Buy article online - an online subscription or single-article purchase is required to access this article.
Diethyl 2-[(2-hydroxyanilino)methylidene]malonate, (I), and diethyl 2-[(4-hydroxyanilino)methylidene]malonate, (II), both C
14H
17NO
5, crystallize in centrosymmetric orthorhombic and monoclinic crystal systems, respectively. Compound (I) resides on a crystallographic mirror plane and displays bifurcated intramolecular hydrogen bonding, as well as intermolecular hydrogen bonding due to the position of the hydroxy group. Compound (II) has a single intramolecular N—H
O hydrogen bond. Infinite one-dimensional head-to-tail chains formed by O—H
O hydrogen bonding are present in both structures. The molecular packing is mainly influenced by the intermolecular O—H
O interactions. Additionally, C—H
O interactions crosslinking the chains are found in (II).
Supporting information
CCDC references: 678847; 925265
Diethyl ethoxymethylene malonate (1 equivalent) was added to a solution of 2-
or 4-aminophenol (1 equivalent) in ethanol (5 times w/v) and the
resulting solution stirred for 15 min at room temperature (301 K). After
completion of the reaction, the ethanol was evaporated under reduced pressure
to give compounds (I) and (II) as white solids [99% yields; m.p. 402 and 412 K
for (I) and (II), respectively].
All H atoms, except as noted, were placed in their geometrically idealized
positions and a riding model was used for their refinement, with
Uiso(H) = 1.2Ueq(C,N). For compound (I), the amino and
hydroxy H atoms were located in a difference map and refined isotropically.
For both compounds, data collection: SMART (Bruker, 2008); cell refinement: SMART (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).
(I) Diethyl 2-[(2-hydroxyanilino)methylidene]malonate
top
Crystal data top
C14H17NO5 | F(000) = 592 |
Mr = 279.29 | Dx = 1.276 Mg m−3 |
Orthorhombic, Pbcm | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2c 2b | Cell parameters from 2008 reflections |
a = 11.3011 (3) Å | θ = 3.1–25.2° |
b = 19.2760 (4) Å | µ = 0.10 mm−1 |
c = 6.6725 (2) Å | T = 296 K |
V = 1453.54 (7) Å3 | Plate, yellow |
Z = 4 | 0.22 × 0.22 × 0.20 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 1165 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.027 |
Graphite monochromator | θmax = 26.8°, θmin = 1.8° |
phi and ω scans | h = −11→14 |
7641 measured reflections | k = −24→24 |
1690 independent reflections | l = −7→8 |
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)] = 0.049 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.154 | w = 1/[σ2(Fo2) + (0.0764P)2 + 0.2553P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
1690 reflections | Δρmax = 0.23 e Å−3 |
132 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0072 (16) |
Crystal data top
C14H17NO5 | V = 1453.54 (7) Å3 |
Mr = 279.29 | Z = 4 |
Orthorhombic, Pbcm | Mo Kα radiation |
a = 11.3011 (3) Å | µ = 0.10 mm−1 |
b = 19.2760 (4) Å | T = 296 K |
c = 6.6725 (2) Å | 0.22 × 0.22 × 0.20 mm |
Data collection top
Bruker SMART CCD area-detector diffractometer | 1165 reflections with I > 2σ(I) |
7641 measured reflections | Rint = 0.027 |
