organic papers
o3828
Qu and Sun C16H16N2O4 doi:10.1107/S1600536805032435 Acta Cryst.(2005). E61, o3828–o3830 Acta Crystallographica Section E
Structure Reports Online
ISSN 1600-5368
(
E
,
E
)-4-Hydroxy-3-methoxybenzaldehyde azine
Yang Qua* and Xian-Ming Sunb
aDepartment of Chemistry, Huazhong
Agricul-tural University, Wuhan 430070, People’s Republic of China, andbSchool of Material Science and Technology, Wuhan Institute of Chemical Technology, Wuhan 430073, People’s Republic of China
Correspondence e-mail: [email protected]
Key indicators
Single-crystal X-ray study T= 292 K
Mean(C–C) = 0.002 A˚ Rfactor = 0.042 wRfactor = 0.117
Data-to-parameter ratio = 14.3
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2005 International Union of Crystallography Printed in Great Britain – all rights reserved
The title compound, C16H16N2O4, contains two vanillin aromatic rings, which are bridged by a C N—N C unit. There are two half-molecules in the asymmetric unit; the mid-points of the N—N bonds lie on centres of symmetry. The molecular structure is stabilized by two intramolecular O— H O and intermolecular O—H O and O—H N hydrogen bonds.
Comment
Much work has been devoted to the physicochemical char-acterization of substituted aromatic Schiff bases, because these compounds show remarkable photochromic properties. Photochromism arises from intramolecular H-atom transfer, together with a change in the-electron system. The effect of intermolecular interactions, such as – charge transfer or hydrogen bonding, on H-atom transfer processes has been investigated in the solid state (Hadjoudiset al., 1987; Puranik
et al., 1992).
The hydrogen bond is important in a vast number of chemical, biological and materials systems (Steiner & Saenger, 1993). The weak hydrogen bond of the C—H Xtype (X= O, N and acceptors) has been well established in structural, supramolecular and biological chemistry, and it has been widely used as a tool for the crystal engineering of organic and organometallic solids (Desiraju, 1996; Braga & Grepioni, 2000). In the literature, there are only a few structural reports of Schiff bases derived from vanillin (4-hydroxy-3-methoxy-benzaldehyde) (Kaitner & Pavlovic, 1995; Linet al., 2005).
The crystal structure of the title compound, (I) (Fig. 1), has two half-molecules in the asymmetric unit; the mid-points of the N—N bonds lie on centres of symmetry. The molecules contain two vanillin aromatic rings, which are bridged by C N—N C units. As expected, the non-H atoms are nearly coplanar, forming an extended conjugated system. The mol-ecules crystallize in the (E,E) configuration, with the two 4-hydroxy-3-methoxyphenyl groups trans to each other. This configuration agrees with those commonly found in similar compounds (Glaseret al., 1995; Huniget al., 2000).
The bond lengths and angles (Table 1) are within the expected ranges (Allenet al., 1987). The molecules are stacked along thebaxis in a parallel fashion (Fig. 2). The centroid-to-centroid and perpendicular distances between the aromatic rings are 4.0886 (9) and 3.503 A˚ , respectively, which may indicate weak – interactions. The molecular structure is stabilized by two intramolecular O—H O and inter-molecular O—H O and O—H N hydrogen bonds (Table 2), which cause the formation of an infinite two-dimensional network by linking the neighbouring molecules in theacplane (Fig. 2).
Experimental
The title compound was prepared by the condensation reaction of vanillin (1.52 g) in ethanol (20 ml) and hydrazine hydrochloride (0.34 g) in ethanol (20 ml). The reaction mixture was refluxed and
stirred for 2 h. The resulting clear solution was kept in air and, after slow evaporation of the solvent over a period of a week, yellow crystals were formed at the bottom of the vessel. The crystals were isolated, washed three times with ethanol and dried in a vacuum desiccator using anhydrous CaCl2(yield 68%). Analysis calculated
for C16H16N2O4: C 63.93, H 5.37, N 9.33%; found: C 63.66, H 5.48, N
9.31%.
