Acta Cryst.(2003). E59, o1241±o1243 DOI: 10.1107/S1600536803016660 Tokiko Imaiet al. C13H14N2O6
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organic papers
Acta Crystallographica Section E Structure Reports Online
ISSN 1600-5368
The 2-methoxyphenylhydrazone derivative of
dehydroascorbic acid
Tokiko Imai,aYoshihiro
Yokoyama,bAkiko Sekine,c
Hidediro Uekusac* and Yuji
Ohashic
aDepartment of Householding, Kyoritu
Womens' University, Hitotsubashi, Chiyoda-ku, Tokyo 110, Japan,bDepartment of Chemistry,
Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152-8551, Japan, and
cDepartment of Materials Science and
Chemistry, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152-8551, Japan
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study
T= 295 K
Mean(C±C) = 0.013 AÊ
Rfactor = 0.073
wRfactor = 0.221 Data-to-parameter ratio = 8.2
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2003 International Union of Crystallography Printed in Great Britain ± all rights reserved
The title compound, (3Z )-5-(1,2-dihydroxyethyl)furan-2,3,4-(3H,5H)-trione 3-[(2-methoxyphenyl)hydrazone], C13H14
-N2O6, is produced when dehydro-l-ascorbic acid reacts with
2-methoxyphenylhydrazine. A two-dimensional structure is generated by extensive hydrogen-bonding interactions.
Comment
Vegetables and fruit may turn red±brown when they are kept under aerobic conditions for a long time. A mechanism proposed to account for this indicated that reactions of de-hydroascorbic acid with amino acids play an important role in the process of oxidation of l-ascorbic acid to 2,20
-nitrilo-di-2(20)-deoxy-l-ascorbic acid monoammonium salt, which is
red±brown (Kurataet al., 1973a,b).
In the course of structural studies of the red±brown pigment, hydrazones were prepared by reaction of dehydro-ascorbic acid with hydrazines. The crystal structure of one of the eight hydrazones synthesized, 2-methoxyphenylhydrazone dehydroascorbic acid, (I), has been determined by single-crystal X-ray diffraction methods (Fig. 1 and Table 1).
The molecular structure of (I) comprises an ethylene glycol open chain, linked to the hydrazone groupviaa lactone ring. The 15 non-H atoms of the phenylhydrazone and lactone ring are effectively coplanar, the maximum deviation from the least-squares plane through these atoms being 0.066 (9) AÊ for C8. The bond lengths and angles in (I) are quite similar to those reported for the closely related structure of p -bromo-phenylhydrazone derivative of dehydroascorbic acid (Hvoslef & Nordenson, 1976).
The hydrogen-bonding distances and angles are listed in Table 2. An intramolecular N2ÐH O2 hydrogen bond is observed. Both the OH groups of the ethylene glycol residue participate in hydrogen bonds. The terminal OH group (O5) is connected to the carbonyl atom O3. These interactions link the molecules into ribbons that are aligned along theaaxis, as shown in Fig. 2. The ribbons are stacked along [011], and are connected by hydrogen bonds formed between two OH groups (O3ÐH O5). The stacking distance between ribbons is approximately 3.4 AÊ. The intermolecular hydrogen bonds described above combine to generate a two-dimensional layer structure.
organic papers
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Tokiko Imaiet al. C13H14N2O6 Acta Cryst.(2003). E59, o1241±o1243Experimental
The title compound was prepared according to a literature procedure (Hvoslef & Nordenson, 1976). Plate-like yellow crystals were obtained by recrystallization from an ethanol solution of the compound.
Crystal data
C13H14N2O6
Mr= 294.26
Triclinic,P1
a= 8.194 (2) AÊ
b= 8.308 (2) AÊ
c= 5.463 (3) AÊ
= 106.12 (3)
= 101.98 (3)
= 95.69 (2) V= 344.6 (2) AÊ3
Z= 1
Dx= 1.418 Mg mÿ3
MoKradiation Cell parameters from 25
re¯ections
= 28.0±30.0
= 0.11 mmÿ1
T= 295 (2) K Plate, clear pale yellow 0.300.150.05 mm
Data collection
Rigaku AFC-7Sdiffractometer
-2scans
Absorption correction: scan (Northet al., 1968)
Tmin= 0.960,Tmax= 0.998
1680 measured re¯ections 1575 independent re¯ections 961 re¯ections withI> 2(I)
Rint= 0.030
max= 27.5
h= 0!10
k=ÿ10!10
l=ÿ7!6 3 standard re¯ections
every 150 re¯ections intensity decay: 0.8%
Re®nement
Re®nement onF2
R[F2> 2(F2)] = 0.073
wR(F2) = 0.221
S= 1.05 1575 re¯ections 193 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0983P)2
+ 0.4777P]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001 max= 0.31 e AÊÿ3 min=ÿ0.30 e AÊÿ3
Table 1
Selected geometric parameters (AÊ,).
