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The title compound, C21H19N3, first synthesized by Lemke [Chem. Ber. (1970), 103, 1894–1898], due to its solvatochromic behaviour is supposed to be a good candidate for non-linear optical (NLO) and electrooptical applications. The mol­ecule is nearly planar, with the exception of the C(CH3)2 group; the disubstituted C atom is displaced by 0.627 (2) Å from the mean plane of the remaining atoms of the cyclo­hexene ring. The hydrogen bond formed by the indolyl NH group with the N atom of one of the cyano groups [N...N 3.168 (3) Å and N—H...N 148°], links the mol­ecules into infinite chains stretching along the [10\overline 1] direction of the crystal. The existence of this hydrogen bond was also confirmed by FT–IR spectral data [νN—H = 3388 cm−1 in the solid state (KBr pellet)].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801011291/ya6043sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801011291/ya6043Isup2.hkl
Contains datablock I

CCDC reference: 170919

Key indicators

  • Single-crystal X-ray study
  • T = 291 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.052
  • wR factor = 0.130
  • Data-to-parameter ratio = 18.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
ABSMU_01 Alert C The ratio of given/expected absorption coefficient lies outside the range 0.99 <> 1.01 Calculated value of mu = 0.072 Value of mu given = 0.070 PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(7) - C(8) = 1.43 Ang. PLAT_371 Alert C Long C(sp2)-C(sp1) Bond C(7) - C(9) = 1.43 Ang. PLAT_601 Alert C Structure Contains Solvent Accessible VOIDS of 37.00 A   3
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
4 Alert Level C = Please check

Comment top

No comment.

Experimental top

The title compound was synthesized according to the general procedure described by Lemke (1970). The preparation of the starting compound, [3,5,5-trimethyl(cyclohex-2-enylidene)]malonodinitrile, C12H14N2, is described in one of our previous papers (Kolev et al., 2001). The starting compound (6 mmol, 20% excess) was dissolved in 80 ml of dry toluene under continuous stirring. Indole-3-aldehyde (5 mmol Across), dissolved in 50 ml of dry toluene, was added to the solution. Nearly 1 ml of triethylamine was used as a catalyst. The solution became dark-red after a few minutes and the resulting compound started precipitating. After 16 h reaction time, the solution was cooled and the resulting title compound was isolated and recrystallized twice from glacial acetic acid and from dry toluene [m.p. 519–521 K; literature m.p. 520–522 K (Lemke, 1970)]. The purity of the compound was confirmed by elemental analysis, IR, UV-vis and mass spectrometry. Crystals were grown from a glacial acetic acid solution by slow evaporation at room temperature over a period of several weeks.

Refinement top

H atoms were placed in calculated positions with Uiso constrained to be 1.5Ueq of the carrier atom for the methyl H atoms and 1.2Ueq for the remaining H atoms.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO and SCALEPACK; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus (Sheldrick, 1991); software used to prepare material for publication: SHELXL97, PARST95 (Nardelli, 1995) PLATON (Spek, 2001).

Figures top
[Figure 1] Fig. 1. View of the title compound showing the labelling of all non-H atoms. Displacement ellipsoids are shown at 50% probability levels. H atoms are drawn as circles of arbitrary radii.
(I) top
Crystal data top
C21H19N3F(000) = 664
Mr = 313.39Dx = 1.195 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 15.5033 (3) ÅCell parameters from 15212 reflections
b = 7.5309 (2) Åθ = 3.0–27.5°
c = 15.9609 (4) ŵ = 0.07 mm1
β = 110.774 (1)°T = 291 K
V = 1742.34 (7) Å3Plate, red
Z = 40.40 × 0.30 × 0.05 mm
Data collection top
Nonius KappaCCD
diffractometer
1785 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.027
Graphite monochromatorθmax = 27.5°, θmin = 3.0°
Detector resolution: 10 vertical, 18 horizontal pixels mm-1h = 2020
292 frames via ω–rotation (Δω=1°) with 3 sets at different κ–angles and two times 20 s per frame scansk = 99
3946 measured reflectionsl = 2018
3946 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)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130H-atom parameters constrained
S = 0.92 w = 1/[σ2(Fo2) + (0.0595P)2]
where P = (Fo2 + 2Fc2)/3
3946 reflections(Δ/σ)max < 0.001
219 parametersΔρmax = 0.13 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C21H19N3V = 1742.34 (7) Å3
Mr = 313.39Z = 4
Monoclinic, P21/nMo Kα radiation
a = 15.5033 (3) ŵ = 0.07 mm1
b = 7.5309 (2) ÅT = 291 K
c = 15.9609 (4) Å0.40 × 0.30 × 0.05 mm
β = 110.774 (1)°
Data collection top
Nonius KappaCCD
diffractometer
1785 reflections with I > 2σ(I)
3946 measured reflectionsRint = 0.027
3946 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0520 restraints
wR(F2) = 0.130H-atom parameters constrained
S = 0.92Δρmax = 0.13 e Å3
3946 reflectionsΔρmin = 0.18 e Å3
219 parameters
Special details top

