Four cytotoxic N4-substituted thiosemicarbazones derived from 2-hydroxynaphthalene-1-carboxaldehyde

The X-ray crystal structures are reported of four novel and potentially O,N,S-tridentate donor ligands that demonstrate antitumour activity. These ligands are 1-[(4-methyl­thio­semicarbazono)methyl]-2-naphthol, C₁₃H₁₃N₃OS, (III), 1-[(4-ethylthio­semicarbazono)­methyl]-2-naphthol, C₁₄H₁₅N₃OS, (IV), 1-[(4-phenyl­thio­semicarbazono)­methyl]-2-naphthol, C₁₈H₁₅N₃OS, (V), and 1-[(4,4-di­methyl­thio­semicarbazono)­methyl]-2-naphthol di­methyl sulfoxide solvate, C₁₄H₁₅N₃OS·C₂H₆OS, (VI). These chelators are N4-substituted thio­semicarbazones, each based on the same parent aldehyde, namely 2-­zhydroxynaphthalene-1-carboxaldehyde isonicotinoylhydrazone. Conformational variations within this series are discussed in relation to the optimum conformation for metal-ion binding.

S1. Comment

Due to its critical role in DNA synthesis and proliferation, iron is a potential target for the treatment of cancer (Richardson, 2002). To this end, the cellular antiproliferative effects of a number of Fe-specific chelators and their complexes have been examined. A class of chelators with pronounced, and selective, activity against tumour cells are the thiosemicarbazones. The mechanism by which these compounds act is still not well understood, but chelation of intracellular Fe and other metal ions is believed to be important. A pertinent example is 3-aminopyridine-2-carbaldehyde thiosemicarbazone, (I) (also known as Triapine), which is a potent inhibitor of ribonucleotide reductase (Finch et al., 1999), an enzyme which catalyzes the rate-limiting step in DNA synthesis.

Recently, we reported (Lovejoy & Richardson, 2002) the antiproliferative activity of a series of novel thiosemicarbazones based on 2-hydroxy-1-naphthaldehyde, and found that many of them were highly active against neoplastic cellular proliferation but had much less effect on normal cells. Interestingly, structural variations at the thiosemicarbazide moiety have a marked effect on biological activity. For example, the N2-methyl substituted thiosemicarbazone (II) exhibits poor antiproliferative activity (Lovejoy & Richardson, 2002), and we have reported the crystal structure of this compound (Lovejoy et al., 2000). The absence of an ionisable H atom on N2 and the consequential lowering of Fe binding affinity were attributed to this feature. Herein, we report the crystal structures of four N4-substituted thiosemicarbazones, (III)-(VI), each derived from the same parent aldehyde (2-hydroxy-1-naphthaldehyde) and all displaying high antiproliferative activity (Lovejoy & Richardson, 2002). In each case, N2 is protonated, but the conformation of the thiosemicarbazide group varies across the series. \sch

Selected bond lengths and angles are shown in Tables 1, 3, 5 and 7 for compounds (III)-(VI), respectively. It can be seen that there is little variation in the bond lengths within this series, but there are some subtle distinctions between their overall structures, as discussed below, particularly with regard to hydrogen bonding.

The structure of (III) (Fig. 1 and Table 1) reveals an almost planar molecule, with all non-H atoms within 0.04 Å of the least-squares plane, and the dihedral angles are all within 2° of either 0 or 180°. Intramolecular hydrogen bonding is a feature of the structure. The hydroxyl group is hydrogen-bonded to the adjacent imine N atom (Table 2). A weaker and more acute hydrogen bond is formed between the imine N atom and the adjacent NH group. In this conformation, the S atom is anti to atom N1 and is able to form a hydrogen bond with the remaining hydrazide H atom. This interaction creates a polymeric hydrogen-bonded chain, shown in the packing diagram of (III) (Fig. 2).

The N-ethyl analogue, (IV) (Fig. 3 and Table 3), exhibits a similar conformation and intramolecular hydrogen-bonding interactions to the N-methyl analogue, (III) (Table 4). Again, an intermolecular hydrogen bond involving the S atom is observed in (IV). In contrast with the hydrogen-bonded polymer found in (III), the intermolecular hydrogen bonds in (IV) result in C₂-symmetric dimers, as shown in Fig. 4. The molecule of (IV) is somewhat less planar than that of (III); the largest torsion angle deviation from either 0 or 180° is 7.6 (3)° for N3—C12—N2—N1, which may be attributed to the distortion resulting from the cyclic intermolecular hydrogen-bonding motif.

A similar structure is again seen in the N-phenyl compound, (V) (Fig. 5 and Table 5), although the phenyl ring is rotated by ca 37° out of the plane defined by the rest of the molecule to minimize ortho H-atom repulsions with atoms S1 and H3A (the H atom attached to N3). The relevant intramolecular hydrogen bonds (Table 6) are again similar in (V). Like (IV), the N-phenyl analogue forms C₂-symmetric hydrogen-bonded dimers (Fig. 6). The unique intermolecular interaction again involves the S atom as acceptor.

The structure of the N-dimethylated analogue, (VI), is unique among the compounds reported here. The potentially coordinating atoms O1, N1 and S1 are adjacent and define a syn conformation (Fig. 7 and Table 7). In this case, there are only two significant hydrogen bonds and both are intramolecular (Table 8), involving the hydroxyl group and the syn N1 and S1 atoms. The structure of (VI) also contains a molecule of dimethyl sulfoxide (DMSO; not shown), which is disordered about a pseudo mirror plane that includes the two methyl C atoms. There are no significant intermolecular hydrogen bonds in (VI), except that between the minor (15%) DMSO contributor and the NH group.

It is known from the coordination chemistry of similar thiosemicarbazones (Gyepes et al., 1981; Soriano-García et al., 1985; Zimmer et al., 1991) that they bind as meridional O,N,S chelators (in the syn conformation shown in the Scheme above), while the terminal N3 atom does not participate in coordinate bonding. Of the four structures presented here, only (VI) is preorganized for metal binding, while the other compounds must undergo a 180° rotation of the N2—C12 bond.

In conclusion, there are two factors which result in the conformational differences between (VI) (syn) and the group of (III), (IV) and (V) (anti). The N3—H3A···N1 intramolecular hydrogen-bond interaction seen in compounds (III), (IV) and (V), albeit weak, appears to favour the anti conformer. In (VI), this hydrogen bond is not possible and the anti conformer is further destabilized by steric clashing between the N-methyl groups and the hydroxyl group, and the syn conformer ensues.

Tables 2, 4, 6 should be 'Hydrogen bonding and contact geometry.

S2. Experimental

All compounds were prepared by Schiff base condensation of 2-hydroxy-1-naphthaldehyde with the appropriate thiosemicarbazide in refluxing ethanol. The compounds precipitated readily from the reaction mixture and were found to be pure by elemental analysis and NMR. Crystals of (III) were obtained from a saturated dimethylformamide solution, (IV) and (V) were crystallized from ethanol solutions, and (VI) was crystallized from a concentrated dimethyl sulfoxide solution.

S3. Refinement

In each structure, the H atoms attached to N and O atoms were located from difference maps and refined without any constraints on their positional or isotropic displacement parameters. H atoms on C atoms? 14 Friedel pairs were measured for the structure of (III) and the absolute structure determination is indicated by the derived Flack value (Bernardinelli & Flack, 1985) of 0.01 (13).

