4-tert-Butyl-2-[2-(1,3,3-trimethyl­indolin-2-yl­idene)ethyl­idene]cyclo­hexa­none

Gainsford, G.J.; Ashraf, M.; Kay, A.J.

doi:10.1107/S1600536811014590

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1210

doi:10.1107/S1600536811014590

Open

access

4-tert-Butyl-2-[2-(1,3,3-trimethylindolin-2-ylidene)ethylidene]cyclohexanone

Graeme J. Gainsford,^a ^* Mohamed Ashraf ^a and Andrew J. Kay ^a

^aIndustrial Research Limited, PO Box 31-310, Lower Hutt, New Zealand
^*Correspondence e-mail: g.gainsford@irl.cri.nz

(Received 23 March 2011; accepted 19 April 2011; online 29 April 2011)

The title molecule, C₂₃H₃₁NO, has two alternative cyclohexanone configurations at the 4-position in a ratio of 0.663 (3):0.337 (3). The plane of the five-membered planar ring in the indolin-2-ylidene subtends an angle of 2.19 (7)° with its fused aromatic ring, an angle of 16.24 (8)° with the plane of the major cyclohexanone configuration and an angle of 8.54 (15)° with the bridging planar ethylidene C atoms. These last atoms subtend an angle of 8.37 (16)° with the mean plane through the major cyclohexanone configuration. The molecules pack approximately parallel to the ( $[\overline{1}]$ 01) plane via C—H⋯π and C—H⋯O interactions.

Related literature

For background information on potential applications of NLO (organic nonlinear optical material) compounds, see: Denk et al. (1990 ); Ma et al. (2002 ); Parthenopoulos & Rentzepis (1989 ). For synthesis details, see: Ainsworth (1963 ). For related compounds, see: Kawamata et al. (1998 ); Higham et al. (2010 ); Bhuiyan et al. (2011 ); Teshome et al. (2011 ). For the Cambridge Structural Database, see: Allen (2002 ). For graph-set notation of hydrogen bonds, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₂₃H₃₁NO
M_r = 337.49
Monoclinic, P 2₁ /n
a = 9.7327 (4) Å
b = 17.2187 (6) Å
c = 12.1303 (4) Å
β = 100.045 (2)°
V = 2001.69 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 116 K
0.62 × 0.49 × 0.25 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (Blessing, 1995 ) T_min = 0.668, T_max = 0.746
44399 measured reflections
4500 independent reflections
3690 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.134
S = 1.05
4500 reflections
308 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O1ⁱ	0.95	2.45	3.3293 (19)	154
C9—H9A⋯Cg1ⁱⁱ	0.98	2.65	3.5705 (17)	156
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+2, -y+1, -z+2.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT and SADABS (Sheldrick, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ) and Mercury (Macrae et al., 2008 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811014590/jj2085sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811014590/jj2085Isup2.hkl

checkCIF report

Comment top

Organic nonlinear optical (NLO) materials show much promise due to their potential application in areas such as optical power limiting, optical data storage and two-photon fluorescence imaging (Ma et al., 2002; Parthenopoulos & Rentzepis, 1989; Denk et al., 1990). Such compounds are typically push–pull conjugated systems that can be modified by altering either the donor, acceptor or conjugated interconnect moieties. However these modifications can involve trade-offs insofar as improvements to the nonlinear optical properties typically result in compounds that are more complex to prepare, have lower stabilities and higher optical losses. Conjugated ketones are useful intermediates for increasing the chain length and/or substituting different donors and acceptors onto a basic chromophore backbone. This is because conjugated ketones are quite reactive species and are able to undergo a range of carbon–carbon double bond forming reactions including the Wittig reaction, Knoevenagel condensation and Peterson olefination. With this in mind, and in line with our ongoing work on the development of novel organic NLO compounds, we sought to prepare the title compound 3 using the method outlined in Fig. 1. This compound is a useful synthon for the preparation of a range of chromophore systems as it contains an electron-rich indoline donor unit and a conjugated ketone onto which a range of acceptors can be coupled. The title molecule 3 is conveniently prepared in excellent yield by the condensation of 4-tert-butyl-2-hydroxymethylenecyclohexanone 1 with Fisher's base 2. Compound 1 was prepared from 4-tert-butylcyclohexanone using the general procedure reported by Ainsworth (1963).

Compound REFCODES below are from the CSD (Version 5.32, with Feb. 2011 updates; Allen, 2002). In the title compound 3 (Fig. 2), the cyclohexanone ring exists in two configurations, S (C18a) and R (C18b), in the ratio a:b of 0.663 (3):0.337 (3). This model made chemical sense, was stable in refinement, with insignificant difference Fourier residual density. The data supported refinement in the centrosymmetric space group P2₁/n even though there were 57 weak reflections (with intensities between values between 0.08 (2) and 0.87 (7)) that violated the n glide absence condition. Refinement in P2₁ did not improve the fit significantly as would be expected with such weak contributing data, and gave some very large correlations between thermal and positional parameters of the n glide related molecules.

