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The title compound, C34H40N2O2S2, adopts a trans conformation. The four conjugated Csp2—Csp2 single and double bonds of the polymethinic moiety, which bridges both heterocyclic end groups and the central four-membered ring, display nearly equal bond lengths. The mol­ecule is nearly planar, with interplanar angles between the benzo­thia­zole end groups and the central four-membered ring of 6.9 (1) and 7.7 (1)°; the angle between the heterocyclic systems is 1.8 (1)°. The crystal packing involves π-stacking effects, with intermolecular C...C distances varying from 3.755 (3) to 3.991 (3) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100015626/gg1026sup1.cif
Contains datablocks IV, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100015626/gg1026IVsup2.hkl
Contains datablock IV

CCDC reference: 158284

Comment top

Squaraines (or squarylium dyes) such as the title compound, (IV), exhibit cyanine-like light absorption, with a sharp and intense absorption band in the long-wavelength range of the visible spectrum and in the near IR region. They have gained importance as promising materials, e.g. as labels in fluorescence microscopy (Terpetschnig et al., 1993) and as photoconductive materials (Law, 1993). More recently, their remarkably high third-order optical nonlinearity was investigated intensively, with special respect to the contribution of two-photon states. A strong dependence of the optical properties on the molecular structure is expected (Andrews et al., 1998). Although the crystal structure of a related dye, 2,4-bis(1,3,3-trimethyl-2-indolinylidenemethyl)cyclobutenediylium-1,3-diolate, (V) (CCD reference DONXEJ; Allen & Kennard, 1993?), was determined more than ten years ago (Kobayashi et al., 1986), no structure of an analogous benzothiazole derivative has been reported so far, probably because of the extremely low solubility of these dyes. We assume that merely lengthening the N-alkyl chain to increase the solubility would hamper crystallization. Therefore, we decided to introduce additional lipophilic substituents in the benzothiazole end groups. A comparison of the UV-visible spectrum of (IV) with that of an unsubstituted dye (Terpetschnig et al., 1993) reveals that, as expected, the optical properties are essentially unaffected by this kind of substitution. \sch

The structure of (IV) is shown in Fig. 1. The benzothiazole ring systems S1/C2/N1/C9/C4/C5/C6/C7/C8 and S2/C2'/N2/C9'/C4'/C5'/C6'/C7'/C8' are planar, with mean deviations from planarity of 0.021 and 0.023 Å, respectively. The central four-membered ring C11/C12/C11'/C12' is also planar, with a mean deviation of 0.019 Å, and is a nearly perfect square, with bond lengths from 1.461 (3) to 1.468 (3) Å and bond angles from 89.72 (16) to 90.13 (16)° (Table 1). This geometry is slightly more regular than that of the related compound, (V) [1.450 to 1.485 Å and 89.8 to 90.5°, respectively].

The two O atoms are displaced from the square plane by 0.132 (4) Å (O1) and 0.091 (4) Å (O2) in the same direction, whereas the bridging atoms C10 and C10' lie 0.011 (4) and 0.056 (4) Å, respectively, on the other side of the plane. The deviation of these C atoms from the plane of the respective heterocyclic end group is distinctly larger, at 0.132 (3) Å for C10 and 0.110 (2) Å for C10'.

The entire molecule of (IV) is nearly planar, with interplanar angles between the benzothiazole ring systems and the central four-membered ring of 6.9 (1)° (S1—C8) and 7.7 (1)° (S2—C8'). The interplanar angle between the two heterocyclic end groups is 1.8 (1)°. These small but non-zero interplanar angles lead to a highly flattened `S'-form of the molecule when viewed sideways on. Compound (V) shows markedly larger corresponding interplanar angles of 24.6, 20.4 and 7.8°. Additionally, a considerable decrease in bond-length alternation within the conjugated polymethinic chain of (IV) can be recognized. This is a typical feature of cyanine-like molecules. The bond lengths of C2—C10, C10—C11, C2'-C10' and C10'-C11' vary from 1.381 (3) to 1.398 (3) Å. In contrast, the bond length alternation in compound (V) is more distinct, with bond lengths varying from 1.372 (12) to 1.404 (12) Å, although the e.s.d.s in (V) are much larger. The angles in the polymethinic chains C2—C10—C11 and C2'-C10'-C11' are 127.24 (19) and 126.60 (19)°, respectively. The analogous trimethylindoline derivative, (V), shows a significantly larger value of 133.1 (8)°. The enlargement of these angles was stated (ref?) to be caused by interactions of the geminal methyl groups and the O atoms.

The molecules of (IV) pack as antiparallel pairs which are oriented nearly perpendicular to each other (Fig. 2). The angle between two orthogonal planes (defined as the whole molecule but excluding the alkyl substituents) is 89.4 (2)°. The intermolecular C···C distances vary from 3.755 (3) Å for C7···C7'i to 3.991 (3) Å for C12···C12'i [symmetry code: (i) 1 - x, 1 - y, 1 - z]. These C···C distances are similar to those observed in bisanilinosquaraines (ca 3.5 Å). In contrast, the O···O distance is larger, at 4.147 (2) Å for O1···O2i.

