4-(9,10-Dihydro­acridin-9-yl­idene)thio­semicarbazide and its five-membered thia­zole and six-membered thia­zine derivatives

Two methyl derivatives, five-membered methyl 2-{2-[2-(9,10-dihydro­acridin-9-yl­idene)-1-methyl­hydrazin­yl]-4-oxo-4,5-dihydro-1,3-thia­zol-5-yl­idene}acetate, C₂₀H₁₆N₄O₃S, (I), and six-membered 2-[2-(9,10-dihydro­acridin-9-yl­idene)-1-methyl­hydrazin­yl]-4H-1,3-thia­zin-4-one, C₁₈H₁₄N₄OS, (II), were pre­pared by the reaction of the N-methyl derivative of 4-(9,10-dihydro­acridin-9-yl­idene)thio­semicarbazide, C₁₄H₁₂N₄S, (III), with dimethyl acetyl­enedicarboxyl­ate and methyl propiolate, respectively. The crystal structures of (I), (II) and (III) are mol­ecular and can be considered in two parts: (i) the nearly planar acridine moiety and (ii) the singular heterocyclic ring portion [thia­zolidine for (I) and thia­zine for (II)] including the linking amine and imine N atoms and the methyl C atom, or the full side chain in the case of (III). The structures of (I) and (II) are stabilized by N—H...O hydrogen bonds and different π–π inter­actions between acridine moieties and thia­zolidine and thia­zine rings, respectively.

S1. Comment

Acridinylthiosemicarbazides are especially interesting for their inherent proclivity towards spiro-open-chain tautomerism (Tomaščiková, Danihel et al., 2008; Tomaščiková, Imrich et al., 2008; Klika et al., 2006a,b) which can lead to an array of structures and, on occasion, confusion regarding the identity of products arising from a reaction. Previously we had found that thiosemicarbazides or thioureas differ in their behaviour towards bielectrophilic reagents in substitution reactions and hence the consequent cyclization to form a heterocyclic ring can yield unexpected or difficult to rationalize structures (Klika et al., 2006a,b; Klika, Imrich et al., 2006; Balentová et al., 2006).

Herein we continue our study of the products of reaction of thiosemicarbazides with dimethyl acetylenedicarboxylate (DMAD) (Tomaščiková et al., 2007; Tomaščiková, Danihel et al., 2008; Tomaščiková, Imrich et al., 2008) and augment it by contrasting it [comparison] with methyl propiolate (MP). This is because it seemed plausible to us that control of five- versus six-membered ring formation (i.e.1,3-thiazolidin-4-one versus 1,3-thiazin-4-one products, respectively) using ethyne acid esters could be accomplished by adduct reagent selection.

For unequivocal gross structural confirmation, in particular the size of the newly formed rings, as well as to elucidate the structural fine elements, crystals of the three derivatives, five-membered methyl 2-{2-[2-(9,10-dihydroacridin-9-ylidene)-1-methylhydrazino]-4-oxo-4,5-dihydro-1,3-thiazol-5-ylidene}acetate, (I), six-membered 2-[2-(9,10-dihydroacridin-9-ylidene)-1-methylhydrazino]-4H-1,3-thiazin-4-one, (II), and the unsubstituted thiosemicarbazide, (III), were obtained (Imrich et al., 2010) and subjected to X-ray single-crystal analysis. Of more than 70 crystallographic descriptions of structures containing an acridine moiety and several hundred descriptions of structures containing thiazolidine rings (Allen, 2002), only four reports exist which contain both acridine and thiazolidine entities linked in some manner (Klika et al., 2001; Tomaščiková, Danihel et al., 2008; Imrich et al., 2005; Černák et al., 1995). Furthermore, there are no reports of structures having been examined that contain both acridine and thiazine entities. The structures obtained for (I), (II) and (III) are shown in Figs. 1, 2 and 3, respectively. Selected bond lengths, bond angles and dihedral angles are presented in Tables 1, 3 and 5. The crystal structures of all three compounds are molecular and can be conveniently considered in two parts: the acridine moiety and the singular heterocyclic ring portion [thiazolidine for (I) and thiazine for (II)] including the linking amine N12' and imine N11' N atoms and the C1" methyl [the second part is the full side chain in the case of (III)].

The geometric parameters for the acridine moiety in (I), (II) and (III) correspond to aromatic portions (outer rings) whilst the central C9'–C9a' and C8a'–C9' bonds pertain very much to typical C–C single bonds and overall the parameters are similar to previous reports (Klika et al., 2001; Tomaščiková, Danihel et al., 2008; Imrich et al., 2005; Černák et al., 1995). The placement of a labile H atom on N10' confirms the NMR assignments (Imrich et al., 2010). Although the acridine moieties are not aromatic over the entire segment, they are, nevertheless, almost planar in all structures; the largest deviations of C9' from the mean planes of the 14 non-H atoms of the acridine moieties are 0.184 (3) and 0.180 (3) Å for (I) and (II), respectively. These deviations from planarity, though, are larger than the deviation of 0.088 (1) Å observed in a previous study (Tomaščiková, Danihel et al., 2008) for an acridine moiety that was aromatic over the entire segment. On the other hand, not only is the acridine moiety itself in (III) very planar, with the largest deviation observed for C7' from the mean plane of the 14 non-H atoms of the acridine moiety at 0.101 (3) Å, but even all non-H atoms, excluding the disordered S1 atom, lie nearly in the one plane with the largest deviation observed for N3 from the mean plane of the 18 non-H atoms at 0.197 (3) Å.

The geometric parameters for the 1,3-thiazolidin-4-one ring in (I) resemble those found in similar compounds containing a 1,3-thiazolidin-4-one ring (Tomaščiková, Danihel et al., 2008; Orrell & Wallis, 1984; Heravi et al., 2006; Cameron & Hair, 1971; Deepthi et al., 2001). Also, the geometric parameters of the 1,3-thiazin-4-one ring in (II) are similar to those reported in the literature (Hilton et al., 1994). Both of the 1,3-thiazolidin-4-one and 1,3-thiazin-4-one rings of (I) and (II), respectively, are also planar. Moreover, not only are these singular heterocyclic rings themselves planar, but all of the heavy atoms from N11' on one side of the rings, including the C1'' methyl, all the way to O8 on the other side of the 1,3-thiazolidin-4-one ring for (I) lie almost in the one plane in each case. The largest deviation, 0.166 (2) Å, from the mean plane of these 13 atoms in (I) was observed for O8. For (II), the largest deviation, 0.189 (3) Å, was observed for N11'. Most interestingly, the angle between the acridine ring plane and the plane of the singular heterocyclic rings was 79.61 (3)° in (I) whilst in (II) the corresponding angle was only 56.48 (4)°. These compare to planar angles of ca 59° and ca 58° for (I) and (II), respectively, from modelling studies (Böhm et al., 2009). Thus, only in the solid state is a wide planar angle observed. As a result of the widened angle in the crystal structure of (I), a weak intramolecular hydrogen bond C1'—H1'···N12' (see Table 2) is present in (I) but not in (II) and the N12'—C2 bond in (I) is much shorter than in (II) as a consequence [1.309 (3) versus 1.341 (4) Å, respectively]. This is consistent with the known conformational mobility and geometric flexibility of N which can easily adopt flattened geometries (Tähtinen et al., 2003; Rosling, Hotokka et al., 1999; Rosling et al., 1999a,b; Pawłowicz et al., 2006, 2007; Olsen et al., 2007; Klika, Mäki et al., 2006) to permit such interactions although in this instance the geometric permutation is driven by other factors since N12' is also flattened in (II) and the only requirement is for an increase in the dihedral angle between the segmental planes to enable the hydrogen-bonding interaction to occur.

