The title compound, C
21H
19ClN
2O
3, was synthesized by the reaction of 4-chlorobenzaldehyde, 4-methoxyacetophenone, ethyl cyanoacetate and ammonium acetate under microwave irradiation. X-ray analysis reveals that the benzene rings are orthogonal to each other and form dihedral angles of 29.34 (6) and 79.45 (6)° with the pyridine ring. In the solid state, the molecules exist as centrosymmetric N—H
O hydrogen-bonded dimers.
Supporting information
CCDC reference: 259847
Key indicators
- Single-crystal X-ray study
- T = 193 K
- Mean (C-C) = 0.002 Å
- R factor = 0.050
- wR factor = 0.115
- Data-to-parameter ratio = 16.7
checkCIF/PLATON results
No syntax errors found
Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.98
PLAT063_ALERT_3_C Crystal Probably too Large for Beam Size ....... 0.70 mm
0 ALERT level A = In general: serious problem
0 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
0 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
0 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: CrystalClear (Rigaku, 1999); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2000–2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
4-(4-chlorophenyl)-6-(4-methoxyphenyl) 2-amino-3-ethoxycarbonly-pyridine
top
Crystal data top
C21H19ClN2O3 | Z = 2 |
Mr = 382.83 | F(000) = 400 |
Triclinic, P1 | Dx = 1.341 Mg m−3 |
Hall symbol: -P 1 | Melting point = 442–443 K |
a = 8.5398 (14) Å | Mo Kα radiation, λ = 0.71070 Å |
b = 10.1117 (13) Å | Cell parameters from 4130 reflections |
c = 12.729 (2) Å | θ = 3.1–27.5° |
α = 72.153 (14)° | µ = 0.23 mm−1 |
β = 81.338 (16)° | T = 193 K |
γ = 65.053 (13)° | Block, colourless |
V = 948.3 (3) Å3 | 0.70 × 0.41 × 0.34 mm |
Data collection top
Rigaku Mercury diffractometer | 4254 independent reflections |
Radiation source: fine-focus sealed tube | 3813 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
Detector resolution: 7.31 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ω scans | h = −11→9 |
Absorption correction: multi-scan (Jacobson, 1998) | k = −13→13 |
Tmin = 0.858, Tmax = 0.927 | l = −16→13 |
10603 measured reflections | |
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)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.115 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.11 | w = 1/[σ2(Fo2) + (0.0457P)2 + 0.3701P] where P = (Fo2 + 2Fc2)/3 |
4254 reflections | (Δ/σ)max < 0.001 |
