Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270113031661/eg3141sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113031661/eg31411sup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270113031661/eg31412sup3.hkl |
CCDC references: 972879; 972880
Phenothiazines are known to be good electron donors and have attracted interest from the aspects of photoinduced electron transfer and magnetism (Sun et al., 2004; Okamoto et al., 2004; Okada et al., 1996). The phenothiazine derivative 10-(prop-1-yn-1-yl)-10H-phenothiazine, which incorporates an ynamine moiety, is well known as the first ynamine compound (Zaugg et al., 1958), and its structure has recently been reported (Umezono & Okuno, 2012). In 10-(prop-1-yn-1-yl)-10H-phenothiazines, the effect of oxidation at the S atom was shown to extend towards a terminal methyl group through an acetylene unit and was explained with a transannular interaction (Umezono & Okuno, 2013). Despite the presence of a polar substituent such as sulfoxide or sulfone, however, no relevant intermolecular contacts could be detected. In order to clearly demonstrate the transannular effect on the acetylene unit, we prepared and structurally characterized 10-ethynyl-10H-phenothiazines with a terminal H atom instead of a methyl group at the peripheral acetylene. In this paper, we report the structures of 10-ethynyl-10H-phenothiazine 5-oxide, (1), and 10-ethynyl-10H-phenothiazine 5,5-dioxide, (2), and discuss their differences with respect to intermolecular interactions as a consequence of transannular S···N interaction. We have not been able to grow single crystals of the low-melting unsubstituted parent compound 10-ethynyl-10H-phenothiazine.
Single crystals of (1) and (2) of sufficient quality for X-ray analysis were obtained by concentrating solutions of the compounds in dichloromethane. Compound (1) was prepared by mcpba oxidation of 10-ethynyl-10H-phenothiazine as follows: to a solution of 10-ethynyl-10H-phenothiazine (1.00 g, 4.48 mmol) in CH2Cl2 (100 ml), 3-chloroperbenzoic acid (mcpba; 1.07 g, 4.03 mmol) was added at 233 K and the solution was stirred for 1 h. It was then poured into water and washed with aqueous NaHCO3. The organic layer was dried over Na2SO4 and concentrated under reduced pressure. The residue was purified by gel-permeation chromatography to give colorless crystals of (1) (yield 0.90 g, 93%).
1H NMR (CDCl3): δ 7.95 (dd, J = 8.5, 0.8 Hz, 2H), 7.92 (dd, J = 7.8, 1.5 Hz, 2H), 7.64 (dt, J = 8.0, 1.6 Hz, 2H), 7.35 (dt, J = 7.5, 1.1 Hz, 2H), 3.60 (s, 1H). Compound (2) was prepared according to the published procedure of Okuno et al. (2006).
Crystal data, data collection and structure refinement details are summarized in Table 1. Csp-bound H atoms were located in difference Fourier maps and refined isotropically without any restrictions. The remaining H atoms were refined as riding on their parent C atoms, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C).
In 10-ethynyl-10H-phenothiazine 5-oxide, (1), the phenothiazine moiety has a butterfly structure as shown in Fig. 1; the two benzene rings subtend a dihedral angle of 149.66 (8)°. The central six-membered ring adopts a boat conformation in which the transannular S1···N1 distance is 3.090 (2) Å. The coordination around atom N1 is slightly pyramidal (Table 2), with the distance of N1 to the C1/C12/C13 plane of 0.113 (2) Å. These structural features of (1) are in good agreement with those in compounds reported earlier (Okuno et al., 2006; Umezono & Okuno, 2013). The acetylenic H atom is involved in an intermolecular Csp—H···O hydrogen bond (Table 3). Several examples of close Csp—H···O contacts have been documented (Allen et al., 1996; Aurora et al., 2006; Howard et al., 1979; Kariuki et al., 1997; Lovas et al., 1977; Makal & Wozniak, 2009; Murty & Vasella, 2001; Souweha et al., 2007; Steiner et al., 1997; Yamauchi et al., 2007). The hydrogen bond in (1) can be classified as rather strong; it generates a helix along the a axis. Between neighbouring helices, π–π stacking interactions are recognized as shown in Fig. 2, with a C1···C8iii distance of 3.337 (3) Å and a C8···C8iv distance of 3.321 (3) Å [symmetry codes: (iii) -x+2, y, -z+3/2; (iv) -x+1, y, -z+3/2]. The centroid–centroid distances are 4.637 and 4.209 Å [between which types of rings?].