1690 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.154 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.23 e Å−3 |
1690 reflections | Δρmin = −0.20 e Å−3 |
132 parameters | |
Special details top
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell esds is used for estimating esds 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) |
O1 | 0.93175 (16) | 0.39737 (8) | 0.2500 | 0.0719 (6) | |
O4 | 1.12614 (17) | 0.24764 (10) | 0.2500 | 0.0973 (8) | |
O5 | 1.20132 (18) | 0.14140 (9) | 0.2500 | 0.1018 (8) | |
O3 | 0.86035 (15) | 0.06136 (8) | 0.2500 | 0.0689 (5) | |
O2 | 1.05136 (16) | 0.03504 (7) | 0.2500 | 0.0770 (6) | |
N1 | 0.8942 (2) | 0.26400 (9) | 0.2500 | 0.0609 (6) | |
C1 | 0.7941 (2) | 0.30708 (11) | 0.2500 | 0.0571 (6) | |
C2 | 0.8167 (2) | 0.37835 (11) | 0.2500 | 0.0573 (6) | |
C3 | 0.7241 (3) | 0.42457 (14) | 0.2500 | 0.0724 (8) | |
H3 | 0.7390 | 0.4720 | 0.2500 | 0.087* | |
C4 | 0.6101 (3) | 0.40078 (16) | 0.2500 | 0.0918 (10) | |
H4 | 0.5475 | 0.4321 | 0.2500 | 0.110* | |
C5 | 0.5875 (3) | 0.33043 (17) | 0.2500 | 0.0931 (10) | |
H5 | 0.5098 | 0.3145 | 0.2500 | 0.112* | |
C6 | 0.6789 (3) | 0.28407 (14) | 0.2500 | 0.0749 (8) | |
H6 | 0.6632 | 0.2367 | 0.2500 | 0.090* | |
C7 | 0.8954 (2) | 0.19499 (11) | 0.2500 | 0.0572 (6) | |
C8 | 0.9933 (2) | 0.15357 (10) | 0.2500 | 0.0584 (6) | |
C12 | 1.1103 (3) | 0.18519 (12) | 0.2500 | 0.0737 (8) | |
C13 | 1.3185 (3) | 0.17212 (17) | 0.2500 | 0.159 (2) | |
H13A | 1.3277 | 0.2012 | 0.1323 | 0.191* | 0.50 |
H13B | 1.3277 | 0.2012 | 0.3677 | 0.191* | 0.50 |
C14 | 1.4055 (3) | 0.1209 (2) | 0.2500 | 0.1268 (15) | |
H14A | 1.3874 | 0.0869 | 0.3504 | 0.190* | 0.50 |
H14B | 1.4810 | 0.1415 | 0.2787 | 0.190* | 0.50 |
H14C | 1.4082 | 0.0990 | 0.1208 | 0.190* | 0.50 |
C9 | 0.9745 (2) | 0.07839 (11) | 0.2500 | 0.0569 (6) | |
C10 | 0.8306 (2) | −0.01136 (12) | 0.2500 | 0.0701 (7) | |
H10A | 0.8627 | −0.0339 | 0.3680 | 0.084* | 0.50 |
H10B | 0.8627 | −0.0339 | 0.1320 | 0.084* | 0.50 |
C11 | 0.6988 (3) | −0.01584 (16) | 0.2500 | 0.0891 (9) | |
H11A | 0.6752 | −0.0637 | 0.2500 | 0.134* | |
H11B | 0.6682 | 0.0066 | 0.1325 | 0.134* | 0.50 |
H11C | 0.6682 | 0.0066 | 0.3675 | 0.134* | 0.50 |
H1O | 0.939 (3) | 0.4416 (19) | 0.2500 | 0.112 (11)* | |
H1N | 0.963 (3) | 0.2803 (13) | 0.2500 | 0.075 (9)* | |
H7 | 0.818 (2) | 0.1746 (12) | 0.2500 | 0.055 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0698 (12) | 0.0349 (8) | 0.1110 (15) | 0.0018 (8) | 0.000 | 0.000 |
O4 | 0.0854 (13) | 0.0402 (8) | 0.166 (2) | −0.0118 (10) | 0.000 | 0.000 |
O5 | 0.0682 (12) | 0.0469 (10) | 0.190 (2) | −0.0076 (9) | 0.000 | 0.000 |
O3 | 0.0659 (11) | 0.0405 (9) | 0.1001 (13) | −0.0064 (7) | 0.000 | 0.000 |
O2 | 0.0664 (11) | 0.0337 (8) | 0.1309 (17) | −0.0012 (8) | 0.000 | 0.000 |
N1 | 0.0690 (14) | 0.0368 (10) | 0.0767 (14) | −0.0001 (9) | 0.000 | 0.000 |
C1 | 0.0705 (15) | 0.0415 (11) | 0.0592 (14) | 0.0020 (11) | 0.000 | 0.000 |
C2 | 0.0659 (14) | 0.0426 (11) | 0.0634 (14) | 0.0027 (10) | 0.000 | 0.000 |
C3 | 0.0755 (18) | 0.0494 (12) | 0.092 (2) | 0.0104 (12) | 0.000 | 0.000 |
C4 | 0.072 (2) | 0.0776 (19) | 0.126 (3) | 0.0148 (15) | 0.000 | 0.000 |
C5 | 0.0661 (17) | 0.082 (2) | 0.131 (3) | −0.0057 (15) | 0.000 | 0.000 |
