Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052361/sg2190sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052361/sg2190Isup2.hkl |
CCDC reference: 672851
The title compound was prepared from acetyl chloride, monomethylamine and diflunisal, according to the procedure of Rao & Hu (2005).
H atoms were added at calculated positions and refined using a riding model. H atoms were given isotropic displacement parameters equal to 1.2(or 1.5 for methyl H atoms) times the equivalent isotropic displacement parameters of their parent atoms and C—H distances were restrained to 0.93 Å for those bonded to phenyl ring and 0.96 Å for those bonded to methyl. N—H distance was restrained to 0.86 Å.
Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
C16H13F2NO3 | F(000) = 632 |
Mr = 305.27 | Dx = 1.437 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 9.8972 (5) Å | θ = 9.9–13.9° |
b = 19.9625 (11) Å | µ = 0.12 mm−1 |
c = 7.4737 (4) Å | T = 298 K |
β = 107.180 (2)° | Prismatic, colourless |
V = 1410.72 (13) Å3 | 0.25 × 0.20 × 0.20 mm |
Z = 4 |
Enraf–Nonius CAD-4 diffractometer | 2741 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 28.3°, θmin = 2.0° |
ω/2θ scans | h = −13→12 |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | k = −25→25 |
Tmin = 0.971, Tmax = 0.976 | l = −9→9 |
18835 measured reflections | 3 standard reflections every 60 min |
3441 independent reflections | intensity decay: 0.3% |
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)] = 0.044 | H-atom parameters constrained |
wR(F2) = 0.130 | w = 1/[σ2(Fo2) + (0.0643P)2 + 0.396P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
3441 reflections | Δρmax = 0.30 e Å−3 |
202 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.010 (2) |
C16H13F2NO3 | V = 1410.72 (13) Å3 |
Mr = 305.27 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.8972 (5) Å | µ = 0.12 mm−1 |
b = 19.9625 (11) Å | T = 298 K |
c = 7.4737 (4) Å | 0.25 × 0.20 × 0.20 mm |
β = 107.180 (2)° |
Enraf–Nonius CAD-4 diffractometer | 2741 reflections with I > 2σ(I) |
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) | Rint = 0.024 |
Tmin = 0.971, Tmax = 0.976 | 3 standard reflections every 60 min |
18835 measured reflections | intensity decay: 0.3% |
3441 independent reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.30 e Å−3 |
3441 reflections | Δρmin = −0.23 e Å−3 |
202 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
F1 | 0.32311 (11) | 0.74045 (5) | 0.49721 (19) | 0.0707 (4) | |
F2 | 0.76499 (10) | 0.83535 (6) | 0.5573 (2) | 0.0824 (4) | |
O1 | −0.26535 (10) | 0.87205 (5) | 0.07940 (16) | 0.0442 (3) | |
O2 | −0.25482 (12) | 0.94857 (6) | −0.13686 (17) | 0.0528 (3) | |
O3 | −0.21960 (11) | 0.99622 (6) | 0.27918 (18) | 0.0510 (3) | |
N1 | −0.03370 (13) | 1.04551 (6) | 0.21903 (19) | 0.0418 (3) | |
H1 | 0.0471 | 1.0401 | 0.1998 | 0.050* | |
C1 | −0.03767 (13) | 0.92526 (7) | 0.23466 (19) | 0.0339 (3) | |
C2 | −0.11773 (14) | 0.86970 (7) | 0.1527 (2) | 0.0382 (3) | |
C3 | −0.05561 (16) | 0.80854 (8) | 0.1458 (2) | 0.0468 (4) | |
H3 | −0.1109 | 0.7722 | 0.0903 | 0.056* | |
C4 | 0.08875 (15) | 0.80110 (7) | 0.2211 (2) | 0.0431 (3) | |
H4 | 0.1300 | 0.7595 | 0.2167 | 0.052* | |
C5 | 0.17344 (14) | 0.85508 (7) | 0.30349 (19) | 0.0341 (3) | |
C6 | 0.10768 (13) | 0.91656 (7) | 0.30923 (18) | 0.0331 (3) | |
H6 | 0.1629 | 0.9530 | 0.3648 | 0.040* | |
C7 | 0.32962 (14) | 0.84948 (7) | 0.37554 (19) | 0.0346 (3) | |