254 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.28 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 | |
Cl1 | −0.36874 (6) | 0.64643 (7) | 1.00745 (4) | 0.05602 (18) | |
O1 | −0.06986 (14) | 0.30136 (14) | 0.48870 (9) | 0.0358 (3) | |
O2 | −0.16972 (13) | 0.42870 (13) | 0.61599 (10) | 0.0366 (3) | |
O3 | 1.12798 (15) | −0.09275 (15) | 0.86376 (11) | 0.0442 (3) | |
N1 | 0.43780 (15) | 0.12257 (14) | 0.60536 (10) | 0.0269 (3) | |
N2 | 0.2679 (2) | 0.14298 (19) | 0.47500 (12) | 0.0399 (4) | |
C1 | 0.27752 (19) | 0.18219 (17) | 0.56473 (12) | 0.0266 (3) | |
C2 | 0.12839 (18) | 0.27774 (16) | 0.61470 (12) | 0.0253 (3) | |
C3 | 0.15457 (19) | 0.31001 (16) | 0.70878 (12) | 0.0261 (3) | |
C4 | 0.32100 (19) | 0.25055 (18) | 0.74673 (13) | 0.0310 (3) | |
H4 | 0.3411 | 0.2742 | 0.8088 | 0.037* | |
C5 | 0.45867 (19) | 0.15654 (17) | 0.69466 (12) | 0.0267 (3) | |
C6 | −0.04288 (19) | 0.33482 (17) | 0.56609 (12) | 0.0264 (3) | |
C7 | −0.34247 (19) | 0.4815 (2) | 0.57695 (14) | 0.0346 (4) | |
H7A | −0.3688 | 0.3944 | 0.5787 | 0.042* | |
H7B | −0.3525 | 0.5466 | 0.5001 | 0.042* | |
C8 | −0.4653 (2) | 0.5699 (3) | 0.65237 (19) | 0.0556 (5) | |
H8A | −0.4565 | 0.5035 | 0.7277 | 0.083* | |
H8B | −0.5836 | 0.6100 | 0.6272 | 0.083* | |
H8C | −0.4359 | 0.6541 | 0.6514 | 0.083* | |
C9 | 0.01684 (18) | 0.39919 (16) | 0.77761 (12) | 0.0256 (3) | |
C10 | −0.0768 (2) | 0.3304 (2) | 0.85508 (15) | 0.0421 (4) | |
H10 | −0.0596 | 0.2296 | 0.8599 | 0.051* | |
C11 | −0.1951 (2) | 0.4061 (2) | 0.92572 (15) | 0.0448 (4) | |
H11 | −0.2592 | 0.3581 | 0.9787 | 0.054* | |
C12 | −0.2186 (2) | 0.55120 (19) | 0.91814 (13) | 0.0336 (4) | |
C13 | −0.1267 (2) | 0.6220 (2) | 0.84303 (16) | 0.0412 (4) | |
H13 | −0.1446 | 0.7229 | 0.8387 | 0.049* | |
C14 | −0.0070 (2) | 0.54465 (19) | 0.77323 (14) | 0.0355 (4) | |
H14 | 0.0591 | 0.5922 | 0.7219 | 0.043* | |
C15 | 0.63592 (19) | 0.08819 (16) | 0.73725 (12) | 0.0270 (3) | |
C16 | 0.6636 (2) | 0.05664 (18) | 0.84974 (13) | 0.0321 (3) | |
H16 | 0.5674 | 0.0777 | 0.8996 | 0.039* | |
C17 | 0.8285 (2) | −0.00446 (19) | 0.88919 (14) | 0.0346 (4) | |
H17 | 0.8450 | −0.0252 | 0.9657 | 0.042* | |
C18 | 0.9705 (2) | −0.03560 (17) | 0.81702 (14) | 0.0319 (3) | |
C19 | 0.9464 (2) | −0.00591 (18) | 0.70544 (14) | 0.0317 (3) | |
H19 | 1.0430 | −0.0279 | 0.6559 | 0.038* | |
C20 | 0.77961 (19) | 0.05629 (17) | 0.66686 (13) | 0.0288 (3) | |
H20 | 0.7636 | 0.0775 | 0.5903 | 0.035* | |
C21 | 1.2770 (2) | −0.1490 (3) | 0.79712 (18) | 0.0585 (6) | |
