Cl^−	F(000) = 752
Mr = 359.82	Dx = 1.366 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.7725 (9) Å	Cell parameters from 3293 reflections
b = 11.9161 (10) Å	θ = 2.9–29.2°
c = 17.1473 (15) Å	µ = 0.24 mm^−1
β = 102.626 (10)°	T = 100 K
V = 1749.1 (3) Å^3	Block, yellow
Z = 4	0.14 × 0.13 × 0.12 mm

Data collection

Rigaku OD SuperNova Dual source diffractometer with an AtlasS2 detector	3252 independent reflections
Radiation source: micro-focus sealed X-ray tube	2698 reflections with I > 2σ(I)
Detector resolution: 5.2684 pixels mm^-1	Rint = 0.038
CCD plate scans	θmax = 25.5°, θmin = 2.1°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −6→10
Tmin = 0.623, Tmax = 1.000	k = −14→12
7647 measured reflections	l = −20→19

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.052	H-atom parameters constrained
wR(F^2) = 0.126	w = 1/[σ^2(Fo^2) + (0.0568P)^2 + 0.5265P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max < 0.001
3252 reflections	Δρmax = 0.44 e Å^−3
227 parameters	Δρmin = −0.28 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
C1	0.7237 (3)	0.41733 (18)	0.01749 (12)	0.0220 (5)
H1	0.685629	0.391456	0.060749	0.026*
C2	0.7722 (3)	0.34112 (18)	−0.03294 (13)	0.0240 (5)
C3	0.8267 (3)	0.3780 (2)	−0.09863 (14)	0.0298 (6)
H3	0.858213	0.327105	−0.133078	0.036*
C4	0.8330 (3)	0.4930 (2)	−0.11171 (14)	0.0301 (6)
H4	0.869802	0.518080	−0.155538	0.036*
C5	0.8048 (3)	0.6958 (2)	−0.07423 (14)	0.0287 (6)
H5A	0.793537	0.710667	−0.130825	0.034*
H5B	0.909185	0.718567	−0.047246	0.034*
C6	0.6859 (3)	0.76604 (19)	−0.04282 (13)	0.0268 (5)
H6A	0.720334	0.843593	−0.038034	0.032*
H6B	0.586342	0.763266	−0.080872	0.032*
C7	0.6646 (3)	0.72529 (18)	0.03717 (13)	0.0223 (5)
C8	0.6820 (3)	0.61643 (19)	0.05654 (12)	0.0208 (5)
C9	0.7312 (3)	0.53259 (19)	0.00423 (12)	0.0217 (5)
C10	0.7867 (3)	0.57126 (19)	−0.06215 (13)	0.0243 (5)
C11	0.6067 (3)	0.80917 (19)	0.08976 (13)	0.0235 (5)
H11	0.515783	0.847237	0.057131	0.028*
C12	0.5789 (3)	0.64421 (19)	0.17382 (13)	0.0226 (5)
C13	0.7269 (3)	0.89892 (18)	0.12430 (12)	0.0215 (5)
C14	0.8745 (3)	0.86765 (19)	0.16765 (14)	0.0264 (5)
H14	0.899674	0.791916	0.174142	0.032*
C15	0.9841 (3)	0.9475 (2)	0.20118 (14)	0.0299 (6)
H15	1.082311	0.926620	0.230247	0.036*
C16	0.9433 (3)	1.0583 (2)	0.19013 (14)	0.0308 (6)