C8 | 0.41649 (15) | 0.90169 (8) | 0.3515 (2) | 0.0406 (3) | |
H8 | 0.3745 | 0.9407 | 0.2925 | 0.049* | |
C9 | 0.56228 (16) | 0.89772 (9) | 0.4118 (2) | 0.0482 (4) | |
H9 | 0.6180 | 0.9332 | 0.3943 | 0.058* | |
C10 | 0.62193 (16) | 0.84022 (9) | 0.4978 (3) | 0.0511 (4) | |
C11 | 0.54416 (17) | 0.78679 (9) | 0.5286 (3) | 0.0524 (4) | |
H11 | 0.5873 | 0.7482 | 0.5889 | 0.063* | |
C12 | 0.39927 (16) | 0.79306 (8) | 0.4659 (2) | 0.0432 (3) | |
C13 | −0.32361 (15) | 0.91518 (7) | −0.0630 (2) | 0.0406 (3) | |
C14 | −0.48084 (16) | 0.91338 (10) | −0.1116 (3) | 0.0536 (4) | |
H14A | −0.5095 | 0.9279 | −0.0059 | 0.080* | |
H14B | −0.5135 | 0.8685 | −0.1445 | 0.080* | |
H14C | −0.5208 | 0.9426 | −0.2158 | 0.080* | |
C15 | −0.10582 (14) | 0.99183 (7) | 0.2462 (2) | 0.0353 (3) | |
C16 | −0.08854 (18) | 1.11262 (8) | 0.2203 (3) | 0.0502 (4) | |
H16A | −0.0248 | 1.1442 | 0.1914 | 0.075* | |
H16B | −0.0978 | 1.1223 | 0.3420 | 0.075* | |
H16C | −0.1795 | 1.1159 | 0.1283 | 0.075* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0535 (6) | 0.0495 (6) | 0.1028 (9) | −0.0014 (5) | 0.0133 (6) | 0.0329 (6) |
F2 | 0.0277 (5) | 0.0760 (8) | 0.1328 (11) | 0.0125 (5) | 0.0070 (6) | −0.0009 (8) |
O1 | 0.0253 (5) | 0.0412 (6) | 0.0621 (7) | −0.0064 (4) | 0.0067 (4) | 0.0045 (5) |
O2 | 0.0378 (6) | 0.0616 (7) | 0.0559 (7) | −0.0040 (5) | 0.0091 (5) | 0.0097 (5) |
O3 | 0.0343 (6) | 0.0470 (6) | 0.0782 (8) | −0.0002 (4) | 0.0267 (5) | −0.0036 (6) |
N1 | 0.0324 (6) | 0.0342 (6) | 0.0618 (8) | 0.0017 (5) | 0.0186 (5) | 0.0021 (5) |
C1 | 0.0278 (6) | 0.0332 (7) | 0.0409 (7) | −0.0013 (5) | 0.0108 (5) | 0.0023 (5) |
C2 | 0.0250 (6) | 0.0373 (7) | 0.0507 (8) | −0.0041 (5) | 0.0089 (6) | 0.0048 (6) |
C3 | 0.0356 (8) | 0.0331 (7) | 0.0679 (10) | −0.0085 (6) | 0.0093 (7) | −0.0020 (7) |
C4 | 0.0352 (7) | 0.0308 (7) | 0.0618 (9) | 0.0001 (6) | 0.0121 (7) | 0.0022 (6) |
C5 | 0.0284 (6) | 0.0345 (7) | 0.0393 (7) | 0.0003 (5) | 0.0096 (5) | 0.0047 (5) |
C6 | 0.0274 (6) | 0.0331 (7) | 0.0383 (6) | −0.0030 (5) | 0.0090 (5) | 0.0006 (5) |
C7 | 0.0293 (7) | 0.0355 (7) | 0.0384 (7) | 0.0023 (5) | 0.0092 (5) | 0.0011 (5) |
C8 | 0.0319 (7) | 0.0390 (8) | 0.0500 (8) | 0.0016 (6) | 0.0108 (6) | 0.0076 (6) |
C9 | 0.0328 (7) | 0.0477 (9) | 0.0644 (10) | −0.0034 (6) | 0.0145 (7) | 0.0022 (7) |
C10 | 0.0266 (7) | 0.0557 (10) | 0.0673 (10) | 0.0074 (6) | 0.0082 (7) | −0.0046 (8) |
C11 | 0.0409 (8) | 0.0442 (9) | 0.0653 (10) | 0.0139 (7) | 0.0053 (7) | 0.0051 (8) |
C12 | 0.0384 (8) | 0.0369 (8) | 0.0524 (8) | 0.0018 (6) | 0.0107 (6) | 0.0070 (6) |
C13 | 0.0311 (7) | 0.0405 (8) | 0.0470 (7) | −0.0013 (6) | 0.0064 (6) | −0.0051 (6) |
C14 | 0.0299 (8) | 0.0669 (11) | 0.0591 (10) | 0.0022 (7) | 0.0057 (7) | −0.0045 (8) |
C15 | 0.0271 (6) | 0.0366 (7) | 0.0406 (7) | −0.0003 (5) | 0.0076 (5) | −0.0001 (5) |
C16 | 0.0493 (9) | 0.0363 (8) | 0.0674 (10) | 0.0049 (7) | 0.0208 (8) | 0.0040 (7) |
F1—C12 | 1.3529 (18) | C5—C7 | 1.4833 (18) |
F2—C10 | 1.3565 (17) | C6—H6 | 0.9300 |
O1—C13 | 1.3579 (19) | C7—C12 | 1.387 (2) |
O1—C2 | 1.4014 (16) | C7—C8 | 1.3961 (19) |
O2—C13 | 1.1978 (18) | C8—C9 | 1.381 (2) |
O3—C15 | 1.2248 (17) | C8—H8 | 0.9300 |
N1—C15 | 1.3361 (18) | C9—C10 | 1.362 (2) |
N1—C16 | 1.4464 (19) | C9—H9 | 0.9300 |
N1—H1 | 0.8599 | C10—C11 | 1.374 (3) |
C1—C6 | 1.3916 (18) | C11—C12 | 1.376 (2) |
C1—C2 | 1.3951 (19) | C11—H11 | 0.9300 |