In 10-ethynyl-10H-phenothiazine 5,5-dioxide, (2), the asymmetric unit comprises half a molecule; a mirror plane passes through the S atom, the ynamine fragment and the acetylenic H atom. The phenothiazine moiety adopts a butterfly structure (Fig. 3), with a dihedral angle of 142.67 (10)° between the C1–C6 and C1i–C6i benzene rings [symmetry code: (i) x, -y+1/2, z], which is slightly smaller than in previously reported compounds. The central six-membered ring again is in boat conformation, with a shorter transannular S1···N1 distance of 2.967 (3) Å. Atom N1 is also pyramidal (Table 4), with a distance of 0.098 (3) Å to the C1/C1i/C7 plane. The acetylenic H atom is engaged in an intermolecular Csp—H···O hydrogen bond (Table 5). This contact gives rise to a chain along the a axis, with π–π interactions between the chains as depicted in Fig. 4 and a distance between atoms C8 and C1iv or C1v of 3.391 (4) Å [symmetry codes: (iv) x+1/2, -y+1/2, -z+1/2; (v) x+1/2, y, -z+1/2].
The central six-membered rings in boat conformations correspond to the usual geometry for phenothiazine 5-oxides and 5,5-dioxides, except for a few examples (Kormos et al., 2012). When one or both benzene rings are removed or replaced by a heteroaromatic ring, however, the resulting 1,4-thiazine 5,5-dioxides are planar (Akkurt et al., 2005; Andreetti et al., 1974; Barazarte et al., 2008, 2009; Charris et al., 2007; Chia et al., 2008; Fraenkel et al., 1986; Girard et al., 1987; Wang, Mudraboyina et al., 2010; Wang, Wisner & Jennings, 2010) because ofeffective conjugation between the aromatic systems. Compound (2) shows a shorter transannular S···N contact than (1), indicating a stronger interaction. As a result, (2) is thought to have a smaller dihedral angle than (1) or the compounds reported earlier.
As for intermolecular contacts, the hydrogen-bonding pattern differs significantly. Almost linear hydrogen bonds are formed in (1), with a tendency towards a longer Csp—H bond. The H···O separation of 2.13 (3) Å is shorter than average Csp—H···O hydrogen-bond distances. On the other hand, the hydrogen bond in (2) is considered to be weaker. In the IR spectrum, a higher value for νC—H (3394 cm-1) was observed in (2) than in (1) (3151 cm-1), also suggesting that the hydrogen bond in (2) is weaker than that in (1). This weakening of the intermolecular hydrogen bond in (2) can be explained by the transannular S···N interaction in the phenothiazine unit (Umezono & Okuno, 2013). The higher oxidation state in (2) results in a more positive charge on the S atom, thus enhancing the interaction between S and the transannular N-atom donor. This interaction also induces a more negative charge on the N atom and hence a higher π-electron density on the acetylene group of (2) and lower acidity of the Csp—H atom. In 1H NMR spectroscopy, this is reflected in a high field shift of the Csp—H with respect to the situation in (1).
In summary, we succeeded in a structural comparison of (1) and (2), both with terminal H atoms at the acetylene moiety. The relatively short intramolecular S···N distance results in a significant transannular interaction in (2). Intermolecular Csp—H···O hydrogen bonds were encountered in both structures, and stronger hydrogen bonds were found in (1). The increase in π-electron density, originating from the transannular S···N interaction, is consistent with a decrease in the acidity of the Csp—H group in (2).
For both compounds, data collection: CrystalClear (Rigaku, 2008). Cell refinement: CrystalClear (Rigaku, 2008) for (2). For both compounds, data reduction: CrystalClear (Rigaku, 2008); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012); software used to prepare material for publication: CrystalStructure (Rigaku, 2010).
