The title compound, C16H10Cl2N2O3·C2H6O, was synthesized by the reaction of 4-hydroxy-6-methylpyran-2-one, 2,4-dichlorobenzaldehyde and malononitrile in the presence of triethylbenzylammonium chloride in an aqueous medium. X-ray analysis reveals that the pyranone ring is almost planar, while the pyran ring adopts a flattened boat conformation.
Supporting information
CCDC reference: 255891
Key indicators
- Single-crystal X-ray study
- T = 193 K
- Mean (C-C) = 0.004 Å
- H-atom completeness 69%
- Disorder in solvent or counterion
- R factor = 0.050
- wR factor = 0.147
- Data-to-parameter ratio = 13.2
checkCIF/PLATON results
No syntax errors found
Alert level C
CELLV02_ALERT_1_C The supplied cell volume s.u. differs from that
calculated from the cell parameter s.u.'s by > 2
Calculated cell volume su = 20.49
Cell volume su given = 18.00
CHEMW03_ALERT_2_C The ratio of given/expected molecular weight as
calculated from the _atom_site* data lies outside
the range 0.99 <> 1.01
From the CIF: _cell_formula_units_Z 2
From the CIF: _chemical_formula_weight 395.23
TEST: Calculate formula weight from _atom_site_*
atom mass num sum
C 12.01 18.00 216.20
H 1.01 11.00 11.09
Cl 35.45 2.00 70.91
N 14.01 2.00 28.01
O 16.00 4.00 64.00
Calculated formula weight 390.20
PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ?
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ?
PLAT043_ALERT_1_C Check Reported Molecular Weight ................ 395.23
PLAT044_ALERT_1_C Calculated and Reported Dx Differ .............. ?
PLAT068_ALERT_1_C Reported F000 Differs from Calcd (or Missing)... ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent ..... ?
PLAT302_ALERT_4_C Anion/Solvent Disorder ......................... 25.00 Perc.
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 33
C1 -C2 -C9 -N2 162.00 13.00 1.555 1.555 1.555 1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 34
C3 -C2 -C9 -N2 -16.00 13.00 1.555 1.555 1.555 1.555
Alert level G
FORMU01_ALERT_2_G There is a discrepancy between the atom counts in the
_chemical_formula_sum and the formula from the _atom_site* data.
Atom count from _chemical_formula_sum:C18 H16 Cl2 N2 O4
Atom count from the _atom_site data: C18 H11 Cl2 N2 O4
CELLZ01_ALERT_1_G Difference between formula and atom_site contents detected.
CELLZ01_ALERT_1_G WARNING: H atoms missing from atom site list. Is this intentional?
From the CIF: _cell_formula_units_Z 2
From the CIF: _chemical_formula_sum C18 H16 Cl2 N2 O4
TEST: Compare cell contents of formula and atom_site data
atom Z*formula cif sites diff
C 36.00 36.00 0.00
H 32.00 22.00 10.00
Cl 4.00 4.00 0.00
N 4.00 4.00 0.00
O 8.00 8.00 0.00
0 ALERT level A = In general: serious problem
0 ALERT level B = Potentially serious problem
11 ALERT level C = Check and explain
3 ALERT level G = General alerts; check
9 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
2 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
3 ALERT type 4 Improvement, methodology, query or suggestion
Data collection: CrystalClear (Rigaku, 2000); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2003); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL.
