Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805027947/dn6248sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536805027947/dn6248Isup2.hkl |
CCDC reference: 287549
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.053
- wR factor = 0.135
- Data-to-parameter ratio = 8.3
checkCIF/PLATON results
No syntax errors found
Alert level C REFNR01_ALERT_3_C Ratio of reflections to parameters is < 10 for a centrosymmetric structure sine(theta)/lambda 0.6484 Proportion of unique data used 0.5145 Ratio reflections to parameters 8.3084 PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low .... 0.92 PLAT088_ALERT_3_C Poor Data / Parameter Ratio .................... 8.31 PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature 293 K PLAT230_ALERT_2_C Hirshfeld Test Diff for C17 - C18 .. 5.61 su PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C5 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C18 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C3 PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C10 - C11 ... 1.43 Ang. PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C13 - C14 ... 1.44 Ang.
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 10 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 6 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion
A mixture of 4-formyl-benzoic acid methyl ester (10 mmol), cyclohexanone (20 mmol), propanedinitrile (30 mmol) and ammonium acetate (10 mmol) was placed in the cavity of a microwave synthesizer. After irradiation at 300 W for 2 min, the reaction mixture was extracted with ethyl acetate (50 ml). The organic phase was separated, dried with anhydrous Na2SO4 and evaporated in vacuo. The residue was purified by flash column chromatography on silica gel (eluting with hexane–ethyl acetate, 3:1) to give the desired product (yield 50%). Needle crystals of (I) were obtained from an EtOH solution after allowing it to stand for 4 d (m.p. 499–500 K). MS (EI): m/z = 331 [M]+; HRMS: m/z [M]+ calculated for C20H17N3O2: 331.13; found: 331.13.
The H atoms were treated as riding on their parent atoms, with C—H = 0.93 (phenyl) or 0.97 Å (CH2 and CH3) and N—H = 0.86 Å, and with Uiso(H) = 1.2Ueq (phenyl, CH2, NH2) or 1.5Ueq (CH3).
Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: Crystal Structure (Rigaku/MSC, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
C20H17N3O2 | F(000) = 696.00 |
Mr = 331.37 | Dx = 1.259 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2ybc | Cell parameters from 7944 reflections |
a = 7.9614 (4) Å | θ = 2.6–27.4° |
b = 22.054 (1) Å | µ = 0.08 mm−1 |
c = 10.1707 (6) Å | T = 293 K |
β = 101.747 (2)° | Block, colourless |
V = 1748.38 (16) Å3 | 0.28 × 0.21 × 0.16 mm |
Z = 4 |
Rigaku R-AXIS RAPID diffractometer | 1873 reflections with I > 2σ(I) |
Detector resolution: 10.00 pixels mm-1 | Rint = 0.039 |
ω scans | θmax = 27.4° |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | h = −9→10 |
Tmin = 0.953, Tmax = 0.987 | k = −28→28 |
13708 measured reflections | l = −13→11 |
3666 independent reflections |
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)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0841P)2 + 0.3435P] where P = (Fo2 + 2Fc2)/3 |
1886 reflections | (Δ/σ)max < 0.001 |