C14H9NOS | F(000) = 992.00 |
Mr = 239.29 | Dx = 1.452 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: -P 2n 2ab | Cell parameters from 5559 reflections |
a = 7.9006 (19) Å | θ = 2.4–31.1° |
b = 16.302 (4) Å | µ = 0.27 mm−1 |
c = 16.998 (5) Å | T = 93 K |
V = 2189.3 (10) Å3 | Block, colorless |
Z = 8 | 0.10 × 0.05 × 0.05 mm |
Rigaku Saturn724+ diffractometer | 2029 reflections with F2 > 2σ(F2) |
Detector resolution: 28.445 pixels mm-1 | Rint = 0.063 |
ω scans | θmax = 27.5° |
Absorption correction: numerical (NUMABS; Rigaku, 1999) | h = −10→8 |
Tmin = 0.980, Tmax = 0.986 | k = −21→15 |
16927 measured reflections | l = −22→22 |
2516 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.147 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0798P)2 + 0.6466P] where P = (Fo2 + 2Fc2)/3 |
2515 reflections | (Δ/σ)max < 0.001 |
158 parameters | Δρmax = 0.49 e Å−3 |
0 restraints | Δρmin = −0.47 e Å−3 |
Primary atom site location: structure-invariant direct methods |
C14H9NOS | V = 2189.3 (10) Å3 |
Mr = 239.29 | Z = 8 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 7.9006 (19) Å | µ = 0.27 mm−1 |
b = 16.302 (4) Å | T = 93 K |
c = 16.998 (5) Å | 0.10 × 0.05 × 0.05 mm |
Rigaku Saturn724+ diffractometer | 2516 independent reflections |
Absorption correction: numerical (NUMABS; Rigaku, 1999) | 2029 reflections with F2 > 2σ(F2) |
Tmin = 0.980, Tmax = 0.986 | Rint = 0.063 |
16927 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.147 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | Δρmax = 0.49 e Å−3 |
2515 reflections | Δρmin = −0.47 e Å−3 |
158 parameters |
Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY |
Refinement. Refinement was performed using all reflections except for one with very negative F2. 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 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
S1 | 0.75165 (6) | 0.06008 (3) | 0.68675 (3) | 0.01792 (19) | |
O1 | 0.61110 (19) | 0.05632 (9) | 0.62728 (9) | 0.0231 (4) | |
N1 | 0.9343 (3) | 0.19889 (11) | 0.59667 (11) | 0.0194 (4) | |
C1 | 1.0078 (3) | 0.11984 (13) | 0.59044 (12) | 0.0188 (5) | |
C2 | 1.1464 (3) | 0.10709 (14) | 0.54108 (13) | 0.0227 (5) | |
C3 | 1.2235 (3) | 0.03169 (15) | 0.53857 (13) | 0.0241 (5) | |
C4 | 1.1651 (3) | −0.03340 (14) | 0.58384 (13) | 0.0244 (5) | |
C5 | 1.0252 (3) | −0.02186 (13) | 0.63138 (13) | 0.0225 (5) | |
C6 | 0.9441 (3) | 0.05471 (12) | 0.63481 (12) | 0.0183 (5) | |
C7 | 0.7718 (3) | 0.16400 (14) | 0.71501 (13) | 0.0188 (5) | |
C8 | 0.6956 (3) | 0.18743 (13) | 0.78573 (13) | 0.0203 (5) | |
