Three derivatives of 4-fluoro-5-sulfonyl­isoquinoline

In 4-fluoro­isoquinoline-5-sulfonyl chloride, C₉H₅ClFNO₂S, (I), one of the two sulfonyl O atoms lies approximately on the isoquinoline plane as a result of minimizing the steric repulsion between the chloro­sulfonyl group and the neighbouring F atom. In (S)-(−)-4-fluoro-N-(1-hy­droxy­propan-2-yl)isoquinoline-5-sulfonamide, C₁₂H₁₃FN₂O₃S, (II), there are two crystallographically independent mol­ecules (Z′ = 2). The mol­ecular conformations of these two mol­ecules differ in that the amine group of one forms an intra­molecular bifurcated hydrogen bond with the F and OH groups, whilst the other forms only a single intra­molecular N—H...F hydrogen bond. The N—H...F hydrogen bonds correspond to weak coupling between the N(H) and ¹⁹F nuclei, observed in the ¹H NMR solution-state spectra. In (S)-(−)-4-[(4-fluoro­isoquinolin-5-yl)sulfon­yl]-3-methyl-1,4-diazepan-1-ium chloride, C₁₅H₁₉FN₃O₂S⁺·Cl⁻, (III), the isoquinoline plane is slightly deformed, suggestive of a steric effect induced by the bulky substituent on the sulfonyl group.

S1. Comment

Fasudil hydrochloride, (IV), is a synthetic protein kinase inhibitor which is known to have a potent vasodilatory effect on the vertebral arteries (Morikawa et al., 1992). Crystal structure analyses of complexes of protein kinase A with fasudil or related compounds have been undertaken to investigate the nature of these ligands in the binding pocket (Engh et al., 1996; Breitenlechner et al., 2003). Various derivatives of fasudil have been explored, and it was found that (S)-(-)-4-[(4-fluoroisoquinolin-5-yl)sulfonyl]-3-methyl-1,4-diazepan-1-ium chloride, (III), has a much more potent and selective Rho-kinase inhibitory activity than (IV), i.e. the incorporation of an F atom at the 4-position of the isoquinoline system and the chiral attachment of a methyl group at the 2-position of the 1,4-diazepane ring dramatically improve the pharmacological action. As an illustration, the half-maximum inhibitory concentration (IC₅₀) of (III) and fasudil are 0.03 and 0.50 µM, respectively (Gomi et al., 2011). A practical synthesis of (III) may be achieved by starting from 4-fluoroisoquinoline and passing through the intermediates 4-fluoroisoquinoline-5-sulfonyl chloride, (I), and (S)-(-)-4-fluoro-N-(1-hydroxypropan-2-yl)isoquinoline-5-sulfonamide, (II) (Gomi et al., 2011), despite (I) being less reactive than its nonfluorinated analogue.

The ¹H NMR spectra of (II) suggested a coupling between N(H) and ¹⁹F through an intramolecular N—H···F hydrogen bond (Manjunatha Reddy et al., 2010). In the present study, the structures of (I), (II) and (III) have been determined in order to investigate the intramolecular interactions between the sulfonyl and F atoms at the vicinal positions. Although there is no entry for such an SO₂···F combination in a naphthalene-like compound in the Cambridge Structural Database (CSD, Version 5.33 of November 2011; Allen, 2002), the structures of four naphthalene-1-sulfonates (e.g. Vennila et al., 2008) and seven naphthalene-1-sulfonamides (e.g. Navarrete-Vázquez et al., 2010) are available. These all show similar conformations of the S(═O)₂O or S(═O)₂N group with the naphthalene ring, namely that the C₆—C₅—S═O torsion angles range from -7 to 7°. This suggests that there is an intramolecular repulsion between the H atom at the vicinal 4-position and the sulfonyl O atoms. An exception is N-(2-aminoethyl)-N-methylisoquinoline-5-sulfonamide hydrochloride (Vasdev et al., 2008). There, the C₆—C₅—S═O torsion angle is ca -86° with a short C₄—H···O(═S) nonbonded distance of 2.28 Å. Replacing the H atom at the 4-position with an F atom should mean that such short contacts are not allowed.

The orientations of the S(═O)₂Cl group in (I) and the S(═O)₂N groups in (II) and (III) relative to the isoquinoline ring are similar to each other, as expected (Figs. 1–3). The C6—C5—S12—O13 torsion angle in (I) is 1.6 (3)°, the corresponding angles for the two crystallographically independent molecules in (II) are -2.5 (5) and -0.2 (5)°, and that in (III) is 9.3 (6)°. In (I), the F11···S12, F11···O14 and F11···Cl15 distances are 3.037 (3), 2.667 (4) and 3.104 (3) Å, respectively, which are shorter by 0.1 to ~0.3 Å than the sum of their van der Waals radii (Bondi, 1964). The molecular packing pattern of (I) is a typical herringbone (Fig. 4), and there is an intermolecular short contact, the N2···Cl15(-x+1/2, y-1/2, -z1/2) distance being 3.129 (3) Å.

In the ¹H NMR spectrum of (II), the multiplicity of the amide proton is triplet (δ 5.34), but doublet (δ 5.40) for the non-fluorinated analogue, suggesting spin–spin coupling between the amide N—H group and the active ¹⁹F nuclei (J_N—H···F = 7.1 Hz). Similar through-space nuclear spin–spin couplings due to intramolecular N—H···F hydrogen bonds have been observed for 2-fluoro-N-(pyridyl)benzamides, the N···F distances being 2.722 (5)–2.753 (6) Å (Mocilac et al., 2012). The 2-fluorophenylsulfonamides do not show such intramolecular spin–spin coupling (Samarakoon et al., 2010), and this agrees with the fact that the conformations of these molecules are not suitable for the formation of intramolecular N—H···X hydrogen bonds (X = Cl: Fernandes et al., 2011; Shakuntala et al., 2011; X = I: Arshad et al., 2011). Somewhat weaker intramolecular N—H···F hydrogen bonds are observed in (II), with N···F distances of 2.884 (5) and 2.893 (6) Å and N—H···F angles of 115 (5) and 137 (6)° (Fig. 2 and Table 1).

In the following discussion, the two independent molecules of (II) are labelled A and B (for the molecules containing atoms S12 and S31, respectively). The amide N15—H15 group has another hydrogen-bond acceptor, O14(-x+1, y+1/2, -z), and this hydrogen bond links molecule A and its equivalents to form a chain around the twofold screw axis parallel to b passing through (1/2, 0, 0) (Fig. 5 and Table 1). Molecules A and B are connected by an O38—H38···N2(x, y-1, z) hydrogen bond, and these pairs are further connected by another hydrogen bond, O19—H19···O38(x, y+1, z-1), to form a zigzag molecular chain along the c axis. The N34—H34 group in molecule B forms an intramolecular bifurcated hydrogen bond, which is achieved by a pyramidal configuration around atom N34.

