The title compound, C
20H
17FN
2, has been synthesized by the reductive cyclization induced by a low-valent titanium reagent. The cyclopentene ring adopts an envelope conformation, while the partially saturated six-membered ring adopts a distorted half-chair conformation. Intermolecular N—H
N hydrogen bonds between the amino and cyano groups result in the formation of a dimer structure.
Supporting information
CCDC reference: 225789
Key indicators
- Single-crystal X-ray study
- T = 291 K
- Mean (C-C) = 0.003 Å
- R factor = 0.038
- wR factor = 0.091
- Data-to-parameter ratio = 14.4
checkCIF/PLATON results
No syntax errors found
Alert level B
PLAT230_ALERT_2_B Hirshfeld Test Diff for C8 - C20 = 8.41 su
PLAT230_ALERT_2_B Hirshfeld Test Diff for C13 - C14 = 8.31 su
PLAT230_ALERT_2_B Hirshfeld Test Diff for C16 - C17 = 8.94 su
Alert level C
PLAT242_ALERT_2_C Check Low U(eq) as Compared to Neighbors .... C3
PLAT420_ALERT_2_C D-H Without Acceptor N1 - H1B ... ?
0 ALERT level A = In general: serious problem
3 ALERT level B = Potentially serious problem
2 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
5 ALERT type 2 Indicator that the structure model may be wrong or deficient
0 ALERT type 3 Indicator that the structure quality may be low
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 1997); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
3-Amino-1-(4-fluorophenyl)-3a,3 b,6,7-tetrahydrobenzo[4,5]indene-2-carbonitrile
top
Crystal data top
C20H17FN2 | F(000) = 640 |
Mr = 304.36 | Dx = 1.249 Mg m−3 |
Monoclinic, P21/n | Melting point = 472–473 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 11.516 (2) Å | Cell parameters from 30 reflections |
b = 9.710 (1) Å | θ = 2.9–14.4° |
c = 14.914 (2) Å | µ = 0.08 mm−1 |
β = 103.97 (1)° | T = 291 K |
V = 1618.4 (4) Å3 | Block, colorless |
Z = 4 | 0.52 × 0.42 × 0.30 mm |
Data collection top
Siemens P4 diffractometer | Rint = 0.009 |
Radiation source: normal-focus sealed tube | θmax = 25.5°, θmin = 2.0° |
Graphite monochromator | h = 0→13 |
ω scans | k = 0→11 |
3487 measured reflections | l = −18→17 |
3005 independent reflections | 3 standard reflections every 97 reflections |
1534 reflections with I > 2σ(I) | intensity decay: 2.9% |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.091 | w = 1/[σ2(Fo2) + (0.0443P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.83 | (Δ/σ)max < 0.001 |
3005 reflections | Δρmax = 0.12 e Å−3 |
209 parameters | Δρmin = −0.09 e Å−3 |
0 restraints | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0113 (12) |
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 | |
F | 0.55958 (12) | 0.56213 (13) | 0.10083 (8) | 0.1177 (5) | |
N1 | 0.32501 (13) | 0.17485 (15) | 0.55782 (10) | 0.0807 (5) | |
H1A | 0.3819 | 0.1152 | 0.5665 | 0.097* | |
H1B | 0.2857 | 0.1874 | 0.5994 | 0.097* | |
