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In the mol­ecule of the title compound, C20H17N3O2, the two benzene rings are nearly perpendicular, whereas the acetate group is slightly twisted with respect to the attached benzene ring. Inter­molecular N—H...N and N—H...O hydrogen bonds generate a zigzag chain which extends parallel to the b axis.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805027947/dn6248sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805027947/dn6248Isup2.hkl
Contains datablock I

CCDC reference: 287549

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](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

Comment top

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).

Experimental top

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.

Refinement top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A view of the molecule of compound (I). Displacement ellipsoids are drawn at the 40% probability level.
[Figure 2] Fig. 2. The molecular packing of (I), showing the hydrogen-bonding network. Hydrogen bonds are shown as dashed lines. H atoms not involved in the hydrogen bonding have been omitted for clarity. [Symmetry codes: (i) −x, −y, 1/2 − z; (ii) x − 1, 1/2 − y, z − 1/2.]
Methyl 4-(3-amino-2,4-dicyano-5,6,7,8-tetrahydronaphthalen-1-yl)benzoate top
Crystal data top
C20H17N3O2F(000) = 696.00
Mr = 331.37Dx = 1.259 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.7107 Å
Hall symbol: -P 2ybcCell parameters from 7944 reflections
a = 7.9614 (4) Åθ = 2.6–27.4°
b = 22.054 (1) ŵ = 0.08 mm1
c = 10.1707 (6) ÅT = 293 K
β = 101.747 (2)°Block, colourless
V = 1748.38 (16) Å30.28 × 0.21 × 0.16 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer
1873 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm-1Rint = 0.039
ω scansθmax = 27.4°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 910
Tmin = 0.953, Tmax = 0.987k = 2828
13708 measured reflectionsl = 1311
3666 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)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.135H-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 parametersΔρmax = 0.59 e Å3
0 restraintsΔρmin = 0.33 e Å3
Crystal data top
C20H17N3O2V = 1748.38 (16) Å3
Mr = 331.37Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.9614 (4) ŵ = 0.08 mm1
b = 22.054 (1) ÅT = 293 K
c = 10.1707 (6) Å0.28 × 0.21 × 0.16 mm
β = 101.747 (2)°
Data collection top
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 = 0.987Rint = 0.039
13708 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.135H-atom parameters constrained
S = 1.08Δρmax = 0.59 e Å3
1886 reflectionsΔρmin = 0.33 e Å3
227 parameters
Special details top