Computing details

For all compounds, data collection: CAD-4 EXPRESS (Enraf Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS86 (Sheldrick, 1985); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLUTON (Spek, 1990); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. A view of the molecule of (III), showing the atom-numbering scheme and with 30% probability displacement ellipsoids.
	Fig. 2. A diagram of the hydrogen-bonded chain in (III) with the unit cell. H atoms on C atoms have been omitted for clarity. Atom S1' is at the symmetry position (1 − x, y + 1/2, 1 − z).
	Fig. 3. A view of the molecule of (IV), showing the atom-numbering scheme and with 30% probability displacement ellipsoids.
	Fig. 4. A diagram of the hydrogen-bonded dimer of (IV). H atoms on C atoms have been omitted for clarity. Atom S1' is at the symmetry position (1 − x, y, 3/2 − z).
	Fig. 5. A view of the molecule of (V), showing the atom-numbering scheme and with 30% probability displacement ellipsoids.
	Fig. 6. A diagram of the hydrogen-bonded dimer of (V). H atoms on C atoms have been omitted for clarity. Atom S1' is at the symmetry position (1 − x, y, 3/2 − z).
	Fig. 7. A view of the molecule of (VI), showing the atom-numbering scheme and with 30% probability displacement ellipsoids. For clarity, the dimethyl sulfoxide solvent molecule is not shown.

(III) 1-[(4-methylthiosemicarbazono)methyl]-2-naphthol

Crystal data

C13H13N3OS	F(000) = 272
Mr = 259.32	Dx = 1.43 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 25 reflections
a = 9.293 (1) Å	θ = 10.5–16.0°
b = 5.1612 (3) Å	µ = 0.26 mm^−1
c = 12.563 (1) Å	T = 296 K
β = 91.31 (2)°	Prism, yellow
V = 602.40 (9) Å^3	0.5 × 0.17 × 0.1 mm
Z = 2

Data collection

Enraf-Nonius TurboCAD-4 diffractometer	960 reflections with I > 2σ(I)
Radiation source: Enraf-Nonius FR590	Rint = 0.023
Graphite monochromator	θmax = 25.0°, θmin = 1.6°
non–profiled ω/2θ scans	h = 0→11
Absorption correction: ψ scan (North et al., 1968)	k = 0→6
Tmin = 0.912, Tmax = 0.971	l = −14→14
1262 measured reflections	3 standard reflections every 120 min
1185 independent reflections	intensity decay: −2%

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)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.080	w = 1/[σ^2(Fo^2) + (0.0508P)^2 + 0.0084P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
1185 reflections	Δρmax = 0.14 e Å^−3
176 parameters	Δρmin = −0.16 e Å^−3
1 restraint	Absolute structure: Bernardinelli & Flack (1985)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.01 (13)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
C1	0.7189 (3)	1.2636 (7)	0.7834 (2)	0.0316 (7)
C2	0.6973 (3)	1.2471 (7)	0.8929 (2)	0.0370 (8)
C3	0.7709 (3)	1.4128 (10)	0.9641 (2)	0.0449 (8)
H3	0.7553	1.3986	1.0367	0.054*
C4	0.8635 (3)	1.5918 (8)	0.9288 (2)	0.0420 (8)
H4	0.9114	1.6981	0.9777	0.05*
C5	0.8896 (3)	1.6221 (7)	0.8192 (2)	0.0347 (7)
C6	0.9850 (3)	1.8124 (7)	0.7823 (2)	0.0411 (9)
H6	1.0304	1.9224	0.8311	0.049*
C7	1.0123 (3)	1.8391 (7)	0.6774 (3)	0.0446 (9)
H7	1.0769	1.9639	0.6545	0.054*
C8	0.9418 (3)	1.6760 (8)	0.6037 (3)	0.0437 (9)
H8	0.9595	1.6946	0.5316	0.052*
C9	0.8475 (3)	1.4902 (7)	0.6359 (2)	0.0393 (9)
H9	0.802	1.3847	0.5854	0.047*
C10	0.8180 (3)	1.4559 (6)	0.7452 (2)	0.0297 (7)
C11	0.6458 (3)	1.0903 (7)	0.7094 (2)	0.0344 (8)
H11	0.6622	1.1093	0.6371	0.041*
C12	0.4029 (3)	0.5752 (7)	0.6778 (2)	0.0322 (7)
C13	0.2726 (4)	0.3358 (7)	0.8131 (3)	0.0491 (10)
H13A	0.1792	0.3689	0.7818	0.074*
H13B	0.2666	0.3386	0.8892	0.074*
H13C	0.3059	0.169	0.7905	0.074*
N1	0.5593 (2)	0.9109 (7)	0.73939 (17)	0.0350 (6)
N2	0.4992 (3)	0.7659 (6)	0.65886 (19)	0.0378 (7)
N3	0.3719 (3)	0.5329 (6)	0.7795 (2)	0.0393 (7)
O1	0.6057 (3)	1.0745 (6)	0.93639 (18)	0.0474 (6)
S1	0.32963 (8)	0.4069 (2)	0.57655 (6)	0.0454 (3)
H1A	0.566 (5)	0.993 (13)	0.874 (4)	0.12 (2)*
H2A	0.518 (3)	0.806 (7)	0.589 (2)	0.041 (9)*
H3A	0.417 (4)	0.622 (9)	0.827 (3)	0.064 (13)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0317 (15)	0.0314 (19)	0.0318 (14)	0.0035 (15)	−0.0005 (12)	−0.0044 (15)
C2	0.0369 (16)	0.036 (2)	0.0383 (16)	0.0003 (17)	0.0017 (13)	0.0008 (17)
C3	0.0576 (18)	0.049 (2)	0.0285 (14)	−0.005 (2)	0.0004 (13)	−0.002 (2)
C4	0.0491 (18)	0.041 (2)	0.0357 (17)	−0.0047 (19)	−0.0031 (14)	−0.0063 (18)
C5	0.0325 (15)	0.0331 (19)	0.0383 (15)	0.0058 (16)	−0.0026 (12)	−0.0039 (16)
C6	0.0416 (18)	0.036 (2)	0.0454 (18)	−0.0065 (16)	−0.0055 (14)	−0.0030 (16)
C7	0.0428 (17)	0.039 (2)	0.0518 (18)	−0.0024 (16)	0.0007 (14)	0.0049 (16)
C8	0.0448 (18)	0.048 (3)	0.0388 (16)	−0.0023 (18)	0.0054 (14)	0.0004 (17)
C9	0.0421 (17)	0.040 (2)	0.0357 (16)	−0.0030 (17)	−0.0008 (13)	−0.0058 (16)
C10	0.0322 (14)	0.024 (2)	0.0326 (14)	0.0083 (14)	−0.0009 (11)	0.0003 (14)
C11	0.0386 (15)	0.034 (2)	0.0310 (15)	0.0027 (17)	0.0013 (13)	0.0004 (15)
C12	0.0295 (14)	0.033 (2)	0.0339 (15)	0.0043 (16)	0.0018 (12)	−0.0029 (15)
C13	0.056 (2)	0.045 (3)	0.0464 (18)	−0.0097 (18)	0.0121 (16)	0.0063 (17)
N1	0.0387 (12)	0.0340 (14)	0.0323 (12)	−0.0031 (16)	−0.0009 (10)	−0.0016 (16)
N2	0.0427 (15)	0.0430 (18)	0.0278 (13)	−0.0111 (15)	0.0006 (11)	−0.0011 (14)
N3	0.0462 (16)	0.0417 (18)	0.0303 (14)	−0.0052 (14)	0.0047 (12)	−0.0013 (13)
O1	0.0546 (13)	0.0503 (17)	0.0376 (12)	−0.0130 (14)	0.0047 (11)	0.0012 (13)
S1	0.0512 (5)	0.0498 (6)	0.0350 (4)	−0.0126 (5)	−0.0009 (3)	−0.0055 (5)

Geometric parameters (Å, º)