C9 | 0.6888 (3) | 0.26913 (14) | 0.80688 (13) | 0.0227 (5) | |
C10 | 0.7554 (3) | 0.32764 (14) | 0.75571 (14) | 0.0230 (5) | |
C11 | 0.8311 (3) | 0.30590 (13) | 0.68552 (13) | 0.0216 (5) | |
C12 | 0.8446 (3) | 0.22317 (13) | 0.66499 (12) | 0.0179 (5) | |
C13 | 0.9856 (3) | 0.25802 (13) | 0.54515 (13) | 0.0208 (5) | |
C14 | 1.0316 (3) | 0.30852 (14) | 0.49945 (14) | 0.0249 (5) | |
H2 | 1.1874 | 0.1506 | 0.5092 | 0.0273* | |
H3 | 1.3186 | 0.0239 | 0.5052 | 0.0289* | |
H4 | 1.2206 | −0.0851 | 0.5821 | 0.0293* | |
H5 | 0.9834 | −0.0662 | 0.6620 | 0.0270* | |
H8 | 0.6482 | 0.1470 | 0.8194 | 0.0244* | |
H9 | 0.6396 | 0.2852 | 0.8555 | 0.0272* | |
H10 | 0.7485 | 0.3840 | 0.7695 | 0.0276* | |
H11 | 0.8739 | 0.3471 | 0.6513 | 0.0259* | |
H14 | 1.064 (4) | 0.3513 (16) | 0.4587 (17) | 0.032 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0149 (3) | 0.0209 (4) | 0.0180 (3) | 0.00059 (19) | −0.00005 (18) | 0.00298 (18) |
O1 | 0.0173 (8) | 0.0290 (9) | 0.0229 (9) | −0.0014 (6) | −0.0040 (6) | −0.0004 (6) |
N1 | 0.0170 (9) | 0.0244 (10) | 0.0167 (9) | 0.0000 (7) | 0.0014 (7) | 0.0033 (7) |
C1 | 0.0157 (10) | 0.0234 (12) | 0.0173 (10) | 0.0012 (8) | −0.0027 (8) | −0.0024 (8) |
C2 | 0.0182 (11) | 0.0316 (13) | 0.0184 (10) | −0.0025 (9) | 0.0000 (9) | −0.0018 (9) |
C3 | 0.0171 (11) | 0.0353 (14) | 0.0199 (11) | 0.0030 (10) | −0.0005 (8) | −0.0050 (10) |
C4 | 0.0204 (12) | 0.0255 (12) | 0.0273 (12) | 0.0047 (9) | −0.0030 (9) | −0.0043 (9) |
C5 | 0.0206 (11) | 0.0250 (12) | 0.0220 (11) | 0.0003 (9) | −0.0030 (9) | −0.0001 (9) |
C6 | 0.0159 (11) | 0.0232 (11) | 0.0156 (10) | −0.0005 (8) | −0.0010 (8) | −0.0012 (8) |
C7 | 0.0150 (10) | 0.0231 (12) | 0.0183 (11) | 0.0001 (9) | −0.0018 (8) | 0.0016 (9) |
C8 | 0.0132 (10) | 0.0280 (13) | 0.0199 (11) | 0.0018 (9) | −0.0010 (9) | 0.0034 (8) |
C9 | 0.0174 (11) | 0.0299 (13) | 0.0209 (11) | 0.0038 (9) | 0.0018 (9) | −0.0028 (9) |
C10 | 0.0193 (12) | 0.0243 (12) | 0.0254 (12) | 0.0026 (9) | 0.0007 (9) | −0.0012 (9) |
C11 | 0.0172 (12) | 0.0242 (13) | 0.0233 (12) | −0.0013 (9) | −0.0026 (9) | 0.0035 (9) |
C12 | 0.0107 (10) | 0.0251 (12) | 0.0180 (10) | 0.0015 (8) | 0.0002 (8) | 0.0011 (8) |
C13 | 0.0164 (11) | 0.0261 (12) | 0.0199 (11) | 0.0008 (9) | −0.0022 (8) | −0.0010 (9) |
C14 | 0.0195 (12) | 0.0308 (14) | 0.0245 (12) | −0.0000 (9) | 0.0019 (9) | 0.0022 (10) |
S1—O1 | 1.5029 (17) | C8—C9 | 1.381 (4) |
S1—C6 | 1.760 (3) | C9—C10 | 1.394 (4) |
S1—C7 | 1.768 (3) | C10—C11 | 1.381 (4) |
N1—C1 | 1.417 (3) | C11—C12 | 1.397 (3) |
N1—C12 | 1.417 (3) | C13—C14 | 1.189 (4) |
N1—C13 | 1.364 (3) | C2—H2 | 0.950 |