C6 | 0.0738 (18) | 0.0538 (14) | 0.097 (2) | −0.0059 (13) | 0.000 | 0.000 |
C7 | 0.0737 (16) | 0.0392 (11) | 0.0587 (14) | −0.0033 (11) | 0.000 | 0.000 |
C8 | 0.0695 (15) | 0.0347 (10) | 0.0711 (15) | −0.0029 (10) | 0.000 | 0.000 |
C12 | 0.0782 (18) | 0.0403 (12) | 0.103 (2) | −0.0058 (12) | 0.000 | 0.000 |
C13 | 0.071 (2) | 0.0586 (18) | 0.348 (7) | −0.0150 (17) | 0.000 | 0.000 |
C14 | 0.085 (2) | 0.128 (3) | 0.167 (4) | −0.028 (2) | 0.000 | 0.000 |
C9 | 0.0653 (15) | 0.0372 (10) | 0.0683 (15) | −0.0036 (10) | 0.000 | 0.000 |
C10 | 0.0707 (16) | 0.0446 (12) | 0.0949 (19) | −0.0137 (11) | 0.000 | 0.000 |
C11 | 0.0776 (19) | 0.0799 (19) | 0.110 (2) | −0.0232 (16) | 0.000 | 0.000 |
Geometric parameters (Å, º) top
O1—C2 | 1.351 (3) | C5—C6 | 1.366 (4) |
O1—H1O | 0.86 (4) | C5—H5 | 0.9300 |
O4—C12 | 1.217 (3) | C6—H6 | 0.9300 |
O5—C12 | 1.331 (3) | C7—C8 | 1.364 (3) |
O5—C13i | 1.451 (4) | C7—H7 | 0.96 (2) |
O5—C13 | 1.451 (4) | C8—C12 | 1.456 (4) |
O3—C9 | 1.331 (3) | C8—C9 | 1.465 (3) |
O3—C10 | 1.442 (3) | C13—C14 | 1.393 (5) |
O2—C9 | 1.205 (3) | C13—H13A | 0.9700 |
N1—C7 | 1.330 (3) | C13—H13B | 0.9700 |
N1—C1 | 1.404 (3) | C14—H14A | 0.9600 |
N1—H1N | 0.84 (3) | C14—H14B | 0.9600 |
C1—C6 | 1.375 (4) | C14—H14C | 0.9600 |
C1—C2 | 1.398 (3) | C10—C11 | 1.492 (4) |
C2—C3 | 1.374 (3) | C10—H10A | 0.9700 |
C3—C4 | 1.368 (4) | C10—H10B | 0.9700 |
C3—H3 | 0.9300 | C11—H11A | 0.9600 |
C4—C5 | 1.380 (4) | C11—H11B | 0.9600 |
C4—H4 | 0.9300 | C11—H11C | 0.9600 |
| | | |
C2—O1—H1O | 111 (2) | C8—C7—H7 | 120.0 (14) |
C12—O5—C13i | 116.5 (2) | C7—C8—C12 | 119.4 (2) |
C12—O5—C13 | 116.5 (2) | C7—C8—C9 | 117.5 (2) |
C13i—O5—C13 | 0.0 (2) | C12—C8—C9 | 123.1 (2) |
C9—O3—C10 | 117.77 (19) | O4—C12—O5 | 120.9 (3) |
C7—N1—C1 | 126.8 (2) | O4—C12—C8 | 123.2 (3) |
C7—N1—H1N | 111.4 (18) | O5—C12—C8 | 115.9 (2) |
C1—N1—H1N | 121.7 (18) | C14—C13—O5 | 110.8 (3) |
C6—C1—C2 | 119.4 (2) | C14—C13—H13A | 109.5 |
C6—C1—N1 | 124.9 (2) | O5—C13—H13A | 109.5 |
C2—C1—N1 | 115.7 (2) | C14—C13—H13B | 109.5 |
O1—C2—C3 | 123.8 (2) | O5—C13—H13B | 109.5 |
O1—C2—C1 | 116.3 (2) | H13A—C13—H13B | 108.1 |
C3—C2—C1 | 119.9 (2) | O2—C9—O3 | 121.8 (2) |
C4—C3—C2 | 120.0 (3) | O2—C9—C8 | 125.6 (2) |
C4—C3—H3 | 120.0 | O3—C9—C8 | 112.6 (2) |
C2—C3—H3 | 120.0 | O3—C10—C11 | 106.8 (2) |
C3—C4—C5 | 120.2 (3) | O3—C10—H10A | 110.4 |
C3—C4—H4 | 119.9 | C11—C10—H10A | 110.4 |
C5—C4—H4 | 119.9 | O3—C10—H10B | 110.4 |
C6—C5—C4 | 120.2 (3) | C11—C10—H10B | 110.4 |
C6—C5—H5 | 119.9 | H10A—C10—H10B | 108.6 |
C4—C5—H5 | 119.9 | C10—C11—H11A | 109.5 |
C5—C6—C1 | 120.3 (2) | C10—C11—H11B | 109.5 |
C5—C6—H6 | 119.8 | H11A—C11—H11B | 109.5 |
C1—C6—H6 | 119.8 | C10—C11—H11C | 109.5 |
N1—C7—C8 | 126.4 (2) | H11A—C11—H11C | 109.5 |
N1—C7—H7 | 113.6 (14) | H11B—C11—H11C | 109.5 |
| | | |
C7—N1—C1—C6 | 0.0 | C13—O5—C12—O4 | 0.0 |
C7—N1—C1—C2 | 180.0 | C13i—O5—C12—C8 | 180.0 |
C6—C1—C2—O1 | 180.0 | C13—O5—C12—C8 | 180.0 |
N1—C1—C2—O1 | 0.0 | C7—C8—C12—O4 | 0.0 |
C6—C1—C2—C3 | 0.0 | C9—C8—C12—O4 | 180.0 |
N1—C1—C2—C3 | 180.0 | C7—C8—C12—O5 | 180.0 |
O1—C2—C3—C4 | 180.0 | C9—C8—C12—O5 | 0.0 |
C1—C2—C3—C4 | 0.0 | C12—O5—C13—C14 | 180.0 |
C2—C3—C4—C5 | 0.0 | C13i—O5—C13—C14 | 0 (100) |
