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The combinatorial chemistry approach has been used to synthesize an array of Schiff bases. The structures of five of these Schiff bases have been confirmed by X-ray analysis [Nesterov, Timofeeva, Borbulevych, Antipin & Clark (2000). Acta Cryst. C56, 971-975]. In two cases, the reaction conditions were not sufficient to obtain the products in question. In one case, a molecular complex, C10H10O2·­C6H5N3O4, of the starting products 4-methoxy­cinnam­aldehyde and 2,4-di­nitro­aniline was found. X-ray analysis revealed hydrogen-bond formation between the mol­ecules of these reagents in the crystal. In the other case, X-ray analysis demonstrated that no chemical reaction occurred under the reaction conditions, and only one starting reagent, 4-(di­methyl­amino)­cinnam­aldehyde, C11H13NO, was found in the precipitate.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100006351/bm1394sup1.cif
Contains datablocks 4a, b, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100006351/bm13944asup2.hkl
Contains datablock 4a

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100006351/bm1394bsup3.hkl
Contains datablock b

CCDC references: 150333; 150334

Comment top

In Part I of our communication (Nesterov et al., 2000) we described the combinatorial reaction of aldehydes and amines to obtain a series of polar Schiff bases with nonlinear optical properties. X-ray analysis was used to confirm the formulae and structures of the final products of the condensation reactions. It was shown that in most reactions the final products (Schiff bases) were obtained by a one-step reaction under the same conditions. In two cases we were not able to obtain Schiff bases: in one case we found a molecular complex, (4a), of the starting reagents 4-methoxycinnamaldehyde, (a), and 2,4-dinitroaniline, (4), in the precipitate, and in the second case one of the starting reagents, 4,4-dimethylaminocinnamaldehyde, (b), was found. The structure identification numbers of all the compounds mentioned in the present paper are in accordance with those used in Part I (Nesterov et al., 2000). These results show that not all reagents belonging to the same starting groups of materials will give desirable final products under the same reaction conditions. Nevertheless, most of the expected Schiff bases were obtained (see Part I, Nesterov et al., 2000), and most probably we would also be able to obtain the two Schiff bases in question, (4a) and (4 b), by varying the reaction conditions. \sch

The molecular structure of (4), which is part of the hydrogen-bonded complex (4a) (Fig. 1), has been investigated several times, both in the compound itself (Prasad et al., 1982), and as a clathrate with 1,4,7,10,13,16-hexaoxacyclooctadecane [(5); Weber & Sheldrick, 1981] and 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane [(6); Watson et al., 1988]. In all these crystals the 2,4-dinitroaniline molecules have almost planar structures. The distances between the N atom of the amino group and the O atom of the nitro group in the ortho-positions are 2.652 (2) in (4a), 2.638 in (5), 2.657 in (6) and 2.621 Å in (4). QUERY! These data, together with the planar molecular structure, indicate the presence of intramolecular hydrogen bonds in these molecules. Details of the geometry of the intramolecular hydrogen bond in (4a) are presented in Table 2.

Molecule (a) in (4a) is also almost planar and shows no specific differences in comparison with the analogous derivative 4-nitrophenylcinnamaldehyde (Riassanen et al., 1989). Molecules of the aldehyde, (a), and the amine, (4), are linked in the crystal of (4a) by intermolecular hydrogen bonding (Table 2). The crystal of complex (4a) consists of hydrogen-bonded dimers packed in layers; no other specific intermolecular contacts between dimers were found.

Molecule (b) also has an almost planar structure, with bond lengths and angles similar to the standard values. Molecules of (b) are packed in a head-to-tail manner forming antiparallel chains.

In Part I (Nesterov et al., 2000), the results of the successful syntheses of five Schiff bases were presented, showing that three nitroanilines, (1)-(3) (see Part I), give adducts with 4-methoxycinnamaldehyde, (a), or 4-dimethylaminocinnamaldehyde, (b). On the other hand, 2,4-dinitroaniline, (4), does not react with the two aldehydes mentioned above. Apparently the lower reactivity of molecule (4) in comparison with molecules (1)-(3) under the same reaction conditions is due to the presence of an intramolecular hydrogen bond between the O atom of the nitro group and one of the H atoms of the amino group in the ortho-position of (4). It is likely that redistribution of the electron density in the amino group makes the other H atom less active. In both the present and the earlier paper we have shown that combinatorial synthesis and X-ray characterization are a powerful combination.