Crystal data
C16H16N2O4
Mr= 300.31 Monoclinic,P21=c a= 11.6941 (8) A˚
b= 7.5492 (5) A˚
c= 16.7683 (12) A˚
= 94.169 (1)
V= 1476.41 (18) A˚3
Z= 4
Dx= 1.351 Mg m
3
MoKradiation Cell parameters from 3000
reflections
= 2.0–28.4
= 0.10 mm1
T= 292 (2) K Block, yellow 0.360.330.30 mm
Data collection
Bruker SMART CCD area-detector diffractometer
’and!scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)
Tmin= 0.971,Tmax= 0.971
12220 measured reflections
2905 independent reflections 2573 reflections withI> 2(I)
Rint= 0.047 max= 26.0
h=14!14
k=8!9
l=20!20
Refinement
Refinement onF2
R[F2> 2(F2)] = 0.042
wR(F2) = 0.117
S= 1.06 2905 reflections 203 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0725P)2
+ 0.1651P]
whereP= (Fo2+ 2Fc2)/3
(/)max< 0.001
max= 0.18 e A˚3
min=0.22 e A˚3
Table 1
Selected geometric parameters (A˚ ,).
C2—N1 1.274 (2) C2—C5 1.463 (2) C10—N2 1.2817 (16)
C10—C13 1.4572 (15) N1—N1i
1.413 (2) N2—N2ii
1.4094 (17)
N1—C2—C5 122.71 (14) N2—C10—C13 122.03 (10)
C2—N1—N1i
111.66 (17) C10—N2—N2ii 112.95 (11)
N1—C2—C5—C6 175.98 (14) N1—C2—C5—C4 2.7 (2) O1—C3—C8—O2 0.65 (18) C4—C3—C8—O2 178.27 (12) O1—C3—C8—C7 178.43 (12) O3—C11—C12—C13 177.08 (11)
N2—C10—C13—C14 167.39 (11) N2—C10—C13—C12 9.42 (18) O3—C11—C16—O4 4.44 (17) C12—C11—C16—O4 175.05 (11) C5—C2—N1—N1i 178.95 (13) C13—C10—N2—N2ii
179.90 (11)
[image:2.610.45.296.70.245.2]Symmetry codes: (i)xþ2;yþ2;zþ1; (ii)xþ1;y;zþ1.
Table 2
Hydrogen-bond geometry (A˚ ,).
D—H A D—H H A D A D—H A
O2—H2A O1 0.82 2.22 2.6658 (14) 114 O4—H4A O3 0.82 2.24 2.6731 (12) 114 O2—H2A O4iii 0.82 2.34 2.9973 (14) 138 O4—H4A N2iv
0.82 2.05 2.8346 (12) 159
Symmetry codes: (iii)xþ1;y1 2;zþ
1
2; (iv)xþ1;yþ 1 2;zþ
1 2.
organic papers
Acta Cryst.(2005). E61, o3828–o3830 Qu and Sun C
16H16N2O4
o3829
Figure 2 [image:2.610.45.296.297.498.2]A packing diagram of (I); O—H O and N—H O hydrogen bonds are shown as dashed lines.
Figure 1
[image:2.610.313.567.661.715.2]Hydroxy H atoms were located in a difference map, while the remaining H atoms were positioned geometrically [0.82 (OH), 0.93 (CH) and 0.96 A˚ (CH3)] and constrained to ride on their parent
atoms with Uiso(H) values of 1.2 (1.5 for methyl and hydroxy H
atoms) timesUeq(C,O).
Data collection:SMART(Siemens, 1996); cell refinement:SAINT
(Siemens, 1996); data reduction: SAINT; program(s) used to solve structure:SHELXS97(Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics:
SHELXTL(Sheldrick, 1997b); software used to prepare material for publication:SHELXTL.