The closest comparable structures for the cyclochexanone section of the molecule is QADZUQ, 4-tert-butyl-2,6-bis(4-methylbenzylidene)cyclohexanone (Kawamata et al., 1998) which has a mirror plane passing through the carbonyl, tert-butyl and their bound ring C atoms. A comparision of the cyclohexanone dimensions indicates that some electronic delocalization along the ethylidene chain is observed with the C14—C15 bond length shortened (1.472 (2), 1.490 Å), the C13—C14 bond length lengthened (1.3619 (18), 1.332 Å) and the C12—C13 bond shortened (1.4204 (19), 1.466 Å) for 3 and QADZUQ respectively. The dienone-ether macrocyclic compound WUYMIN (Higham et al., 2010) also contains copies of the 4-tert-butyl-cyclohexanone at a lower resolution (R 9.0%), with similar configurational disorder in the ratio of 0.70:0.30 as observed here.

As noted before in related indoline-based compounds there is minor buckling between the planar 5- and 6-membered rings in the indolin-2-ylidene ring of 2.19 (7)° compared with 1.81 (13)° in compound 17 (Teshome et al., 2011) and 1.38 (9)° in compound TMIPI (Bhuiyan et al., 2011). The interplanar angles confirm the consistent twist along the electronic delocalization plane: 8.54 (15)° between the 5-membered indoline ring (N1,C1,C6–C8) and the ethylidene atoms plane (C8,C12–C14) with a further 8.37 (16)° angle subtended between the latter and the average plane through the major configuration cyclohexanone atoms (C14–C16, C17a, C18a and C19). The indoline dimensions are identical to those found in the above-listed compounds.

The molecules are held in the lattice by weak C—H···π interactions (Table 1) over cell inversion centres and C—H···O hydrogen bonds, the latter forming C(10) motifs (Bernstein et al., 1995), Fig. 3.

Related literature top

For background information, see: Denk et al. (1990); Ma et al. (2002); Parthenopoulos & Rentzepis (1989). For synthesis details, see: Ainsworth (1963). For related compounds, see: Kawamata et al. (1998); Higham et al. (2010); Bhuiyan et al. (2011); Teshome et al. (2011). For the Cambridge Structural Database, see: Allen (2002). For graph-set notation of hydrogen bonds, see: Bernstein et al. (1995).

Experimental top

To a stirred solution of Fisher's base 2 (0.865 g, 5 mmole) in methanol was added compound 1 (0.91 g, 5 mmole). The mixture was refluxed for 2 h by which time its colour had changed from deep red to brown. The solvent was removed at reduced pressure and the residue purified by crystallization in ethanol, giving the title compound 3 as a yellow solid (1.5 g, 88% yield). X-ray quality crystals were grown by slow evaporation from methanol. m.p.: 450 K.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005) and SADABS (Sheldrick, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. Reaction scheme showing the synthetic procedure for obtaining the title compound.
	Fig. 2. Molecular structure of the asymmetric unit (Farrugia, 1997); displacement ellipsoids are shown at the 30% probability level. H atoms not shown for clarity. Dashed bonds indicate positions of the minor (b) configuration atoms (see text).
	Fig. 3. Partial packing diagram of the unit cell showing key interactions (see text and Table 1) [Macrae et al., 2008]. Only significant H atoms are shown as balls for clarity. Symmetry (i) x - 1/2, 3/2 - y, z - 1/2 (ii) 2 - x, 1 - y, 2 - z Two ring centres are shown as purple balls: Cg1 is the centre of the C1–C6 ring at symmetry (ii).

4-tert-Butyl-2-[2-(1,3,3-trimethylindolin-2- ylidene)ethylidene]cyclohexanone top

Crystal data top

C₂₃H₃₁NO	F(000) = 736
M_r = 337.49	D_x = 1.120 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9800 reflections
a = 9.7327 (4) Å	θ = 2.4–27.3°
b = 17.2187 (6) Å	µ = 0.07 mm⁻¹
c = 12.1303 (4) Å	T = 116 K
β = 100.045 (2)°	Block, orange
V = 2001.69 (13) Å³	0.62 × 0.49 × 0.25 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	4500 independent reflections
Radiation source: fine-focus sealed tube	3690 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
Detector resolution: 8.333 pixels mm^-1	θ_max = 27.3°, θ_min = 2.4°
ϕ and ω scans	h = −12→12
Absorption correction: multi-scan (Blessing, 1995)	k = −22→22
T_min = 0.668, T_max = 0.746	l = −15→15
44399 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0594P)² + 0.720P] where P = (F_o² + 2F_c²)/3
4500 reflections	(Δ/σ)_max < 0.001
308 parameters	Δρ_max = 0.26 e Å⁻³
5 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₂₃H₃₁NO	V = 2001.69 (13) Å³
M_r = 337.49	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.7327 (4) Å	µ = 0.07 mm⁻¹
b = 17.2187 (6) Å	T = 116 K
c = 12.1303 (4) Å	0.62 × 0.49 × 0.25 mm
β = 100.045 (2)°

