Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803010882/wn6162sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803010882/wn6162Isup2.hkl |
CCDC reference: 214857
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.002 Å
- R factor = 0.034
- wR factor = 0.088
- Data-to-parameter ratio = 16.2
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
A solution of p-toluidine (0.03 mol, 4.86 g) in dichloromethane (20 ml) was added dropwise to a solution of ω-chloroisonitrosoacetophenone (0.015 mol, 2.75 g) in dichloromethane (40 ml). The precipitated product was filtered off, and the resulting solution was allowed to stand for 3 d at room temperature for crystallization to occur.
The H-atom positions were located in a difference synthesis and refined isotropically [C—H = 0.929 (15)–0.988 (17) Å].
Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2001); 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).
| Fig. 1. An ORTEP-3 (Farrugia, 1997) drawing of the title molecule with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. |
C14H12N2O2 | F(000) = 504 |
Mr = 240.26 | Dx = 1.288 Mg m−3 |
Monoclinic, P21/a | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yab | Cell parameters from 10547 reflections |
a = 10.0106 (9) Å | θ = 1.7–29.5° |
b = 10.2280 (6) Å | µ = 0.09 mm−1 |
c = 12.1627 (7) Å | T = 293 K |
β = 95.763 (6)° | Block, yellow |
V = 1239.03 (15) Å3 | 0.35 × 0.25 × 0.15 mm |
Z = 4 |
Stoe IPDS-II diffractometer | 1990 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.036 |
Plane graphite monochromator | θmax = 29.5°, θmin = 1.7° |
Detector resolution: 6.67 pixels mm-1 | h = −13→13 |
ϕ scans | k = −14→14 |
12031 measured reflections | l = −16→16 |
3434 independent reflections |
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)] = 0.034 | All H-atom parameters refined |
wR(F2) = 0.088 | w = 1/[σ2(Fo2) + (0.0572P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.81 | (Δ/σ)max < 0.001 |
3434 reflections | Δρmax = 0.11 e Å−3 |
212 parameters | Δρmin = −0.11 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.062 (5) |
C14H12N2O2 | V = 1239.03 (15) Å3 |
Mr = 240.26 | Z = 4 |
Monoclinic, P21/a | Mo Kα radiation |
a = 10.0106 (9) Å | µ = 0.09 mm−1 |
b = 10.2280 (6) Å | T = 293 K |
c = 12.1627 (7) Å | 0.35 × 0.25 × 0.15 mm |
β = 95.763 (6)° |
Stoe IPDS-II diffractometer | 1990 reflections with I > 2σ(I) |
12031 measured reflections | Rint = 0.036 |
3434 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.088 | All H-atom parameters refined |
S = 0.81 | Δρmax = 0.11 e Å−3 |
3434 reflections | Δρmin = −0.11 e Å−3 |
212 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 | ||
O2 | 0.08246 (7) | 0.03456 (9) | 0.39551 (7) | 0.0601 (2) | |
O1 | −0.28128 (7) | 0.22626 (8) | 0.24449 (6) | 0.0588 (2) | |
N2 | −0.05908 (8) | 0.04650 (9) | 0.38944 (7) | 0.0485 (2) | |