Various types of intermolecular donor-acceptor (D—A) interactions have been described for squaraines. Firstly, for several dyes an intermolecular charge transfer between a donor anilino moiety of one dye molecule and an acceptor C4O2 unit of another has been proposed (Wingard, 1982; Tristani-Kendra & Eckhardt, 1984; Bernstein & Goldstein, 1988: CCD reference VAYSET). A similar D—A arrangement was observed for a benzothiazole-substituted ethoxycyclobutene-1,2-dione, which is a squaraine precursor (Jones et al., 1997: CCD reference RUHFIJ). Dipole-dipole interactions represent a second possibility. A staircase-like arrangement of the compound with CCD reference MXPBUQ (Law, 1988; a redetermination of the structure first reported by Farnum et al., 1974) results from the interaction of polarized C—O units of neighbouring molecules. Similar effects have also been observed for several squaraines in Langmuir-Blodgett films (Law & Chen, 1989). Finally, in contrast with the previous two types of interaction, π-stacking can be recognized in the crystal packing of (IV); the mean distance between two aligned molecules is 3.86 Å. The molecules in an antiparallel aligned pair do not lie exactly above one another. However, the plane defined by the whole molecule (except the alkyl substituents; mean deviation of planarity 0.111 Å) subtends an angle of 76° with a line connecting C11 and C11'i, indicating a reasonable degree of overlap.

Experimental top

3-Ethyl-6-(2,2-dimethylpropyl)-2-methylbenzothiazolium iodide, (III), was obtained from 6-bromo-2-methylbenzothiazole, (I), via Kumada coupling with 2,2-dimethylpropylmagnesium bromide and subsequent N-alkylation with ethyl iodide according to known methods (Tamao et al., 1976; Goerdeler, 1958) in an overall yield of 15%. Condensation of (III) (500 mg, 1.33 mmol) with squaric acid (76 mg, 0.66 mmol) was carried out in the presence of quinoline (0.16 ml, 1.35 mmol) in refluxing toluene/n-butanol 1:1 (20 ml) using a Dean-Stark trap for 20 h (Sprenger & Ziegenbein, 1967). After removal of solvent and column chromatography (SiO2; chloroform/ethanol 20:1), the product was extracted with boiling methanol and the resulting deep-blue solution was concentrated to ca 5 ml. Compound (IV) was obtained in 16% yield as metallic green square plates (60 mg, m.p. 557 K). Analytical data for compound (IV): 1H NMR (δ, p.p.m.): 7.28 (broad s, 2H, H-7,7'), 7.11 (dd, 3J5,4 = 3J5',4' = 8.4 Hz, 4J5,7 = 4J5',7' = 1.5 Hz, 2H, H-5,5'), 7.03 (d, 3J4,5 = 3J4',5' = 8.4 Hz, 2H, H-4,4'), 5.84 (s, 2H, H-10,10'), 4.13 (q, 3J13,14 = 3J13',14' = 7.2 Hz, 4H, H-13,13'), 2.52 (s, 4H, H-15,15'), 1.41 (t, 3J14,13 = 3J14',13' = 7.2 Hz, 6H, H-14,14'), 0.90 (s, 18H, H-17,17',18,18',19,19'); 13C NMR (δ, p.p.m.): 158.8 (s, C-2,2'), 139.0 (s, C-9,9'), 136.0 (s, C-8,8'), 129.3 (d, C-5,5'), 128.3 (s, C-6,6'), 123.5 (d, C-7,7'), 110.1 (d, C-4,4'), 84.7 (d, C-10,10'), 49.7 (t, C-15,15'), 40.9 (t, C-13,13'), 31.9 (s, C-16,16'), 29.2 (q, C-17,17',18,18',19,19'), 12.4 (q, C-14,14'); signals for C-11,11',12,12' were not observed; mass spectroscopy (m/z, %): 572 (100) (M+); UV-visible spectroscopy [CHCl3, λmax (log ε)]: 672 nm (5.41). Analysis calculated for C34H40N2O2S2: C 71.29, H 7.04, N 4.89, S 11.20%; found: C 70.93, H 7.10, N 4.76, S 11.24%.

