organic compounds
2-[4-(2-{5-tert-Butyl-2-chloro-3-[2-(3-pentyl-1,3-benzothiazol-2-ylidene)ethylidene]cyclohex-1-enyl}ethenyl)-3-cyano-5,5-dimethylfuran-2-ylidene]malononitrile
aIndustrial Research Limited, PO Box 31-310, Lower Hutt, New Zealand
*Correspondence e-mail: g.gainsford@irl.cri.nz
In the title molecule, C36H39ClN4OS, the non-aromatic part of the cyclohex-1-enyl ring and the attached tert-butyl group are disordered over two conformations with occupancy ratios of 0.52 (3):0.48 (3) and 0.53 (3):0.47 (3), respectively. The polyene chain single- and double-bond dimensions contrast with a closely related compound [Bouit et al. (2007). Chem. Mater. 19, 5325–5335] with an approximate 19° twist between donor and acceptor ends of the molecule, related to the additional intramolecular C—H⋯S interaction. In the title compound, the molecules pack into dimeric units about centres of symmetry utilizing weak C—H⋯N(cyano) and C—H⋯O attractive interactions, building both chain and ring motifs about the centres [R22(8) and R22(9)]. Adjacent dimeric sets then form a herringbone configuration.
Related literature
For general background to our ongoing research involving the development of organic non-linear optical (NLO) chromophores, see: Kay et al. (2004); Bhuiyan et al. (2011). For related structures, see: Bouit et al. (2007, 2008); Gainsford et al. (2008). For a description of the Cambridge Structural Database, see: Allen (2002). For the BLA parameter, see: Marder et al. (1993).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2005); cell SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009).
Supporting information
https://doi.org/10.1107/S1600536812050842/bx2431sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812050842/bx2431Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812050842/bx2431Isup3.cml
A mixture of compound 2 (5.26 g, 10 mmol) and 3-pentyl-2-methylbenzothiazolum iodide (4.51 g, 13 mmol) was stirred in the minimum amount of acetic anhydride (c. 20 ml). To this suspension, and at room temperature, was added one equivalent of triethylamine (1.4 ml, 20 mmol). The mixture was then allowed to reflux for 3 hrs, by which time its colour had changed to deep greenish black. The solvent was removed in vacuum and the residue washed with diethylether. The oily residue was then dissolved in hot isopropyl ether and kept in a fridge overnight whereupon a solid separated out. This was collected by filtration, dried under vacuum and recrystallized with hot methanol to give the title compound as a pinkish-green solid (3.66 g, 60% yield). X-Ray quality crystals were grown by slow evaporation of a solution of compound 3 in 1:1 CHCl3—MeOH. M.p. 225.8 °C. 1H NMR (500 MHz, CDCl3): δ 8.06 (d, 1H, J 15 Hz), 7.58 (d, 1H, J 10 Hz), 7.52 (d, 1H, J 10 Hz), 7.38 (t, 1H, J 4 Hz), 7.20 (t, 1H, J 4 Hz), 7.11 (d, 1H, J 8 Hz), 6.26 (d, 1H, J 15 Hz), 5.84 (d, 1H, J 12 Hz), 4.03 (t, 2H, J 7.2 Hz), 2.76 (t, 1H, J 4 Hz), 2.10 (t, 1H, J 4 Hz). 13C NMR (125 MHz, CDCl3): δ 175.81, 167.92, 161.02, 155.88, 153.48, 144.42, 143.37, 141.47, 135.36, 128.94, 127.57, 127.08, 123.85, 116.87, 115.97, 115.43, 114.42, 107.04, 103.02, 47.32, 42.11, 28.16, 27.95, 27.68, 27.12, 26.90, 26.25, 21.62, 13.73. LCMS Found: MNa+ 633.2422; C36H39ClN4NaOS requires MNa+ 633.2431; Δ = -1.4 p.p.m..
Nine reflections affected by the backstop and 12 others which were clearly outlier data (mostly at low angle) were omitted from the refinements (using OMIT). The methyl and other H atoms were refined with Uiso 1.5 & 1.2 times respectively that of the Ueq of their parent atom. All H atoms bound to carbon were constrained to their expected geometries (C—H 0.95, 0.98 & 0.99 Å).
The title compound, C36H39ClN4OS (3, Figure 1) was synthesized as part of our ongoing research involving the development of organic nonlinear optical (NLO) chromophores. As part of this we have previously reported the crystallographic parameters for chromophores containing an indoline donor coupled to a 2-(3-cyano-4,5,5-trimethyl-5H-furan-2-ylidene)-malononitrile
group (Bhuiyan et al., 2011). Compound 3 was synthesized to check the impact of using a benzothiazole based donor as this should influence both the degree of both length alternation (viz. bond order) as well as the crystal packing. Compound 3 was conveniently prepared in good yield by the condensation of N-pentyl-2-methylbenzothiazolinium iodide 1 with precursor 2 (Figure 1). Compound 2 was prepared by the procedure previously reported in the literature (Kay et al., 2004).Compound REFCODES are from the C.S.D. (Version 5.33, with August 2012 updates; Allen, 2002). The ~7° to the polyene chain atoms (C13—C16,C23,C24), which in turn is ~18° from the "CDFP" plane. These twists in the adjacent near-planar moieties contrasts with the closely related molecule HITVIQ (Bouit et al.,2007) where the benzothiazole entity is replaced by a 1-benzyl-3,3-dimethyl-1,3-dihydro-2H-indol-2-ylidene: here the CDFP and terminal donor rings make an angle of ~10°. As in HITVIQ, there are close intramolecular H···Cl interactions involving the adjacent polyene hydrogen atoms (entries 7 & 8, Table 1) but here there is an additional H···S interaction (2.68 Å, entry 9, Table 1) contributing to the twist.
contents of the title compound(I) are shown in Figure 1. The 5-membered ring plane of atoms O1,C4—C7 (hereafter "CDFP", [3-cyano-5,5-dimethyl-2,5-dihydrofuran-2-ylidene]propanedinitrile) can be regarded as planar with maximum out of plane deviation for C4 of 0.029 (4) Å. The dicyano group (N1,C1,C2,C3,N2,C6) is planar but twisted by 9.4 (3) ° with respect to the "CDFP" group; this is similar to the twist in related compound NOJKUT (Gainsford et al., 2008) of 5.69 (17)°, and is consistent with alleviating intramolecular contacts with the cyano group (C10–N3). The benzothiazol-2-ylidene fused ring is approximately planar with maximum out of plane distance for N4 0.026 (3) Å. This plane makes an angle ofThe different deviation from molecular planarity is also reflected in a significant difference between the two structures in the alternation of double and single bonds beginning at the C2–C6 CDFP bond (Table 2). This alternation is described by the BLA parameter (Marder et al., 1993), reflecting the average change in bond length alternation. A related sodium salt (with the CDFP ring at both ends of the molecule EGOSOJ, Bouit et al., 2008)) appears to be have intermediate BLA values between the two.