H141 | −0.2382 (14) | −0.1326 (13) | 0.3454 (11) | 0.074 (4)* | |
H61 | −0.2295 (14) | −0.0217 (14) | 0.0926 (13) | 0.079 (4)* | |
H111 | −0.6741 (17) | 0.0310 (15) | 0.3595 (12) | 0.093 (5)* | |
H21 | 0.0439 (15) | 0.2600 (13) | 0.0610 (11) | 0.075 (4)* | |
H131 | −0.4004 (17) | −0.2629 (19) | 0.4131 (14) | 0.104 (5)* | |
H51 | −0.3160 (16) | 0.0040 (15) | −0.0883 (13) | 0.088 (5)* | |
H101 | −0.5068 (16) | 0.1648 (16) | 0.2997 (13) | 0.092 (5)* | |
H121 | −0.6202 (16) | −0.1854 (16) | 0.4198 (13) | 0.095 (5)* | |
H31 | −0.0308 (17) | 0.2798 (16) | −0.1280 (14) | 0.099 (5)* | |
H41 | −0.2172 (16) | 0.1578 (16) | −0.2007 (15) | 0.099 (5)* | |
H1 | 0.0526 (14) | 0.1113 (12) | 0.2210 (10) | 0.063 (3)* | |
H2 | 0.1033 (14) | 0.0063 (15) | 0.4702 (13) | 0.088 (5)* | |
C8 | −0.25389 (9) | 0.11823 (10) | 0.28165 (8) | 0.0437 (2) | |
C7 | −0.10764 (9) | 0.07955 (9) | 0.29114 (8) | 0.0422 (2) | |
N1 | −0.03461 (9) | 0.10130 (9) | 0.20572 (7) | 0.0504 (2) | |
C9 | −0.35594 (9) | 0.02925 (10) | 0.31971 (8) | 0.0454 (2) | |
C1 | −0.08763 (10) | 0.11680 (11) | 0.09424 (8) | 0.0487 (2) | |
C14 | −0.32688 (13) | −0.09844 (12) | 0.35132 (11) | 0.0607 (3) | |
C10 | −0.48633 (11) | 0.07446 (14) | 0.32117 (10) | 0.0597 (3) | |
C11 | −0.58403 (13) | −0.00463 (16) | 0.35623 (11) | 0.0717 (4) | |
C2 | −0.02954 (13) | 0.20653 (13) | 0.02900 (9) | 0.0608 (3) | |
C3 | −0.07830 (15) | 0.22127 (15) | −0.08039 (11) | 0.0752 (4) | |
C12 | −0.55340 (15) | −0.12870 (16) | 0.39080 (12) | 0.0767 (4) | |
C5 | −0.24206 (15) | 0.05794 (16) | −0.06027 (11) | 0.0754 (4) | |
C6 | −0.19269 (12) | 0.04083 (13) | 0.04916 (10) | 0.0611 (3) | |
C4 | −0.18491 (16) | 0.14771 (16) | −0.12421 (11) | 0.0780 (4) | |
C13 | −0.42587 (16) | −0.17721 (15) | 0.38677 (13) | 0.0782 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O2 | 0.0358 (4) | 0.0903 (6) | 0.0533 (4) | 0.0054 (4) | 0.0000 (3) | 0.0140 (4) |
O1 | 0.0511 (4) | 0.0564 (5) | 0.0691 (5) | 0.0101 (3) | 0.0073 (3) | 0.0150 (4) |
N2 | 0.0351 (4) | 0.0621 (5) | 0.0477 (5) | 0.0038 (4) | 0.0007 (3) | 0.0072 (4) |
C8 | 0.0415 (5) | 0.0486 (6) | 0.0402 (5) | 0.0042 (4) | 0.0005 (4) | 0.0006 (4) |
C7 | 0.0393 (5) | 0.0447 (5) | 0.0422 (5) | 0.0007 (4) | 0.0016 (4) | 0.0011 (4) |
N1 | 0.0379 (4) | 0.0710 (6) | 0.0417 (4) | 0.0007 (4) | 0.0016 (3) | 0.0027 (4) |
C9 | 0.0411 (5) | 0.0514 (6) | 0.0427 (5) | −0.0010 (4) | −0.0004 (4) | −0.0024 (4) |
C1 | 0.0454 (5) | 0.0593 (6) | 0.0410 (5) | 0.0069 (4) | 0.0026 (4) | −0.0019 (4) |
C14 | 0.0556 (7) | 0.0502 (7) | 0.0753 (8) | −0.0032 (5) | 0.0020 (5) | −0.0008 (5) |
C10 | 0.0424 (6) | 0.0698 (8) | 0.0668 (7) | 0.0016 (5) | 0.0048 (5) | 0.0019 (6) |
C11 | 0.0456 (7) | 0.0915 (10) | 0.0785 (9) | −0.0113 (6) | 0.0093 (6) | −0.0066 (7) |
C2 | 0.0619 (7) | 0.0713 (8) | 0.0483 (6) | −0.0042 (6) | 0.0011 (5) | 0.0030 (5) |