C3—C4—C5—C6 | 0.0 | C10—O3—C9—O2 | 0.0 |
C4—C5—C6—C1 | 0.0 | C10—O3—C9—C8 | 180.0 |
C2—C1—C6—C5 | 0.0 | C7—C8—C9—O2 | 180.0 |
N1—C1—C6—C5 | 180.0 | C12—C8—C9—O2 | 0.0 |
C1—N1—C7—C8 | 180.0 | C7—C8—C9—O3 | 0.0 |
N1—C7—C8—C12 | 0.0 | C12—C8—C9—O3 | 180.0 |
N1—C7—C8—C9 | 180.0 | C9—O3—C10—C11 | 180.0 |
C13i—O5—C12—O4 | 0.0 | | |
Symmetry code: (i) x, y, −z+1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O1 | 0.84 (3) | 2.28 (3) | 2.606 (2) | 103 (2) |
N1—H1N···O4 | 0.84 (3) | 1.95 (3) | 2.640 (3) | 139 (2) |
O1—H1O···O2ii | 0.86 (4) | 1.81 (4) | 2.661 (2) | 178 (3) |
Symmetry code: (ii) −x+2, y+1/2, z. |
(II) Diethyl 2-[(4-hydroxyanilino)methylidene]malonate
top
Crystal data top
C14H17NO5 | F(000) = 592 |
Mr = 279.29 | Dx = 1.302 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 7526 reflections |
a = 10.9970 (11) Å | θ = 2.2–27.6° |
b = 10.8919 (11) Å | µ = 0.10 mm−1 |
c = 12.3244 (12) Å | T = 296 K |
β = 105.206 (1)° | Plate, yellow |
V = 1424.5 (2) Å3 | 0.25 × 0.25 × 0.20 mm |
Z = 4 | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2826 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.027 |
Graphite monochromator | θmax = 27.6°, θmin = 2.2° |
phi and ω scans | h = −14→14 |
12064 measured reflections | k = −14→13 |
3297 independent reflections | l = −15→16 |
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) = 0.117 | w = 1/[σ2(Fo2) + (0.0643P)2 + 0.2345P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
3297 reflections | Δρmax = 0.25 e Å−3 |
182 parameters | Δρmin = −0.17 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.033 (3) |
Crystal data top
C14H17NO5 | V = 1424.5 (2) Å3 |
Mr = 279.29 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.9970 (11) Å | µ = 0.10 mm−1 |
b = 10.8919 (11) Å | T = 296 K |
c = 12.3244 (12) Å | 0.25 × 0.25 × 0.20 mm |
β = 105.206 (1)° | |
Data collection top
Bruker SMART CCD area-detector diffractometer | 2826 reflections with I > 2σ(I) |
12064 measured reflections | Rint = 0.027 |
3297 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.25 e Å−3 |
3297 reflections | Δρmin = −0.17 e Å−3 |
182 parameters | |
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 | |
O2 | 0.89430 (8) | 0.89700 (9) | 0.10761 (8) | 0.0515 (2) | |
O1 | 1.76120 (8) | 1.11032 (9) | 0.09308 (8) | 0.0526 (2) | |
H1O | 1.7967 | 1.0435 | 0.0990 | 0.079* | |
O3 | 1.06830 (8) | 0.80048 (8) | 0.09127 (8) | 0.0496 (2) | |
N1 | 1.29994 (9) | 1.08073 (9) | 0.19856 (9) | 0.0444 (2) | |
H1N | 1.2826 | 1.1387 | 0.2395 | 0.053* | |
O5 | 0.96576 (8) | 1.04595 (8) | 0.29964 (7) | 0.0456 (2) | |
C1 | 1.41932 (10) | 1.08441 (10) | 0.17351 (9) | 0.0377 (2) | |
C3 | 1.58631 (11) | 1.20500 (11) | 0.13509 (10) | 0.0433 (3) | |
H3 | 1.6213 | 1.2813 | 0.1276 | 0.052* | |
C4 | 1.64991 (10) | 1.09859 (10) | 0.12128 (9) | 0.0383 (2) | |
C5 | 1.59877 (10) | 0.98497 (10) | 0.13553 (10) | 0.0416 (3) | |
H5 | 1.6416 | 0.9135 | 0.1269 | 0.050* | |
C2 | 1.47084 (11) | 1.19783 (11) | 0.15998 (10) | 0.0427 (3) | |
H2 | 1.4276 | 1.2693 | 0.1677 | 0.051* | |
O4 | 1.11922 (9) | 1.17548 (9) | 0.28488 (10) | 0.0615 (3) | |
C6 | 1.48409 (10) | 0.97759 (10) | 0.16256 (10) | 0.0414 (3) | |