The molecules pack into dimeric units about centres of symmetry utilizing weak C–H···Cyano(N) and C–H···O attractive interactions, building both chain and ring motifs about the centres (R22(8) & R22(9)). Table 2 summarizes those attractive interactions and key elements are shown in Figure 3. The adjacent dimeric sets then form a typical "herringbone" configuration. In contrast, the HITVIQ molecules have mainly weak, close to in-plane interactions (C–H···Cl), linked via chain motif weak C–H···N(cyano) interactions.
For general background to our ongoing research involving the development of organic non-linear optical (NLO) chromophores, see: Kay et al. (2004); Bhuiyan et al. (2011). For related structures, see: Bouit et al. (2007, 2008); Gainsford et al. (2008). For a description of the Cambridge Structural Database, see: Allen (2002). For the BLA parameter, see: Marder et al. (1993).
Data collection: APEX2 (Bruker, 2005); cell
SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 2012) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).C36H39ClN4OS | F(000) = 1296 |
Mr = 611.22 | Dx = 1.225 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -p 2yn | Cell parameters from 3784 reflections |
a = 8.6293 (5) Å | θ = 2.1–22.6° |
b = 20.1267 (11) Å | µ = 0.21 mm−1 |
c = 19.5299 (11) Å | T = 116 K |
β = 102.236 (4)° | Wedge, green |
V = 3314.9 (3) Å3 | 0.71 × 0.30 × 0.10 mm |
Z = 4 |
Bruker–Nonius APEXII CCD area-detector diffractometer | 5943 independent reflections |
Radiation source: fine-focus sealed tube | 3121 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.106 |
Detector resolution: 8.333 pixels mm-1 | θmax = 25.2°, θmin = 2.9° |
φ and ω scans | h = −10→10 |
Absorption correction: multi-scan (Blessing, 1995) and SADABS (Bruker, 2005) | k = 0→24 |
Tmin = 0.614, Tmax = 0.746 | l = 0→23 |
32003 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.059 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.177 | w = 1/[σ2(Fo2) + (0.0638P)2 + 4.4837P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
5943 reflections | Δρmax = 0.45 e Å−3 |
451 parameters | Δρmin = −0.29 e Å−3 |
75 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0116 (12) |
C36H39ClN4OS | V = 3314.9 (3) Å3 |
Mr = 611.22 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 8.6293 (5) Å | µ = 0.21 mm−1 |
b = 20.1267 (11) Å | T = 116 K |
c = 19.5299 (11) Å | 0.71 × 0.30 × 0.10 mm |
β = 102.236 (4)° |
Bruker–Nonius APEXII CCD area-detector diffractometer | 5943 independent reflections |
Absorption correction: multi-scan (Blessing, 1995) and SADABS (Bruker, 2005) | 3121 reflections with I > 2σ(I) |
Tmin = 0.614, Tmax = 0.746 | Rint = 0.106 |
32003 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 75 restraints |
wR(F2) = 0.177 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.45 e Å−3 |
5943 reflections | Δρmin = −0.29 e Å−3 |
451 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
S1 | 0.84867 (14) | 0.56424 (5) | 0.56589 (5) | 0.0354 (3) | |
Cl1 | 0.59822 (18) | 0.34404 (6) | 0.56970 (6) | 0.0578 (4) | |
O1 | 0.2567 (4) | 0.01211 (13) | 0.53229 (13) | 0.0371 (8) | |
N1 | 0.3033 (5) | −0.11885 (17) | 0.6490 (2) | 0.0515 (11) | |
N2 | 0.4423 (6) | 0.05365 (18) | 0.7780 (2) | 0.0587 (12) | |
N3 | 0.4426 (5) | 0.20025 (18) | 0.6737 (2) | 0.0510 (11) | |
N4 | 0.8980 (4) | 0.60153 (15) | 0.44692 (17) | 0.0339 (9) | |
C1 | 0.3163 (5) | −0.0619 (2) | 0.6503 (2) | 0.0375 (11) | |
C2 | 0.3386 (5) | 0.00825 (19) | 0.6541 (2) | 0.0335 (10) | |
C3 | 0.3961 (6) | 0.0353 (2) | 0.7218 (2) | 0.0381 (11) | |
C4 | 0.3103 (5) | 0.1229 (2) | 0.5049 (2) | 0.0358 (11) | |
C5 | 0.3436 (5) | 0.11290 (18) | 0.5781 (2) | 0.0306 (10) | |
C6 | 0.3136 (5) | 0.04571 (19) | 0.5921 (2) | 0.0307 (10) | |
C7 | 0.2428 (5) | 0.0579 (2) | 0.4718 (2) | 0.0361 (11) | |
C8 | 0.0673 (6) | 0.0629 (2) | 0.4383 (2) | 0.0508 (13) | |
H8A | 0.0288 | 0.0197 | 0.4187 | 0.076* | |
H8B | 0.0518 | 0.0962 | 0.4009 | 0.076* | |