Experimental top

The molecular complex (4a) was obtained by the reaction of (a) (0.005 mol) with (4) (0.005 mol) in the presence of a catalytic amount of acetic acid in ethanol (20 ml) under reflux for 1–3 min. The precipitate was separated from the solution (yield 61%, m.p. 366 K). Reaction of (4) with (b) under the same conditions gave one of the starting materials, (b), as a precipitate, as confirmed by its melting point of 408 K. In both cases we used samples obtained from the reaction mixture for X-ray investigation. Crystals of (b) were thin and of poor quality; recrystallization gave no improvement in their quality.

Refinement top

For the molecular complex (4a), all H atoms were freely refined. For compound (b), H atoms were treated as riding, with Uiso(H) = ?. Query.

Computing details top

Data collection: CAD-4 Software (Enraf-Nonius, 1989) for (4a); P3/PC Diffractometer Program (Siemens, 1989) for b. Cell refinement: CAD-4 Software for (4a); P3/PC Diffractometer Program for b. For both compounds, data reduction: SHELXTL-Plus (Sheldrick, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-Plus; software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A molecular view of complex (4a). Displacement ellipsoids are drawn at the 50% probability level and H atoms are drawn as circles of arbitrary small radius for clarity.
[Figure 2] Fig. 2. A molecular view of aldehyde (b). Displacement ellipsoids are drawn at the 50% probability level and H atoms are drawn as circles of arbitrary small radius for clarity.
(4a) molecular complex of 4-methoxycinnamaldehyde with 2,4-dinitroaniline top
Crystal data top
C10H10O2·C6H5N3O4Z = 2
Mr = 345.31F(000) = 360
Triclinic, P1Dx = 1.426 Mg m3
a = 7.3490 (15) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.2520 (19) ÅCell parameters from 24 reflections
c = 12.523 (3) Åθ = 11–12°
α = 108.01 (3)°µ = 0.11 mm1
β = 93.48 (3)°T = 298 K
γ = 94.40 (3)°Parallelepiped prism, yellow
V = 804.2 (3) Å30.50 × 0.35 × 0.25 mm
Data collection top
Enraf-Nonius CAD4
diffractometer
Rint = 0.042
Radiation source: fine-focus sealed tubeθmax = 28.0°, θmin = 1.7°
Graphite monochromatorh = 09
θ/2θ scank = 1212
4088 measured reflectionsl = 1616
3786 independent reflections3 standard reflections every 97 reflections
2370 reflections with I > 2σ(I) intensity decay: 5%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: difference Fourier map
wR(F2) = 0.156All H-atom parameters refined
S = 1.02 w = 1/[σ2(Fo2) + (0.08P)2 + 0.152P]
where P = (Fo2 + 2Fc2)/3
3786 reflections(Δ/σ)max = 0.001
286 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C10H10O2·C6H5N3O4γ = 94.40 (3)°
Mr = 345.31V = 804.2 (3) Å3
Triclinic, P1Z = 2
a = 7.3490 (15) ÅMo Kα radiation
b = 9.2520 (19) ŵ = 0.11 mm1
c = 12.523 (3) ÅT = 298 K
α = 108.01 (3)°0.50 × 0.35 × 0.25 mm
β = 93.48 (3)°
Data collection top
Enraf-Nonius CAD4
diffractometer
