Triclinic form of 2-{5,5-di­methyl-3-[2-(2,4,6-tri­methoxy­phenyl)­vinyl]­cyclo­hex-2-enyl­idene}malono­nitrile

On slow evaporation of an ethyl­acetate solution, the title compound, C₂₂H₂₄N₂O₃, (I), crystallizes in two crystalline forms differing in colour, size and shape. For the structural data on the monoclinic violet form, as well as comment on the differences between the two structures and the details of preparation, see Kolev et al. [Acta Cryst. (2001). E57, o964-o965]. This paper reports the structural results of the red triclinic modification.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.053
• wR factor = 0.118
• Data-to-parameter ratio = 17.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 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 =     0.083
          Value of mu given      =     0.080

PLAT_371  Alert C Long   C(sp2)-C(sp1) Bond  C(7)   -   C(8)   =       1.44 Ang.

PLAT_371  Alert C Long   C(sp2)-C(sp1) Bond  C(7)   -   C(9)   =       1.43 Ang.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 3 Alert Level C = Please check

---

S1. Comment

No Comment

S2. Experimental

The preparation of the title compound is described in Kolev et al. (2001).

S3. Refinement

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

Computing details

Data collection: COLLECT (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; 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 (Sheldrick, 1997), PARST95 (Nardelli, 1995) and PLATON (Spek, 2001).

Figures

Fig. 1. View of the title compound showing the labelling of all non-H atoms. Displacement ellipsoids are shown at 50% probability level. H atoms are drawn as circles of arbitrary radii.

(I)

Crystal data

C22H24N2O3	Z = 2
Mr = 364.43	F(000) = 388
Triclinic, P1	Dx = 1.235 Mg m^−3
a = 7.5983 (3) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.4757 (4) Å	Cell parameters from 8836 reflections
c = 11.5774 (4) Å	θ = 3.4–27.4°
α = 84.8457 (15)°	µ = 0.08 mm^−1
β = 82.2149 (16)°	T = 291 K
γ = 79.0257 (17)°	Block, red
V = 979.77 (6) Å^3	0.25 × 0.23 × 0.23 mm