C1—C2	1.397 (4)	C8—H8	0.9300
C1—C10	1.444 (4)	C9—C10	1.417 (4)
C1—C11	1.447 (4)	C9—H9	0.9300
C2—O1	1.356 (4)	C11—N1	1.288 (4)
C2—C3	1.404 (5)	C11—H11	0.9300
C3—C4	1.345 (5)	C12—N3	1.333 (4)
C3—H3	0.9300	C12—N2	1.355 (4)
C4—C5	1.412 (4)	C12—S1	1.672 (3)
C4—H4	0.9300	C13—N3	1.443 (4)
C5—C6	1.409 (4)	C13—H13A	0.9600
C5—C10	1.420 (4)	C13—H13B	0.9600
C6—C7	1.355 (5)	C13—H13C	0.9600
C6—H6	0.9300	N1—N2	1.367 (4)
C7—C8	1.402 (5)	N2—H2A	0.92 (3)
C7—H7	0.9300	N3—H3A	0.85 (4)
C8—C9	1.367 (5)	O1—H1A	0.95 (5)
C2—C1—C10	118.4 (3)	C8—C9—H9	119.5
C2—C1—C11	121.2 (3)	C10—C9—H9	119.5
C10—C1—C11	120.3 (2)	C9—C10—C5	117.5 (3)
O1—C2—C1	122.8 (3)	C9—C10—C1	123.1 (3)
O1—C2—C3	116.4 (3)	C5—C10—C1	119.4 (2)
C1—C2—C3	120.7 (3)	N1—C11—C1	122.9 (3)
C4—C3—C2	120.9 (3)	N1—C11—H11	118.5
C4—C3—H3	119.5	C1—C11—H11	118.5
C2—C3—H3	119.5	N3—C12—N2	116.4 (3)
C3—C4—C5	121.6 (3)	N3—C12—S1	123.4 (3)
C3—C4—H4	119.2	N2—C12—S1	120.2 (2)
C5—C4—H4	119.2	N3—C13—H13A	109.5
C6—C5—C4	121.5 (3)	N3—C13—H13B	109.5
C6—C5—C10	119.6 (3)	H13A—C13—H13B	109.5
C4—C5—C10	118.9 (3)	N3—C13—H13C	109.5
C7—C6—C5	121.7 (3)	H13A—C13—H13C	109.5
C7—C6—H6	119.2	H13B—C13—H13C	109.5
C5—C6—H6	119.2	C11—N1—N2	115.1 (2)
C6—C7—C8	119.0 (3)	C12—N2—N1	121.8 (2)
C6—C7—H7	120.5	C12—N2—H2A	118 (2)
C8—C7—H7	120.5	N1—N2—H2A	120 (2)
C9—C8—C7	121.3 (3)	C12—N3—C13	123.3 (3)
C9—C8—H8	119.4	C12—N3—H3A	118 (3)
C7—C8—H8	119.4	C13—N3—H3A	119 (3)
C8—C9—C10	120.9 (3)	C2—O1—H1A	101 (3)
C10—C1—C2—O1	179.5 (3)	C6—C5—C10—C9	0.3 (4)
C11—C1—C2—O1	−1.5 (5)	C4—C5—C10—C9	−179.5 (3)
C10—C1—C2—C3	−0.3 (5)	C6—C5—C10—C1	−179.2 (3)
C11—C1—C2—C3	178.7 (3)	C4—C5—C10—C1	1.0 (4)
O1—C2—C3—C4	−179.6 (3)	C2—C1—C10—C9	−179.7 (3)
C1—C2—C3—C4	0.2 (5)	C11—C1—C10—C9	1.2 (4)
C2—C3—C4—C5	0.5 (6)	C2—C1—C10—C5	−0.3 (4)
C3—C4—C5—C6	179.0 (3)	C11—C1—C10—C5	−179.3 (3)
C3—C4—C5—C10	−1.1 (5)	C2—C1—C11—N1	−0.9 (5)
C4—C5—C6—C7	178.8 (3)	C10—C1—C11—N1	178.1 (3)
C10—C5—C6—C7	−1.0 (5)	C1—C11—N1—N2	179.7 (3)
C5—C6—C7—C8	1.1 (5)	N3—C12—N2—N1	−1.3 (4)
C6—C7—C8—C9	−0.6 (5)	S1—C12—N2—N1	178.7 (2)
C7—C8—C9—C10	−0.1 (5)	C11—N1—N2—C12	−178.1 (3)
C8—C9—C10—C5	0.2 (4)	N2—C12—N3—C13	−179.5 (3)
C8—C9—C10—C1	179.7 (3)	S1—C12—N3—C13	0.5 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.95 (5)	1.75 (5)	2.641 (3)	155 (5)
N3—H3A···N1	0.85 (4)	2.29 (4)	2.671 (4)	107 (3)
N2—H2A···S1^i	0.92 (3)	2.60 (3)	3.467 (3)	158 (2)

Symmetry code: (i) −x+1, y+1/2, −z+1.

(IV) 1-[(4-ethylthiosemicarbazono)methyl]-2-naphthol

Crystal data

C14H15N3OS	F(000) = 1152
Mr = 273.35	Dx = 1.329 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 21 reflections
a = 26.608 (8) Å	θ = 11.0–14.0°
b = 7.0551 (6) Å	µ = 0.23 mm^−1
c = 18.918 (5) Å	T = 296 K
β = 129.71 (1)°	Prism, yellow
V = 2732.0 (11) Å^3	0.5 × 0.5 × 0.5 mm
Z = 8

Data collection

Enraf-Nonius TurboCAD-4 diffractometer	1847 reflections with I > 2σ(I)
Radiation source: Enraf-Nonius FR590	Rint = 0.039
Graphite monochromator	θmax = 25.0°, θmin = 2.0°
non–profiled ω scans	h = 0→31
Absorption correction: ψ scan (North et al., 1968)	k = 0→8
Tmin = 0.698, Tmax = 0.883	l = −22→17
2466 measured reflections	3 standard reflections every 120 min
2410 independent reflections	intensity decay: −1%