Financial support from the Bureau of Science and Tech-nology of Wuhan City, Hubei Province, People’s Republic of China, through research grant No. 20055003059-28 is grate-fully acknowledged.
References
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L. & Orpen, A. G. (1987).
J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Braga, D. & Grepioni, F. (2000).Acc. Chem. Res.33, 601–608. Desiraju, G. R. (1996).Acc. Chem. Res.29, 441–449.
Glaser, R., Chen, G. S., Anthamatten, M. & Barnes, C. L. (1995).J. Chem. Soc. Perkin Trans. 2, pp. 1449–1458.
Hadjoudis, E., Vittorakis, M. & Moustakali-Mavridis, I. (1987).Tetrahedron,
43, 1345–1360.
Hunig, S., Kemmer, M., Wenner, H., Barbosa, F., Gescheidt, G., Perepichka, I. F., Bauerle, P., Emge, A. & Peters, K. (2000).Chem. Eur. J.6, 2618–2632. Kaitner, B. & Pavlovic, G. (1995).Acta Cryst.C51, 1875–1878.
Lin, Z.-D., Lin, Z.-D., Li, X. & Huang Y.-M. (2005).Acta Cryst.E61, o3032– o3033.
Puranik, V. G., Tavale, S. S., Kumbhar, A. S., Yerande, R. G., Padhye, S. B. & Butcher, R. J. (1992).J. Crystallogr. Spectrosc. Res.22, 725–731.
Sheldrick, G. M. (1996).SADABS. University of Go¨ttingen, Germany. Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of
Go¨ttingen, Germany.
Sheldrick, G. M. (1997b).SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.
Siemens (1996).SMARTandSAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
Steiner, T. & Saenger, W. (1993).J. Am. Chem. Soc.115, 4540–4547.
organic papers
o3830
Qu and Sun Csupporting information
sup-1 Acta Cryst. (2005). E61, o3828–o3830
supporting information
Acta Cryst. (2005). E61, o3828–o3830 [https://doi.org/10.1107/S1600536805032435]
(
E
,
E
)-4-Hydroxy-3-methoxybenzaldehyde azine
Yang Qu and Xian-Ming Sun
(E,E)-4-Hydroxy-3-methoxybenzaldehyde azine
Crystal data
C16H16N2O4
Mr = 300.31
Monoclinic, P21/c
Hall symbol: -P 2ybc
a = 11.6941 (8) Å
b = 7.5492 (5) Å
c = 16.7683 (12) Å
β = 94.169 (1)°
V = 1476.41 (18) Å3
Z = 4
F(000) = 632
Dx = 1.351 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 3000 reflections
θ = 2.0–28.4°
µ = 0.10 mm−1
T = 292 K Block, yellow
0.36 × 0.33 × 0.30 mm
Data collection
Bruker SMART CCD area-detector diffractometer
Radiation source: fine-focus sealed tube Graphite monochromator
φ and ω scans
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)