H8C | 0.0083 | 0.0761 | 0.4738 | 0.076* | |
C9 | 0.3402 (6) | 0.0276 (2) | 0.4235 (2) | 0.0473 (12) | |
H9A | 0.4529 | 0.0292 | 0.4462 | 0.071* | |
H9B | 0.3227 | 0.0528 | 0.3796 | 0.071* | |
H9C | 0.3079 | −0.0187 | 0.4136 | 0.071* | |
C10 | 0.3996 (5) | 0.1602 (2) | 0.6312 (2) | 0.0359 (11) | |
C11 | 0.3377 (6) | 0.1756 (2) | 0.4638 (2) | 0.0444 (12) | |
H11 | 0.2991 | 0.1716 | 0.4147 | 0.053* | |
C12 | 0.4175 (5) | 0.2346 (2) | 0.4881 (2) | 0.0359 (11) | |
H12 | 0.4429 | 0.2408 | 0.5375 | 0.043* | |
C13 | 0.4633 (5) | 0.2847 (2) | 0.4481 (2) | 0.0372 (11) | |
C14 | 0.5547 (5) | 0.33952 (19) | 0.4780 (2) | 0.0320 (10) | |
C15 | 0.6128 (5) | 0.38858 (18) | 0.4412 (2) | 0.0294 (10) | |
C16 | 0.5855 (6) | 0.38354 (19) | 0.3622 (2) | 0.0331 (10) | |
H16A | 0.690 (2) | 0.381 (2) | 0.349 (2) | 0.040* | |
H16B | 0.517 (4) | 0.4212 (13) | 0.3440 (19) | 0.040* | |
C19 | 0.4468 (5) | 0.32423 (18) | 0.2493 (2) | 0.0364 (11) | |
C23 | 0.6969 (5) | 0.44466 (18) | 0.4748 (2) | 0.0323 (10) | |
H23 | 0.7070 | 0.4486 | 0.5240 | 0.039* | |
C24 | 0.7642 (5) | 0.49323 (18) | 0.4417 (2) | 0.0315 (10) | |
H24 | 0.7642 | 0.4882 | 0.3933 | 0.038* | |
C25 | 0.8342 (5) | 0.55100 (18) | 0.4771 (2) | 0.0313 (10) | |
C26 | 0.9572 (5) | 0.65384 (19) | 0.4932 (2) | 0.0351 (10) | |
C27 | 1.0259 (6) | 0.7125 (2) | 0.4767 (2) | 0.0436 (12) | |
H27 | 1.0343 | 0.7220 | 0.4300 | 0.052* | |
C28 | 1.0818 (6) | 0.7565 (2) | 0.5310 (3) | 0.0497 (13) | |
H28 | 1.1303 | 0.7967 | 0.5212 | 0.060* | |
C29 | 1.0687 (6) | 0.7433 (2) | 0.5994 (3) | 0.0482 (13) | |
H29 | 1.1084 | 0.7745 | 0.6353 | 0.058* | |
C30 | 0.9981 (6) | 0.6849 (2) | 0.6158 (2) | 0.0426 (12) | |
H30 | 0.9885 | 0.6757 | 0.6624 | 0.051* | |
C31 | 0.9420 (5) | 0.64050 (19) | 0.5616 (2) | 0.0363 (11) | |
C32 | 0.9094 (6) | 0.6037 (2) | 0.3720 (2) | 0.0404 (11) | |
H32A | 0.9185 | 0.5578 | 0.3552 | 0.061* | |
H32B | 1.0070 | 0.6279 | 0.3681 | 0.061* | |
C33 | 0.7674 (6) | 0.6372 (2) | 0.3252 (2) | 0.0476 (13) | |
H33A | 0.7448 | 0.6791 | 0.3478 | 0.071* | |
H33B | 0.7963 | 0.6491 | 0.2803 | 0.071* | |
C34 | 0.6170 (6) | 0.5956 (2) | 0.3094 (2) | 0.0455 (13) | |
H34A | 0.5902 | 0.5822 | 0.3543 | 0.068* | |
H34B | 0.6381 | 0.5546 | 0.2849 | 0.068* | |
C35 | 0.4739 (7) | 0.6309 (2) | 0.2647 (2) | 0.0566 (15) | |
H35A | 0.4951 | 0.6397 | 0.2177 | 0.085* | |
H35B | 0.4586 | 0.6741 | 0.2865 | 0.085* | |
C36 | 0.3223 (7) | 0.5897 (3) | 0.2571 (3) | 0.0679 (18) | |
H36A | 0.3330 | 0.5488 | 0.2312 | 0.102* | |
H36B | 0.2321 | 0.6155 | 0.2315 | 0.102* | |
H36C | 0.3046 | 0.5784 | 0.3036 | 0.102* | |
C17A | 0.456 (2) | 0.3354 (9) | 0.3291 (9) | 0.030 (3) | 0.52 (3) |
H17B | 0.3546 | 0.3578 | 0.3321 | 0.045* | 0.52 (3) |
C18A | 0.457 (3) | 0.2721 (7) | 0.3690 (5) | 0.041 (4) | 0.52 (3) |
H18A | 0.5507 | 0.2453 | 0.3641 | 0.061* | 0.52 (3) |
H18B | 0.3610 | 0.2462 | 0.3488 | 0.061* | 0.52 (3) |
C20A | 0.327 (3) | 0.2697 (10) | 0.2179 (17) | 0.065 (7) | 0.53 (3) |
H20D | 0.2282 | 0.2761 | 0.2341 | 0.097* | 0.53 (3) |
H20E | 0.3716 | 0.2260 | 0.2331 | 0.097* | 0.53 (3) |
H20F | 0.3059 | 0.2723 | 0.1667 | 0.097* | 0.53 (3) |
C21A | 0.5878 (18) | 0.3349 (16) | 0.2147 (10) | 0.082 (7) | 0.53 (3) |
H21D | 0.5520 | 0.3323 | 0.1637 | 0.123* | 0.53 (3) |
H21E | 0.6678 | 0.3006 | 0.2307 | 0.123* | 0.53 (3) |
H21F | 0.6342 | 0.3788 | 0.2276 | 0.123* | 0.53 (3) |
C22A | 0.389 (4) | 0.3895 (7) | 0.2107 (8) | 0.076 (7) | 0.53 (3) |
H22D | 0.2902 | 0.4036 | 0.2232 | 0.113* | 0.53 (3) |
H22E | 0.3711 | 0.3823 | 0.1600 | 0.113* | 0.53 (3) |
H22F | 0.4700 | 0.4240 | 0.2244 | 0.113* | 0.53 (3) |
C17B | 0.515 (2) | 0.3180 (8) | 0.3303 (9) | 0.023 (3) | 0.48 (3) |
H17A | 0.6009 | 0.2839 | 0.3379 | 0.035* | 0.48 (3) |
C18B | 0.385 (2) | 0.2951 (8) | 0.3710 (5) | 0.034 (4) | 0.48 (3) |
H18C | 0.3012 | 0.3293 | 0.3667 | 0.051* | 0.48 (3) |
H18D | 0.3357 | 0.2531 | 0.3507 | 0.051* | 0.48 (3) |
C20B | 0.387 (3) | 0.2544 (7) | 0.225 (2) | 0.055 (6) | 0.47 (3) |