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0694P)^2 + 1.4628P] where P = (Fo^2 + 2Fc^2)/3
2410 reflections	(Δ/σ)max < 0.001
184 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.21 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
C1	0.74168 (8)	0.4910 (3)	0.97852 (12)	0.0323 (4)
C2	0.77555 (9)	0.5070 (3)	1.07198 (13)	0.0363 (4)
C3	0.84101 (10)	0.5649 (3)	1.13317 (14)	0.0455 (5)
H3	0.8629	0.5701	1.1959	0.055*
C4	0.87240 (10)	0.6134 (3)	1.10104 (15)	0.0483 (5)
H4	0.9155	0.6547	1.1421	0.058*
C5	0.84120 (9)	0.6026 (3)	1.00670 (15)	0.0427 (5)
C6	0.87402 (12)	0.6544 (4)	0.9734 (2)	0.0578 (6)
H6	0.9167	0.6992	1.0142	0.069*
C7	0.84451 (14)	0.6401 (4)	0.8833 (2)	0.0671 (7)
H7	0.8668	0.6754	0.8625	0.081*
C8	0.78082 (13)	0.5727 (4)	0.82158 (18)	0.0631 (7)
H8	0.7609	0.5613	0.7597	0.076*
C9	0.74709 (11)	0.5227 (3)	0.85109 (15)	0.0483 (5)
H9	0.7046	0.4776	0.8087	0.058*
C10	0.77540 (9)	0.5381 (3)	0.94379 (13)	0.0356 (4)
C11	0.67393 (9)	0.4318 (3)	0.91622 (13)	0.0346 (4)
H11	0.6528	0.4208	0.8539	0.041*
C12	0.54281 (9)	0.2883 (3)	0.90517 (13)	0.0382 (5)
C13	0.54078 (11)	0.2611 (4)	1.03312 (15)	0.0520 (6)
H13A	0.5344	0.1248	1.0279	0.062*
H13B	0.4984	0.321	1.0006	0.062*
C14	0.58437 (13)	0.3175 (4)	1.13218 (16)	0.0637 (7)
H14A	0.5649	0.2791	1.1586	0.096*
H14B	0.59	0.4525	1.1371	0.096*
H14C	0.6261	0.257	1.1644	0.096*
N1	0.64227 (7)	0.3942 (2)	0.94472 (11)	0.0366 (4)
N2	0.57843 (8)	0.3377 (3)	0.87986 (12)	0.0407 (4)
N3	0.56957 (9)	0.3178 (3)	0.99193 (13)	0.0481 (5)
O1	0.74878 (8)	0.4638 (3)	1.11118 (10)	0.0505 (4)
S1	0.46774 (2)	0.19586 (10)	0.82647 (4)	0.0532 (2)
H1A	0.7074 (14)	0.436 (4)	1.065 (2)	0.073 (9)*
H2A	0.5643 (12)	0.304 (3)	0.8232 (18)	0.057 (7)*
H3A	0.6065 (13)	0.352 (4)	1.0253 (18)	0.059 (8)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0313 (10)	0.0312 (10)	0.0353 (10)	0.0023 (8)	0.0217 (9)	0.0027 (8)
C2	0.0393 (11)	0.0333 (10)	0.0379 (10)	0.0038 (8)	0.0254 (9)	0.0031 (8)
C3	0.0374 (11)	0.0462 (12)	0.0374 (10)	0.0030 (9)	0.0168 (9)	−0.0019 (9)
C4	0.0301 (10)	0.0459 (13)	0.0548 (13)	−0.0019 (9)	0.0205 (10)	−0.0049 (10)
C5	0.0369 (11)	0.0373 (11)	0.0590 (13)	0.0026 (9)	0.0330 (10)	0.0032 (10)
C6	0.0485 (13)	0.0557 (15)	0.0861 (18)	−0.0010 (11)	0.0508 (13)	0.0034 (13)
C7	0.0737 (17)	0.0702 (17)	0.099 (2)	0.0059 (14)	0.0747 (17)	0.0152 (16)
C8	0.0761 (17)	0.0747 (18)	0.0639 (15)	0.0082 (14)	0.0566 (15)	0.0121 (13)
C9	0.0477 (12)	0.0589 (14)	0.0469 (12)	0.0021 (11)	0.0341 (10)	0.0064 (10)
C10	0.0363 (10)	0.0315 (10)	0.0443 (11)	0.0049 (8)	0.0282 (9)	0.0049 (8)
C11	0.0350 (10)	0.0371 (11)	0.0340 (9)	0.0009 (8)	0.0232 (8)	0.0013 (8)
C12	0.0364 (10)	0.0399 (11)	0.0418 (11)	−0.0012 (9)	0.0266 (9)	0.0001 (9)
C13	0.0532 (13)	0.0645 (15)	0.0519 (12)	−0.0096 (11)	0.0399 (11)	−0.0010 (11)
C14	0.0713 (16)	0.0751 (18)	0.0501 (13)	−0.0014 (14)	0.0413 (13)	0.0026 (13)
N1	0.0322 (8)	0.0402 (9)	0.0392 (9)	−0.0040 (7)	0.0237 (7)	−0.0023 (7)
N2	0.0320 (8)	0.0532 (11)	0.0376 (9)	−0.0077 (8)	0.0225 (7)	−0.0051 (8)
N3	0.0393 (10)	0.0664 (13)	0.0441 (10)	−0.0186 (10)	0.0291 (9)	−0.0106 (9)
O1	0.0512 (9)	0.0679 (11)	0.0380 (8)	−0.0067 (8)	0.0311 (8)	−0.0004 (7)
S1	0.0357 (3)	0.0780 (5)	0.0436 (3)	−0.0158 (3)	0.0242 (3)	−0.0066 (3)

Geometric parameters (Å, º)

C1—C2	1.384 (3)	C9—H9	0.9300
C1—C11	1.449 (3)	C11—N1	1.285 (2)
C1—C10	1.449 (2)	C11—H11	0.9300
C2—O1	1.351 (2)	C12—N3	1.323 (3)
C2—C3	1.402 (3)	C12—N2	1.353 (2)
C3—C4	1.354 (3)	C12—S1	1.683 (2)
C3—H3	0.9300	C13—N3	1.455 (3)
C4—C5	1.410 (3)	C13—C14	1.496 (3)
C4—H4	0.9300	C13—H13A	0.9700
C5—C6	1.413 (3)	C13—H13B	0.9700
C5—C10	1.423 (3)	C14—H14A	0.9600
C6—C7	1.350 (4)	C14—H14B	0.9600
C6—H6	0.9300	C14—H14C	0.9600
C7—C8	1.391 (4)	N1—N2	1.373 (2)
C7—H7	0.9300	N2—H2A	0.91 (3)
C8—C9	1.372 (3)	N3—H3A	0.79 (3)
C8—H8	0.9300	O1—H1A	0.89 (3)
C9—C10	1.402 (3)
C2—C1—C11	121.28 (16)	C9—C10—C1	123.75 (18)
C2—C1—C10	118.30 (17)	C5—C10—C1	118.77 (17)
C11—C1—C10	120.42 (16)	N1—C11—C1	121.79 (17)
O1—C2—C1	122.79 (17)	N1—C11—H11	119.1
O1—C2—C3	115.17 (17)	C1—C11—H11	119.1
C1—C2—C3	122.02 (18)	N3—C12—N2	117.07 (18)
C4—C3—C2	120.03 (19)	N3—C12—S1	123.53 (15)
C4—C3—H3	120.0	N2—C12—S1	119.40 (15)
C2—C3—H3	120.0	N3—C13—C14	110.23 (19)
C3—C4—C5	121.44 (19)	N3—C13—H13A	109.6
C3—C4—H4	119.3	C14—C13—H13A	109.6
C5—C4—H4	119.3	N3—C13—H13B	109.6
C4—C5—C6	121.3 (2)	C14—C13—H13B	109.6
C4—C5—C10	119.39 (18)	H13A—C13—H13B	108.1
C6—C5—C10	119.4 (2)	C13—C14—H14A	109.5
C7—C6—C5	121.2 (2)	C13—C14—H14B	109.5
C7—C6—H6	119.4	H14A—C14—H14B	109.5
C5—C6—H6	119.4	C13—C14—H14C	109.5
C6—C7—C8	119.9 (2)	H14A—C14—H14C	109.5
C6—C7—H7	120.0	H14B—C14—H14C	109.5
C8—C7—H7	120.0	C11—N1—N2	116.94 (16)
C9—C8—C7	120.7 (2)	C12—N2—N1	120.32 (17)
C9—C8—H8	119.7	C12—N2—H2A	119.6 (15)
C7—C8—H8	119.7	N1—N2—H2A	118.1 (15)
C8—C9—C10	121.4 (2)	C12—N3—C13	124.81 (19)
C8—C9—H9	119.3	C12—N3—H3A	116.5 (19)
C10—C9—H9	119.3	C13—N3—H3A	117.8 (19)
C9—C10—C5	117.48 (18)	C2—O1—H1A	105.4 (18)
C11—C1—C2—O1	2.0 (3)	C6—C5—C10—C9	2.4 (3)
C10—C1—C2—O1	−178.99 (18)	C4—C5—C10—C1	1.9 (3)
C11—C1—C2—C3	−179.69 (18)	C6—C5—C10—C1	−178.10 (19)
C10—C1—C2—C3	−0.7 (3)	C2—C1—C10—C9	178.15 (19)
O1—C2—C3—C4	−179.4 (2)	C11—C1—C10—C9	−2.8 (3)
C1—C2—C3—C4	2.2 (3)	C2—C1—C10—C5	−1.4 (3)
C2—C3—C4—C5	−1.6 (3)	C11—C1—C10—C5	177.65 (17)
C3—C4—C5—C6	179.6 (2)	C2—C1—C11—N1	0.9 (3)
C3—C4—C5—C10	−0.4 (3)	C10—C1—C11—N1	−178.08 (18)
C4—C5—C6—C7	178.6 (2)	C1—C11—N1—N2	−179.47 (17)
C10—C5—C6—C7	−1.4 (4)	N3—C12—N2—N1	7.6 (3)
C5—C6—C7—C8	−0.3 (4)	S1—C12—N2—N1	−172.97 (15)
C6—C7—C8—C9	0.9 (4)	C11—N1—N2—C12	177.31 (18)
C7—C8—C9—C10	0.1 (4)	N2—C12—N3—C13	−175.3 (2)
C8—C9—C10—C5	−1.7 (3)	S1—C12—N3—C13	5.3 (3)
C8—C9—C10—C1	178.7 (2)	C14—C13—N3—C12	−179.9 (2)
C4—C5—C10—C9	−177.6 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.89 (3)	1.80 (3)	2.605 (2)	151 (3)
N3—H3A···N1	0.79 (3)	2.27 (3)	2.653 (2)	110 (2)
N2—H2A···S1^i	0.91 (3)	2.50 (3)	3.409 (2)	176 (2)

Symmetry code: (i) −x+1, y, −z+3/2.