H6 | 1.4508 | 0.9014 | 0.1733 | 0.050* | |
C9 | 1.00865 (10) | 0.89389 (10) | 0.12661 (10) | 0.0395 (3) | |
C8 | 1.09731 (10) | 0.98743 (10) | 0.18571 (10) | 0.0392 (3) | |
C7 | 1.21404 (10) | 0.99437 (11) | 0.16325 (10) | 0.0403 (3) | |
H7 | 1.2340 | 0.9323 | 0.1190 | 0.048* | |
C12 | 1.06250 (10) | 1.07905 (11) | 0.25894 (10) | 0.0412 (3) | |
C14 | 0.82810 (14) | 1.07958 (17) | 0.41761 (14) | 0.0667 (4) | |
H14A | 0.7956 | 1.1397 | 0.4596 | 0.100* | |
H14B | 0.8706 | 1.0162 | 0.4674 | 0.100* | |
H14C | 0.7599 | 1.0443 | 0.3611 | 0.100* | |
C13 | 0.91915 (13) | 1.13979 (14) | 0.36247 (12) | 0.0551 (3) | |
H13A | 0.8773 | 1.2044 | 0.3123 | 0.066* | |
H13B | 0.9885 | 1.1758 | 0.4189 | 0.066* | |
C10 | 0.99000 (14) | 0.71243 (13) | 0.01554 (13) | 0.0566 (3) | |
H10A | 0.9289 | 0.7547 | −0.0438 | 0.068* | |
H10B | 0.9451 | 0.6608 | 0.0562 | 0.068* | |
C11 | 1.07613 (18) | 0.63637 (14) | −0.03301 (16) | 0.0726 (5) | |
H11A | 1.0277 | 0.5766 | −0.0836 | 0.109* | |
H11B | 1.1362 | 0.5952 | 0.0265 | 0.109* | |
H11C | 1.1198 | 0.6885 | −0.0731 | 0.109* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O2 | 0.0363 (4) | 0.0528 (5) | 0.0674 (6) | −0.0014 (3) | 0.0169 (4) | −0.0126 (4) |
O1 | 0.0402 (4) | 0.0524 (5) | 0.0711 (6) | −0.0024 (4) | 0.0251 (4) | 0.0081 (4) |
O3 | 0.0427 (4) | 0.0434 (5) | 0.0679 (6) | −0.0042 (3) | 0.0238 (4) | −0.0179 (4) |
N1 | 0.0389 (5) | 0.0461 (5) | 0.0526 (6) | −0.0041 (4) | 0.0201 (4) | −0.0109 (4) |
O5 | 0.0457 (4) | 0.0461 (5) | 0.0518 (5) | −0.0001 (3) | 0.0250 (4) | −0.0096 (4) |
C1 | 0.0343 (5) | 0.0417 (6) | 0.0384 (5) | −0.0024 (4) | 0.0118 (4) | −0.0032 (4) |
C3 | 0.0431 (6) | 0.0353 (5) | 0.0514 (7) | −0.0057 (4) | 0.0124 (5) | 0.0029 (5) |
C4 | 0.0333 (5) | 0.0431 (6) | 0.0387 (5) | −0.0019 (4) | 0.0095 (4) | 0.0040 (4) |
C5 | 0.0380 (5) | 0.0367 (6) | 0.0517 (6) | 0.0021 (4) | 0.0148 (5) | 0.0019 (5) |
C2 | 0.0431 (6) | 0.0352 (5) | 0.0500 (6) | 0.0013 (4) | 0.0128 (5) | −0.0040 (4) |
O4 | 0.0564 (5) | 0.0506 (5) | 0.0872 (7) | −0.0113 (4) | 0.0359 (5) | −0.0265 (5) |
C6 | 0.0403 (6) | 0.0357 (6) | 0.0502 (6) | −0.0034 (4) | 0.0154 (5) | 0.0028 (4) |
C9 | 0.0398 (5) | 0.0391 (6) | 0.0439 (6) | −0.0001 (4) | 0.0188 (5) | −0.0026 (4) |
C8 | 0.0375 (5) | 0.0394 (6) | 0.0440 (6) | −0.0003 (4) | 0.0168 (4) | −0.0047 (4) |
C7 | 0.0396 (5) | 0.0418 (6) | 0.0427 (6) | −0.0009 (4) | 0.0164 (5) | −0.0047 (4) |
C12 | 0.0370 (5) | 0.0423 (6) | 0.0464 (6) | 0.0019 (4) | 0.0148 (5) | −0.0053 (5) |
C14 | 0.0558 (8) | 0.0920 (12) | 0.0611 (9) | 0.0019 (7) | 0.0312 (7) | −0.0147 (8) |
C13 | 0.0529 (7) | 0.0594 (8) | 0.0593 (8) | 0.0033 (6) | 0.0260 (6) | −0.0193 (6) |
C10 | 0.0583 (8) | 0.0473 (7) | 0.0673 (9) | −0.0124 (6) | 0.0222 (6) | −0.0175 (6) |
C11 | 0.0962 (12) | 0.0515 (8) | 0.0874 (11) | −0.0186 (8) | 0.0549 (10) | −0.0250 (8) |
Geometric parameters (Å, º) top
O2—C9 | 1.2177 (13) | O4—C12 | 1.2206 (15) |
O1—C4 | 1.3631 (13) | C6—H6 | 0.9300 |
O1—H1O | 0.8200 | C9—C8 | 1.4651 (16) |
O3—C9 | 1.3435 (13) | C7—C8 | 1.3844 (14) |
O3—C10 | 1.4527 (15) | C8—C12 | 1.4623 (15) |
N1—C1 | 1.4259 (13) | C7—H7 | 0.9300 |
N1—C7 | 1.3232 (15) | C14—C13 | 1.500 (2) |
N1—H1N | 0.8600 | C14—H14A | 0.9600 |