In (III), the isoquinoline ring is a little skewed, the C8—C9—C10—C5 torsion angle being 6.1 (8)°. Atoms F11 and S12 are displaced below and above the average plane of the isoquinoline ring by -0.233 (8) and 0.556 (7) Å, respectively, and the resulting F···S distance is 3.053 (5) Å. This may be due to the strain introduced by the bulky group attached to the sulfonyl group. A similar twist in the naphthalene ring was observed in 1,8-bis(methylsulfanyl)naphthalene, which has a nonbonded S···S distance of 2.918 (2)–2.934 (2) Å. There, the S atoms are displaced from the naphthalene ring by 0.306 (2) and -0.291 (2) Å (Glass et al., 1989). On the other hand, the twist of the naphthalene ring in 1-bromo-8-(ethysulfanyl)naphthalene is very slight, with the shifts of the S and Br atoms from the naphthalene plane both less than 0.12 Å and with S···Br distances of 3.050 (2)–3.056 (2) Å. This relative planarity is achieved mainly by the imbalance of the Br—C—C bond angles, viz. 124.1 (4)–124.5 (4)° inside and 112.3 (5)–112.8 (5)° outside (Fuller et al., 2007). In the packing structure of (III), the 1,4-diazepan-1-ium group acts as a hydrogen-bond donor to the chloride anions (Fig. 6 and Table 2). A (Cl···H—N—H···)_n chain is formed around the twofold screw axis parallel to c, passing through (1/4, 0, 0).

Related literature

For related literature, see: Allen (2002); Arshad et al. (2011); Bondi (1964); Breitenlechner et al. (2003); Engh et al. (1996); Fernandes et al. (2011); Flack (1983); Fuller et al. (2007); Glass et al. (1989); Gomi et al. (2011, 2012); Manjunatha Reddy, Vasantha Kumar, Guru Row & Suryaprakash (2010); Mocilac et al. (2012); Morikawa et al. (1992); Navarrete-Vázquez, Morales-Vilchis, Estrada-Soto, Rodríguez-López & Tlahuext (2010); Samarakoon et al. (2010); Shakuntala et al. (2011); Vasdev et al. (2008); Vennila et al. (2008).

S2. Experimental

A pilot-scale production of (III) was achieved, where (I) and (II) were the reaction intermediates (Gomi et al., 2011). Compound (I) was synthesized from 4-fluoroisoquinoline. Plate-like crystals of (I) were grown by slow diffusion of hexane vapour into a chloroform solution.

Compound (II) was prepared by the reaction of (I) with (S)-(+)-2-aminopropan-1-ol. The specific rotation, [α]_D, of (II) at 292 K is -18.36° (c = 0.54, CHCl₃, where c is the concentration in units of grams per 100 ml). ¹H NMR (400 MHz, CDCl₃): δ 1.06 (3H, d, J = 6.3 Hz), 1.78 (1H, t, J = 5.1 Hz), 3.43–3.59 (3H, m), 5.34 (1H, t, J = 7.1 Hz), 7.77 (1H, t, J = 7.8 Hz), 8.23–8.28 (1H, m), 8.60 (1H, d, J = 5.4 Hz), 8.68 (1H, dd, J = 7.8, 1.2 Hz), 9.19 (1H, s) (Gomi et al., 2011). Plate-like crystals of (II) were grown by slow diffusion of hexane vapour into an acetone solution.

Compound (III) was prepared from (I) and (S)-(+)-tert-butyl 3-methyl-1,4-diazepane-1-carboxylate (Gomi et al., 2012). The specific rotation, [α]_D, of (III) at 293 K is -8.82° (c = 1.00, H₂O). Plate-like crystals of (III) were grown by slow diffusion of ethyl acetate vapour into a methanol solution.

S3. Refinement

The coordinates of the amide H atoms in (II) were refined with the N—H distances restrained to 0.86 (1) Å. This revealed a pyramidal configuration around the N34 atom of molecule B with reasonable hydrogen-bond geometry in contrast to the almost flat configuration around the N15 atom of molecule A. All the other H atoms were positioned geometrically and refined as riding, with C—H = 0.93 (aromatic), 0.96 (methyl), 0.97 (CH₂) or 0.98 Å (sp³ CH), O—H = 0.82 Å, and 0.90 Å (NH₂), and with U_iso(H) = 1.2U_eq(parent). Methyl-group orientations were obtained by allowing rotation about the C—C bond.

For (II), Friedel pairs were averaged before the final refinement, since the Flack (1983) parameter was estimated to be 0.4 (3). The absolute structure was assigned based on the known absolute configuration of the (S)-2-aminopropan-1-ol group.

For (III), the absolute structure was assigned based on the known absolute configuration of the (S)-3-methyl-1,4-diazepane group. This assignment is tentatively supported by the value obtained for the Flack (1983) parameter.

Computing details

For all compounds, data collection: WinAFC Diffractometer Control Software (Rigaku, 1999); cell refinement: WinAFC Diffractometer Control Software (Rigaku, 1999); data reduction: CrystalStructure (Rigaku, 2010); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).

Figures

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The molecular structure of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Dashed lines indicate N—H···F and N—H···O interactions.
	Fig. 3. The molecular structure of (III), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. The dashed line indicates the N—H···Cl interaction.
	Fig. 4. The crystal structure of (I), projected along c.
	Fig. 5. The crystal structure of (II), projected along b. Dashed lines indicate hydrogen bonds. [Symmetry codes: (i) -x + 1, y + 1/2, -z; (ii) x, y + 1, z - 1.]
	Fig. 6. The crystal structure of (III), projected along c. Dashed lines indicate hydrogen bonds. [Symmetry code: (iv) -x + 1/2, -y, z - 1/2.]

(I) 4-Fluoroisoquinoline-5-sulfonyl chloride

Crystal data

C9H5ClFNO2S	F(000) = 496.00
Mr = 245.66	Dx = 1.700 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 8.070 (3) Å	θ = 10.0–12.5°
b = 15.353 (3) Å	µ = 0.61 mm^−1
c = 7.789 (2) Å	T = 293 K
β = 96.08 (3)°	Plate, colourless
V = 959.6 (5) Å^3	0.55 × 0.50 × 0.30 mm
Z = 4

Data collection

Rigaku AFC-7R diffractometer	1621 reflections with F^2 > 2σ(F^2)
Radiation source: Rigaku rotating Mo anode	Rint = 0.040
Graphite plate monochromator	θmax = 27.5°
ω/2θ scans	h = −10→3
Absorption correction: ψ scan (North et al., 1968)	k = 0→19
Tmin = 0.730, Tmax = 0.834	l = −10→10
2444 measured reflections	3 standard reflections every 150 reflections
2202 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.059	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.164	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.1016P)^2 + 0.2981P] where P = (Fo^2 + 2Fc^2)/3
2202 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.70 e Å^−3