Refinement top

The methyl groups were obtained from difference syntheses and were treated as rigid groups allowed to rotate but not tip from the starting positions. The remaining H atoms were included with a riding model starting from calculated positions (C—H distances?).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Siemens 1994); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure of (IV) with displacement ellipsoids at the 50% probability levels. Selected H atoms are shown (see text) as small spheres of arbitrary radii.
[Figure 2] Fig. 2. The packing diagram for (IV) viewed parallel to the z axis. H atoms have been omitted for clarity.
2,4-Bis{[6-(2,2-dimethylpropyl)-3-ethyl-1,3-benzothiazol-2(3H)-ylidene]methyl}- cyclobutenediylium-1,3-diolate top
Crystal data top
C34H40N2O2S2Dx = 1.208 Mg m3
Mr = 572.80Melting point: 557 K
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 12.4285 (14) ÅCell parameters from 6569 reflections
b = 14.4182 (14) Åθ = 2–28°
c = 17.8511 (18) ŵ = 0.20 mm1
β = 100.129 (3)°T = 143 K
V = 3149.0 (6) Å3Tablet, metallic green
Z = 40.42 × 0.31 × 0.08 mm
F(000) = 1224
Data collection top
Bruker SMART 1000 CCD
diffractometer
3919 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.119
Graphite monochromatorθmax = 26.4°, θmin = 1.8°
Detector resolution: 8.192 pixels mm-1h = 1515
ω scank = 1818
42373 measured reflectionsl = 2222
6437 independent reflections
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)] = 0.041Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.092H-atom parameters constrained
S = 0.90 w = 1/[σ2(Fo2) + (0.0396P)2]
where P = (Fo2 + 2Fc2)/3
6437 reflections(Δ/σ)max = 0.001
369 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.21 e Å3
Crystal data top
C34H40N2O2S2V = 3149.0 (6) Å3
Mr = 572.80Z = 4
Monoclinic, P21/nMo Kα radiation
a = 12.4285 (14) ŵ = 0.20 mm1
b = 14.4182 (14) ÅT = 143 K
c = 17.8511 (18) Å0.42 × 0.31 × 0.08 mm
β = 100.129 (3)°
Data collection top
Bruker SMART 1000 CCD
diffractometer
3919 reflections with I > 2σ(I)
42373 measured reflectionsRint = 0.119
6437 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0410 restraints
wR(F2) = 0.092H-atom parameters constrained
S = 0.90Δρmax = 0.31 e Å3
6437 reflectionsΔρmin = 0.21 e Å3
369 parameters
Special details top

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.

Operators for generating equivalent atoms:

$1 - x + 1, -y + 1, -z + 1 $2 x - 1/2, -y + 3/2, z - 1/2

Intermolecular distances

4.1469 (0.0022) O1 - O2_$1 4.1469 (0.0022) O2 - O1_$1 3.7545 (0.0028) C7 - C7'_$1 3.9907 (0.0029) C12 - C12'_$1 3.8723 (0.0027) C2 - C2'_$1 3.8862 (0.0029) C4 - C4'_$1 3.8335 (0.0029) C5 - C5'_$1 3.7793 (0.0028) C6 - C6'_$1 3.8057 (0.0027) C8 - C8'_$1 3.8644 (0.0027) C9 - C9'_$1 3.9159 (0.0028) C10 - C10'_$1 3.9235 (0.0028) C11 - C11'_$1 3.8797 (0.0023) N1 - N2_$1 3.8026 (0.0008) S1 - S2_$1

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

- 8.1335 (0.0025) x + 10.5667 (0.0127) y - 1.2159 (0.0236) z = 2.3099 (0.0145)

* -0.0192 (0.0010) C11 * 0.0193 (0.0010) C12 * -0.0193 (0.0010) C11' * 0.0192 (0.0010) C12' 0.1321 (0.0036) O1 0.0911 (0.0037) O2

Rms deviation of fitted atoms = 0.0193

- 8.4110 (0.0064) x + 9.7581 (0.0063) y - 2.9675 (0.0084) z = 0.5842 (0.0046)

Angle to previous plane (with approximate e.s.d.) = 6.88 (0.16)

* -0.0056 (0.0012) S1 * 0.0411 (0.0020) C2 * -0.0083 (0.0015) N1 * -0.0231 (0.0018) C9 * -0.0090 (0.0017) C4 * 0.0131 (0.0018) C5 * 0.0266 (0.0020) C6 * -0.0081 (0.0017) C7 * -0.0267 (0.0017) C8 0.1317 (0.0029) C10

Rms deviation of fitted atoms = 0.0212

- 8.1335 (0.0125) x + 10.5667 (0.0127) y - 1.2159 (0.0236) z = 2.3099 (0.0145)

Angle to previous plane (with approximate e.s.d.) = 6.88 (0.16)

* -0.0192 (0.0010) C11 * 0.0193 (0.0010) C12 * -0.0193 (0.0010) C11' * 0.0192 (0.0010) C12' -0.0105 (0.0038) C10 - 0.0563 (0.0038) C10'

Rms deviation of fitted atoms = 0.0193

- 8.1732 (0.0053) x + 9.8852 (0.0053) y - 3.4221 (0.0072) z = 1.2818 (0.0035)

Angle to previous plane (with approximate e.s.d.) = 7.72 (0.14)

* 0.0122 (0.0010) S2 * -0.0371 (0.0014) C2' * -0.0095 (0.0014) N2 * 0.0278 (0.0018) C9' * 0.0213 (0.0016) C4' * -0.0161 (0.0016) C5' * -0.0263 (0.0016) C6' * -0.0012 (0.0015) C7' * 0.0290 (0.0017) C8' -0.1098 (0.0024) C10'