Tmin = 0.971, Tmax = 0.971
12220 measured reflections 2905 independent reflections 2573 reflections with I > 2σ(I)
Rint = 0.047
θmax = 26.0°, θmin = 1.8°
h = −14→14
k = −8→9
l = −20→20
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.042
wR(F2) = 0.117
S = 1.06 2905 reflections 203 parameters 0 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) + (0.0725P)2 + 0.1651P]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max < 0.001
Δρmax = 0.18 e Å−3
Δρmin = −0.22 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
supporting information
sup-2 Acta Cryst. (2005). E61, o3828–o3830
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 0.66795 (19) 0.4278 (3) 0.49558 (14) 0.0873 (7) C2 1.01028 (13) 0.83209 (19) 0.43616 (9) 0.0538 (4) C3 0.83179 (11) 0.41874 (18) 0.42008 (8) 0.0439 (3) C4 0.87042 (12) 0.58421 (18) 0.44377 (8) 0.0462 (3) C5 0.96476 (12) 0.65944 (18) 0.40990 (8) 0.0473 (3) C6 1.01723 (12) 0.5664 (2) 0.35152 (9) 0.0552 (4) C7 0.97863 (12) 0.3992 (2) 0.32810 (9) 0.0551 (4) C8 0.88803 (11) 0.32391 (18) 0.36279 (8) 0.0443 (3) C9 0.65566 (12) 0.2693 (2) 0.20614 (10) 0.0582 (4) C10 0.40458 (10) 0.10424 (15) 0.43595 (6) 0.0343 (3) C11 0.45800 (10) 0.26816 (15) 0.23087 (7) 0.0331 (3) C12 0.47801 (10) 0.20697 (15) 0.30823 (7) 0.0352 (3) C13 0.38654 (10) 0.18237 (15) 0.35657 (6) 0.0339 (3) C14 0.27598 (11) 0.22508 (17) 0.32687 (7) 0.0386 (3) C15 0.25633 (10) 0.29107 (18) 0.24966 (7) 0.0399 (3) C16 0.34615 (10) 0.31513 (15) 0.20202 (6) 0.0336 (3) N1 0.96999 (11) 0.91975 (16) 0.49266 (8) 0.0580 (3) N2 0.50030 (8) 0.03368 (13) 0.46082 (5) 0.0325 (2) O1 0.74100 (9) 0.33069 (14) 0.44868 (7) 0.0609 (3) O2 0.85337 (9) 0.15802 (13) 0.33983 (6) 0.0547 (3) O3 0.53890 (7) 0.29012 (13) 0.17738 (5) 0.0438 (3) O4 0.32559 (7) 0.38795 (13) 0.12836 (5) 0.0428 (2)
H1A 0.7097 0.4649 0.5441 0.131*
H1B 0.6046 0.3547 0.5082 0.131*
H1C 0.6397 0.5301 0.4663 0.131*
H2 1.0711 0.8798 0.4105 0.065*
H4 0.8336 0.6461 0.4824 0.055*
H6 1.0790 0.6165 0.3277 0.066*
H7 1.0144 0.3381 0.2887 0.066*
H9A 0.6722 0.3457 0.2513 0.087*
H9B 0.7044 0.2996 0.1646 0.087*
H9C 0.6692 0.1485 0.2220 0.087*
H10 0.3448 0.1056 0.4696 0.041*
H12 0.5525 0.1820 0.3283 0.042*
H14 0.2149 0.2095 0.3587 0.046*
H15 0.1821 0.3191 0.2301 0.048*
H2A 0.8045 0.1231 0.3688 0.082*
supporting information
sup-3 Acta Cryst. (2005). E61, o3828–o3830
