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Diethyl 2-[(2-hy­droxy­anilino)methyl­idene]malonate, (I), and diethyl 2-[(4-hy­droxy­anilino)methyl­idene]malonate, (II), both C14H17NO5, 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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270112047257/fn3116sup1.cif
Contains datablocks I, II, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112047257/fn3116Isup2.hkl
Contains datablock I

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112047257/fn3116Isup4.cml
Supplementary material

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270112047257/fn3116IIsup3.hkl
Contains datablock 1

cml

Chemical Markup Language (CML) file https://doi.org/10.1107/S0108270112047257/fn3116IIsup5.cml
Supplementary material

CCDC references: 678847; 925265

Comment top

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···O2C9 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.

Related literature top

For related literature, see: Adam et al. (2010); Candeias et al. (2009); Desiraju (2011); Furneaux & Tyler (1999); Fustero et al. (2011); Ilangovan & Ganeashkumar (2010); Johnson & Ambler (1911); Niedermeier et al. (2009); Petric et al. (1983); Santilli et al. (1964); Steck (1962); Yang et al. (2009).

Experimental top

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].

Refinement top

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.

Computing details top

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).

Figures top
Fig. 1. Perspective view of compounds (I) and (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radius.

Fig. 2. (a) The one-dimensional hydrogen-bonded chains along the a axis in compound (I). (b) The one-dimensional hydrogen-bonded chains along the a axis. Dashed lines indicate the hydrogen-bonding interactions.

Fig. 3. The one-dimensional hydrogen-bonded chain along the a axis in compound (II). Dashed lines indicate the hydrogen-bonding interactions.

Fig. 4. The hydrogen-bonded ladder in compound (II). Dashed lines indicate the hydrogen-bonding interactions. Obscurred H atoms and one ester group have been removed for clarity. [Please define parts (a), (b) and (c)] [What do the suffixes "b" and "c" represent in part (b)?]

