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Indigo and thio­indigo pigments are used for a wide range of applications. The crystal structure of the mixed compound monothio­indigo [systematic name: (E)-2-(3-oxo-2,3-dihydro-1-benzothio­phen-2-yl­idene)-2,3-dihydro-1H-indol-3-one], C16H9NO2S, has been determined by microcrystal structure analysis from a crystal with a size of just 1 × 2 × 10 µm. The crystal structure of monothio­indigo resembles those of indigo and thio­indigo. The molecules show orientational disorder, with site-occupation factors of 0.962 (2) and 0.038 (2) for the major and minor disorder components, respectively. The indigo fragment donates an inter­molecular hydrogen bond, leading to a criss-cross arrangement of mol­ecules similar to that in indigo, whereas the thio­indigo fragment exhibits only van der Waals inter­actions and mol­ecular stacking, similar to that in thio­indigo.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270110027800/gd3356sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270110027800/gd3356Isup2.hkl
Contains datablock I

CCDC reference: 796077

Comment top

Indigo pigments are the most important vat pigment hitherto. Indigo, also known as Pigment Blue 66 and referred to hereinafter as (II) (Schmidt, 1997; Zollinger, 2003; Herbst & Hunger, 2004), has been known since ancient times and is nowadays the most frequently used natural organic pigment. The development of the technical synthesis of (II) (Baeyer & Emmerling, 1870; Baeyer, 1880; Baeyer & Drewsen, 1882; Heumann, 1890a,b) was one of the major inventions in the field of colorants in the nineteenth century. The molecular structure was determined in 1883 (Baeyer & Drewsen, 1883) and finally confirmed by X-ray crystal structure analysis in 1928 (Reis & Schneider, 1928). Replacement of the two NH groups by S atoms leads to thioindigo pigments (Formanek, 1928; Sadler, 1956; Sadler & Warren, 1956; Herbst & Hunger, 2004), e.g. Pigment Red 88, Pigment Red 181 and Vat Red 41, referred to hereinafter as (III). Thioindigo pigments are used for specialist applications, such as in cosmetics, for the coloration of rigid PVC or polystyrene, and in industrial coatings. Monothioindigo [systematic name: (E)-2-(3-oxo-2,3-dihydro-1-benzothiophen-2-ylidene)-2,3-dihydro-1H-indol-3-one], (I), has been known since 1905 (Gesellschaft für chemische Industrie in Basel, 1905, 1906). Originally, the compound was described as `gemischter schwefel- und stickstoffhaltiger Farbstoff der Thioindigoreihe' (Rosenberg, 1909), but later it was included in the class of asymmetrical thioindigo dyes (Formanek, 1928). Compound (I) is synthesized from condensation of salicylthioacetic acid with isatinanilide (see Fig. 1).

Compound (I) shows a reddish-violet colour, which is between the colours of (II) (blue) and (III) (red). The absorption maximum of (I) in solution is at 581.4 nm (Schuster, 1928) and its lifetime in the excited state (in acetone) is about 67 ps (± 5) (Lill et al., 1980). In the vat, i.e. in reduced form, it shows a yellow colour. Compound (I) was industrially produced by the Gesellschaft für chemische Industrie in Basel (CIBA) under the brand names Ciba Violett A and Küpenblau, and the 5-monobromo derivative was sold as Ciba Grau (Farbwerke Höchst, 1911; Formanek, 1928). For indigo and thioindigo derivatives, a series of crystal structures have been determined and are included in the Cambridge Structural Database (CSD; Allen, 2002; CSD refcodes: DBRING, DCINDG, DMINDG, INDIGO, KIGZOQ, KIGZUW, OXINGO, OXTIND, SEINDI, SINDIG). Here, we present the first crystal structure determination of a monothioindigo compound, (I), the crystal structure of which was determined by microcrystal structure analysis using synchrotron radiation as the crystals were extremely small.