Rint = 0.042
4088 measured reflections3 standard reflections every 97 reflections
3786 independent reflections intensity decay: 5%
2370 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.156All H-atom parameters refined
S = 1.02Δρmax = 0.21 e Å3
3786 reflectionsΔρmin = 0.25 e Å3
286 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. All H atoms were located from a difference Fourier map and were refined isotropically.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.3360 (3)0.9726 (2)0.10703 (16)0.0932 (6)
O20.0914 (2)0.25456 (18)0.20034 (14)0.0710 (5)
C10.1500 (2)0.6433 (2)0.10727 (14)0.0457 (4)
C20.2401 (3)0.5005 (2)0.04665 (16)0.0520 (5)
C30.2182 (3)0.3745 (2)0.07944 (18)0.0574 (5)
C40.1038 (3)0.3862 (2)0.17518 (16)0.0508 (5)
C50.0134 (3)0.5267 (2)0.23743 (17)0.0542 (5)
C60.0375 (3)0.6526 (2)0.20332 (16)0.0529 (5)
C70.1699 (3)0.7791 (2)0.07555 (18)0.0546 (5)
C80.2626 (3)0.7951 (2)0.01365 (18)0.0575 (5)
C90.2629 (4)0.9426 (3)0.0289 (2)0.0716 (6)
C100.0271 (4)0.2591 (4)0.2959 (3)0.0782 (8)
O210.7915 (2)0.82378 (16)0.50985 (13)0.0676 (4)
O220.8674 (2)0.98320 (17)0.59450 (12)0.0659 (4)
O310.6885 (2)1.51358 (18)0.44630 (15)0.0761 (5)
O320.4914 (3)1.60099 (16)0.30196 (16)0.0818 (5)
N10.5672 (3)0.9164 (2)0.32234 (17)0.0600 (5)
N20.7861 (2)0.95381 (18)0.51607 (13)0.0499 (4)
N30.5879 (2)1.49569 (19)0.37112 (15)0.0569 (4)
C1'0.5766 (2)1.0516 (2)0.33846 (15)0.0437 (4)
C2'0.6798 (2)1.07733 (19)0.42970 (14)0.0434 (4)
C3'0.6831 (2)1.2224 (2)0.44006 (15)0.0445 (4)
C4'0.5826 (3)1.34294 (19)0.36198 (15)0.0455 (4)
C5'0.4757 (3)1.3233 (2)0.27291 (16)0.0498 (4)
C6'0.4743 (3)1.1829 (2)0.26136 (16)0.0502 (4)
H1.10.494 (3)0.914 (3)0.262 (2)0.076 (7)*
H1.20.628 (3)0.839 (3)0.371 (2)0.066 (7)*
H20.317 (3)0.485 (2)0.0231 (19)0.062 (6)*
H30.276 (3)0.278 (3)0.036 (2)0.065 (6)*
H50.064 (3)0.544 (2)0.3071 (19)0.060 (6)*
H60.021 (3)0.751 (3)0.2456 (19)0.060 (6)*
H70.112 (3)0.874 (3)0.130 (2)0.075 (7)*
H80.327 (3)0.720 (3)0.072 (2)0.067 (6)*
H90.190 (4)1.023 (4)0.031 (3)0.110 (10)*
H1010.160 (4)0.292 (3)0.285 (2)0.089 (8)*
H1020.004 (4)0.325 (3)0.364 (3)0.087 (9)*
H1030.019 (4)0.168 (4)0.301 (3)0.103 (10)*
H3'0.750 (3)1.236 (2)0.4981 (19)0.058 (6)*
H5'0.407 (3)1.405 (3)0.220 (2)0.063 (6)*
H6'0.399 (3)1.174 (3)0.196 (2)0.068 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.1303 (16)0.0711 (11)0.0865 (12)0.0144 (10)0.0271 (11)0.0426 (9)
O20.0831 (11)0.0626 (9)0.0774 (10)0.0048 (8)0.0121 (8)0.0411 (8)
C10.0490 (10)0.0459 (9)0.0436 (9)0.0048 (7)0.0006 (7)0.0169 (7)
C20.0606 (12)0.0506 (10)0.0433 (9)0.0063 (8)0.0091 (8)0.0152 (8)
C30.0666 (13)0.0455 (10)0.0571 (12)0.0002 (9)0.0119 (10)0.0165 (9)
C40.0533 (11)0.0543 (11)0.0514 (10)0.0086 (8)0.0017 (8)0.0261 (9)
C50.0536 (11)0.0605 (12)0.0486 (10)0.0016 (9)0.0081 (8)0.0209 (9)
C60.0566 (11)0.0495 (11)0.0487 (10)0.0025 (9)0.0065 (8)0.0137 (8)
C70.0628 (12)0.0455 (10)0.0549 (11)0.0058 (9)0.0022 (9)0.0163 (9)
