The title compound, C
19H
17N
3, was synthesized by the reaction of 4-methylbenzaldehyde and cyclohexane with malononitrile under solvent-free conditions at 293 K. Conformational disorder is observed in the cyclohexene ring and both the major and minor components adopt half-chair conformations. N—H
N hydrogen bonds generate a centrosymmetric
R22(12) dimer.
Supporting information
CCDC reference: 613640
Key indicators
- Single-crystal X-ray study
- T = 294 K
- Mean (C-C) = 0.004 Å
- Disorder in main residue
- R factor = 0.049
- wR factor = 0.157
- Data-to-parameter ratio = 12.1
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT026_ALERT_3_C Ratio Observed / Unique Reflections too Low .... 48 Perc.
PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C16
PLAT301_ALERT_3_C Main Residue Disorder ......................... 8.00 Perc.
PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C2 - C11 ... 1.44 Ang.
PLAT371_ALERT_2_C Long C(sp2)-C(sp1) Bond C4 - C12 ... 1.44 Ang.
PLAT420_ALERT_2_C D-H Without Acceptor N2 - H2A ... ?
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........ 4
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
7 ALERT level C = Check and explain
0 ALERT level G = General alerts; check
0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
4 ALERT type 2 Indicator that the structure model may be wrong or deficient
2 ALERT type 3 Indicator that the structure quality may be low
1 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL.
2-amino-5,6,7,8-tetrahydro-4-
p-tolylnaphthalene-1,3-dicarbonitrile
top
Crystal data top
C19H17N3 | F(000) = 1216 |
Mr = 287.36 | Dx = 1.227 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1184 reflections |
a = 22.837 (6) Å | θ = 2.7–21.3° |
b = 7.906 (2) Å | µ = 0.07 mm−1 |
c = 17.920 (4) Å | T = 294 K |
β = 105.955 (5)° | Plate, colourless |
V = 3110.7 (14) Å3 | 0.24 × 0.20 × 0.08 mm |
Z = 8 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2752 independent reflections |
Radiation source: fine-focus sealed tube | 1327 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
φ and ω scans | θmax = 25.0°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −27→26 |
Tmin = 0.972, Tmax = 0.994 | k = −9→8 |
7651 measured reflections | l = −12→21 |
Refinement top
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)] = 0.049 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.157 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0708P)2 + 0.4798P] where P = (Fo2 + 2Fc2)/3 |
2752 reflections | (Δ/σ)max = 0.001 |