Experimental. The data collection covered the whole sphere of reciprocal space. The crystal-to-detector distance was 34 mm. Crystal decay was monitored by repeating the initial frames at the end of data collection and analysing the duplicate reflections.

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
xyzUiso*/Ueq
N10.77182 (14)0.7498 (3)0.33635 (14)0.1010 (7)
N20.92484 (13)0.2631 (3)0.36515 (14)0.0878 (6)
N31.31308 (10)0.3652 (2)0.01387 (11)0.0607 (5)
H31.34790.37710.04520.073*
C11.03138 (11)0.5987 (2)0.14831 (11)0.0422 (4)
C20.98908 (11)0.5345 (2)0.20362 (11)0.0454 (5)
H21.00380.42030.22640.054*
C30.92340 (11)0.6330 (2)0.22840 (12)0.0446 (5)
C40.89425 (11)0.8097 (2)0.18518 (12)0.0478 (5)
H4A0.87390.88310.22450.057*
H4B0.84210.79310.12990.057*
C50.97066 (11)0.9071 (2)0.16431 (11)0.0433 (5)
C61.00848 (12)0.7823 (2)0.10977 (12)0.0476 (5)
H6A0.96320.77280.04960.057*
H6B1.06370.83490.10510.057*
C70.88658 (12)0.5679 (2)0.28792 (13)0.0513 (5)
C80.82267 (15)0.6688 (3)0.31439 (14)0.0672 (6)
C90.90860 (13)0.3979 (3)0.32954 (14)0.0608 (6)
C100.93022 (13)1.0729 (2)0.10920 (13)0.0588 (5)
H10A0.88231.03890.05440.088*
H10B0.97791.13450.09570.088*
H10C0.90511.14940.14290.088*
C111.04724 (12)0.9601 (2)0.25218 (13)0.0590 (5)
H11A1.02211.03610.28610.088*
H11B1.09501.02200.23900.088*
H11C1.07250.85540.28640.088*
C121.09727 (11)0.4906 (2)0.12729 (11)0.0467 (5)
H121.10900.37900.15380.056*
C131.14364 (11)0.5335 (2)0.07342 (11)0.0485 (5)
H131.13120.64530.04710.058*
C141.21002 (11)0.4295 (2)0.05107 (12)0.0460 (5)
C151.24434 (11)0.2509 (2)0.07679 (11)0.0444 (5)
C161.22783 (12)0.1170 (3)0.12974 (12)0.0535 (5)
H161.18690.13600.15960.064*
C171.27243 (13)0.0424 (3)0.13735 (13)0.0637 (6)
H171.26060.13180.17200.076*
C181.33486 (14)0.0740 (3)0.09456 (14)0.0692 (6)
H181.36400.18370.10090.083*
C191.35395 (13)0.0548 (3)0.04322 (14)0.0650 (6)
H191.39630.03510.01510.078*
C201.30800 (12)0.2156 (3)0.03455 (12)0.0510 (5)
C211.25459 (12)0.4895 (3)0.00406 (12)0.0569 (5)
H211.24570.60080.03100.068*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.1147 (17)0.1093 (17)0.1101 (17)0.0341 (13)0.0783 (15)0.0100 (13)
N20.1057 (15)0.0763 (15)0.1108 (17)0.0105 (12)0.0747 (14)0.0251 (12)
N30.0642 (10)0.0671 (12)0.0694 (12)0.0082 (9)0.0467 (9)0.0109 (10)
C10.0467 (10)0.0404 (11)0.0433 (11)0.0001 (9)0.0208 (9)0.0008 (9)
C20.0530 (11)0.0398 (11)0.0506 (13)0.0008 (9)0.0272 (10)0.0008 (9)
C30.0455 (10)0.0441 (11)0.0476 (12)0.0033 (9)0.0207 (9)0.0032 (9)
C40.0500 (10)0.0462 (11)0.0522 (12)0.0031 (9)0.0242 (9)0.0003 (9)
C50.0483 (10)0.0384 (10)0.0467 (12)0.0016 (8)0.0211 (9)0.0001 (9)
C60.0535 (11)0.0469 (11)0.0478 (12)0.0003 (9)0.0246 (9)0.0000 (9)