H21A | 1.2699 | −0.2268 | 0.7697 | 0.088* | |
H21B | 1.3806 | −0.1931 | 0.8412 | 0.088* | |
H21C | 1.2832 | −0.0657 | 0.7345 | 0.088* | |
H2A | 0.360 (3) | 0.074 (3) | 0.4534 (18) | 0.055 (6)* | |
H2B | 0.168 (3) | 0.176 (2) | 0.4489 (17) | 0.045 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0391 (3) | 0.0800 (4) | 0.0457 (3) | −0.0042 (2) | 0.00587 (19) | −0.0442 (3) |
O1 | 0.0276 (6) | 0.0500 (7) | 0.0310 (6) | −0.0095 (5) | −0.0023 (4) | −0.0203 (5) |
O2 | 0.0214 (5) | 0.0443 (7) | 0.0448 (7) | −0.0025 (5) | −0.0042 (5) | −0.0268 (6) |
O3 | 0.0276 (6) | 0.0500 (8) | 0.0502 (7) | −0.0076 (5) | −0.0129 (5) | −0.0129 (6) |
N1 | 0.0239 (6) | 0.0298 (6) | 0.0280 (6) | −0.0065 (5) | −0.0008 (5) | −0.0152 (5) |
N2 | 0.0263 (7) | 0.0528 (9) | 0.0409 (8) | −0.0005 (6) | −0.0061 (6) | −0.0327 (7) |
C1 | 0.0254 (7) | 0.0285 (7) | 0.0269 (7) | −0.0077 (6) | 0.0000 (6) | −0.0134 (6) |
C2 | 0.0232 (7) | 0.0258 (7) | 0.0271 (7) | −0.0068 (6) | −0.0006 (5) | −0.0119 (6) |
C3 | 0.0259 (7) | 0.0255 (7) | 0.0281 (7) | −0.0079 (6) | 0.0012 (6) | −0.0130 (6) |
C4 | 0.0277 (8) | 0.0358 (8) | 0.0326 (8) | −0.0070 (6) | −0.0017 (6) | −0.0211 (7) |
C5 | 0.0243 (7) | 0.0282 (7) | 0.0294 (7) | −0.0078 (6) | −0.0018 (6) | −0.0136 (6) |
C6 | 0.0245 (7) | 0.0274 (7) | 0.0266 (7) | −0.0080 (6) | 0.0007 (5) | −0.0101 (6) |
C7 | 0.0201 (7) | 0.0392 (9) | 0.0434 (9) | −0.0057 (6) | −0.0041 (6) | −0.0172 (7) |
C8 | 0.0277 (9) | 0.0713 (14) | 0.0670 (13) | −0.0066 (9) | 0.0052 (9) | −0.0395 (12) |
C9 | 0.0235 (7) | 0.0265 (7) | 0.0259 (7) | −0.0051 (6) | −0.0019 (5) | −0.0124 (6) |
C10 | 0.0501 (10) | 0.0289 (8) | 0.0463 (10) | −0.0170 (8) | 0.0156 (8) | −0.0147 (7) |
C11 | 0.0473 (10) | 0.0435 (10) | 0.0385 (9) | −0.0182 (8) | 0.0155 (8) | −0.0121 (8) |
C12 | 0.0276 (8) | 0.0423 (9) | 0.0270 (7) | −0.0030 (7) | 0.0000 (6) | −0.0201 (7) |
C13 | 0.0448 (10) | 0.0336 (9) | 0.0502 (10) | −0.0130 (7) | 0.0069 (8) | −0.0257 (8) |
C14 | 0.0387 (9) | 0.0327 (8) | 0.0389 (9) | −0.0162 (7) | 0.0096 (7) | −0.0172 (7) |
C15 | 0.0244 (7) | 0.0261 (7) | 0.0335 (8) | −0.0075 (6) | −0.0031 (6) | −0.0149 (6) |
C16 | 0.0292 (8) | 0.0354 (8) | 0.0319 (8) | −0.0083 (6) | 0.0002 (6) | −0.0166 (7) |
C17 | 0.0351 (8) | 0.0354 (9) | 0.0326 (8) | −0.0086 (7) | −0.0075 (7) | −0.0130 (7) |
C18 | 0.0276 (8) | 0.0278 (8) | 0.0410 (9) | −0.0083 (6) | −0.0088 (6) | −0.0108 (7) |
C19 | 0.0260 (7) | 0.0322 (8) | 0.0387 (8) | −0.0109 (6) | 0.0010 (6) | −0.0139 (7) |