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
O11.2329 (3)0.30626 (11)0.4536 (3)0.0769 (8)
O21.1484 (3)0.36794 (10)0.6006 (2)0.0639 (6)
N10.4359 (4)0.20860 (16)0.2830 (3)0.0808 (10)
N20.2123 (3)0.08705 (12)0.3905 (2)0.0560 (7)
H2A0.13450.06080.39690.067*
H2B0.19850.11110.32270.067*
N30.1456 (4)0.02143 (14)0.6284 (3)0.0771 (9)
C11.3629 (6)0.3498 (2)0.4357 (5)0.1090 (16)
H1A1.30850.38550.39290.164*
H1B1.43490.33230.38070.164*
H1C1.43130.36040.52170.164*
C21.1356 (4)0.32077 (15)0.5399 (3)0.0519 (8)
C31.0089 (3)0.27279 (13)0.5488 (3)0.0452 (7)
C41.0115 (4)0.21798 (16)0.4871 (4)0.0701 (10)
H41.09670.21000.43910.084*
C50.8908 (4)0.17445 (16)0.4945 (4)0.0734 (11)
H50.89390.13770.45010.088*
C60.7647 (3)0.18458 (13)0.5671 (3)0.0459 (7)
C70.7616 (4)0.23973 (15)0.6284 (4)0.0624 (9)
H70.67630.24790.67630.075*
C80.8828 (4)0.28330 (15)0.6200 (3)0.0604 (9)
H80.87910.32030.66320.072*
C90.6358 (3)0.13687 (13)0.5790 (3)0.0457 (7)
C100.4862 (3)0.13337 (13)0.4802 (3)0.0465 (7)
C110.4602 (3)0.17515 (16)0.3707 (3)0.0535 (8)
C120.3571 (3)0.09045 (13)0.4876 (3)0.0438 (7)
C130.3865 (3)0.05258 (13)0.5997 (3)0.0441 (7)
C140.2538 (4)0.01048 (15)0.6159 (3)0.0546 (8)
C150.5386 (3)0.05455 (13)0.6985 (3)0.0462 (7)
C160.5613 (4)0.01043 (15)0.8130 (3)0.0556 (8)
H16A0.57670.02990.77940.067*
H16B0.45770.01000.84930.067*
C170.7129 (4)0.0252 (2)0.9251 (4)0.0801 (11)
H17A0.67920.05660.98140.096*
H17B0.74290.01060.98030.096*
C180.8631 (5)0.0456 (2)0.8770 (4)0.0891 (13)
H18A0.90220.01310.82650.107*
H18B0.95430.05440.95350.107*
C190.8303 (4)0.10014 (16)0.7908 (3)0.0655 (10)
H19A0.92490.10560.74520.079*
H19B0.82630.13540.84720.079*
C200.6648 (3)0.09653 (13)0.6873 (3)0.0473 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0759 (15)0.0670 (16)0.0995 (19)0.0304 (12)0.0456 (14)0.0087 (14)
O20.0651 (14)0.0462 (14)0.0763 (15)0.0130 (11)0.0045 (11)0.0030 (12)
N10.0683 (19)0.095 (3)0.076 (2)0.0210 (17)0.0066 (16)0.020 (2)
N20.0442 (13)0.0638 (18)0.0591 (16)0.0159 (12)0.0084 (12)0.0003 (13)
N30.0630 (17)0.075 (2)0.095 (2)0.0290 (16)0.0209 (16)0.0058 (18)
C10.103 (3)0.083 (3)0.159 (4)0.045 (3)0.069 (3)0.002 (3)
C20.0469 (16)0.049 (2)0.0575 (19)0.0053 (15)0.0046 (14)0.0045 (17)
C30.0396 (14)0.0423 (18)0.0513 (17)0.0063 (13)0.0039 (13)0.0003 (14)
C40.0566 (18)0.062 (2)0.104 (3)0.0160 (17)0.0463 (19)0.022 (2)
C50.065 (2)0.053 (2)0.116 (3)0.0237 (17)0.050 (2)0.033 (2)
C60.0355 (14)0.0491 (19)0.0527 (17)0.0063 (13)0.0081 (13)0.0006 (15)
C70.0606 (18)0.055 (2)0.081 (2)0.0103 (16)0.0383 (17)0.0139 (18)
C80.0663 (19)0.0458 (19)0.075 (2)0.0096 (16)0.0272 (17)0.0151 (17)
C90.0363 (14)0.0463 (18)0.0572 (18)0.0066 (13)0.0157 (13)0.0065 (15)
C100.0390 (15)0.0507 (19)0.0522 (17)0.0063 (13)0.0149 (13)0.0005 (15)
C110.0412 (16)0.061 (2)0.057 (2)0.0150 (15)0.0083 (14)0.0036 (18)
C120.0370 (14)0.0456 (17)0.0507 (18)0.0052 (13)0.0134 (13)0.0087 (15)
C130.0390 (14)0.0431 (17)0.0545 (18)0.0071 (12)0.0198 (13)0.0077 (14)
C140.0477 (17)0.054 (2)0.064 (2)0.0062 (16)0.0157 (14)0.0026 (16)
C150.0428 (15)0.0435 (17)0.0555 (17)0.0021 (13)0.0173 (13)0.0048 (15)
C160.0566 (18)0.0482 (19)0.066 (2)0.0004 (15)0.0219 (16)0.0051 (16)
C170.068 (2)0.102 (3)0.067 (2)0.000 (2)0.0081 (18)0.024 (2)