C1ÐN1 1.334 (11) C1ÐC2 1.431 (12) C1ÐC4 1.443 (10) C2ÐO2 1.232 (9) C2ÐC3 1.501 (12)
O1ÐC4 1.363 (10) O1ÐC3 1.458 (10) N1ÐN2 1.298 (8) N2ÐC7 1.404 (11) N1ÐC1ÐC2 128.3 (7)
N1ÐC1ÐC4 122.4 (7) C2ÐC1ÐC4 109.0 (8) O2ÐC2ÐC1 128.2 (9) O2ÐC2ÐC3 125.4 (8) C1ÐC2ÐC3 106.4 (7) C4ÐO1ÐC3 110.9 (6) O1ÐC3ÐC2 104.9 (6)
O1ÐC3ÐC5 109.7 (6) C2ÐC3ÐC5 110.3 (6) O3ÐC4ÐO1 119.1 (7) O3ÐC4ÐC1 132.2 (8) O1ÐC4ÐC1 108.6 (7) N2ÐN1ÐC1 115.3 (7) N1ÐN2ÐC7 122.8 (7)
Table 2
Hydrogen-bonding geometry (AÊ,).
DÐH A DÐH H A D A DÐH A
N2ÐH2 O2 0.86 2.04 2.743 (10) 139 O4ÐH4 O5i 0.82 1.86 2.680 (8) 178
O5ÐH5A O3ii 0.82 1.91 2.721 (8) 172 Symmetry codes: (i)x;y;1z; (ii) 1x;y;z.
All H atoms were included in the riding-model approximation, with Uiso(methyl and hydroxy H) = 1.5Ueq(parent atom) and
Uiso(other H) = 1.2Ueq(parent atom). H atoms on C, O and N atoms were ®xed at 0.98, 0.97, 0.96, 0.93, 0.82, and 0.86 AÊ for methine, methylene, methyl, phenyl, hydroxy and NH H atoms, respectively. Friedel pairs were merged and thef00 term was set to zero. The calculated absolute structure parameter (Flack, 1983) of 0 (10) is thus meaningless in this analysis, and the absolute con®guration was assumed from that of the starting material.
Data collection: MSC/AFC Diffractometer Control Software
(Molecular Structure Corporation, 1992); cell re®nement:MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Mole-cular Structure Corporation, 2000); program(s) used to solve
struc-ture: SHELXS97 (Sheldrick, 1990); program(s) used to re®ne
structure: SHELXL97 (Sheldrick, 1997); molecular graphics:
PLATON (Spek, 2003) and MERCURY (CCDC, 2003); software used to prepare material for publication:SHELXL97.
References
Flack, H. D. (1983).Acta Cryst.A39, 876±881.
Hvoslef, J. & Nordenson, S. (1976).Acta Cryst.B32, 448±452.
Kurata, T., Fujimaki, M. & Sakurai, Y. (1973a).Agric. Biol. Chem.37, 1471± 1477.
Kurata, T., Fujimaki, M. & Sakurai, Y. (1973b).J. Agric. Food Chem.21, 676± 680.
CCDC (2003).MERCURY. Version 1.1.2. Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, England.
Figure 1
Displacement ellipsoid drawing (50% probability level), showing the atom-labelling scheme.
Figure 2
Molecular Structure Corporation (1992).MSC/AFC Diffractometer Control Software. MSC, 3200 Research Forest Drive, The Woodlands, TX 77381, USA.
Molecular Structure Corporation (2000).TEXSAN.Version 1.10. MSC, 9009 New Trails Drive, The Woodlands, TX 77381±5209, USA.
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968).Acta Cryst.A24, 351± 359.
Sheldrick, G. M. (1990).Acta Cryst.A46, 467±473.
Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Spek, A. L. (2003).PLATON.University of Utrecht, The Netherlands.