Rms deviation of fitted atoms = 0.0227

- 8.4110 (0.0064) x + 9.7581 (0.0063) y - 2.9675 (0.0084) z = 0.5842 (0.0046)

Angle to previous plane (with approximate e.s.d.) = 6.88 (0.16)

* -0.0056 (0.0012) S1 * 0.0411 (0.0020) C2 * -0.0083 (0.0015) N1 * -0.0231 (0.0018) C9 * -0.0090 (0.0017) C4 * 0.0131 (0.0018) C5 * 0.0266 (0.0020) C6 * -0.0081 (0.0017) C7 * -0.0267 (0.0017) C8 0.1317 (0.0029) C10

Rms deviation of fitted atoms = 0.0212

- 8.1807 (0.0102) x + 10.4981 (0.0076) y - 1.2952 (0.0212) z = 2.2068 (0.0059)

Angle to previous plane (with approximate e.s.d.) = 6.45 (0.16)

* -0.0187 (0.0012) C10 * -0.0164 (0.0017) C11 * 0.0304 (0.0012) C12 * 0.0304 (0.0012) C12' * 0.0001 (0.0017) C11' * -0.0257 (0.0013) C10'

Rms deviation of fitted atoms = 0.0228

- 8.1493 (0.0031) x + 10.2650 (0.0029) y - 2.3590 (0.0029) z = 1.5919 (0.0018)

Angle to previous plane (with approximate e.s.d.) = 3.57 (0.10)

* -0.1828 (0.0007) S1 * -0.1213 (0.0018) C2 * -0.0958 (0.0015) N1 * 0.0289 (0.0018) C4 * 0.0865 (0.0019) C5 * 0.0611 (0.0018) C6 * -0.0521 (0.0017) C7 * -0.1068 (0.0018) C8 * -0.0633 (0.0018) C9 * -0.0875 (0.0018) C10 * -0.0249 (0.0018) C11 * 0.1127 (0.0019) C12 * 0.2720 (0.0014) O1 * 0.0541 (0.0016) O2 * 0.0298 (0.0020) C12' * 0.0903 (0.0019) C11' * 0.1268 (0.0018) C10' * 0.0233 (0.0018) C9' * 0.0338 (0.0018) C8' * -0.0693 (0.0018) C7' * -0.1795 (0.0018) C6' * -0.1772 (0.0019) C5' * -0.0672 (0.0019) C4' * 0.0674 (0.0015) N2 * 0.1121 (0.0018) C2' * 0.1289 (0.0007) S2

Rms deviation of fitted atoms = 0.1107

8.2029 (0.0033) x + 10.2238 (0.0030) y + 2.2888 (0.0032) z = 8.5115 (0.0029)

Angle to previous plane (with approximate e.s.d.) = 89.44 (0.02)

* 0.1740 (0.0008) S1_$2 * 0.1232 (0.0018) C2_$2 * 0.1011 (0.0015) N1_$2 * -0.0278 (0.0018) C4_$2 * -0.0919 (0.0019) C5_$2 * -0.0746 (0.0018) C6_$2 * 0.0372 (0.0014) C7_$2 * 0.0984 (0.0018) C8_$2 * 0.0629 (0.0018) C9_$2 * 0.0938 (0.0018) C10_$2 * 0.0281 (0.0018) C11_$2 * -0.1050 (0.0019) C12_$2 * -0.2570 (0.0014) O1_$2 * -0.0659 (0.0016) O2_$2 * -0.0343 (0.0020) C12'_$2 * -0.0904 (0.0019) C11'_$2 * -0.1297 (0.0018) C10'_$2 * -0.0185 (0.0018) C9'_$2 * -0.0212 (0.0018) C8'_$2 * 0.0372 (0.0014) C7_$2' * 0.1978 (0.0018) C6'_$2 * 0.1875 (0.0019) C5'_$2 * 0.0707 (0.0019) C4'_$2 * -0.0686 (0.0015) N2_$2 * -0.1104 (0.0018) C2'_$2 * -0.1165 (0.0007) S2_$2