227 parameters | Δρmax = 0.19 e Å−3 |
10 restraints | Δρmin = −0.16 e Å−3 |
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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
N1 | 0.23869 (12) | 0.3183 (4) | 0.07116 (14) | 0.0797 (9) | |
N2 | 0.11484 (13) | 0.2528 (3) | −0.10063 (15) | 0.0593 (7) | |
N3 | −0.04379 (11) | 0.2146 (3) | −0.19567 (14) | 0.0757 (8) | |
C1 | 0.09492 (11) | 0.2774 (3) | 0.09710 (13) | 0.0434 (7) | |
C2 | 0.12202 (11) | 0.2754 (3) | 0.03559 (14) | 0.0452 (7) | |
C3 | 0.08756 (11) | 0.2571 (3) | −0.04203 (14) | 0.0442 (7) | |
C4 | 0.02418 (11) | 0.2435 (3) | −0.05495 (14) | 0.0443 (7) | |
C5 | −0.00350 (11) | 0.2471 (3) | 0.00609 (14) | 0.0417 (6) | |
C6 | −0.07189 (11) | 0.2307 (4) | −0.01321 (14) | 0.0546 (8) | |
H6A | −0.0847 | 0.1388 | −0.0499 | 0.065* | 0.487 (10) |
H6B | −0.0902 | 0.3340 | −0.0384 | 0.065* | 0.487 (10) |
H6C | −0.0828 | 0.1162 | −0.0288 | 0.065* | 0.513 (10) |
H6D | −0.0900 | 0.3027 | −0.0566 | 0.065* | 0.513 (10) |
C7 | −0.0959 (4) | 0.1977 (13) | 0.0569 (4) | 0.057 (3) | 0.487 (10) |
H7A | −0.0894 | 0.0800 | 0.0722 | 0.068* | 0.487 (10) |
H7B | −0.1393 | 0.2200 | 0.0433 | 0.068* | 0.487 (10) |
C8 | −0.0632 (3) | 0.3113 (12) | 0.1251 (4) | 0.054 (2) | 0.487 (10) |
H8A | −0.0687 | 0.4291 | 0.1096 | 0.065* | 0.487 (10) |
H8B | −0.0804 | 0.2941 | 0.1683 | 0.065* | 0.487 (10) |
C7' | −0.0985 (3) | 0.2749 (13) | 0.0529 (4) | 0.053 (3) | 0.513 (10) |
H7'A | −0.1399 | 0.2332 | 0.0412 | 0.063* | 0.513 (10) |
H7'B | −0.0996 | 0.3969 | 0.0581 | 0.063* | 0.513 (10) |
C8' | −0.0611 (3) | 0.1983 (14) | 0.1292 (3) | 0.058 (2) | 0.513 (10) |
H8'A | −0.0600 | 0.0762 | 0.1244 | 0.069* | 0.513 (10) |
H8'B | −0.0798 | 0.2252 | 0.1702 | 0.069* | 0.513 (10) |
C9 | 0.00368 (11) | 0.2690 (4) | 0.14959 (15) | 0.0557 (8) | |
H9A | 0.0092 | 0.1600 | 0.1754 | 0.067* | 0.487 (10) |
H9B | 0.0249 | 0.3529 | 0.1868 | 0.067* | 0.487 (10) |
H9C | 0.0031 | 0.3853 | 0.1666 | 0.067* | 0.513 (10) |
H9D | 0.0289 | 0.2045 | 0.1925 | 0.067* | 0.513 (10) |
C10 | 0.03186 (11) | 0.2633 (3) | 0.08256 (13) | 0.0437 (7) | |
C11 | 0.18703 (13) | 0.2987 (4) | 0.05462 (15) | 0.0553 (8) | |
C12 | −0.01342 (12) | 0.2273 (4) | −0.13334 (17) | 0.0529 (7) | |
C13 | 0.13542 (11) | 0.2928 (4) | 0.17762 (14) | 0.0460 (7) | |
C14 | 0.15436 (12) | 0.4482 (4) | 0.20935 (15) | 0.0609 (8) | |
H14A | 0.1402 | 0.5457 | 0.1811 | 0.073* | |
C15 | 0.19417 (12) | 0.4616 (4) | 0.28271 (15) | 0.0670 (9) | |
H15A | 0.2066 | 0.5681 | 0.3030 | 0.080* | |
C16 | 0.21563 (12) | 0.3209 (5) | 0.32594 (15) | 0.0593 (8) | |