The molecules of (I) are essentially planar (Fig. 2). The geometries of the indoxyl and thioindoxyl fragments, i.e. of the two halves of the molecule of (I), are almost identical to those of (II) and (III), respectively (Fig. 3). Due to the lack of inversion symmetry in the molecule, it is slightly nonplanar (Fig. 2). The S atom requires more space than the NH group, leading to an in-plane bending of about 14°. The N—H group forms a bifurcated hydrogen bond: an intramolecular hydrogen bond to the neighbouring O atom, and an intermolecular one to the carbonyl group of a neighbouring molecule (Fig. 4b), as in (II) (Fig. 4a). The carbonyl group (atoms C13 and O13) of the indoxyl moiety forms only intramolecular van der Waals interactions. Via the hydrogen bonds, each molecule is connected to two neighbouring molecules, leading to a helical arrangement propagating in the [010] direction. The resulting columns are connected to neighbouring columns by van der Waals (and eletrostatic) interactions only. Within the helix, the angle between the molecular planes is 85.05° (Fig. 5b). Graph-set analysis (Etter, 1990; Bernstein et al., 1995) reveals two patterns, of S11(6) and C11(6) graph sets.

The molecular packing of (I) is a combination of the arrangements found in the crystal structures of (II) (polymorph A; Süsse et al. 1988) and (III) (Haase-Wessel et al., 1977). In indigo, (II), the molecules form hydrogen bonds on both sides of the molecule, with S11(6) and C11(6) graph sets as in (I). This results in a helical arrangement on both sides of the molecule, leading to a criss-cross pattern (Fig. 5a). In contrast, thioindigo, (III), does not contain hydrogen bonds. The molecules form stacks, as in (I) and (II). Each molecule contacts two neighbouring molecules via S···S contacts, leading to chains with a herringbone arrangement (Figs. 4c and 5c). The space group of (I) is the same as for (II) and (III) (P21/c or P21/n), but with Z = 4 (molecules on general positions) instead of Z = 2 (molecules on inversion centres).

Some years ago, Day & Motherwell (2006) showed by an experiment that crystal structure prediction by popular vote does not give good results. However, for monothioindigo a popular vote among crystallographers, based upon the structures of indigo and thioindigo, might possibly have given the correct crystal packing.

Related literature top

For related literature, see: Allen (2002); Baeyer (1880); Baeyer & Drewsen (1882, 1883); Baeyer & Emmerling (1870); Bernstein et al. (1995); Day & Motherwell (2006); Etter (1990); Farbwerke (1911); Formanek (1928); Gesellschaft (1905, 1906); Haase-Wessel, Ohmasa & Süsse (1977); Herbst & Hunger (2004); Heumann (1890a, 1890b); Lill et al. (1980); Reis & Schneider (1928); Rosenberg (1909); Süsse et al. (1988); Sadler (1956); Sadler & Warren (1956); Schmidt (1997); Schuster (1928); Zollinger (2003).

Experimental top

Small felted reddish–violet [Violet given in CIF tables - please clarify] crystals of (I) with sizes of about 1 × 2 × 10 µm were obtained from Professor Dr Wolfgang Lüttke, University of Göttingen.

Refinement top

All H atoms were refined using a riding model, with C—H = 0.95 Å and N—H = 0.88 Å, and with Uiso(H) = 1.2Ueq(C,N).

The molecules show orientational disorder, with a site-occupation factor of 0.962 (2) for the major occupied site. Bond lengths and 1,3 distances in both disorder components were restrained to be equal with an effective standard uncertainty of 0.02Å. The anisotropic displacement parameters of equivalent atoms in the two components were constrained to be equal.

Computing details top

Data collection: XDS (Kabsch, 1993); cell refinement: XDS (Kabsch, 1993); data reduction: XDS (Kabsch, 1993); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Version 2.2; Macrae et al., 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1]
[Figure 2]
[Figure 3]
[Figure 4]
Fig. 1. The synthesis of monothioindigo, (I) (from Gesellschaft für chemische Industrie in Basel, 1906).

Fig. 2. Perspective views of (a) the major orientation, (b) the minor orientation and (c) both orientations of (I), showing the atom-numbering scheme. The major orientation is shown with full bonds and the minor orientation with open bonds. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

Fig. 3. Comparison of the molecular structure of (I) (light shading; orange in the electronic version of the journal) with those of (II) (dark shading, top; blue in the electronic version of the journal) and (III) (dark shading, bottom; blue in the electronic version of the journal). For (I), only the major occupancy components are shown.

Fig. 4. The molecular arrangements in (a) (II), (b) (I) and (c) (III). For (I), only the major occupancy components are shown.