H20A | 0.2956 | 0.2430 | 0.2455 | 0.083* | 0.47 (3) |
H20B | 0.4715 | 0.2219 | 0.2402 | 0.083* | 0.47 (3) |
H20C | 0.3541 | 0.2537 | 0.1738 | 0.083* | 0.47 (3) |
C21B | 0.6072 (14) | 0.3068 (11) | 0.2329 (10) | 0.059 (5) | 0.47 (3) |
H21A | 0.5937 | 0.2972 | 0.1828 | 0.089* | 0.47 (3) |
H21B | 0.6509 | 0.2676 | 0.2601 | 0.089* | 0.47 (3) |
H21C | 0.6801 | 0.3443 | 0.2454 | 0.089* | 0.47 (3) |
C22B | 0.3139 (19) | 0.3755 (8) | 0.2311 (13) | 0.063 (5) | 0.47 (3) |
H22A | 0.2369 | 0.3684 | 0.2607 | 0.095* | 0.47 (3) |
H22B | 0.2610 | 0.3707 | 0.1817 | 0.095* | 0.47 (3) |
H22C | 0.3586 | 0.4203 | 0.2391 | 0.095* | 0.47 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0532 (8) | 0.0223 (5) | 0.0285 (6) | −0.0038 (5) | 0.0034 (5) | −0.0020 (4) |
Cl1 | 0.1076 (12) | 0.0406 (6) | 0.0267 (6) | −0.0273 (7) | 0.0177 (6) | −0.0036 (5) |
O1 | 0.058 (2) | 0.0241 (14) | 0.0249 (15) | −0.0138 (14) | 0.0002 (14) | 0.0032 (12) |
N1 | 0.079 (3) | 0.027 (2) | 0.045 (2) | −0.009 (2) | 0.006 (2) | 0.0054 (17) |
N2 | 0.105 (4) | 0.035 (2) | 0.029 (2) | 0.005 (2) | −0.001 (2) | 0.0003 (18) |
N3 | 0.077 (3) | 0.030 (2) | 0.046 (2) | −0.008 (2) | 0.014 (2) | −0.0047 (18) |
N4 | 0.047 (2) | 0.0196 (16) | 0.033 (2) | −0.0038 (16) | 0.0037 (17) | −0.0035 (14) |
C1 | 0.053 (3) | 0.028 (2) | 0.028 (2) | −0.006 (2) | 0.002 (2) | 0.0060 (18) |
C2 | 0.050 (3) | 0.022 (2) | 0.027 (2) | −0.0055 (19) | 0.005 (2) | −0.0002 (16) |
C3 | 0.055 (3) | 0.024 (2) | 0.033 (3) | 0.002 (2) | 0.006 (2) | 0.0050 (19) |
C4 | 0.041 (3) | 0.028 (2) | 0.037 (3) | −0.010 (2) | 0.007 (2) | 0.0028 (19) |
C5 | 0.042 (3) | 0.0221 (19) | 0.026 (2) | −0.0084 (19) | 0.0049 (19) | 0.0000 (16) |
C6 | 0.040 (3) | 0.025 (2) | 0.027 (2) | −0.0045 (19) | 0.0082 (19) | 0.0009 (17) |
C7 | 0.051 (3) | 0.029 (2) | 0.023 (2) | −0.014 (2) | −0.002 (2) | 0.0077 (17) |
C8 | 0.062 (3) | 0.040 (3) | 0.044 (3) | −0.016 (3) | −0.003 (2) | 0.014 (2) |
C9 | 0.068 (4) | 0.042 (3) | 0.030 (2) | −0.008 (2) | 0.005 (2) | 0.003 (2) |
C10 | 0.050 (3) | 0.025 (2) | 0.034 (2) | −0.003 (2) | 0.009 (2) | 0.0043 (19) |
C11 | 0.061 (3) | 0.037 (2) | 0.031 (2) | −0.018 (2) | 0.000 (2) | 0.0072 (19) |
C12 | 0.046 (3) | 0.031 (2) | 0.030 (2) | −0.009 (2) | 0.005 (2) | 0.0071 (18) |
C13 | 0.047 (3) | 0.033 (2) | 0.030 (2) | −0.011 (2) | 0.006 (2) | 0.0041 (18) |
C14 | 0.044 (3) | 0.024 (2) | 0.029 (2) | −0.004 (2) | 0.010 (2) | 0.0002 (17) |
C15 | 0.041 (3) | 0.0191 (19) | 0.027 (2) | −0.0022 (18) | 0.0034 (19) | −0.0011 (16) |
C16 | 0.049 (3) | 0.023 (2) | 0.028 (2) | −0.005 (2) | 0.008 (2) | −0.0001 (17) |
C19 | 0.049 (3) | 0.029 (2) | 0.030 (2) | −0.007 (2) | 0.007 (2) | −0.0017 (18) |
C23 | 0.045 (3) | 0.024 (2) | 0.025 (2) | −0.0021 (19) | 0.0005 (19) | −0.0014 (16) |
C24 | 0.042 (3) | 0.025 (2) | 0.025 (2) | 0.0014 (19) | 0.0030 (19) | −0.0003 (17) |
C25 | 0.042 (3) | 0.022 (2) | 0.029 (2) | −0.0008 (19) | 0.005 (2) | 0.0027 (16) |
C26 | 0.046 (3) | 0.020 (2) | 0.037 (2) | −0.0007 (19) | 0.001 (2) | −0.0027 (18) |
C27 | 0.060 (3) | 0.025 (2) | 0.045 (3) | −0.002 (2) | 0.010 (2) | 0.007 (2) |
C28 | 0.063 (4) | 0.020 (2) | 0.062 (3) | −0.004 (2) | 0.003 (3) | −0.002 (2) |
C29 | 0.057 (3) | 0.024 (2) | 0.055 (3) | −0.001 (2) | −0.006 (3) | −0.007 (2) |
C30 | 0.053 (3) | 0.032 (2) | 0.040 (3) | 0.003 (2) | 0.001 (2) | −0.008 (2) |
C31 | 0.046 (3) | 0.0175 (19) | 0.041 (3) | 0.0009 (19) | 0.001 (2) | −0.0007 (18) |
C32 | 0.067 (3) | 0.022 (2) | 0.033 (2) | −0.005 (2) | 0.015 (2) | 0.0000 (18) |
C33 | 0.085 (4) | 0.026 (2) | 0.031 (2) | 0.001 (2) | 0.010 (3) | 0.0016 (19) |
C34 | 0.076 (4) | 0.026 (2) | 0.033 (3) | 0.009 (2) | 0.007 (2) | −0.0007 (19) |
C35 | 0.096 (5) | 0.037 (3) | 0.029 (3) | 0.017 (3) | −0.005 (3) | −0.005 (2) |
C36 | 0.093 (5) | 0.050 (3) | 0.044 (3) | 0.018 (3) | −0.024 (3) | −0.016 (2) |
C17A | 0.042 (10) | 0.023 (7) | 0.028 (5) | −0.002 (6) | 0.015 (7) | −0.007 (5) |