2-Amino-3-cyano-4-(2,4-dichlorophenyl)-8-methylpyrano[3,2-
c]pyran-5(4
H)-one ethanol solvate
top
Crystal data top
C16H10Cl2N2O3·C2H6O | Z = 2 |
Mr = 395.23 | F(000) = 408 |
Triclinic, P1 | Dx = 1.406 Mg m−3 |
Hall symbol: -P 1 | Melting point = 503–504 K |
a = 9.2879 (12) Å | Mo Kα radiation, λ = 0.71070 Å |
b = 10.4526 (12) Å | Cell parameters from 3571 reflections |
c = 11.0678 (10) Å | θ = 3.0–25.3° |
α = 63.905 (10)° | µ = 0.37 mm−1 |
β = 75.826 (14)° | T = 193 K |
γ = 80.288 (15)° | Block, colorless |
V = 933.29 (18) Å3 | 0.50 × 0.31 × 0.20 mm |
Data collection top
Rigaku Mercury diffractometer | 3403 independent reflections |
Radiation source: fine-focus sealed tube | 2985 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
Detector resolution: 7.31 pixels mm-1 | θmax = 25.4°, θmin = 3.3° |
ω scans | h = −10→11 |
Absorption correction: multi-scan (Jacobson, 1998) | k = −12→12 |
Tmin = 0.835, Tmax = 0.929 | l = −11→13 |
9269 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) = 0.147 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0852P)2 + 0.4955P] where P = (Fo2 + 2Fc2)/3 |
3403 reflections | (Δ/σ)max = 0.001 |
258 parameters | Δρmax = 0.65 e Å−3 |
2 restraints | Δρmin = −0.43 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) |
Cl1 | 0.13535 (7) | 0.13002 (7) | 0.90105 (6) | 0.0371 (2) | |
Cl2 | 0.42099 (14) | −0.35050 (10) | 0.88044 (11) | 0.0789 (4) | |
O1 | −0.01040 (18) | 0.44676 (18) | 0.69492 (18) | 0.0300 (4) | |
O2 | −0.0972 (2) | 0.0657 (2) | 0.6044 (2) | 0.0395 (5) | |
O3 | −0.27994 (19) | 0.1663 (2) | 0.71198 (19) | 0.0351 (4) | |
O4 | 0.0135 (3) | 0.2371 (2) | 0.3022 (2) | 0.0526 (6) | |
N1 | 0.1967 (3) | 0.5552 (2) | 0.6383 (3) | 0.0344 (5) | |
N2 | 0.4792 (2) | 0.3789 (3) | 0.4595 (3) | 0.0400 (6) | |
C1 | 0.1377 (3) | 0.4510 (3) | 0.6331 (2) | 0.0261 (5) | |
C2 | 0.2047 (3) | 0.3575 (3) | 0.5777 (2) | 0.0260 (5) | |
C3 | 0.1283 (3) | 0.2354 (2) | 0.5865 (2) | 0.0257 (5) | |
H3 | 0.1355 | 0.2467 | 0.4907 | 0.031* | |
C4 | −0.0338 (3) | 0.2500 (3) | 0.6468 (2) | 0.0261 (5) | |
C5 | −0.0928 (3) | 0.3496 (3) | 0.6958 (2) | 0.0262 (5) | |
C6 | −0.1320 (3) | 0.1556 (3) | 0.6500 (3) | 0.0298 (6) | |
C7 | −0.3347 (3) | 0.2676 (3) | 0.7613 (3) | 0.0327 (6) | |
C8 | −0.2458 (3) | 0.3597 (3) | 0.7544 (3) | 0.0308 (6) | |
H8 | −0.2844 | 0.4305 | 0.7880 | 0.037* | |
C9 | 0.3559 (3) | 0.3707 (3) | 0.5124 (3) | 0.0286 (5) | |
C10 | 0.2035 (2) | 0.0898 (3) | 0.6642 (3) | 0.0252 (5) | |
C11 | 0.2106 (3) | 0.0333 (3) | 0.8029 (3) | 0.0291 (5) | |