Fig. 5. The crystal structures of (a) (II), (b) (I) and (c) (III). For (I), only the major occupancy components are shown.
(E)-2-(3-oxo-2,3-dihydro-1-benzothiophen-2-ylidene)-2,3- dihydro-1H-indol-3-one top
Crystal data top
C16H9NO2SF(000) = 576
Mr = 279.30Dx = 1.540 Mg m3
Monoclinic, P21/nSynchrotron radiation, λ = 0.70840 Å
Hall symbol: -P 2ynCell parameters from 16267 reflections
a = 14.185 (3) Åθ = 2.2–26.3°
b = 4.6280 (9) ŵ = 0.27 mm1
c = 18.483 (4) ÅT = 100 K
β = 96.91 (3)°Needle, violet
V = 1204.6 (4) Å30.01 × 0.002 × 0.001 mm
Z = 4
Data collection top
Beamline X06SA (SLS, Villigen) with MAR225 CCD area-detector
diffractometer
1913 reflections with I > 2σ(I)
Radiation source: undulator radiationRint = 0.091
Silicon(111) double crystal monochromatorθmax = 26.3°, θmin = 2.2°
rotation photographs scansh = 1717
16267 measured reflectionsk = 55
2453 independent reflectionsl = 2323
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.160H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0928P)2 + 1.5911P]
where P = (Fo2 + 2Fc2)/3
2453 reflections(Δ/σ)max < 0.001
242 parametersΔρmax = 0.59 e Å3
57 restraintsΔρmin = 0.56 e Å3
Crystal data top
C16H9NO2SV = 1204.6 (4) Å3
Mr = 279.30Z = 4
Monoclinic, P21/nSynchrotron radiation, λ = 0.70840 Å
a = 14.185 (3) ŵ = 0.27 mm1
b = 4.6280 (9) ÅT = 100 K
c = 18.483 (4) Å0.01 × 0.002 × 0.001 mm
β = 96.91 (3)°
Data collection top
Beamline X06SA (SLS, Villigen) with MAR225 CCD area-detector
diffractometer
1913 reflections with I > 2σ(I)
16267 measured reflectionsRint = 0.091
2453 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.05957 restraints
wR(F2) = 0.160H-atom parameters constrained
S = 1.03Δρmax = 0.59 e Å3
2453 reflectionsΔρmin = 0.56 e Å3
242 parameters
Special details top

Experimental. The diffraction measurements were performed at the SLS beamline PXI (X06SA, Villigen, Switzerland). A small crystal of (I) with a size of only 1 × 2 × 10µm was glued on top of a tiny glass fibre using a microscope equipped with a micromanipulator. Diffraction data were recorded at an X-ray energy of 17.5 keV, corresponding to a wavelength of 0.7084 Å. The beam size at the sample position was as small as 10 × 50 µm (vertical × horizontal). Data were collected at 100 K on a MAR225 CCD detector and processed with the XDS program package (Kabsch, 1993). The final R1 value of 0.0585 turned out to be relatively high and is probably a result of the very small crystal dimension and the resulting very weak diffraction power.

Eight very strong reflections were excluded from refinement because they caused an overflow of the detector and their intensities were not measured reliably.