C18A | 0.063 (10) | 0.024 (6) | 0.032 (5) | −0.011 (6) | 0.003 (5) | 0.005 (4) |
C20A | 0.093 (17) | 0.066 (10) | 0.028 (7) | −0.042 (11) | −0.006 (13) | −0.009 (9) |
C21A | 0.063 (10) | 0.14 (2) | 0.042 (9) | −0.036 (10) | 0.011 (7) | −0.008 (10) |
C22A | 0.127 (19) | 0.057 (8) | 0.033 (7) | 0.043 (10) | −0.005 (9) | 0.002 (5) |
C17B | 0.028 (9) | 0.014 (7) | 0.030 (5) | −0.006 (5) | 0.012 (6) | −0.011 (5) |
C18B | 0.044 (9) | 0.022 (6) | 0.034 (5) | −0.012 (5) | 0.004 (5) | 0.000 (4) |
C20B | 0.072 (15) | 0.050 (9) | 0.040 (13) | −0.017 (9) | 0.004 (12) | −0.015 (9) |
C21B | 0.079 (11) | 0.073 (12) | 0.019 (8) | 0.002 (8) | −0.001 (6) | −0.021 (7) |
C22B | 0.079 (12) | 0.051 (8) | 0.049 (11) | 0.001 (8) | −0.013 (7) | 0.004 (7) |
S1—C25 | 1.732 (4) | C24—H24 | 0.9500 |
S1—C31 | 1.743 (4) | C26—C27 | 1.389 (6) |
Cl1—C14 | 1.752 (4) | C26—C31 | 1.394 (6) |
O1—C6 | 1.349 (4) | C27—C28 | 1.388 (6) |
O1—C7 | 1.482 (4) | C27—H27 | 0.9500 |
N1—C1 | 1.151 (5) | C28—C29 | 1.389 (6) |
N2—C3 | 1.147 (5) | C28—H28 | 0.9500 |
N3—C10 | 1.160 (5) | C29—C30 | 1.393 (6) |
N4—C25 | 1.350 (5) | C29—H29 | 0.9500 |
N4—C26 | 1.411 (5) | C30—C31 | 1.392 (6) |
N4—C32 | 1.487 (5) | C30—H30 | 0.9500 |
C1—C2 | 1.426 (5) | C32—C33 | 1.523 (6) |
C2—C6 | 1.404 (5) | C32—H32A | 0.9900 |
C2—C3 | 1.418 (6) | C32—H32B | 0.9900 |
C4—C11 | 1.380 (5) | C33—C34 | 1.521 (6) |
C4—C5 | 1.412 (5) | C33—H33A | 0.9900 |
C4—C7 | 1.519 (5) | C33—H33B | 0.9900 |
C5—C6 | 1.414 (5) | C34—C35 | 1.528 (6) |
C5—C10 | 1.415 (6) | C34—H34A | 0.9900 |
C7—C9 | 1.517 (6) | C34—H34B | 0.9900 |
C7—C8 | 1.520 (6) | C35—C36 | 1.529 (7) |
C8—H8A | 0.9800 | C35—H35A | 0.9900 |
C8—H8B | 0.9800 | C35—H35B | 0.9900 |
C8—H8C | 0.9800 | C36—H36A | 0.9800 |
C9—H9A | 0.9800 | C36—H36B | 0.9800 |
C9—H9B | 0.9800 | C36—H36C | 0.9800 |
C9—H9C | 0.9800 | C17A—C18A | 1.49 (3) |
C11—C12 | 1.404 (6) | C17A—H17B | 1.0000 |
C11—H11 | 0.9500 | C18A—H18A | 0.9900 |
C12—C13 | 1.384 (5) | C18A—H18B | 0.9900 |
C12—H12 | 0.9500 | C20A—H20D | 0.9800 |
C13—C14 | 1.410 (5) | C20A—H20E | 0.9800 |
C13—C18B | 1.529 (10) | C20A—H20F | 0.9800 |
C13—C18A | 1.556 (10) | C21A—H21D | 0.9800 |
C14—C15 | 1.377 (5) | C21A—H21E | 0.9800 |
C15—C23 | 1.424 (5) | C21A—H21F | 0.9800 |
C15—C16 | 1.513 (5) | C22A—H22D | 0.9800 |
C16—C17A | 1.515 (17) | C22A—H22E | 0.9800 |
C16—C17B | 1.530 (15) | C22A—H22F | 0.9800 |
C16—H16A | 0.992 (10) | C17B—C18B | 1.57 (3) |
C16—H16B | 0.982 (10) | C17B—H17A | 1.0000 |
C19—C21B | 1.526 (8) | C18B—H18C | 0.9900 |
C19—C21A | 1.527 (8) | C18B—H18D | 0.9900 |
C19—C22B | 1.528 (8) | C20B—H20A | 0.9800 |
C19—C20B | 1.539 (8) | C20B—H20B | 0.9800 |
C19—C20A | 1.542 (8) | C20B—H20C | 0.9800 |
C19—C22A | 1.544 (7) | C21B—H21A | 0.9800 |
C19—C17A | 1.559 (17) | C21B—H21B | 0.9800 |
C19—C17B | 1.571 (18) | C21B—H21C | 0.9800 |
C23—C24 | 1.367 (5) | C22B—H22A | 0.9800 |
C23—H23 | 0.9500 | C22B—H22B | 0.9800 |
C24—C25 | 1.421 (5) | C22B—H22C | 0.9800 |
C25—S1—C31 | 91.3 (2) | C27—C28—H28 | 119.1 |
C6—O1—C7 | 109.4 (3) | C29—C28—H28 | 119.1 |
C25—N4—C26 | 114.1 (3) | C28—C29—C30 | 120.7 (4) |
C25—N4—C32 | 124.8 (3) | C28—C29—H29 | 119.6 |
C26—N4—C32 | 121.2 (3) | C30—C29—H29 | 119.6 |
N1—C1—C2 | 177.6 (5) | C31—C30—C29 | 117.8 (4) |
C6—C2—C3 | 123.9 (3) | C31—C30—H30 | 121.1 |
C6—C2—C1 | 119.5 (4) | C29—C30—H30 | 121.1 |
C3—C2—C1 | 116.4 (3) | C30—C31—C26 | 121.1 (4) |
N2—C3—C2 | 176.2 (4) | C30—C31—S1 | 128.2 (4) |
C11—C4—C5 | 132.4 (4) | C26—C31—S1 | 110.7 (3) |
C11—C4—C7 | 120.8 (4) | N4—C32—C33 | 113.1 (4) |
C5—C4—C7 | 106.6 (3) | N4—C32—H32A | 109.0 |
C4—C5—C6 | 108.9 (3) | C33—C32—H32A | 109.0 |
C4—C5—C10 | 127.6 (4) | N4—C32—H32B | 109.0 |
C6—C5—C10 | 123.4 (4) | C33—C32—H32B | 109.0 |
O1—C6—C2 | 116.0 (3) | H32A—C32—H32B | 107.8 |
O1—C6—C5 | 111.1 (3) | C34—C33—C32 | 114.9 (3) |
C2—C6—C5 | 132.8 (4) | C34—C33—H33A | 108.6 |
O1—C7—C9 | 106.5 (3) | C32—C33—H33A | 108.6 |
O1—C7—C4 | 103.7 (3) | C34—C33—H33B | 108.6 |