C17	0.7997 (3)	1.0935 (2)	0.14859 (14)	0.0336 (6)
H17	0.775413	1.169412	0.142865	0.040*
C18	0.6917 (3)	1.01208 (19)	0.11531 (13)	0.0282 (6)
H18	0.593781	1.034006	0.086438	0.034*
C19	0.8260 (3)	0.1480 (2)	−0.05647 (15)	0.0314 (6)
H19A	0.771824	0.150163	−0.111524	0.047*
H19B	0.815415	0.074746	−0.034969	0.047*
H19C	0.934652	0.164097	−0.052610	0.047*
Cl1	0.61929 (7)	0.34193 (5)	0.21592 (3)	0.02544 (19)
F1	1.0514 (2)	1.13792 (13)	0.22292 (9)	0.0471 (4)
N1	0.6463 (2)	0.57731 (15)	0.12857 (10)	0.0233 (4)
H1A	0.653950	0.506828	0.140628	0.035*
N2	0.5551 (2)	0.75145 (16)	0.15503 (11)	0.0254 (5)
H2A	0.510166	0.789471	0.188447	0.038*
N3	0.5390 (2)	0.60322 (16)	0.23876 (11)	0.0262 (5)
H3A	0.477973	0.652851	0.264895	0.039*
H3B	0.534473	0.521451	0.242195	0.039*
O1	0.76094 (19)	0.22971 (13)	−0.01237 (9)	0.0278 (4)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0224 (13)	0.0237 (12)	0.0212 (11)	−0.0021 (10)	0.0078 (9)	0.0007 (9)
C2	0.0212 (12)	0.0233 (12)	0.0271 (12)	−0.0011 (10)	0.0047 (9)	0.0012 (10)
C3	0.0354 (15)	0.0292 (13)	0.0279 (12)	−0.0022 (11)	0.0135 (11)	−0.0073 (11)
C4	0.0353 (15)	0.0320 (14)	0.0279 (12)	−0.0036 (11)	0.0180 (11)	0.0012 (11)
C5	0.0334 (15)	0.0286 (13)	0.0267 (12)	−0.0064 (11)	0.0125 (10)	0.0004 (10)
C6	0.0320 (14)	0.0214 (12)	0.0272 (12)	−0.0051 (10)	0.0070 (10)	0.0018 (10)
C7	0.0203 (12)	0.0212 (12)	0.0258 (11)	−0.0026 (9)	0.0060 (9)	0.0001 (9)
C8	0.0182 (12)	0.0232 (12)	0.0219 (11)	−0.0010 (9)	0.0064 (9)	0.0019 (10)
C9	0.0166 (12)	0.0252 (12)	0.0238 (11)	−0.0006 (9)	0.0052 (9)	0.0013 (9)
C10	0.0242 (13)	0.0242 (12)	0.0257 (11)	−0.0014 (10)	0.0082 (10)	0.0013 (10)
C11	0.0213 (13)	0.0210 (12)	0.0290 (12)	0.0035 (10)	0.0073 (10)	0.0059 (10)
C12	0.0220 (13)	0.0223 (12)	0.0251 (11)	0.0008 (10)	0.0089 (10)	−0.0018 (10)
C13	0.0239 (13)	0.0202 (12)	0.0240 (11)	0.0022 (9)	0.0129 (9)	0.0014 (9)
C14	0.0271 (14)	0.0209 (12)	0.0338 (12)	0.0050 (10)	0.0123 (10)	−0.0002 (10)
C15	0.0253 (13)	0.0341 (14)	0.0323 (13)	0.0001 (11)	0.0109 (10)	−0.0085 (11)
C16	0.0386 (16)	0.0271 (13)	0.0310 (13)	−0.0112 (12)	0.0169 (11)	−0.0081 (11)
C17	0.0536 (18)	0.0153 (12)	0.0344 (13)	0.0005 (12)	0.0151 (12)	0.0008 (11)
C18	0.0339 (14)	0.0234 (12)	0.0289 (12)	0.0083 (11)	0.0103 (10)	0.0043 (10)