(V) 1-[(4-phenylthiosemicarbazono)methyl]-2-naphthol

Crystal data

C18H15N3OS	F(000) = 1344
Mr = 321.39	Dx = 1.34 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 25 reflections
a = 19.243 (4) Å	θ = 9.7–14.3°
b = 6.7948 (6) Å	µ = 0.21 mm^−1
c = 24.471 (6) Å	T = 296 K
β = 95.48 (1)°	Prism, yellow
V = 3185.0 (11) Å^3	0.5 × 0.4 × 0.3 mm
Z = 8

Data collection

Enraf-Nonius TurboCAD-4 diffractometer	1425 reflections with I > 2σ(I)
Radiation source: Enraf-Nonius FR590	Rint = 0.014
Graphite monochromator	θmax = 25.0°, θmin = 1.7°
non–profiled ω/2θ scans	h = 0→22
Absorption correction: ψ scan (North et al., 1968)	k = 0→8
Tmin = 0.911, Tmax = 0.936	l = −29→28
2834 measured reflections	3 standard reflections every 120 min
2747 independent reflections	intensity decay: −5%

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ^2(Fo^2) + (0.0576P)^2 + 0.9608P] where P = (Fo^2 + 2Fc^2)/3
2747 reflections	(Δ/σ)max < 0.001
220 parameters	Δρmax = 0.16 e Å^−3
0 restraints	Δρmin = −0.25 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq
C1	0.48619 (11)	0.2486 (4)	0.01483 (9)	0.0419 (6)
C2	0.43538 (13)	0.2363 (4)	−0.02902 (10)	0.0501 (6)
C3	0.36460 (13)	0.2115 (4)	−0.02146 (11)	0.0619 (8)
H3	0.3314	0.2053	−0.0517	0.074*
C4	0.34470 (13)	0.1965 (4)	0.03009 (12)	0.0626 (8)
H4	0.2979	0.1757	0.0347	0.075*
C5	0.39304 (13)	0.2115 (4)	0.07659 (10)	0.0505 (7)
C6	0.37140 (15)	0.1996 (4)	0.13032 (12)	0.0639 (8)
H6	0.3246	0.1771	0.1348	0.077*
C7	0.41766 (18)	0.2204 (5)	0.17500 (12)	0.0751 (10)
H7	0.4026	0.2137	0.21	0.09*
C8	0.48783 (17)	0.2518 (5)	0.16862 (11)	0.0763 (9)
H8	0.5194	0.2668	0.1996	0.092*
C9	0.51119 (15)	0.2611 (4)	0.11772 (10)	0.0626 (8)
H9	0.5584	0.2815	0.1146	0.075*
C10	0.46500 (12)	0.2402 (4)	0.06970 (9)	0.0469 (6)
C11	0.55942 (12)	0.2633 (4)	0.00645 (9)	0.0461 (6)
H11	0.592	0.2639	0.037	0.055*
C12	0.68278 (12)	0.2865 (4)	−0.09027 (10)	0.0502 (7)
C13	0.65146 (13)	0.3281 (4)	−0.19175 (10)	0.0520 (7)
C14	0.70859 (15)	0.4233 (5)	−0.20872 (11)	0.0662 (8)
H14	0.7426	0.4755	−0.1832	0.079*
C15	0.71459 (18)	0.4402 (5)	−0.26474 (13)	0.0759 (9)
H15	0.7533	0.5032	−0.2767	0.091*
C17	0.60859 (17)	0.2716 (5)	−0.28513 (12)	0.0856 (11)
H17	0.5749	0.2188	−0.3107	0.103*
C18	0.60151 (14)	0.2537 (5)	−0.22952 (11)	0.0682 (8)
H18	0.5626	0.1909	−0.2179	0.082*
C16	0.66484 (19)	0.3663 (6)	−0.30226 (13)	0.0841 (11)
H16	0.6692	0.3804	−0.3396	0.101*
N1	0.58142 (10)	0.2756 (3)	−0.04149 (8)	0.0464 (5)
N2	0.65255 (11)	0.2785 (4)	−0.04284 (9)	0.0527 (6)
N3	0.63899 (12)	0.3115 (4)	−0.13526 (8)	0.0552 (7)
O1	0.45075 (11)	0.2448 (4)	−0.08171 (7)	0.0691 (6)
S1	0.76909 (3)	0.25906 (17)	−0.08846 (3)	0.0886 (4)
H1A	0.4938 (17)	0.258 (5)	−0.0812 (12)	0.086 (11)*
H2A	0.6754 (15)	0.274 (4)	−0.0133 (12)	0.076 (10)*
H3A	0.5987 (15)	0.312 (4)	−0.1284 (11)	0.070 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0436 (12)	0.0411 (15)	0.0411 (12)	0.0035 (12)	0.0044 (9)	0.0003 (13)
C2	0.0495 (14)	0.0547 (18)	0.0456 (14)	0.0078 (14)	0.0023 (10)	0.0025 (13)
C3	0.0443 (14)	0.083 (2)	0.0567 (16)	0.0034 (15)	−0.0031 (11)	0.0020 (16)
C4	0.0394 (14)	0.074 (2)	0.075 (2)	0.0029 (14)	0.0103 (13)	0.0048 (16)
C5	0.0514 (15)	0.0462 (18)	0.0555 (15)	0.0059 (13)	0.0137 (12)	0.0038 (13)
C6	0.0633 (17)	0.069 (2)	0.0635 (18)	0.0033 (15)	0.0251 (15)	0.0048 (16)
C7	0.092 (2)	0.086 (3)	0.0515 (17)	0.003 (2)	0.0286 (16)	0.0059 (17)
C8	0.083 (2)	0.104 (3)	0.0410 (15)	0.003 (2)	0.0031 (13)	0.0029 (18)
C9	0.0594 (15)	0.083 (2)	0.0457 (15)	−0.0048 (17)	0.0063 (12)	−0.0018 (16)
C10	0.0506 (14)	0.0452 (16)	0.0455 (13)	0.0043 (14)	0.0083 (10)	0.0024 (13)
C11	0.0419 (12)	0.0538 (18)	0.0423 (13)	−0.0005 (13)	0.0032 (10)	−0.0008 (13)
C12	0.0480 (14)	0.0597 (19)	0.0439 (13)	−0.0078 (13)	0.0101 (11)	−0.0062 (13)
C13	0.0535 (15)	0.0616 (19)	0.0423 (14)	0.0042 (14)	0.0111 (12)	0.0038 (13)
C14	0.0711 (19)	0.074 (2)	0.0562 (17)	−0.0087 (17)	0.0185 (14)	−0.0037 (16)
C15	0.087 (2)	0.078 (2)	0.069 (2)	−0.0049 (19)	0.0350 (18)	0.0078 (18)
C17	0.082 (2)	0.127 (3)	0.0457 (17)	−0.011 (2)	−0.0015 (15)	0.0085 (19)
C18	0.0577 (16)	0.097 (3)	0.0494 (16)	−0.0063 (18)	0.0026 (12)	0.0137 (17)
C16	0.097 (3)	0.109 (3)	0.0485 (18)	0.007 (2)	0.0151 (18)	0.0134 (19)
N1	0.0420 (10)	0.0555 (15)	0.0421 (11)	−0.0001 (11)	0.0069 (8)	−0.0009 (10)
N2	0.0409 (11)	0.0768 (19)	0.0408 (12)	−0.0032 (12)	0.0054 (9)	−0.0029 (12)
N3	0.0434 (13)	0.0801 (19)	0.0429 (13)	−0.0006 (12)	0.0082 (10)	0.0040 (11)
O1	0.0538 (12)	0.1139 (19)	0.0387 (10)	−0.0012 (13)	−0.0006 (8)	0.0019 (11)
S1	0.0412 (4)	0.1749 (11)	0.0501 (4)	−0.0072 (5)	0.0062 (3)	−0.0090 (5)