Data collection top

Bruker APEXII CCD diffractometer	4500 independent reflections
Absorption correction: multi-scan (Blessing, 1995)	3690 reflections with I > 2σ(I)
T_min = 0.668, T_max = 0.746	R_int = 0.043
44399 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	5 restraints
wR(F²) = 0.134	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.26 e Å⁻³
4500 reflections	Δρ_min = −0.21 e Å⁻³
308 parameters

Special details top

Experimental. ¹H NMR (500 MHz, CDCl₃): δ 8.00 (d, 1H, J 10 Hz), 7.20-7.17 (m, 2H), 6.93 (t, 1H) 7.71 (d, 1H, J 5 Hz), 5.29 (d, 1H, J 10Hz), 3.22 (s, 3H), 2.56 (dd, 2H, J 5 Hz), 2.32(m, 1H), 2.15 (m, 2H), 1.95 (m, 2H), 1.63 (s, 6H), 0.98 (s, 9H). ¹³C NMR (75 MHz, CDCl₃): δ 198.5, 165.1, 144.4, 139.5, 134.5, 127.8, 124.1, 121.8, 121.1, 106.9, 91.5, 46.8, 44.9, 39.3, 32.7, 29.7, 28.7, 27.4, 26.8, 24.0. LCMS found: MH⁺ 338.2475; C₂₃H₃₁NO requires MH⁺ 338.2484; Δ = -2.7 ppm

