Brooker's di-tert-butylmerocyanine

The title compound, 4-[(1-methyl-1,4-di­hydro­pyridinyl­idene)­ethyl­idene]-2,6-di-tert-butyl-2,5-cyclo­hexadien-1-one, C₂₂H₂₉NO, a green organic dye, possesses a quinone and not a zwitterionic structure in the solid state, thus differing significantly from the parent unsubstituted species.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.071
• wR factor = 0.207
• Data-to-parameter ratio = 15.7

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT027_ALERT_3_A _diffrn_reflns_theta_full (too) Low ............      24.93 Deg.

Author Response: The CHECKCIF programs requires 25.24 Deg. The data were collected up to 25 Deg. Mo K\a, Thus, the dataset is essentially complete.

Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for    C3     -   C4      ..      11.96 su

Author Response: This Alert, as well as those reported for DIFMX01/02, PLAT094/097/230/242, derive from the dynamic pedal-like motion of the inner part of the molecule, as extensively studied by Ogawa et al., 1992; Galli et al, 1999; Kwasniewski et al., 2003. A proper description and the list of the pertinent references is indeed present in the discussion section.

PLAT230_ALERT_2_B Hirshfeld Test Diff for    C4     -   C8      ..      15.93 su

Author Response: This Alert, as well as those reported for DIFMX01/02, PLAT094/097/230/242, derive from the dynamic pedal-like motion of the inner part of the molecule, as extensively studied by Ogawa et al., 1992; Galli et al, 1999; Kwasniewski et al., 2003. A proper description and the list of the pertinent references is indeed present in the discussion section.

PLAT230_ALERT_2_B Hirshfeld Test Diff for    C9     -   C10     ..      15.33 su

Author Response: This Alert, as well as those reported for DIFMX01/02, PLAT094/097/230/242, derive from the dynamic pedal-like motion of the inner part of the molecule, as extensively studied by Ogawa et al., 1992; Galli et al, 1999; Kwasniewski et al., 2003. A proper description and the list of the pertinent references is indeed present in the discussion section.

Alert level C
DIFMX01_ALERT_2_C  The maximum difference density is > 0.1*ZMAX*0.75
            _refine_diff_density_max given =      0.683
            Test value =      0.600
DIFMX02_ALERT_1_C  The minimum difference density is > 0.1*ZMAX*0.75
            The relevant atom site should be identified.
PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density ....       2.80
PLAT097_ALERT_2_C Maximum (Positive) Residual Density ............       0.68 e/A   3
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N1     -   C2      ..       5.46 su

Author Response: This Alert, as well as those reported for DIFMX01/02, PLAT094/097/230/242, derive from the dynamic pedal-like motion of the inner part of the molecule, as extensively studied by Ogawa et al., 1992; Galli et al, 1999; Kwasniewski et al., 2003. A proper description and the list of the pertinent references is indeed present in the discussion section.

PLAT230_ALERT_2_C Hirshfeld Test Diff for    C10    -   C11     ..       5.34 su

Author Response: This Alert, as well as those reported for DIFMX01/02, PLAT094/097/230/242, derive from the dynamic pedal-like motion of the inner part of the molecule, as extensively studied by Ogawa et al., 1992; Galli et al, 1999; Kwasniewski et al., 2003. A proper description and the list of the pertinent references is indeed present in the discussion section.

PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N1
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C17

   1 ALERT level A = In general: serious problem
   3 ALERT level B = Potentially serious problem
   8 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
  10 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: CAD-4 Software (Enraf-Nonius); cell refinement: CAD-4 Software (Enraf-Nonius); data reduction: Local programs; program(s) used to solve structure: SHELXS86 (Sheldrick, 1986); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 of WinGX (Farrugia, 1999); software used to prepare material for publication: CIF.