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Acta Cryst. (2003). E59, o1241–o1243
supporting information
Acta Cryst. (2003). E59, o1241–o1243 [doi:10.1107/S1600536803016660]
The 2-methoxyphenylhydrazone derivative of dehydroascorbic acid
Tokiko Imai, Yoshihiro Yokoyama, Akiko Sekine, Hidediro Uekusa and Yuji Ohashi
S1. Comment
Vegetables and fruit may turn red–brown when they are kept under aerobic conditions for a long time. A mechanism
proposed to account for this indicated that reactions of dehydroascorbic acid with amino acids play an important role in
the process of oxidation of L-ascorbic acid to 2,2′-nitrilo-di-2(2′)-deoxy-L-ascorbic acid monoammonium salt, which is
red–brown (Kurata et al., 1973a,b).
In the course of structural studies of the red–brown pigment, the hydrazones were prepared by reaction of
dehydro-ascorbic acid with hydrazines. Among eight hydrazones synthesized, the crystal structures of 2-methoxyphenylhydrazone
dehydroascorbic acid, (I), was determined by single-crystal X-ray diffraction methods (Fig. 1 and Table 1).
The molecular structure of (I) comprises an ethylene glycol open chain linked to the hydrazone group via a lactone ring.
The 15 non-H atoms of the phenylhydrazone and lactone ring are effectively coplanar, with the maximum deviation from
the least-squares plane through these atoms being 0.066 (9) Å for C8. The bond lengths and angles in (I) are quite similar
to those reported for the closely related structure of p-bromophenylhydrazone dehydroascorbic acid (Hvoslef &
Nordenson, 1976).
The hydrogen-bonding distances and angles are listed in Table 2. An intramolecular N2—H···O2 hydrogen bond is
observed. Both of the OH groups of the ethylene glycol residue participate in hydrogen bonds. The terminal OH group
(O5) is connected to the carbonyl atom O3. These interactions link the molecules into ribbons that are aligned along the a
axis, as shown in Fig. 2. The ribbons are stacked along [011] and are connected by hydrogen bonds formed between two
OH groups (O3—H···O5). The stacking distance between ribbons is approximately 3.4 Å. The intermolecular hydrogen
bonds described above combine to generate a two-dimensional layer structure.
S2. Experimental
The title compound was prepared according to a literature procedure (Hvoslef & Nordenson (1976). Plate-like yellow
crystals were obtained from recrystallization from an ethanol solution of the compound.
S3. Refinement
All H atoms were included in the riding-model approximation, with Uiso(methyl-H, hydroxy-H) = 1.5Ueq(parent atom)
and Uiso(H) = 1.2Ueq(parent atom). Friedel pairs were merged and Δf′′ term was set to zero. Thus, the calculated absolute
supporting information
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[image:5.610.126.483.73.244.2]Acta Cryst. (2003). E59, o1241–o1243 Figure 1
Displacement ellipsoid drawing at the 50% probability level showing the atom-labelling scheme.