Fig. 5. The packing of molecules of compound (II) along (a) the b axis and (b) along the a axis. [Not really mentioned. Could it be Supplementary material?]
(I) Diethyl 2-[(2-hydroxyanilino)methylidene]malonate top
Crystal data top
C14H17NO5F(000) = 592
Mr = 279.29Dx = 1.276 Mg m3
Orthorhombic, PbcmMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2c 2bCell parameters from 2008 reflections
a = 11.3011 (3) Åθ = 3.1–25.2°
b = 19.2760 (4) ŵ = 0.10 mm1
c = 6.6725 (2) ÅT = 296 K
V = 1453.54 (7) Å3Plate, yellow
Z = 40.22 × 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 tubeRint = 0.027
Graphite monochromatorθmax = 26.8°, θmin = 1.8°
phi and ω scansh = 1114
7641 measured reflectionsk = 2424
1690 independent reflectionsl = 78
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.049H 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 reflectionsΔρmax = 0.23 e Å3
132 parametersΔρmin = 0.20 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0072 (16)
Crystal data top
C14H17NO5V = 1453.54 (7) Å3
Mr = 279.29Z = 4
Orthorhombic, PbcmMo Kα radiation
a = 11.3011 (3) ŵ = 0.10 mm1
b = 19.2760 (4) ÅT = 296 K
c = 6.6725 (2) Å0.22 × 0.22 × 0.20 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer
1165 reflections with I > 2σ(I)
7641 measured reflectionsRint = 0.027
1690 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0490 restraints
wR(F2) = 0.154H atoms treated by a mixture of independent and constrained refinement
S = 1.05Δρmax = 0.23 e Å3
1690 reflectionsΔρmin = 0.20 e Å3
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
xyzUiso*/UeqOcc. (<1)
O10.93175 (16)0.39737 (8)0.25000.0719 (6)
O41.12614 (17)0.24764 (10)0.25000.0973 (8)
O51.20132 (18)0.14140 (9)0.25000.1018 (8)
O30.86035 (15)0.06136 (8)0.25000.0689 (5)
O21.05136 (16)0.03504 (7)0.25000.0770 (6)
N10.8942 (2)0.26400 (9)0.25000.0609 (6)
C10.7941 (2)0.30708 (11)0.25000.0571 (6)
C20.8167 (2)0.37835 (11)0.25000.0573 (6)
C30.7241 (3)0.42457 (14)0.25000.0724 (8)
H30.73900.47200.25000.087*
C40.6101 (3)0.40078 (16)0.25000.0918 (10)
H40.54750.43210.25000.110*
C50.5875 (3)0.33043 (17)0.25000.0931 (10)
H50.50980.31450.25000.112*
C60.6789 (3)0.28407 (14)0.25000.0749 (8)
H60.66320.23670.25000.090*
C70.8954 (2)0.19499 (11)0.25000.0572 (6)
C80.9933 (2)0.15357 (10)0.25000.0584 (6)
C121.1103 (3)0.18519 (12)0.25000.0737 (8)
C131.3185 (3)0.17212 (17)0.25000.159 (2)
H13A1.32770.20120.13230.191*0.50
H13B1.32770.20120.36770.191*0.50
C141.4055 (3)0.1209 (2)0.25000.1268 (15)
H14A1.38740.08690.35040.190*0.50
H14B1.48100.14150.27870.190*0.50
H14C1.40820.09900.12080.190*0.50
C90.9745 (2)0.07839 (11)0.25000.0569 (6)
C100.8306 (2)0.01136 (12)0.25000.0701 (7)
H10A0.86270.03390.36800.084*0.50
H10B0.86270.03390.13200.084*0.50
C110.6988 (3)0.01584 (16)0.25000.0891 (9)
H11A0.67520.06370.25000.134*
H11B0.66820.00660.13250.134*0.50
H11C0.66820.00660.36750.134*0.50
H1O0.939 (3)0.4416 (19)0.25000.112 (11)*
H1N0.963 (3)0.2803 (13)0.25000.075 (9)*
H70.818 (2)0.1746 (12)0.25000.055 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0698 (12)0.0349 (8)0.1110 (15)0.0018 (8)0.0000.000
O40.0854 (13)0.0402 (8)0.166 (2)0.0118 (10)0.0000.000
O50.0682 (12)0.0469 (10)0.190 (2)0.0076 (9)0.0000.000
O30.0659 (11)0.0405 (9)0.1001 (13)0.0064 (7)0.0000.000