C17 | 0.19562 (13) | 0.1659 (5) | 0.29469 (17) | 0.0674 (9) | |
H17A | 0.2092 | 0.0687 | 0.3235 | 0.081* | |
C18 | 0.15580 (12) | 0.1509 (4) | 0.22148 (16) | 0.0616 (8) | |
H18A | 0.1427 | 0.0445 | 0.2018 | 0.074* | |
C19 | 0.26099 (14) | 0.3362 (5) | 0.40513 (16) | 0.0956 (13) | |
H19A | 0.2694 | 0.2259 | 0.4281 | 0.143* | |
H19B | 0.2443 | 0.4068 | 0.4378 | 0.143* | |
H19C | 0.2980 | 0.3854 | 0.3998 | 0.143* | |
H2A | 0.0927 (12) | 0.237 (3) | −0.1470 (15) | 0.048 (8)* | |
H2B | 0.1591 (19) | 0.246 (4) | −0.091 (2) | 0.117 (14)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0427 (16) | 0.132 (3) | 0.0669 (17) | −0.0140 (17) | 0.0185 (14) | −0.0284 (16) |
N2 | 0.0518 (17) | 0.088 (2) | 0.0409 (15) | −0.0072 (14) | 0.0172 (13) | −0.0078 (14) |
N3 | 0.0565 (17) | 0.120 (2) | 0.0460 (15) | 0.0046 (15) | 0.0066 (13) | −0.0047 (15) |
C1 | 0.0329 (15) | 0.0571 (18) | 0.0382 (15) | 0.0005 (12) | 0.0064 (12) | 0.0005 (12) |
C2 | 0.0337 (15) | 0.0574 (18) | 0.0443 (15) | −0.0041 (12) | 0.0104 (12) | −0.0020 (13) |
C3 | 0.0398 (16) | 0.0509 (17) | 0.0428 (16) | −0.0018 (13) | 0.0127 (13) | −0.0025 (13) |
C4 | 0.0404 (16) | 0.0528 (17) | 0.0375 (14) | 0.0003 (13) | 0.0073 (12) | 0.0010 (12) |
C5 | 0.0362 (15) | 0.0483 (17) | 0.0394 (14) | 0.0019 (12) | 0.0086 (12) | 0.0023 (12) |
C6 | 0.0338 (16) | 0.080 (2) | 0.0462 (16) | 0.0029 (14) | 0.0052 (13) | 0.0020 (15) |
C7 | 0.045 (4) | 0.065 (8) | 0.059 (6) | 0.005 (4) | 0.012 (4) | 0.001 (4) |
C8 | 0.042 (4) | 0.077 (6) | 0.042 (4) | 0.006 (4) | 0.011 (3) | 0.011 (4) |
C7' | 0.035 (4) | 0.069 (7) | 0.054 (5) | −0.004 (4) | 0.013 (3) | −0.002 (4) |
C8' | 0.039 (4) | 0.093 (7) | 0.045 (4) | −0.001 (4) | 0.019 (3) | 0.007 (4) |
C9 | 0.0411 (16) | 0.085 (2) | 0.0422 (15) | 0.0030 (15) | 0.0129 (13) | 0.0029 (15) |
C10 | 0.0365 (15) | 0.0582 (18) | 0.0359 (14) | 0.0000 (13) | 0.0091 (12) | 0.0004 (12) |
C11 | 0.0450 (18) | 0.078 (2) | 0.0451 (17) | −0.0053 (16) | 0.0159 (14) | −0.0119 (15) |
C12 | 0.0440 (17) | 0.071 (2) | 0.0438 (17) | 0.0049 (15) | 0.0113 (14) | 0.0002 (15) |
C13 | 0.0308 (14) | 0.069 (2) | 0.0386 (15) | 0.0013 (14) | 0.0100 (12) | −0.0008 (15) |
C14 | 0.058 (2) | 0.069 (2) | 0.0476 (17) | 0.0019 (16) | 0.0015 (15) | 0.0041 (16) |
C15 | 0.058 (2) | 0.088 (3) | 0.0474 (18) | −0.0096 (18) | 0.0014 (16) | −0.0097 (17) |
C16 | 0.0330 (16) | 0.103 (3) | 0.0392 (16) | 0.0013 (18) | 0.0063 (13) | 0.0043 (18) |
C17 | 0.054 (2) | 0.091 (3) | 0.0528 (19) | 0.0137 (19) | 0.0073 (16) | 0.0213 (18) |
C18 | 0.0548 (19) | 0.071 (2) | 0.0522 (18) | 0.0074 (17) | 0.0042 (15) | 0.0051 (16) |