C19	0.0329 (15)	0.0271 (13)	0.0362 (13)	0.0030 (11)	0.0118 (11)	−0.0048 (11)
Cl1	0.0298 (4)	0.0200 (3)	0.0292 (3)	−0.0009 (2)	0.0124 (2)	0.0028 (2)
F1	0.0534 (11)	0.0371 (9)	0.0523 (9)	−0.0186 (8)	0.0149 (8)	−0.0149 (7)
N1	0.0290 (11)	0.0163 (9)	0.0274 (10)	0.0031 (8)	0.0121 (8)	0.0036 (8)
N2	0.0297 (12)	0.0180 (10)	0.0335 (10)	0.0019 (9)	0.0177 (9)	0.0021 (8)
N3	0.0329 (12)	0.0187 (10)	0.0315 (10)	0.0029 (9)	0.0168 (9)	0.0023 (8)
O1	0.0329 (10)	0.0205 (9)	0.0340 (9)	0.0023 (7)	0.0163 (7)	−0.0026 (7)

Geometric parameters (Å, º)

C1—C2	1.383 (3)	C11—H11	0.9800
C1—C9	1.396 (3)	C12—N2	1.323 (3)
C1—H1	0.9300	C12—N3	1.331 (3)
C2—O1	1.383 (3)	C12—N1	1.337 (3)
C2—C3	1.388 (3)	C13—C18	1.384 (3)
C3—C4	1.391 (3)	C13—C14	1.395 (3)
C3—H3	0.9300	C14—C15	1.386 (3)
C4—C10	1.381 (3)	C14—H14	0.9300
C4—H4	0.9300	C15—C16	1.370 (3)
C5—C10	1.512 (3)	C15—H15	0.9300
C5—C6	1.524 (3)	C16—C17	1.370 (4)
C5—H5A	0.9700	C16—F1	1.372 (3)
C5—H5B	0.9700	C17—C18	1.389 (3)
C6—C7	1.505 (3)	C17—H17	0.9300
C6—H6A	0.9700	C18—H18	0.9300
C6—H6B	0.9700	C19—O1	1.426 (3)
C7—C8	1.339 (3)	C19—H19A	0.9600
C7—C11	1.506 (3)	C19—H19B	0.9600
C8—N1	1.418 (3)	C19—H19C	0.9600
C8—C9	1.469 (3)	N1—H1A	0.8640
C9—C10	1.410 (3)	N2—H2A	0.8876
C11—N2	1.467 (3)	N3—H3A	0.9707
C11—C13	1.527 (3)	N3—H3B	0.9775
C2—C1—C9	120.8 (2)	C7—C11—H11	107.7
C2—C1—H1	119.6	C13—C11—H11	107.7
C9—C1—H1	119.6	N2—C12—N3	120.1 (2)
O1—C2—C1	115.0 (2)	N2—C12—N1	120.0 (2)
O1—C2—C3	124.6 (2)	N3—C12—N1	119.8 (2)
C1—C2—C3	120.5 (2)	C18—C13—C14	118.6 (2)
C2—C3—C4	118.4 (2)	C18—C13—C11	121.4 (2)
C2—C3—H3	120.8	C14—C13—C11	120.1 (2)
C4—C3—H3	120.8	C15—C14—C13	121.1 (2)
C10—C4—C3	122.6 (2)	C15—C14—H14	119.4
C10—C4—H4	118.7	C13—C14—H14	119.4
C3—C4—H4	118.7	C16—C15—C14	117.9 (2)
C10—C5—C6	112.98 (19)	C16—C15—H15	121.1
C10—C5—H5A	109.0	C14—C15—H15	121.1
C6—C5—H5A	109.0	C17—C16—C15	123.3 (2)
C10—C5—H5B	109.0	C17—C16—F1	118.4 (2)
C6—C5—H5B	109.0	C15—C16—F1	118.2 (2)
H5A—C5—H5B	107.8	C16—C17—C18	117.9 (2)
C7—C6—C5	112.09 (19)	C16—C17—H17	121.1
C7—C6—H6A	109.2	C18—C17—H17	121.1
C5—C6—H6A	109.2	C13—C18—C17	121.3 (2)
C7—C6—H6B	109.2	C13—C18—H18	119.4
C5—C6—H6B	109.2	C17—C18—H18	119.4
H6A—C6—H6B	107.9	O1—C19—H19A	109.5
C8—C7—C6	120.5 (2)	O1—C19—H19B	109.5
C8—C7—C11	122.0 (2)	H19A—C19—H19B	109.5
C6—C7—C11	117.18 (18)	O1—C19—H19C	109.5
C7—C8—N1	119.9 (2)	H19A—C19—H19C	109.5