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.28457 (12)	0.66246 (6)	0.71213 (10)	0.0437 (3)
N1	0.79474 (12)	0.49759 (7)	1.02889 (9)	0.0283 (3)
C1	0.89106 (14)	0.53885 (8)	1.10624 (11)	0.0270 (3)
C2	1.00469 (15)	0.51059 (9)	1.18053 (12)	0.0331 (3)
H2	1.0261	0.4567	1.1848	0.040*
C3	1.08596 (16)	0.56435 (10)	1.24853 (12)	0.0379 (4)
H3	1.1654	0.5469	1.2995	0.045*
C4	1.05364 (16)	0.64254 (10)	1.24352 (12)	0.0384 (4)
H4	1.1103	0.6779	1.2915	0.046*
C5	0.93804 (15)	0.67029 (9)	1.16829 (12)	0.0320 (3)
H5	0.9150	0.7239	1.1654	0.038*
C6	0.85852 (14)	0.61754 (8)	1.09849 (11)	0.0265 (3)
C7	0.73269 (13)	0.63014 (8)	1.00634 (11)	0.0259 (3)
C8	0.70101 (13)	0.54643 (8)	0.96512 (11)	0.0262 (3)
C9	0.79355 (16)	0.41346 (8)	1.02159 (13)	0.0335 (3)
H9A	0.8428	0.3971	0.9616	0.050*
H9B	0.6969	0.3950	1.0053	0.050*
H9C	0.8401	0.3915	1.0929	0.050*
C10	0.77348 (15)	0.68104 (9)	0.91287 (12)	0.0329 (3)
H10A	0.8527	0.6574	0.8854	0.049*
H10B	0.7997	0.7329	0.9425	0.049*
H10C	0.6940	0.6852	0.8512	0.049*
C11	0.61232 (15)	0.66848 (9)	1.05326 (12)	0.0340 (3)
H11A	0.6454	0.7166	1.0921	0.051*
H11B	0.5790	0.6329	1.1059	0.051*
H11C	0.5358	0.6803	0.9916	0.051*
C12	0.60291 (14)	0.52054 (8)	0.87812 (11)	0.0299 (3)
H12	0.6070	0.4673	0.8587	0.036*
C13	0.49551 (14)	0.56575 (8)	0.81416 (11)	0.0291 (3)
H13	0.4886	0.6184	0.8360	0.035*
C14	0.40147 (14)	0.54095 (8)	0.72454 (11)	0.0286 (3)
C15	0.29387 (14)	0.59685 (9)	0.67486 (12)	0.0308 (3)
C16	0.19053 (16)	0.57155 (10)	0.57339 (14)	0.0418 (4)
H16A	0.0979	0.5924	0.5811	0.063*
H16B	0.2175	0.5965	0.5068	0.063*
C19	0.4067 (2)	0.46039 (9)	0.67678 (13)	0.0394 (4)
H19A	0.496 (2)	0.4472 (12)	0.6680 (17)	0.059*
H19B	0.375 (2)	0.4235 (12)	0.7229 (18)	0.059*
C17A	0.1748 (3)	0.48893 (14)	0.5508 (2)	0.0303 (5)	0.663 (3)
H17A	0.118 (3)	0.4799 (16)	0.480 (2)	0.045*	0.663 (3)
H17B	0.129 (3)	0.4671 (16)	0.610 (2)	0.045*	0.663 (3)
C18A	0.3166 (2)	0.45000 (15)	0.5576 (2)	0.0255 (5)	0.663 (3)
H18A	0.366 (3)	0.4800 (15)	0.507 (2)	0.038*	0.663 (3)
C20A	0.3096 (6)	0.3654 (4)	0.5180 (5)	0.0281 (10)	0.663 (3)
C21A	0.4546 (3)	0.32873 (16)	0.5326 (3)	0.0469 (7)	0.663 (3)
H21A	0.4482	0.2777	0.4964	0.070*	0.663 (3)
H21B	0.4919	0.3228	0.6126	0.070*	0.663 (3)
H21C	0.5168	0.3622	0.4982	0.070*	0.663 (3)
C22A	0.2492 (3)	0.36163 (15)	0.39073 (19)	0.0434 (6)	0.663 (3)
H22A	0.1527	0.3805	0.3776	0.065*	0.663 (3)
H22B	0.2511	0.3078	0.3648	0.065*	0.663 (3)
H22C	0.3056	0.3942	0.3496	0.065*	0.663 (3)
C23A	0.2173 (3)	0.31416 (14)	0.5787 (2)	0.0400 (6)	0.663 (3)
H23A	0.2166	0.2610	0.5497	0.060*	0.663 (3)
H23B	0.1219	0.3347	0.5659	0.060*	0.663 (3)
H23C	0.2544	0.3141	0.6591	0.060*	0.663 (3)
C17B	0.2366 (6)	0.4922 (3)	0.5221 (4)	0.0331 (11)	0.337 (3)
H17C	0.1547	0.4715	0.4705	0.050*	0.337 (3)
H17D	0.3085	0.5048	0.4764	0.050*	0.337 (3)
C18B	0.2938 (5)	0.4273 (3)	0.6024 (5)	0.0268 (10)	0.337 (3)
H18B	0.225 (6)	0.421 (3)	0.653 (4)	0.040*	0.337 (3)