O5—C12 | 1.3391 (13) | C14—H14B | 0.9600 |
O5—C13 | 1.4544 (14) | C14—H14C | 0.9600 |
C1—C2 | 1.3872 (16) | C13—H13A | 0.9700 |
C1—C6 | 1.3891 (16) | C13—H13B | 0.9700 |
C3—C2 | 1.3845 (16) | C10—C11 | 1.496 (2) |
C3—C4 | 1.3870 (16) | C10—H10A | 0.9700 |
C3—H3 | 0.9300 | C10—H10B | 0.9700 |
C4—C5 | 1.3894 (15) | C11—H11A | 0.9600 |
C5—C6 | 1.3887 (15) | C11—H11B | 0.9600 |
C5—H5 | 0.9300 | C11—H11C | 0.9600 |
C2—H2 | 0.9300 | | |
| | | |
C4—O1—H1O | 109.5 | N1—C7—C8 | 126.34 (10) |
C9—O3—C10 | 116.79 (10) | N1—C7—H7 | 116.8 |
C7—N1—C1 | 124.56 (10) | C8—C7—H7 | 116.8 |
C7—N1—H1N | 117.7 | O4—C12—O5 | 122.36 (10) |
C1—N1—H1N | 117.7 | O4—C12—C8 | 123.39 (10) |
C12—O5—C13 | 115.83 (10) | O5—C12—C8 | 114.19 (10) |
C2—C1—C6 | 119.88 (10) | C13—C14—H14A | 109.5 |
C2—C1—N1 | 118.64 (10) | C13—C14—H14B | 109.5 |
C6—C1—N1 | 121.48 (10) | H14A—C14—H14B | 109.5 |
C2—C3—C4 | 120.09 (10) | C13—C14—H14C | 109.5 |
C2—C3—H3 | 120.0 | H14A—C14—H14C | 109.5 |
C4—C3—H3 | 120.0 | H14B—C14—H14C | 109.5 |
O1—C4—C3 | 117.93 (10) | O5—C13—C14 | 107.71 (12) |
O1—C4—C5 | 122.41 (10) | O5—C13—H13A | 110.2 |
C3—C4—C5 | 119.66 (10) | C14—C13—H13A | 110.2 |
C6—C5—C4 | 120.34 (10) | O5—C13—H13B | 110.2 |
C6—C5—H5 | 119.8 | C14—C13—H13B | 110.2 |
C4—C5—H5 | 119.8 | H13A—C13—H13B | 108.5 |
C3—C2—C1 | 120.27 (10) | O3—C10—C11 | 106.96 (11) |
C3—C2—H2 | 119.9 | O3—C10—H10A | 110.3 |
C1—C2—H2 | 119.9 | C11—C10—H10A | 110.3 |
C5—C6—C1 | 119.73 (10) | O3—C10—H10B | 110.3 |
C5—C6—H6 | 120.1 | C11—C10—H10B | 110.3 |
C1—C6—H6 | 120.1 | H10A—C10—H10B | 108.6 |
O2—C9—O3 | 121.74 (10) | C10—C11—H11A | 109.5 |
O2—C9—C8 | 126.53 (10) | C10—C11—H11B | 109.5 |
O3—C9—C8 | 111.71 (9) | H11A—C11—H11B | 109.5 |
C7—C8—C12 | 119.52 (10) | C10—C11—H11C | 109.5 |
C7—C8—C9 | 118.01 (10) | H11A—C11—H11C | 109.5 |
C12—C8—C9 | 122.25 (9) | H11B—C11—H11C | 109.5 |
| | | |
C7—N1—C1—C2 | 146.18 (12) | O3—C9—C8—C7 | 23.12 (15) |
C7—N1—C1—C6 | −33.82 (18) | O2—C9—C8—C12 | 19.09 (19) |
C2—C3—C4—O1 | 177.81 (10) | O3—C9—C8—C12 | −162.32 (11) |
C2—C3—C4—C5 | −1.73 (18) | C1—N1—C7—C8 | 179.95 (11) |
O1—C4—C5—C6 | −178.99 (10) | C12—C8—C7—N1 | −2.79 (19) |
C3—C4—C5—C6 | 0.53 (18) | C9—C8—C7—N1 | 171.93 (12) |
C4—C3—C2—C1 | 1.32 (18) | C13—O5—C12—O4 | 9.38 (18) |
C6—C1—C2—C3 | 0.30 (18) | C13—O5—C12—C8 | −173.38 (11) |
N1—C1—C2—C3 | −179.70 (10) | C7—C8—C12—O4 | 14.69 (19) |
C4—C5—C6—C1 | 1.08 (18) | C9—C8—C12—O4 | −159.79 (12) |
C2—C1—C6—C5 | −1.49 (18) | C7—C8—C12—O5 | −162.52 (11) |
N1—C1—C6—C5 | 178.51 (11) | C9—C8—C12—O5 | 23.00 (17) |
C10—O3—C9—O2 | 8.69 (17) | C12—O5—C13—C14 | −170.17 (11) |
C10—O3—C9—C8 | −169.97 (11) | C9—O3—C10—C11 | 166.88 (12) |
O2—C9—C8—C7 | −155.47 (12) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O4 | 0.86 | 2.06 | 2.6936 (13) | 130 |
C7—H7···O3 | 0.93 | 2.27 | 2.6589 (14) | 104 |
O1—H1O···O2i | 0.82 | 1.91 | 2.7268 (13) | 174 |
Symmetry code: (i) x+1, y, z. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C14H17NO5 | C14H17NO5 |
Mr | 279.29 | 279.29 |
Crystal system, space group | Orthorhombic, Pbcm | Monoclinic, P21/n |
Temperature (K) | 296 | 296 |
a, b, c (Å) | 11.3011 (3), 19.2760 (4), 6.6725 (2) | 10.9970 (11), 10.8919 (11), 12.3244 (12) |