Data collection

Nonius KappaCCD diffractometer	1655 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.028
Graphite monochromator	θmax = 27.4°, θmin = 3.4°
Detector resolution: 10 vertical, 18 horizontal pixels mm^-1	h = −9→9
303 frames via ω–rotation (Δω=1°) with 3 sets at different κ–angles and two times 30 s per frame scans	k = −14→14
8836 measured reflections	l = −14→15
4334 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.118	H-atom parameters constrained
S = 0.90	w = 1/[σ^2(Fo^2) + (0.0358P)^2] where P = (Fo^2 + 2Fc^2)/3
4334 reflections	(Δ/σ)max < 0.001
249 parameters	Δρmax = 0.13 e Å^−3
0 restraints	Δρmin = −0.15 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	−0.74169 (19)	−0.08122 (12)	−0.28665 (12)	0.0609 (4)
O2	−0.8013 (2)	0.24708 (15)	−0.55906 (14)	0.0847 (6)
O3	−0.3033 (2)	0.16507 (13)	−0.32776 (13)	0.0679 (5)
N1	−0.2419 (3)	−0.54406 (19)	0.3472 (2)	0.0922 (8)
N2	−0.6795 (3)	−0.49470 (17)	0.13631 (18)	0.0741 (6)
C1	−0.3629 (3)	−0.17593 (16)	−0.04722 (17)	0.0428 (5)
C2	−0.4176 (3)	−0.27016 (16)	0.01834 (17)	0.0457 (6)
H2	−0.5197	−0.2954	0.0008	0.055*
C3	−0.3285 (3)	−0.33195 (17)	0.11146 (17)	0.0422 (5)
C4	−0.1674 (3)	−0.28993 (17)	0.14223 (17)	0.0477 (6)
H4A	−0.0859	−0.3574	0.1734	0.057*
H4B	−0.2063	−0.2344	0.2030	0.057*
C5	−0.0651 (3)	−0.22925 (17)	0.03806 (18)	0.0447 (5)
C6	−0.2004 (3)	−0.13312 (16)	−0.01925 (17)	0.0484 (6)
H6A	−0.2400	−0.0688	0.0326	0.058*
H6B	−0.1398	−0.1011	−0.0909	0.058*
C7	−0.3895 (3)	−0.42658 (18)	0.17406 (17)	0.0465 (6)
C8	−0.3043 (3)	−0.49138 (19)	0.2702 (2)	0.0583 (6)
C9	−0.5491 (3)	−0.46511 (19)	0.15193 (19)	0.0541 (6)
C10	0.0280 (3)	−0.32090 (18)	−0.04900 (18)	0.0594 (6)
H10A	0.1012	−0.2837	−0.1102	0.089*
H10B	−0.0616	−0.3518	−0.0820	0.089*
H10C	0.1029	−0.3848	−0.0095	0.089*
C11	0.0758 (3)	−0.17123 (19)	0.0819 (2)	0.0636 (7)
H11A	0.1394	−0.1321	0.0171	0.095*
H11B	0.1598	−0.2311	0.1194	0.095*
H11C	0.0170	−0.1140	0.1368	0.095*
C12	−0.4641 (3)	−0.11889 (17)	−0.14026 (17)	0.0492 (6)
H12	−0.5619	−0.1514	−0.1541	0.059*
C13	−0.4290 (3)	−0.02245 (17)	−0.20889 (17)	0.0487 (6)
H13	−0.3286	0.0065	−0.1939	0.058*
C14	−0.5230 (3)	0.04287 (17)	−0.30199 (17)	0.0440 (5)
C15	−0.6795 (3)	0.01705 (17)	−0.34007 (17)	0.0475 (6)
C16	−0.7677 (3)	0.08601 (19)	−0.42457 (18)	0.0573 (6)
H16	−0.8717	0.0670	−0.4464	0.069*
C17	−0.7012 (3)	0.1842 (2)	−0.47721 (18)	0.0593 (6)
C18	−0.5456 (3)	0.21331 (18)	−0.44710 (18)	0.0558 (6)
H18	−0.5001	0.2787	−0.4839	0.067*
C19	−0.4591 (3)	0.14241 (18)	−0.36065 (17)	0.0491 (6)
C20	−0.8898 (3)	−0.1165 (2)	−0.3313 (2)	0.0723 (7)