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

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 (Å2) top
xyzUiso*/UeqOcc. (<1)
S10.43857 (6)0.77451 (16)0.06353 (4)0.0187 (3)0.962 (2)
O30.24727 (15)0.5425 (5)0.18505 (11)0.0189 (5)0.962 (2)
O130.59967 (16)0.4112 (6)0.13662 (12)0.0215 (5)0.962 (2)
N110.4090 (2)0.2232 (5)0.22951 (13)0.0152 (5)0.962 (2)
H110.34990.22730.23950.018*0.962 (2)
C20.3930 (2)0.5787 (7)0.13265 (15)0.0154 (6)0.962 (2)
C30.2932 (2)0.6472 (7)0.13851 (15)0.0145 (6)0.962 (2)
C40.1672 (2)0.9685 (7)0.06927 (16)0.0182 (6)0.962 (2)
H40.11920.90800.09760.022*0.962 (2)
C50.1473 (2)1.1705 (8)0.01440 (18)0.0223 (7)0.962 (2)
H50.08551.25150.00530.027*0.962 (2)
C60.2176 (3)1.2549 (8)0.02744 (18)0.0246 (8)0.962 (2)
H60.20271.39430.06480.030*0.962 (2)
C70.3087 (3)1.1422 (8)0.01631 (17)0.0223 (8)0.962 (2)
H70.35581.20010.04570.027*0.962 (2)
C80.3289 (2)0.9405 (10)0.03960 (19)0.0178 (7)0.962 (2)
C90.2584 (2)0.8553 (6)0.08238 (16)0.0148 (6)0.962 (2)
C120.4430 (2)0.3826 (7)0.17655 (16)0.0143 (6)0.962 (2)
C130.5466 (2)0.3072 (6)0.17659 (16)0.0158 (6)0.962 (2)
C140.6471 (2)0.0540 (7)0.26372 (17)0.0175 (6)0.962 (2)
H140.70500.02730.24370.021*0.962 (2)
C150.6416 (2)0.2406 (7)0.32177 (17)0.0199 (7)0.962 (2)
H150.69670.34220.34220.024*0.962 (2)
C160.5562 (2)0.2805 (8)0.3504 (2)0.0198 (7)0.962 (2)
H160.55400.41230.38960.024*0.962 (2)
C170.4739 (4)0.133 (3)0.3234 (6)0.0183 (7)0.962 (2)
H170.41600.15910.34370.022*0.962 (2)
C180.4803 (2)0.0532 (15)0.2656 (3)0.0169 (6)0.962 (2)
C190.5652 (2)0.0930 (7)0.23568 (16)0.0158 (6)0.962 (2)
S1A0.3637 (16)0.266 (5)0.2320 (10)0.0152 (5)0.038 (2)
O3A0.571 (4)0.460 (16)0.122 (3)0.0215 (5)0.038 (2)
O13A0.213 (3)0.617 (13)0.169 (3)0.0189 (5)0.038 (2)
N11A0.379 (4)0.736 (12)0.053 (2)0.0187 (3)0.038 (2)
H11A0.42200.66400.02750.022*0.038 (2)
C2A0.417 (3)0.442 (16)0.163 (3)0.0143 (6)0.038 (2)
C3A0.519 (3)0.382 (15)0.168 (3)0.0158 (6)0.038 (2)
C4A0.631 (3)0.037 (17)0.244 (4)0.0175 (6)0.038 (2)
H4A0.68540.10810.22420.021*0.038 (2)
C5A0.644 (4)0.170 (18)0.298 (4)0.0199 (7)0.038 (2)
H5A0.70130.27620.30670.024*0.038 (2)
C6A0.570 (5)0.22 (3)0.340 (5)0.0198 (7)0.038 (2)
H6A0.58180.33210.38350.024*0.038 (2)
C7A0.480 (9)0.11 (8)0.318 (16)0.0183 (7)0.038 (2)
H7A0.42810.16530.34370.022*0.038 (2)
C8A0.467 (5)0.07 (4)0.259 (9)0.0169 (6)0.038 (2)
C9A0.543 (3)0.144 (16)0.219 (4)0.0158 (6)0.038 (2)
C12A0.366 (3)0.645 (14)0.121 (3)0.0154 (6)0.038 (2)
C13A0.262 (3)0.715 (15)0.126 (3)0.0145 (6)0.038 (2)
C14A0.153 (3)1.065 (16)0.044 (4)0.0182 (6)0.038 (2)
H14A0.09681.01800.06440.022*0.038 (2)
C15A0.151 (4)1.259 (16)0.013 (4)0.0223 (7)0.038 (2)
H15A0.09551.36550.02860.027*0.038 (2)
C16A0.233 (5)1.296 (18)0.048 (5)0.0246 (8)0.038 (2)
H16A0.23571.45250.08050.030*0.038 (2)
C17A0.310 (6)1.11 (2)0.035 (4)0.0223 (8)0.038 (2)
H17A0.35411.08260.06900.027*0.038 (2)
C18A0.317 (5)0.96 (2)0.030 (5)0.0178 (7)0.038 (2)
C19A0.239 (3)0.940 (15)0.070 (3)0.0148 (6)0.038 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0225 (5)0.0190 (4)0.0150 (4)0.0019 (3)0.0033 (3)0.0051 (3)