Special details

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.2772 (4)	−0.0232 (2)	−0.1594 (5)	0.0571 (8)
N2	0.3504 (4)	−0.00576 (19)	−0.2983 (4)	0.0606 (7)
C3	0.4284 (4)	0.0726 (3)	−0.3023 (4)	0.0549 (7)
C4	0.4338 (4)	0.13116 (19)	−0.1704 (4)	0.0473 (7)
C5	0.3604 (4)	0.16752 (17)	0.1359 (4)	0.0432 (6)
C6	0.2727 (4)	0.14193 (19)	0.2702 (4)	0.0500 (7)
C7	0.1881 (4)	0.0621 (2)	0.2652 (5)	0.0581 (8)
C8	0.1916 (4)	0.0083 (2)	0.1275 (5)	0.0534 (7)
C9	0.2763 (4)	0.03319 (17)	−0.0155 (4)	0.0455 (6)
C10	0.3607 (3)	0.11463 (17)	−0.0163 (4)	0.0410 (6)
F11	0.5097 (3)	0.20776 (13)	−0.1929 (3)	0.0639 (6)
S12	0.47932 (10)	0.26332 (5)	0.17663 (9)	0.0495 (3)
O13	0.4622 (4)	0.29341 (16)	0.3466 (3)	0.0660 (7)
O14	0.6413 (3)	0.25348 (16)	0.1227 (4)	0.0628 (6)
Cl15	0.35201 (12)	0.35169 (5)	0.01771 (11)	0.0638 (3)
H1	0.2221	−0.0762	−0.1553	0.0685*
H3	0.4805	0.0868	−0.3994	0.0658*
H6	0.2698	0.1782	0.3655	0.0600*
H7	0.1293	0.0459	0.3566	0.0697*
H8	0.1380	−0.0454	0.1267	0.0640*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0610 (18)	0.0481 (17)	0.0599 (19)	0.0014 (13)	−0.0039 (14)	−0.0092 (14)
N2	0.0691 (17)	0.0590 (16)	0.0517 (15)	0.0040 (13)	−0.0032 (13)	−0.0130 (12)
C3	0.0578 (17)	0.0630 (19)	0.0435 (15)	0.0060 (14)	0.0041 (13)	−0.0051 (13)
C4	0.0498 (15)	0.0480 (15)	0.0442 (14)	0.0014 (12)	0.0058 (12)	0.0011 (12)
C5	0.0487 (14)	0.0393 (13)	0.0421 (14)	0.0070 (11)	0.0075 (11)	0.0038 (11)
C6	0.0605 (17)	0.0447 (15)	0.0468 (15)	0.0089 (12)	0.0144 (13)	0.0021 (12)
C7	0.0607 (18)	0.0538 (17)	0.0630 (18)	0.0023 (14)	0.0216 (15)	0.0121 (15)
C8	0.0529 (16)	0.0408 (14)	0.0667 (19)	−0.0031 (12)	0.0074 (14)	0.0067 (13)
C9	0.0436 (13)	0.0393 (13)	0.0525 (16)	0.0040 (11)	−0.0002 (11)	0.0012 (12)
C10	0.0411 (13)	0.0401 (13)	0.0417 (13)	0.0035 (10)	0.0035 (11)	−0.0007 (10)
F11	0.0786 (13)	0.0614 (12)	0.0545 (11)	−0.0165 (9)	0.0202 (9)	−0.0002 (9)
S12	0.0606 (5)	0.0420 (4)	0.0454 (4)	−0.0027 (3)	0.0027 (3)	−0.0029 (3)
O13	0.0945 (18)	0.0575 (14)	0.0453 (12)	−0.0042 (12)	0.0038 (11)	−0.0126 (10)
O14	0.0506 (12)	0.0685 (15)	0.0689 (15)	−0.0076 (10)	0.0049 (11)	−0.0032 (12)
Cl15	0.0857 (6)	0.0441 (5)	0.0614 (5)	0.0055 (4)	0.0069 (4)	0.0083 (3)

Geometric parameters (Å, º)

C1—N2	1.314 (5)	C8—C9	1.419 (5)
C1—C9	1.417 (5)	C9—C10	1.424 (4)
N2—C3	1.359 (5)	S12—O13	1.423 (3)
C3—C4	1.363 (5)	S12—O14	1.423 (3)
C4—C10	1.415 (4)	S12—Cl15	2.0394 (12)
C4—F11	1.346 (4)	C1—H1	0.930
C5—C6	1.381 (5)	C3—H3	0.930
C5—C10	1.437 (4)	C6—H6	0.930
C5—S12	1.766 (3)	C7—H7	0.930
C6—C7	1.402 (5)	C8—H8	0.930
C7—C8	1.356 (5)
N2—C1—C9	124.6 (3)	C5—C10—C9	116.7 (3)
C1—N2—C3	116.7 (3)	C5—S12—O13	109.46 (15)
N2—C3—C4	123.0 (3)	C5—S12—O14	110.93 (15)
C3—C4—C10	122.6 (3)	C5—S12—Cl15	102.46 (10)
C3—C4—F11	117.2 (3)	O13—S12—O14	119.46 (16)
C10—C4—F11	120.3 (3)	O13—S12—Cl15	104.86 (12)
C6—C5—C10	120.7 (3)	O14—S12—Cl15	108.12 (12)
C6—C5—S12	114.4 (2)	N2—C1—H1	117.715
C10—C5—S12	124.8 (2)	C9—C1—H1	117.718
C5—C6—C7	121.0 (3)	N2—C3—H3	118.507
C6—C7—C8	120.3 (4)	C4—C3—H3	118.508
C7—C8—C9	120.5 (3)	C5—C6—H6	119.507
C1—C9—C8	120.0 (3)	C7—C6—H6	119.505
C1—C9—C10	119.3 (3)	C6—C7—H7	119.866
C8—C9—C10	120.7 (3)	C8—C7—H7	119.873
C4—C10—C5	129.5 (3)	C7—C8—H8	119.729
C4—C10—C9	113.8 (3)	C9—C8—H8	119.726
N2—C1—C9—C8	179.3 (3)	C6—C5—S12—Cl15	−109.3 (2)
N2—C1—C9—C10	−0.6 (5)	S12—C5—C6—C7	−172.64 (18)
C9—C1—N2—C3	−0.7 (5)	C10—C5—S12—O13	−173.8 (2)
C1—N2—C3—C4	0.5 (5)	C10—C5—S12—O14	−39.8 (3)
N2—C3—C4—C10	1.1 (5)	C10—C5—S12—Cl15	75.3 (3)
N2—C3—C4—F11	−177.6 (3)	S12—C5—C10—C4	−8.8 (4)
C3—C4—C10—C5	177.5 (3)	S12—C5—C10—C9	171.04 (16)
C3—C4—C10—C9	−2.4 (4)	C5—C6—C7—C8	0.2 (5)
F11—C4—C10—C5	−3.8 (4)	C6—C7—C8—C9	−2.0 (5)
F11—C4—C10—C9	176.3 (2)	C7—C8—C9—C1	−179.2 (3)
C6—C5—C10—C4	176.1 (3)	C7—C8—C9—C10	0.7 (5)
C6—C5—C10—C9	−4.0 (4)	C1—C9—C10—C4	2.1 (4)
C10—C5—C6—C7	2.9 (4)	C1—C9—C10—C5	−177.8 (3)
C6—C5—S12—O13	1.6 (3)	C8—C9—C10—C4	−177.9 (3)
C6—C5—S12—O14	135.5 (2)	C8—C9—C10—C5	2.2 (4)

(II) (S)-(-)-4-Fluoro-N-(1-hydroxypropan-2-yl)isoquinoline-5- sulfonamide

Crystal data

C12H13FN2O3S	F(000) = 592.00
Mr = 284.31	Dx = 1.475 Mg m^−3
Monoclinic, P21	Melting point = 422–424 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71069 Å
a = 18.907 (8) Å	Cell parameters from 25 reflections
b = 7.543 (3) Å	θ = 10.4–12.4°
c = 9.173 (4) Å	µ = 0.27 mm^−1
β = 101.88 (3)°	T = 292 K
V = 1280.2 (9) Å^3	Plate, colourless
Z = 4	0.50 × 0.50 × 0.30 mm