α, β, γ (°) | 90, 90, 90 | 90, 105.206 (1), 90 |
V (Å3) | 1453.54 (7) | 1424.5 (2) |
Z | 4 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.10 |
Crystal size (mm) | 0.22 × 0.22 × 0.20 | 0.25 × 0.25 × 0.20 |
|
Data collection |
Diffractometer | Bruker SMART CCD area-detector diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7641, 1690, 1165 | 12064, 3297, 2826 |
Rint | 0.027 | 0.027 |
(sin θ/λ)max (Å−1) | 0.634 | 0.653 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.154, 1.05 | 0.038, 0.117, 1.05 |
No. of reflections | 1690 | 3297 |
No. of parameters | 132 | 182 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.20 | 0.25, −0.17 |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O1 | 0.84 (3) | 2.28 (3) | 2.606 (2) | 103 (2) |
N1—H1N···O4 | 0.84 (3) | 1.95 (3) | 2.640 (3) | 139 (2) |
O1—H1O···O2i | 0.86 (4) | 1.81 (4) | 2.661 (2) | 178 (3) |
Symmetry code: (i) −x+2, y+1/2, z. |
Comparison of selected bond lengths (Å) in (I) and (II). top | (I) | (II) |
N1—C1 | 1.404 (3) | 1.4259 (13) |
N1—C7 | 1.330 (3) | 1.3232 (15) |
C7—C8 | 1.364 (3) | 1.3844 (14) |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O4 | 0.86 | 2.06 | 2.6936 (13) | 130.3 |
C7—H7···O3 | 0.93 | 2.27 | 2.6589 (14) | 104.1 |
O1—H1O···O2i | 0.82 | 1.91 | 2.7268 (13) | 173.6 |
Symmetry code: (i) x+1, y, z. |
Subscribe to Acta Crystallographica Section C: Structural Chemistry
The full text of this article is available to subscribers to the journal.
If you have already registered and are using a computer listed in your registration details, please email
support@iucr.org for assistance.
Hydrogen bonding is an important force central to the functioning of several complex and large biomolecules such as enzymes, DNA and RNA. It plays a major role in the design of novel supramolecular architectures and allows recognition among many organic molecules. Crystal engineering pertains to the directionality of hydrogen bonds and the ways in which hydrogen bonding influences crystal geometries depending on their strengths (Desiraju, 2011; Adam et al., 2010). Phenol compounds can exhibit inter- and intramolecular hydrogen bonding depending on the nature and position of the other functional groups. The electronic nature and ortho, para or meta position of the substituent strongly influences the acidity of the phenolic H atom and hence the strength of the hydrogen bond.
Diethyl 2-[(alkyl/aryl)methylidene]malonate derivatives (BECV) are important intermediates useful in the synthesis of various nitrogen- and oxygen-containing heterocycles, as ligands in inorganic metal complexes, in the detection of amino acids etc. 2,2-Bis(ethoxycarbonyl)vinyl-(BECV) amine derivatives are mainly used as building blocks for the synthesis of a variety of bioactive nitrogen-containing heterocycles such as pyrazoles, 4-oxoquinoline-3-carboxylic acid esters, pyrimidine, pyrimido[1,2-a]pyrimidines, 3H,5H-pyrrolo[3,2-d]pyrimidines and pyrido[2,3-d]pyrimidines (Johnson & Ambler, 1911; Fustero et al., 2011; Niedermeier et al., 2009; Yang et al., 2009; Candeias et al., 2009; Petric et al., 1983; Furneaux & Tyler, 1999). [Put the specific references with the specific compund class?]