H20A	−0.9971	−0.0580	−0.3153	0.109*
H20B	−0.9091	−0.1920	−0.2943	0.109*
H20C	−0.8623	−0.1229	−0.4142	0.109*
C21	−0.7421 (4)	0.3488 (2)	−0.6206 (2)	0.1027 (10)
H21A	−0.7395	0.4066	−0.5662	0.154*
H21B	−0.8238	0.3826	−0.6762	0.154*
H21C	−0.6231	0.3254	−0.6608	0.154*
C22	−0.2380 (3)	0.27014 (19)	−0.37544 (19)	0.0646 (7)
H22A	−0.2101	0.2671	−0.4586	0.097*
H22B	−0.1311	0.2753	−0.3420	0.097*
H22C	−0.3290	0.3387	−0.3578	0.097*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0653 (10)	0.0610 (10)	0.0601 (10)	−0.0203 (8)	−0.0208 (8)	0.0153 (8)
O2	0.0824 (12)	0.0934 (12)	0.0798 (12)	−0.0254 (10)	−0.0364 (10)	0.0470 (10)
O3	0.0627 (10)	0.0669 (11)	0.0774 (11)	−0.0259 (9)	−0.0218 (9)	0.0279 (8)
N1	0.1013 (18)	0.0922 (17)	0.0789 (16)	−0.0136 (14)	−0.0302 (13)	0.0375 (13)
N2	0.0756 (15)	0.0687 (14)	0.0825 (16)	−0.0277 (13)	−0.0195 (12)	0.0177 (11)
C1	0.0403 (13)	0.0374 (12)	0.0482 (14)	−0.0035 (10)	−0.0057 (10)	0.0032 (10)
C2	0.0407 (12)	0.0441 (13)	0.0525 (14)	−0.0083 (11)	−0.0123 (10)	0.0077 (11)
C3	0.0410 (13)	0.0394 (13)	0.0433 (13)	−0.0029 (11)	−0.0048 (10)	0.0026 (10)
C4	0.0475 (13)	0.0469 (13)	0.0475 (14)	−0.0058 (11)	−0.0103 (10)	0.0048 (10)
C5	0.0420 (12)	0.0426 (13)	0.0491 (14)	−0.0069 (11)	−0.0102 (10)	0.0045 (11)
C6	0.0476 (13)	0.0429 (13)	0.0522 (14)	−0.0061 (11)	−0.0058 (11)	0.0049 (10)
C7	0.0481 (14)	0.0435 (13)	0.0456 (14)	−0.0073 (11)	−0.0057 (11)	0.0067 (11)
C8	0.0640 (16)	0.0529 (15)	0.0553 (16)	−0.0116 (13)	−0.0062 (13)	0.0117 (12)
C9	0.0630 (17)	0.0448 (14)	0.0518 (15)	−0.0117 (14)	−0.0068 (13)	0.0146 (11)
C10	0.0519 (14)	0.0618 (15)	0.0583 (15)	0.0023 (12)	−0.0078 (11)	0.0042 (12)
C11	0.0547 (15)	0.0636 (16)	0.0747 (17)	−0.0155 (13)	−0.0174 (12)	0.0084 (12)
C12	0.0469 (13)	0.0472 (14)	0.0520 (15)	−0.0068 (11)	−0.0105 (11)	0.0083 (11)
C13	0.0453 (13)	0.0494 (14)	0.0481 (14)	−0.0037 (11)	−0.0074 (10)	0.0073 (11)
C14	0.0455 (13)	0.0418 (13)	0.0417 (13)	−0.0029 (11)	−0.0067 (11)	0.0051 (10)
C15	0.0532 (14)	0.0430 (14)	0.0436 (14)	−0.0089 (12)	−0.0031 (11)	0.0075 (11)
C16	0.0582 (15)	0.0619 (15)	0.0521 (15)	−0.0131 (13)	−0.0170 (12)	0.0152 (12)
C17	0.0612 (16)	0.0659 (17)	0.0460 (15)	−0.0013 (14)	−0.0162 (12)	0.0155 (12)
C18	0.0582 (15)	0.0558 (15)	0.0499 (14)	−0.0106 (13)	−0.0066 (12)	0.0158 (11)
C19	0.0477 (14)	0.0503 (14)	0.0458 (14)	−0.0051 (12)	−0.0051 (11)	0.0064 (11)
C20	0.0826 (18)	0.0746 (17)	0.0691 (17)	−0.0334 (15)	−0.0242 (14)	0.0087 (13)
C21	0.109 (2)	0.099 (2)	0.101 (2)	−0.0326 (19)	−0.0406 (17)	0.0647 (18)
C22	0.0667 (16)	0.0614 (16)	0.0664 (17)	−0.0221 (13)	−0.0029 (12)	0.0067 (12)