N2 | 0.50964 (16) | 0.0696 (2) | 0.39359 (12) | 0.1024 (6) | |
C1 | 0.31100 (16) | 0.41981 (17) | 0.17674 (12) | 0.0674 (5) | |
H1 | 0.2316 | 0.3956 | 0.1518 | 0.081* | |
C2 | 0.3779 (2) | 0.47465 (19) | 0.11946 (13) | 0.0786 (6) | |
H2 | 0.3447 | 0.4861 | 0.0566 | 0.094* | |
C3 | 0.4929 (2) | 0.51117 (19) | 0.15768 (16) | 0.0779 (6) | |
C4 | 0.54439 (18) | 0.4964 (2) | 0.24833 (15) | 0.0846 (6) | |
H4 | 0.6232 | 0.5235 | 0.2726 | 0.102* | |
C5 | 0.47689 (17) | 0.4397 (2) | 0.30476 (13) | 0.0772 (5) | |
H5 | 0.5116 | 0.4281 | 0.3674 | 0.093* | |
C6 | 0.35956 (16) | 0.40037 (17) | 0.26997 (11) | 0.0594 (5) | |
C7 | 0.28426 (15) | 0.33778 (18) | 0.32966 (11) | 0.0624 (5) | |
H7 | 0.2211 | 0.2836 | 0.2890 | 0.075* | |
C8 | 0.34837 (14) | 0.24344 (18) | 0.40675 (11) | 0.0610 (5) | |
C9 | 0.29754 (15) | 0.24840 (18) | 0.47928 (11) | 0.0608 (4) | |
C10 | 0.19256 (14) | 0.34703 (17) | 0.45904 (11) | 0.0605 (5) | |
H10 | 0.1213 | 0.2935 | 0.4299 | 0.073* | |
C11 | 0.22250 (15) | 0.43921 (18) | 0.38362 (11) | 0.0621 (5) | |
H11 | 0.1486 | 0.4747 | 0.3430 | 0.075* | |
C12 | 0.30073 (16) | 0.55799 (18) | 0.42890 (12) | 0.0713 (5) | |
H12A | 0.3197 | 0.6163 | 0.3816 | 0.086* | |
H12B | 0.3752 | 0.5222 | 0.4668 | 0.086* | |
C13 | 0.23723 (17) | 0.64316 (19) | 0.48891 (13) | 0.0792 (6) | |
H13A | 0.2928 | 0.7109 | 0.5228 | 0.095* | |
H13B | 0.1713 | 0.6925 | 0.4491 | 0.095* | |
C14 | 0.18961 (15) | 0.5582 (2) | 0.55654 (12) | 0.0698 (5) | |
C15 | 0.16320 (17) | 0.6195 (2) | 0.63399 (14) | 0.0871 (6) | |
H15 | 0.1784 | 0.7128 | 0.6451 | 0.104* | |
C16 | 0.11502 (18) | 0.5436 (3) | 0.69408 (14) | 0.0952 (7) | |
H16 | 0.0989 | 0.5858 | 0.7457 | 0.114* | |
C17 | 0.09061 (18) | 0.4068 (3) | 0.67860 (15) | 0.0912 (7) | |
H17 | 0.0584 | 0.3556 | 0.7194 | 0.109* | |
C18 | 0.11431 (16) | 0.3463 (2) | 0.60208 (13) | 0.0792 (6) | |
H18 | 0.0956 | 0.2538 | 0.5904 | 0.095* | |
C19 | 0.16579 (14) | 0.41953 (19) | 0.54108 (12) | 0.0636 (5) | |
C20 | 0.43796 (18) | 0.1485 (2) | 0.39943 (12) | 0.0728 (5) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
F | 0.1610 (12) | 0.1039 (10) | 0.1118 (9) | −0.0299 (9) | 0.0787 (9) | 0.0055 (8) |
N1 | 0.0949 (11) | 0.0819 (11) | 0.0768 (10) | 0.0396 (9) | 0.0430 (9) | 0.0244 (9) |
N2 | 0.1227 (15) | 0.0974 (14) | 0.1077 (13) | 0.0522 (12) | 0.0679 (12) | 0.0289 (11) |
C1 | 0.0797 (12) | 0.0605 (11) | 0.0622 (11) | 0.0032 (10) | 0.0176 (10) | −0.0044 (10) |
C2 | 0.1215 (18) | 0.0591 (12) | 0.0581 (12) | 0.0008 (13) | 0.0275 (13) | 0.0040 (10) |
C3 | 0.1061 (17) | 0.0626 (13) | 0.0776 (15) | −0.0048 (12) | 0.0469 (14) | 0.0016 (11) |
C4 | 0.0761 (13) | 0.0939 (16) | 0.0889 (16) | −0.0013 (12) | 0.0300 (12) | 0.0057 (12) |
C5 | 0.0674 (12) | 0.0973 (15) | 0.0683 (12) | 0.0072 (12) | 0.0189 (10) | 0.0129 (11) |
C6 | 0.0627 (11) | 0.0600 (11) | 0.0578 (11) | 0.0105 (9) | 0.0187 (9) | 0.0036 (9) |