4-[(1-Methyl-1,4-dihydropyridinylidene)ethylidene]-2,6-di-tert-butyl-2,5- cyclohexadien-1-one

Crystal data

C22H29NO	F(000) = 704
Mr = 323.46	Dx = 1.091 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 10.216 (2) Å	θ = 9–16°
b = 15.445 (4) Å	µ = 0.07 mm^−1
c = 13.010 (6) Å	T = 295 K
β = 106.37 (2)°	Prism, green
V = 1969.6 (11) Å^3	0.20 × 0.20 × 0.10 mm
Z = 4

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.016
Radiation source: fine-focus sealed tube, Enraf-Nonius X-ray Generator	θmax = 24.9°, θmin = 3.1°
Graphite monochromator	h = 0→12
ω scan	k = 0→18
3631 measured reflections	l = −15→14
3429 independent reflections	3 standard reflections every 10800 min
1756 reflections with I > 2σ(I)	intensity decay: none

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)] = 0.071	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.207	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.079P)^2 + 1.2544P] where P = (Fo^2 + 2Fc^2)/3
3429 reflections	(Δ/σ)max = 0.002
218 parameters	Δρmax = 0.68 e Å^−3
0 restraints	Δρmin = −0.24 e Å^−3

Special details

Experimental. Data collection performed with an Enraf–Nonius CAD-4 four-circle diffractometer equipped with a scintillation caounter, sealed X-ray tube with Mo Kα radiation, graphite monochromator. Omega scan method applied with Δω=1.2 + 0.35tanθ, 90 s per reflection. Lattice parameters obtained by the indexing and least-squares refinement procedures of the setting angles of25 strong reflections randomly distributed in the 9<θ<16% range. No absorption correction was applied.

Geometry. All e.s.d.'s 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.