227 parameters | Δρmax = 0.59 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
C20H17N3O2 | V = 1748.38 (16) Å3 |
Mr = 331.37 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.9614 (4) Å | µ = 0.08 mm−1 |
b = 22.054 (1) Å | T = 293 K |
c = 10.1707 (6) Å | 0.28 × 0.21 × 0.16 mm |
β = 101.747 (2)° |
Rigaku R-AXIS RAPID diffractometer | 3666 independent reflections |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | 1873 reflections with I > 2σ(I) |
Tmin = 0.953, Tmax = 0.987 | Rint = 0.039 |
13708 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.59 e Å−3 |
1886 reflections | Δρmin = −0.33 e Å−3 |
227 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 | ||
O1 | 1.2329 (3) | 0.30626 (11) | 0.4536 (3) | 0.0769 (8) | |
O2 | 1.1484 (3) | 0.36794 (10) | 0.6006 (2) | 0.0639 (6) | |
N1 | 0.4359 (4) | 0.20860 (16) | 0.2830 (3) | 0.0808 (10) | |
N2 | 0.2123 (3) | 0.08705 (12) | 0.3905 (2) | 0.0560 (7) | |
H2A | 0.1345 | 0.0608 | 0.3969 | 0.067* | |
H2B | 0.1985 | 0.1111 | 0.3227 | 0.067* | |
N3 | 0.1456 (4) | −0.02143 (14) | 0.6284 (3) | 0.0771 (9) | |
C1 | 1.3629 (6) | 0.3498 (2) | 0.4357 (5) | 0.1090 (16) | |
H1A | 1.3085 | 0.3855 | 0.3929 | 0.164* | |
H1B | 1.4349 | 0.3323 | 0.3807 | 0.164* | |
H1C | 1.4313 | 0.3604 | 0.5217 | 0.164* | |
C2 | 1.1356 (4) | 0.32077 (15) | 0.5399 (3) | 0.0519 (8) | |
C3 | 1.0089 (3) | 0.27279 (13) | 0.5488 (3) | 0.0452 (7) | |
C4 | 1.0115 (4) | 0.21798 (16) | 0.4871 (4) | 0.0701 (10) | |
H4 | 1.0967 | 0.2100 | 0.4391 | 0.084* | |
C5 | 0.8908 (4) | 0.17445 (16) | 0.4945 (4) | 0.0734 (11) | |
H5 | 0.8939 | 0.1377 | 0.4501 | 0.088* | |
C6 | 0.7647 (3) | 0.18458 (13) | 0.5671 (3) | 0.0459 (7) | |
C7 | 0.7616 (4) | 0.23973 (15) | 0.6284 (4) | 0.0624 (9) | |
H7 | 0.6763 | 0.2479 | 0.6763 | 0.075* | |
C8 | 0.8828 (4) | 0.28330 (15) | 0.6200 (3) | 0.0604 (9) | |
H8 | 0.8791 | 0.3203 | 0.6632 | 0.072* | |
C9 | 0.6358 (3) | 0.13687 (13) | 0.5790 (3) | 0.0457 (7) | |
C10 | 0.4862 (3) | 0.13337 (13) | 0.4802 (3) | 0.0465 (7) | |
C11 | 0.4602 (3) | 0.17515 (16) | 0.3707 (3) | 0.0535 (8) | |
C12 | 0.3571 (3) | 0.09045 (13) | 0.4876 (3) | 0.0438 (7) | |
C13 | 0.3865 (3) | 0.05258 (13) | 0.5997 (3) | 0.0441 (7) | |
C14 | 0.2538 (4) | 0.01048 (15) | 0.6159 (3) | 0.0546 (8) | |
C15 | 0.5386 (3) | 0.05455 (13) | 0.6985 (3) | 0.0462 (7) | |
C16 | 0.5613 (4) | 0.01043 (15) | 0.8130 (3) | 0.0556 (8) | |
H16A | 0.5767 | −0.0299 | 0.7794 | 0.067* | |
H16B | 0.4577 | 0.0100 | 0.8493 | 0.067* | |
C17 | 0.7129 (4) | 0.0252 (2) | 0.9251 (4) | 0.0801 (11) | |
H17A | 0.6792 | 0.0566 | 0.9814 | 0.096* | |
H17B | 0.7429 | −0.0106 | 0.9803 | 0.096* | |
C18 | 0.8631 (5) | 0.0456 (2) | 0.8770 (4) | 0.0891 (13) | |
H18A | 0.9022 | 0.0131 | 0.8265 | 0.107* | |
H18B | 0.9543 | 0.0544 | 0.9535 | 0.107* | |
C19 | 0.8303 (4) | 0.10014 (16) | 0.7908 (3) | 0.0655 (10) | |
H19A | 0.9249 | 0.1056 | 0.7452 | 0.079* | |
H19B | 0.8263 | 0.1354 | 0.8472 | 0.079* | |
C20 | 0.6648 (3) | 0.09653 (13) | 0.6873 (3) | 0.0473 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0759 (15) | 0.0670 (16) | 0.0995 (19) | −0.0304 (12) | 0.0456 (14) | −0.0087 (14) |
O2 | 0.0651 (14) | 0.0462 (14) | 0.0763 (15) | −0.0130 (11) | 0.0045 (11) | −0.0030 (12) |