Geometric parameters (Å, º)

C1—C2	1.384 (3)	C11—H11	0.9300
C1—C10	1.441 (3)	C12—N3	1.332 (3)
C1—C11	1.447 (3)	C12—N2	1.348 (3)
C2—O1	1.351 (3)	C12—S1	1.668 (2)
C2—C3	1.402 (3)	C13—C18	1.365 (4)
C3—C4	1.357 (3)	C13—C14	1.374 (4)
C3—H3	0.9300	C13—N3	1.430 (3)
C4—C5	1.403 (4)	C14—C15	1.391 (4)
C4—H4	0.9300	C14—H14	0.9300
C5—C6	1.419 (3)	C15—C16	1.358 (4)
C5—C10	1.424 (3)	C15—H15	0.9300
C6—C7	1.350 (4)	C17—C16	1.359 (4)
C6—H6	0.9300	C17—C18	1.386 (4)
C7—C8	1.390 (4)	C17—H17	0.9300
C7—H7	0.9300	C18—H18	0.9300
C8—C9	1.366 (3)	C16—H16	0.9300
C8—H8	0.9300	N1—N2	1.372 (3)
C9—C10	1.411 (3)	N2—H2A	0.81 (3)
C9—H9	0.9300	N3—H3A	0.81 (3)
C11—N1	1.288 (3)	O1—H1A	0.83 (3)
C2—C1—C10	118.6 (2)	N1—C11—H11	118.6
C2—C1—C11	121.3 (2)	C1—C11—H11	118.6
C10—C1—C11	120.1 (2)	N3—C12—N2	115.2 (2)
O1—C2—C1	122.3 (2)	N3—C12—S1	125.88 (19)
O1—C2—C3	115.8 (2)	N2—C12—S1	118.89 (19)
C1—C2—C3	121.9 (2)	C18—C13—C14	120.1 (2)
C4—C3—C2	119.7 (2)	C18—C13—N3	116.9 (2)
C4—C3—H3	120.1	C14—C13—N3	122.8 (2)
C2—C3—H3	120.1	C13—C14—C15	118.7 (3)
C3—C4—C5	121.6 (2)	C13—C14—H14	120.6
C3—C4—H4	119.2	C15—C14—H14	120.6
C5—C4—H4	119.2	C16—C15—C14	121.1 (3)
C4—C5—C6	121.1 (2)	C16—C15—H15	119.5
C4—C5—C10	119.4 (2)	C14—C15—H15	119.5
C6—C5—C10	119.5 (2)	C16—C17—C18	120.0 (3)
C7—C6—C5	121.0 (3)	C16—C17—H17	120.0
C7—C6—H6	119.5	C18—C17—H17	120.0
C5—C6—H6	119.5	C13—C18—C17	120.2 (3)
C6—C7—C8	119.9 (3)	C13—C18—H18	119.9
C6—C7—H7	120.1	C17—C18—H18	119.9
C8—C7—H7	120.1	C15—C16—C17	119.8 (3)
C9—C8—C7	121.1 (3)	C15—C16—H16	120.1
C9—C8—H8	119.4	C17—C16—H16	120.1
C7—C8—H8	119.4	C11—N1—N2	116.0 (2)
C8—C9—C10	121.3 (3)	C12—N2—N1	122.3 (2)
C8—C9—H9	119.4	C12—N2—H2A	122 (2)
C10—C9—H9	119.4	N1—N2—H2A	116 (2)
C9—C10—C5	117.2 (2)	C12—N3—C13	131.1 (2)
C9—C10—C1	124.1 (2)	C12—N3—H3A	112 (2)
C5—C10—C1	118.7 (2)	C13—N3—H3A	117 (2)
N1—C11—C1	122.9 (2)	C2—O1—H1A	107 (2)
C10—C1—C2—O1	179.4 (3)	C11—C1—C10—C9	5.3 (4)
C11—C1—C2—O1	−2.6 (4)	C2—C1—C10—C5	2.5 (4)
C10—C1—C2—C3	−1.5 (4)	C11—C1—C10—C5	−175.5 (2)
C11—C1—C2—C3	176.5 (3)	C2—C1—C11—N1	3.5 (4)
O1—C2—C3—C4	178.4 (3)	C10—C1—C11—N1	−178.5 (2)
C1—C2—C3—C4	−0.8 (4)	C18—C13—C14—C15	−0.6 (5)
C2—C3—C4—C5	2.1 (5)	N3—C13—C14—C15	−176.9 (3)
C3—C4—C5—C6	178.7 (3)	C13—C14—C15—C16	0.7 (5)
C3—C4—C5—C10	−1.0 (4)	C14—C13—C18—C17	0.8 (5)
C4—C5—C6—C7	−177.9 (3)	N3—C13—C18—C17	177.4 (3)
C10—C5—C6—C7	1.8 (4)	C16—C17—C18—C13	−1.1 (5)
C5—C6—C7—C8	−0.7 (5)	C14—C15—C16—C17	−0.9 (6)
C6—C7—C8—C9	−0.4 (5)	C18—C17—C16—C15	1.1 (6)
C7—C8—C9—C10	0.4 (5)	C1—C11—N1—N2	−176.8 (2)
C8—C9—C10—C5	0.7 (4)	N3—C12—N2—N1	6.5 (4)
C8—C9—C10—C1	179.9 (3)	S1—C12—N2—N1	−171.86 (19)
C4—C5—C10—C9	177.9 (3)	C11—N1—N2—C12	178.5 (3)
C6—C5—C10—C9	−1.8 (4)	N2—C12—N3—C13	179.5 (3)
C4—C5—C10—C1	−1.3 (4)	S1—C12—N3—C13	−2.3 (5)
C6—C5—C10—C1	179.0 (2)	C18—C13—N3—C12	147.0 (3)
C2—C1—C10—C9	−176.7 (3)	C14—C13—N3—C12	−36.5 (5)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.83 (4)	1.86 (4)	2.620 (3)	150 (3)
N3—H3A···N1	0.81 (3)	2.20 (3)	2.653 (3)	116 (3)
N2—H2A···S1^i	0.82 (3)	2.62 (3)	3.425 (3)	171 (3)

Symmetry code: (i) −x+3/2, −y+1/2, −z.