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	Occ. (<1)
N1	0.2367 (2)	0.41316 (15)	0.23225 (17)	0.0532 (6)
C2	0.3709 (3)	0.3962 (2)	0.2734 (3)	0.0700 (9)
H2	0.4043	0.3414	0.2648	0.084*
C3	0.4593 (3)	0.4593 (2)	0.3281 (3)	0.0742 (10)
H3	0.5516	0.4466	0.3549	0.089*
C4	0.4126 (3)	0.5416 (2)	0.3440 (2)	0.0640 (9)
C5	0.2763 (3)	0.5544 (2)	0.2980 (3)	0.0704 (10)
H5	0.2396	0.6085	0.3044	0.084*
C6	0.1941 (3)	0.4930 (2)	0.2448 (2)	0.0652 (9)
H6	0.1024	0.5062	0.2147	0.078*
C7	0.1417 (4)	0.3452 (2)	0.1768 (3)	0.0834 (11)
H7A	0.1913	0.2926	0.1756	0.125*	0.43 (4)
H7B	0.0978	0.3633	0.1047	0.125*	0.43 (4)
H7C	0.0741	0.3355	0.2140	0.125*	0.43 (4)
H7D	0.0509	0.3683	0.1539	0.125*	0.57 (4)
H7E	0.1444	0.2976	0.2248	0.125*	0.57 (4)
H7F	0.1681	0.3255	0.1155	0.125*	0.57 (4)
C8	0.4969 (3)	0.6130 (2)	0.4025 (3)	0.0772 (10)
H8	0.4530	0.6641	0.4111	0.093*
C9	0.6283 (3)	0.6094 (2)	0.4430 (2)	0.0719 (10)
H9	0.6681	0.5565	0.4352	0.086*
C10	0.7207 (3)	0.67485 (18)	0.4976 (2)	0.0563 (8)
C11	0.8609 (3)	0.65887 (18)	0.5192 (2)	0.0555 (8)
H11	0.8881	0.6052	0.5001	0.067*
C12	0.9586 (3)	0.71633 (17)	0.5658 (2)	0.0502 (7)
C13	0.9183 (3)	0.79983 (17)	0.6001 (2)	0.0494 (7)
C14	0.7727 (3)	0.81764 (17)	0.5807 (2)	0.0471 (7)
C15	0.6816 (3)	0.75622 (19)	0.5302 (2)	0.0554 (8)
H15	0.5890	0.7682	0.5163	0.066*
O16	1.0066 (2)	0.85455 (13)	0.64470 (18)	0.0736 (7)
C17	1.1105 (3)	0.69690 (19)	0.5818 (2)	0.0638 (9)
C18	1.1746 (3)	0.7658 (3)	0.5260 (3)	0.1002 (13)
H18A	1.1626	0.8220	0.5536	0.150*
H18B	1.1311	0.7644	0.4503	0.150*
H18C	1.2702	0.7541	0.5392	0.150*
C19	1.1865 (4)	0.6945 (2)	0.7022 (3)	0.0870 (12)
H19A	1.1748	0.7488	0.7344	0.131*
H19B	1.2819	0.6845	0.7114	0.131*
H19C	1.1502	0.6487	0.7359	0.131*
C20	1.1317 (4)	0.6089 (2)	0.5348 (3)	0.0950 (13)
H20A	1.0926	0.5643	0.5682	0.143*
H20B	1.2276	0.5983	0.5477	0.143*
H20C	1.0883	0.6089	0.4591	0.143*
C21	0.7294 (3)	0.90488 (19)	0.6167 (2)	0.0585 (8)
C22	0.7954 (4)	0.9179 (2)	0.7373 (2)	0.0826 (11)
H22A	0.7689	0.8714	0.7762	0.124*
H22B	0.7656	0.9720	0.7593	0.124*
H22C	0.8928	0.9183	0.7518	0.124*
C23	0.7702 (4)	0.9785 (2)	0.5532 (3)	0.0745 (10)
H23A	0.7281	0.9698	0.4781	0.112*
H23B	0.8676	0.9791	0.5669	0.112*
H23C	0.7406	1.0328	0.5749	0.112*
C24	0.5741 (3)	0.9091 (2)	0.5977 (3)	0.0885 (12)
H24A	0.5460	0.8634	0.6368	0.133*
H24B	0.5294	0.9025	0.5226	0.133*
H24C	0.5500	0.9640	0.6217	0.133*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0540 (13)	0.0558 (14)	0.0472 (13)	−0.0096 (12)	0.0103 (11)	−0.0019 (11)
C2	0.075 (2)	0.0612 (19)	0.076 (2)	0.0151 (17)	0.0258 (17)	0.0082 (16)
C3	0.0379 (16)	0.106 (3)	0.071 (2)	−0.0020 (18)	0.0026 (15)	0.013 (2)
C4	0.0736 (19)	0.0580 (19)	0.0596 (18)	−0.0165 (16)	0.0175 (16)	−0.0026 (15)
C5	0.069 (2)	0.0597 (19)	0.075 (2)	−0.0029 (17)	0.0075 (17)	−0.0099 (17)
C6	0.0518 (17)	0.067 (2)	0.071 (2)	0.0074 (16)	0.0073 (15)	−0.0045 (17)
C7	0.097 (2)	0.080 (2)	0.074 (2)	−0.042 (2)	0.0246 (18)	−0.0203 (18)
C8	0.080 (2)	0.077 (2)	0.079 (2)	0.0120 (19)	0.0293 (18)	0.0063 (18)
C9	0.075 (2)	0.082 (2)	0.0616 (19)	−0.0055 (18)	0.0233 (16)	0.0053 (17)
C10	0.0730 (18)	0.0479 (16)	0.0482 (15)	−0.0210 (15)	0.0173 (14)	−0.0094 (13)
C11	0.0687 (18)	0.0422 (15)	0.0557 (17)	0.0015 (14)	0.0176 (14)	−0.0024 (13)
C12	0.0617 (17)	0.0432 (15)	0.0431 (14)	0.0030 (14)	0.0105 (13)	0.0033 (12)
C13	0.0521 (16)	0.0435 (15)	0.0489 (16)	−0.0023 (13)	0.0083 (13)	−0.0013 (13)
C14	0.0486 (15)	0.0468 (15)	0.0442 (15)	−0.0025 (13)	0.0104 (12)	−0.0015 (12)
C15	0.0486 (15)	0.0667 (18)	0.0507 (16)	−0.0058 (14)	0.0137 (13)	−0.0029 (14)
O16	0.0536 (12)	0.0528 (12)	0.1040 (17)	−0.0038 (10)	0.0053 (11)	−0.0196 (12)
C17	0.0600 (17)	0.0617 (18)	0.0644 (19)	0.0187 (15)	0.0090 (15)	0.0034 (15)
C18	0.064 (2)	0.117 (3)	0.127 (3)	0.024 (2)	0.039 (2)	0.036 (3)
C19	0.080 (2)	0.091 (3)	0.076 (2)	0.022 (2)	0.0000 (19)	0.001 (2)
C20	0.091 (2)	0.093 (3)	0.093 (3)	0.041 (2)	0.012 (2)	−0.014 (2)
C21	0.0606 (17)	0.0554 (17)	0.0592 (18)	0.0079 (15)	0.0166 (14)	−0.0041 (14)
C22	0.109 (3)	0.077 (2)	0.061 (2)	0.008 (2)	0.0227 (19)	−0.0174 (17)
C23	0.092 (2)	0.0539 (18)	0.078 (2)	0.0104 (17)	0.0250 (18)	0.0012 (17)
C24	0.073 (2)	0.086 (2)	0.112 (3)	0.0177 (19)	0.034 (2)	−0.009 (2)