C20B	0.3155 (11)	0.3475 (7)	0.5420 (9)	0.030 (2)	0.337 (3)
C21B	0.3865 (6)	0.2909 (3)	0.6310 (5)	0.0512 (15)	0.337 (3)
H21D	0.4037	0.2415	0.5954	0.077*	0.337 (3)
H21E	0.3259	0.2818	0.6863	0.077*	0.337 (3)
H21F	0.4754	0.3128	0.6683	0.077*	0.337 (3)
C22B	0.4077 (6)	0.3596 (3)	0.4542 (5)	0.0498 (15)	0.337 (3)
H22D	0.4241	0.3096	0.4203	0.075*	0.337 (3)
H22E	0.4970	0.3820	0.4897	0.075*	0.337 (3)
H22F	0.3612	0.3950	0.3962	0.075*	0.337 (3)
C23B	0.1757 (5)	0.3156 (3)	0.4890 (5)	0.0526 (16)	0.337 (3)
H23D	0.1150	0.3123	0.5454	0.079*	0.337 (3)
H23E	0.1878	0.2638	0.4589	0.079*	0.337 (3)
H23F	0.1331	0.3501	0.4282	0.079*	0.337 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0452 (6)	0.0324 (6)	0.0489 (7)	0.0034 (5)	−0.0046 (5)	−0.0071 (5)
N1	0.0312 (6)	0.0245 (6)	0.0280 (6)	−0.0020 (4)	0.0014 (5)	0.0022 (4)
C1	0.0286 (7)	0.0298 (7)	0.0231 (6)	−0.0024 (5)	0.0057 (5)	0.0015 (5)
C2	0.0356 (8)	0.0353 (8)	0.0280 (7)	0.0050 (6)	0.0044 (6)	0.0057 (6)
C3	0.0327 (8)	0.0506 (10)	0.0279 (7)	0.0025 (7)	−0.0018 (6)	0.0026 (6)
C4	0.0362 (8)	0.0451 (9)	0.0311 (7)	−0.0066 (7)	−0.0018 (6)	−0.0062 (6)
C5	0.0327 (7)	0.0315 (7)	0.0313 (7)	−0.0029 (6)	0.0040 (6)	−0.0027 (6)
C6	0.0239 (6)	0.0303 (7)	0.0252 (6)	−0.0007 (5)	0.0040 (5)	0.0022 (5)
C7	0.0250 (6)	0.0247 (7)	0.0271 (6)	−0.0030 (5)	0.0017 (5)	0.0007 (5)
C8	0.0261 (6)	0.0270 (7)	0.0264 (6)	−0.0026 (5)	0.0066 (5)	0.0025 (5)
C9	0.0392 (8)	0.0237 (7)	0.0367 (7)	−0.0017 (6)	0.0046 (6)	0.0022 (6)
C10	0.0331 (7)	0.0302 (7)	0.0342 (7)	−0.0038 (6)	0.0026 (6)	0.0063 (6)
C11	0.0285 (7)	0.0367 (8)	0.0363 (7)	0.0006 (6)	0.0046 (6)	−0.0049 (6)
C12	0.0331 (7)	0.0267 (7)	0.0291 (7)	−0.0051 (5)	0.0033 (6)	−0.0007 (5)
C13	0.0276 (7)	0.0299 (7)	0.0299 (7)	−0.0049 (5)	0.0050 (5)	−0.0018 (5)
C14	0.0297 (7)	0.0292 (7)	0.0263 (6)	−0.0046 (5)	0.0031 (5)	−0.0010 (5)
C15	0.0277 (7)	0.0321 (8)	0.0322 (7)	−0.0048 (5)	0.0040 (6)	−0.0023 (6)
C16	0.0269 (7)	0.0476 (10)	0.0470 (9)	0.0031 (6)	−0.0046 (6)	−0.0127 (7)
C19	0.0522 (10)	0.0295 (8)	0.0313 (8)	0.0017 (7)	−0.0068 (7)	−0.0026 (6)
C17A	0.0213 (12)	0.0320 (12)	0.0342 (13)	0.0011 (10)	−0.0042 (10)	−0.0044 (10)
C18A	0.0219 (11)	0.0286 (13)	0.0249 (12)	−0.0020 (9)	0.0009 (9)	−0.0001 (10)
C20A	0.0269 (14)	0.023 (3)	0.034 (2)	−0.0007 (14)	0.0050 (12)	0.0008 (14)
C21A	0.0356 (13)	0.0441 (15)	0.0596 (18)	0.0067 (11)	0.0046 (12)	−0.0154 (13)
C22A	0.0568 (16)	0.0425 (14)	0.0300 (12)	−0.0024 (11)	0.0047 (11)	−0.0081 (10)
C23A	0.0465 (14)	0.0316 (12)	0.0440 (14)	−0.0074 (10)	0.0137 (11)	−0.0016 (10)
C17B	0.027 (3)	0.036 (3)	0.032 (2)	0.001 (2)	−0.005 (2)	−0.0046 (19)
C18B	0.028 (2)	0.024 (2)	0.029 (2)	−0.0033 (17)	0.0057 (19)	0.0004 (19)
C20B	0.040 (3)	0.013 (5)	0.039 (5)	−0.005 (3)	0.009 (3)	−0.009 (3)
C21B	0.069 (4)	0.028 (3)	0.053 (3)	−0.003 (2)	0.002 (3)	−0.004 (2)
C22B	0.054 (3)	0.049 (3)	0.052 (3)	−0.005 (2)	0.024 (3)	−0.013 (3)
C23B	0.039 (3)	0.049 (3)	0.068 (4)	−0.009 (2)	0.005 (3)	−0.029 (3)