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
C1 0.0878 (13) 0.0708 (12) 0.1098 (15) −0.0253 (10) 0.0523 (12) −0.0298 (11) C2 0.0531 (8) 0.0446 (8) 0.0615 (9) −0.0081 (6) −0.0107 (7) 0.0093 (7) C3 0.0424 (7) 0.0409 (7) 0.0478 (7) −0.0009 (5) −0.0012 (5) 0.0008 (5) C4 0.0495 (7) 0.0404 (7) 0.0480 (7) 0.0011 (6) −0.0016 (6) −0.0013 (5) C5 0.0455 (7) 0.0431 (7) 0.0513 (7) −0.0022 (6) −0.0109 (6) 0.0067 (6) C6 0.0435 (7) 0.0626 (9) 0.0590 (8) −0.0080 (7) 0.0011 (6) 0.0040 (7) C7 0.0455 (7) 0.0632 (10) 0.0568 (8) 0.0008 (7) 0.0048 (6) −0.0095 (7) C8 0.0406 (7) 0.0438 (7) 0.0469 (7) 0.0021 (5) −0.0076 (5) −0.0046 (5) C9 0.0384 (7) 0.0679 (10) 0.0699 (9) 0.0125 (6) 0.0145 (6) 0.0301 (8) C10 0.0412 (6) 0.0356 (6) 0.0264 (5) 0.0017 (5) 0.0045 (4) −0.0004 (4) C11 0.0369 (6) 0.0313 (6) 0.0314 (6) 0.0003 (4) 0.0048 (4) 0.0032 (4) C12 0.0354 (6) 0.0361 (6) 0.0336 (6) 0.0032 (5) −0.0008 (4) 0.0058 (5) C13 0.0420 (6) 0.0326 (6) 0.0268 (5) 0.0019 (5) 0.0016 (4) 0.0017 (4) C14 0.0376 (6) 0.0448 (7) 0.0339 (6) 0.0018 (5) 0.0070 (5) 0.0053 (5) C15 0.0329 (6) 0.0491 (7) 0.0372 (6) 0.0014 (5) −0.0009 (5) 0.0078 (5) C16 0.0392 (6) 0.0336 (6) 0.0273 (5) −0.0019 (5) −0.0014 (4) 0.0026 (4) N1 0.0654 (8) 0.0400 (7) 0.0660 (8) −0.0120 (6) −0.0128 (6) 0.0057 (6) N2 0.0418 (5) 0.0339 (5) 0.0219 (4) −0.0005 (4) 0.0022 (4) 0.0016 (4) O1 0.0619 (7) 0.0456 (6) 0.0776 (7) −0.0115 (5) 0.0215 (5) −0.0125 (5) O2 0.0545 (6) 0.0477 (6) 0.0615 (6) −0.0030 (5) 0.0016 (5) −0.0143 (5) O3 0.0390 (5) 0.0543 (6) 0.0389 (5) 0.0064 (4) 0.0094 (4) 0.0160 (4) O4 0.0389 (4) 0.0588 (6) 0.0301 (4) −0.0043 (4) −0.0022 (3) 0.0128 (4)
Geometric parameters (Å, º)
C1—O1 1.408 (2) C9—H9B 0.9600
C1—H1A 0.9600 C9—H9C 0.9600
C1—H1B 0.9600 C10—N2 1.2817 (16)
C1—H1C 0.9600 C10—C13 1.4572 (15)
C2—N1 1.274 (2) C10—H10 0.9300
C2—C5 1.463 (2) C11—O3 1.3602 (14)
C2—H2 0.9300 C11—C12 1.3808 (16)
C3—O1 1.3686 (16) C11—C16 1.4066 (17)
C3—C4 1.3771 (19) C12—C13 1.4006 (16)
C3—C8 1.3999 (19) C12—H12 0.9300
C4—C5 1.398 (2) C13—C14 1.3892 (17)
C4—H4 0.9300 C14—C15 1.3906 (17)
C5—C6 1.384 (2) C14—H14 0.9300
C6—C7 1.388 (2) C15—C16 1.3771 (17)
C6—H6 0.9300 C15—H15 0.9300
C7—C8 1.369 (2) C16—O4 1.3573 (13)
C7—H7 0.9300 N1—N1i 1.413 (2)
C8—O2 1.3631 (16) N2—N2ii 1.4094 (17)
C9—O3 1.4233 (16) O2—H2A 0.8200
supporting information
sup-4 Acta Cryst. (2005). E61, o3828–o3830