C20 | 0.0272 (7) | 0.0303 (8) | 0.0309 (7) | −0.0094 (6) | −0.0021 (6) | −0.0136 (6) |
C21 | 0.0258 (9) | 0.0714 (14) | 0.0571 (12) | −0.0107 (9) | −0.0062 (8) | 0.0013 (10) |
Geometric parameters (Å, º) top
Cl1—C12 | 1.7474 (15) | C8—H8C | 0.98 |
O1—C6 | 1.2151 (18) | C9—C10 | 1.381 (2) |
O2—C6 | 1.3314 (17) | C9—C14 | 1.381 (2) |
O2—C7 | 1.4499 (18) | C10—C11 | 1.382 (2) |
O3—C18 | 1.3680 (19) | C10—H10 | 0.95 |
O3—C21 | 1.422 (2) | C11—C12 | 1.369 (3) |
N1—C5 | 1.3393 (18) | C11—H11 | 0.95 |
N1—C1 | 1.3529 (19) | C12—C13 | 1.368 (3) |
N2—C1 | 1.3423 (19) | C13—C14 | 1.387 (2) |
N2—H2A | 0.88 (2) | C13—H13 | 0.95 |
N2—H2B | 0.85 (2) | C14—H14 | 0.95 |
C1—C2 | 1.4334 (19) | C15—C20 | 1.387 (2) |
C2—C3 | 1.404 (2) | C15—C16 | 1.402 (2) |
C2—C6 | 1.482 (2) | C16—C17 | 1.380 (2) |
C3—C4 | 1.387 (2) | C16—H16 | 0.95 |
C3—C9 | 1.4978 (19) | C17—C18 | 1.390 (2) |
C4—C5 | 1.391 (2) | C17—H17 | 0.95 |
C4—H4 | 0.95 | C18—C19 | 1.387 (2) |
C5—C15 | 1.483 (2) | C19—C20 | 1.390 (2) |
C7—C8 | 1.501 (2) | C19—H19 | 0.95 |
C7—H7A | 0.99 | C20—H20 | 0.95 |
C7—H7B | 0.99 | C21—H21A | 0.98 |
C8—H8A | 0.98 | C21—H21B | 0.98 |
C8—H8B | 0.98 | C21—H21C | 0.98 |
| | | |
C6—O2—C7 | 116.25 (12) | C9—C10—C11 | 120.99 (16) |
C18—O3—C21 | 117.28 (15) | C9—C10—H10 | 119.5 |
C5—N1—C1 | 118.71 (12) | C11—C10—H10 | 119.5 |
C1—N2—H2A | 118.7 (15) | C12—C11—C10 | 119.01 (16) |
C1—N2—H2B | 117.1 (14) | C12—C11—H11 | 120.5 |
H2A—N2—H2B | 123 (2) | C10—C11—H11 | 120.5 |
N2—C1—N1 | 114.94 (13) | C13—C12—C11 | 121.46 (15) |
N2—C1—C2 | 122.36 (14) | C13—C12—Cl1 | 119.73 (13) |
N1—C1—C2 | 122.69 (13) | C11—C12—Cl1 | 118.81 (14) |
C3—C2—C1 | 117.13 (13) | C12—C13—C14 | 119.09 (16) |
C3—C2—C6 | 123.91 (13) | C12—C13—H13 | 120.5 |
C1—C2—C6 | 118.95 (13) | C14—C13—H13 | 120.5 |
C4—C3—C2 | 118.84 (13) | C9—C14—C13 | 120.65 (15) |
C4—C3—C9 | 115.00 (13) | C9—C14—H14 | 119.7 |
C2—C3—C9 | 126.11 (13) | C13—C14—H14 | 119.7 |
C3—C4—C5 | 120.53 (13) | C20—C15—C16 | 117.83 (14) |
C3—C4—H4 | 119.7 | C20—C15—C5 | 121.12 (13) |
C5—C4—H4 | 119.7 | C16—C15—C5 | 121.04 (14) |
N1—C5—C4 | 122.07 (13) | C17—C16—C15 | 121.10 (15) |
N1—C5—C15 | 117.15 (13) | C17—C16—H16 | 119.5 |
C4—C5—C15 | 120.78 (13) | C15—C16—H16 | 119.5 |
O1—C6—O2 | 121.64 (13) | C16—C17—C18 | 120.00 (15) |
O1—C6—C2 | 124.97 (13) | C16—C17—H17 | 120.0 |
O2—C6—C2 | 113.39 (12) | C18—C17—H17 | 120.0 |
O2—C7—C8 | 107.12 (14) | O3—C18—C19 | 124.48 (15) |