Rms deviation of fitted atoms = 0.1100

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*/Ueq
S10.44301 (4)0.63693 (3)0.64377 (3)0.02383 (13)
S20.36893 (4)0.50910 (3)0.21133 (3)0.02324 (13)
O10.47618 (13)0.63576 (10)0.33133 (8)0.0341 (4)
O20.30818 (13)0.52403 (11)0.51790 (8)0.0420 (4)
N10.58921 (13)0.75773 (11)0.62757 (9)0.0232 (4)
N20.22015 (14)0.38715 (11)0.22076 (9)0.0238 (4)
C20.52304 (16)0.69329 (13)0.58653 (11)0.0215 (5)
C2'0.28322 (16)0.45159 (13)0.26433 (11)0.0220 (5)
C40.62736 (17)0.82995 (14)0.75715 (12)0.0267 (5)
H40.68090.87190.74530.032*
C4'0.18988 (18)0.31995 (14)0.08992 (11)0.0278 (5)
H4'0.13380.27880.09900.033*
C50.59874 (17)0.82922 (14)0.82843 (12)0.0272 (5)
H50.63400.87150.86560.033*
C5'0.22467 (18)0.32088 (14)0.02045 (12)0.0294 (5)
H5'0.19220.27880.01790.035*
C60.52034 (17)0.76907 (14)0.84830 (11)0.0243 (5)
C6'0.30552 (17)0.38116 (14)0.00448 (11)0.0259 (5)
C70.47039 (16)0.70581 (13)0.79353 (11)0.0224 (5)
H70.41780.66300.80550.027*
C7'0.35293 (17)0.44267 (14)0.06159 (11)0.0250 (5)
H7'0.40810.48470.05250.030*
C80.49822 (16)0.70612 (13)0.72194 (11)0.0216 (4)
C8'0.31887 (16)0.44167 (13)0.13123 (11)0.0228 (5)
C90.57549 (16)0.76737 (13)0.70311 (11)0.0219 (5)
C9'0.23894 (16)0.38062 (13)0.14610 (11)0.0232 (5)
C100.51879 (16)0.67561 (13)0.50994 (11)0.0228 (5)
H100.56960.70830.48580.027*
C10'0.28191 (17)0.46941 (13)0.34020 (11)0.0228 (5)
H10'0.22940.43670.36270.027*
C110.44854 (16)0.61548 (13)0.46441 (11)0.0234 (5)
C11'0.35005 (17)0.53077 (13)0.38725 (11)0.0234 (5)
C120.43508 (17)0.59930 (14)0.38219 (12)0.0251 (5)
C12'0.35881 (18)0.55052 (14)0.46857 (12)0.0269 (5)
C130.65792 (17)0.82210 (14)0.59233 (12)0.0291 (5)
H13A0.68620.78960.55090.035*
H13B0.72130.84130.63090.035*
C13'0.14042 (17)0.32814 (14)0.24998 (12)0.0298 (5)
H13C0.16710.31530.30460.036*
H13D0.13430.26820.22250.036*
C140.59498 (19)0.90745 (15)0.56027 (13)0.0383 (6)
H14A0.53320.88880.52120.046*
H14B0.64330.94850.53760.046*
H14C0.56780.94030.60120.046*
C14'0.0293 (2)0.37254 (19)0.24085 (16)0.0542 (7)
H14D0.03420.43030.27020.065*
H14E0.02170.33010.25950.065*
H14F0.00290.38610.18700.065*
C150.48974 (17)0.77370 (14)0.92613 (11)0.0266 (5)
H15A0.55510.79310.96280.032*
H15B0.47040.71040.94050.032*
C15'0.34501 (18)0.37823 (15)0.07093 (11)0.0329 (5)
H15C0.34410.31280.08780.039*
H15D0.42210.39910.06230.039*
C160.39452 (18)0.83935 (14)0.93539 (12)0.0294 (5)
C16'0.28109 (18)0.43615 (16)0.13643 (12)0.0322 (5)
C170.28588 (18)0.80404 (16)0.89063 (13)0.0391 (6)
H17A0.22730.84730.89700.047*
H17B0.26990.74270.90960.047*
H17C0.29090.79950.83660.047*
C17'0.16539 (19)0.40016 (18)0.15955 (14)0.0466 (7)
H17D0.12720.43690.20230.056*
H17E0.12670.40520.11640.056*
H17F0.16750.33500.17500.056*
C180.3867 (2)0.84076 (16)1.02004 (13)0.0416 (6)
H18A0.45450.86621.04930.050*
H18B0.37590.77751.03730.050*
H18C0.32490.87961.02770.050*
C18'0.3403 (2)0.4300 (2)0.20422 (13)0.0532 (7)
H18D0.34870.36470.21740.064*
H18E0.41260.45880.19100.064*
H18F0.29770.46250.24780.064*
C190.4159 (2)0.93736 (14)0.90934 (13)0.0391 (6)
H19A0.41790.93690.85470.047*
H19B0.48620.95950.93730.047*
H19C0.35740.97870.91930.047*
C19'0.2769 (2)0.53795 (17)0.11306 (14)0.0535 (8)
H19D0.35130.56050.09490.064*
H19E0.23380.54370.07230.064*
H19F0.24290.57490.15700.064*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0309 (3)0.0204 (3)0.0202 (3)0.0028 (2)0.0047 (2)0.0026 (2)
S20.0268 (3)0.0226 (3)0.0202 (3)0.0024 (2)0.0037 (2)0.0021 (2)