Data collection

Rigaku AFC-7R diffractometer	2458 reflections with F^2 > 2σ(F^2)
Radiation source: Rigaku rotating Mo anode	Rint = 0.038
Graphite plate monochromator	θmax = 27.5°, θmin = 3°
ω scans	h = −9→24
Absorption correction: numerical (NUMABS; Rigaku, 1999b)	k = −9→3
Tmin = 0.887, Tmax = 0.922	l = −11→11
3554 measured reflections	3 standard reflections every 150 reflections
3163 independent reflections	intensity decay: 12%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.159	w = 1/[σ^2(Fo^2) + (0.0972P)^2 + 0.2545P] where P = (Fo^2 + 2Fc^2)/3
S = 1.08	(Δ/σ)max < 0.001
3163 reflections	Δρmax = 0.39 e Å^−3
351 parameters	Δρmin = −0.32 e Å^−3
3 restraints	Absolute structure: see text
Primary atom site location: structure-invariant direct methods

Special details

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.7840 (3)	0.7844 (9)	0.3945 (7)	0.0591 (14)
N2	0.7384 (3)	0.8562 (8)	0.4656 (5)	0.0622 (12)
C3	0.6692 (4)	0.8725 (8)	0.3907 (6)	0.0578 (14)
C4	0.6459 (3)	0.8168 (8)	0.2484 (6)	0.0476 (11)
C5	0.6762 (3)	0.6646 (7)	0.0179 (5)	0.0437 (10)
C6	0.7299 (3)	0.5931 (8)	−0.0423 (6)	0.0527 (12)
C7	0.8026 (4)	0.5858 (9)	0.0369 (7)	0.0627 (15)
C8	0.8199 (3)	0.6481 (9)	0.1773 (7)	0.0594 (13)
C9	0.7670 (3)	0.7223 (7)	0.2465 (6)	0.0481 (11)
C10	0.6928 (3)	0.7348 (7)	0.1668 (6)	0.0425 (10)
F11	0.57628 (15)	0.8427 (6)	0.1855 (4)	0.0638 (9)
S12	0.58687 (6)	0.65236 (16)	−0.09721 (13)	0.0455 (3)
O13	0.5968 (3)	0.5723 (6)	−0.2328 (5)	0.0623 (11)
O14	0.5419 (3)	0.5691 (7)	−0.0106 (5)	0.0663 (11)
N15	0.5572 (2)	0.8509 (7)	−0.1345 (5)	0.0484 (10)
C16	0.5773 (3)	0.9590 (7)	−0.2524 (5)	0.0439
C17	0.5111 (4)	0.9955 (12)	−0.3764 (7)	0.0691 (17)
C18	0.6133 (3)	1.1316 (9)	−0.1867 (7)	0.0599 (14)
O19	0.6795 (3)	1.1016 (9)	−0.0888 (5)	0.0836 (16)
H1	0.8317	0.7730	0.4455	0.0709*
H3	0.6359	0.9246	0.4393	0.0693*
H6	0.7185	0.5475	−0.1386	0.0633*
H7	0.8382	0.5381	−0.0079	0.0752*
H8	0.8676	0.6419	0.2293	0.0713*
H15	0.531 (3)	0.893 (8)	−0.077 (5)	0.0581*
H16	0.6125	0.8922	−0.2954	0.0526*
H17A	0.4902	0.8850	−0.4156	0.0829*
H17B	0.5256	1.0621	−0.4545	0.0829*
H17C	0.4761	1.0621	−0.3367	0.0829*
H18A	0.6211	1.2076	−0.2672	0.0719*
H18B	0.5810	1.1930	−0.1340	0.0719*
H19	0.7058	1.0429	−0.1310	0.1003*
C20	0.6944 (3)	0.2775 (9)	0.2561 (6)	0.0574 (13)
N21	0.6526 (3)	0.3453 (9)	0.3387 (6)	0.0647 (13)
C22	0.6850 (3)	0.3957 (9)	0.4770 (7)	0.0592 (14)
C23	0.7575 (3)	0.3761 (8)	0.5328 (6)	0.0505 (12)
C24	0.8813 (3)	0.2777 (8)	0.4884 (6)	0.0465 (11)
C25	0.9183 (3)	0.2007 (8)	0.3908 (6)	0.0547 (13)
C26	0.8813 (3)	0.1472 (10)	0.2472 (6)	0.0588 (13)
C27	0.8089 (3)	0.1738 (8)	0.2034 (6)	0.0538 (12)
C28	0.7699 (3)	0.2505 (7)	0.3022 (6)	0.0467 (11)
C29	0.8044 (3)	0.3054 (7)	0.4472 (5)	0.0429 (10)
F30	0.78313 (18)	0.4294 (6)	0.6742 (4)	0.0684 (10)
S31	0.93581 (7)	0.33073 (19)	0.66727 (14)	0.0528 (4)
O32	1.0075 (2)	0.2767 (7)	0.6646 (5)	0.0695 (12)
O33	0.9239 (3)	0.5136 (7)	0.7014 (6)	0.0720 (12)
N34	0.9070 (3)	0.2080 (7)	0.7889 (5)	0.0515 (10)
C35	0.9142 (3)	0.0149 (8)	0.7768 (6)	0.0499
C36	0.9832 (4)	−0.0566 (11)	0.8768 (8)	0.0726 (17)