O20.0664 (11)0.0337 (8)0.1309 (17)0.0012 (8)0.0000.000
N10.0690 (14)0.0368 (10)0.0767 (14)0.0001 (9)0.0000.000
C10.0705 (15)0.0415 (11)0.0592 (14)0.0020 (11)0.0000.000
C20.0659 (14)0.0426 (11)0.0634 (14)0.0027 (10)0.0000.000
C30.0755 (18)0.0494 (12)0.092 (2)0.0104 (12)0.0000.000
C40.072 (2)0.0776 (19)0.126 (3)0.0148 (15)0.0000.000
C50.0661 (17)0.082 (2)0.131 (3)0.0057 (15)0.0000.000
C60.0738 (18)0.0538 (14)0.097 (2)0.0059 (13)0.0000.000
C70.0737 (16)0.0392 (11)0.0587 (14)0.0033 (11)0.0000.000
C80.0695 (15)0.0347 (10)0.0711 (15)0.0029 (10)0.0000.000
C120.0782 (18)0.0403 (12)0.103 (2)0.0058 (12)0.0000.000
C130.071 (2)0.0586 (18)0.348 (7)0.0150 (17)0.0000.000
C140.085 (2)0.128 (3)0.167 (4)0.028 (2)0.0000.000
C90.0653 (15)0.0372 (10)0.0683 (15)0.0036 (10)0.0000.000
C100.0707 (16)0.0446 (12)0.0949 (19)0.0137 (11)0.0000.000
C110.0776 (19)0.0799 (19)0.110 (2)0.0232 (16)0.0000.000
Geometric parameters (Å, º) top
O1—C21.351 (3)C5—C61.366 (4)
O1—H1O0.86 (4)C5—H50.9300
O4—C121.217 (3)C6—H60.9300
O5—C121.331 (3)C7—C81.364 (3)
O5—C13i1.451 (4)C7—H70.96 (2)
O5—C131.451 (4)C8—C121.456 (4)
O3—C91.331 (3)C8—C91.465 (3)
O3—C101.442 (3)C13—C141.393 (5)
O2—C91.205 (3)C13—H13A0.9700
N1—C71.330 (3)C13—H13B0.9700
N1—C11.404 (3)C14—H14A0.9600
N1—H1N0.84 (3)C14—H14B0.9600
C1—C61.375 (4)C14—H14C0.9600
C1—C21.398 (3)C10—C111.492 (4)
C2—C31.374 (3)C10—H10A0.9700
C3—C41.368 (4)C10—H10B0.9700
C3—H30.9300C11—H11A0.9600
C4—C51.380 (4)C11—H11B0.9600
C4—H40.9300C11—H11C0.9600
C2—O1—H1O111 (2)C8—C7—H7120.0 (14)
C12—O5—C13i116.5 (2)C7—C8—C12119.4 (2)
C12—O5—C13116.5 (2)C7—C8—C9117.5 (2)
C13i—O5—C130.0 (2)C12—C8—C9123.1 (2)
C9—O3—C10117.77 (19)O4—C12—O5120.9 (3)
C7—N1—C1126.8 (2)O4—C12—C8123.2 (3)
C7—N1—H1N111.4 (18)O5—C12—C8115.9 (2)
C1—N1—H1N121.7 (18)C14—C13—O5110.8 (3)
C6—C1—C2119.4 (2)C14—C13—H13A109.5
C6—C1—N1124.9 (2)O5—C13—H13A109.5
C2—C1—N1115.7 (2)C14—C13—H13B109.5
O1—C2—C3123.8 (2)O5—C13—H13B109.5
O1—C2—C1116.3 (2)H13A—C13—H13B108.1
C3—C2—C1119.9 (2)O2—C9—O3121.8 (2)
C4—C3—C2120.0 (3)O2—C9—C8125.6 (2)
C4—C3—H3120.0O3—C9—C8112.6 (2)
C2—C3—H3120.0O3—C10—C11106.8 (2)
C3—C4—C5120.2 (3)O3—C10—H10A110.4
C3—C4—H4119.9C11—C10—H10A110.4
C5—C4—H4119.9O3—C10—H10B110.4
C6—C5—C4120.2 (3)C11—C10—H10B110.4
C6—C5—H5119.9H10A—C10—H10B108.6
C4—C5—H5119.9C10—C11—H11A109.5
C5—C6—C1120.3 (2)C10—C11—H11B109.5
C5—C6—H6119.8H11A—C11—H11B109.5
C1—C6—H6119.8C10—C11—H11C109.5
N1—C7—C8126.4 (2)H11A—C11—H11C109.5
N1—C7—H7113.6 (14)H11B—C11—H11C109.5
C7—N1—C1—C60.0C13—O5—C12—O40.0
C7—N1—C1—C2180.0C13i—O5—C12—C8180.0
C6—C1—C2—O1180.0C13—O5—C12—C8180.0
N1—C1—C2—O10.0C7—C8—C12—O40.0
C6—C1—C2—C30.0C9—C8—C12—O4180.0
N1—C1—C2—C3180.0C7—C8—C12—O5180.0
O1—C2—C3—C4180.0C9—C8—C12—O50.0
C1—C2—C3—C40.0C12—O5—C13—C14180.0
C2—C3—C4—C50.0C13i—O5—C13—C140 (100)
C3—C4—C5—C60.0C10—O3—C9—O20.0
C4—C5—C6—C10.0C10—O3—C9—C8180.0
C2—C1—C6—C50.0C7—C8—C9—O2180.0
N1—C1—C6—C5180.0C12—C8—C9—O20.0
C1—N1—C7—C8180.0C7—C8—C9—O30.0
N1—C7—C8—C120.0C12—C8—C9—O3180.0
N1—C7—C8—C9180.0C9—O3—C10—C11180.0
C13i—O5—C12—O40.0
Symmetry code: (i) x, y, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O10.84 (3)2.28 (3)2.606 (2)103 (2)
N1—H1N···O40.84 (3)1.95 (3)2.640 (3)139 (2)
O1—H1O···O2ii0.86 (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
C14H17NO5F(000) = 592