C7 | 0.0600 (10) | 0.0697 (12) | 0.0601 (10) | 0.0055 (9) | 0.0193 (9) | 0.0030 (9) |
C8 | 0.0642 (11) | 0.0590 (11) | 0.0653 (10) | 0.0157 (9) | 0.0266 (9) | 0.0062 (9) |
C9 | 0.0671 (11) | 0.0539 (10) | 0.0653 (11) | 0.0120 (9) | 0.0235 (9) | 0.0066 (9) |
C10 | 0.0571 (10) | 0.0630 (11) | 0.0651 (11) | 0.0107 (9) | 0.0219 (9) | 0.0030 (9) |
C11 | 0.0586 (10) | 0.0667 (11) | 0.0617 (11) | 0.0140 (10) | 0.0156 (9) | 0.0079 (10) |
C12 | 0.0763 (12) | 0.0623 (12) | 0.0799 (12) | 0.0116 (11) | 0.0279 (10) | 0.0111 (10) |
C13 | 0.0850 (14) | 0.0628 (12) | 0.0892 (14) | 0.0185 (11) | 0.0203 (11) | 0.0011 (11) |
C14 | 0.0685 (12) | 0.0744 (13) | 0.0680 (12) | 0.0229 (11) | 0.0194 (10) | 0.0058 (11) |
C15 | 0.0814 (14) | 0.0926 (16) | 0.0873 (14) | 0.0274 (12) | 0.0205 (12) | −0.0149 (13) |
C16 | 0.0798 (15) | 0.141 (2) | 0.0694 (14) | 0.0328 (16) | 0.0276 (12) | −0.0111 (16) |
C17 | 0.0818 (15) | 0.116 (2) | 0.0861 (15) | 0.0259 (14) | 0.0406 (12) | 0.0078 (14) |
C18 | 0.0764 (13) | 0.0877 (14) | 0.0843 (13) | 0.0220 (11) | 0.0406 (11) | 0.0084 (12) |
C19 | 0.0587 (11) | 0.0683 (13) | 0.0676 (11) | 0.0202 (10) | 0.0226 (9) | 0.0090 (10) |
C20 | 0.0871 (14) | 0.0701 (13) | 0.0715 (12) | 0.0189 (12) | 0.0393 (11) | 0.0172 (10) |
Geometric parameters (Å, º) top
F—C3 | 1.367 (2) | C10—C19 | 1.507 (2) |
N1—C9 | 1.343 (2) | C10—C11 | 1.540 (2) |
N1—H1A | 0.8600 | C10—H10 | 0.9800 |
N1—H1B | 0.8600 | C11—C12 | 1.518 (2) |
N2—C20 | 1.145 (2) | C11—H11 | 0.9800 |
C1—C6 | 1.381 (2) | C12—C13 | 1.528 (2) |
C1—C2 | 1.387 (2) | C12—H12A | 0.9700 |
C1—H1 | 0.9300 | C12—H12B | 0.9700 |
C2—C3 | 1.356 (3) | C13—C14 | 1.505 (2) |
C2—H2 | 0.9300 | C13—H13A | 0.9700 |
C3—C4 | 1.346 (3) | C13—H13B | 0.9700 |
C4—C5 | 1.390 (2) | C14—C19 | 1.383 (2) |
C4—H4 | 0.9300 | C14—C15 | 1.396 (2) |
C5—C6 | 1.379 (2) | C15—C16 | 1.376 (3) |
C5—H5 | 0.9300 | C15—H15 | 0.9300 |
C6—C7 | 1.512 (2) | C16—C17 | 1.365 (3) |
C7—C8 | 1.515 (2) | C16—H16 | 0.9300 |
C7—C11 | 1.549 (2) | C17—C18 | 1.369 (2) |
C7—H7 | 0.9800 | C17—H17 | 0.9300 |
C8—C9 | 1.349 (2) | C18—C19 | 1.395 (2) |
C8—C20 | 1.407 (2) | C18—H18 | 0.9300 |
C9—C10 | 1.514 (2) | | |
| | | |
C9—N1—H1A | 120.0 | C11—C10—H10 | 107.2 |
C9—N1—H1B | 120.0 | C12—C11—C10 | 109.27 (14) |
H1A—N1—H1B | 120.0 | C12—C11—C7 | 114.62 (13) |
C6—C1—C2 | 121.51 (18) | C10—C11—C7 | 102.8 (1) |
C6—C1—H1 | 119.2 | C12—C11—H11 | 110.0 |
C2—C1—H1 | 119.2 | C10—C11—H11 | 110.0 |
C3—C2—C1 | 118.19 (18) | C7—C11—H11 | 110.0 |
C3—C2—H2 | 120.9 | C11—C12—C13 | 110.80 (14) |
C1—C2—H2 | 120.9 | C11—C12—H12A | 109.5 |
C4—C3—C2 | 122.89 (18) | C13—C12—H12A | 109.5 |
C4—C3—F | 118.9 (2) | C11—C12—H12B | 109.5 |
C2—C3—F | 118.2 (2) | C13—C12—H12B | 109.5 |
C3—C4—C5 | 118.34 (19) | H12A—C12—H12B | 108.1 |
C3—C4—H4 | 120.8 | C14—C13—C12 | 113.53 (15) |