O30.0186 (11)0.0220 (12)0.0165 (11)0.0034 (9)0.0036 (9)0.0027 (9)
O130.0222 (12)0.0239 (14)0.0194 (12)0.0003 (11)0.0060 (10)0.0068 (9)
N110.0126 (14)0.0174 (13)0.0162 (12)0.0015 (12)0.0039 (10)0.0056 (10)
C20.0201 (15)0.0144 (16)0.0119 (13)0.0007 (12)0.0017 (12)0.0014 (11)
C30.0188 (15)0.0129 (15)0.0115 (14)0.0010 (12)0.0001 (11)0.0026 (11)
C40.0231 (15)0.0165 (16)0.0145 (15)0.0006 (13)0.0004 (12)0.0058 (11)
C50.0289 (16)0.0199 (18)0.0158 (17)0.0050 (14)0.0067 (13)0.0037 (12)
C60.043 (2)0.0166 (16)0.0121 (18)0.0017 (15)0.0056 (14)0.0012 (12)
C70.0331 (17)0.0204 (17)0.0122 (16)0.0016 (14)0.0016 (14)0.0011 (14)
C80.0214 (16)0.0181 (16)0.0135 (16)0.0014 (13)0.0009 (13)0.0038 (12)
C90.0212 (15)0.0097 (15)0.0128 (14)0.0019 (12)0.0005 (11)0.0016 (11)
C120.0200 (15)0.0127 (15)0.0102 (14)0.0020 (12)0.0022 (11)0.0001 (11)
C130.0189 (15)0.0139 (16)0.0144 (14)0.0023 (12)0.0013 (12)0.0010 (11)
C140.0193 (14)0.0155 (17)0.0181 (16)0.0021 (12)0.0035 (11)0.0044 (12)
C150.0220 (15)0.0185 (17)0.0181 (17)0.0034 (13)0.0023 (12)0.0010 (12)
C160.0287 (17)0.017 (2)0.0132 (16)0.0011 (15)0.0022 (12)0.0037 (12)
C170.0221 (16)0.019 (3)0.014 (2)0.0018 (18)0.0034 (12)0.0016 (11)
C180.0238 (17)0.0136 (18)0.0129 (18)0.0006 (15)0.0005 (16)0.0017 (11)
C190.0200 (15)0.0154 (16)0.0121 (15)0.0008 (13)0.0019 (12)0.0006 (11)
S1A0.0126 (14)0.0174 (13)0.0162 (12)0.0015 (12)0.0039 (10)0.0056 (10)
O3A0.0222 (12)0.0239 (14)0.0194 (12)0.0003 (11)0.0060 (10)0.0068 (9)
O13A0.0186 (11)0.0220 (12)0.0165 (11)0.0034 (9)0.0036 (9)0.0027 (9)
N11A0.0225 (5)0.0190 (4)0.0150 (4)0.0019 (3)0.0033 (3)0.0051 (3)
C2A0.0200 (15)0.0127 (15)0.0102 (14)0.0020 (12)0.0022 (11)0.0001 (11)
C3A0.0189 (15)0.0139 (16)0.0144 (14)0.0023 (12)0.0013 (12)0.0010 (11)
C4A0.0193 (14)0.0155 (17)0.0181 (16)0.0021 (12)0.0035 (11)0.0044 (12)
C5A0.0220 (15)0.0185 (17)0.0181 (17)0.0034 (13)0.0023 (12)0.0010 (12)
C6A0.0287 (17)0.017 (2)0.0132 (16)0.0011 (15)0.0022 (12)0.0037 (12)
C7A0.0221 (16)0.019 (3)0.014 (2)0.0018 (18)0.0034 (12)0.0016 (11)
C8A0.0238 (17)0.0136 (18)0.0129 (18)0.0006 (15)0.0005 (16)0.0017 (11)
C9A0.0200 (15)0.0154 (16)0.0121 (15)0.0008 (13)0.0019 (12)0.0006 (11)
C12A0.0201 (15)0.0144 (16)0.0119 (13)0.0007 (12)0.0017 (12)0.0014 (11)
C13A0.0188 (15)0.0129 (15)0.0115 (14)0.0010 (12)0.0001 (11)0.0026 (11)
C14A0.0231 (15)0.0165 (16)0.0145 (15)0.0006 (13)0.0004 (12)0.0058 (11)
C15A0.0289 (16)0.0199 (18)0.0158 (17)0.0050 (14)0.0067 (13)0.0037 (12)
C16A0.043 (2)0.0166 (16)0.0121 (18)0.0017 (15)0.0056 (14)0.0012 (12)
C17A0.0331 (17)0.0204 (17)0.0122 (16)0.0016 (14)0.0016 (14)0.0011 (14)
C18A0.0214 (16)0.0181 (16)0.0135 (16)0.0014 (13)0.0009 (13)0.0038 (12)
C19A0.0212 (15)0.0097 (15)0.0128 (14)0.0019 (12)0.0005 (11)0.0016 (11)
Geometric parameters (Å, º) top
S1—C81.744 (3)S1A—C8A1.735 (19)
S1—C21.752 (3)S1A—C2A1.764 (19)
O3—C31.238 (4)O3A—C3A1.252 (19)
O13—C131.215 (4)O13A—C13A1.215 (18)