O10.0506 (10)0.0311 (8)0.0221 (8)0.0116 (8)0.0107 (7)0.0017 (7)
O20.0478 (11)0.0549 (11)0.0267 (9)0.0211 (9)0.0157 (8)0.0112 (8)
N10.0256 (10)0.0235 (9)0.0209 (10)0.0022 (8)0.0049 (7)0.0031 (7)
N20.0271 (10)0.0240 (9)0.0199 (9)0.0018 (8)0.0029 (7)0.0003 (7)
C20.0233 (11)0.0178 (11)0.0237 (12)0.0035 (9)0.0052 (9)0.0004 (8)
C2'0.0205 (11)0.0185 (10)0.0260 (12)0.0019 (9)0.0017 (9)0.0021 (9)
C40.0269 (12)0.0268 (12)0.0266 (12)0.0048 (9)0.0053 (10)0.0029 (9)
C4'0.0327 (13)0.0264 (12)0.0224 (12)0.0041 (10)0.0003 (10)0.0009 (9)
C50.0288 (12)0.0290 (12)0.0233 (12)0.0010 (10)0.0027 (9)0.0075 (9)
C5'0.0349 (13)0.0265 (12)0.0243 (12)0.0025 (10)0.0016 (10)0.0071 (9)
C60.0286 (12)0.0236 (11)0.0206 (11)0.0049 (9)0.0043 (9)0.0002 (8)
C6'0.0270 (12)0.0298 (12)0.0204 (11)0.0032 (9)0.0026 (9)0.0008 (9)
C70.0263 (12)0.0207 (10)0.0213 (11)0.0007 (9)0.0070 (9)0.0025 (9)
C7'0.0241 (12)0.0270 (12)0.0239 (12)0.0010 (9)0.0046 (9)0.0010 (9)
C80.0238 (11)0.0173 (10)0.0229 (11)0.0025 (9)0.0014 (9)0.0019 (8)
C8'0.0238 (12)0.0214 (11)0.0217 (11)0.0018 (9)0.0002 (9)0.0007 (9)
C90.0245 (11)0.0213 (11)0.0204 (11)0.0044 (9)0.0054 (9)0.0004 (8)
C9'0.0247 (12)0.0232 (11)0.0211 (11)0.0032 (9)0.0021 (9)0.0003 (8)
C100.0256 (12)0.0213 (11)0.0225 (12)0.0016 (9)0.0072 (9)0.0006 (9)
C10'0.0268 (12)0.0229 (11)0.0197 (11)0.0000 (9)0.0065 (9)0.0012 (8)
C110.0272 (12)0.0200 (11)0.0233 (11)0.0054 (9)0.0055 (9)0.0003 (8)
C11'0.0280 (12)0.0202 (11)0.0219 (11)0.0047 (9)0.0046 (9)0.0001 (8)
C120.0317 (13)0.0206 (11)0.0229 (12)0.0049 (9)0.0046 (9)0.0019 (9)
C12'0.0337 (13)0.0252 (11)0.0227 (12)0.0015 (10)0.0078 (10)0.0027 (9)
C130.0289 (13)0.0356 (13)0.0248 (12)0.0099 (10)0.0101 (10)0.0082 (10)
C13'0.0339 (13)0.0293 (12)0.0271 (13)0.0081 (10)0.0075 (10)0.0003 (9)
C140.0450 (15)0.0343 (14)0.0371 (14)0.0132 (12)0.0116 (12)0.0032 (11)
C14'0.0374 (16)0.0641 (19)0.0642 (19)0.0083 (14)0.0174 (14)0.0048 (15)
C150.0330 (13)0.0263 (12)0.0212 (12)0.0001 (10)0.0063 (9)0.0008 (9)
C15'0.0306 (13)0.0421 (14)0.0269 (13)0.0003 (11)0.0073 (10)0.0080 (10)
C160.0411 (14)0.0262 (12)0.0233 (12)0.0020 (10)0.0122 (10)0.0032 (9)
C16'0.0329 (13)0.0423 (14)0.0226 (12)0.0092 (11)0.0079 (10)0.0023 (10)
C170.0385 (15)0.0410 (14)0.0395 (14)0.0056 (11)0.0119 (11)0.0001 (11)
C17'0.0383 (15)0.0627 (17)0.0360 (15)0.0144 (13)0.0011 (12)0.0102 (13)
C180.0557 (17)0.0401 (14)0.0332 (14)0.0024 (12)0.0193 (12)0.0018 (11)
C18'0.0440 (16)0.086 (2)0.0302 (15)0.0132 (15)0.0086 (12)0.0060 (14)
C190.0561 (17)0.0275 (13)0.0380 (14)0.0057 (12)0.0198 (12)0.0026 (10)
C19'0.085 (2)0.0409 (15)0.0356 (15)0.0102 (14)0.0134 (14)0.0057 (12)
Geometric parameters (Å, º) top
S1—C21.747 (2)C6'—C7'1.401 (3)
S1—C81.7539 (19)C6'—C15'1.512 (3)
S2—C8'1.750 (2)C7—C81.382 (3)
S2—C2'1.753 (2)C7'—C8'1.382 (3)
O1—C121.235 (2)C8—C91.389 (3)
O2—C12'1.230 (2)C8'—C9'1.387 (3)
N1—C21.365 (2)C10—C111.387 (3)
N1—C91.396 (2)C10'—C11'1.398 (3)
N1—C131.475 (2)C11—C121.466 (3)
N2—C2'1.367 (2)C11—C12'1.468 (3)
N2—C9'1.396 (2)C11'—C121.461 (3)
N2—C13'1.469 (2)C11'—C12'1.465 (3)
C2—C101.383 (3)C13—C141.515 (3)
C2'—C10'1.381 (3)C13'—C14'1.505 (3)
C4—C51.380 (3)C15—C161.547 (3)
C4—C91.393 (3)C15'—C16'1.539 (3)
C4'—C5'1.383 (3)C16—C191.526 (3)
C4'—C9'1.388 (3)C16—C171.530 (3)
C5—C61.396 (3)C16—C181.531 (3)
C5'—C6'1.395 (3)C16'—C17'1.516 (3)
C6—C71.400 (3)C16'—C18'1.526 (3)
C6—C151.505 (3)C16'—C19'1.529 (3)
C2—S1—C891.00 (9)C4—C9—N1127.82 (19)
C8'—S2—C2'90.90 (10)C8'—C9'—C4'119.99 (19)
C2—N1—C9114.95 (17)C8'—C9'—N2112.68 (17)