C7—C8—C9	122.71 (19)	H19B—C19—H19C	109.5
N1—C8—C9	117.30 (18)	C12—N1—C8	121.30 (18)
C1—C9—C10	119.3 (2)	C12—N1—H1A	117.5
C1—C9—C8	122.63 (19)	C8—N1—H1A	120.5
C10—C9—C8	118.0 (2)	C12—N2—C11	125.46 (19)
C4—C10—C9	118.4 (2)	C12—N2—H2A	113.8
C4—C10—C5	121.7 (2)	C11—N2—H2A	120.5
C9—C10—C5	119.8 (2)	C12—N3—H3A	115.8
N2—C11—C7	110.25 (18)	C12—N3—H3B	116.0
N2—C11—C13	109.53 (18)	H3A—N3—H3B	123.1
C7—C11—C13	113.74 (19)	C2—O1—C19	117.46 (18)
N2—C11—H11	107.7
C9—C1—C2—O1	179.0 (2)	C6—C7—C11—N2	165.84 (19)
C9—C1—C2—C3	−1.2 (3)	C8—C7—C11—C13	115.7 (2)
O1—C2—C3—C4	−179.4 (2)	C6—C7—C11—C13	−70.7 (2)
C1—C2—C3—C4	0.8 (4)	N2—C11—C13—C18	−109.5 (2)
C2—C3—C4—C10	−0.2 (4)	C7—C11—C13—C18	126.6 (2)
C10—C5—C6—C7	42.8 (3)	N2—C11—C13—C14	68.9 (3)
C5—C6—C7—C8	−30.8 (3)	C7—C11—C13—C14	−55.0 (3)
C5—C6—C7—C11	155.5 (2)	C18—C13—C14—C15	0.0 (3)
C6—C7—C8—N1	−173.6 (2)	C11—C13—C14—C15	−178.4 (2)
C11—C7—C8—N1	−0.2 (3)	C13—C14—C15—C16	−0.3 (3)
C6—C7—C8—C9	3.7 (3)	C14—C15—C16—C17	0.7 (4)
C11—C7—C8—C9	177.0 (2)	C14—C15—C16—F1	−179.8 (2)
C2—C1—C9—C10	1.0 (3)	C15—C16—C17—C18	−0.9 (4)
C2—C1—C9—C8	−179.5 (2)	F1—C16—C17—C18	179.6 (2)
C7—C8—C9—C1	−168.7 (2)	C14—C13—C18—C17	−0.2 (3)
N1—C8—C9—C1	8.7 (3)	C11—C13—C18—C17	178.3 (2)
C7—C8—C9—C10	10.8 (3)	C16—C17—C18—C13	0.6 (4)
N1—C8—C9—C10	−171.83 (19)	N2—C12—N1—C8	−5.2 (3)
C3—C4—C10—C9	0.1 (4)	N3—C12—N1—C8	176.32 (19)
C3—C4—C10—C5	175.8 (2)	C7—C8—N1—C12	7.5 (3)
C1—C9—C10—C4	−0.4 (3)	C9—C8—N1—C12	−170.0 (2)
C8—C9—C10—C4	−179.9 (2)	N3—C12—N2—C11	174.0 (2)
C1—C9—C10—C5	−176.2 (2)	N1—C12—N2—C11	−4.5 (3)
C8—C9—C10—C5	4.3 (3)	C7—C11—N2—C12	10.5 (3)
C6—C5—C10—C4	153.1 (2)	C13—C11—N2—C12	−115.4 (2)
C6—C5—C10—C9	−31.2 (3)	C1—C2—O1—C19	−172.8 (2)
C8—C7—C11—N2	−7.8 (3)	C3—C2—O1—C19	7.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3B···Cl1	0.98	2.34	3.235 (2)	152
N3—H3A···Cl1^i	0.97	2.46	3.331 (2)	150
N2—H2A···Cl1^i	0.89	2.28	3.143 (2)	165
N1—H1A···Cl1	0.86	2.41	3.2127 (19)	155
C19—H19A···Cl1^ii	0.96	2.97	3.929 (3)	177
C17—H17···Cl1^iii	0.93	2.90	3.661 (3)	140
C15—H15···Cl1^iv	0.93	2.77	3.681 (3)	167
C11—H11···O1^v	0.98	2.55	3.242 (3)	127
C1—H1···Cl1	0.93	2.91	3.819 (2)	168

Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) x, −y+1/2, z−1/2; (iii) x, y+1, z; (iv) −x+2, y+1/2, −z+1/2; (v) −x+1, −y+1, −z.