C9—C7—C4 | 113.3 (4) | C32—C33—H33B | 108.6 |
O1—C7—C8 | 106.8 (3) | H33A—C33—H33B | 107.5 |
C9—C7—C8 | 113.1 (4) | C33—C34—C35 | 114.3 (4) |
C4—C7—C8 | 112.5 (4) | C33—C34—H34A | 108.7 |
C7—C8—H8A | 109.5 | C35—C34—H34A | 108.7 |
C7—C8—H8B | 109.5 | C33—C34—H34B | 108.7 |
H8A—C8—H8B | 109.5 | C35—C34—H34B | 108.7 |
C7—C8—H8C | 109.5 | H34A—C34—H34B | 107.6 |
H8A—C8—H8C | 109.5 | C34—C35—C36 | 112.0 (4) |
H8B—C8—H8C | 109.5 | C34—C35—H35A | 109.2 |
C7—C9—H9A | 109.5 | C36—C35—H35A | 109.2 |
C7—C9—H9B | 109.5 | C34—C35—H35B | 109.2 |
H9A—C9—H9B | 109.5 | C36—C35—H35B | 109.2 |
C7—C9—H9C | 109.5 | H35A—C35—H35B | 107.9 |
H9A—C9—H9C | 109.5 | C35—C36—H36A | 109.5 |
H9B—C9—H9C | 109.5 | C35—C36—H36B | 109.5 |
N3—C10—C5 | 178.1 (5) | H36A—C36—H36B | 109.5 |
C4—C11—C12 | 125.8 (4) | C35—C36—H36C | 109.5 |
C4—C11—H11 | 117.1 | H36A—C36—H36C | 109.5 |
C12—C11—H11 | 117.1 | H36B—C36—H36C | 109.5 |
C13—C12—C11 | 127.1 (4) | C18A—C17A—C16 | 113.6 (15) |
C13—C12—H12 | 116.4 | C18A—C17A—C19 | 113.1 (13) |
C11—C12—H12 | 116.4 | C16—C17A—C19 | 113.4 (11) |
C12—C13—C14 | 122.6 (4) | C18A—C17A—H17B | 105.2 |
C12—C13—C18B | 122.5 (6) | C16—C17A—H17B | 105.2 |
C14—C13—C18B | 113.1 (6) | C19—C17A—H17B | 105.2 |
C12—C13—C18A | 119.3 (5) | C17A—C18A—C13 | 112.0 (13) |
C14—C13—C18A | 115.9 (5) | C17A—C18A—H18A | 109.2 |
C15—C14—C13 | 125.3 (4) | C13—C18A—H18A | 109.2 |
C15—C14—Cl1 | 118.3 (3) | C17A—C18A—H18B | 109.2 |
C13—C14—Cl1 | 116.4 (3) | C13—C18A—H18B | 109.2 |
C14—C15—C23 | 122.3 (4) | H18A—C18A—H18B | 107.9 |
C14—C15—C16 | 119.3 (3) | C19—C20A—H20D | 109.5 |
C23—C15—C16 | 118.5 (3) | C19—C20A—H20E | 109.5 |
C15—C16—C17A | 114.8 (7) | C19—C20A—H20F | 109.5 |
C15—C16—C17B | 115.8 (7) | C19—C21A—H21D | 109.5 |
C15—C16—H16A | 109 (2) | C19—C21A—H21E | 109.5 |
C17A—C16—H16A | 119 (3) | C19—C21A—H21F | 109.5 |
C15—C16—H16B | 106 (2) | C19—C22A—H22D | 109.5 |
C17B—C16—H16B | 111 (3) | C19—C22A—H22E | 109.5 |
C21B—C19—C22B | 140.9 (18) | C19—C22A—H22F | 109.5 |
C21B—C19—C20B | 89.3 (17) | C16—C17B—C18B | 108.3 (14) |
C22B—C19—C20B | 110.9 (12) | C16—C17B—C19 | 111.9 (10) |
C21B—C19—C20A | 108.2 (17) | C18B—C17B—C19 | 112.3 (13) |
C21A—C19—C20A | 116.9 (18) | C16—C17B—H17A | 108.1 |
C22B—C19—C20A | 89.0 (12) | C18B—C17B—H17A | 108.1 |
C21B—C19—C22A | 107.8 (19) | C19—C17B—H17A | 108.1 |
C21A—C19—C22A | 82 (2) | C13—C18B—C17B | 109.0 (13) |
C20A—C19—C22A | 107.0 (12) | C13—C18B—H18C | 109.9 |
C21A—C19—C17A | 123.0 (11) | C17B—C18B—H18C | 109.9 |
C20A—C19—C17A | 112.9 (15) | C13—C18B—H18D | 109.9 |
C22A—C19—C17A | 108.0 (10) | C17B—C18B—H18D | 109.9 |
C21B—C19—C17B | 91.9 (11) | H18C—C18B—H18D | 108.3 |
C22B—C19—C17B | 112.9 (12) | C19—C20B—H20A | 109.5 |
C20B—C19—C17B | 105.5 (16) | C19—C20B—H20B | 109.5 |
C24—C23—C15 | 125.1 (4) | H20A—C20B—H20B | 109.5 |
C24—C23—H23 | 117.4 | C19—C20B—H20C | 109.5 |
C15—C23—H23 | 117.4 | H20A—C20B—H20C | 109.5 |
C23—C24—C25 | 122.3 (4) | H20B—C20B—H20C | 109.5 |
C23—C24—H24 | 118.8 | C19—C21B—H21A | 109.5 |
C25—C24—H24 | 118.8 | C19—C21B—H21B | 109.5 |
N4—C25—C24 | 125.0 (4) | H21A—C21B—H21B | 109.5 |
N4—C25—S1 | 111.8 (3) | C19—C21B—H21C | 109.5 |
C24—C25—S1 | 123.1 (3) | H21A—C21B—H21C | 109.5 |
C27—C26—C31 | 121.2 (4) | H21B—C21B—H21C | 109.5 |
C27—C26—N4 | 126.8 (4) | C19—C22B—H22A | 109.5 |
C31—C26—N4 | 112.0 (3) | C19—C22B—H22B | 109.5 |
C28—C27—C26 | 117.4 (4) | H22A—C22B—H22B | 109.5 |
C28—C27—H27 | 121.3 | C19—C22B—H22C | 109.5 |
C26—C27—H27 | 121.3 | H22A—C22B—H22C | 109.5 |
C27—C28—C29 | 121.8 (4) | H22B—C22B—H22C | 109.5 |
C11—C4—C5—C6 | −170.6 (5) | C23—C24—C25—S1 | 2.7 (6) |
C7—C4—C5—C6 | 4.6 (5) | C31—S1—C25—N4 | 0.5 (3) |
C11—C4—C5—C10 | 8.7 (9) | C31—S1—C25—C24 | −180.0 (4) |
C7—C4—C5—C10 | −176.1 (4) | C25—N4—C26—C27 | −178.6 (4) |
C7—O1—C6—C2 | −177.9 (4) | C32—N4—C26—C27 | 2.2 (7) |
C7—O1—C6—C5 | −0.8 (5) | C25—N4—C26—C31 | 2.3 (5) |
C3—C2—C6—O1 | −179.3 (4) | C32—N4—C26—C31 | −177.0 (4) |