Mr = 279.29Dx = 1.302 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 7526 reflections
a = 10.9970 (11) Åθ = 2.2–27.6°
b = 10.8919 (11) ŵ = 0.10 mm1
c = 12.3244 (12) ÅT = 296 K
β = 105.206 (1)°Plate, yellow
V = 1424.5 (2) Å30.25 × 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 tubeRint = 0.027
Graphite monochromatorθmax = 27.6°, θmin = 2.2°
phi and ω scansh = 1414
12064 measured reflectionsk = 1413
3297 independent reflectionsl = 1516
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038H-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 reflectionsΔρmax = 0.25 e Å3
182 parametersΔρmin = 0.17 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.033 (3)
Crystal data top
C14H17NO5V = 1424.5 (2) Å3
Mr = 279.29Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.9970 (11) ŵ = 0.10 mm1
b = 10.8919 (11) ÅT = 296 K
c = 12.3244 (12) Å0.25 × 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 reflectionsRint = 0.027
3297 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0380 restraints
wR(F2) = 0.117H-atom parameters constrained
S = 1.05Δρmax = 0.25 e Å3
3297 reflectionsΔρmin = 0.17 e Å3
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
xyzUiso*/Ueq
O20.89430 (8)0.89700 (9)0.10761 (8)0.0515 (2)
O11.76120 (8)1.11032 (9)0.09308 (8)0.0526 (2)
H1O1.79671.04350.09900.079*
O31.06830 (8)0.80048 (8)0.09127 (8)0.0496 (2)
N11.29994 (9)1.08073 (9)0.19856 (9)0.0444 (2)
H1N1.28261.13870.23950.053*
O50.96576 (8)1.04595 (8)0.29964 (7)0.0456 (2)
C11.41932 (10)1.08441 (10)0.17351 (9)0.0377 (2)
C31.58631 (11)1.20500 (11)0.13509 (10)0.0433 (3)
H31.62131.28130.12760.052*
C41.64991 (10)1.09859 (10)0.12128 (9)0.0383 (2)
C51.59877 (10)0.98497 (10)0.13553 (10)0.0416 (3)
H51.64160.91350.12690.050*
C21.47084 (11)1.19783 (11)0.15998 (10)0.0427 (3)
H21.42761.26930.16770.051*
O41.11922 (9)1.17548 (9)0.28488 (10)0.0615 (3)
C61.48409 (10)0.97759 (10)0.16256 (10)0.0414 (3)
H61.45080.90140.17330.050*
C91.00865 (10)0.89389 (10)0.12661 (10)0.0395 (3)
C81.09731 (10)0.98743 (10)0.18571 (10)0.0392 (3)
C71.21404 (10)0.99437 (11)0.16325 (10)0.0403 (3)
H71.23400.93230.11900.048*
C121.06250 (10)1.07905 (11)0.25894 (10)0.0412 (3)
C140.82810 (14)1.07958 (17)0.41761 (14)0.0667 (4)
H14A0.79561.13970.45960.100*
H14B0.87061.01620.46740.100*
H14C0.75991.04430.36110.100*
C130.91915 (13)1.13979 (14)0.36247 (12)0.0551 (3)
H13A0.87731.20440.31230.066*
H13B0.98851.17580.41890.066*
C100.99000 (14)0.71243 (13)0.01554 (13)0.0566 (3)
H10A0.92890.75470.04380.068*
H10B0.94510.66080.05620.068*
C111.07613 (18)0.63637 (14)0.03301 (16)0.0726 (5)
H11A1.02770.57660.08360.109*
H11B1.13620.59520.02650.109*
H11C1.11980.68850.07310.109*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O20.0363 (4)0.0528 (5)0.0674 (6)0.0014 (3)0.0169 (4)0.0126 (4)
O10.0402 (4)0.0524 (5)0.0711 (6)0.0024 (4)0.0251 (4)0.0081 (4)
O30.0427 (4)0.0434 (5)0.0679 (6)0.0042 (3)0.0238 (4)0.0179 (4)
N10.0389 (5)0.0461 (5)0.0526 (6)0.0041 (4)0.0201 (4)0.0109 (4)
O50.0457 (4)0.0461 (5)0.0518 (5)0.0001 (3)0.0250 (4)0.0096 (4)
C10.0343 (5)0.0417 (6)0.0384 (5)0.0024 (4)0.0118 (4)0.0032 (4)
C30.0431 (6)0.0353 (5)0.0514 (7)0.0057 (4)0.0124 (5)0.0029 (5)
C40.0333 (5)0.0431 (6)0.0387 (5)0.0019 (4)0.0095 (4)0.0040 (4)