C2—N1—C13122.58 (16)C4'—C9'—N2127.30 (19)
C9—N1—C13121.86 (16)C2—C10—C11127.24 (19)
C2'—N2—C9'114.43 (17)C2'—C10'—C11'126.60 (19)
C2'—N2—C13'123.13 (17)C10—C11—C12129.42 (19)
C9'—N2—C13'122.43 (17)C10—C11—C12'140.75 (19)
N1—C2—C10124.80 (18)C12—C11—C12'89.72 (16)
N1—C2—S1110.73 (14)C10'—C11'—C12139.38 (19)
C10—C2—S1124.47 (15)C10'—C11'—C12'130.54 (19)
N2—C2'—C10'125.44 (18)C12—C11'—C12'90.07 (16)
N2—C2'—S2110.89 (14)O1—C12—C11'136.93 (19)
C10'—C2'—S2123.66 (16)O1—C12—C11132.77 (19)
C5—C4—C9118.1 (2)C11'—C12—C1190.13 (16)
C5'—C4'—C9'118.3 (2)O2—C12'—C11'133.7 (2)
C4—C5—C6122.93 (19)O2—C12'—C11136.32 (19)
C4'—C5'—C6'122.62 (19)C11'—C12'—C1189.92 (16)
C5—C6—C7118.09 (19)N1—C13—C14111.90 (17)
C5—C6—C15120.53 (18)N2—C13'—C14'112.25 (18)
C7—C6—C15121.37 (19)C6—C15—C16116.62 (17)
C5'—C6'—C7'118.13 (19)C6'—C15'—C16'117.13 (18)
C5'—C6'—C15'121.50 (18)C19—C16—C17109.52 (19)
C7'—C6'—C15'120.32 (19)C19—C16—C18109.46 (18)
C8—C7—C6119.45 (19)C17—C16—C18108.47 (19)
C8'—C7'—C6'119.47 (19)C19—C16—C15110.89 (18)
C7—C8—C9121.48 (18)C17—C16—C15111.23 (17)
C7—C8—S1127.42 (16)C18—C16—C15107.21 (18)
C9—C8—S1111.08 (15)C17'—C16'—C18'109.33 (18)
C7'—C8'—C9'121.44 (18)C17'—C16'—C19'109.1 (2)
C7'—C8'—S2127.44 (16)C18'—C16'—C19'108.5 (2)
C9'—C8'—S2111.08 (15)C17'—C16'—C15'111.05 (18)
C8—C9—C4119.98 (19)C18'—C16'—C15'108.31 (19)
C8—C9—N1112.19 (17)C19'—C16'—C15'110.57 (18)
C9—N1—C2—C10176.57 (18)C5'—C4'—C9'—C8'1.5 (3)
C13—N1—C2—C105.4 (3)C5'—C4'—C9'—N2176.26 (19)
C9—N1—C2—S12.7 (2)C2'—N2—C9'—C8'0.0 (2)
C13—N1—C2—S1173.93 (14)C13'—N2—C9'—C8'178.92 (17)
C8—S1—C2—N12.14 (14)C2'—N2—C9'—C4'177.92 (19)
C8—S1—C2—C10177.16 (18)C13'—N2—C9'—C4'1.0 (3)
C9'—N2—C2'—C10'178.27 (18)N1—C2—C10—C11175.54 (19)
C13'—N2—C2'—C10'0.7 (3)S1—C2—C10—C113.7 (3)
C9'—N2—C2'—S21.0 (2)N2—C2'—C10'—C11'175.82 (19)
C13'—N2—C2'—S2179.94 (15)S2—C2'—C10'—C11'3.4 (3)
C8'—S2—C2'—N21.33 (15)C2—C10—C11—C12175.0 (2)
C8'—S2—C2'—C10'177.97 (18)C2—C10—C11—C12'0.0 (4)
C9—C4—C5—C60.2 (3)C2'—C10'—C11'—C125.0 (4)
C9'—C4'—C5'—C6'1.0 (3)C2'—C10'—C11'—C12'176.3 (2)
C4—C5—C6—C71.2 (3)C10'—C11'—C12—O16.6 (5)
C4—C5—C6—C15177.89 (19)C12'—C11'—C12—O1172.4 (3)
C4'—C5'—C6'—C7'0.2 (3)C10'—C11'—C12—C11177.9 (3)
C4'—C5'—C6'—C15'177.7 (2)C12'—C11'—C12—C113.02 (16)
C5—C6—C7—C81.3 (3)C10—C11—C12—O14.0 (4)
C15—C6—C7—C8177.75 (18)C12'—C11—C12—O1172.8 (2)
C5'—C6'—C7'—C8'0.2 (3)C10—C11—C12—C11'179.8 (2)
C15'—C6'—C7'—C8'177.34 (18)C12'—C11—C12—C11'3.01 (16)
C6—C7—C8—C90.6 (3)C10'—C11'—C12'—O23.9 (4)
C6—C7—C8—S1177.35 (15)C12—C11'—C12'—O2175.3 (3)
C2—S1—C8—C7176.98 (19)C10'—C11'—C12'—C11177.8 (2)
C2—S1—C8—C91.10 (15)C12—C11'—C12'—C113.02 (16)
C6'—C7'—C8'—C9'0.4 (3)C10—C11—C12'—O20.9 (5)
C6'—C7'—C8'—S2177.88 (15)C12—C11—C12'—O2175.2 (3)
C2'—S2—C8'—C7'176.40 (19)C10—C11—C12'—C11'179.1 (3)
C2'—S2—C8'—C9'1.34 (15)C12—C11—C12'—C11'3.00 (16)
C7—C8—C9—C40.4 (3)C2—N1—C13—C1484.6 (2)
S1—C8—C9—C4178.62 (16)C9—N1—C13—C1486.0 (2)
C7—C8—C9—N1178.41 (17)C2'—N2—C13'—C14'89.2 (2)
S1—C8—C9—N10.2 (2)C9'—N2—C13'—C14'92.0 (2)
C5—C4—C9—C80.6 (3)C5—C6—C15—C1690.1 (2)
C5—C4—C9—N1178.06 (19)C7—C6—C15—C1689.0 (2)
C2—N1—C9—C81.9 (2)C5'—C6'—C15'—C16'87.0 (3)
C13—N1—C9—C8173.20 (17)C7'—C6'—C15'—C16'95.5 (2)
C2—N1—C9—C4176.79 (19)C6—C15—C16—C1954.4 (2)
C13—N1—C9—C45.5 (3)C6—C15—C16—C1767.7 (2)
C7'—C8'—C9'—C4'1.2 (3)C6—C15—C16—C18173.86 (18)
S2—C8'—C9'—C4'179.11 (16)C6'—C15'—C16'—C17'64.9 (3)
C7'—C8'—C9'—N2176.86 (18)C6'—C15'—C16'—C18'175.06 (19)
S2—C8'—C9'—N21.0 (2)C6'—C15'—C16'—C19'56.3 (3)