Geometric parameters (Å, º) top

O1—C15	1.2260 (18)	C19—C18B	1.415 (4)
N1—C8	1.3754 (17)	C19—C18A	1.565 (3)
N1—C1	1.3989 (17)	C19—H19A	0.92 (2)
N1—C9	1.4513 (17)	C19—H19B	0.93 (2)
C1—C2	1.3872 (19)	C17A—C18A	1.524 (4)
C1—C6	1.3910 (19)	C17A—H17A	0.95 (3)
C2—C3	1.391 (2)	C17A—H17B	0.98 (3)
C2—H2	0.9500	C18A—C20A	1.531 (7)
C3—C4	1.381 (2)	C18A—H18A	0.99 (3)
C3—H3	0.9500	C20A—C21A	1.528 (6)
C4—C5	1.403 (2)	C20A—C23A	1.537 (5)
C4—H4	0.9500	C20A—C22A	1.554 (7)
C5—C6	1.3828 (19)	C21A—H21A	0.9800
C5—H5	0.9500	C21A—H21B	0.9800
C6—C7	1.5228 (18)	C21A—H21C	0.9800
C7—C11	1.5378 (19)	C22A—H22A	0.9800
C7—C10	1.5389 (19)	C22A—H22B	0.9800
C7—C8	1.5392 (18)	C22A—H22C	0.9800
C8—C12	1.3684 (18)	C23A—H23A	0.9800
C9—H9A	0.9800	C23A—H23B	0.9800
C9—H9B	0.9800	C23A—H23C	0.9800
C9—H9C	0.9800	C17B—C18B	1.523 (7)
C10—H10A	0.9800	C17B—H17C	0.9900
C10—H10B	0.9800	C17B—H17D	0.9900
C10—H10C	0.9800	C18B—C20B	1.587 (14)
C11—H11A	0.9800	C18B—H18B	0.99 (5)
C11—H11B	0.9800	C20B—C23B	1.504 (11)
C11—H11C	0.9800	C20B—C22B	1.521 (11)
C12—C13	1.4204 (19)	C20B—C21B	1.527 (9)
C12—H12	0.9500	C21B—H21D	0.9800
C13—C14	1.3619 (18)	C21B—H21E	0.9800
C13—H13	0.9500	C21B—H21F	0.9800
C14—C15	1.472 (2)	C22B—H22D	0.9800
C14—C19	1.508 (2)	C22B—H22E	0.9800
C15—C16	1.5114 (19)	C22B—H22F	0.9800
C16—C17A	1.452 (3)	C23B—H23D	0.9800
C16—C17B	1.597 (5)	C23B—H23E	0.9800
C16—H16A	0.9900	C23B—H23F	0.9800
C16—H16B	0.9900

C8—N1—C1	111.58 (11)	H16A—C16—H16B	107.1
C8—N1—C9	125.35 (12)	C18B—C19—C14	122.8 (2)
C1—N1—C9	123.04 (11)	C14—C19—C18A	114.15 (14)
C2—C1—C6	122.14 (13)	C18B—C19—H19A	118.0 (13)
C2—C1—N1	128.51 (13)	C14—C19—H19A	111.5 (13)
C6—C1—N1	109.35 (11)	C18A—C19—H19A	104.6 (13)
C1—C2—C3	117.27 (14)	C18B—C19—H19B	78.9 (13)
C1—C2—H2	121.4	C14—C19—H19B	111.0 (13)
C3—C2—H2	121.4	C18A—C19—H19B	106.6 (13)
C4—C3—C2	121.39 (14)	H19A—C19—H19B	108.5 (18)
C4—C3—H3	119.3	C16—C17A—C18A	110.9 (2)
C2—C3—H3	119.3	C16—C17A—H17A	110.8 (17)
C3—C4—C5	120.74 (14)	C18A—C17A—H17A	111.0 (17)
C3—C4—H4	119.6	C16—C17A—H17B	106.3 (16)
C5—C4—H4	119.6	C18A—C17A—H17B	108.2 (17)
C6—C5—C4	118.31 (14)	H17A—C17A—H17B	109 (2)
C6—C5—H5	120.8	C17A—C18A—C20A	114.3 (3)
C4—C5—H5	120.8	C17A—C18A—C19	110.9 (2)
C5—C6—C1	120.13 (12)	C20A—C18A—C19	112.7 (3)
C5—C6—C7	130.43 (13)	C17A—C18A—H18A	105.7 (15)
C1—C6—C7	109.44 (11)	C20A—C18A—H18A	107.5 (15)
C6—C7—C11	110.89 (11)	C19—C18A—H18A	105.0 (15)
C6—C7—C10	110.13 (11)	C21A—C20A—C18A	111.6 (4)
C11—C7—C10	109.83 (12)	C21A—C20A—C23A	108.2 (3)
C6—C7—C8	101.24 (10)	C18A—C20A—C23A	113.2 (5)
C11—C7—C8	113.57 (11)	C21A—C20A—C22A	106.3 (5)
C10—C7—C8	110.91 (11)	C18A—C20A—C22A	109.9 (3)
C12—C8—N1	122.67 (13)	C23A—C20A—C22A	107.5 (4)
C12—C8—C7	128.96 (12)	C18B—C17B—C16	118.4 (4)
N1—C8—C7	108.32 (11)	C18B—C17B—H17A	111.2 (14)
N1—C9—H9A	109.5	C16—C17B—H18A	122.0 (12)
N1—C9—H9B	109.5	C16—C17B—H17C	107.7
H9A—C9—H9B	109.5	H18A—C17B—H17C	122.5
N1—C9—H9C	109.5	C18B—C17B—H17D	107.7
H9A—C9—H9C	109.5	C16—C17B—H17D	107.7
H9B—C9—H9C	109.5	H17A—C17B—H17D	121.5
C7—C10—H10A	109.5	H17C—C17B—H17D	107.1
C7—C10—H10B	109.5	C19—C18B—C17B	105.6 (4)
H10A—C10—H10B	109.5	C19—C18B—C20B	119.4 (5)
C7—C10—H10C	109.5	C17B—C18B—C20B	113.8 (5)
H10A—C10—H10C	109.5	C19—C18B—H18B	100 (3)
H10B—C10—H10C	109.5	C17B—C18B—H18B	106 (3)
C7—C11—H11A	109.5	C20B—C18B—H18B	110 (3)
C7—C11—H11B	109.5	C23B—C20B—C22B	110.5 (8)
H11A—C11—H11B	109.5	C23B—C20B—C21B	109.4 (7)
C7—C11—H11C	109.5	C22B—C20B—C21B	109.4 (8)
H11A—C11—H11C	109.5	C23B—C20B—C18B	109.2 (8)
H11B—C11—H11C	109.5	C22B—C20B—C18B	110.3 (7)
C8—C12—C13	126.21 (13)	C21B—C20B—C18B	107.9 (8)
C8—C12—H12	116.9	C20B—C21B—H21D	109.5
C13—C12—H12	116.9	C20B—C21B—H21E	109.5
C14—C13—C12	126.32 (14)	H21D—C21B—H21E	109.5
C14—C13—H13	116.8	C20B—C21B—H21F	109.5
C12—C13—H13	116.8	H21D—C21B—H21F	109.5
C13—C14—C15	116.93 (13)	H21E—C21B—H21F	109.5
C13—C14—C19	122.16 (13)	C20B—C22B—H22D	109.5
C15—C14—C19	120.91 (12)	C20B—C22B—H22E	109.5
O1—C15—C14	123.00 (13)	H22D—C22B—H22E	109.5
O1—C15—C16	118.98 (13)	C20B—C22B—H22F	109.5
C14—C15—C16	118.03 (13)	H22D—C22B—H22F	109.5
C17A—C16—C15	118.01 (16)	H22E—C22B—H22F	109.5
C15—C16—C17B	111.8 (2)	C20B—C23B—H23D	109.5
C17A—C16—H16A	107.8	C20B—C23B—H23E	109.5
C15—C16—H16A	107.8	H23D—C23B—H23E	109.5
C17B—C16—H16A	132.0	C20B—C23B—H23F	109.5
C17A—C16—H16B	107.8	H23D—C23B—H23F	109.5
C15—C16—H16B	107.8	H23E—C23B—H23F	109.5
C17B—C16—H16B	85.5