C80.0683 (13)0.0472 (11)0.0566 (12)0.0077 (9)0.0059 (10)0.0175 (9)
C90.0904 (17)0.0535 (12)0.0730 (15)0.0115 (11)0.0131 (13)0.0259 (11)
C100.088 (2)0.0847 (19)0.0802 (18)0.0144 (15)0.0038 (14)0.0531 (16)
O210.0805 (10)0.0417 (7)0.0761 (10)0.0035 (7)0.0065 (8)0.0167 (7)
O220.0706 (10)0.0633 (9)0.0574 (8)0.0025 (7)0.0176 (7)0.0153 (7)
O310.0930 (12)0.0611 (10)0.0901 (12)0.0205 (8)0.0049 (9)0.0443 (9)
O320.1037 (13)0.0384 (8)0.0972 (13)0.0049 (8)0.0008 (10)0.0170 (8)
N10.0728 (12)0.0486 (10)0.0642 (11)0.0057 (9)0.0076 (10)0.0282 (9)
N20.0485 (9)0.0464 (9)0.0520 (9)0.0033 (6)0.0001 (7)0.0128 (7)
N30.0678 (11)0.0435 (9)0.0667 (11)0.0113 (8)0.0145 (9)0.0251 (8)
C1'0.0474 (10)0.0421 (9)0.0471 (9)0.0089 (7)0.0067 (7)0.0207 (7)
C2'0.0435 (9)0.0421 (9)0.0448 (9)0.0044 (7)0.0013 (7)0.0145 (7)
C3'0.0469 (10)0.0463 (9)0.0446 (9)0.0102 (7)0.0025 (8)0.0195 (8)
C4'0.0524 (10)0.0379 (9)0.0506 (10)0.0084 (7)0.0084 (8)0.0186 (7)
C5'0.0566 (11)0.0449 (10)0.0434 (9)0.0009 (8)0.0015 (8)0.0095 (8)
C6'0.0570 (11)0.0506 (10)0.0442 (9)0.0049 (8)0.0047 (8)0.0188 (8)
Geometric parameters (Å, º) top
O1—C91.204 (3)C10—H1020.93 (3)
O2—C41.357 (2)C10—H1030.86 (3)
O2—C101.424 (3)O21—N21.227 (2)
C1—C61.394 (3)O22—N21.231 (2)
C1—C21.395 (3)O31—N31.221 (2)
C1—C71.445 (3)O32—N31.225 (2)
C2—C31.367 (3)N1—C1'1.333 (2)
C2—H20.98 (2)N1—H1.10.91 (3)
C3—C41.393 (3)N1—H1.20.85 (3)
C3—H30.94 (2)N2—C2'1.443 (2)
C4—C51.384 (3)N3—C4'1.456 (2)
C5—C61.379 (3)C1'—C6'1.421 (3)
C5—H50.97 (2)C1'—C2'1.424 (2)
C6—H60.95 (2)C2'—C3'1.389 (2)
C7—C81.326 (3)C3'—C4'1.363 (3)
C7—H70.98 (3)C3'—H3'0.90 (2)
C8—C91.435 (3)C4'—C5'1.391 (3)
C8—H80.91 (3)C5'—C6'1.351 (3)
C9—H90.98 (3)C5'—H5'0.93 (2)
C10—H1011.03 (3)C6'—H6'0.98 (2)
C4—O2—C10118.1 (2)O2—C10—H103107 (2)
C6—C1—C2117.19 (17)H101—C10—H103110 (3)
C6—C1—C7119.62 (17)H102—C10—H103108 (3)
C2—C1—C7123.19 (17)C1'—N1—H1.1117.4 (16)
C3—C2—C1121.53 (18)C1'—N1—H1.2117.3 (16)
C3—C2—H2116.8 (13)H1.1—N1—H1.2125 (2)
C1—C2—H2121.6 (13)O21—N2—O22122.24 (16)
C2—C3—C4120.28 (19)O21—N2—C2'119.52 (15)
C2—C3—H3120.8 (14)O22—N2—C2'118.24 (15)
C4—C3—H3118.9 (14)O31—N3—O32122.96 (17)
O2—C4—C5124.86 (17)O31—N3—C4'118.96 (18)
O2—C4—C3115.64 (17)O32—N3—C4'118.08 (17)
C5—C4—C3119.50 (17)N1—C1'—C6'119.12 (17)
C6—C5—C4119.45 (18)N1—C1'—C2'125.32 (18)
C6—C5—H5116.8 (13)C6'—C1'—C2'115.54 (15)
C4—C5—H5123.7 (13)C3'—C2'—C1'121.72 (16)
C5—C6—C1122.05 (18)C3'—C2'—N2116.72 (15)
C5—C6—H6121.3 (13)C1'—C2'—N2121.56 (15)
C1—C6—H6116.7 (13)C4'—C3'—C2'119.24 (16)
C8—C7—C1129.6 (2)C4'—C3'—H3'120.6 (14)
C8—C7—H7115.0 (14)C2'—C3'—H3'120.2 (14)
C1—C7—H7115.3 (14)C3'—C4'—C5'121.27 (16)
C7—C8—C9120.3 (2)C3'—C4'—N3119.57 (16)
C7—C8—H8127.4 (15)C5'—C4'—N3119.16 (17)
C9—C8—H8112.3 (15)C6'—C5'—C4'119.77 (18)
O1—C9—C8127.2 (2)C6'—C5'—H5'118.6 (14)
O1—C9—H9119.6 (19)C4'—C5'—H5'121.6 (14)
C8—C9—H9113.1 (19)C5'—C6'—C1'122.42 (17)
O2—C10—H101109.7 (15)C5'—C6'—H6'117.4 (14)