Experimental details

Crystal data
Chemical formulaC34H40N2O2S2
Mr572.80
Crystal system, space groupMonoclinic, P21/n
Temperature (K)143
a, b, c (Å)12.4285 (14), 14.4182 (14), 17.8511 (18)
β (°) 100.129 (3)
V3)3149.0 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.20
Crystal size (mm)0.42 × 0.31 × 0.08
Data collection
DiffractometerBruker SMART 1000 CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
42373, 6437, 3919
Rint0.119
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.092, 0.90
No. of reflections6437
No. of parameters369
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.31, 0.21

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), XP (Siemens 1994), SHELXL97.

Selected geometric parameters (Å, º) top
C2—C101.383 (3)C11—C121.466 (3)
C2'—C10'1.381 (3)C11—C12'1.468 (3)
C10—C111.387 (3)C11'—C121.461 (3)
C10'—C11'1.398 (3)C11'—C12'1.465 (3)
C2—C10—C11127.24 (19)C12—C11'—C12'90.07 (16)
C2'—C10'—C11'126.60 (19)C11'—C12—C1190.13 (16)
C12—C11—C12'89.72 (16)C11'—C12'—C1189.92 (16)
C9—N1—C13—C1486.0 (2)C7—C6—C15—C1689.0 (2)
C9'—N2—C13'—C14'92.0 (2)C7'—C6'—C15'—C16'95.5 (2)
 

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