C50.0380 (5)0.0367 (6)0.0517 (6)0.0021 (4)0.0148 (5)0.0019 (5)
C20.0431 (6)0.0352 (5)0.0500 (6)0.0013 (4)0.0128 (5)0.0040 (4)
O40.0564 (5)0.0506 (5)0.0872 (7)0.0113 (4)0.0359 (5)0.0265 (5)
C60.0403 (6)0.0357 (6)0.0502 (6)0.0034 (4)0.0154 (5)0.0028 (4)
C90.0398 (5)0.0391 (6)0.0439 (6)0.0001 (4)0.0188 (5)0.0026 (4)
C80.0375 (5)0.0394 (6)0.0440 (6)0.0003 (4)0.0168 (4)0.0047 (4)
C70.0396 (5)0.0418 (6)0.0427 (6)0.0009 (4)0.0164 (5)0.0047 (4)
C120.0370 (5)0.0423 (6)0.0464 (6)0.0019 (4)0.0148 (5)0.0053 (5)
C140.0558 (8)0.0920 (12)0.0611 (9)0.0019 (7)0.0312 (7)0.0147 (8)
C130.0529 (7)0.0594 (8)0.0593 (8)0.0033 (6)0.0260 (6)0.0193 (6)
C100.0583 (8)0.0473 (7)0.0673 (9)0.0124 (6)0.0222 (6)0.0175 (6)
C110.0962 (12)0.0515 (8)0.0874 (11)0.0186 (8)0.0549 (10)0.0250 (8)
Geometric parameters (Å, º) top
O2—C91.2177 (13)O4—C121.2206 (15)
O1—C41.3631 (13)C6—H60.9300
O1—H1O0.8200C9—C81.4651 (16)
O3—C91.3435 (13)C7—C81.3844 (14)
O3—C101.4527 (15)C8—C121.4623 (15)
N1—C11.4259 (13)C7—H70.9300
N1—C71.3232 (15)C14—C131.500 (2)
N1—H1N0.8600C14—H14A0.9600
O5—C121.3391 (13)C14—H14B0.9600
O5—C131.4544 (14)C14—H14C0.9600
C1—C21.3872 (16)C13—H13A0.9700
C1—C61.3891 (16)C13—H13B0.9700
C3—C21.3845 (16)C10—C111.496 (2)
C3—C41.3870 (16)C10—H10A0.9700
C3—H30.9300C10—H10B0.9700
C4—C51.3894 (15)C11—H11A0.9600
C5—C61.3887 (15)C11—H11B0.9600
C5—H50.9300C11—H11C0.9600
C2—H20.9300
C4—O1—H1O109.5N1—C7—C8126.34 (10)
C9—O3—C10116.79 (10)N1—C7—H7116.8
C7—N1—C1124.56 (10)C8—C7—H7116.8
C7—N1—H1N117.7O4—C12—O5122.36 (10)
C1—N1—H1N117.7O4—C12—C8123.39 (10)
C12—O5—C13115.83 (10)O5—C12—C8114.19 (10)
C2—C1—C6119.88 (10)C13—C14—H14A109.5
C2—C1—N1118.64 (10)C13—C14—H14B109.5
C6—C1—N1121.48 (10)H14A—C14—H14B109.5
C2—C3—C4120.09 (10)C13—C14—H14C109.5
C2—C3—H3120.0H14A—C14—H14C109.5
C4—C3—H3120.0H14B—C14—H14C109.5
O1—C4—C3117.93 (10)O5—C13—C14107.71 (12)
O1—C4—C5122.41 (10)O5—C13—H13A110.2
C3—C4—C5119.66 (10)C14—C13—H13A110.2
C6—C5—C4120.34 (10)O5—C13—H13B110.2
C6—C5—H5119.8C14—C13—H13B110.2
C4—C5—H5119.8H13A—C13—H13B108.5
C3—C2—C1120.27 (10)O3—C10—C11106.96 (11)
C3—C2—H2119.9O3—C10—H10A110.3
C1—C2—H2119.9C11—C10—H10A110.3
C5—C6—C1119.73 (10)O3—C10—H10B110.3
C5—C6—H6120.1C11—C10—H10B110.3
C1—C6—H6120.1H10A—C10—H10B108.6
O2—C9—O3121.74 (10)C10—C11—H11A109.5
O2—C9—C8126.53 (10)C10—C11—H11B109.5
O3—C9—C8111.71 (9)H11A—C11—H11B109.5
C7—C8—C12119.52 (10)C10—C11—H11C109.5
C7—C8—C9118.01 (10)H11A—C11—H11C109.5
C12—C8—C9122.25 (9)H11B—C11—H11C109.5
C7—N1—C1—C2146.18 (12)O3—C9—C8—C723.12 (15)
C7—N1—C1—C633.82 (18)O2—C9—C8—C1219.09 (19)
C2—C3—C4—O1177.81 (10)O3—C9—C8—C12162.32 (11)
C2—C3—C4—C51.73 (18)C1—N1—C7—C8179.95 (11)
O1—C4—C5—C6178.99 (10)C12—C8—C7—N12.79 (19)
C3—C4—C5—C60.53 (18)C9—C8—C7—N1171.93 (12)
C4—C3—C2—C11.32 (18)C13—O5—C12—O49.38 (18)
C6—C1—C2—C30.30 (18)C13—O5—C12—C8173.38 (11)
N1—C1—C2—C3179.70 (10)C7—C8—C12—O414.69 (19)
C4—C5—C6—C11.08 (18)C9—C8—C12—O4159.79 (12)
C2—C1—C6—C51.49 (18)C7—C8—C12—O5162.52 (11)
N1—C1—C6—C5178.51 (11)C9—C8—C12—O523.00 (17)
C10—O3—C9—O28.69 (17)C12—O5—C13—C14170.17 (11)
C10—O3—C9—C8169.97 (11)C9—O3—C10—C11166.88 (12)
O2—C9—C8—C7155.47 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O40.862.062.6936 (13)130
C7—H7···O30.932.272.6589 (14)104
O1—H1O···O2i0.821.912.7268 (13)174
Symmetry code: (i) x+1, y, z.