Geometric parameters (Å, º)

N1—C6	1.333 (4)	C13—C14	1.463 (4)
N1—C2	1.350 (4)	C14—C15	1.362 (4)
N1—C7	1.472 (4)	C14—C21	1.532 (4)
C2—C3	1.382 (4)	C15—H15	0.9300
C2—H2	0.9300	C17—C20	1.530 (4)
C3—C4	1.394 (4)	C17—C18	1.535 (5)
C3—H3	0.9300	C17—C19	1.541 (4)
C4—C5	1.366 (4)	C18—H18A	0.9600
C4—C8	1.472 (4)	C18—H18B	0.9600
C5—C6	1.325 (4)	C18—H18C	0.9600
C5—H5	0.9300	C19—H19A	0.9600
C6—H6	0.9300	C19—H19B	0.9600
C7—H7A	0.9600	C19—H19C	0.9600
C7—H7B	0.9600	C20—H20A	0.9600
C7—H7C	0.9600	C20—H20B	0.9600
C7—H7D	0.9600	C20—H20C	0.9600
C7—H7E	0.9600	C21—C23	1.531 (4)
C7—H7F	0.9600	C21—C22	1.536 (4)
C8—C9	1.297 (4)	C21—C24	1.537 (4)
C8—H8	0.9300	C22—H22A	0.9600
C9—C10	1.429 (4)	C22—H22B	0.9600
C9—H9	0.9300	C22—H22C	0.9600
C10—C11	1.402 (4)	C23—H23A	0.9600
C10—C15	1.419 (4)	C23—H23B	0.9600
C11—C12	1.346 (4)	C23—H23C	0.9600
C11—H11	0.9300	C24—H24A	0.9600
C12—C13	1.461 (4)	C24—H24B	0.9600
C12—C17	1.535 (4)	C24—H24C	0.9600
C13—O16	1.253 (3)
C6—N1—C2	117.5 (3)	C12—C13—C14	118.3 (2)
C6—N1—C7	121.8 (3)	C15—C14—C13	118.4 (2)
C2—N1—C7	120.7 (3)	C15—C14—C21	122.9 (3)
N1—C2—C3	120.7 (3)	C13—C14—C21	118.7 (2)
N1—C2—H2	119.7	C14—C15—C10	123.3 (3)
C3—C2—H2	119.7	C14—C15—H15	118.4
C2—C3—C4	121.3 (3)	C10—C15—H15	118.4
C2—C3—H3	119.4	C20—C17—C18	107.4 (3)
C4—C3—H3	119.4	C20—C17—C12	111.8 (3)
C5—C4—C3	114.6 (3)	C18—C17—C12	110.5 (2)
C5—C4—C8	119.6 (3)	C20—C17—C19	107.3 (3)
C3—C4—C8	125.8 (3)	C18—C17—C19	109.7 (3)
C6—C5—C4	122.9 (3)	C12—C17—C19	110.0 (3)
C6—C5—H5	118.5	C17—C18—H18A	109.5
C4—C5—H5	118.5	C17—C18—H18B	109.5
C5—C6—N1	123.0 (3)	H18A—C18—H18B	109.5
C5—C6—H6	118.5	C17—C18—H18C	109.5
N1—C6—H6	118.5	H18A—C18—H18C	109.5
N1—C7—H7A	109.5	H18B—C18—H18C	109.5
N1—C7—H7B	109.5	C17—C19—H19A	109.5
H7A—C7—H7B	109.5	C17—C19—H19B	109.5
N1—C7—H7C	109.5	H19A—C19—H19B	109.5
H7A—C7—H7C	109.5	C17—C19—H19C	109.5
H7B—C7—H7C	109.5	H19A—C19—H19C	109.5
N1—C7—H7D	109.5	H19B—C19—H19C	109.5
H7A—C7—H7D	141.1	C17—C20—H20A	109.5
H7B—C7—H7D	56.3	C17—C20—H20B	109.5
H7C—C7—H7D	56.3	H20A—C20—H20B	109.5
N1—C7—H7E	109.5	C17—C20—H20C	109.5
H7A—C7—H7E	56.3	H20A—C20—H20C	109.5