C19 | 0.062 (2) | 0.166 (4) | 0.0461 (19) | −0.007 (2) | −0.0060 (16) | 0.012 (2) |
Geometric parameters (Å, º) top
N1—C11 | 1.145 (3) | C8—H8B | 0.97 |
N2—C3 | 1.361 (3) | C7'—C8' | 1.524 (8) |
N2—H2A | 0.85 (3) | C7'—H7'A | 0.97 |
N2—H2B | 0.98 (4) | C7'—H7'B | 0.97 |
N3—C12 | 1.146 (3) | C8'—C9 | 1.529 (6) |
C1—C10 | 1.396 (3) | C8'—H8'A | 0.97 |
C1—C2 | 1.405 (3) | C8'—H8'B | 0.97 |
C1—C13 | 1.489 (3) | C9—C10 | 1.511 (4) |
C2—C3 | 1.405 (3) | C9—H9A | 0.97 |
C2—C11 | 1.441 (4) | C9—H9B | 0.97 |
C3—C4 | 1.406 (3) | C9—H9C | 0.97 |
C4—C5 | 1.406 (3) | C9—H9D | 0.97 |
C4—C12 | 1.437 (4) | C13—C14 | 1.373 (4) |
C5—C10 | 1.392 (3) | C13—C18 | 1.375 (4) |
C5—C6 | 1.509 (3) | C14—C15 | 1.382 (3) |
C6—C7' | 1.512 (7) | C14—H14A | 0.93 |
C6—C7 | 1.525 (8) | C15—C16 | 1.367 (4) |
C6—H6A | 0.97 | C15—H15A | 0.93 |
C6—H6B | 0.97 | C16—C17 | 1.372 (4) |
C6—H6C | 0.96 | C16—C19 | 1.514 (4) |
C6—H6D | 0.96 | C17—C18 | 1.381 (4) |
C7—C8 | 1.534 (8) | C17—H17A | 0.93 |
C7—H7A | 0.97 | C18—H18A | 0.93 |
C7—H7B | 0.97 | C19—H19A | 0.96 |
C8—C9 | 1.506 (6) | C19—H19B | 0.96 |
C8—H8A | 0.97 | C19—H19C | 0.96 |
| | | |
C3—N2—H2A | 118.7 (18) | C7'—C8'—H8'A | 109.7 |
C3—N2—H2B | 122 (2) | C9—C8'—H8'A | 109.7 |
H2A—N2—H2B | 118 (3) | C7'—C8'—H8'B | 109.7 |
C10—C1—C2 | 120.5 (2) | C9—C8'—H8'B | 109.7 |
C10—C1—C13 | 121.4 (2) | H8'A—C8'—H8'B | 108.2 |
C2—C1—C13 | 118.1 (2) | C8—C9—C10 | 113.2 (3) |
C3—C2—C1 | 122.0 (2) | C10—C9—C8' | 113.2 (3) |
C3—C2—C11 | 120.5 (2) | C8—C9—H9A | 108.9 |
C1—C2—C11 | 117.4 (2) | C10—C9—H9A | 108.9 |
N2—C3—C2 | 121.1 (2) | C8—C9—H9B | 108.9 |
N2—C3—C4 | 122.7 (2) | C10—C9—H9B | 108.9 |
C2—C3—C4 | 116.3 (2) | C8'—C9—H9B | 133.1 |
C3—C4—C5 | 122.2 (2) | H9A—C9—H9B | 107.8 |
C3—C4—C12 | 118.7 (2) | C10—C9—H9C | 108.9 |
C5—C4—C12 | 119.1 (2) | C8'—C9—H9C | 109.0 |
C10—C5—C4 | 120.3 (2) | H9A—C9—H9C | 134.7 |
C10—C5—C6 | 121.1 (2) | C8—C9—H9D | 133.0 |
C4—C5—C6 | 118.6 (2) | C10—C9—H9D | 108.9 |
C5—C6—C7' | 114.4 (3) | C8'—C9—H9D | 108.8 |
C5—C6—C7 | 114.2 (4) | H9C—C9—H9D | 107.8 |
C5—C6—H6A | 108.7 | C5—C10—C1 | 118.7 (2) |
C7—C6—H6A | 108.7 | C5—C10—C9 | 121.8 (2) |
C5—C6—H6B | 108.7 | C1—C10—C9 | 119.5 (2) |
C7—C6—H6B | 108.7 | N1—C11—C2 | 178.7 (3) |
H6A—C6—H6B | 107.6 | N3—C12—C4 | 179.5 (3) |
C5—C6—H6C | 108.5 | C14—C13—C18 | 118.3 (2) |
C7'—C6—H6C | 108.5 | C14—C13—C1 | 121.0 (2) |
C5—C6—H6D | 108.8 | C18—C13—C1 | 120.6 (3) |
C7'—C6—H6D | 108.7 | C13—C14—C15 | 120.8 (3) |
H6C—C6—H6D | 107.7 | C13—C14—H14A | 119.6 |