C8—N1—C1—C2	−176.44 (14)	C12—C13—C14—C19	−4.0 (2)
C9—N1—C1—C2	5.6 (2)	C13—C14—C15—O1	−1.7 (2)
C8—N1—C1—C6	2.69 (16)	C19—C14—C15—O1	178.83 (15)
C9—N1—C1—C6	−175.30 (13)	C13—C14—C15—C16	178.40 (13)
C6—C1—C2—C3	0.3 (2)	C19—C14—C15—C16	−1.1 (2)
N1—C1—C2—C3	179.35 (13)	O1—C15—C16—C17A	−161.6 (2)
C1—C2—C3—C4	1.0 (2)	C14—C15—C16—C17A	18.3 (3)
C2—C3—C4—C5	−0.7 (2)	O1—C15—C16—C17B	168.3 (3)
C3—C4—C5—C6	−0.8 (2)	C14—C15—C16—C17B	−11.7 (3)
C4—C5—C6—C1	2.0 (2)	C13—C14—C19—C18B	164.7 (3)
C4—C5—C6—C7	−177.19 (14)	C15—C14—C19—C18B	−15.8 (4)
C2—C1—C6—C5	−1.9 (2)	C13—C14—C19—C18A	−164.90 (17)
N1—C1—C6—C5	178.95 (12)	C15—C14—C19—C18A	14.5 (2)
C2—C1—C6—C7	177.53 (12)	C15—C16—C17A—C18A	−48.0 (3)
N1—C1—C6—C7	−1.67 (15)	C16—C17A—C18A—C20A	−171.4 (3)
C5—C6—C7—C11	−59.72 (19)	C16—C17A—C18A—C19	60.0 (3)
C1—C6—C7—C11	120.99 (13)	C14—C19—C18A—C17A	−43.3 (3)
C5—C6—C7—C10	62.06 (19)	C14—C19—C18A—C20A	−172.8 (3)
C1—C6—C7—C10	−117.23 (13)	C17A—C18A—C20A—C21A	−177.1 (3)
C5—C6—C7—C8	179.47 (14)	C19—C18A—C20A—C21A	−49.3 (4)
C1—C6—C7—C8	0.18 (14)	C17A—C18A—C20A—C23A	−54.8 (4)
C1—N1—C8—C12	175.08 (12)	C19—C18A—C20A—C23A	73.0 (4)
C9—N1—C8—C12	−7.0 (2)	C17A—C18A—C20A—C22A	65.3 (4)
C1—N1—C8—C7	−2.53 (15)	C19—C18A—C20A—C22A	−166.9 (3)
C9—N1—C8—C7	175.40 (12)	C15—C16—C17B—C18B	42.5 (6)
C6—C7—C8—C12	−176.03 (14)	C14—C19—C18B—C17B	41.3 (5)
C11—C7—C8—C12	65.07 (18)	C14—C19—C18B—C20B	171.0 (4)
C10—C7—C8—C12	−59.19 (18)	C16—C17B—C18B—C19	−55.4 (6)
C6—C7—C8—N1	1.39 (13)	C16—C17B—C18B—C20B	171.7 (5)
C11—C7—C8—N1	−117.52 (12)	C19—C18B—C20B—C23B	167.3 (5)
C10—C7—C8—N1	118.23 (12)	C17B—C18B—C20B—C23B	−66.8 (7)
N1—C8—C12—C13	174.55 (13)	C19—C18B—C20B—C22B	−71.0 (7)
C7—C8—C12—C13	−8.4 (2)	C17B—C18B—C20B—C22B	54.9 (8)
C8—C12—C13—C14	177.00 (14)	C19—C18B—C20B—C21B	48.5 (8)
C12—C13—C14—C15	176.56 (13)	C17B—C18B—C20B—C21B	174.4 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O1ⁱ	0.95	2.45	3.3293 (19)	154
C9—H9A···Cg1ⁱⁱ	0.98	2.65	3.5705 (17)	156