C5—C4—H4 | 120.8 | C14—C13—H13A | 108.9 |
C6—C5—C4 | 121.49 (18) | C12—C13—H13A | 108.9 |
C6—C5—H5 | 119.3 | C14—C13—H13B | 108.9 |
C4—C5—H5 | 119.3 | C12—C13—H13B | 108.9 |
C5—C6—C1 | 117.56 (16) | H13A—C13—H13B | 107.7 |
C5—C6—C7 | 122.61 (16) | C19—C14—C15 | 118.59 (19) |
C1—C6—C7 | 119.83 (16) | C19—C14—C13 | 120.78 (16) |
C6—C7—C8 | 116.5 (1) | C15—C14—C13 | 120.6 (2) |
C6—C7—C11 | 116.79 (14) | C16—C15—C14 | 120.9 (2) |
C8—C7—C11 | 101.0 (1) | C16—C15—H15 | 119.6 |
C6—C7—H7 | 107.3 | C14—C15—H15 | 119.6 |
C8—C7—H7 | 107.3 | C17—C16—C15 | 120.6 (2) |
C11—C7—H7 | 107.3 | C17—C16—H16 | 119.7 |
C9—C8—C20 | 123.62 (15) | C15—C16—H16 | 119.7 |
C9—C8—C7 | 111.1 (1) | C16—C17—C18 | 119.0 (2) |
C20—C8—C7 | 124.7 (1) | C16—C17—H17 | 120.5 |
N1—C9—C8 | 128.6 (2) | C18—C17—H17 | 120.5 |
N1—C9—C10 | 121.3 (1) | C17—C18—C19 | 121.8 (2) |
C8—C9—C10 | 110.0 (1) | C17—C18—H18 | 119.1 |
C19—C10—C9 | 116.33 (14) | C19—C18—H18 | 119.1 |
C19—C10—C11 | 116.57 (14) | C14—C19—C18 | 119.09 (17) |
C9—C10—C11 | 101.8 (1) | C14—C19—C10 | 121.28 (16) |
C19—C10—H10 | 107.2 | C18—C19—C10 | 119.62 (17) |
C9—C10—H10 | 107.2 | N2—C20—C8 | 178.9 (2) |
| | | |
C6—C1—C2—C3 | −1.0 (3) | C9—C10—C11—C12 | −87.82 (15) |
C1—C2—C3—C4 | 0.0 (3) | C19—C10—C11—C7 | 161.99 (14) |
C1—C2—C3—F | 178.46 (16) | C9—C10—C11—C7 | 34.32 (16) |
C2—C3—C4—C5 | 0.8 (3) | C6—C7—C11—C12 | −42.9 (2) |
F—C3—C4—C5 | −177.64 (16) | C8—C7—C11—C12 | 84.48 (16) |
C3—C4—C5—C6 | −0.7 (3) | C6—C7—C11—C10 | −161.37 (14) |
C4—C5—C6—C1 | −0.3 (3) | C8—C7—C11—C10 | −33.98 (16) |
C4—C5—C6—C7 | 179.68 (16) | C10—C11—C12—C13 | −59.07 (17) |
C2—C1—C6—C5 | 1.1 (3) | C7—C11—C12—C13 | −173.82 (14) |
C2—C1—C6—C7 | −178.85 (16) | C11—C12—C13—C14 | 51.5 (2) |
C5—C6—C7—C8 | −35.8 (2) | C12—C13—C14—C19 | −23.0 (2) |
C1—C6—C7—C8 | 144.18 (15) | C12—C13—C14—C15 | 160.10 (16) |
C5—C6—C7—C11 | 83.6 (2) | C19—C14—C15—C16 | 0.3 (3) |
C1—C6—C7—C11 | −96.44 (19) | C13—C14—C15—C16 | 177.31 (17) |
C6—C7—C8—C9 | 149.35 (16) | C14—C15—C16—C17 | −0.8 (3) |
C11—C7—C8—C9 | 21.76 (19) | C15—C16—C17—C18 | −0.3 (3) |
C6—C7—C8—C20 | −39.0 (2) | C16—C17—C18—C19 | 1.9 (3) |
C11—C7—C8—C20 | −166.62 (17) | C15—C14—C19—C18 | 1.2 (3) |
C20—C8—C9—N1 | 4.6 (3) | C13—C14—C19—C18 | −175.78 (15) |
C7—C8—C9—N1 | 176.29 (17) | C15—C14—C19—C10 | −179.77 (15) |
C20—C8—C9—C10 | −171.6 (2) | C13—C14—C19—C10 | 3.2 (3) |
C7—C8—C9—C10 | 0.1 (2) | C17—C18—C19—C14 | −2.3 (3) |
N1—C9—C10—C19 | 33.5 (2) | C17—C18—C19—C10 | 178.62 (16) |
C8—C9—C10—C19 | −150.00 (16) | C9—C10—C19—C14 | 107.93 (19) |
N1—C9—C10—C11 | 161.3 (2) | C11—C10—C19—C14 | −12.2 (2) |
C8—C9—C10—C11 | −22.17 (19) | C9—C10—C19—C18 | −73.1 (2) |
C19—C10—C11—C12 | 39.85 (19) | C11—C10—C19—C18 | 166.77 (15) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···N2i | 0.86 | 2.19 | 3.019 (2) | 163 |
Symmetry code: (i) −x+1, −y, −z+1. |