C12 | 0.2769 (3) | −0.1000 (3) | 0.8696 (3) | 0.0395 (6) | |
H12 | 0.2788 | −0.1365 | 0.9645 | 0.047* | |
C13 | 0.3407 (3) | −0.1795 (3) | 0.7954 (3) | 0.0446 (7) | |
C14 | 0.3400 (3) | −0.1281 (3) | 0.6580 (3) | 0.0413 (7) | |
H14 | 0.3861 | −0.1829 | 0.6078 | 0.050* | |
C15 | 0.2705 (3) | 0.0053 (3) | 0.5946 (3) | 0.0340 (6) | |
H15 | 0.2684 | 0.0407 | 0.4999 | 0.041* | |
C16 | −0.4959 (3) | 0.2581 (4) | 0.8216 (3) | 0.0445 (7) | |
H16A | −0.5322 | 0.3371 | 0.8488 | 0.067* | |
H16B | −0.5118 | 0.1670 | 0.9023 | 0.067* | |
H16C | −0.5502 | 0.2639 | 0.7537 | 0.067* | |
C17 | 0.0689 (7) | 0.2488 (5) | 0.1691 (4) | 0.0993 (18) | |
C18A | 0.2278 (16) | 0.2732 (18) | 0.1393 (17) | 0.130 (6) | 0.45 |
C18B | 0.1302 (18) | 0.3840 (11) | 0.0673 (9) | 0.133 (5) | 0.55 |
H1A | 0.137 (3) | 0.621 (3) | 0.657 (3) | 0.035 (8)* | |
H1B | 0.281 (4) | 0.567 (3) | 0.609 (3) | 0.039 (9)* | |
H4 | 0.010 (5) | 0.149 (5) | 0.363 (4) | 0.076 (13)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0425 (4) | 0.0398 (4) | 0.0317 (4) | −0.0020 (3) | −0.0049 (3) | −0.0188 (3) |
Cl2 | 0.1105 (9) | 0.0423 (5) | 0.0759 (7) | 0.0369 (5) | −0.0395 (6) | −0.0212 (5) |
O1 | 0.0236 (9) | 0.0298 (9) | 0.0420 (10) | −0.0032 (7) | −0.0019 (7) | −0.0216 (8) |
O2 | 0.0398 (11) | 0.0341 (10) | 0.0542 (12) | −0.0060 (8) | −0.0089 (9) | −0.0259 (10) |
O3 | 0.0279 (9) | 0.0352 (10) | 0.0432 (11) | −0.0073 (7) | −0.0056 (8) | −0.0162 (9) |
O4 | 0.0723 (16) | 0.0337 (12) | 0.0480 (13) | 0.0006 (11) | −0.0030 (11) | −0.0197 (11) |
N1 | 0.0261 (12) | 0.0320 (12) | 0.0519 (15) | −0.0045 (10) | −0.0009 (10) | −0.0262 (11) |
N2 | 0.0287 (13) | 0.0404 (13) | 0.0563 (15) | −0.0060 (10) | 0.0030 (11) | −0.0294 (12) |
C1 | 0.0226 (12) | 0.0255 (12) | 0.0299 (12) | −0.0022 (9) | −0.0047 (9) | −0.0111 (10) |
C2 | 0.0254 (12) | 0.0230 (12) | 0.0295 (12) | −0.0031 (9) | −0.0035 (9) | −0.0112 (10) |
C3 | 0.0273 (12) | 0.0238 (12) | 0.0281 (12) | −0.0022 (9) | −0.0047 (9) | −0.0130 (10) |
C4 | 0.0258 (12) | 0.0238 (12) | 0.0285 (12) | −0.0020 (9) | −0.0071 (9) | −0.0096 (10) |
C5 | 0.0251 (12) | 0.0246 (12) | 0.0289 (12) | −0.0042 (9) | −0.0064 (9) | −0.0096 (10) |
C6 | 0.0281 (13) | 0.0284 (13) | 0.0321 (13) | −0.0033 (10) | −0.0074 (10) | −0.0105 (11) |
C7 | 0.0270 (13) | 0.0359 (14) | 0.0314 (13) | −0.0015 (10) | −0.0063 (10) | −0.0104 (11) |
C8 | 0.0256 (12) | 0.0314 (13) | 0.0352 (14) | 0.0004 (10) | −0.0035 (10) | −0.0156 (11) |
C9 | 0.0308 (14) | 0.0237 (12) | 0.0346 (13) | −0.0027 (10) | −0.0050 (11) | −0.0154 (11) |