Figure 2
A perspective packing diagram. Dotted lines indicate the intermolecular hydrogen-bonding interactions.
(3Z)-5-(1,2-dihydroxyethyl) −2,3,4(5H)-furantrione 3-[(2-methoxyphenyl)hydrazone]
Crystal data
C13H14N2O6
Mr = 294.26
Triclinic, P1 Hall symbol: P 1 a = 8.194 (2) Å b = 8.308 (2) Å c = 5.463 (3) Å α = 106.12 (3)° β = 101.98 (3)° γ = 95.69 (2)° V = 344.6 (2) Å3
Z = 1 F(000) = 154 Dx = 1.418 Mg m−3
Mo Kα radiation, λ = 0.71069 Å Cell parameters from 25 reflections θ = 28.0–30.0°
µ = 0.11 mm−1
T = 295 K
[image:5.610.128.483.277.491.2]supporting information
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Acta Cryst. (2003). E59, o1241–o1243
Data collection
Rigaku AFC-7S diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
q–2θ scans
Absorption correction: psi scan (North et al., 1968)
Tmin = 0.960, Tmax = 0.998
1680 measured reflections
1575 independent reflections 961 reflections with I > 2σ(I)′ Rint = 0.030
θmax = 27.5°, θmin = 2.6°
h = 0→10 k = −10→10 l = −7→6
3 standard reflections every 150 reflections intensity decay: 0.8%
Refinement
Refinement on F2
Least-squares matrix: full R[F2 > 2σ(F2)] = 0.073
wR(F2) = 0.221
S = 1.05 1575 reflections 193 parameters 3 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained w = 1/[σ2(F
o2) + (0.0983P)2 + 0.4777P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.31 e Å−3
Δρmin = −0.30 e Å−3
Special details
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)
x y z Uiso*/Ueq
C1 0.4426 (10) 0.5773 (9) 0.3686 (16) 0.050 (2) C2 0.6015 (11) 0.5223 (10) 0.3550 (17) 0.054 (2) O1 0.5632 (7) 0.7339 (7) 0.1498 (10) 0.0518 (15) C3 0.6861 (10) 0.6288 (11) 0.2206 (16) 0.0476 (19)
H3 0.7123 0.5567 0.0632 0.057*
C4 0.4256 (11) 0.7107 (10) 0.2478 (15) 0.051 (2) O2 0.6631 (8) 0.4145 (8) 0.4432 (14) 0.0678 (19) O3 0.3158 (7) 0.7941 (8) 0.2163 (14) 0.0679 (19) C5 0.8457 (9) 0.7414 (10) 0.4088 (15) 0.0467 (19)
H5 0.9269 0.6699 0.4576 0.056*
O4 0.7992 (8) 0.8347 (8) 0.6371 (11) 0.0624 (17)
H4 0.8535 0.8149 0.7664 0.094*
C6 0.9284 (10) 0.8667 (12) 0.2985 (17) 0.055 (2)
H6A 0.8504 0.9414 0.2571 0.066*
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O5 0.9750 (8) 0.7782 (10) 0.0684 (13) 0.070 (2)
H5A 1.0761 0.7729 0.1047 0.105*
N1 0.3299 (8) 0.5304 (8) 0.4909 (13) 0.0486 (17) N2 0.3639 (9) 0.4106 (8) 0.5937 (13) 0.0497 (17)
H2 0.4559 0.3709 0.5818 0.060*
C7 0.2568 (11) 0.3431 (10) 0.7237 (16) 0.052 (2) C8 0.1011 (13) 0.3893 (12) 0.7335 (19) 0.065 (3)
H8 0.0612 0.4661 0.6497 0.078*
C9 0.0057 (13) 0.3198 (13) 0.870 (2) 0.070 (3)
H9 −0.0982 0.3524 0.8836 0.085*
C10 0.0631 (13) 0.2033 (12) 0.984 (2) 0.066 (3)
H10 −0.0042 0.1557 1.0725 0.080*
C11 0.2164 (13) 0.1544 (10) 0.9740 (17) 0.058 (2)
H11 0.2546 0.0764 1.0567 0.070*
C12 0.3128 (11) 0.2230 (10) 0.8386 (18) 0.055 (2) O13 0.4690 (8) 0.1896 (8) 0.8125 (14) 0.0701 (19) C14 0.5285 (15) 0.0537 (14) 0.901 (2) 0.079 (3)
H14A 0.5451 0.0830 1.0879 0.118*
H14B 0.6337 0.0353 0.8553 0.118*