The geometric parameters between non-H atoms in the side chain of (III) correspond to the single and double bonds represented between the associated atoms. The H atoms of the two amine groups were all located from a difference electron map with all N—H bond distances adopting typical values, as do the angles concerned with N3. On the other hand, the C2—N12'—H12' angle of 112 (2)° strongly deviates from the expected value of 120°. As a consequence, the H12' atom deviates from the mean plane of all seven atoms of the side chain (excluding the disordered S1atom) by 0.25 (3) Å. Probably because of the terminal bonding of the S1 atom in the side chain, the thermal motion of this atom is much larger than the motion of the S1 atoms in the 1,3-thiazolidin-4-one and 1,3-thiazin-4-one rings of (I) and (II), respectively. Disordering of the S1 atom in (III) over two positions with site-occupation factors of 0.73 and 0.27 resulted in a substantially better R factor and GOOF [goodness of fit?] values in comparison to a model containing a single S1 atom, hence the preference for a model with a statistically disordered S1 atom. The Z configuration about the C5═ C6 double bond and the s–cis configuration of the C5═ C6—C7═O7 segment in (I) were both re-confirmed (Tomaščiková, Danihel et al., 2008).

Regarding the crystal packing of the molecules, for both (I) and (II) (see Figs. 4 and 5) intermolecular hydrogen bonds N10'–H10'···O4 (Tables 2 and 4) link pairs of molecules, giving rise to the formation of chains of molecules. By contrast, in (III) only intramolecular hydrogen bonding is present, N3—H5···N11' (Table 6), and thus the molecules are, for all intensive [intents and purposes, isolated from one another. For both compounds (I) and (II) the acridine rings exhibit π–π stacking to other acridine units in neighbouring molecules. Probably because of the different dihedral angles for the two compounds between the planes of the acridine and singular heterocyclic rings, the stacking of the acridine moieties, however, is different for the two compounds. In (I), the neighbouring acridine moieties, with a centroid–centroid distance of 4.03 Å, are staggered similarly as in graphite and with acridine moieties from next-but-one planes wholly aligned. In (II), the acridine moieties from neighbouring layers are shifted with respect to one another (centroid–centroid distance, 3.60 Å) and thus only two of the three six-membered rings of neighbouring acridine moieties are appropriately aligned. The distances between the mean planes of neighbouring acridine moieties are 3.64 and 3.42 Å for (I) and (II), respectively, and the offset angles adopt the values of 25.6 and 18.9° for (I) and (II), respectively. Thus it can be realized that these face-to-face π-stacking interactions dictate to a certain degree the crystal packing of the molecules. Such parallel π-stacking with a ring separation of 3.3–3.8 Å is an important non-covalent organizational force in supramolecular aggregates (Janiak et al., 2000) although in this instance the contribution of the intermolecular hydrogen-bonding interactions to the crystal packing of the molecules dominates. Nevertheless, the alignment of the planes between neighbouring acridine moieties appears to be influenced by the π–π interactions. The respective planes of neighbouring thiazolidine rings in (I) and thiazine rings in (II) are also parallel and the distances between the mean planes of these rings are 3.58 and 3.97 Å, respectively. However, the thiazine rings in (II) are staggered (centroid–centroid distance, 4.70 Å) and therefore considerable π–π interactions can only be expected between neighbouring thiazolidine rings in (I) and as borne out by its more comparable interplanar distance. Since the natural interplanar angle for both (I) and (II) seems to be acute, based on the calculated isolated states for both (I) and (II) (Böhm et al., 2009), the allowance for greater π–π interaction between the thiazolidine rings in (I) in the solid state leads to an increase in the interplanar angle. The resultant obtuse angle then promulgates change to the acridine–acridine interactions for (I), hence the observed differences between (I) and (II).

The acridine rings in (III) exhibit different π–π stacking than in (I) and (II). Acridine units in neighbouring molecules of (III) are nearly planar; however, they are not in a parallel but in an almost perpendicular orientation [83.2 (1)°; see Fig. 7]. Thus, only the central ring from one acridine unit is overlapped with one of the outer rings of an acridine unit from a neighbouring molecule with the dihedral angle between these two rings being 6.0 (1)°. The distance between the centroids of these two rings is 3.62 (1)Å, while the offset angle is 5.2°.

Related literature

For related literature, see: Allen (2002); Böhm et al. (2009); Balentová et al. (2006); Brandenburg (2000); Cameron & Hair (1971); Deepthi et al. (2001); Heravi et al. (2006); Hilton et al. (1994); Imrich et al. (2005, 2010); Janiak et al. (2000); Klika et al. (2001, 2006a, 2006b, 2006c, 2006d); Nardelli (1995); Olsen et al. (2007); Orrell & Wallis (1984); Pawłowicz et al. (2006, 2007); Rosling et al. (1999a, 1999b, 1999c); Tähtinen et al. (2003); Tomaščiková et al. (2007, 2008a, 2008b); Černák et al. (1995).

S2. Experimental

The studied compounds (I), (II) and (III) were prepared according to Imrich et al. (2010) and recrystallized from hot saturated methanol solutions.

S3. Refinement

All H atoms of (I) and (II), as well as the C-bound H atoms of (III), were placed in calculated positions and refined riding on their parent C/N atoms, with C—H = 0.93 (aromatic) or 0.96Å (methyl) and N—H = 0.86Å, and with U_iso(H) = 1.5U_eq(C) for the methyl groups and 1.2U_eq(C,N) otherwise. The amine H atoms of (III) were found by a difference electron-density map and were refined with free isotropic displacement parameters.

Computing details

For all compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis RED (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2000); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008); PARST ? (Nardelli, 1995).

Figures

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are plotted at the 50% probability level; H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. The molecular structure of (II). Displacement ellipsoids are plotted at the 50% probability level; H atoms are shown as small spheres of arbitrary radii.
	Fig. 3. The molecular structure of (III). Displacement ellipsoids are plotted at the 50% probability level; H atoms are shown as small spheres of arbitrary radii. For clarity, only one disordered S atom is depicted.
	Fig. 4. Packing diagram showing the parallel stacking of molecules in (I). Intermolecular hydrogen bonding, N10'–H10'···O4 (solid black dashed line), links the molecules into chains and the π-stacking of both the acridine moieties (acridine-to-acridine) and the thiazolidine rings (thiazolidine-to-thiazolidine) is evident. Intramolecular hydrogen bonding, C1'–H1'···N12' (hollow dashed line), is also present. For clarity, only H atoms involved in hydrogen bonds are depicted. [Symmetry codes: (i) x, y, z - 1.]
	Fig. 5. π-stacking in (II) showing an overlap of two of the three six-membered rings of neighbouring acridine moieties. For clarity, H atoms have been omitted and black, grey and hollow lines are used to represent bonds in upper, middle and bottom molecules, respectively.
	Fig. 6. Packing diagram showing the parallel stacking of molecules in (II). Intermolecular hydrogen bonding, N10'–H10'···O4, links the molecules into chains. For clarity, only H atoms involved in hydrogen bonds are depicted. [Symmetry codes: (i) -x + 1, y + 1/2, -z + 2.]
	Fig. 7. Packing diagram showing the parallel stacking of acridine units in (III). Intramolecular N3—H5···N11' hydrogen bonding and the π-stacking of the central and outer rings is evident. For clarity, only H atoms involved in hydrogen bonds are depicted and hollow lines are used to represent bonds in bottom molecules.