Simple N-diethyl-2-[(alkyl/aryl)methylidene]malonate (N-BECV) derivatives are biologically active compounds. Steck (1962) observed that N-BECV derivatives of diisopropylamine, piperidine [diethyl 2-[(piperidin-1-yl)methylidene]malonate, see (1) in Scheme 2], pyrrolidine and morpholine are central nervous system stimulants. Similarly, Santilli et al. (1964) prepared a number of enamine derivatives containing the N-BECV unit, such as a 4-aminomethylbezoic acid derivative, diethyl 2-({[3-(dimethylamino)propyl]amino}methylidene)malonate [see (2) in Scheme 2] and diethyl 2-{[(diphenylmethoxy)amino]methylidene}malonate [see (3) in Scheme 2], and established their muscle relaxation and sedative properties (Santilli et al., 1964). In addition, N-BECV derivatives show a very low cytotoxicity to normal cells.
Recently, we have demonstrated that diethyl 2-[(alkyl/aryl)aminomethylidene]malonates (N-BECV) can be used as a chemo-selective amine-protecting group useful for several sensitive organic functional group transformations (Ilangovan & Ganeashkumar, 2010). In a continuation of this work, we studied the crystal structures of diethyl 2-[(2-hydroxyanilino)methylidene]malonate, (I), and diethyl 2-[(4-hydroxyanilino)methylidene]malonate, (II), and the effect of hydroxy-group substitution on their supramolecular architectures. To the best of our knowledge, single-crystal structures of diethyl 2-[(alkyl/aryl)methylidene]malonate derivatives (BECV) have not been reported previously.
Compounds (I) and (II) were obtained by the condensation of 2-aminophenol or 4-aminophenol with diethyl ethoxymethylenemalonate in ethanol (Ilangovan & Ganeashkumar, 2010) as white solids in quantitative yield (Fig. 1). Good quality single crystals used for XRD study were obtained from hexane and ethyl acetate mixtures (8:2 v/v). The compounds are positional isomers. Compound (I) occupies a crystallographic mirror and is totally planar, but the benzene ring in compound (II) deviates from planarity by 0.0158 Å. Atom C13 of compound (I) is split and occupies two positions related by the mirror plane. The angles between the plane of the aminophenol ring and the plane of the vinylic double bond are 0 and 33.59 (12)° in (I) and (II), respectively. In both compounds, the C1—N1 (Car—N) bonds (Table 1) are shorter than the normal N—C bond length because of conjugation between π-electrons in the vinylic double bond and the lone pair electrons in the N atom. The vinylic C7—C8 bond distances are similarly longer than normal vinylic C—C bonds.
The presence of a phenolic –OH group at the ortho position to the amine group in compound (I) favours a strong bifurcated O—H···N—H···O hydrogen bond between the O1—H1O and N1—H1N groups and the O2 and O4 atoms of the ester carbonyl groups (Table 2). This gives rise to two pseudo-R(6) and R(5) ring motifs in compound (I) and helps in achieving rigorous planarity. A one-dimensional O1···H1N···O2═C9 chain is formed along the a axis (Fig. 2) by the –OH group of one molecule and the the ester carbonyl group of another molecule. No interactions are observed between the chains.
In the case of (II), two hydrogen-bond interactions (N1—H1H···O3 and O1—H1O···O5) are observed, the former giving rise to an R(6) ring motif (Table 3). Intermolecular O1—H1O···O5 hydrogen bonding gives rise to a one-dimensional chain along the a axis (Fig. 3). In addition to head-to-tail hydrogen bonding, there is a macrocyclic dimer motif R22(26) formed by a C11—H···O1 interaction between two adjacent one-dimensional chains (Fig. 4). [None of the four mentioned interactions are in Table 3] This gives rise to a ladder-like structure (Fig. 5). Along the b axis, compound (II) forms a helical structure and a channel could be visualized along the a axis. Neither compound shows any significant centroid–centroid or C—H···π interactions.
In conclusion, we have studied crystal structure properties such as motifs, chains, the nature of hydrogen bonding and other interactions of the title compounds (I) and (II). Variations in the ortho and para substitution of hydroxy groups was analysed. The presence of an –OH group adjacent to an –NH group favours bifurcated hydrogen bonding and the formation of two pseudo-R(6) and R(5) ring motifs, and gives rise to strict planarity for compound (I). In a supramolecular framework it gives rise to a layer-like structure. In case of compound (II), a pseudo-R(6) ring and a macrocyclic R22(26) ring motif was observed between chains. Both compounds form a head-to-tail one-dimensional hydrogen-bonded chain and a zigzag arrangement. We believe that this study will be helpful in understanding the ability of these molecules to interact with biological systems, geometrical parameters useful in formation of metal complexes and synthesis of different heterocyclic compounds.