C1—C2—C6—O1 | 5.2 (6) | C31—C26—C27—C28 | 1.4 (7) |
C3—C2—C6—C5 | 4.4 (8) | N4—C26—C27—C28 | −177.7 (4) |
C1—C2—C6—C5 | −171.1 (5) | C26—C27—C28—C29 | −0.7 (7) |
C4—C5—C6—O1 | −2.5 (5) | C27—C28—C29—C30 | −0.1 (8) |
C10—C5—C6—O1 | 178.1 (4) | C28—C29—C30—C31 | 0.2 (7) |
C4—C5—C6—C2 | 174.0 (5) | C29—C30—C31—C26 | 0.5 (7) |
C10—C5—C6—C2 | −5.4 (8) | C29—C30—C31—S1 | −179.8 (4) |
C6—O1—C7—C9 | 123.3 (4) | C27—C26—C31—C30 | −1.4 (7) |
C6—O1—C7—C4 | 3.5 (4) | N4—C26—C31—C30 | 177.9 (4) |
C6—O1—C7—C8 | −115.6 (4) | C27—C26—C31—S1 | 179.0 (4) |
C11—C4—C7—O1 | 171.0 (4) | N4—C26—C31—S1 | −1.8 (5) |
C5—C4—C7—O1 | −4.8 (5) | C25—S1—C31—C30 | −178.9 (4) |
C11—C4—C7—C9 | 55.9 (6) | C25—S1—C31—C26 | 0.8 (3) |
C5—C4—C7—C9 | −119.9 (4) | C25—N4—C32—C33 | 91.7 (5) |
C11—C4—C7—C8 | −73.9 (5) | C26—N4—C32—C33 | −89.1 (5) |
C5—C4—C7—C8 | 110.3 (4) | N4—C32—C33—C34 | −75.2 (5) |
C5—C4—C11—C12 | 3.2 (9) | C32—C33—C34—C35 | 177.7 (4) |
C7—C4—C11—C12 | −171.5 (4) | C33—C34—C35—C36 | −173.9 (4) |
C4—C11—C12—C13 | 171.7 (5) | C15—C16—C17A—C18A | −41 (2) |
C11—C12—C13—C14 | −174.6 (5) | C15—C16—C17A—C19 | −172.2 (9) |
C11—C12—C13—C18B | 21.9 (12) | C21A—C19—C17A—C18A | −107 (2) |
C11—C12—C13—C18A | −12.4 (12) | C20A—C19—C17A—C18A | 43 (3) |
C12—C13—C14—C15 | 175.5 (4) | C22A—C19—C17A—C18A | 161 (2) |
C18B—C13—C14—C15 | −19.7 (11) | C21A—C19—C17A—C16 | 25 (2) |
C18A—C13—C14—C15 | 12.7 (11) | C20A—C19—C17A—C16 | 173.9 (16) |
C12—C13—C14—Cl1 | −3.8 (6) | C22A—C19—C17A—C16 | −68 (2) |
C18B—C13—C14—Cl1 | 161.1 (9) | C16—C17A—C18A—C13 | 50 (3) |
C18A—C13—C14—Cl1 | −166.6 (10) | C19—C17A—C18A—C13 | −178.8 (8) |
C13—C14—C15—C23 | 176.4 (4) | C12—C13—C18A—C17A | 160.6 (15) |
Cl1—C14—C15—C23 | −4.4 (6) | C14—C13—C18A—C17A | −36 (2) |
C13—C14—C15—C16 | −3.0 (7) | C15—C16—C17B—C18B | 39.7 (18) |
Cl1—C14—C15—C16 | 176.2 (3) | C17A—C16—C17B—C18B | −53 (3) |
C14—C15—C16—C17A | 17.0 (11) | C15—C16—C17B—C19 | 164.0 (8) |
C23—C15—C16—C17A | −162.4 (10) | C21B—C19—C17B—C16 | 88.1 (15) |
C14—C15—C16—C17B | −8.5 (10) | C22B—C19—C17B—C16 | −60.8 (17) |
C23—C15—C16—C17B | 172.1 (9) | C20B—C19—C17B—C16 | 177.9 (16) |
C14—C15—C23—C24 | 176.6 (4) | C21B—C19—C17B—C18B | −149.9 (17) |
C16—C15—C23—C24 | −4.1 (6) | C22B—C19—C17B—C18B | 61.1 (19) |
C15—C23—C24—C25 | 174.2 (4) | C20B—C19—C17B—C18B | −60 (2) |
C26—N4—C25—C24 | 178.8 (4) | C12—C13—C18B—C17B | −143.8 (11) |
C32—N4—C25—C24 | −2.0 (7) | C14—C13—C18B—C17B | 51.3 (18) |
C26—N4—C25—S1 | −1.6 (5) | C16—C17B—C18B—C13 | −61 (2) |
C32—N4—C25—S1 | 177.6 (3) | C19—C17B—C18B—C13 | 175.3 (7) |
C23—C24—C25—N4 | −177.8 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9A···O1i | 0.98 | 2.59 | 3.494 (6) | 154 |
C32—H32A···N2ii | 0.98 | 2.73 | 3.702 (5) | 166 |
C33—H33B···N1ii | 0.98 | 2.65 | 3.539 (6) | 150 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1/2, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C36H39ClN4OS |
Mr | 611.22 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 116 |
a, b, c (Å) | 8.6293 (5), 20.1267 (11), 19.5299 (11) |
β (°) | 102.236 (4) |
V (Å3) | 3314.9 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.21 |
Crystal size (mm) | 0.71 × 0.30 × 0.10 |
Data collection | |
Diffractometer | Bruker–Nonius APEXII CCD area-detector |
Absorption correction | Multi-scan (Blessing, 1995) and SADABS (Bruker, 2005) |
Tmin, Tmax | 0.614, 0.746 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32003, 5943, 3121 |
Rint | 0.106 |
(sin θ/λ)max (Å−1) | 0.599 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.177, 1.01 |
No. of reflections | 5943 |
No. of parameters | 451 |
No. of restraints | 75 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.45, −0.29 |
Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
C9—H9A···O1i | 0.98 | 2.59 | 3.494 (6) | 154 |
C32—H32A···N2ii | 0.98 | 2.73 | 3.702 (5) | 166 |
C33—H33B···N1ii | 0.98 | 2.65 | 3.539 (6) | 150 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x+1/2, −y+1/2, z−1/2. |