C1—C2 | 1.395 (3) | C3—H3 | 0.950 |
C1—C6 | 1.396 (3) | C4—H4 | 0.950 |
C2—C3 | 1.373 (4) | C5—H5 | 0.950 |
C3—C4 | 1.390 (4) | C8—H8 | 0.950 |
C4—C5 | 1.382 (4) | C9—H9 | 0.950 |
C5—C6 | 1.404 (3) | C10—H10 | 0.950 |
C7—C8 | 1.398 (4) | C11—H11 | 0.950 |
C7—C12 | 1.408 (3) | C14—H14 | 1.02 (3) |
O1—S1—C6 | 107.38 (10) | C10—C11—C12 | 119.8 (2) |
O1—S1—C7 | 106.76 (10) | N1—C12—C7 | 120.50 (19) |
C6—S1—C7 | 96.09 (10) | N1—C12—C11 | 120.83 (19) |
C1—N1—C12 | 121.35 (18) | C7—C12—C11 | 118.6 (2) |
C1—N1—C13 | 118.21 (18) | N1—C13—C14 | 178.9 (3) |
C12—N1—C13 | 118.52 (18) | C1—C2—H2 | 119.979 |
N1—C1—C2 | 120.13 (19) | C3—C2—H2 | 119.983 |
N1—C1—C6 | 120.21 (19) | C2—C3—H3 | 119.360 |
C2—C1—C6 | 119.6 (2) | C4—C3—H3 | 119.360 |
C1—C2—C3 | 120.0 (2) | C3—C4—H4 | 120.481 |
C2—C3—C4 | 121.3 (2) | C5—C4—H4 | 120.484 |
C3—C4—C5 | 119.0 (2) | C4—C5—H5 | 119.659 |
C4—C5—C6 | 120.7 (2) | C6—C5—H5 | 119.667 |
S1—C6—C1 | 123.00 (16) | C7—C8—H8 | 119.865 |
S1—C6—C5 | 117.33 (16) | C9—C8—H8 | 119.851 |
C1—C6—C5 | 119.3 (2) | C8—C9—H9 | 120.547 |
S1—C7—C8 | 117.17 (17) | C10—C9—H9 | 120.567 |
S1—C7—C12 | 121.94 (17) | C9—C10—H10 | 119.093 |
C8—C7—C12 | 120.5 (2) | C11—C10—H10 | 119.108 |
C7—C8—C9 | 120.3 (2) | C10—C11—H11 | 120.109 |
C8—C9—C10 | 118.9 (2) | C12—C11—H11 | 120.118 |
C9—C10—C11 | 121.8 (2) | C13—C14—H14 | 176.5 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···O1i | 1.02 (3) | 2.13 (3) | 3.145 (3) | 175 (2) |
Symmetry code: (i) x+1/2, −y+1/2, −z+1. |
C14H9NO2S | F(000) = 528.00 |
Mr = 255.29 | Dx = 1.482 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71075 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 3716 reflections |
a = 9.177 (3) Å | θ = 2.2–31.4° |
b = 11.520 (4) Å | µ = 0.27 mm−1 |
c = 10.819 (3) Å | T = 93 K |
V = 1143.8 (7) Å3 | Block, colorless |
Z = 4 | 0.10 × 0.10 × 0.10 mm |
Rigaku Saturn724+ diffractometer | 1297 reflections with F2 > 2σ(F2) |
Detector resolution: 28.445 pixels mm-1 | Rint = 0.050 |
ω scans | θmax = 27.5° |
Absorption correction: numerical (NUMABS; Rigaku, 1999) | h = −11→11 |
Tmin = 0.958, Tmax = 0.973 | k = −14→14 |
8777 measured reflections | l = −14→13 |
1375 independent reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.128 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0558P)2 + 1.1593P] where P = (Fo2 + 2Fc2)/3 |
1375 reflections | (Δ/σ)max < 0.001 |
94 parameters | Δρmax = 0.84 e Å−3 |
0 restraints | Δρmin = −0.49 e Å−3 |
Primary atom site location: structure-invariant direct methods |
C14H9NO2S | V = 1143.8 (7) Å3 |