(VI) 1-[(4,4-dimethylthiosemicarbazono)methyl]-2-naphthol dimethyl sulfoxide solvate

Crystal data

C14H15N3OS·C2H6OS	F(000) = 744
Mr = 351.48	Dx = 1.331 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 12.012 (2) Å	θ = 11.3–14.0°
b = 7.8776 (9) Å	µ = 0.32 mm^−1
c = 18.631 (3) Å	T = 296 K
β = 95.78 (1)°	Prism, yellow
V = 1754.0 (5) Å^3	0.5 × 0.4 × 0.4 mm
Z = 4

Data collection

Enraf-Nonius TurboCAD-4 diffractometer	1929 reflections with I > 2σ(I)
Radiation source: Enraf-Nonius FR590	Rint = 0.011
Graphite monochromator	θmax = 25.0°, θmin = 1.9°
non–profiled ω/2θ scans	h = 0→14
Absorption correction: ψ scan (North et al., 1968)	k = 0→9
Tmin = 0.854, Tmax = 0.881	l = −22→22
3226 measured reflections	3 standard reflections every 120 min
3069 independent reflections	intensity decay: 5%

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.120	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0571P)^2 + 0.6902P] where P = (Fo^2 + 2Fc^2)/3
3069 reflections	(Δ/σ)max < 0.001
227 parameters	Δρmax = 0.20 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
C1	0.92779 (19)	0.0640 (3)	0.64669 (12)	0.0354 (6)
C2	0.9990 (2)	0.0209 (3)	0.70724 (13)	0.0423 (6)
C3	0.9589 (2)	−0.0645 (4)	0.76594 (14)	0.0505 (7)
H3	1.0083	−0.0958	0.8053	0.061*
C4	0.8492 (2)	−0.1007 (4)	0.76515 (14)	0.0514 (7)
H4	0.8244	−0.1592	0.8039	0.062*
C5	0.7705 (2)	−0.0522 (3)	0.70690 (14)	0.0433 (6)
C6	0.6552 (2)	−0.0843 (4)	0.70766 (16)	0.0564 (8)
H6	0.6298	−0.1409	0.7467	0.068*
C7	0.5808 (2)	−0.0338 (4)	0.65226 (18)	0.0641 (8)
H7	0.5048	−0.0537	0.6539	0.077*
C8	0.6181 (2)	0.0481 (4)	0.59287 (16)	0.0586 (8)
H8	0.5666	0.0822	0.555	0.07*
C9	0.7294 (2)	0.0788 (4)	0.58972 (14)	0.0460 (7)
H9	0.7527	0.132	0.5493	0.055*
C10	0.80996 (19)	0.0312 (3)	0.64686 (13)	0.0378 (6)
C11	0.97100 (19)	0.1394 (3)	0.58415 (12)	0.0378 (6)
H11	0.9223	0.1694	0.5442	0.045*
C12	1.22536 (19)	0.2717 (3)	0.52545 (13)	0.0391 (6)
C13	1.3706 (2)	0.4062 (4)	0.46267 (18)	0.0679 (9)
H13A	1.3817	0.5219	0.4779	0.102*
H13B	1.3869	0.3952	0.4135	0.102*
H13C	1.4196	0.3337	0.4928	0.102*
C14	1.1735 (2)	0.4124 (4)	0.40950 (15)	0.0602 (8)
H14A	1.1303	0.3167	0.3909	0.09*
H14B	1.2123	0.4608	0.3718	0.09*
H14C	1.1246	0.4959	0.4269	0.09*
N1	1.07608 (16)	0.1645 (3)	0.58409 (10)	0.0393 (5)
N2	1.11380 (17)	0.2365 (3)	0.52409 (11)	0.0410 (5)
N3	1.25434 (17)	0.3573 (3)	0.46842 (12)	0.0472 (6)
O1	1.11013 (16)	0.0539 (3)	0.71364 (11)	0.0531 (5)
S1	1.31713 (6)	0.20829 (11)	0.59423 (4)	0.0573 (3)
S2A	1.13290 (8)	−0.29251 (14)	0.62655 (5)	0.0591 (4)	0.842 (4)
O2A	1.08950 (19)	−0.3682 (4)	0.55516 (13)	0.0585 (7)	0.842 (4)
S2B	1.1653 (5)	−0.3920 (9)	0.6077 (3)	0.063 (2)*	0.158 (4)
O2B	1.0770 (12)	−0.2710 (19)	0.5737 (8)	0.055 (4)*	0.158 (4)
C15	1.1292 (3)	−0.4538 (5)	0.69201 (17)	0.0773 (11)
H15A	1.0528	−0.4781	0.6992	0.116*	0.842 (4)
H15B	1.1684	−0.4163	0.7367	0.116*	0.842 (4)
H15C	1.1642	−0.5545	0.6759	0.116*	0.842 (4)
H15D	1.0638	−0.5243	0.6861	0.116*	0.158 (4)
H15E	1.113	−0.3524	0.7176	0.116*	0.158 (4)
H15F	1.1891	−0.5144	0.7188	0.116*	0.158 (4)
C16	1.2806 (3)	−0.2804 (5)	0.62676 (19)	0.0782 (10)
H16A	1.2991	−0.1957	0.5929	0.117*	0.842 (4)
H16B	1.3092	−0.3885	0.6134	0.117*	0.842 (4)
H16C	1.3134	−0.2503	0.6742	0.117*	0.842 (4)
H16D	1.309	−0.2438	0.583	0.117*	0.158 (4)
H16E	1.337	−0.345	0.655	0.117*	0.158 (4)
H16F	1.2609	−0.1831	0.6538	0.117*	0.158 (4)
H1A	1.128 (3)	0.091 (4)	0.6773 (17)	0.064 (11)*
H2A	1.066 (2)	0.280 (4)	0.4926 (16)	0.058 (9)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0362 (13)	0.0340 (13)	0.0358 (13)	0.0031 (10)	0.0034 (10)	−0.0025 (11)
C2	0.0408 (14)	0.0454 (15)	0.0402 (14)	0.0047 (12)	0.0011 (11)	−0.0036 (12)
C3	0.0571 (17)	0.0589 (18)	0.0345 (14)	0.0134 (14)	0.0008 (12)	0.0050 (13)
C4	0.0630 (19)	0.0495 (17)	0.0442 (15)	0.0064 (14)	0.0168 (13)	0.0081 (13)
C5	0.0471 (15)	0.0393 (15)	0.0447 (15)	0.0029 (12)	0.0106 (12)	−0.0029 (12)
C6	0.0525 (18)	0.0572 (19)	0.0629 (19)	−0.0081 (14)	0.0227 (15)	−0.0017 (15)
C7	0.0399 (16)	0.075 (2)	0.079 (2)	−0.0093 (16)	0.0103 (16)	−0.0115 (19)
C8	0.0387 (15)	0.072 (2)	0.0639 (19)	−0.0010 (14)	−0.0026 (14)	−0.0063 (17)
C9	0.0396 (14)	0.0562 (17)	0.0416 (14)	0.0009 (13)	0.0010 (11)	−0.0033 (13)
C10	0.0382 (13)	0.0376 (14)	0.0380 (13)	0.0005 (11)	0.0065 (11)	−0.0072 (11)
C11	0.0347 (13)	0.0419 (14)	0.0355 (13)	0.0023 (11)	−0.0021 (10)	−0.0005 (11)
C12	0.0347 (13)	0.0392 (14)	0.0435 (14)	−0.0006 (11)	0.0043 (11)	−0.0043 (12)
C13	0.0483 (17)	0.078 (2)	0.080 (2)	−0.0132 (16)	0.0189 (16)	0.0055 (19)
C14	0.0573 (18)	0.074 (2)	0.0501 (17)	−0.0068 (16)	0.0068 (14)	0.0154 (16)
N1	0.0350 (11)	0.0448 (13)	0.0378 (11)	−0.0025 (9)	0.0025 (9)	0.0022 (10)
N2	0.0360 (11)	0.0479 (14)	0.0383 (12)	−0.0016 (10)	0.0008 (10)	0.0066 (10)
N3	0.0367 (12)	0.0551 (14)	0.0504 (13)	−0.0045 (10)	0.0071 (10)	0.0060 (11)
O1	0.0424 (11)	0.0715 (14)	0.0434 (12)	0.0004 (10)	−0.0056 (9)	0.0057 (11)
S1	0.0388 (4)	0.0711 (5)	0.0595 (5)	0.0012 (4)	−0.0077 (3)	0.0061 (4)
S2A	0.0630 (6)	0.0563 (7)	0.0553 (6)	0.0162 (5)	−0.0077 (4)	−0.0081 (5)
O2A	0.0545 (15)	0.0753 (19)	0.0418 (14)	0.0089 (13)	−0.0150 (11)	−0.0018 (13)
C15	0.065 (2)	0.112 (3)	0.0529 (19)	−0.010 (2)	−0.0012 (15)	0.0158 (19)
C16	0.066 (2)	0.090 (3)	0.074 (2)	−0.0208 (19)	−0.0164 (17)	0.018 (2)