C10 | 0.0212 (11) | 0.0250 (12) | 0.0309 (12) | −0.0041 (9) | −0.0044 (9) | −0.0124 (10) |
C11 | 0.0285 (13) | 0.0278 (13) | 0.0328 (13) | −0.0022 (10) | −0.0036 (10) | −0.0154 (11) |
C12 | 0.0446 (16) | 0.0345 (15) | 0.0375 (15) | 0.0020 (12) | −0.0138 (12) | −0.0121 (12) |
C13 | 0.0483 (17) | 0.0298 (15) | 0.0534 (18) | 0.0108 (12) | −0.0192 (14) | −0.0152 (13) |
C14 | 0.0431 (16) | 0.0330 (15) | 0.0535 (18) | 0.0061 (12) | −0.0105 (13) | −0.0257 (14) |
C15 | 0.0360 (14) | 0.0321 (14) | 0.0380 (14) | −0.0004 (11) | −0.0070 (11) | −0.0190 (12) |
C16 | 0.0274 (14) | 0.0550 (19) | 0.0495 (17) | −0.0074 (13) | −0.0029 (12) | −0.0210 (15) |
C17 | 0.162 (5) | 0.075 (3) | 0.049 (2) | −0.015 (3) | 0.009 (3) | −0.027 (2) |
C18A | 0.143 (12) | 0.121 (12) | 0.129 (12) | −0.070 (10) | 0.061 (10) | −0.079 (11) |
C18B | 0.236 (15) | 0.082 (7) | 0.046 (5) | −0.026 (8) | 0.035 (7) | −0.021 (5) |
Geometric parameters (Å, º) top
Cl1—C11 | 1.745 (2) | C4—C6 | 1.437 (3) |
Cl2—C13 | 1.746 (3) | C5—C8 | 1.417 (3) |
O1—C5 | 1.366 (3) | C7—C8 | 1.337 (4) |
O1—C1 | 1.377 (3) | C7—C16 | 1.483 (4) |
O2—C6 | 1.215 (3) | C8—H8 | 0.9500 |
O3—C7 | 1.367 (3) | C10—C15 | 1.392 (4) |
O3—C6 | 1.387 (3) | C10—C11 | 1.397 (4) |
O4—C17 | 1.393 (5) | C11—C12 | 1.376 (4) |
O4—H4 | 0.87 (5) | C12—C13 | 1.383 (4) |
N1—C1 | 1.327 (3) | C12—H12 | 0.9500 |
N1—H1A | 0.87 (3) | C13—C14 | 1.374 (4) |
N1—H1B | 0.78 (3) | C14—C15 | 1.382 (4) |
N2—C9 | 1.150 (3) | C14—H14 | 0.9500 |
C1—C2 | 1.361 (3) | C15—H15 | 0.9500 |
C2—C9 | 1.412 (3) | C16—H16A | 0.9800 |
C2—C3 | 1.518 (3) | C16—H16B | 0.9800 |
C3—C4 | 1.502 (3) | C16—H16C | 0.9800 |
C3—C10 | 1.526 (3) | C17—C18B | 1.466 (10) |
C3—H3 | 1.0000 | C17—C18A | 1.473 (14) |
C4—C5 | 1.356 (3) | | |
| | | |
C5—O1—C1 | 118.89 (18) | C7—C8—H8 | 120.7 |
C7—O3—C6 | 122.3 (2) | C5—C8—H8 | 120.7 |
C17—O4—H4 | 113 (3) | N2—C9—C2 | 178.7 (3) |
C1—N1—H1A | 119 (2) | C15—C10—C11 | 116.4 (2) |
C1—N1—H1B | 120 (2) | C15—C10—C3 | 119.1 (2) |
H1A—N1—H1B | 120 (3) | C11—C10—C3 | 124.4 (2) |
N1—C1—C2 | 128.6 (2) | C12—C11—C10 | 122.5 (2) |
N1—C1—O1 | 109.9 (2) | C12—C11—Cl1 | 116.4 (2) |
C2—C1—O1 | 121.6 (2) | C10—C11—Cl1 | 121.16 (19) |
C1—C2—C9 | 118.5 (2) | C11—C12—C13 | 118.5 (3) |
C1—C2—C3 | 123.9 (2) | C11—C12—H12 | 120.8 |
C9—C2—C3 | 117.5 (2) | C13—C12—H12 | 120.8 |
C4—C3—C2 | 108.54 (19) | C14—C13—C12 | 121.6 (3) |
C4—C3—C10 | 113.02 (19) | C14—C13—Cl2 | 119.7 (2) |
C2—C3—C10 | 112.40 (19) | C12—C13—Cl2 | 118.7 (2) |
C4—C3—H3 | 107.5 | C13—C14—C15 | 118.4 (3) |