H7B—C7—H7E	141.1	H20B—C20—H20C	109.5
H7C—C7—H7E	56.3	C23—C21—C14	110.0 (3)
H7D—C7—H7E	109.5	C23—C21—C22	110.2 (3)
N1—C7—H7F	109.5	C14—C21—C22	110.2 (2)
H7A—C7—H7F	56.3	C23—C21—C24	107.9 (3)
H7B—C7—H7F	56.3	C14—C21—C24	111.2 (3)
H7C—C7—H7F	141.1	C22—C21—C24	107.1 (3)
H7D—C7—H7F	109.5	C21—C22—H22A	109.5
H7E—C7—H7F	109.5	C21—C22—H22B	109.5
C9—C8—C4	124.4 (3)	H22A—C22—H22B	109.5
C9—C8—H8	117.8	C21—C22—H22C	109.5
C4—C8—H8	117.8	H22A—C22—H22C	109.5
C8—C9—C10	129.4 (3)	H22B—C22—H22C	109.5
C8—C9—H9	115.3	C21—C23—H23A	109.5
C10—C9—H9	115.3	C21—C23—H23B	109.5
C11—C10—C15	117.0 (2)	H23A—C23—H23B	109.5
C11—C10—C9	118.0 (3)	C21—C23—H23C	109.5
C15—C10—C9	125.0 (3)	H23A—C23—H23C	109.5
C12—C11—C10	124.1 (3)	H23B—C23—H23C	109.5
C12—C11—H11	118.0	C21—C24—H24A	109.5
C10—C11—H11	118.0	C21—C24—H24B	109.5
C11—C12—C13	118.9 (3)	H24A—C24—H24B	109.5
C11—C12—C17	121.6 (3)	C21—C24—H24C	109.5
C13—C12—C17	119.5 (2)	H24A—C24—H24C	109.5
O16—C13—C12	120.6 (2)	H24B—C24—H24C	109.5
O16—C13—C14	121.1 (2)
C6—N1—C2—C3	1.3 (5)	C17—C12—C13—C14	178.0 (2)
C7—N1—C2—C3	−178.1 (3)	O16—C13—C14—C15	178.9 (3)
N1—C2—C3—C4	1.0 (5)	C12—C13—C14—C15	−1.0 (4)
C2—C3—C4—C5	−2.3 (5)	O16—C13—C14—C21	−0.3 (4)
C2—C3—C4—C8	178.9 (3)	C12—C13—C14—C21	179.8 (2)
C3—C4—C5—C6	1.5 (5)	C13—C14—C15—C10	1.6 (4)
C8—C4—C5—C6	−179.6 (3)	C21—C14—C15—C10	−179.3 (3)
C4—C5—C6—N1	0.7 (5)	C11—C10—C15—C14	−0.3 (4)
C2—N1—C6—C5	−2.2 (5)	C9—C10—C15—C14	−178.9 (3)
C7—N1—C6—C5	177.2 (3)	C11—C12—C17—C20	2.3 (4)
C5—C4—C8—C9	−175.3 (3)	C13—C12—C17—C20	−176.5 (3)
C3—C4—C8—C9	3.4 (6)	C11—C12—C17—C18	121.9 (3)
C4—C8—C9—C10	177.6 (3)	C13—C12—C17—C18	−56.9 (4)
C8—C9—C10—C11	−170.3 (3)	C11—C12—C17—C19	−116.8 (3)
C8—C9—C10—C15	8.3 (5)	C13—C12—C17—C19	64.4 (3)
C15—C10—C11—C12	−1.7 (4)	C15—C14—C21—C23	−114.3 (3)
C9—C10—C11—C12	177.0 (3)	C13—C14—C21—C23	64.9 (3)
C10—C11—C12—C13	2.2 (4)	C15—C14—C21—C22	123.9 (3)
C10—C11—C12—C17	−176.6 (3)	C13—C14—C21—C22	−56.9 (3)
C11—C12—C13—O16	179.3 (3)	C15—C14—C21—C24	5.2 (4)
C17—C12—C13—O16	−1.9 (4)	C13—C14—C21—C24	−175.6 (3)
C11—C12—C13—C14	−0.8 (4)