Geometric parameters (Å, º)

C1—C2	1.387 (3)	C14—H14A	0.9600
C1—C10	1.439 (3)	C14—H14B	0.9600
C1—C11	1.450 (3)	C14—H14C	0.9600
C2—O1	1.354 (3)	N1—N2	1.371 (3)
C2—C3	1.409 (4)	N2—H2A	0.85 (3)
C3—C4	1.347 (4)	O1—H1A	0.79 (3)
C3—H3	0.9300	S2A—O2A	1.502 (3)
C4—C5	1.418 (4)	S2A—C15	1.765 (3)
C4—H4	0.9300	S2A—C16	1.777 (3)
C5—C6	1.410 (4)	S2A—H15E	1.8003
C5—C10	1.419 (3)	S2A—H16F	1.7915
C6—C7	1.355 (4)	S2B—O2B	1.517 (18)
C6—H6	0.9300	S2B—C16	1.648 (6)
C7—C8	1.393 (4)	S2B—C15	1.740 (6)
C7—H7	0.9300	S2B—H15C	1.8038
C8—C9	1.366 (4)	S2B—H16B	1.7210
C8—H8	0.9300	C15—H15A	0.9600
C9—C10	1.415 (3)	C15—H15B	0.9600
C9—H9	0.9300	C15—H15C	0.9600
C11—N1	1.278 (3)	C15—H15D	0.9600
C11—H11	0.9300	C15—H15E	0.9600
C12—N2	1.366 (3)	C15—H15F	0.9600
C12—N3	1.334 (3)	C16—H16A	0.9600
C12—S1	1.680 (3)	C16—H16B	0.9600
C13—N3	1.463 (3)	C16—H16C	0.9600
C13—H13A	0.9600	C16—H16D	0.9600
C13—H13B	0.9600	C16—H16E	0.9600
C13—H13C	0.9600	C16—H16F	0.9600
C14—N3	1.457 (3)
C2—C1—C10	118.7 (2)	H14A—C14—H14B	109.5
C2—C1—C11	120.8 (2)	N3—C14—H14C	109.5
C10—C1—C11	120.5 (2)	H14A—C14—H14C	109.5
O1—C2—C1	123.1 (2)	H14B—C14—H14C	109.5
O1—C2—C3	115.7 (2)	C11—N1—N2	118.2 (2)
C1—C2—C3	121.2 (2)	C12—N2—N1	118.2 (2)
C4—C3—C2	120.2 (2)	C12—N2—H2A	121.8 (19)
C4—C3—H3	119.9	N1—N2—H2A	118.1 (19)
C2—C3—H3	119.9	C12—N3—C13	121.3 (2)
C3—C4—C5	121.8 (2)	C12—N3—C14	122.9 (2)
C3—C4—H4	119.1	C14—N3—C13	115.8 (2)
C5—C4—H4	119.1	C2—O1—H1A	110 (2)
C6—C5—C4	121.6 (2)	O2A—S2A—C15	107.20 (18)
C6—C5—C10	119.8 (2)	O2A—S2A—C16	106.30 (17)
C4—C5—C10	118.6 (2)	C15—S2A—C16	97.56 (16)
C7—C6—C5	120.9 (3)	O2B—S2B—C16	107.0 (7)
C7—C6—H6	119.6	O2B—S2B—C15	109.0 (7)
C5—C6—H6	119.6	C16—S2B—C15	103.6 (3)
C6—C7—C8	120.0 (3)	S2A—C15—H15A	109.3
C6—C7—H7	120.0	S2B—C15—H15B	123.4
C8—C7—H7	120.0	S2A—C15—H15B	109.5
C9—C8—C7	120.7 (3)	H15A—C15—H15B	109.5
C9—C8—H8	119.6	S2A—C15—H15C	109.6
C7—C8—H8	119.6	H15A—C15—H15C	109.5
C8—C9—C10	121.3 (3)	H15B—C15—H15C	109.5
C8—C9—H9	119.4	S2B—C15—H15D	109.6
C10—C9—H9	119.4	S2B—C15—H15E	107.3
C9—C10—C5	117.3 (2)	H15D—C15—H15E	109.5
C9—C10—C1	123.3 (2)	S2B—C15—H15F	111.5
C5—C10—C1	119.4 (2)	H15D—C15—H15F	109.5
N1—C11—C1	119.9 (2)	H15E—C15—H15F	109.5
N1—C11—H11	120.1	S2A—C16—H16A	109.4
C1—C11—H11	120.1	S2A—C16—H16B	109.6
N3—C12—N2	114.9 (2)	H16A—C16—H16B	109.5
N3—C12—S1	123.64 (18)	S2A—C16—H16C	109.4
N2—C12—S1	121.41 (19)	H16A—C16—H16C	109.5
N3—C13—H13A	109.5	H16B—C16—H16C	109.5
N3—C13—H13B	109.5	S2B—C16—H16D	109.9
H13A—C13—H13B	109.5	S2B—C16—H16E	111.5
N3—C13—H13C	109.5	H16D—C16—H16E	109.5
H13A—C13—H13C	109.5	S2B—C16—H16F	107.0
H13B—C13—H13C	109.5	H16D—C16—H16F	109.5
N3—C14—H14A	109.5	H16E—C16—H16F	109.5
N3—C14—H14B	109.5
C10—C1—C2—O1	−176.8 (2)	C4—C5—C10—C9	−179.7 (2)
C11—C1—C2—O1	3.7 (4)	C6—C5—C10—C1	179.7 (2)
C10—C1—C2—C3	4.5 (4)	C4—C5—C10—C1	0.0 (4)
C11—C1—C2—C3	−175.0 (2)	C2—C1—C10—C9	176.3 (2)
O1—C2—C3—C4	179.0 (3)	C11—C1—C10—C9	−4.2 (4)
C1—C2—C3—C4	−2.2 (4)	C2—C1—C10—C5	−3.4 (3)
C2—C3—C4—C5	−1.3 (4)	C11—C1—C10—C5	176.1 (2)
C3—C4—C5—C6	−177.3 (3)	C2—C1—C11—N1	1.0 (4)
C3—C4—C5—C10	2.4 (4)	C10—C1—C11—N1	−178.5 (2)
C4—C5—C6—C7	178.5 (3)	C1—C11—N1—N2	−179.8 (2)
C10—C5—C6—C7	−1.2 (4)	N3—C12—N2—N1	−173.4 (2)
C5—C6—C7—C8	1.3 (5)	S1—C12—N2—N1	7.2 (3)
C6—C7—C8—C9	−0.2 (5)	C11—N1—N2—C12	176.6 (2)
C7—C8—C9—C10	−1.0 (4)	N2—C12—N3—C14	1.1 (4)
C8—C9—C10—C5	1.1 (4)	S1—C12—N3—C14	−179.5 (2)
C8—C9—C10—C1	−178.7 (3)	N2—C12—N3—C13	179.1 (2)
C6—C5—C10—C9	0.0 (4)	S1—C12—N3—C13	−1.5 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N1	0.79 (3)	1.88 (3)	2.560 (3)	145 (3)
O1—H1A···S1	0.79 (3)	3.02 (3)	3.705 (2)	147 (3)