Geometric parameters (Å, º)

O1—C15	1.369 (2)	C10—H10B	0.960
O1—C20	1.438 (2)	C10—H10C	0.960
O2—C17	1.364 (2)	C11—H11A	0.960
O2—C21	1.426 (2)	C11—H11B	0.960
O3—C19	1.368 (2)	C11—H11C	0.960
O3—C22	1.428 (2)	C12—C13	1.351 (2)
N1—C8	1.137 (2)	C12—H12	0.930
N2—C9	1.147 (3)	C13—C14	1.447 (2)
C1—C2	1.363 (2)	C13—H13	0.930
C1—C12	1.444 (3)	C14—C19	1.408 (2)
C1—C6	1.496 (2)	C14—C15	1.413 (3)
C2—C3	1.415 (2)	C15—C16	1.367 (2)
C2—H2	0.9300	C16—C17	1.381 (3)
C3—C7	1.371 (2)	C16—H16	0.930
C3—C4	1.494 (3)	C17—C18	1.383 (3)
C4—C5	1.531 (3)	C18—C19	1.387 (3)
C4—H4A	0.9700	C18—H18	0.930
C4—H4B	0.9700	C20—H20A	0.960
C5—C11	1.526 (2)	C20—H20B	0.960
C5—C6	1.528 (2)	C20—H20C	0.960
C5—C10	1.529 (3)	C21—H21A	0.960
C6—H6A	0.9700	C21—H21B	0.960
C6—H6B	0.9700	C21—H21C	0.960
C7—C9	1.428 (3)	C22—H22A	0.960
C7—C8	1.441 (3)	C22—H22B	0.960
C10—H10A	0.960	C22—H22C	0.960
C15—O1—C20	117.67 (16)	H11A—C11—H11C	109.5
C17—O2—C21	118.81 (19)	H11B—C11—H11C	109.5
C19—O3—C22	119.17 (16)	C13—C12—C1	125.62 (19)
C2—C1—C12	119.46 (18)	C13—C12—H12	117.2
C2—C1—C6	118.78 (17)	C1—C12—H12	117.2
C12—C1—C6	121.75 (16)	C12—C13—C14	130.2 (2)
C1—C2—C3	123.91 (19)	C12—C13—H13	114.9
C1—C2—H2	118.0	C14—C13—H13	114.9
C3—C2—H2	118.0	C19—C14—C15	115.25 (18)
C7—C3—C2	121.28 (19)	C19—C14—C13	119.21 (19)
C7—C3—C4	120.35 (18)	C15—C14—C13	125.53 (18)
C2—C3—C4	118.36 (17)	C16—C15—O1	120.8 (2)
C3—C4—C5	113.13 (16)	C16—C15—C14	122.74 (19)
C3—C4—H4A	109.0	O1—C15—C14	116.45 (17)
C5—C4—H4A	109.0	C15—C16—C17	119.4 (2)
C3—C4—H4B	109.0	C15—C16—H16	120.3
C5—C4—H4B	109.0	C17—C16—H16	120.3
H4A—C4—H4B	107.8	O2—C17—C16	114.3 (2)
C11—C5—C6	109.17 (16)	O2—C17—C18	124.5 (2)
C11—C5—C10	109.66 (17)	C16—C17—C18	121.2 (2)
C6—C5—C10	110.68 (17)	C17—C18—C19	118.3 (2)
C11—C5—C4	109.04 (17)	C17—C18—H18	120.9
C6—C5—C4	108.26 (16)	C19—C18—H18	120.9
C10—C5—C4	110.00 (16)	O3—C19—C18	121.32 (19)
C1—C6—C5	114.07 (15)	O3—C19—C14	115.64 (17)
C1—C6—H6A	108.7	C18—C19—C14	123.0 (2)
C5—C6—H6A	108.7	O1—C20—H20A	109.5
C1—C6—H6B	108.7	O1—C20—H20B	109.5
C5—C6—H6B	108.7	H20A—C20—H20B	109.5
H6A—C6—H6B	107.6	O1—C20—H20C	109.5
C3—C7—C9	122.09 (18)	H20A—C20—H20C	109.5
C3—C7—C8	123.23 (19)	H20B—C20—H20C	109.5
C9—C7—C8	114.62 (18)	O2—C21—H21A	109.5
N1—C8—C7	177.8 (2)	O2—C21—H21B	109.5
N2—C9—C7	178.4 (2)	H21A—C21—H21B	109.5
C5—C10—H10A	109.5	O2—C21—H21C	109.5
C5—C10—H10B	109.5	H21A—C21—H21C	109.5
H10A—C10—H10B	109.5	H21B—C21—H21C	109.5
C5—C10—H10C	109.5	O3—C22—H22A	109.5
H10A—C10—H10C	109.5	O3—C22—H22B	109.5
H10B—C10—H10C	109.5	H22A—C22—H22B	109.5
C5—C11—H11A	109.5	O3—C22—H22C	109.5
C5—C11—H11B	109.5	H22A—C22—H22C	109.5
H11A—C11—H11B	109.5	H22B—C22—H22C	109.5
C5—C11—H11C	109.5
C12—C1—C2—C3	−179.83 (19)	C20—O1—C15—C16	6.7 (3)
C6—C1—C2—C3	−0.8 (3)	C20—O1—C15—C14	−174.00 (18)
C1—C2—C3—C7	−179.71 (19)	C19—C14—C15—C16	−2.5 (3)
C1—C2—C3—C4	1.7 (3)	C13—C14—C15—C16	176.5 (2)
C7—C3—C4—C5	152.78 (19)	C19—C14—C15—O1	178.29 (17)
C2—C3—C4—C5	−28.6 (3)	C13—C14—C15—O1	−2.8 (3)
C3—C4—C5—C11	170.40 (16)	O1—C15—C16—C17	−179.68 (18)
C3—C4—C5—C6	51.7 (2)	C14—C15—C16—C17	1.1 (3)
C3—C4—C5—C10	−69.3 (2)	C21—O2—C17—C16	−178.6 (2)
C2—C1—C6—C5	27.2 (3)	C21—O2—C17—C18	1.3 (4)
C12—C1—C6—C5	−153.78 (18)	C15—C16—C17—O2	−179.2 (2)
C11—C5—C6—C1	−169.97 (17)	C15—C16—C17—C18	0.8 (3)
C10—C5—C6—C1	69.2 (2)	O2—C17—C18—C19	178.9 (2)
C4—C5—C6—C1	−51.4 (2)	C16—C17—C18—C19	−1.2 (3)
C2—C3—C7—C9	−2.4 (3)	C22—O3—C19—C18	6.0 (3)
C4—C3—C7—C9	176.24 (19)	C22—O3—C19—C14	−174.54 (18)
C2—C3—C7—C8	−179.4 (2)	C17—C18—C19—O3	179.05 (19)
C4—C3—C7—C8	−0.7 (3)	C17—C18—C19—C14	−0.3 (3)
C2—C1—C12—C13	177.44 (19)	C15—C14—C19—O3	−177.34 (18)
C6—C1—C12—C13	−1.5 (3)	C13—C14—C19—O3	3.7 (3)
C1—C12—C13—C14	−178.5 (2)	C15—C14—C19—C18	2.1 (3)
C12—C13—C14—C19	179.6 (2)	C13—C14—C19—C18	−176.9 (2)
C12—C13—C14—C15	0.7 (4)