C70.0555 (11)0.0500 (12)0.0610 (13)0.0014 (10)0.0363 (11)0.0006 (10)
C80.0755 (14)0.0720 (15)0.0717 (16)0.0094 (12)0.0479 (13)0.0080 (12)
C90.0675 (13)0.0628 (15)0.0723 (15)0.0005 (11)0.0495 (12)0.0060 (13)
C100.0698 (12)0.0455 (12)0.0654 (14)0.0057 (10)0.0293 (11)0.0042 (10)
C110.0638 (12)0.0567 (13)0.0577 (14)0.0048 (10)0.0232 (11)0.0073 (10)
C120.0545 (11)0.0420 (11)0.0499 (12)0.0041 (9)0.0264 (10)0.0001 (9)
C130.0584 (11)0.0463 (12)0.0486 (12)0.0002 (9)0.0285 (10)0.0013 (9)
C140.0497 (10)0.0471 (12)0.0494 (12)0.0056 (9)0.0275 (9)0.0045 (9)
C150.0421 (10)0.0498 (12)0.0436 (12)0.0041 (9)0.0181 (9)0.0072 (9)
C160.0523 (11)0.0565 (13)0.0545 (13)0.0003 (10)0.0223 (10)0.0000 (10)
C170.0651 (13)0.0589 (14)0.0625 (15)0.0031 (11)0.0172 (11)0.0058 (11)
C180.0653 (14)0.0623 (15)0.0700 (16)0.0147 (11)0.0115 (12)0.0073 (12)
C190.0533 (12)0.0767 (16)0.0665 (15)0.0080 (12)0.0234 (11)0.0165 (12)
C200.0471 (10)0.0578 (13)0.0514 (13)0.0052 (10)0.0216 (10)0.0109 (10)
C210.0688 (13)0.0521 (12)0.0621 (14)0.0065 (11)0.0384 (11)0.0059 (10)
Geometric parameters (Å, º) top
N1—C81.146 (2)C10—H10B0.9600
N2—C91.147 (2)C10—H10C0.9600
N3—C211.350 (2)C11—H11A0.9600
N3—C201.384 (2)C11—H11B0.9600
N3—H30.8600C11—H11C0.9600
C1—C21.362 (2)C12—C131.341 (2)
C1—C121.436 (2)C12—H120.9300
C1—C61.504 (2)C13—C141.436 (2)
C2—C31.425 (2)C13—H130.9300
C2—H20.9300C14—C211.374 (2)
C3—C71.361 (2)C14—C151.451 (2)
C3—C41.493 (2)C15—C161.397 (2)
C4—C51.527 (2)C15—C201.404 (2)
C4—H4A0.9700C16—C171.370 (3)
C4—H4B0.9700C16—H160.9300
C5—C101.528 (2)C17—C181.389 (3)
C5—C61.532 (2)C17—H170.9300
C5—C111.535 (2)C18—C191.368 (3)
C6—H6A0.9700C18—H180.9300
C6—H6B0.9700C19—C201.387 (3)
C7—C81.426 (3)C19—H190.9300
C7—C91.427 (3)C21—H210.9300
C10—H10A0.9600
C21—N3—C20109.03 (15)H10A—C10—H10C109.5
C21—N3—H3125.5H10B—C10—H10C109.5
C20—N3—H3125.5C5—C11—H11A109.5
C2—C1—C12119.74 (16)C5—C11—H11B109.5
C2—C1—C6119.60 (15)H11A—C11—H11B109.5
C12—C1—C6120.66 (15)C5—C11—H11C109.5
C1—C2—C3123.42 (17)H11A—C11—H11C109.5
C1—C2—H2118.3H11B—C11—H11C109.5
C3—C2—H2118.3C13—C12—C1126.93 (17)
C7—C3—C2121.61 (17)C13—C12—H12116.5
C7—C3—C4120.68 (15)C1—C12—H12116.5
C2—C3—C4117.70 (15)C12—C13—C14128.49 (18)
C3—C4—C5113.43 (14)C12—C13—H13115.8
C3—C4—H4A108.9C14—C13—H13115.8
C5—C4—H4A108.9C21—C14—C13123.19 (18)
C3—C4—H4B108.9C21—C14—C15105.60 (15)
C5—C4—H4B108.9C13—C14—C15131.22 (16)
H4A—C4—H4B107.7C16—C15—C20117.69 (17)
C4—C5—C10109.05 (14)C16—C15—C14135.48 (16)
C4—C5—C6108.20 (14)C20—C15—C14106.83 (16)
C10—C5—C6109.61 (14)C17—C16—C15119.46 (18)
C4—C5—C11109.53 (14)C17—C16—H16120.3
C10—C5—C11109.86 (14)C15—C16—H16120.3