Mr = 255.29 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 9.177 (3) Å | µ = 0.27 mm−1 |
b = 11.520 (4) Å | T = 93 K |
c = 10.819 (3) Å | 0.10 × 0.10 × 0.10 mm |
Rigaku Saturn724+ diffractometer | 1375 independent reflections |
Absorption correction: numerical (NUMABS; Rigaku, 1999) | 1297 reflections with F2 > 2σ(F2) |
Tmin = 0.958, Tmax = 0.973 | Rint = 0.050 |
8777 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.128 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | Δρmax = 0.84 e Å−3 |
1375 reflections | Δρmin = −0.49 e Å−3 |
94 parameters |
Geometry. ENTER SPECIAL DETAILS OF THE MOLECULAR GEOMETRY |
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 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
S1 | 0.23021 (7) | 0.2500 | −0.03905 (6) | 0.0258 (3) | |
O1 | 0.3021 (2) | 0.2500 | −0.15688 (18) | 0.0301 (5) | |
O2 | 0.0733 (2) | 0.2500 | −0.0386 (2) | 0.0401 (6) | |
N1 | 0.5097 (3) | 0.2500 | 0.0988 (2) | 0.0243 (5) | |
C1 | 0.4337 (3) | 0.14262 (17) | 0.10106 (16) | 0.0245 (4) | |
C2 | 0.4924 (3) | 0.04626 (19) | 0.16022 (18) | 0.0318 (5) | |
C3 | 0.4104 (3) | −0.05549 (18) | 0.1686 (2) | 0.0382 (6) | |
C4 | 0.2723 (3) | −0.06268 (19) | 0.1188 (3) | 0.0377 (6) | |
C5 | 0.2150 (3) | 0.0317 (2) | 0.0571 (2) | 0.0334 (5) | |
C6 | 0.2959 (3) | 0.13401 (17) | 0.04785 (17) | 0.0241 (4) | |
C7 | 0.6558 (3) | 0.2500 | 0.1211 (3) | 0.0289 (7) | |
C8 | 0.7830 (4) | 0.2500 | 0.1366 (3) | 0.0363 (7) | |
H2 | 0.5876 | 0.0496 | 0.1947 | 0.0382* | |
H3 | 0.4505 | −0.1211 | 0.2094 | 0.0458* | |
H4 | 0.2171 | −0.1320 | 0.1269 | 0.0452* | |
H5 | 0.1208 | 0.0271 | 0.0210 | 0.0401* | |
H8 | 0.885 (5) | 0.2500 | 0.136 (4) | 0.037 (10)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0264 (4) | 0.0263 (4) | 0.0246 (4) | 0.0000 | −0.0009 (3) | 0.0000 |
O1 | 0.0395 (12) | 0.0311 (11) | 0.0196 (10) | 0.0000 | −0.0018 (9) | 0.0000 |
O2 | 0.0252 (11) | 0.0451 (14) | 0.0501 (15) | 0.0000 | −0.0021 (10) | 0.0000 |
N1 | 0.0263 (11) | 0.0256 (12) | 0.0211 (11) | 0.0000 | −0.0006 (9) | 0.0000 |
C1 | 0.0339 (10) | 0.0224 (9) | 0.0171 (8) | 0.0008 (8) | 0.0065 (7) | −0.0010 (7) |
C2 | 0.0425 (12) | 0.0323 (11) | 0.0206 (9) | 0.0094 (9) | 0.0073 (8) | 0.0025 (8) |
C3 | 0.0642 (15) | 0.0219 (10) | 0.0285 (10) | 0.0098 (10) | 0.0194 (11) | 0.0055 (8) |
C4 | 0.0569 (15) | 0.0218 (11) | 0.0343 (11) | −0.0049 (10) | 0.0196 (10) | −0.0023 (9) |
C5 | 0.0417 (12) | 0.0281 (11) | 0.0304 (10) | −0.0084 (9) | 0.0117 (9) | −0.0048 (9) |
C6 | 0.0310 (10) | 0.0223 (9) | 0.0190 (9) | −0.0001 (8) | 0.0059 (7) | −0.0014 (7) |