(I) 2-{2-[2-(9,10-dihydroacridin-9-ylidene)-1-methylhydrazinyl]-4-oxo-4,5-dihydro- 1,3-thiazol-5-ylidene}acetate

Crystal data

C20H16N4O3S	Z = 2
Mr = 392.43	F(000) = 408
Triclinic, P1	Dx = 1.420 Mg m^−3
Hall symbol: -P 1	Melting point: 565 K
a = 9.059 (2) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.238 (3) Å	Cell parameters from 2152 reflections
c = 10.983 (2) Å	θ = 2.9–22.8°
α = 74.18 (2)°	µ = 0.21 mm^−1
β = 76.324 (18)°	T = 298 K
γ = 71.74 (2)°	Needle, orange
V = 917.9 (4) Å^3	0.58 × 0.07 × 0.05 mm

Data collection

Oxford Diffraction Gemini R CCD diffractometer	3237 independent reflections
Radiation source: fine-focus sealed tube	1591 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
Rotation method data acquisition using ω and ϕ scans	θmax = 25.1°, θmin = 3.2°
Absorption correction: analytical (Clark & Reid, 1995)	h = −10→10
Tmin = 0.987, Tmax = 0.992	k = −11→12
9089 measured reflections	l = −10→13

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) = 0.079	H-atom parameters constrained
S = 0.89	w = 1/[σ^2(Fo^2) + (0.0253P)^2] where P = (Fo^2 + 2Fc^2)/3
3237 reflections	(Δ/σ)max < 0.001
255 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.18 e Å^−3

Special details

Experimental. face-indexed (CrysAlis RED; Oxford Diffraction, 2006)

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
S1	0.09891 (9)	0.33631 (7)	0.93697 (7)	0.0453 (2)
C2	0.2487 (3)	0.4062 (2)	0.9490 (3)	0.0391 (7)
N3	0.3067 (3)	0.3667 (2)	1.0570 (2)	0.0447 (6)
C4	0.2351 (3)	0.2720 (3)	1.1432 (3)	0.0429 (7)
O4	0.2636 (2)	0.21897 (17)	1.25334 (17)	0.0556 (6)
C5	0.1138 (3)	0.2375 (2)	1.0925 (2)	0.0404 (7)
C6	0.0291 (3)	0.1484 (3)	1.1593 (3)	0.0490 (8)
H6	0.0483	0.0990	1.2411	0.059*
C7	−0.0930 (4)	0.1259 (3)	1.1078 (3)	0.0538 (8)
O7	−0.1168 (3)	0.1729 (2)	0.9990 (2)	0.0709 (7)
O8	−0.1806 (2)	0.04969 (19)	1.19778 (19)	0.0644 (6)
C9	−0.3081 (4)	0.0243 (3)	1.1567 (3)	0.0804 (11)
H9A	−0.3871	0.1114	1.1375	0.121*
H9B	−0.3538	−0.0408	1.2241	0.121*
H9C	−0.2678	−0.0147	1.0815	0.121*
C8'	0.0839 (3)	0.7043 (3)	0.5334 (2)	0.0461 (7)
H8'	0.0693	0.7460	0.6023	0.055*
C7'	0.0057 (3)	0.7758 (3)	0.4324 (3)	0.0530 (8)
H7'	−0.0619	0.8653	0.4332	0.064*
C6'	0.0270 (3)	0.7153 (3)	0.3290 (3)	0.0519 (8)
H6'	−0.0257	0.7649	0.2603	0.062*
C5'	0.1245 (3)	0.5836 (3)	0.3268 (3)	0.0508 (8)
H5'	0.1373	0.5430	0.2576	0.061*
C4'	0.5116 (4)	0.1798 (3)	0.4984 (3)	0.0533 (8)
H4'	0.5136	0.1433	0.4290	0.064*
C3'	0.6146 (4)	0.1084 (3)	0.5820 (3)	0.0575 (8)
H3'	0.6860	0.0233	0.5699	0.069*
C2'	0.6131 (4)	0.1630 (3)	0.6855 (3)	0.0570 (8)
H2'	0.6850	0.1156	0.7413	0.068*
C1'	0.5060 (3)	0.2862 (3)	0.7048 (3)	0.0490 (8)
H1'	0.5065	0.3210	0.7745	0.059*
C10A'	0.2049 (3)	0.5101 (3)	0.4296 (3)	0.0402 (7)
C8A'	0.1855 (3)	0.5697 (3)	0.5344 (2)	0.0367 (7)
C9A'	0.3945 (3)	0.3628 (2)	0.6233 (2)	0.0370 (7)
C4A'	0.4023 (3)	0.3081 (3)	0.5164 (3)	0.0410 (7)
N10'	0.3051 (3)	0.3781 (2)	0.42686 (19)	0.0471 (6)
H10'	0.3070	0.3380	0.3669	0.057*
C9'	0.2712 (3)	0.4916 (2)	0.6420 (2)	0.0366 (7)
N11'	0.2174 (3)	0.5501 (2)	0.7425 (2)	0.0457 (6)
N12'	0.2998 (3)	0.4932 (2)	0.8481 (2)	0.0449 (6)
C1"	0.4140 (4)	0.5675 (3)	0.8521 (3)	0.0606 (9)
H1A"	0.3812	0.6073	0.9270	0.091*
H1B"	0.4187	0.6414	0.7767	0.091*
H1C"	0.5163	0.5022	0.8552	0.091*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0494 (5)	0.0538 (4)	0.0396 (4)	−0.0180 (4)	−0.0155 (4)	−0.0092 (3)
C2	0.0427 (19)	0.0425 (14)	0.0362 (17)	−0.0136 (14)	−0.0113 (15)	−0.0084 (13)
N3	0.0489 (16)	0.0559 (13)	0.0333 (14)	−0.0162 (13)	−0.0158 (13)	−0.0058 (11)
C4	0.047 (2)	0.0473 (16)	0.0353 (18)	−0.0069 (15)	−0.0089 (15)	−0.0160 (14)
O4	0.0742 (16)	0.0611 (12)	0.0368 (12)	−0.0203 (11)	−0.0229 (11)	−0.0049 (9)
C5	0.0439 (19)	0.0428 (15)	0.0387 (17)	−0.0063 (14)	−0.0134 (15)	−0.0163 (13)
C6	0.053 (2)	0.0532 (17)	0.0430 (18)	−0.0169 (16)	−0.0083 (16)	−0.0110 (14)
C7	0.053 (2)	0.0502 (18)	0.057 (2)	−0.0205 (17)	0.000 (2)	−0.0101 (16)
O7	0.0742 (17)	0.0950 (15)	0.0559 (15)	−0.0449 (13)	−0.0165 (13)	−0.0051 (12)
O8	0.0611 (15)	0.0666 (13)	0.0688 (15)	−0.0324 (12)	−0.0002 (12)	−0.0114 (11)
C9	0.063 (3)	0.079 (2)	0.113 (3)	−0.040 (2)	−0.003 (2)	−0.028 (2)
C8'	0.050 (2)	0.0506 (17)	0.0368 (18)	−0.0078 (16)	−0.0123 (15)	−0.0098 (13)
C7'	0.058 (2)	0.0521 (17)	0.0450 (19)	−0.0090 (16)	−0.0168 (17)	−0.0037 (15)
C6'	0.056 (2)	0.0608 (19)	0.0402 (19)	−0.0173 (18)	−0.0251 (16)	0.0038 (15)
C5'	0.059 (2)	0.0599 (18)	0.0397 (18)	−0.0195 (17)	−0.0173 (17)	−0.0089 (15)
C4'	0.065 (2)	0.0469 (17)	0.051 (2)	−0.0163 (18)	−0.0077 (18)	−0.0147 (15)
C3'	0.052 (2)	0.0430 (16)	0.068 (2)	−0.0049 (16)	−0.0054 (19)	−0.0091 (16)
C2'	0.047 (2)	0.0538 (19)	0.063 (2)	−0.0088 (17)	−0.0151 (17)	−0.0001 (16)
C1'	0.048 (2)	0.0567 (18)	0.0455 (18)	−0.0178 (17)	−0.0147 (16)	−0.0053 (14)
C10A'	0.0381 (18)	0.0441 (16)	0.0407 (18)	−0.0160 (14)	−0.0089 (15)	−0.0051 (14)
C8A'	0.0381 (18)	0.0464 (16)	0.0291 (16)	−0.0161 (14)	−0.0073 (14)	−0.0065 (13)
C9A'	0.0386 (19)	0.0418 (15)	0.0327 (16)	−0.0174 (15)	−0.0059 (14)	−0.0037 (12)
C4A'	0.0430 (19)	0.0423 (16)	0.0391 (17)	−0.0192 (15)	−0.0032 (15)	−0.0051 (14)
N10'	0.0604 (18)	0.0520 (15)	0.0365 (14)	−0.0181 (13)	−0.0140 (13)	−0.0130 (11)
C9'	0.0379 (18)	0.0432 (16)	0.0328 (17)	−0.0211 (14)	−0.0076 (14)	−0.0014 (13)
N11'	0.0520 (16)	0.0532 (13)	0.0328 (14)	−0.0110 (12)	−0.0153 (13)	−0.0070 (11)
N12'	0.0512 (16)	0.0571 (14)	0.0362 (14)	−0.0222 (13)	−0.0164 (12)	−0.0088 (12)
C1"	0.073 (2)	0.0730 (19)	0.0486 (19)	−0.0420 (18)	−0.0185 (17)	−0.0002 (15)