N11—C121.360 (4)N11A—C12A1.36 (2)
N11—C181.387 (4)N11A—C18A1.39 (2)
N11—H110.8800N11A—H11A0.8800
C2—C121.359 (4)C2A—C12A1.360 (18)
C2—C31.468 (4)C2A—C3A1.462 (18)
C3—C91.457 (4)C3A—C9A1.464 (19)
C4—C51.383 (4)C4A—C5A1.38 (2)
C4—C91.390 (4)C4A—C9A1.379 (19)
C4—H40.9500C4A—H4A0.9500
C5—C61.389 (5)C5A—C6A1.39 (2)
C5—H50.9500C5A—H5A0.9500
C6—C71.386 (5)C6A—C7A1.39 (2)
C6—H60.9500C6A—H6A0.9500
C7—C81.396 (4)C7A—C8A1.396 (19)
C7—H70.9500C7A—H7A0.9500
C8—C91.404 (4)C8A—C9A1.409 (19)
C12—C131.510 (4)C12A—C13A1.517 (19)
C13—C191.475 (4)C13A—C19A1.466 (18)
C14—C151.387 (4)C14A—C19A1.383 (19)
C14—C191.391 (4)C14A—C15A1.38 (2)
C14—H140.9500C14A—H14A0.9500
C15—C161.392 (5)C15A—C16A1.39 (2)
C15—H150.9500C15A—H15A0.9500
C16—C171.392 (4)C16A—C17A1.40 (2)
C16—H160.9500C16A—H16A0.9500
C17—C181.385 (4)C17A—C18A1.39 (2)
C17—H170.9500C17A—H17A0.9500
C18—C191.397 (4)C18A—C19A1.405 (19)
C8—S1—C290.96 (15)C8A—S1A—C2A91.4 (13)
C12—N11—C18110.6 (3)C12A—N11A—C18A111 (2)
C12—N11—H11124.7C12A—N11A—H11A124.6
C18—N11—H11124.7C18A—N11A—H11A124.6
C12—C2—C3122.7 (3)C12A—C2A—C3A129 (3)
C12—C2—S1124.6 (2)C12A—C2A—S1A118.8 (19)
C3—C2—S1112.7 (2)C3A—C2A—S1A111.3 (16)
O3—C3—C9126.3 (3)O3A—C3A—C2A124 (3)
O3—C3—C2124.0 (3)O3A—C3A—C9A123 (3)
C9—C3—C2109.7 (2)C2A—C3A—C9A110.1 (19)
C5—C4—C9119.1 (3)C5A—C4A—C9A122 (3)
C5—C4—H4120.5C5A—C4A—H4A118
C9—C4—H4120.5C9A—C4A—H4A119.2
C4—C5—C6120.1 (3)C4A—C5A—C6A119 (3)
C4—C5—H5120.0C4A—C5A—H5A120.6
C6—C5—H5120.0C6A—C5A—H5A120.6
C7—C6—C5122.0 (3)C7A—C6A—C5A120 (3)
C7—C6—H6119.0C7A—C6A—H6A121
C5—C6—H6119.0C5A—C6A—H6A119.8
C6—C7—C8117.8 (3)C6A—C7A—C8A119 (3)
C6—C7—H7121.1C6A—C7A—H7A119
C8—C7—H7121.1C8A—C7A—H7A120.6
C7—C8—C9120.5 (3)C7A—C8A—C9A121 (2)
C7—C8—S1125.4 (3)C7A—C8A—S1A125 (3)
C9—C8—S1114.0 (2)C9A—C8A—S1A114.0 (17)
C4—C9—C8120.5 (3)C4A—C9A—C8A118 (2)
C4—C9—C3127.0 (3)C4A—C9A—C3A128 (3)
C8—C9—C3112.6 (3)C8A—C9A—C3A112 (2)
C2—C12—N11125.9 (3)C2A—C12A—N11A127 (3)
C2—C12—C13126.4 (3)C2A—C12A—C13A125 (2)
N11—C12—C13107.7 (2)N11A—C12A—C13A103 (2)
O13—C13—C19130.4 (3)O13A—C13A—C19A129 (3)
O13—C13—C12125.5 (3)O13A—C13A—C12A126 (3)
C19—C13—C12104.0 (2)C19A—C13A—C12A104.7 (17)
C15—C14—C19118.1 (3)C19A—C14A—C15A118 (3)
C15—C14—H14120.9C19A—C14A—H14A120.8
C19—C14—H14120.9C15A—C14A—H14A120.8
C14—C15—C16120.6 (3)C14A—C15A—C16A119 (3)
C14—C15—H15119.7C14A—C15A—H15A120.3
C16—C15—H15119.7C16A—C15A—H15A120.3
C17—C16—C15122.0 (3)C15A—C16A—C17A121 (3)
C17—C16—H16119.0C15A—C16A—H16A119.4
C15—C16—H16119.0C17A—C16A—H16A119.4
C18—C17—C16116.9 (3)C18A—C17A—C16A116 (3)
C18—C17—H17121.5C18A—C17A—H17A122.1
C16—C17—H17121.5C16A—C17A—H17A122.1
C17—C18—N11127.8 (3)C17A—C18A—N11A128 (4)
C17—C18—C19121.8 (3)C17A—C18A—C19A120 (3)
N11—C18—C19110.4 (3)N11A—C18A—C19A108 (2)
C14—C19—C18120.6 (3)C14A—C19A—C18A120 (2)
C14—C19—C13132.2 (3)C14A—C19A—C13A131 (3)
C18—C19—C13107.2 (3)C18A—C19A—C13A106.4 (18)
C8—S1—C2—C12178.3 (3)C8A—S1A—C2A—C12A177 (11)
C8—S1—C2—C31.4 (3)C8A—S1A—C2A—C3A9 (10)
C12—C2—C3—O32.8 (5)C12A—C2A—C3A—O3A19 (14)