C3 | 0.0857 (9) | 0.0875 (10) | 0.0511 (7) | −0.0005 (8) | 0.0010 (6) | 0.0118 (7) |
C12 | 0.0677 (9) | 0.0879 (10) | 0.0753 (8) | −0.0362 (8) | 0.0108 (6) | −0.0102 (7) |
C5 | 0.0708 (8) | 0.0948 (10) | 0.0572 (7) | −0.0034 (8) | −0.0098 (6) | −0.0163 (7) |
C6 | 0.0604 (7) | 0.0713 (8) | 0.0508 (6) | −0.0059 (6) | 0.0022 (5) | −0.0057 (6) |
C4 | 0.0875 (10) | 0.0964 (11) | 0.0469 (7) | 0.0090 (8) | −0.0098 (6) | 0.0014 (7) |
C13 | 0.0818 (10) | 0.0557 (8) | 0.0962 (10) | −0.0188 (7) | 0.0037 (7) | 0.0041 (7) |
O2—N2 | 1.4167 (10) | C10—H101 | 0.977 (16) |
O2—H2 | 0.956 (16) | C11—C12 | 1.362 (2) |
O1—C8 | 1.2147 (12) | C11—H111 | 0.977 (17) |
N2—C7 | 1.2897 (12) | C2—C3 | 1.3786 (17) |
C8—C9 | 1.4768 (14) | C2—H21 | 0.966 (15) |
C8—C7 | 1.5098 (13) | C3—C4 | 1.369 (2) |
C7—N1 | 1.3475 (13) | C3—H31 | 0.988 (17) |
N1—C1 | 1.4145 (13) | C12—C13 | 1.375 (2) |
N1—H1 | 0.880 (13) | C12—H121 | 0.977 (17) |
C9—C14 | 1.3841 (16) | C5—C4 | 1.365 (2) |
C9—C10 | 1.3866 (15) | C5—C6 | 1.3836 (18) |
C1—C6 | 1.3765 (16) | C5—H51 | 0.959 (16) |
C1—C2 | 1.3795 (17) | C6—H61 | 0.929 (15) |
C14—C13 | 1.3794 (18) | C4—H41 | 0.959 (18) |
C14—H141 | 0.964 (14) | C13—H131 | 0.959 (19) |
C10—C11 | 1.3698 (18) | ||
N2—O2—H2 | 101.4 (8) | C12—C11—H111 | 121.0 (9) |
C7—N2—O2 | 110.66 (8) | C10—C11—H111 | 118.9 (9) |
O1—C8—C9 | 122.67 (9) | C3—C2—C1 | 119.94 (12) |
O1—C8—C7 | 116.60 (9) | C3—C2—H21 | 120.5 (8) |
C9—C8—C7 | 120.70 (8) | C1—C2—H21 | 119.5 (8) |
N2—C7—N1 | 125.09 (9) | C4—C3—C2 | 120.15 (14) |
N2—C7—C8 | 114.32 (8) | C4—C3—H31 | 120.5 (10) |
N1—C7—C8 | 119.66 (8) | C2—C3—H31 | 119.2 (10) |
C7—N1—C1 | 125.25 (9) | C11—C12—C13 | 120.41 (13) |
C7—N1—H1 | 117.4 (8) | C11—C12—H121 | 121.5 (9) |
C1—N1—H1 | 117.2 (8) | C13—C12—H121 | 118.1 (9) |
C14—C9—C10 | 118.88 (10) | C4—C5—C6 | 120.23 (13) |
C14—C9—C8 | 122.40 (9) | C4—C5—H51 | 122.5 (9) |
C10—C9—C8 | 118.70 (10) | C6—C5—H51 | 117.3 (10) |
C6—C1—C2 | 119.72 (10) | C1—C6—C5 | 119.78 (13) |
C6—C1—N1 | 121.11 (10) | C1—C6—H61 | 119.5 (9) |
C2—C1—N1 | 119.13 (10) | C5—C6—H61 | 120.7 (9) |
C13—C14—C9 | 120.03 (13) | C5—C4—C3 | 120.16 (12) |
C13—C14—H141 | 120.5 (8) | C5—C4—H41 | 120.4 (10) |
C9—C14—H141 | 119.4 (8) | C3—C4—H41 | 119.4 (10) |
C11—C10—C9 | 120.63 (13) | C12—C13—C14 | 119.94 (14) |
C11—C10—H101 | 120.3 (9) | C12—C13—H131 | 122.3 (10) |
C9—C10—H101 | 119.0 (9) | C14—C13—H131 | 117.6 (10) |
C12—C11—C10 | 120.04 (13) | ||
O2—N2—C7—N1 | −0.65 (14) | C8—C9—C14—C13 | 179.66 (11) |
O2—N2—C7—C8 | −169.51 (8) | C14—C9—C10—C11 | 1.81 (17) |
O1—C8—C7—N2 | 123.44 (10) | C8—C9—C10—C11 | −179.76 (11) |
C9—C8—C7—N2 | −54.57 (12) | C9—C10—C11—C12 | 0.4 (2) |
O1—C8—C7—N1 | −46.09 (13) | C6—C1—C2—C3 | 1.09 (19) |
C9—C8—C7—N1 | 135.90 (10) | N1—C1—C2—C3 | 178.81 (11) |
N2—C7—N1—C1 | 169.24 (10) | C1—C2—C3—C4 | 0.5 (2) |
C8—C7—N1—C1 | −22.45 (15) | C10—C11—C12—C13 | −2.5 (2) |