AtomA—AtomB | Here | HITVIQ | EGOSOJ |
C2–C6 | 1.404 (5) | 1.378 (3) | 1.385 (6) |
C6–C7 | 1.414 (5) | 1.429 (3) | 1.417 (6) |
C7–C4 | 1.412 (5) | 1.370 (3) | 1.402 (6) |
C4–c11 | 1.381 (6) | 1.416 (3) | 1.373 (5) |
Average dba | 1.411 (9) | 1.368 (7) | 1.397 (8) |
Average sba | 1.385 (18) | 1.426 (10) | 1.395 (16) |
BLAb | -0.026 | 0.058 | -0.002 |
a. db,sb double,single bonds (10). b. Marder et al., 1993. |
Acknowledgements
We thank Drs J. Wikaira & C. Fitchett of the University of Canterbury, New Zealand, for the data collection.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The title compound, C36H39ClN4OS (3, Figure 1) was synthesized as part of our ongoing research involving the development of organic nonlinear optical (NLO) chromophores. As part of this we have previously reported the crystallographic parameters for chromophores containing an indoline donor coupled to a 2-(3-cyano-4,5,5-trimethyl-5H-furan-2-ylidene)-malononitrile electron acceptor group (Bhuiyan et al., 2011). Compound 3 was synthesized to check the impact of using a benzothiazole based donor as this should influence both the degree of both length alternation (viz. bond order) as well as the crystal packing. Compound 3 was conveniently prepared in good yield by the condensation of N-pentyl-2-methylbenzothiazolinium iodide 1 with precursor 2 (Figure 1). Compound 2 was prepared by the procedure previously reported in the literature (Kay et al., 2004).
Compound REFCODES are from the C.S.D. (Version 5.33, with August 2012 updates; Allen, 2002). The asymmetric unit contents of the title compound(I) are shown in Figure 1. The 5-membered ring plane of atoms O1,C4—C7 (hereafter "CDFP", [3-cyano-5,5-dimethyl-2,5-dihydrofuran-2-ylidene]propanedinitrile) can be regarded as planar with maximum out of plane deviation for C4 of 0.029 (4) Å. The dicyano group (N1,C1,C2,C3,N2,C6) is planar but twisted by 9.4 (3) ° with respect to the "CDFP" group; this is similar to the twist in related compound NOJKUT (Gainsford et al., 2008) of 5.69 (17)°, and is consistent with alleviating intramolecular contacts with the cyano group (C10–N3). The benzothiazol-2-ylidene fused ring is approximately planar with maximum out of plane distance for N4 0.026 (3) Å. This plane makes an angle of ~7° to the polyene chain atoms (C13—C16,C23,C24), which in turn is ~18° from the "CDFP" plane. These twists in the adjacent near-planar moieties contrasts with the closely related molecule HITVIQ (Bouit et al.,2007) where the benzothiazole entity is replaced by a 1-benzyl-3,3-dimethyl-1,3-dihydro-2H-indol-2-ylidene: here the CDFP and terminal donor rings make an angle of ~10°. As in HITVIQ, there are close intramolecular H···Cl interactions involving the adjacent polyene hydrogen atoms (entries 7 & 8, Table 1) but here there is an additional H···S interaction (2.68 Å, entry 9, Table 1) contributing to the twist.
The different deviation from molecular planarity is also reflected in a significant difference between the two structures in the alternation of double and single bonds beginning at the C2–C6 CDFP bond (Table 2). This alternation is described by the BLA parameter (Marder et al., 1993), reflecting the average change in bond length alternation. A related sodium salt (with the CDFP ring at both ends of the molecule EGOSOJ, Bouit et al., 2008)) appears to be have intermediate BLA values between the two.
The molecules pack into dimeric units about centres of symmetry utilizing weak C–H···Cyano(N) and C–H···O attractive interactions, building both chain and ring motifs about the centres (R22(8) & R22(9)). Table 2 summarizes those attractive interactions and key elements are shown in Figure 3. The adjacent dimeric sets then form a typical "herringbone" configuration. In contrast, the HITVIQ molecules have mainly weak, close to in-plane interactions (C–H···Cl), linked via chain motif weak C–H···N(cyano) interactions.