H14C 0.4464 −0.0481 0.8177 0.118*
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
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Geometric parameters (Å, º)
C1—N1 1.334 (11) N1—N2 1.298 (8)
C1—C2 1.431 (12) N2—C7 1.404 (11)
C1—C4 1.443 (10) N2—H2 0.8600
C2—O2 1.232 (9) C7—C8 1.375 (13)
C2—C3 1.501 (12) C7—C12 1.386 (11)
O1—C4 1.363 (10) C8—C9 1.374 (14)
O1—C3 1.458 (10) C8—H8 0.9300
C3—C5 1.519 (11) C9—C10 1.362 (13)
C3—H3 0.9800 C9—H9 0.9300
C4—O3 1.202 (10) C10—C11 1.366 (14)
C5—O4 1.421 (10) C10—H10 0.9300
C5—C6 1.511 (11) C11—C12 1.372 (13)
C5—H5 0.9800 C11—H11 0.9300
O4—H4 0.8200 C12—O13 1.364 (11)
C6—O5 1.417 (11) O13—C14 1.434 (10)
C6—H6A 0.9700 C14—H14A 0.9600
C6—H6B 0.9700 C14—H14B 0.9600
O5—H5A 0.8200 C14—H14C 0.9600
N1—C1—C2 128.3 (7) N2—N1—C1 115.3 (7)
N1—C1—C4 122.4 (7) N1—N2—C7 122.8 (7)
C2—C1—C4 109.0 (8) N1—N2—H2 118.6
O2—C2—C1 128.2 (9) C7—N2—H2 118.6
O2—C2—C3 125.4 (8) C8—C7—C12 120.6 (9)
C1—C2—C3 106.4 (7) C8—C7—N2 122.4 (7)
C4—O1—C3 110.9 (6) C12—C7—N2 117.0 (8)
O1—C3—C2 104.9 (6) C9—C8—C7 118.7 (8)
O1—C3—C5 109.7 (6) C9—C8—H8 120.7
C2—C3—C5 110.3 (6) C7—C8—H8 120.7
O1—C3—H3 110.6 C10—C9—C8 120.1 (10)
C2—C3—H3 110.6 C10—C9—H9 119.9
C5—C3—H3 110.6 C8—C9—H9 119.9
O3—C4—O1 119.1 (7) C9—C10—C11 122.0 (9)
O3—C4—C1 132.2 (8) C9—C10—H10 119.0
O1—C4—C1 108.6 (7) C11—C10—H10 119.0
O4—C5—C6 108.1 (7) C10—C11—C12 118.4 (8)
O4—C5—C3 107.3 (6) C10—C11—H11 120.8
C6—C5—C3 113.7 (6) C12—C11—H11 120.8
O4—C5—H5 109.2 O13—C12—C11 125.8 (8)
C6—C5—H5 109.2 O13—C12—C7 114.0 (8)
C3—C5—H5 109.2 C11—C12—C7 120.2 (9)
C5—O4—H4 109.5 C12—O13—C14 117.5 (8)
O5—C6—C5 109.8 (7) O13—C14—H14A 109.5
O5—C6—H6A 109.7 O13—C14—H14B 109.5
C5—C6—H6A 109.7 H14A—C14—H14B 109.5
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Acta Cryst. (2003). E59, o1241–o1243
C5—C6—H6B 109.7 H14A—C14—H14C 109.5
H6A—C6—H6B 108.2 H14B—C14—H14C 109.5
C6—O5—H5A 109.5
N1—C1—C2—O2 3.7 (14) O4—C5—C6—O5 −179.4 (6) C4—C1—C2—O2 177.8 (9) C3—C5—C6—O5 −60.3 (8) N1—C1—C2—C3 −173.6 (8) C2—C1—N1—N2 −5.5 (11) C4—C1—C2—C3 0.4 (9) C4—C1—N1—N2 −178.8 (7) C4—O1—C3—C2 5.3 (8) C1—N1—N2—C7 −178.4 (7) C4—O1—C3—C5 −113.1 (7) N1—N2—C7—C8 5.3 (12) O2—C2—C3—O1 179.2 (8) N1—N2—C7—C12 −176.2 (7) C1—C2—C3—O1 −3.3 (8) C12—C7—C8—C9 2.9 (13) O2—C2—C3—C5 −62.7 (12) N2—C7—C8—C9 −178.6 (9) C1—C2—C3—C5 114.7 (7) C7—C8—C9—C10 −2.2 (15) C3—O1—C4—O3 176.7 (8) C8—C9—C10—C11 1.4 (16) C3—O1—C4—C1 −5.2 (8) C9—C10—C11—C12 −1.4 (15) N1—C1—C4—O3 −4.9 (14) C10—C11—C12—O13 179.0 (9) C2—C1—C4—O3 −179.4 (9) C10—C11—C12—C7 2.1 (12) N1—C1—C4—O1 177.4 (7) C8—C7—C12—O13 179.8 (8) C2—C1—C4—O1 2.9 (8) N2—C7—C12—O13 1.3 (10) O1—C3—C5—O4 60.9 (7) C8—C7—C12—C11 −2.9 (12) C2—C3—C5—O4 −54.1 (8) N2—C7—C12—C11 178.5 (8) O1—C3—C5—C6 −58.6 (9) C11—C12—O13—C14 9.5 (13) C2—C3—C5—C6 −173.7 (7) C7—C12—O13—C14 −173.4 (8)
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
N2—H2···O2 0.86 2.04 2.743 (10) 139
O4—H4···O5i 0.82 1.86 2.680 (8) 178
O5—H5A···O3ii 0.82 1.91 2.721 (8) 172