C2—C3—H3 | 107.5 | C13—C14—H14 | 120.8 |
C10—C3—H3 | 107.5 | C15—C14—H14 | 120.8 |
C5—C4—C6 | 118.3 (2) | C14—C15—C10 | 122.6 (3) |
C5—C4—C3 | 123.4 (2) | C14—C15—H15 | 118.7 |
C6—C4—C3 | 118.4 (2) | C10—C15—H15 | 118.7 |
C4—C5—O1 | 123.2 (2) | C7—C16—H16A | 109.5 |
C4—C5—C8 | 122.3 (2) | C7—C16—H16B | 109.5 |
O1—C5—C8 | 114.5 (2) | H16A—C16—H16B | 109.5 |
O2—C6—O3 | 116.6 (2) | C7—C16—H16C | 109.5 |
O2—C6—C4 | 125.9 (2) | H16A—C16—H16C | 109.5 |
O3—C6—C4 | 117.4 (2) | H16B—C16—H16C | 109.5 |
C8—C7—O3 | 120.9 (2) | O4—C17—C18B | 117.3 (5) |
C8—C7—C16 | 126.9 (3) | O4—C17—C18A | 106.2 (7) |
O3—C7—C16 | 112.2 (2) | C18B—C17—C18A | 57.3 (9) |
C7—C8—C5 | 118.6 (2) | | |
| | | |
C5—O1—C1—N1 | 177.7 (2) | C6—O3—C7—C8 | −1.5 (4) |
C5—O1—C1—C2 | −2.5 (3) | C6—O3—C7—C16 | 179.5 (2) |
N1—C1—C2—C9 | −2.0 (4) | O3—C7—C8—C5 | −0.6 (4) |
O1—C1—C2—C9 | 178.2 (2) | C16—C7—C8—C5 | 178.3 (3) |
N1—C1—C2—C3 | 175.6 (2) | C4—C5—C8—C7 | 0.0 (4) |
O1—C1—C2—C3 | −4.2 (4) | O1—C5—C8—C7 | −179.1 (2) |
C1—C2—C3—C4 | 7.9 (3) | C1—C2—C9—N2 | 162 (13) |
C9—C2—C3—C4 | −174.6 (2) | C3—C2—C9—N2 | −16 (13) |
C1—C2—C3—C10 | −117.9 (3) | C4—C3—C10—C15 | 121.3 (2) |
C9—C2—C3—C10 | 59.7 (3) | C2—C3—C10—C15 | −115.4 (2) |
C2—C3—C4—C5 | −5.8 (3) | C4—C3—C10—C11 | −58.8 (3) |
C10—C3—C4—C5 | 119.6 (3) | C2—C3—C10—C11 | 64.5 (3) |
C2—C3—C4—C6 | 172.8 (2) | C15—C10—C11—C12 | −1.4 (4) |
C10—C3—C4—C6 | −61.8 (3) | C3—C10—C11—C12 | 178.6 (2) |
C6—C4—C5—O1 | −178.5 (2) | C15—C10—C11—Cl1 | 178.30 (18) |
C3—C4—C5—O1 | 0.1 (4) | C3—C10—C11—Cl1 | −1.6 (3) |
C6—C4—C5—C8 | 2.5 (4) | C10—C11—C12—C13 | 1.0 (4) |
C3—C4—C5—C8 | −178.9 (2) | Cl1—C11—C12—C13 | −178.7 (2) |
C1—O1—C5—C4 | 4.6 (3) | C11—C12—C13—C14 | 0.4 (5) |
C1—O1—C5—C8 | −176.3 (2) | C11—C12—C13—Cl2 | −178.4 (2) |
C7—O3—C6—O2 | −176.8 (2) | C12—C13—C14—C15 | −1.4 (5) |
C7—O3—C6—C4 | 3.9 (3) | Cl2—C13—C14—C15 | 177.5 (2) |
C5—C4—C6—O2 | 176.5 (2) | C13—C14—C15—C10 | 0.9 (4) |
C3—C4—C6—O2 | −2.2 (4) | C11—C10—C15—C14 | 0.4 (4) |
C5—C4—C6—O3 | −4.3 (3) | C3—C10—C15—C14 | −179.6 (2) |
C3—C4—C6—O3 | 177.0 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14···N2i | 0.95 | 2.52 | 3.439 (4) | 164 |
O4—H4···O2 | 0.87 (5) | 2.42 (4) | 3.020 (3) | 127 (3) |
O4—H4···O2ii | 0.87 (5) | 2.15 (5) | 2.894 (3) | 143 (4) |
N1—H1B···N2iii | 0.78 (3) | 2.26 (3) | 3.026 (3) | 172 (3) |
N1—H1A···O4iv | 0.87 (3) | 1.99 (3) | 2.856 (3) | 175 (3) |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x, −y, −z+1; (iii) −x+1, −y+1, −z+1; (iv) −x, −y+1, −z+1. |