Geometric parameters (Å, º)

S1—C5	1.744 (3)	C5'—H5'	0.9300
S1—C2	1.765 (3)	C4'—C3'	1.364 (4)
C2—N12'	1.309 (3)	C4'—C4A'	1.406 (4)
C2—N3	1.321 (3)	C4'—H4'	0.9300
N3—C4	1.364 (3)	C3'—C2'	1.392 (4)
C4—O4	1.235 (3)	C3'—H3'	0.9300
C4—C5	1.511 (4)	C2'—C1'	1.363 (4)
C5—C6	1.330 (3)	C2'—H2'	0.9300
C6—C7	1.457 (4)	C1'—C9A'	1.409 (3)
C6—H6	0.9300	C1'—H1'	0.9300
C7—O7	1.203 (3)	C10A'—N10'	1.376 (3)
C7—O8	1.346 (3)	C10A'—C8A'	1.395 (3)
O8—C9	1.450 (3)	C8A'—C9'	1.473 (3)
C9—H9A	0.9600	C9A'—C4A'	1.411 (3)
C9—H9B	0.9600	C9A'—C9'	1.464 (3)
C9—H9C	0.9600	C4A'—N10'	1.373 (3)
C8'—C7'	1.368 (3)	N10'—H10'	0.8600
C8'—C8A'	1.396 (3)	C9'—N11'	1.318 (3)
C8'—H8'	0.9300	N11'—N12'	1.418 (3)
C7'—C6'	1.384 (4)	N12'—C1"	1.477 (3)
C7'—H7'	0.9300	C1"—H1A"	0.9600
C6'—C5'	1.363 (3)	C1"—H1B"	0.9600
C6'—H6'	0.9300	C1"—H1C"	0.9600
C5'—C10A'	1.398 (3)
C5—S1—C2	87.50 (13)	C4A'—C4'—H4'	119.7
N12'—C2—N3	123.0 (2)	C4'—C3'—C2'	120.0 (3)
N12'—C2—S1	117.8 (2)	C4'—C3'—H3'	120.0
N3—C2—S1	119.23 (19)	C2'—C3'—H3'	120.0
C2—N3—C4	110.0 (2)	C1'—C2'—C3'	119.9 (3)
O4—C4—N3	124.3 (3)	C1'—C2'—H2'	120.1
O4—C4—C5	122.0 (2)	C3'—C2'—H2'	120.1
N3—C4—C5	113.7 (2)	C2'—C1'—C9A'	122.6 (3)
C6—C5—C4	124.4 (2)	C2'—C1'—H1'	118.7
C6—C5—S1	126.0 (2)	C9A'—C1'—H1'	118.7
C4—C5—S1	109.6 (2)	N10'—C10A'—C8A'	119.7 (2)
C5—C6—C7	121.8 (3)	N10'—C10A'—C5'	119.6 (3)
C5—C6—H6	119.1	C8A'—C10A'—C5'	120.7 (3)
C7—C6—H6	119.1	C10A'—C8A'—C8'	118.2 (2)
O7—C7—O8	123.5 (3)	C10A'—C8A'—C9'	120.3 (2)
O7—C7—C6	124.5 (3)	C8'—C8A'—C9'	121.6 (2)
O8—C7—C6	111.9 (3)	C1'—C9A'—C4A'	116.5 (2)
C7—O8—C9	116.2 (3)	C1'—C9A'—C9'	125.4 (3)
O8—C9—H9A	109.5	C4A'—C9A'—C9'	118.1 (2)
O8—C9—H9B	109.5	N10'—C4A'—C4'	118.1 (3)
H9A—C9—H9B	109.5	N10'—C4A'—C9A'	121.4 (2)
O8—C9—H9C	109.5	C4'—C4A'—C9A'	120.5 (3)
H9A—C9—H9C	109.5	C4A'—N10'—C10A'	122.3 (2)
H9B—C9—H9C	109.5	C4A'—N10'—H10'	118.8
C7'—C8'—C8A'	120.9 (3)	C10A'—N10'—H10'	118.8
C7'—C8'—H8'	119.6	N11'—C9'—C9A'	131.0 (2)
C8A'—C8'—H8'	119.6	N11'—C9'—C8A'	112.2 (2)
C8'—C7'—C6'	120.1 (3)	C9A'—C9'—C8A'	116.8 (2)
C8'—C7'—H7'	119.9	C9'—N11'—N12'	117.8 (2)
C6'—C7'—H7'	119.9	C2—N12'—N11'	120.6 (2)
C5'—C6'—C7'	120.7 (3)	C2—N12'—C1"	121.9 (2)
C5'—C6'—H6'	119.6	N11'—N12'—C1"	115.3 (2)
C7'—C6'—H6'	119.6	N12'—C1"—H1A"	109.5
C6'—C5'—C10A'	119.4 (3)	N12'—C1"—H1B"	109.5
C6'—C5'—H5'	120.3	H1A"—C1"—H1B"	109.5
C10A'—C5'—H5'	120.3	N12'—C1"—H1C"	109.5
C3'—C4'—C4A'	120.5 (3)	H1A"—C1"—H1C"	109.5
C3'—C4'—H4'	119.7	H1B"—C1"—H1C"	109.5
C5—S1—C2—N12'	177.0 (2)	C7'—C8'—C8A'—C10A'	0.0 (4)
C5—S1—C2—N3	−1.4 (2)	C7'—C8'—C8A'—C9'	179.7 (2)
N12'—C2—N3—C4	−177.7 (2)	C2'—C1'—C9A'—C4A'	−2.2 (4)
S1—C2—N3—C4	0.6 (3)	C2'—C1'—C9A'—C9'	176.7 (2)
C2—N3—C4—O4	−178.6 (3)	C3'—C4'—C4A'—N10'	177.6 (2)
C2—N3—C4—C5	0.8 (3)	C3'—C4'—C4A'—C9A'	−1.9 (4)
O4—C4—C5—C6	−0.5 (4)	C1'—C9A'—C4A'—N10'	−176.4 (2)
N3—C4—C5—C6	−179.9 (2)	C9'—C9A'—C4A'—N10'	4.6 (3)
O4—C4—C5—S1	177.6 (2)	C1'—C9A'—C4A'—C4'	3.2 (3)
N3—C4—C5—S1	−1.8 (3)	C9'—C9A'—C4A'—C4'	−175.8 (2)
C2—S1—C5—C6	179.7 (3)	C4'—C4A'—N10'—C10A'	−173.8 (2)
C2—S1—C5—C4	1.64 (18)	C9A'—C4A'—N10'—C10A'	5.7 (4)
C4—C5—C6—C7	176.2 (2)	C8A'—C10A'—N10'—C4A'	−7.9 (4)
S1—C5—C6—C7	−1.6 (4)	C5'—C10A'—N10'—C4A'	171.6 (2)
C5—C6—C7—O7	7.9 (5)	C1'—C9A'—C9'—N11'	−13.6 (4)
C5—C6—C7—O8	−170.0 (2)	C4A'—C9A'—C9'—N11'	165.3 (2)
O7—C7—O8—C9	0.7 (4)	C1'—C9A'—C9'—C8A'	169.1 (2)
C6—C7—O8—C9	178.6 (2)	C4A'—C9A'—C9'—C8A'	−12.0 (3)
C8A'—C8'—C7'—C6'	−0.3 (4)	C10A'—C8A'—C9'—N11'	−167.8 (2)
C8'—C7'—C6'—C5'	0.7 (4)	C8'—C8A'—C9'—N11'	12.5 (3)
C7'—C6'—C5'—C10A'	−0.8 (4)	C10A'—C8A'—C9'—C9A'	10.0 (3)
C4A'—C4'—C3'—C2'	−0.5 (4)	C8'—C8A'—C9'—C9A'	−169.7 (2)
C4'—C3'—C2'—C1'	1.5 (4)	C9A'—C9'—N11'—N12'	8.7 (4)
C3'—C2'—C1'—C9A'	−0.1 (4)	C8A'—C9'—N11'—N12'	−173.92 (19)
C6'—C5'—C10A'—N10'	−179.0 (2)	N3—C2—N12'—N11'	−169.7 (2)
C6'—C5'—C10A'—C8A'	0.5 (4)	S1—C2—N12'—N11'	12.0 (3)
N10'—C10A'—C8A'—C8'	179.4 (2)	N3—C2—N12'—C1"	−7.4 (4)
C5'—C10A'—C8A'—C8'	−0.1 (4)	S1—C2—N12'—C1"	174.2 (2)
N10'—C10A'—C8A'—C9'	−0.3 (3)	C9'—N11'—N12'—C2	−99.6 (3)
C5'—C10A'—C8A'—C9'	−179.8 (2)	C9'—N11'—N12'—C1"	97.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N10′—H10′···O4^i	0.86	2.13	2.974 (3)	165
C1′—H1′···N12′	0.93	2.29	2.899 (4)	122