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x+2, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₂₃H₃₁NO
M_r	337.49
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	116
a, b, c (Å)	9.7327 (4), 17.2187 (6), 12.1303 (4)
β (°)	100.045 (2)
V (Å³)	2001.69 (13)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.62 × 0.49 × 0.25

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (Blessing, 1995)
T_min, T_max	0.668, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	44399, 4500, 3690
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.646

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.134, 1.05
No. of reflections	4500
No. of parameters	308
No. of restraints	5
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.21

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005) and SADABS (Sheldrick, 1995), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and Mercury (Macrae et al., 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O1ⁱ	0.95	2.45	3.3293 (19)	154
C9—H9A···Cg1ⁱⁱ	0.98	2.65	3.5705 (17)	156

Symmetry codes: (i) x+1/2, −y+3/2, z+1/2; (ii) −x+2, −y+1, −z+2.

Acknowledgements

The authors thank Dr J. Wikaira of the University of Canterbury for her assistance in the data collection.

References

Ainsworth, C. (1963). Org. Synth. Coll. 4, 536. Google Scholar
Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Bhuiyan, M. D. H., Ashraf, M., Teshomne, A., Gainsford, G. J., Kay, A. J., Asselberghs, I. & Clays, K. (2011). Dyes Pigm. 89, 177–187. CrossRef CAS Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Denk, W., Strickler, J. H. & Webb, W. W. (1990). Science, 248, 73–76. CrossRef CAS PubMed Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Higham, L. T., Scott, J. L. & Strauss, C. R. (2010). Cryst. Growth Des. 10, 2409–2420. CrossRef CAS Google Scholar
Kawamata, J., Inoue, K. & Inabe, T. (1998). Bull. Chem. Soc. Jpn, 71, 2777–2786. Web of Science CrossRef CAS Google Scholar
Ma, H., Jen, A. K.-Y. & Dalton, L. R. (2002). Adv. Mater. 14, 1339–1365. Web of Science CrossRef CAS Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CrossRef CAS IUCr Journals Google Scholar
Parthenopoulos, D. A. & Rentzepis, P. M. (1989). Science, 245, 843–845. CrossRef PubMed CAS Web of Science Google Scholar
Sheldrick, G. M. (1995). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Teshome, A., Bhuiyan, M. D. H., Gainsford, G. J., Ashraf, M., Asselberghs, I., Williams, G. V. M., Kay, A. J. & Clays, K. (2011). Opt. Mater. 33, 336–345. CrossRef CAS Google Scholar

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.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1210

doi:10.1107/S1600536811014590

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

4-tert-Butyl-2-[2-(1,3,3-tri­methyl­indolin-2-yl­­idene)ethyl­­idene]cyclo­hexa­none

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

4-tert-Butyl-2-[2-(1,3,3-trimethylindolin-2-ylidene)ethylidene]cyclohexanone