C7 | 0.0328 (15) | 0.0372 (16) | 0.0167 (12) | 0.0000 | −0.0019 (11) | 0.0000 |
C8 | 0.0331 (17) | 0.049 (2) | 0.0269 (15) | 0.0000 | −0.0045 (13) | 0.0000 |
S1—O1 | 1.435 (2) | C3—C4 | 1.379 (4) |
S1—O2 | 1.440 (2) | C4—C5 | 1.380 (4) |
S1—C6 | 1.742 (2) | C5—C6 | 1.397 (3) |
S1—C6i | 1.742 (2) | C7—C8 | 1.179 (5) |
N1—C1 | 1.420 (3) | C2—H2 | 0.950 |
N1—C1i | 1.420 (3) | C3—H3 | 0.950 |
N1—C7 | 1.362 (4) | C4—H4 | 0.950 |
C1—C2 | 1.390 (3) | C5—H5 | 0.950 |
C1—C6 | 1.393 (3) | C8—H8 | 0.94 (4) |
C2—C3 | 1.396 (4) | ||
O1—S1—O2 | 117.56 (13) | C4—C5—C6 | 119.8 (3) |
O1—S1—C6 | 108.68 (9) | S1—C6—C1 | 118.87 (15) |
O1—S1—C6i | 108.68 (9) | S1—C6—C5 | 120.13 (16) |
O2—S1—C6 | 110.14 (9) | C1—C6—C5 | 120.88 (19) |
O2—S1—C6i | 110.14 (9) | N1—C7—C8 | 178.0 (4) |
C6—S1—C6i | 100.22 (10) | C1—C2—H2 | 120.282 |
C1—N1—C1i | 121.2 (3) | C3—C2—H2 | 120.288 |
C1—N1—C7 | 118.69 (13) | C2—C3—H3 | 119.316 |
C1i—N1—C7 | 118.69 (13) | C4—C3—H3 | 119.316 |
N1—C1—C2 | 120.9 (2) | C3—C4—H4 | 120.264 |
N1—C1—C6 | 120.04 (19) | C5—C4—H4 | 120.266 |
C2—C1—C6 | 119.03 (19) | C4—C5—H5 | 120.116 |
C1—C2—C3 | 119.4 (2) | C6—C5—H5 | 120.110 |
C2—C3—C4 | 121.4 (2) | C7—C8—H8 | 172 (3) |
C3—C4—C5 | 119.5 (3) |
Symmetry code: (i) x, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O2ii | 0.94 (4) | 2.56 (4) | 3.270 (5) | 133 (3) |
Symmetry code: (ii) x+1, y, z. |
Experimental details
(1) | (2) | |
Crystal data | ||
Chemical formula | C14H9NOS | C14H9NO2S |
Mr | 239.29 | 255.29 |
Crystal system, space group | Orthorhombic, Pbcn | Orthorhombic, Pnma |
Temperature (K) | 93 | 93 |
a, b, c (Å) | 7.9006 (19), 16.302 (4), 16.998 (5) | 9.177 (3), 11.520 (4), 10.819 (3) |
V (Å3) | 2189.3 (10) | 1143.8 (7) |
Z | 8 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.27 | 0.27 |
Crystal size (mm) | 0.10 × 0.05 × 0.05 | 0.10 × 0.10 × 0.10 |
Data collection | ||
Diffractometer | Rigaku Saturn724+ diffractometer | Rigaku Saturn724+ diffractometer |
Absorption correction | Numerical (NUMABS; Rigaku, 1999) | Numerical (NUMABS; Rigaku, 1999) |
Tmin, Tmax | 0.980, 0.986 | 0.958, 0.973 |
No. of measured, independent and observed [F2 > 2σ(F2)] reflections | 16927, 2516, 2029 | 8777, 1375, 1297 |
Rint | 0.063 | 0.050 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.147, 1.11 | 0.050, 0.128, 1.11 |
No. of reflections | 2515 | 1375 |
No. of parameters | 158 | 94 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.49, −0.47 | 0.84, −0.49 |
Computer programs: CrystalClear (Rigaku, 2008), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012), CrystalStructure (Rigaku, 2010).