Symmetry code: (i) x, y, z−1.

(II) 2-[2-(9,10-dihydroacridin-9-ylidene)-1-methylhydrazinyl]-4H-1,3- thiazin-4-one

Crystal data

C18H14N4OS	F(000) = 348
Mr = 334.39	Dx = 1.434 Mg m^−3
Monoclinic, P21	Melting point: 576 K
Hall symbol: P 2yb	Mo Kα radiation, λ = 0.71073 Å
a = 4.7035 (2) Å	Cell parameters from 3449 reflections
b = 18.5073 (4) Å	θ = 2.3–25.9°
c = 9.1172 (2) Å	µ = 0.22 mm^−1
β = 102.689 (3)°	T = 100 K
V = 774.26 (4) Å^3	Plate, orange
Z = 2	0.12 × 0.08 × 0.04 mm

Data collection

Oxford Diffraction Gemini R CCD diffractometer	2659 independent reflections
Radiation source: fine-focus sealed tube	2207 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
Rotation method data acquisition using ω and ϕ scans	θmax = 25.1°, θmin = 3.2°
Absorption correction: analytical (Clark & Reid, 1995)	h = −5→5
Tmin = 0.968, Tmax = 0.993	k = −22→21
3900 measured reflections	l = −10→8

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)] = 0.042	H-atom parameters constrained
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0543P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max = 0.001
2659 reflections	Δρmax = 0.41 e Å^−3
218 parameters	Δρmin = −0.25 e Å^−3
1 restraint	Absolute structure: Refinement of the Flack parameter (Flack, 1983) based on 1240 Friedel pairs.
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.03 (9)

Special details

Experimental. face-indexed (CrysAlis RED; Oxford Diffraction, 2006)

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
S1	0.57879 (18)	0.55172 (4)	0.56218 (9)	0.0281 (2)
C2	0.5515 (7)	0.49331 (16)	0.7093 (3)	0.0225 (7)
N3	0.6146 (6)	0.42381 (13)	0.7209 (3)	0.0249 (6)
C4	0.7094 (7)	0.38584 (16)	0.6122 (4)	0.0248 (7)
O4	0.7421 (5)	0.31950 (11)	0.6275 (2)	0.0313 (6)
C5	0.7783 (7)	0.42190 (17)	0.4833 (3)	0.0265 (8)
H5	0.8640	0.3950	0.4184	0.032*
C6	0.7248 (8)	0.49189 (17)	0.4531 (4)	0.0311 (8)
H6	0.7701	0.5100	0.3658	0.037*
C1'	0.8389 (7)	0.59887 (16)	1.0703 (4)	0.0241 (7)
H1'	0.8642	0.5643	1.0002	0.029*
C2'	1.0333 (7)	0.60190 (17)	1.2047 (3)	0.0241 (7)
H2'	1.1884	0.5696	1.2252	0.029*
C3'	1.0010 (7)	0.65372 (17)	1.3129 (4)	0.0261 (7)
H3'	1.1317	0.6547	1.4056	0.031*
C4'	0.7791 (7)	0.70227 (17)	1.2821 (3)	0.0238 (7)
H4'	0.7586	0.7366	1.3535	0.029*
C5'	−0.0202 (7)	0.81521 (16)	0.9494 (3)	0.0272 (8)
H5'	−0.0251	0.8482	1.0256	0.033*
C6'	−0.2110 (7)	0.82220 (18)	0.8142 (4)	0.0308 (8)
H6'	−0.3434	0.8602	0.7985	0.037*
C7'	−0.2088 (7)	0.77263 (17)	0.6990 (4)	0.0307 (8)
H7'	−0.3401	0.7774	0.6070	0.037*
C8'	−0.0097 (7)	0.71635 (16)	0.7226 (4)	0.0252 (7)
H8'	−0.0071	0.6836	0.6455	0.030*
C8A'	0.1878 (7)	0.70806 (15)	0.8610 (3)	0.0210 (7)
C10A'	0.1843 (7)	0.75846 (15)	0.9749 (3)	0.0205 (7)
C9A'	0.6008 (6)	0.64644 (15)	1.0341 (3)	0.0206 (7)
C4A'	0.5803 (6)	0.70056 (15)	1.1420 (3)	0.0202 (7)
C9'	0.3805 (6)	0.64493 (16)	0.8923 (3)	0.0204 (7)
N10'	0.3717 (6)	0.75209 (13)	1.1118 (3)	0.0232 (6)
H10'	0.3564	0.7821	1.1817	0.028*
N11'	0.3275 (6)	0.59434 (13)	0.7891 (3)	0.0244 (6)
N12'	0.4652 (6)	0.52642 (12)	0.8230 (3)	0.0219 (6)
C1"	0.3755 (8)	0.48205 (17)	0.9385 (4)	0.0276 (8)
H1A"	0.1867	0.4617	0.8983	0.041*
H1B"	0.3669	0.5116	1.0239	0.041*
H1C"	0.5141	0.4439	0.9687	0.041*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0407 (5)	0.0180 (4)	0.0256 (4)	0.0011 (4)	0.0077 (3)	0.0006 (4)
C2	0.0276 (17)	0.0203 (16)	0.0211 (16)	−0.0010 (14)	0.0084 (14)	−0.0028 (14)
N3	0.0364 (16)	0.0161 (13)	0.0231 (14)	−0.0021 (12)	0.0088 (12)	0.0015 (12)
C4	0.0311 (18)	0.0178 (16)	0.0249 (18)	−0.0002 (14)	0.0046 (15)	0.0004 (14)
O4	0.0516 (15)	0.0138 (11)	0.0319 (13)	0.0043 (11)	0.0167 (11)	0.0030 (11)
C5	0.038 (2)	0.0238 (17)	0.0203 (17)	0.0042 (15)	0.0122 (16)	−0.0037 (14)
C6	0.047 (2)	0.0271 (18)	0.0232 (17)	−0.0064 (17)	0.0159 (16)	0.0011 (15)
C1'	0.0284 (18)	0.0205 (15)	0.0271 (18)	−0.0014 (14)	0.0143 (16)	0.0010 (14)
C2'	0.0230 (17)	0.0251 (16)	0.0263 (18)	0.0058 (14)	0.0098 (15)	0.0075 (14)
C3'	0.0302 (19)	0.0273 (17)	0.0205 (17)	−0.0068 (14)	0.0053 (15)	0.0029 (14)
C4'	0.0320 (18)	0.0193 (15)	0.0210 (16)	−0.0016 (14)	0.0079 (14)	−0.0031 (13)
C5'	0.042 (2)	0.0172 (16)	0.0261 (18)	0.0023 (15)	0.0153 (17)	−0.0031 (15)
C6'	0.037 (2)	0.0223 (16)	0.0339 (19)	0.0057 (15)	0.0087 (17)	0.0072 (16)
C7'	0.037 (2)	0.0275 (19)	0.0289 (19)	0.0026 (16)	0.0101 (16)	0.0044 (15)
C8'	0.0303 (19)	0.0219 (16)	0.0237 (17)	0.0017 (14)	0.0067 (15)	−0.0010 (14)
C8A'	0.0290 (17)	0.0147 (15)	0.0209 (16)	−0.0036 (13)	0.0095 (14)	−0.0003 (13)
C10A'	0.0237 (17)	0.0187 (15)	0.0217 (17)	−0.0026 (13)	0.0106 (14)	0.0022 (14)
C9A'	0.0261 (17)	0.0185 (15)	0.0197 (16)	−0.0010 (13)	0.0102 (14)	0.0030 (13)
C4A'	0.0260 (17)	0.0147 (14)	0.0226 (16)	−0.0043 (13)	0.0113 (14)	0.0026 (13)
C9'	0.0260 (18)	0.0169 (15)	0.0218 (17)	−0.0005 (13)	0.0130 (15)	−0.0027 (14)
N10'	0.0335 (15)	0.0165 (12)	0.0208 (14)	0.0005 (12)	0.0085 (13)	−0.0045 (11)
N11'	0.0341 (17)	0.0173 (14)	0.0225 (14)	0.0040 (12)	0.0074 (13)	−0.0018 (11)
N12'	0.0303 (15)	0.0139 (12)	0.0221 (14)	0.0037 (11)	0.0067 (12)	−0.0007 (11)
C1"	0.037 (2)	0.0197 (17)	0.0288 (19)	−0.0027 (15)	0.0132 (16)	−0.0001 (15)