S1—C2—C3—O3177.4 (2)S1A—C2A—C3A—O3A173 (7)
C12—C2—C3—C9177.7 (3)C12A—C2A—C3A—C9A180 (9)
S1—C2—C3—C92.1 (3)S1A—C2A—C3A—C9A13 (9)
C9—C4—C5—C60.8 (5)C9A—C4A—C5A—C6A16 (16)
C4—C5—C6—C70.2 (5)C4A—C5A—C6A—C7A13 (26)
C5—C6—C7—C80.8 (5)C5A—C6A—C7A—C8A6 (43)
C6—C7—C8—C90.4 (6)C6A—C7A—C8A—C9A1 (43)
C6—C7—C8—S1179.4 (3)C6A—C7A—C8A—S1A171 (25)
C2—S1—C8—C7179.8 (4)C2A—S1A—C8A—C7A176 (25)
C2—S1—C8—C90.4 (3)C2A—S1A—C8A—C9A2 (15)
C5—C4—C9—C81.2 (5)C5A—C4A—C9A—C8A11 (17)
C5—C4—C9—C3178.4 (3)C5A—C4A—C9A—C3A173 (9)
C7—C8—C9—C40.6 (6)C7A—C8A—C9A—C4A3 (28)
S1—C8—C9—C4179.6 (3)S1A—C8A—C9A—C4A170 (11)
C7—C8—C9—C3179.1 (4)C7A—C8A—C9A—C3A169 (23)
S1—C8—C9—C30.7 (4)S1A—C8A—C9A—C3A5 (18)
O3—C3—C9—C41.9 (5)O3A—C3A—C9A—C4A25 (15)
C2—C3—C9—C4178.6 (3)C2A—C3A—C9A—C4A174 (9)
O3—C3—C9—C8177.7 (3)O3A—C3A—C9A—C8A172 (13)
C2—C3—C9—C81.7 (4)C2A—C3A—C9A—C8A11 (14)
C3—C2—C12—N111.2 (5)C3A—C2A—C12A—N11A36 (14)
S1—C2—C12—N11178.5 (2)S1A—C2A—C12A—N11A157 (6)
C3—C2—C12—C13177.3 (3)C3A—C2A—C12A—C13A172 (8)
S1—C2—C12—C133.0 (5)S1A—C2A—C12A—C13A6 (12)
C18—N11—C12—C2177.7 (5)C18A—N11A—C12A—C2A177 (9)
C18—N11—C12—C131.1 (5)C18A—N11A—C12A—C13A27 (8)
C2—C12—C13—O130.6 (5)C2A—C12A—C13A—O13A5 (14)
N11—C12—C13—O13179.3 (3)N11A—C12A—C13A—O13A162 (9)
C2—C12—C13—C19178.1 (3)C2A—C12A—C13A—C19A179 (8)
N11—C12—C13—C190.6 (3)N11A—C12A—C13A—C19A22 (8)
C19—C14—C15—C160.6 (5)C19A—C14A—C15A—C16A8 (14)
C14—C15—C16—C171.2 (10)C14A—C15A—C16A—C17A12 (15)
C15—C16—C17—C181.0 (16)C15A—C16A—C17A—C18A23 (15)
C16—C17—C18—N11179.9 (9)C16A—C17A—C18A—N11A172 (11)
C16—C17—C18—C190.2 (16)C16A—C17A—C18A—C19A16 (15)
C12—N11—C18—C17178.6 (9)C12A—N11A—C18A—C17A179 (11)
C12—N11—C18—C191.1 (7)C12A—N11A—C18A—C19A22 (11)
C15—C14—C19—C180.2 (6)C15A—C14A—C19A—C18A14 (13)
C15—C14—C19—C13178.6 (3)C15A—C14A—C19A—C13A175 (9)
C17—C18—C19—C140.4 (11)C17A—C18A—C19A—C14A2 (15)
N11—C18—C19—C14179.4 (4)N11A—C18A—C19A—C14A158 (9)
C17—C18—C19—C13179.1 (9)C17A—C18A—C19A—C13A167 (10)
N11—C18—C19—C130.7 (7)N11A—C18A—C19A—C13A7 (11)
O13—C13—C19—C140.0 (6)O13A—C13A—C19A—C14A13 (16)
C12—C13—C19—C14178.6 (3)C12A—C13A—C19A—C14A172 (9)
O13—C13—C19—C18178.6 (5)O13A—C13A—C19A—C18A175 (10)
C12—C13—C19—C180.0 (5)C12A—C13A—C19A—C18A9 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11···O30.882.222.769 (4)121
N11—H11···O3i0.882.242.992 (3)143
Symmetry code: (i) x+1/2, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC16H9NO2S
Mr279.30
Crystal system, space groupMonoclinic, P21/n
Temperature (K)100
a, b, c (Å)14.185 (3), 4.6280 (9), 18.483 (4)
β (°) 96.91 (3)
V3)1204.6 (4)
Z4
Radiation typeSynchrotron, λ = 0.70840 Å
µ (mm1)0.27
Crystal size (mm)0.01 × 0.002 × 0.001
Data collection
DiffractometerBeamline X06SA (SLS, Villigen) with MAR225 CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
16267, 2453, 1913
Rint0.091
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.059, 0.160, 1.03
No. of reflections2453
No. of parameters242
No. of restraints57
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.59, 0.56