Experimental details

(I)(II)
Crystal data
Chemical formulaC14H17NO5C14H17NO5
Mr279.29279.29
Crystal system, space groupOrthorhombic, PbcmMonoclinic, P21/n
Temperature (K)296296
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, 9090, 105.206 (1), 90
V3)1453.54 (7)1424.5 (2)
Z44
Radiation typeMo KαMo Kα
µ (mm1)0.100.10
Crystal size (mm)0.22 × 0.22 × 0.200.25 × 0.25 × 0.20
Data collection
DiffractometerBruker 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
Rint0.0270.027
(sin θ/λ)max1)0.6340.653
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.049, 0.154, 1.05 0.038, 0.117, 1.05
No. of reflections16903297
No. of parameters132182
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.23, 0.200.25, 0.17

Computer programs: SMART (Bruker, 2008), SAINT (Bruker, 2008), SHELXTL (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O10.84 (3)2.28 (3)2.606 (2)103 (2)
N1—H1N···O40.84 (3)1.95 (3)2.640 (3)139 (2)
O1—H1O···O2i0.86 (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—C11.404 (3)1.4259 (13)
N1—C71.330 (3)1.3232 (15)
C7—C81.364 (3)1.3844 (14)
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
N1—H1N···O40.862.062.6936 (13)130.3
C7—H7···O30.932.272.6589 (14)104.1
O1—H1O···O2i0.821.912.7268 (13)173.6
Symmetry code: (i) x+1, y, z.
 

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