C37	0.8483 (3)	−0.0711 (9)	0.8195 (6)	0.0570 (13)
O38	0.78193 (19)	0.0050 (7)	0.7446 (5)	0.0641 (11)
H20	0.6729	0.2444	0.1595	0.0689*
H22	0.6567	0.4463	0.5378	0.0710*
H25	0.9679	0.1834	0.4192	0.0656*
H26	0.9067	0.0936	0.1824	0.0705*
H27	0.7852	0.1413	0.1080	0.0645*
H34	0.8650 (16)	0.245 (9)	0.796 (7)	0.0618*
H35	0.9147	−0.0152	0.6731	0.0599*
H36A	1.0246	−0.0075	0.8459	0.0871*
H36B	0.9842	−0.1835	0.8690	0.0871*
H36C	0.9841	−0.0237	0.9783	0.0871*
H37A	0.8481	−0.1966	0.7964	0.0683*
H37B	0.8521	−0.0594	0.9261	0.0683*
H38	0.7781	−0.0057	0.6544	0.0769*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.053 (3)	0.058 (4)	0.060 (3)	−0.005 (3)	−0.003 (3)	0.006 (3)
N2	0.076 (3)	0.055 (3)	0.049 (3)	−0.002 (3)	−0.003 (2)	−0.003 (3)
C3	0.073 (4)	0.053 (4)	0.048 (3)	0.005 (3)	0.014 (3)	−0.004 (3)
C4	0.052 (3)	0.043 (3)	0.047 (3)	−0.001 (3)	0.0083 (19)	0.003 (3)
C5	0.043 (3)	0.042 (3)	0.047 (3)	−0.001 (2)	0.0111 (18)	0.007 (3)
C6	0.062 (3)	0.049 (3)	0.050 (3)	0.006 (3)	0.018 (3)	0.005 (3)
C7	0.058 (3)	0.062 (4)	0.075 (4)	0.014 (3)	0.030 (3)	0.014 (4)
C8	0.046 (3)	0.056 (3)	0.077 (4)	0.005 (3)	0.013 (3)	0.011 (4)
C9	0.050 (3)	0.038 (3)	0.054 (3)	−0.003 (2)	0.005 (2)	0.006 (3)
C10	0.049 (3)	0.034 (3)	0.046 (3)	−0.0001 (19)	0.0112 (19)	0.0052 (19)
F11	0.0520 (16)	0.089 (3)	0.0505 (15)	0.0160 (19)	0.0116 (12)	−0.0043 (19)
S12	0.0494 (6)	0.0416 (6)	0.0451 (6)	−0.0060 (6)	0.0090 (5)	−0.0007 (6)
O13	0.076 (3)	0.055 (3)	0.053 (2)	0.003 (2)	0.0046 (19)	−0.0087 (18)
O14	0.062 (3)	0.065 (3)	0.071 (3)	−0.021 (2)	0.0117 (19)	0.007 (3)
N15	0.048 (2)	0.052 (3)	0.050 (2)	0.006 (2)	0.0181 (16)	0.002 (2)
C16	0.0428	0.0467	0.0425	0.0028	0.0098	0.0026
C17	0.057 (4)	0.086 (5)	0.059 (4)	0.006 (4)	0.001 (3)	0.006 (4)
C18	0.058 (3)	0.056 (4)	0.068 (4)	−0.007 (3)	0.018 (3)	−0.004 (3)
O19	0.058 (3)	0.123 (5)	0.068 (3)	−0.018 (3)	0.010 (2)	−0.036 (3)
C20	0.052 (3)	0.062 (4)	0.054 (3)	−0.002 (3)	0.002 (3)	0.004 (3)
N21	0.054 (3)	0.074 (4)	0.066 (3)	0.010 (3)	0.011 (2)	0.010 (3)
C22	0.047 (3)	0.060 (4)	0.074 (4)	0.014 (3)	0.020 (3)	0.011 (3)
C23	0.056 (3)	0.048 (3)	0.048 (3)	0.006 (3)	0.012 (2)	0.001 (3)
C24	0.048 (3)	0.047 (3)	0.045 (3)	−0.000 (2)	0.0111 (19)	0.002 (2)
C25	0.053 (3)	0.055 (4)	0.058 (3)	0.005 (3)	0.019 (3)	0.001 (3)
C26	0.063 (3)	0.063 (4)	0.055 (3)	0.006 (3)	0.022 (3)	−0.007 (3)
C27	0.060 (3)	0.055 (4)	0.046 (3)	−0.001 (3)	0.011 (2)	−0.003 (3)
C28	0.053 (3)	0.040 (3)	0.047 (3)	−0.002 (2)	0.012 (2)	0.004 (2)
C29	0.047 (3)	0.037 (3)	0.046 (3)	0.004 (2)	0.0111 (18)	0.002 (2)
F30	0.073 (2)	0.082 (3)	0.0513 (17)	0.0201 (19)	0.0154 (15)	−0.0150 (17)
S31	0.0486 (7)	0.0520 (8)	0.0557 (7)	−0.0092 (6)	0.0057 (5)	−0.0051 (7)
O32	0.055 (2)	0.078 (3)	0.073 (3)	−0.015 (2)	0.0061 (18)	−0.006 (3)
O33	0.082 (3)	0.056 (3)	0.076 (3)	−0.013 (3)	0.009 (3)	−0.010 (3)
N34	0.052 (3)	0.055 (3)	0.046 (2)	−0.000 (2)	0.0075 (18)	−0.006 (2)
C35	0.0547	0.0541	0.0418	0.0014	0.0120	−0.0019
C36	0.063 (4)	0.076 (5)	0.074 (4)	0.008 (4)	0.004 (3)	0.010 (4)
C37	0.062 (3)	0.063 (4)	0.046 (3)	−0.006 (3)	0.011 (3)	−0.003 (3)
O38	0.052 (2)	0.084 (3)	0.055 (2)	−0.009 (2)	0.0097 (16)	−0.015 (3)