Computer programs: XDS (Kabsch, 1993), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Version 2.2; Macrae et al., 2008), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N11—H11···O30.882.222.769 (4)121
N11—H11···O3i0.882.242.992 (3)143
Symmetry code: (i) x+1/2, y1/2, z+1/2.
Comparison of the crystal structures of (I), (II) and (III) top
(II)(I)(III)
CompoundIndigoaMonothioindigoThioindigob
Formula sumC16H10N2O2C16H9NO2SC16H8O2S2
Space groupP21/cP21/nP21/n
Z242
Z'0.510.5
Site symmetry111
a (Å)9.2414.185 (3)3.981 (3)
b (Å)5.774.6280 (9)20.65 (2)
c (Å)12.2218.483 (4)7.930 (7)
β (°)117.096.91 (3)98.84 (5)
V3)580.4971204.6 (4)644.2 (10)
ρ (Mg m-3)1.501.541.57
Distance between molecular mean planes (Å)3.3453.4113.526
Interplanar angle between neighbouring molecules (°)109.1485.0538.17
N—H distance (Å)0.98 (4)0.88
H···O distance (Å)2.11 (4)2.22
N···O distance (Å)2.862 (4)2.769 (4)
N—H···O angle (°)132 (2)121.0
Notes: (a) CSD refcode INDIGO03 (Süsse et al., 1988); (b) CSD refcode SINDIG02 (Haase-Wessel et al., 1977).
 

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