O2—C7—H7A | 110.3 | O3—C18—C17 | 115.53 (15) |
C8—C7—H7A | 110.3 | C19—C18—C17 | 119.97 (14) |
O2—C7—H7B | 110.3 | C18—C19—C20 | 119.36 (15) |
C8—C7—H7B | 110.3 | C18—C19—H19 | 120.3 |
H7A—C7—H7B | 108.5 | C20—C19—H19 | 120.3 |
C7—C8—H8A | 109.5 | C15—C20—C19 | 121.73 (14) |
C7—C8—H8B | 109.5 | C15—C20—H20 | 119.1 |
H8A—C8—H8B | 109.5 | C19—C20—H20 | 119.1 |
C7—C8—H8C | 109.5 | O3—C21—H21A | 109.5 |
H8A—C8—H8C | 109.5 | O3—C21—H21B | 109.5 |
H8B—C8—H8C | 109.5 | H21A—C21—H21B | 109.5 |
C10—C9—C14 | 118.77 (14) | O3—C21—H21C | 109.5 |
C10—C9—C3 | 119.68 (14) | H21A—C21—H21C | 109.5 |
C14—C9—C3 | 121.23 (14) | H21B—C21—H21C | 109.5 |
| | | |
C5—N1—C1—N2 | 179.78 (14) | C14—C9—C10—C11 | 1.3 (3) |
C5—N1—C1—C2 | −1.3 (2) | C3—C9—C10—C11 | 174.88 (16) |
N2—C1—C2—C3 | 179.57 (15) | C9—C10—C11—C12 | −0.1 (3) |
N1—C1—C2—C3 | 0.8 (2) | C10—C11—C12—C13 | −0.5 (3) |
N2—C1—C2—C6 | 0.3 (2) | C10—C11—C12—Cl1 | 179.86 (15) |
N1—C1—C2—C6 | −178.47 (14) | C11—C12—C13—C14 | −0.1 (3) |
C1—C2—C3—C4 | 0.9 (2) | Cl1—C12—C13—C14 | 179.52 (13) |
C6—C2—C3—C4 | −179.85 (14) | C10—C9—C14—C13 | −2.0 (3) |
C1—C2—C3—C9 | −176.20 (14) | C3—C9—C14—C13 | −175.40 (15) |
C6—C2—C3—C9 | 3.0 (2) | C12—C13—C14—C9 | 1.3 (3) |
C2—C3—C4—C5 | −2.1 (2) | N1—C5—C15—C20 | 30.8 (2) |
C9—C3—C4—C5 | 175.36 (14) | C4—C5—C15—C20 | −149.80 (15) |
C1—N1—C5—C4 | 0.2 (2) | N1—C5—C15—C16 | −150.57 (15) |
C1—N1—C5—C15 | 179.56 (13) | C4—C5—C15—C16 | 28.8 (2) |
C3—C4—C5—N1 | 1.6 (2) | C20—C15—C16—C17 | −0.1 (2) |
C3—C4—C5—C15 | −177.79 (14) | C5—C15—C16—C17 | −178.82 (15) |
C7—O2—C6—O1 | 3.4 (2) | C15—C16—C17—C18 | 0.1 (3) |
C7—O2—C6—C2 | −176.33 (13) | C21—O3—C18—C19 | −11.1 (2) |
C3—C2—C6—O1 | −175.56 (15) | C21—O3—C18—C17 | 170.07 (17) |
C1—C2—C6—O1 | 3.6 (2) | C16—C17—C18—O3 | 178.59 (15) |
C3—C2—C6—O2 | 4.2 (2) | C16—C17—C18—C19 | −0.3 (2) |
C1—C2—C6—O2 | −176.62 (13) | O3—C18—C19—C20 | −178.18 (15) |
C6—O2—C7—C8 | 173.62 (15) | C17—C18—C19—C20 | 0.6 (2) |
C4—C3—C9—C10 | −97.13 (19) | C16—C15—C20—C19 | 0.4 (2) |
C2—C3—C9—C10 | 80.1 (2) | C5—C15—C20—C19 | 179.13 (14) |
C4—C3—C9—C14 | 76.24 (19) | C18—C19—C20—C15 | −0.7 (2) |
C2—C3—C9—C14 | −106.52 (19) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···N1i | 0.88 (2) | 2.26 (2) | 3.1288 (19) | 169 (2) |
N2—H2B···O1 | 0.85 (2) | 1.97 (2) | 2.6529 (19) | 136 (2) |
C4—H4···Cl1ii | 0.95 | 2.77 | 3.7125 (18) | 175 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y+1, −z+2. |