Geometric parameters (Å, º)

C1—N2	1.301 (9)	S31—O32	1.421 (5)
C1—C9	1.409 (8)	S31—O33	1.442 (5)
N2—C3	1.352 (8)	S31—N34	1.627 (5)
C3—C4	1.356 (7)	N34—C35	1.469 (8)
C4—C10	1.415 (8)	C35—C36	1.531 (8)
C4—F11	1.339 (6)	C35—C37	1.525 (9)
C5—C6	1.364 (8)	C37—O38	1.422 (7)
C5—C10	1.438 (7)	C1—H1	0.930
C5—S12	1.800 (5)	C3—H3	0.930
C6—C7	1.418 (8)	C6—H6	0.930
C7—C8	1.347 (9)	C7—H7	0.930
C8—C9	1.407 (9)	C8—H8	0.930
C9—C10	1.445 (7)	N15—H15	0.858 (10)
S12—O13	1.429 (5)	C16—H16	0.980
S12—O14	1.424 (5)	C17—H17A	0.960
S12—N15	1.611 (6)	C17—H17B	0.960
N15—C16	1.466 (7)	C17—H17C	0.960
C16—C17	1.532 (7)	C18—H18A	0.970
C16—C18	1.533 (8)	C18—H18B	0.970
C18—O19	1.401 (7)	O19—H19	0.820
C20—N21	1.306 (9)	C20—H20	0.930
C20—C28	1.418 (8)	C22—H22	0.930
N21—C22	1.345 (8)	C25—H25	0.930
C22—C23	1.369 (8)	C26—H26	0.930
C23—C29	1.405 (8)	C27—H27	0.930
C23—F30	1.348 (6)	N34—H34	0.858 (10)
C24—C25	1.372 (9)	C35—H35	0.980
C24—C29	1.441 (7)	C36—H36A	0.960
C24—S31	1.794 (5)	C36—H36B	0.960
C25—C26	1.417 (8)	C36—H36C	0.960
C26—C27	1.360 (8)	C37—H37A	0.970
C27—C28	1.405 (8)	C37—H37B	0.970
C28—C29	1.417 (7)	O38—H38	0.820
N2—C1—C9	125.3 (5)	C36—C35—C37	109.7 (5)
C1—N2—C3	117.1 (5)	C35—C37—O38	113.0 (5)
N2—C3—C4	123.3 (6)	N2—C1—H1	117.343
C3—C4—C10	122.0 (5)	C9—C1—H1	117.335
C3—C4—F11	117.7 (5)	N2—C3—H3	118.344
C10—C4—F11	120.3 (4)	C4—C3—H3	118.341
C6—C5—C10	119.6 (4)	C5—C6—H6	118.928
C6—C5—S12	115.4 (4)	C7—C6—H6	118.914
C10—C5—S12	124.9 (4)	C6—C7—H7	120.136
C5—C6—C7	122.2 (5)	C8—C7—H7	120.134
C6—C7—C8	119.7 (6)	C7—C8—H8	119.495
C7—C8—C9	121.0 (5)	C9—C8—H8	119.500
C1—C9—C8	121.7 (5)	C16—N15—H15	121 (4)
C1—C9—C10	118.1 (5)	S12—N15—H15	116 (4)
C8—C9—C10	120.3 (5)	N15—C16—H16	108.150
C4—C10—C5	128.6 (5)	C17—C16—H16	108.149
C4—C10—C9	114.2 (5)	C18—C16—H16	108.141
C5—C10—C9	117.2 (5)	C16—C17—H17A	109.469
C5—S12—O13	104.9 (3)	C16—C17—H17B	109.466
C5—S12—O14	107.0 (3)	C16—C17—H17C	109.470
C5—S12—N15	108.7 (3)	H17A—C17—H17B	109.475
O13—S12—O14	120.0 (3)	H17A—C17—H17C	109.477
O13—S12—N15	108.1 (3)	H17B—C17—H17C	109.470
O14—S12—N15	107.8 (3)	C16—C18—H18A	109.123
S12—N15—C16	122.8 (4)	C16—C18—H18B	109.126
N15—C16—C17	110.6 (5)	O19—C18—H18A	109.124
N15—C16—C18	110.1 (5)	O19—C18—H18B	109.128
C17—C16—C18	111.6 (5)	H18A—C18—H18B	107.855
C16—C18—O19	112.4 (6)	C18—O19—H19	109.468
N21—C20—C28	125.1 (5)	N21—C20—H20	117.430
C20—N21—C22	116.5 (5)	C28—C20—H20	117.430
N21—C22—C23	123.3 (6)	N21—C22—H22	118.364
C22—C23—C29	122.0 (5)	C23—C22—H22	118.368
C22—C23—F30	117.5 (6)	C24—C25—H25	119.753
C29—C23—F30	120.5 (5)	C26—C25—H25	119.754
C25—C24—C29	120.8 (5)	C25—C26—H26	119.787
C25—C24—S31	114.7 (4)	C27—C26—H26	119.790
C29—C24—S31	124.5 (4)	C26—C27—H27	119.993
C24—C25—C26	120.5 (5)	C28—C27—H27	120.009
C25—C26—C27	120.4 (6)	C35—N34—H34	116 (5)
C26—C27—C28	120.0 (5)	S31—N34—H34	108 (5)
C20—C28—C27	119.8 (5)	N34—C35—H35	108.814
C20—C28—C29	118.6 (5)	C36—C35—H35	108.813
C27—C28—C29	121.6 (5)	C37—C35—H35	108.818
C23—C29—C24	128.9 (5)	C35—C36—H36A	109.478
C23—C29—C28	114.5 (5)	C35—C36—H36B	109.471
C24—C29—C28	116.7 (5)	C35—C36—H36C	109.475
C24—S31—O32	106.9 (3)	H36A—C36—H36B	109.473
C24—S31—O33	109.0 (3)	H36A—C36—H36C	109.462
C24—S31—N34	106.9 (3)	H36B—C36—H36C	109.470
O32—S31—O33	118.0 (3)	C35—C37—H37A	108.988
O32—S31—N34	107.7 (3)	C35—C37—H37B	108.984
O33—S31—N34	107.9 (3)	O38—C37—H37A	108.974
S31—N34—C35	117.6 (4)	O38—C37—H37B	108.976
N34—C35—C36	112.6 (5)	H37A—C37—H37B	107.775
N34—C35—C37	108.0 (5)	C37—O38—H38	109.470
N2—C1—C9—C8	179.2 (6)	N21—C20—C28—C27	179.1 (6)
N2—C1—C9—C10	−1.5 (9)	N21—C20—C28—C29	−2.1 (9)
C9—C1—N2—C3	−0.1 (9)	C28—C20—N21—C22	1.3 (10)
C1—N2—C3—C4	0.6 (9)	C20—N21—C22—C23	−1.1 (10)
N2—C3—C4—C10	0.5 (9)	N21—C22—C23—C29	1.8 (10)
N2—C3—C4—F11	−179.0 (5)	N21—C22—C23—F30	−179.0 (6)
C3—C4—C10—C5	178.1 (5)	C22—C23—C29—C24	179.4 (5)
C3—C4—C10—C9	−2.0 (8)	C22—C23—C29—C28	−2.4 (8)
F11—C4—C10—C5	−2.3 (8)	F30—C23—C29—C24	0.2 (9)
F11—C4—C10—C9	177.5 (5)	F30—C23—C29—C28	178.4 (4)
C6—C5—C10—C4	178.8 (5)	C25—C24—C29—C23	177.7 (5)
C6—C5—C10—C9	−1.0 (7)	C25—C24—C29—C28	−0.4 (8)
C10—C5—C6—C7	−0.3 (8)	C29—C24—C25—C26	0.2 (9)
C6—C5—S12—O13	−2.5 (5)	C25—C24—S31—O32	−0.2 (5)
C6—C5—S12—O14	125.9 (4)	C25—C24—S31—O33	128.4 (5)
C6—C5—S12—N15	−117.9 (5)	C25—C24—S31—N34	−115.3 (5)
S12—C5—C6—C7	−177.3 (4)	S31—C24—C25—C26	178.1 (4)
C10—C5—S12—O13	−179.3 (4)	C29—C24—S31—O32	177.6 (5)
C10—C5—S12—O14	−50.9 (5)	C29—C24—S31—O33	−53.8 (5)
C10—C5—S12—N15	65.3 (5)	C29—C24—S31—N34	62.5 (5)
S12—C5—C10—C4	−4.5 (8)	S31—C24—C29—C23	0.0 (8)
S12—C5—C10—C9	175.7 (3)	S31—C24—C29—C28	−178.1 (4)
C5—C6—C7—C8	1.2 (10)	C24—C25—C26—C27	0.9 (10)
C6—C7—C8—C9	−0.7 (10)	C25—C26—C27—C28	−1.7 (10)
C7—C8—C9—C1	178.5 (6)	C26—C27—C28—C20	−179.8 (6)
C7—C8—C9—C10	−0.7 (9)	C26—C27—C28—C29	1.4 (9)
C1—C9—C10—C4	2.5 (7)	C20—C28—C29—C23	2.5 (7)
C1—C9—C10—C5	−177.7 (5)	C20—C28—C29—C24	−179.1 (5)
C8—C9—C10—C4	−178.3 (5)	C27—C28—C29—C23	−178.8 (5)
C8—C9—C10—C5	1.5 (8)	C27—C28—C29—C24	−0.4 (8)
C5—S12—N15—C16	81.0 (4)	C24—S31—N34—C35	63.4 (4)
O13—S12—N15—C16	−32.3 (4)	O32—S31—N34—C35	−51.2 (4)
O14—S12—N15—C16	−163.3 (3)	O33—S31—N34—C35	−179.5 (3)
S12—N15—C16—C17	114.7 (4)	S31—N34—C35—C36	94.8 (4)
S12—N15—C16—C18	−121.5 (4)	S31—N34—C35—C37	−143.9 (3)
N15—C16—C18—O19	65.4 (6)	N34—C35—C37—O38	49.3 (6)
C17—C16—C18—O19	−171.4 (5)	C36—C35—C37—O38	172.4 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N15—H15···F11	0.86 (1)	2.42 (5)	2.884 (5)	115 (5)
N15—H15···O14^i	0.86 (1)	2.18 (2)	3.003 (6)	161 (6)
O19—H19···O38^ii	0.82	2.03	2.799 (6)	155
N34—H34···F30	0.86 (1)	2.20 (4)	2.893 (6)	137 (6)
N34—H34···O38	0.86 (1)	2.38 (7)	2.777 (6)	109 (5)
O38—H38···N2^iii	0.82	2.03	2.761 (6)	148

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

(III) (S)-(-)-4-[(4-Fluoroisoquinolin-5-yl)sulfonyl]-3-methyl-1,4- diazepan-1-ium chloride