Geometric parameters (Å, º)

S1—C6	1.728 (3)	C5'—H5'	0.9300
S1—C2	1.750 (3)	C6'—C7'	1.396 (4)
C2—N3	1.319 (4)	C6'—H6'	0.9300
C2—N12'	1.341 (4)	C7'—C8'	1.385 (4)
N3—C4	1.367 (4)	C7'—H7'	0.9300
C4—O4	1.241 (3)	C8'—C8A'	1.402 (4)
C4—C5	1.449 (4)	C8'—H8'	0.9300
C5—C6	1.337 (4)	C8A'—C10A'	1.398 (4)
C5—H5	0.9300	C8A'—C9'	1.468 (4)
C6—H6	0.9300	C10A'—N10'	1.366 (4)
C1'—C2'	1.360 (4)	C9A'—C4A'	1.422 (4)
C1'—C9A'	1.406 (4)	C9A'—C9'	1.468 (5)
C1'—H1'	0.9300	C4A'—N10'	1.353 (4)
C2'—C3'	1.408 (4)	C9'—N11'	1.312 (4)
C2'—H2'	0.9300	N10'—H10'	0.8600
C3'—C4'	1.359 (4)	N11'—N12'	1.417 (3)
C3'—H3'	0.9300	N12'—C1"	1.469 (4)
C4'—C4A'	1.407 (4)	C1"—H1A"	0.9600
C4'—H4'	0.9300	C1"—H1B"	0.9600
C5'—C6'	1.362 (4)	C1"—H1C"	0.9600
C5'—C10A'	1.409 (4)
C6—S1—C2	98.68 (15)	C8'—C7'—H7'	120.2
N3—C2—N12'	119.0 (3)	C6'—C7'—H7'	120.2
N3—C2—S1	127.6 (2)	C7'—C8'—C8A'	120.9 (3)
N12'—C2—S1	113.3 (2)	C7'—C8'—H8'	119.5
C2—N3—C4	123.1 (3)	C8A'—C8'—H8'	119.5
O4—C4—N3	118.6 (3)	C10A'—C8A'—C8'	118.8 (3)
O4—C4—C5	120.1 (3)	C10A'—C8A'—C9'	119.6 (3)
N3—C4—C5	121.2 (2)	C8'—C8A'—C9'	121.4 (3)
C6—C5—C4	123.3 (3)	N10'—C10A'—C8A'	120.7 (3)
C6—C5—H5	118.4	N10'—C10A'—C5'	119.7 (3)
C4—C5—H5	118.4	C8A'—C10A'—C5'	119.6 (3)
C5—C6—S1	125.6 (3)	C1'—C9A'—C4A'	116.8 (3)
C5—C6—H6	117.2	C1'—C9A'—C9'	124.5 (3)
S1—C6—H6	117.2	C4A'—C9A'—C9'	118.7 (3)
C2'—C1'—C9A'	122.0 (3)	N10'—C4A'—C4'	118.5 (3)
C2'—C1'—H1'	119.0	N10'—C4A'—C9A'	120.8 (3)
C9A'—C1'—H1'	119.0	C4'—C4A'—C9A'	120.7 (3)
C1'—C2'—C3'	120.3 (3)	N11'—C9'—C9A'	129.1 (3)
C1'—C2'—H2'	119.8	N11'—C9'—C8A'	114.6 (3)
C3'—C2'—H2'	119.8	C9A'—C9'—C8A'	116.2 (3)
C4'—C3'—C2'	120.1 (3)	C4A'—N10'—C10A'	122.7 (3)
C4'—C3'—H3'	119.9	C4A'—N10'—H10'	118.6
C2'—C3'—H3'	119.9	C10A'—N10'—H10'	118.6
C3'—C4'—C4A'	120.0 (3)	C9'—N11'—N12'	118.1 (2)
C3'—C4'—H4'	120.0	C2—N12'—N11'	116.0 (2)
C4A'—C4'—H4'	120.0	C2—N12'—C1"	118.8 (3)
C6'—C5'—C10A'	120.7 (3)	N11'—N12'—C1"	117.6 (2)
C6'—C5'—H5'	119.7	N12'—C1"—H1A"	109.5
C10A'—C5'—H5'	119.7	N12'—C1"—H1B"	109.5
C5'—C6'—C7'	120.4 (3)	H1A"—C1"—H1B"	109.5
C5'—C6'—H6'	119.8	N12'—C1"—H1C"	109.5
C7'—C6'—H6'	119.8	H1A"—C1"—H1C"	109.5
C8'—C7'—C6'	119.6 (3)	H1B"—C1"—H1C"	109.5
C6—S1—C2—N3	−3.0 (3)	C3'—C4'—C4A'—N10'	−176.4 (3)
C6—S1—C2—N12'	174.5 (2)	C3'—C4'—C4A'—C9A'	2.8 (4)
N12'—C2—N3—C4	−178.8 (3)	C1'—C9A'—C4A'—N10'	174.8 (3)
S1—C2—N3—C4	−1.4 (5)	C9'—C9A'—C4A'—N10'	−3.6 (4)
C2—N3—C4—O4	−174.5 (3)	C1'—C9A'—C4A'—C4'	−4.3 (4)
C2—N3—C4—C5	7.1 (5)	C9'—C9A'—C4A'—C4'	177.3 (3)
O4—C4—C5—C6	174.0 (3)	C1'—C9A'—C9'—N11'	14.1 (5)
N3—C4—C5—C6	−7.6 (5)	C4A'—C9A'—C9'—N11'	−167.7 (3)
C4—C5—C6—S1	2.2 (5)	C1'—C9A'—C9'—C8A'	−166.9 (3)
C2—S1—C6—C5	2.4 (4)	C4A'—C9A'—C9'—C8A'	11.3 (4)
C9A'—C1'—C2'—C3'	−0.1 (4)	C10A'—C8A'—C9'—N11'	167.4 (3)
C1'—C2'—C3'—C4'	−1.7 (4)	C8'—C8A'—C9'—N11'	−7.7 (4)
C2'—C3'—C4'—C4A'	0.3 (4)	C10A'—C8A'—C9'—C9A'	−11.8 (4)
C10A'—C5'—C6'—C7'	0.7 (5)	C8'—C8A'—C9'—C9A'	173.1 (3)
C5'—C6'—C7'—C8'	−0.4 (5)	C4'—C4A'—N10'—C10A'	174.5 (3)
C6'—C7'—C8'—C8A'	0.6 (5)	C9A'—C4A'—N10'—C10A'	−4.7 (4)
C7'—C8'—C8A'—C10A'	−1.1 (4)	C8A'—C10A'—N10'—C4A'	4.3 (4)
C7'—C8'—C8A'—C9'	174.1 (3)	C5'—C10A'—N10'—C4A'	−177.5 (3)
C8'—C8A'—C10A'—N10'	179.5 (3)	C9A'—C9'—N11'—N12'	10.6 (5)
C9'—C8A'—C10A'—N10'	4.3 (4)	C8A'—C9'—N11'—N12'	−168.4 (2)
C8'—C8A'—C10A'—C5'	1.3 (4)	N3—C2—N12'—N11'	−163.6 (3)
C9'—C8A'—C10A'—C5'	−173.9 (3)	S1—C2—N12'—N11'	18.7 (3)
C6'—C5'—C10A'—N10'	−179.4 (3)	N3—C2—N12'—C1"	−14.8 (4)
C6'—C5'—C10A'—C8A'	−1.2 (4)	S1—C2—N12'—C1"	167.6 (2)
C2'—C1'—C9A'—C4A'	3.0 (4)	C9'—N11'—N12'—C2	−142.8 (3)
C2'—C1'—C9A'—C9'	−178.7 (3)	C9'—N11'—N12'—C1"	67.9 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N10′—H10′···O4^i	0.86	2.02	2.837 (3)	159