N1 | 0.0683 (19) | 0.095 (3) | 0.076 (2) | −0.0210 (17) | 0.0066 (16) | 0.020 (2) |
N2 | 0.0442 (13) | 0.0638 (18) | 0.0591 (16) | −0.0159 (12) | 0.0084 (12) | −0.0003 (13) |
N3 | 0.0630 (17) | 0.075 (2) | 0.095 (2) | −0.0290 (16) | 0.0209 (16) | 0.0058 (18) |
C1 | 0.103 (3) | 0.083 (3) | 0.159 (4) | −0.045 (3) | 0.069 (3) | −0.002 (3) |
C2 | 0.0469 (16) | 0.049 (2) | 0.0575 (19) | −0.0053 (15) | 0.0046 (14) | 0.0045 (17) |
C3 | 0.0396 (14) | 0.0423 (18) | 0.0513 (17) | −0.0063 (13) | 0.0039 (13) | 0.0003 (14) |
C4 | 0.0566 (18) | 0.062 (2) | 0.104 (3) | −0.0160 (17) | 0.0463 (19) | −0.022 (2) |
C5 | 0.065 (2) | 0.053 (2) | 0.116 (3) | −0.0237 (17) | 0.050 (2) | −0.033 (2) |
C6 | 0.0355 (14) | 0.0491 (19) | 0.0527 (17) | −0.0063 (13) | 0.0081 (13) | −0.0006 (15) |
C7 | 0.0606 (18) | 0.055 (2) | 0.081 (2) | −0.0103 (16) | 0.0383 (17) | −0.0139 (18) |
C8 | 0.0663 (19) | 0.0458 (19) | 0.075 (2) | −0.0096 (16) | 0.0272 (17) | −0.0151 (17) |
C9 | 0.0363 (14) | 0.0463 (18) | 0.0572 (18) | −0.0066 (13) | 0.0157 (13) | −0.0065 (15) |
C10 | 0.0390 (15) | 0.0507 (19) | 0.0522 (17) | −0.0063 (13) | 0.0149 (13) | −0.0005 (15) |
C11 | 0.0412 (16) | 0.061 (2) | 0.057 (2) | −0.0150 (15) | 0.0083 (14) | 0.0036 (18) |
C12 | 0.0370 (14) | 0.0456 (17) | 0.0507 (18) | −0.0052 (13) | 0.0134 (13) | −0.0087 (15) |
C13 | 0.0390 (14) | 0.0431 (17) | 0.0545 (18) | −0.0071 (12) | 0.0198 (13) | −0.0077 (14) |
C14 | 0.0477 (17) | 0.054 (2) | 0.064 (2) | −0.0062 (16) | 0.0157 (14) | −0.0026 (16) |
C15 | 0.0428 (15) | 0.0435 (17) | 0.0555 (17) | −0.0021 (13) | 0.0173 (13) | −0.0048 (15) |
C16 | 0.0566 (18) | 0.0482 (19) | 0.066 (2) | −0.0004 (15) | 0.0219 (16) | 0.0051 (16) |
C17 | 0.068 (2) | 0.102 (3) | 0.067 (2) | 0.000 (2) | 0.0081 (18) | 0.024 (2) |
C18 | 0.071 (2) | 0.090 (3) | 0.095 (3) | −0.012 (2) | −0.009 (2) | 0.019 (3) |
C19 | 0.0539 (18) | 0.066 (2) | 0.070 (2) | −0.0143 (16) | −0.0014 (16) | 0.0114 (19) |
C20 | 0.0393 (15) | 0.0482 (18) | 0.0545 (18) | −0.0062 (13) | 0.0100 (13) | −0.0017 (15) |
O1—C2 | 1.323 (4) | C8—H8 | 0.9300 |
O1—C1 | 1.450 (4) | C9—C10 | 1.395 (4) |
O2—C2 | 1.203 (4) | C9—C20 | 1.398 (4) |
N1—C11 | 1.143 (4) | C10—C12 | 1.411 (4) |
N2—C12 | 1.359 (3) | C10—C11 | 1.428 (4) |
N2—H2A | 0.8600 | C12—C13 | 1.394 (4) |
N2—H2B | 0.8600 | C13—C15 | 1.408 (4) |
N3—C14 | 1.139 (4) | C13—C14 | 1.441 (4) |
C1—H1A | 0.9600 | C15—C20 | 1.387 (4) |
C1—H1B | 0.9600 | C15—C16 | 1.501 (4) |
C1—H1C | 0.9600 | C16—C17 | 1.517 (5) |
C2—C3 | 1.477 (4) | C16—H16A | 0.9700 |
C3—C4 | 1.364 (4) | C16—H16B | 0.9700 |
C3—C8 | 1.372 (4) | C17—C18 | 1.453 (5) |
C4—C5 | 1.371 (4) | C17—H17A | 0.9700 |
C4—H4 | 0.9300 | C17—H17B | 0.9700 |
C5—C6 | 1.379 (4) | C18—C19 | 1.480 (5) |
C5—H5 | 0.9300 | C18—H18A | 0.9700 |
C6—C7 | 1.369 (4) | C18—H18B | 0.9700 |
C6—C9 | 1.492 (4) | C19—C20 | 1.512 (4) |
C7—C8 | 1.377 (4) | C19—H19A | 0.9700 |
C7—H7 | 0.9300 | C19—H19B | 0.9700 |
C2—O1—C1 | 116.9 (3) | N2—C12—C13 | 122.5 (3) |
C12—N2—H2A | 120.0 | N2—C12—C10 | 121.2 (3) |
C12—N2—H2B | 120.0 | C13—C12—C10 | 116.3 (2) |
H2A—N2—H2B | 120.0 | C12—C13—C15 | 122.8 (2) |
O1—C1—H1A | 109.5 | C12—C13—C14 | 118.3 (2) |
O1—C1—H1B | 109.5 | C15—C13—C14 | 118.9 (3) |
H1A—C1—H1B | 109.5 | N3—C14—C13 | 178.0 (3) |
O1—C1—H1C | 109.5 | C20—C15—C13 | 119.6 (3) |