O1—C1—H1A 109.5 O3—C9—H9C 109.5
O1—C1—H1B 109.5 H9A—C9—H9C 109.5
H1A—C1—H1B 109.5 H9B—C9—H9C 109.5
O1—C1—H1C 109.5 N2—C10—C13 122.03 (10)
H1A—C1—H1C 109.5 N2—C10—H10 119.0
H1B—C1—H1C 109.5 C13—C10—H10 119.0
N1—C2—C5 122.71 (14) O3—C11—C12 125.57 (11)
N1—C2—H2 118.6 O3—C11—C16 114.60 (10)
C5—C2—H2 118.6 C12—C11—C16 119.82 (11)
O1—C3—C4 125.88 (13) C11—C12—C13 120.24 (11) O1—C3—C8 114.03 (12) C11—C12—H12 119.9 C4—C3—C8 120.08 (13) C13—C12—H12 119.9 C3—C4—C5 120.23 (13) C14—C13—C12 119.46 (10)
C3—C4—H4 119.9 C14—C13—C10 119.38 (10)
C5—C4—H4 119.9 C12—C13—C10 121.09 (10)
C6—C5—C4 119.02 (13) C13—C14—C15 120.22 (11) C6—C5—C2 119.63 (14) C13—C14—H14 119.9 C4—C5—C2 121.34 (14) C15—C14—H14 119.9 C5—C6—C7 120.65 (14) C16—C15—C14 120.40 (11)
C5—C6—H6 119.7 C16—C15—H15 119.8
C7—C6—H6 119.7 C14—C15—H15 119.8
C8—C7—C6 120.24 (14) O4—C16—C15 119.28 (10)
C8—C7—H7 119.9 O4—C16—C11 120.93 (10)
C6—C7—H7 119.9 C15—C16—C11 119.77 (10)
O2—C8—C7 119.01 (12) C2—N1—N1i 111.66 (17)
O2—C8—C3 121.26 (12) C10—N2—N2ii 112.95 (11)
C7—C8—C3 119.73 (13) C3—O1—C1 117.41 (12)
O3—C9—H9A 109.5 C8—O2—H2A 109.5
O3—C9—H9B 109.5 C11—O3—C9 117.33 (10)
H9A—C9—H9B 109.5 C16—O4—H4A 109.5
O1—C3—C4—C5 179.79 (13) C11—C12—C13—C10 174.88 (11) C8—C3—C4—C5 1.0 (2) N2—C10—C13—C14 167.39 (11) C3—C4—C5—C6 1.0 (2) N2—C10—C13—C12 −9.42 (18) C3—C4—C5—C2 −177.64 (12) C12—C13—C14—C15 0.24 (19) N1—C2—C5—C6 −175.98 (14) C10—C13—C14—C15 −176.62 (11) N1—C2—C5—C4 2.7 (2) C13—C14—C15—C16 −0.2 (2) C4—C5—C6—C7 −1.5 (2) C14—C15—C16—O4 −176.74 (12) C2—C5—C6—C7 177.24 (13) C14—C15—C16—C11 1.73 (19) C5—C6—C7—C8 −0.2 (2) O3—C11—C16—O4 −4.44 (17) C6—C7—C8—O2 −178.67 (13) C12—C11—C16—O4 175.05 (11) C6—C7—C8—C3 2.2 (2) O3—C11—C16—C15 177.12 (11) O1—C3—C8—O2 −0.65 (18) C12—C11—C16—C15 −3.40 (18) C4—C3—C8—O2 178.27 (12) C5—C2—N1—N1i 178.95 (13)
O1—C3—C8—C7 178.43 (12) C13—C10—N2—N2ii 179.90 (11)
supporting information
sup-5 Acta Cryst. (2005). E61, o3828–o3830
C16—C11—C12—C13 3.49 (18) C12—C11—O3—C9 −8.17 (19) C11—C12—C13—C14 −1.93 (18) C16—C11—O3—C9 171.28 (12)
Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x+1, −y, −z+1.
Hydrogen-bond geometry (Å, º)
D—H···A D—H H···A D···A D—H···A
O2—H2A···O1 0.82 2.22 2.6658 (14) 114 O4—H4A···O3 0.82 2.24 2.6731 (12) 114 O2—H2A···O4iii 0.82 2.34 2.9973 (14) 138
O4—H4A···N2iv 0.82 2.05 2.8346 (12) 159