Crystal data

C15H19FN3O2S^+·Cl^−	F(000) = 752.00
Mr = 359.85	Dx = 1.464 Mg m^−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: P 2ac 2ab	Cell parameters from 25 reflections
a = 12.379 (8) Å	θ = 10.1–12.4°
b = 19.294 (14) Å	µ = 0.38 mm^−1
c = 6.835 (4) Å	T = 293 K
V = 1633 (2) Å^3	Plate, colourless
Z = 4	0.50 × 0.40 × 0.30 mm

Data collection

Rigaku AFC-7R diffractometer	1504 reflections with F^2 > 2σ(F^2)
Radiation source: Rigaku rotating anode	Rint = 0.040
Graphite plate monochromator	θmax = 27.5°
ω scans	h = −6→16
Absorption correction: numerical (NUMABS; Rigaku, 1999)	k = 0→25
Tmin = 0.855, Tmax = 0.891	l = −3→8
2428 measured reflections	3 standard reflections every 150 reflections
2215 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.059	H-atom parameters constrained
wR(F^2) = 0.166	w = 1/[σ^2(Fo^2) + (0.0996P)^2 + 0.1864P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
2215 reflections	Δρmax = 0.37 e Å^−3
209 parameters	Δρmin = −0.26 e Å^−3
0 restraints	Absolute structure: Flack (1983), with 60 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (18)

Special details

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2σ(F²) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.1643 (7)	0.5537 (4)	0.3337 (10)	0.069 (2)
N2	0.0597 (6)	0.5408 (3)	0.3303 (10)	0.0736 (18)
C3	0.0293 (6)	0.4728 (4)	0.3272 (11)	0.0645 (18)
C4	0.1022 (5)	0.4205 (3)	0.3408 (10)	0.0501 (14)
C5	0.2988 (5)	0.3809 (3)	0.3769 (9)	0.0449 (13)
C6	0.4048 (5)	0.4022 (4)	0.3592 (11)	0.0603 (17)
C7	0.4329 (6)	0.4718 (4)	0.3327 (12)	0.069 (2)
C8	0.3553 (7)	0.5213 (4)	0.3312 (11)	0.0655 (19)
C9	0.2459 (6)	0.5025 (3)	0.3419 (9)	0.0536 (14)
C10	0.2149 (5)	0.4310 (3)	0.3553 (8)	0.0454 (12)
F11	0.0624 (3)	0.35544 (17)	0.3319 (7)	0.0656 (11)
S12	0.27795 (11)	0.29499 (7)	0.4661 (2)	0.0452 (4)
O13	0.3823 (4)	0.2727 (2)	0.5288 (8)	0.0640 (13)
O14	0.1923 (4)	0.2964 (2)	0.6066 (6)	0.0567 (11)
N15	0.2408 (4)	0.2492 (2)	0.2804 (7)	0.0434 (11)
C16	0.1384 (4)	0.2091 (3)	0.2832 (9)	0.0429 (13)
C17	0.0841 (5)	0.2097 (4)	0.0823 (11)	0.0662 (19)
C18	0.1522 (4)	0.1361 (3)	0.3631 (10)	0.0460 (13)
N19	0.2405 (4)	0.0946 (2)	0.2697 (7)	0.0471 (11)
C20	0.3524 (5)	0.1194 (3)	0.3210 (11)	0.0546 (16)
C21	0.3978 (5)	0.1720 (4)	0.1788 (12)	0.0622 (18)
C22	0.3231 (5)	0.2328 (3)	0.1331 (10)	0.0560 (16)
Cl23	0.25917 (15)	−0.06375 (7)	0.3220 (3)	0.0633 (5)
H1	0.1859	0.5999	0.3305	0.0824*
H3	−0.0436	0.4620	0.3153	0.0774*
H6	0.4594	0.3692	0.3650	0.0724*
H7	0.5049	0.4841	0.3160	0.0833*
H8	0.3745	0.5678	0.3232	0.0786*
H16	0.0895	0.2333	0.3729	0.0515*
H17A	0.0873	0.2556	0.0285	0.0794*
H17B	0.0100	0.1958	0.0955	0.0794*
H17C	0.1209	0.1781	−0.0032	0.0794*
H18A	0.1665	0.1391	0.5023	0.0552*
H18B	0.0846	0.1113	0.3466	0.0552*
H19A	0.2323	0.0963	0.1389	0.0565*
H19B	0.2338	0.0501	0.3068	0.0565*
H20A	0.4005	0.0798	0.3257	0.0655*
H20B	0.3507	0.1399	0.4506	0.0655*
H21A	0.4150	0.1484	0.0574	0.0746*
H21B	0.4647	0.1901	0.2320	0.0746*
H22A	0.3674	0.2736	0.1132	0.0672*
H22B	0.2866	0.2231	0.0104	0.0672*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.113 (7)	0.049 (4)	0.044 (4)	−0.002 (4)	0.002 (5)	0.009 (4)
N2	0.099 (5)	0.056 (4)	0.066 (4)	0.027 (4)	0.006 (4)	0.012 (3)
C3	0.069 (5)	0.060 (4)	0.065 (5)	0.013 (4)	0.005 (4)	0.010 (4)
C4	0.053 (4)	0.047 (3)	0.050 (4)	0.004 (3)	0.002 (3)	0.003 (3)
C5	0.050 (3)	0.039 (3)	0.046 (3)	−0.008 (3)	−0.001 (3)	−0.001 (3)
C6	0.057 (4)	0.063 (4)	0.062 (5)	−0.014 (3)	−0.007 (4)	0.005 (4)
C7	0.064 (4)	0.079 (5)	0.065 (5)	−0.037 (4)	−0.013 (4)	0.011 (5)
C8	0.094 (5)	0.054 (4)	0.048 (4)	−0.025 (4)	−0.005 (4)	0.006 (4)
C9	0.080 (4)	0.043 (3)	0.037 (3)	−0.009 (3)	−0.006 (4)	0.007 (3)
C10	0.057 (3)	0.043 (3)	0.036 (3)	0.001 (3)	0.002 (3)	0.003 (3)
F11	0.0479 (18)	0.0507 (18)	0.098 (3)	−0.0029 (15)	−0.006 (3)	0.004 (3)
S12	0.0489 (7)	0.0385 (6)	0.0482 (7)	−0.0019 (6)	−0.0058 (7)	−0.0006 (6)
O13	0.062 (3)	0.055 (3)	0.076 (3)	−0.002 (2)	−0.021 (3)	0.004 (3)
O14	0.071 (3)	0.048 (2)	0.051 (3)	−0.005 (2)	0.006 (3)	−0.003 (2)
N15	0.041 (3)	0.038 (2)	0.051 (3)	−0.0021 (18)	0.005 (3)	−0.004 (2)
C16	0.037 (3)	0.036 (3)	0.055 (4)	0.003 (3)	0.001 (3)	−0.003 (3)
C17	0.056 (4)	0.059 (4)	0.083 (6)	−0.000 (4)	−0.026 (4)	0.005 (4)
C18	0.036 (3)	0.044 (3)	0.058 (4)	−0.002 (3)	0.000 (3)	0.002 (3)
N19	0.055 (3)	0.0357 (19)	0.051 (3)	−0.000 (2)	−0.001 (3)	0.004 (2)
C20	0.044 (3)	0.046 (3)	0.074 (5)	0.013 (3)	0.002 (4)	−0.004 (4)
C21	0.047 (4)	0.064 (4)	0.075 (5)	0.003 (3)	0.016 (4)	−0.014 (4)
C22	0.056 (4)	0.060 (4)	0.052 (4)	−0.009 (3)	0.010 (3)	0.005 (3)
Cl23	0.0945 (13)	0.0443 (7)	0.0510 (8)	0.0099 (8)	0.0002 (9)	0.0017 (7)