C6—C7—C8 | 110.5 (6) | C15—C14—H14A | 119.6 |
C6—C7—H7A | 109.6 | C16—C15—C14 | 121.1 (3) |
C8—C7—H7A | 109.6 | C16—C15—H15A | 119.4 |
C6—C7—H7B | 109.6 | C14—C15—H15A | 119.4 |
C8—C7—H7B | 109.6 | C15—C16—C17 | 117.9 (3) |
H7A—C7—H7B | 108.1 | C15—C16—C19 | 120.8 (3) |
C9—C8—C7 | 109.6 (7) | C17—C16—C19 | 121.2 (3) |
C9—C8—H8A | 109.8 | C16—C17—C18 | 121.5 (3) |
C7—C8—H8A | 109.8 | C16—C17—H17A | 119.2 |
C9—C8—H8B | 109.8 | C18—C17—H17A | 119.2 |
C7—C8—H8B | 109.8 | C13—C18—C17 | 120.3 (3) |
H8A—C8—H8B | 108.2 | C13—C18—H18A | 119.9 |
C6—C7'—C8' | 111.4 (6) | C17—C18—H18A | 119.9 |
C6—C7'—H7'A | 109.3 | C16—C19—H19A | 109.5 |
C8'—C7'—H7'A | 109.3 | C16—C19—H19B | 109.5 |
C6—C7'—H7'B | 109.3 | H19A—C19—H19B | 109.5 |
C8'—C7'—H7'B | 109.3 | C16—C19—H19C | 109.5 |
H7'A—C7'—H7'B | 108.0 | H19A—C19—H19C | 109.5 |
C7'—C8'—C9 | 109.6 (6) | H19B—C19—H19C | 109.5 |
| | | |
C10—C1—C2—C3 | −0.9 (4) | C7'—C8'—C9—C8 | 49.5 (7) |
C13—C1—C2—C3 | 178.4 (3) | C7'—C8'—C9—C10 | −48.1 (9) |
C10—C1—C2—C11 | 177.1 (2) | C4—C5—C10—C1 | 0.6 (4) |
C13—C1—C2—C11 | −3.6 (4) | C6—C5—C10—C1 | 179.8 (2) |
C1—C2—C3—N2 | −178.9 (2) | C4—C5—C10—C9 | 179.5 (2) |
C11—C2—C3—N2 | 3.2 (4) | C6—C5—C10—C9 | −1.3 (4) |
C1—C2—C3—C4 | 0.9 (4) | C2—C1—C10—C5 | 0.1 (4) |
C11—C2—C3—C4 | −177.0 (2) | C13—C1—C10—C5 | −179.2 (2) |
N2—C3—C4—C5 | 179.6 (2) | C2—C1—C10—C9 | −178.9 (2) |
C2—C3—C4—C5 | −0.2 (4) | C13—C1—C10—C9 | 1.9 (4) |
N2—C3—C4—C12 | −1.2 (4) | C8—C9—C10—C5 | −18.3 (5) |
C2—C3—C4—C12 | 179.0 (2) | C8'—C9—C10—C5 | 19.1 (5) |
C3—C4—C5—C10 | −0.5 (4) | C8—C9—C10—C1 | 160.5 (5) |
C12—C4—C5—C10 | −179.8 (2) | C8'—C9—C10—C1 | −162.0 (5) |
C3—C4—C5—C6 | −179.7 (2) | C10—C1—C13—C14 | −95.6 (3) |
C12—C4—C5—C6 | 1.1 (3) | C2—C1—C13—C14 | 85.1 (3) |
C10—C5—C6—C7' | 13.9 (5) | C10—C1—C13—C18 | 85.7 (3) |
C4—C5—C6—C7' | −167.0 (5) | C2—C1—C13—C18 | −93.5 (3) |
C10—C5—C6—C7 | −11.8 (6) | C18—C13—C14—C15 | 1.7 (4) |
C4—C5—C6—C7 | 167.4 (5) | C1—C13—C14—C15 | −177.0 (2) |
C5—C6—C7—C8 | 43.3 (10) | C13—C14—C15—C16 | −0.3 (4) |
C7'—C6—C7—C8 | −52.7 (10) | C14—C15—C16—C17 | −1.0 (4) |
C6—C7—C8—C9 | −62.8 (11) | C14—C15—C16—C19 | 177.8 (2) |
C5—C6—C7'—C8' | −43.9 (10) | C15—C16—C17—C18 | 1.0 (4) |
C7—C6—C7'—C8' | 50.8 (10) | C19—C16—C17—C18 | −177.9 (3) |
C6—C7'—C8'—C9 | 61.3 (11) | C14—C13—C18—C17 | −1.7 (4) |
C7—C8—C9—C10 | 49.5 (9) | C1—C13—C18—C17 | 176.9 (2) |
C7—C8—C9—C8' | −48.1 (7) | C16—C17—C18—C13 | 0.4 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2B···N1i | 0.98 (4) | 2.32 (4) | 3.288 (4) | 171 (3) |
Symmetry code: (i) −x+1/2, −y+1/2, −z. |