C1—C15 | 1.5042 (19) | C13—C14 | 1.490 (2) |
C2—C3 | 1.375 (2) | C14—H14A | 0.9600 |
C3—C4 | 1.380 (2) | C14—H14B | 0.9600 |
C3—H3 | 0.9300 | C14—H14C | 0.9600 |
C4—C5 | 1.392 (2) | C16—H16A | 0.9600 |
C4—H4 | 0.9300 | C16—H16B | 0.9600 |
C5—C6 | 1.3959 (19) | C16—H16C | 0.9600 |
C13—O1—C2 | 118.69 (11) | C10—C9—H9 | 121.0 |
C15—N1—C16 | 121.57 (12) | C8—C9—H9 | 121.0 |
C15—N1—H1 | 119.2 | F2—C10—C9 | 118.69 (15) |
C16—N1—H1 | 119.2 | F2—C10—C11 | 118.15 (15) |
C6—C1—C2 | 117.55 (12) | C9—C10—C11 | 123.16 (14) |
C6—C1—C15 | 121.01 (12) | C10—C11—C12 | 116.82 (15) |
C2—C1—C15 | 121.42 (12) | C10—C11—H11 | 121.6 |
C3—C2—C1 | 121.34 (13) | C12—C11—H11 | 121.6 |
C3—C2—O1 | 116.18 (12) | F1—C12—C11 | 116.62 (13) |
C1—C2—O1 | 122.44 (12) | F1—C12—C7 | 119.49 (13) |
C2—C3—C4 | 120.06 (13) | C11—C12—C7 | 123.89 (14) |
C2—C3—H3 | 120.0 | O2—C13—O1 | 123.12 (13) |
C4—C3—H3 | 120.0 | O2—C13—C14 | 126.56 (15) |
C3—C4—C5 | 120.82 (13) | O1—C13—C14 | 110.31 (13) |
C3—C4—H4 | 119.6 | C13—C14—H14A | 109.5 |
C5—C4—H4 | 119.6 | C13—C14—H14B | 109.5 |
C4—C5—C6 | 117.97 (12) | H14A—C14—H14B | 109.5 |
C4—C5—C7 | 121.94 (12) | C13—C14—H14C | 109.5 |
C6—C5—C7 | 120.03 (12) | H14A—C14—H14C | 109.5 |
C1—C6—C5 | 122.25 (12) | H14B—C14—H14C | 109.5 |
C1—C6—H6 | 118.9 | O3—C15—N1 | 122.50 (13) |
C5—C6—H6 | 118.9 | O3—C15—C1 | 121.96 (12) |
C12—C7—C8 | 115.62 (13) | N1—C15—C1 | 115.53 (11) |
C12—C7—C5 | 123.54 (12) | N1—C16—H16A | 109.5 |
C8—C7—C5 | 120.83 (12) | N1—C16—H16B | 109.5 |
C9—C8—C7 | 122.60 (14) | H16A—C16—H16B | 109.5 |
C9—C8—H8 | 118.7 | N1—C16—H16C | 109.5 |
C7—C8—H8 | 118.7 | H16A—C16—H16C | 109.5 |
C10—C9—C8 | 117.90 (15) | H16B—C16—H16C | 109.5 |
Experimental details
Crystal data | |
Chemical formula | C16H13F2NO3 |
Mr | 305.27 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 9.8972 (5), 19.9625 (11), 7.4737 (4) |
β (°) | 107.180 (2) |
V (Å3) | 1410.72 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.25 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 diffractometer |
Absorption correction | Multi-scan (ABSCOR; Higashi, 1995) |
Tmin, Tmax | 0.971, 0.976 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18835, 3441, 2741 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.666 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.130, 1.05 |
No. of reflections | 3441 |
No. of parameters | 202 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.23 |
Computer programs: CAD-4 EXPRESS (Enraf–Nonius, 1994), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Diflunisal is a analgesic and non-steroidal anti-inflammatory drug. (Hannah & Ruyle, 1978). In a continuation of our work on the structure–activity relationship of diflunisal derivatives, we have obtained a colorless crystalline compound that was the product of the reaction of acetyl chloride, monomethylamine and diflunisal. The structural identity of our product, (I), was resolved using single-crystal X-ray diffraction.
The molecular structure of (I) is illustrated in Fig. 1. Atoms F1, F2, C5, C7, C8, C9, C10, C11 and C12 are coplanar, the largest deviation being -0.0278 (10) Å for C5. Atoms O1, C1, C2, C3, C4, C5, C6, C7 and C15 are coplanar, the largest deviation being 0.0272 (9) Å for C7. The dihedral angles between the two planes is 37.78 (3)°. The dihedral angles between the O1/C1–C7/C15 plane and the O3/C15/N1/C16 and O1/O2/C13/C14 planes are 61.83 (5) and 48.82 (8)°, respectively.