C180.071 (2)0.090 (3)0.095 (3)0.012 (2)0.009 (2)0.019 (3)
C190.0539 (18)0.066 (2)0.070 (2)0.0143 (16)0.0014 (16)0.0114 (19)
C200.0393 (15)0.0482 (18)0.0545 (18)0.0062 (13)0.0100 (13)0.0017 (15)
Geometric parameters (Å, º) top
O1—C21.323 (4)C8—H80.9300
O1—C11.450 (4)C9—C101.395 (4)
O2—C21.203 (4)C9—C201.398 (4)
N1—C111.143 (4)C10—C121.411 (4)
N2—C121.359 (3)C10—C111.428 (4)
N2—H2A0.8600C12—C131.394 (4)
N2—H2B0.8600C13—C151.408 (4)
N3—C141.139 (4)C13—C141.441 (4)
C1—H1A0.9600C15—C201.387 (4)
C1—H1B0.9600C15—C161.501 (4)
C1—H1C0.9600C16—C171.517 (5)
C2—C31.477 (4)C16—H16A0.9700
C3—C41.364 (4)C16—H16B0.9700
C3—C81.372 (4)C17—C181.453 (5)
C4—C51.371 (4)C17—H17A0.9700
C4—H40.9300C17—H17B0.9700
C5—C61.379 (4)C18—C191.480 (5)
C5—H50.9300C18—H18A0.9700
C6—C71.369 (4)C18—H18B0.9700
C6—C91.492 (4)C19—C201.512 (4)
C7—C81.377 (4)C19—H19A0.9700
C7—H70.9300C19—H19B0.9700
C2—O1—C1116.9 (3)N2—C12—C13122.5 (3)
C12—N2—H2A120.0N2—C12—C10121.2 (3)
C12—N2—H2B120.0C13—C12—C10116.3 (2)
H2A—N2—H2B120.0C12—C13—C15122.8 (2)
O1—C1—H1A109.5C12—C13—C14118.3 (2)
O1—C1—H1B109.5C15—C13—C14118.9 (3)
H1A—C1—H1B109.5N3—C14—C13178.0 (3)
O1—C1—H1C109.5C20—C15—C13119.6 (3)
H1A—C1—H1C109.5C20—C15—C16121.4 (3)
H1B—C1—H1C109.5C13—C15—C16118.9 (2)
O2—C2—O1123.3 (3)C15—C16—C17113.3 (3)
O2—C2—C3125.1 (3)C15—C16—H16A108.9
O1—C2—C3111.5 (3)C17—C16—H16A108.9
C4—C3—C8118.3 (3)C15—C16—H16B108.9
C4—C3—C2122.2 (3)C17—C16—H16B108.9
C8—C3—C2119.6 (3)H16A—C16—H16B107.7
C3—C4—C5121.3 (3)C18—C17—C16113.4 (3)
C3—C4—H4119.4C18—C17—H17A108.9
C5—C4—H4119.4C16—C17—H17A108.9
C4—C5—C6120.7 (3)C18—C17—H17B108.9
C4—C5—H5119.7C16—C17—H17B108.9
C6—C5—H5119.7H17A—C17—H17B107.7
C7—C6—C5118.0 (3)C17—C18—C19113.1 (3)
C7—C6—C9120.8 (3)C17—C18—H18A109.0
C5—C6—C9121.1 (3)C19—C18—H18A109.0
C6—C7—C8120.9 (3)C17—C18—H18B109.0
C6—C7—H7119.5C19—C18—H18B109.0
C8—C7—H7119.5H18A—C18—H18B107.8
C3—C8—C7120.8 (3)C18—C19—C20113.2 (3)
C3—C8—H8119.6C18—C19—H19A108.9
C7—C8—H8119.6C20—C19—H19A108.9
C10—C9—C20120.8 (3)C18—C19—H19B108.9
C10—C9—C6118.7 (3)C20—C19—H19B108.9
C20—C9—C6120.5 (2)H19A—C19—H19B107.8
C9—C10—C12121.5 (3)C15—C20—C9118.9 (3)
C9—C10—C11119.6 (2)C15—C20—C19121.4 (3)
C12—C10—C11118.9 (3)C9—C20—C19119.7 (2)
N1—C11—C10178.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···N3i0.862.363.167 (4)157
N2—H2B···O2ii0.862.263.054 (4)154
Symmetry codes: (i) x, y, z+1; (ii) x1, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC20H17N3O2
Mr331.37
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)7.9614 (4), 22.054 (1), 10.1707 (6)
β (°) 101.747 (2)
V3)1748.38 (16)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.28 × 0.21 × 0.16
Data collection
DiffractometerRigaku R-AXIS RAPID
diffractometer
Absorption correctionMulti-scan
(ABSCOR; Higashi, 1995)
Tmin, Tmax0.953, 0.987
No. of measured, independent and
observed [I > 2σ(I)] reflections
13708, 3666, 1873
Rint0.039
(sin θ/λ)max1)0.648
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.135, 1.08
No. of reflections1886
No. of parameters227
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···N3i0.862.363.167 (4)157
N2—H2B···O2ii0.862.263.054 (4)154
Symmetry codes: (i) x, y, z+1; (ii) x1, y+1/2, z1/2.
 

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