Symmetry code: (i) −x+1, y+1/2, −z+2.

(III) 4-(9,10-dihydroacridin-9-ylidene)thiosemicarbazide

Crystal data

C14H12N4S	F(000) = 560
Mr = 268.34	Dx = 1.430 Mg m^−3
Monoclinic, P21/c	Melting point: 483 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.6535 (5) Å	Cell parameters from 2725 reflections
b = 18.6374 (9) Å	θ = 2.6–29.6°
c = 7.8350 (6) Å	µ = 0.25 mm^−1
β = 99.372 (6)°	T = 293 K
V = 1246.75 (13) Å^3	Prism, orange
Z = 4	0.36 × 0.12 × 0.08 mm

Data collection

Oxford Diffraction Xcalibur2 with Sapphire2 CCD detector diffractometer	2208 independent reflections
Radiation source: fine-focus sealed tube	1077 reflections with I > 2s(I)
Graphite monochromator	Rint = 0.046
Rotation method data acquisition using ω scans	θmax = 25.1°, θmin = 2.9°
Absorption correction: analytical (Clark & Reid, 1995)	h = −10→10
Tmin = 0.942, Tmax = 0.982	k = −22→22
13277 measured reflections	l = −9→9

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) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ^2(Fo^2) + (0.0265P)^2] where P = (Fo^2 + 2Fc^2)/3
2208 reflections	(Δ/σ)max = 0.001
198 parameters	Δρmax = 0.13 e Å^−3
0 restraints	Δρmin = −0.14 e Å^−3

Special details

Experimental. face-indexed (CrysAlis RED; Oxford Diffraction, 2006)

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)
N3	0.4003 (3)	0.40293 (13)	0.5112 (3)	0.0749 (7)
H4	0.471 (3)	0.4309 (14)	0.483 (3)	0.118 (12)*
H5	0.395 (3)	0.3524 (15)	0.490 (3)	0.118 (11)*
C2	0.2959 (3)	0.43085 (11)	0.5905 (3)	0.0529 (6)
S1A	0.3067 (7)	0.51590 (11)	0.6540 (11)	0.0769 (15)	0.730 (15)
S1B	0.2404 (15)	0.5239 (3)	0.558 (2)	0.063 (2)	0.270 (15)
N12'	0.1889 (3)	0.38506 (11)	0.6358 (3)	0.0666 (7)
H12'	0.146 (4)	0.4010 (18)	0.712 (4)	0.168 (17)*
N11'	0.2136 (2)	0.31255 (10)	0.6142 (2)	0.0525 (5)
C9'	0.1116 (3)	0.26535 (11)	0.6485 (3)	0.0415 (6)
C8A'	−0.0407 (3)	0.27492 (11)	0.7008 (3)	0.0412 (6)
C8'	−0.1157 (3)	0.34000 (12)	0.7105 (3)	0.0715 (8)
H8'	−0.0657	0.3817	0.6839	0.086*
C7'	−0.2607 (3)	0.34525 (14)	0.7580 (4)	0.0829 (8)
H7'	−0.3063	0.3901	0.7643	0.100*
C6'	−0.3392 (3)	0.28501 (14)	0.7962 (3)	0.0690 (7)
H6'	−0.4373	0.2888	0.8294	0.083*
C5'	−0.2726 (3)	0.22031 (13)	0.7852 (3)	0.0628 (7)
H5'	−0.3257	0.1792	0.8098	0.075*
C10A'	−0.1258 (3)	0.21421 (12)	0.7375 (3)	0.0482 (6)
N10'	−0.0644 (3)	0.14714 (11)	0.7248 (3)	0.0675 (7)
H10'	−0.114 (3)	0.1130 (12)	0.753 (3)	0.069 (9)*
C4A'	0.0733 (3)	0.13409 (12)	0.6661 (3)	0.0508 (6)
C4'	0.1214 (3)	0.06328 (12)	0.6461 (3)	0.0656 (7)
H4'	0.0599	0.0253	0.6729	0.079*
C3'	0.2576 (4)	0.05016 (14)	0.5876 (3)	0.0773 (8)
H3'	0.2887	0.0031	0.5726	0.093*
C2'	0.3500 (3)	0.10631 (14)	0.5502 (3)	0.0782 (8)
H2'	0.4441	0.0971	0.5114	0.094*
C1'	0.3037 (3)	0.17562 (12)	0.5701 (3)	0.0598 (7)
H1'	0.3675	0.2130	0.5447	0.072*
C9A'	0.1635 (3)	0.19160 (10)	0.6273 (3)	0.0426 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N3	0.0645 (17)	0.0443 (14)	0.126 (2)	−0.0076 (13)	0.0459 (15)	0.0064 (15)
C2	0.0583 (17)	0.0424 (14)	0.0632 (18)	−0.0087 (13)	0.0252 (14)	0.0006 (12)
S1A	0.080 (2)	0.0369 (6)	0.128 (3)	−0.0116 (8)	0.061 (2)	−0.0102 (11)
S1B	0.066 (4)	0.0399 (17)	0.089 (6)	−0.0082 (19)	0.029 (4)	−0.008 (2)
N12'	0.0725 (16)	0.0369 (13)	0.103 (2)	−0.0177 (11)	0.0506 (15)	−0.0107 (12)
N11'	0.0577 (14)	0.0383 (12)	0.0658 (15)	−0.0121 (10)	0.0226 (11)	−0.0044 (9)
C9'	0.0450 (16)	0.0391 (14)	0.0401 (15)	−0.0091 (12)	0.0056 (12)	0.0011 (11)
C8A'	0.0432 (16)	0.0391 (14)	0.0411 (15)	−0.0041 (11)	0.0064 (11)	0.0012 (11)
C8'	0.0486 (17)	0.0522 (16)	0.116 (2)	−0.0048 (14)	0.0208 (16)	−0.0072 (15)
C7'	0.0553 (19)	0.0635 (18)	0.134 (3)	0.0039 (15)	0.0280 (18)	−0.0233 (17)
C6'	0.0452 (17)	0.088 (2)	0.077 (2)	−0.0064 (16)	0.0193 (13)	−0.0011 (17)
C5'	0.0571 (19)	0.0602 (17)	0.074 (2)	−0.0083 (14)	0.0185 (15)	0.0145 (14)
C10A'	0.0423 (16)	0.0520 (16)	0.0509 (17)	−0.0016 (13)	0.0092 (13)	0.0078 (12)
N10'	0.0561 (16)	0.0426 (14)	0.107 (2)	−0.0126 (13)	0.0223 (13)	0.0137 (13)
C4A'	0.0516 (17)	0.0446 (15)	0.0553 (17)	−0.0065 (13)	0.0056 (13)	0.0022 (13)
C4'	0.077 (2)	0.0402 (16)	0.079 (2)	−0.0095 (14)	0.0120 (16)	0.0032 (14)
C3'	0.104 (3)	0.0478 (17)	0.083 (2)	0.0166 (17)	0.0222 (19)	0.0001 (15)
C2'	0.081 (2)	0.0639 (19)	0.097 (2)	0.0167 (17)	0.0383 (17)	0.0122 (17)
C1'	0.0609 (18)	0.0501 (16)	0.0724 (19)	0.0023 (13)	0.0224 (15)	0.0114 (13)
C9A'	0.0456 (15)	0.0387 (14)	0.0428 (15)	−0.0058 (12)	0.0047 (12)	0.0032 (11)