O1—C8—C9—C14 | 173.21 (10) | C2—C1—C6—C5 | −2.07 (18) |
C7—C8—C9—C14 | −8.90 (14) | N1—C1—C6—C5 | −179.75 (11) |
O1—C8—C9—C10 | −5.16 (15) | C4—C5—C6—C1 | 1.5 (2) |
C7—C8—C9—C10 | 172.73 (9) | C6—C5—C4—C3 | 0.1 (2) |
C7—N1—C1—C6 | −39.91 (16) | C2—C3—C4—C5 | −1.0 (2) |
C7—N1—C1—C2 | 142.39 (11) | C11—C12—C13—C14 | 2.4 (2) |
C10—C9—C14—C13 | −1.97 (17) | C9—C14—C13—C12 | −0.1 (2) |
Experimental details
Crystal data | |
Chemical formula | C14H12N2O2 |
Mr | 240.26 |
Crystal system, space group | Monoclinic, P21/a |
Temperature (K) | 293 |
a, b, c (Å) | 10.0106 (9), 10.2280 (6), 12.1627 (7) |
β (°) | 95.763 (6) |
V (Å3) | 1239.03 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.35 × 0.25 × 0.15 |
Data collection | |
Diffractometer | Stoe IPDS-II diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 12031, 3434, 1990 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.693 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.088, 0.81 |
No. of reflections | 3434 |
No. of parameters | 212 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.11, −0.11 |
Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, X-RED (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
O2—N2 | 1.4167 (10) | N1—C1 | 1.4145 (13) |
O1—C8 | 1.2147 (12) | C9—C14 | 1.3841 (16) |
N2—C7 | 1.2897 (12) | C9—C10 | 1.3866 (15) |
C8—C9 | 1.4768 (14) | C1—C6 | 1.3765 (16) |
C8—C7 | 1.5098 (13) | C1—C2 | 1.3795 (17) |
C7—N1 | 1.3475 (13) | C2—C3 | 1.3786 (17) |
C7—N2—O2 | 110.66 (8) | N1—C7—C8 | 119.66 (8) |
O1—C8—C9 | 122.67 (9) | C7—N1—C1 | 125.25 (9) |
O1—C8—C7 | 116.60 (9) | C14—C9—C8 | 122.40 (9) |
C9—C8—C7 | 120.70 (8) | C10—C9—C8 | 118.70 (10) |
N2—C7—N1 | 125.09 (9) | C6—C1—N1 | 121.11 (10) |
N2—C7—C8 | 114.32 (8) | C2—C1—N1 | 119.13 (10) |
O2—N2—C7—C8 | −169.51 (8) | N2—C7—N1—C1 | 169.24 (10) |
O1—C8—C7—N2 | 123.44 (10) | C8—C7—N1—C1 | −22.45 (15) |
C9—C8—C7—N2 | −54.57 (12) | O1—C8—C9—C14 | 173.21 (10) |
O1—C8—C7—N1 | −46.09 (13) | O1—C8—C9—C10 | −5.16 (15) |
C9—C8—C7—N1 | 135.90 (10) | C7—N1—C1—C2 | 142.39 (11) |
(I) | (II) | (III) | (IV) | |
N2-O2 | 1.4167 (10) | 1.4033 (16)/1.3956 (18) | 1.423 (3)/1.396 (3) | 1.429 (4) |
N2-C7 | 1.2897 (12) | 1.2811 (18)/1.2813 (19) | 1.290 (3)/1.282 (3) | 1.241 (6) |
C7-C8 | 1.5098 (13) | 1.477 (3)/1.473 (3) | 1.489 (3) | 1.551 (7) |
C8-C7-N2 | 114.32 (8) | 115.18 (15)/115.03 (17) | 116.59 (19)/115.0 (2) | 118.3 (5) |
C7-N2-O2 | 110.66 (8) | 112.39 (12)/112.15 (13) | 109.37 (18)/111.52 (19) | 112.2 (4) |
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Intermolecular hydrogen bonding combines moderate strength and directionality (Karle et al., 1996) in linking molecules to form supramolecular structures; this has received considerable attention with respect to directional non-covalent intermolecular interactions (Etter et al., 1990).