C6—C5—C11110.56 (13)C16—C17—C18121.6 (2)
C1—C6—C5114.44 (14)C16—C17—H17119.2
C1—C6—H6A108.6C18—C17—H17119.2
C5—C6—H6A108.6C19—C18—C17120.66 (19)
C1—C6—H6B108.6C19—C18—H18119.7
C5—C6—H6B108.6C17—C18—H18119.7
H6A—C6—H6B107.6C18—C19—C20117.79 (19)
C3—C7—C8121.46 (18)C18—C19—H19121.1
C3—C7—C9123.89 (16)C20—C19—H19121.1
C8—C7—C9114.64 (16)N3—C20—C19129.62 (18)
N1—C8—C7179.5 (2)N3—C20—C15107.62 (16)
N2—C9—C7177.5 (2)C19—C20—C15122.76 (19)
C5—C10—H10A109.5N3—C21—C14110.92 (18)
C5—C10—H10B109.5N3—C21—H21124.5
H10A—C10—H10B109.5C14—C21—H21124.5
C5—C10—H10C109.5
C12—C1—C2—C3179.59 (15)C12—C13—C14—C151.9 (3)
C6—C1—C2—C30.5 (3)C21—C14—C15—C16179.28 (19)
C1—C2—C3—C7176.18 (16)C13—C14—C15—C160.2 (3)
C1—C2—C3—C45.2 (3)C21—C14—C15—C200.09 (19)
C7—C3—C4—C5148.38 (16)C13—C14—C15—C20179.40 (18)
C2—C3—C4—C533.0 (2)C20—C15—C16—C171.0 (3)
C3—C4—C5—C10172.35 (15)C14—C15—C16—C17178.10 (19)
C3—C4—C5—C653.19 (19)C15—C16—C17—C180.9 (3)
C3—C4—C5—C1167.40 (19)C16—C17—C18—C190.1 (3)
C2—C1—C6—C523.8 (2)C17—C18—C19—C200.9 (3)
C12—C1—C6—C5156.27 (15)C21—N3—C20—C19178.82 (19)
C4—C5—C6—C148.67 (19)C21—N3—C20—C150.8 (2)
C10—C5—C6—C1167.48 (14)C18—C19—C20—N3178.82 (18)
C11—C5—C6—C171.28 (18)C18—C19—C20—C150.7 (3)
C2—C3—C7—C8178.32 (17)C16—C15—C20—N3179.87 (15)
C4—C3—C7—C83.1 (3)C14—C15—C20—N30.51 (19)
C2—C3—C7—C90.8 (3)C16—C15—C20—C190.2 (3)
C4—C3—C7—C9177.77 (18)C14—C15—C20—C19179.11 (17)
C2—C1—C12—C13179.10 (17)C20—N3—C21—C140.7 (2)
C6—C1—C12—C130.8 (3)C13—C14—C21—N3179.92 (15)
C1—C12—C13—C14179.81 (16)C15—C14—C21—N30.4 (2)
C12—C13—C14—C21178.73 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···N2i0.862.413.168 (3)148
C21—H21···N1ii0.932.553.301 (3)138
Symmetry codes: (i) x+1/2, y+1/2, z1/2; (ii) x+1/2, y+3/2, z1/2.

Experimental details

Crystal data
Chemical formulaC21H19N3
Mr313.39
Crystal system, space groupMonoclinic, P21/n
Temperature (K)291
a, b, c (Å)15.5033 (3), 7.5309 (2), 15.9609 (4)
β (°) 110.774 (1)
V3)1742.34 (7)
Z4
Radiation typeMo Kα
µ (mm1)0.07
Crystal size (mm)0.40 × 0.30 × 0.05
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
3946, 3946, 1785
Rint0.027
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.052, 0.130, 0.92
No. of reflections3946
No. of parameters219
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.13, 0.18

Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus (Sheldrick, 1991), SHELXL97, PARST95 (Nardelli, 1995) PLATON (Spek, 2001).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N3—H3···N2i0.862.413.168 (3)148
C21—H21···N1ii0.932.553.301 (3)138
Symmetry codes: (i) x+1/2, y+1/2, z1/2; (ii) x+1/2, y+3/2, z1/2.
 

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