Geometric parameters (Å, º)

N3—C2	1.286 (3)	C6'—C5'	1.345 (3)
N3—H4	0.86 (3)	C6'—H6'	0.9300
N3—H5	0.96 (3)	C5'—C10A'	1.386 (3)
C2—N12'	1.349 (3)	C5'—H5'	0.9300
C2—S1A	1.659 (3)	C10A'—N10'	1.368 (3)
C2—S1B	1.807 (9)	N10'—C4A'	1.367 (3)
S1A—S1B	0.883 (9)	N10'—H10'	0.82 (2)
N12'—N11'	1.383 (2)	C4A'—C9A'	1.388 (3)
N12'—H12'	0.81 (3)	C4A'—C4'	1.400 (3)
N11'—C9'	1.304 (2)	C4'—C3'	1.354 (3)
C9'—C8A'	1.454 (3)	C4'—H4'	0.9300
C9'—C9A'	1.464 (3)	C3'—C2'	1.377 (3)
C8A'—C8'	1.384 (3)	C3'—H3'	0.9300
C8A'—C10A'	1.405 (3)	C2'—C1'	1.369 (3)
C8'—C7'	1.369 (3)	C2'—H2'	0.9300
C8'—H8'	0.9300	C1'—C9A'	1.393 (3)
C7'—C6'	1.371 (3)	C1'—H1'	0.9300
C7'—H7'	0.9300
C2—N3—H4	117.5 (18)	C7'—C6'—H6'	120.4
C2—N3—H5	117.9 (16)	C6'—C5'—C10A'	120.8 (2)
H4—N3—H5	125 (2)	C6'—C5'—H5'	119.6
N3—C2—N12'	115.9 (2)	C10A'—C5'—H5'	119.6
N3—C2—S1A	121.4 (2)	N10'—C10A'—C5'	118.6 (2)
N12'—C2—S1A	122.2 (2)	N10'—C10A'—C8A'	119.9 (2)
N3—C2—S1B	120.8 (3)	C5'—C10A'—C8A'	121.5 (2)
N12'—C2—S1B	117.8 (3)	C4A'—N10'—C10A'	123.8 (2)
S1A—C2—S1B	29.1 (2)	C4A'—N10'—H10'	118.6 (16)
S1B—S1A—C2	84.8 (5)	C10A'—N10'—H10'	117.6 (16)
S1A—S1B—C2	66.1 (7)	N10'—C4A'—C9A'	119.2 (2)
C2—N12'—N11'	117.4 (2)	N10'—C4A'—C4'	119.8 (2)
C2—N12'—H12'	112 (2)	C9A'—C4A'—C4'	121.0 (2)
N11'—N12'—H12'	123 (2)	C3'—C4'—C4A'	119.9 (2)
C9'—N11'—N12'	120.75 (18)	C3'—C4'—H4'	120.0
N11'—C9'—C8A'	130.54 (19)	C4A'—C4'—H4'	120.0
N11'—C9'—C9A'	112.3 (2)	C4'—C3'—C2'	120.2 (2)
C8A'—C9'—C9A'	117.12 (19)	C4'—C3'—H3'	119.9
C8'—C8A'—C10A'	115.4 (2)	C2'—C3'—H3'	119.9
C8'—C8A'—C9'	125.3 (2)	C1'—C2'—C3'	120.1 (2)
C10A'—C8A'—C9'	119.22 (19)	C1'—C2'—H2'	119.9
C7'—C8'—C8A'	122.4 (2)	C3'—C2'—H2'	119.9
C7'—C8'—H8'	118.8	C2'—C1'—C9A'	121.7 (2)
C8A'—C8'—H8'	118.8	C2'—C1'—H1'	119.2
C8'—C7'—C6'	120.7 (2)	C9A'—C1'—H1'	119.2
C8'—C7'—H7'	119.7	C4A'—C9A'—C1'	117.1 (2)
C6'—C7'—H7'	119.7	C4A'—C9A'—C9'	120.4 (2)
C5'—C6'—C7'	119.2 (2)	C1'—C9A'—C9'	122.4 (2)
C5'—C6'—H6'	120.4
N3—C2—S1A—S1B	97.7 (5)	C9'—C8A'—C10A'—N10'	0.4 (3)
N12'—C2—S1A—S1B	−90.1 (5)	C8'—C8A'—C10A'—C5'	−1.9 (3)
N3—C2—S1B—S1A	−100.3 (5)	C9'—C8A'—C10A'—C5'	−178.96 (19)
N12'—C2—S1B—S1A	107.0 (5)	C5'—C10A'—N10'—C4A'	174.7 (2)
N3—C2—N12'—N11'	8.4 (3)	C8A'—C10A'—N10'—C4A'	−4.7 (3)
S1A—C2—N12'—N11'	−164.1 (4)	C10A'—N10'—C4A'—C9A'	4.5 (3)
S1B—C2—N12'—N11'	162.5 (6)	C10A'—N10'—C4A'—C4'	−175.5 (2)
C2—N12'—N11'—C9'	−177.1 (2)	N10'—C4A'—C4'—C3'	179.8 (2)
N12'—N11'—C9'—C8A'	4.1 (3)	C9A'—C4A'—C4'—C3'	−0.1 (4)
N12'—N11'—C9'—C9A'	−176.6 (2)	C4A'—C4'—C3'—C2'	1.0 (4)
N11'—C9'—C8A'—C8'	6.0 (4)	C4'—C3'—C2'—C1'	−0.8 (4)
C9A'—C9'—C8A'—C8'	−173.2 (2)	C3'—C2'—C1'—C9A'	−0.2 (4)
N11'—C9'—C8A'—C10A'	−177.2 (2)	N10'—C4A'—C9A'—C1'	179.2 (2)
C9A'—C9'—C8A'—C10A'	3.5 (3)	C4'—C4A'—C9A'—C1'	−0.8 (3)
C10A'—C8A'—C8'—C7'	2.0 (3)	N10'—C4A'—C9A'—C9'	−0.1 (3)
C9'—C8A'—C8'—C7'	178.8 (2)	C4'—C4A'—C9A'—C9'	179.9 (2)
C8A'—C8'—C7'—C6'	−0.8 (4)	C2'—C1'—C9A'—C4A'	1.0 (3)
C8'—C7'—C6'—C5'	−0.6 (4)	C2'—C1'—C9A'—C9'	−179.7 (2)
C7'—C6'—C5'—C10A'	0.6 (4)	N11'—C9'—C9A'—C4A'	176.92 (19)
C6'—C5'—C10A'—N10'	−178.7 (2)	C8A'—C9'—C9A'—C4A'	−3.7 (3)
C6'—C5'—C10A'—C8A'	0.7 (3)	N11'—C9'—C9A'—C1'	−2.4 (3)
C8'—C8A'—C10A'—N10'	177.5 (2)	C8A'—C9'—C9A'—C1'	176.99 (19)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H5···N11′	0.96 (3)	2.11 (3)	2.554 (3)	106.3 (19)