Geometric parameters (Å, º)

C1—N2	1.318 (12)	C20—C21	1.512 (10)
C1—C9	1.415 (11)	C21—C22	1.525 (9)
N2—C3	1.366 (9)	C1—H1	0.930
C3—C4	1.356 (9)	C3—H3	0.930
C4—C10	1.413 (9)	C6—H6	0.930
C4—F11	1.350 (7)	C7—H7	0.930
C5—C6	1.381 (9)	C8—H8	0.930
C5—C10	1.425 (8)	C16—H16	0.980
C5—S12	1.785 (6)	C17—H17A	0.960
C6—C7	1.398 (10)	C17—H17B	0.960
C7—C8	1.354 (11)	C17—H17C	0.960
C8—C9	1.405 (11)	C18—H18A	0.970
C9—C10	1.435 (8)	C18—H18B	0.970
S12—O13	1.428 (5)	N19—H19A	0.900
S12—O14	1.430 (5)	N19—H19B	0.900
S12—N15	1.613 (5)	C20—H20A	0.970
N15—C16	1.486 (7)	C20—H20B	0.970
N15—C22	1.467 (8)	C21—H21A	0.970
C16—C17	1.529 (10)	C21—H21B	0.970
C16—C18	1.521 (8)	C22—H22A	0.970
C18—N19	1.497 (7)	C22—H22B	0.970
N19—C20	1.508 (7)
N2—C1—C9	124.7 (7)	C7—C6—H6	118.896
C1—N2—C3	116.9 (7)	C6—C7—H7	119.916
N2—C3—C4	122.0 (7)	C8—C7—H7	119.923
C3—C4—C10	123.8 (6)	C7—C8—H8	119.990
C3—C4—F11	116.5 (6)	C9—C8—H8	119.992
C10—C4—F11	119.7 (5)	N15—C16—H16	106.665
C6—C5—C10	118.8 (5)	C17—C16—H16	106.661
C6—C5—S12	116.3 (5)	C18—C16—H16	106.660
C10—C5—S12	124.0 (5)	C16—C17—H17A	109.467
C5—C6—C7	122.2 (6)	C16—C17—H17B	109.478
C6—C7—C8	120.2 (7)	C16—C17—H17C	109.474
C7—C8—C9	120.0 (7)	H17A—C17—H17B	109.475
C1—C9—C8	120.4 (6)	H17A—C17—H17C	109.457
C1—C9—C10	118.9 (7)	H17B—C17—H17C	109.477
C8—C9—C10	120.7 (6)	C16—C18—H18A	108.495
C4—C10—C5	129.0 (5)	C16—C18—H18B	108.506
C4—C10—C9	113.4 (6)	N19—C18—H18A	108.499
C5—C10—C9	117.6 (6)	N19—C18—H18B	108.492
C5—S12—O13	104.6 (3)	H18A—C18—H18B	107.513
C5—S12—O14	108.5 (3)	C18—N19—H19A	108.823
C5—S12—N15	106.3 (3)	C18—N19—H19B	108.820
O13—S12—O14	118.3 (3)	C20—N19—H19A	108.823
O13—S12—N15	109.2 (3)	C20—N19—H19B	108.820
O14—S12—N15	109.1 (3)	H19A—N19—H19B	107.681
S12—N15—C16	121.2 (4)	N19—C20—H20A	108.787
S12—N15—C22	117.5 (4)	N19—C20—H20B	108.781
C16—N15—C22	119.2 (5)	C21—C20—H20A	108.783
N15—C16—C17	111.1 (5)	C21—C20—H20B	108.781
N15—C16—C18	113.1 (4)	H20A—C20—H20B	107.668
C17—C16—C18	112.3 (5)	C20—C21—H21A	108.521
C16—C18—N19	115.1 (5)	C20—C21—H21B	108.527
C18—N19—C20	113.7 (5)	C22—C21—H21A	108.528
N19—C20—C21	113.9 (6)	C22—C21—H21B	108.520
C20—C21—C22	115.0 (6)	H21A—C21—H21B	107.531
N15—C22—C21	116.5 (6)	N15—C22—H22A	108.170
N2—C1—H1	117.641	N15—C22—H22B	108.158
C9—C1—H1	117.657	C21—C22—H22A	108.164
N2—C3—H3	119.007	C21—C22—H22B	108.162
C4—C3—H3	119.008	H22A—C22—H22B	107.332
C5—C6—H6	118.898
N2—C1—C9—C8	175.6 (6)	C7—C8—C9—C1	−177.8 (6)
N2—C1—C9—C10	−2.6 (10)	C7—C8—C9—C10	0.3 (10)
C9—C1—N2—C3	−2.6 (10)	C1—C9—C10—C4	5.4 (8)
C1—N2—C3—C4	4.6 (11)	C1—C9—C10—C5	−175.8 (5)
N2—C3—C4—C10	−1.3 (11)	C8—C9—C10—C4	−172.7 (5)
N2—C3—C4—F11	−178.7 (6)	C8—C9—C10—C5	6.1 (8)
C3—C4—C10—C5	177.7 (6)	C5—S12—N15—C16	−124.6 (4)
C3—C4—C10—C9	−3.7 (9)	C5—S12—N15—C22	72.0 (4)
F11—C4—C10—C5	−5.1 (10)	O13—S12—N15—C16	123.1 (4)
F11—C4—C10—C9	173.6 (5)	O13—S12—N15—C22	−40.3 (4)
C6—C5—C10—C4	170.5 (6)	O14—S12—N15—C16	−7.7 (4)
C6—C5—C10—C9	−8.1 (8)	O14—S12—N15—C22	−171.1 (3)
C10—C5—C6—C7	4.0 (10)	S12—N15—C16—C17	143.5 (3)
C6—C5—S12—O13	9.3 (6)	S12—N15—C16—C18	−89.3 (5)
C6—C5—S12—O14	136.5 (5)	S12—N15—C22—C21	81.4 (5)
C6—C5—S12—N15	−106.2 (5)	C16—N15—C22—C21	−82.3 (6)
S12—C5—C6—C7	−165.8 (5)	C22—N15—C16—C17	−53.4 (6)
C10—C5—S12—O13	−159.9 (5)	C22—N15—C16—C18	73.8 (6)
C10—C5—S12—O14	−32.7 (6)	N15—C16—C18—N19	−51.7 (7)
C10—C5—S12—N15	84.6 (5)	C17—C16—C18—N19	74.9 (6)
S12—C5—C10—C4	−20.5 (8)	C16—C18—N19—C20	70.4 (6)
S12—C5—C10—C9	160.9 (4)	C18—N19—C20—C21	−91.7 (6)
C5—C6—C7—C8	2.6 (11)	N19—C20—C21—C22	50.1 (7)
C6—C7—C8—C9	−4.7 (11)	C20—C21—C22—N15	23.9 (8)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N19—H19A···Cl23^i	0.90	2.26	3.117 (6)	160
N19—H19B···Cl23	0.90	2.22	3.085 (5)	161

Symmetry code: (i) −x+1/2, −y, z−1/2.