S1—O1 | 1.5029 (17) | C4—C5 | 1.382 (4) |
S1—C6 | 1.760 (3) | C5—C6 | 1.404 (3) |
S1—C7 | 1.768 (3) | C7—C8 | 1.398 (4) |
N1—C1 | 1.417 (3) | C7—C12 | 1.408 (3) |
N1—C12 | 1.417 (3) | C8—C9 | 1.381 (4) |
N1—C13 | 1.364 (3) | C9—C10 | 1.394 (4) |
C1—C2 | 1.395 (3) | C10—C11 | 1.381 (4) |
C1—C6 | 1.396 (3) | C11—C12 | 1.397 (3) |
C2—C3 | 1.373 (4) | C13—C14 | 1.189 (4) |
C3—C4 | 1.390 (4) | ||
O1—S1—C6 | 107.38 (10) | S1—C6—C5 | 117.33 (16) |
O1—S1—C7 | 106.76 (10) | C1—C6—C5 | 119.3 (2) |
C6—S1—C7 | 96.09 (10) | S1—C7—C8 | 117.17 (17) |
C1—N1—C12 | 121.35 (18) | S1—C7—C12 | 121.94 (17) |
C1—N1—C13 | 118.21 (18) | C8—C7—C12 | 120.5 (2) |
C12—N1—C13 | 118.52 (18) | C7—C8—C9 | 120.3 (2) |
N1—C1—C2 | 120.13 (19) | C8—C9—C10 | 118.9 (2) |
N1—C1—C6 | 120.21 (19) | C9—C10—C11 | 121.8 (2) |
C2—C1—C6 | 119.6 (2) | C10—C11—C12 | 119.8 (2) |
C1—C2—C3 | 120.0 (2) | N1—C12—C7 | 120.50 (19) |
C2—C3—C4 | 121.3 (2) | N1—C12—C11 | 120.83 (19) |
C3—C4—C5 | 119.0 (2) | C7—C12—C11 | 118.6 (2) |
C4—C5—C6 | 120.7 (2) | N1—C13—C14 | 178.9 (3) |
S1—C6—C1 | 123.00 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···O1i | 1.02 (3) | 2.13 (3) | 3.145 (3) | 175 (2) |
Symmetry code: (i) x+1/2, −y+1/2, −z+1. |
S1—O1 | 1.435 (2) | C1—C2 | 1.390 (3) |
S1—O2 | 1.440 (2) | C1—C6 | 1.393 (3) |
S1—C6 | 1.742 (2) | C2—C3 | 1.396 (4) |
S1—C6i | 1.742 (2) | C3—C4 | 1.379 (4) |
N1—C1 | 1.420 (3) | C4—C5 | 1.380 (4) |
N1—C1i | 1.420 (3) | C5—C6 | 1.397 (3) |
N1—C7 | 1.362 (4) | C7—C8 | 1.179 (5) |
O1—S1—O2 | 117.56 (13) | N1—C1—C6 | 120.04 (19) |
O1—S1—C6 | 108.68 (9) | C2—C1—C6 | 119.03 (19) |
O1—S1—C6i | 108.68 (9) | C1—C2—C3 | 119.4 (2) |
O2—S1—C6 | 110.14 (9) | C2—C3—C4 | 121.4 (2) |
O2—S1—C6i | 110.14 (9) | C3—C4—C5 | 119.5 (3) |
C6—S1—C6i | 100.22 (10) | C4—C5—C6 | 119.8 (3) |
C1—N1—C1i | 121.2 (3) | S1—C6—C1 | 118.87 (15) |
C1—N1—C7 | 118.69 (13) | S1—C6—C5 | 120.13 (16) |
C1i—N1—C7 | 118.69 (13) | C1—C6—C5 | 120.88 (19) |
N1—C1—C2 | 120.9 (2) | N1—C7—C8 | 178.0 (4) |
Symmetry code: (i) x, −y+1/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8···O2ii | 0.94 (4) | 2.56 (4) | 3.270 (5) | 133 (3) |
Symmetry code: (ii) x+1, y, z. |