H1A—C1—H1C | 109.5 | C20—C15—C16 | 121.4 (3) |
H1B—C1—H1C | 109.5 | C13—C15—C16 | 118.9 (2) |
O2—C2—O1 | 123.3 (3) | C15—C16—C17 | 113.3 (3) |
O2—C2—C3 | 125.1 (3) | C15—C16—H16A | 108.9 |
O1—C2—C3 | 111.5 (3) | C17—C16—H16A | 108.9 |
C4—C3—C8 | 118.3 (3) | C15—C16—H16B | 108.9 |
C4—C3—C2 | 122.2 (3) | C17—C16—H16B | 108.9 |
C8—C3—C2 | 119.6 (3) | H16A—C16—H16B | 107.7 |
C3—C4—C5 | 121.3 (3) | C18—C17—C16 | 113.4 (3) |
C3—C4—H4 | 119.4 | C18—C17—H17A | 108.9 |
C5—C4—H4 | 119.4 | C16—C17—H17A | 108.9 |
C4—C5—C6 | 120.7 (3) | C18—C17—H17B | 108.9 |
C4—C5—H5 | 119.7 | C16—C17—H17B | 108.9 |
C6—C5—H5 | 119.7 | H17A—C17—H17B | 107.7 |
C7—C6—C5 | 118.0 (3) | C17—C18—C19 | 113.1 (3) |
C7—C6—C9 | 120.8 (3) | C17—C18—H18A | 109.0 |
C5—C6—C9 | 121.1 (3) | C19—C18—H18A | 109.0 |
C6—C7—C8 | 120.9 (3) | C17—C18—H18B | 109.0 |
C6—C7—H7 | 119.5 | C19—C18—H18B | 109.0 |
C8—C7—H7 | 119.5 | H18A—C18—H18B | 107.8 |
C3—C8—C7 | 120.8 (3) | C18—C19—C20 | 113.2 (3) |
C3—C8—H8 | 119.6 | C18—C19—H19A | 108.9 |
C7—C8—H8 | 119.6 | C20—C19—H19A | 108.9 |
C10—C9—C20 | 120.8 (3) | C18—C19—H19B | 108.9 |
C10—C9—C6 | 118.7 (3) | C20—C19—H19B | 108.9 |
C20—C9—C6 | 120.5 (2) | H19A—C19—H19B | 107.8 |
C9—C10—C12 | 121.5 (3) | C15—C20—C9 | 118.9 (3) |
C9—C10—C11 | 119.6 (2) | C15—C20—C19 | 121.4 (3) |
C12—C10—C11 | 118.9 (3) | C9—C20—C19 | 119.7 (2) |
N1—C11—C10 | 178.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···N3i | 0.86 | 2.36 | 3.167 (4) | 157 |
N2—H2B···O2ii | 0.86 | 2.26 | 3.054 (4) | 154 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x−1, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | C20H17N3O2 |
Mr | 331.37 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 7.9614 (4), 22.054 (1), 10.1707 (6) |
β (°) | 101.747 (2) |
V (Å3) | 1748.38 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.28 × 0.21 × 0.16 |
Data collection | |
Diffractometer | Rigaku R-AXIS RAPID diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.953, 0.987 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13708, 3666, 1873 |
Rint | 0.039 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.053, 0.135, 1.08 |
No. of reflections | 1886 |
No. of parameters | 227 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.59, −0.33 |
Computer programs: PROCESS-AUTO (Rigaku, 1998), PROCESS-AUTO, Crystal Structure (Rigaku/MSC, 2004), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···N3i | 0.86 | 2.36 | 3.167 (4) | 157 |
N2—H2B···O2ii | 0.86 | 2.26 | 3.054 (4) | 154 |
Symmetry codes: (i) −x, −y, −z+1; (ii) x−1, −y+1/2, z−1/2. |
2,6-Dicyanoanilines comprising one electron donor and two electron acceptors have been reported with high fluorescence quantum yields (References?). The structure determination of the title compound, (I), was undertaken as part of our studies of 2,6-dicyanoaniline derivatives (Cui et al., 2005).
The molecular structure of (I) is shown in Fig. 1. The two phenyl rings are nearly perpendicular, making a dihedral angle of 86.94 (9)°. The COOMe moiety is slightly twisted by 7.4 (3)° with respect to the attached phenyl ring.
N—H···N hydrogen bonding results in the formation of dimers, which are then connected to each other through N—H···O hydrogen bonds, building zigzag chains parallel to the b axis (Fig. 2).