The oxime (–C═N—OH) moiety is a functional group that has not been extensively explored in crystal engineering. It is amphiprotic, with a slightly basic N atom and a mildly acidic hydroxyl group. It is also potentially ambident, with possibilities of coordination through nitrogen and/or O atoms. In the solid state, oximes are usually associated via O—H···N hydrogen bonds of length ~2.8 Å.
Oxime groups possess stronger hydrogen-bonding capabilities than alcohols, phenols and carboxylic acids (Marsman et al., 1999). Structurally characterized oxime moieties are much less common than carboxylic acids and amides, but, from a supramolecular perspective, this functionality does have some unique and desirable features (Aakeröy et al., 2001). In general, oxime and dioxime derivatives are very important compounds in chemical industry and medicine (Sevagapandian et al., 2000).
The structure determination of the title molecule, (I), was carried out in order to investigate the strength of the hydrogen bonding capability of the oxime group and to compare the geometry of the oxime moiety with those found in 2,3-dimethylquinoxaline-dimethylglyoxime (1/1), (II) (Hökelek, T., Batı et al., 2001), 1-(2,6-dimethylphenylamino)propane-1,2-dione dioxime, (III) (Hökelek, T., Zülfikaroğlu et al., 2001), and N-(3,4-dichlorophenyl)-N'-hydroxy-2-oxo-2-phenylacetamidine, (IV) (Hökelek et al., 2003).
The title compound, (I) (Fig. 1), consists of phenylamino and 2-phenyl-1,2-ethanedione 1-oxime moieties. The dihedral angles between the oxime plane A (O2/N2/C7) and the non-coplanar phenyl rings B (C1—C6) and C (C9—C14) are A/B = 46.29 (6), A/C =56.43 (7) and B/C = 68.02 (4)°.
The steric effects of the substituents bonded to the C atom of the oxime group may influence the bond lengths and angles of the oxime moiety (Table 1). Some significant changes in the geometry of the oxime moiety are evident when the bond lengths and angles are compared with the corresponding values in compounds (II)–(IV) (Table 2).
The oxime moiety has an E configuration [C8—C7—N2—O2 = −169.51 (8)°; Chertanova et al., 1994]. In this configuration, the oxime group is involved as a donor in intermolecular hydrogen bonding [O2—H2 0.956 (15) Å, O2···N2i 2.776 (1) Å, H2···N2i 1.885 (16) Å and O2—H2···N2i 153.93(1.37)°; symmetry code: (i) −x, −y, −z + 1]. There are also N1—H1···O2 intramolecular [N1—H1 0.880 (13) Å, N1···O2 2.574 (1) Å, H1···O2 2.255 (12) Å and N1—H1···O2 101.13 (94)°] and N1—H1···O1ii intermolecular [N1—H1 0.880 (13) Å, N1···O1ii 3.086 (1) Å, H1···O1ii 2.348 (13) Å and N1—H1···O1ii 141.57(1.14)°; symmetry code: (ii) x + 0.5, −y + 0.5, z] hydrogen bonds.
The inter- and intramolecular hydrogen bonds are highly effective in forming polymeric chains, thereby stabilizing the crystal structure. As can be seen from the packing diagram (Fig. 2), the chains are approximately parallel to the (110) plane. Dipole–dipole and van der Waals interactions are also effective in the molecular packing in the crystal structure.