O2—C10—H102113.8 (18)C1'—C6'—H6'120.2 (14)
H101—C10—H102109 (2)
C6—C1—C2—C30.4 (3)C6'—C1'—C2'—N2178.24 (16)
C7—C1—C2—C3179.8 (2)O21—N2—C2'—C3'178.41 (17)
C1—C2—C3—C40.1 (3)O22—N2—C2'—C3'2.2 (2)
C10—O2—C4—C51.9 (3)O21—N2—C2'—C1'1.7 (3)
C10—O2—C4—C3178.6 (2)O22—N2—C2'—C1'177.70 (16)
C2—C3—C4—O2179.92 (19)C1'—C2'—C3'—C4'1.1 (3)
C2—C3—C4—C50.5 (3)N2—C2'—C3'—C4'178.82 (16)
O2—C4—C5—C6179.85 (19)C2'—C3'—C4'—C5'0.6 (3)
C3—C4—C5—C60.3 (3)C2'—C3'—C4'—N3178.90 (16)
C4—C5—C6—C10.3 (3)O31—N3—C4'—C3'3.0 (3)
C2—C1—C6—C50.6 (3)O32—N3—C4'—C3'177.58 (18)
C7—C1—C6—C5180.0 (2)O31—N3—C4'—C5'176.57 (18)
C6—C1—C7—C8177.0 (2)O32—N3—C4'—C5'2.9 (3)
C2—C1—C7—C83.6 (4)C3'—C4'—C5'—C6'1.7 (3)
C1—C7—C8—C9179.7 (2)N3—C4'—C5'—C6'177.86 (18)
C7—C8—C9—O1177.6 (3)C4'—C5'—C6'—C1'1.0 (3)
N1—C1'—C2'—C3'179.68 (19)N1—C1'—C6'—C5'179.35 (19)
C6'—C1'—C2'—C3'1.7 (3)C2'—C1'—C6'—C5'0.6 (3)
N1—C1'—C2'—N20.4 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1.2···O210.85 (3)2.02 (2)2.652 (2)130 (1)
N1—H1.1···O10.91 (3)2.09 (3)2.978 (2)164 (1)
C6—H6···O10.98 (2)2.51 (2)3.308 (2)138 (1)
(b) 4,4-dimethylaminocinnamaldehyde top
Crystal data top
C11H13NOF(000) = 752
Mr = 175.22Dx = 1.170 Mg m3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 24 reflections
a = 10.040 (6) Åθ = 10–11°
b = 7.733 (3) ŵ = 0.08 mm1
c = 25.620 (13) ÅT = 298 K
V = 1989.1 (17) Å3Plate, light green
Z = 80.5 × 0.4 × 0.1 mm
Data collection top
Siemens P3/PC
diffractometer
Rint = 0.000
Radiation source: fine-focus sealed tubeθmax = 25.1°, θmin = 1.6°
Graphite monochromatorh = 011
θ/2θ scank = 09
1755 measured reflectionsl = 300
1755 independent reflections2 standard reflections every 98 reflections
1070 reflections with I > 2σ(I) intensity decay: 5%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.123Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.257H-atom parameters constrained
S = 1.14 w = 1/[σ2(Fo2) + (0.038P)2 + 5.11P]
where P = (Fo2 + 2Fc2)/3
1755 reflections(Δ/σ)max = 0.014
120 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C11H13NOV = 1989.1 (17) Å3
Mr = 175.22Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 10.040 (6) ŵ = 0.08 mm1
b = 7.733 (3) ÅT = 298 K
c = 25.620 (13) Å0.5 × 0.4 × 0.1 mm
Data collection top
Siemens P3/PC
diffractometer
Rint = 0.000
1755 measured reflections2 standard reflections every 98 reflections
1755 independent reflections intensity decay: 5%
1070 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.1230 restraints
wR(F2) = 0.257H-atom parameters constrained
S = 1.14Δρmax = 0.26 e Å3
1755 reflectionsΔρmin = 0.25 e Å3
120 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. All H atoms were positioned geometrically and thereafter refined using a riding model.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.8310 (6)0.2284 (9)0.07694 (18)0.132 (2)
N10.8845 (5)0.1833 (7)0.42486 (17)0.0711 (14)
C10.9056 (5)0.2802 (6)0.2636 (2)0.0563 (14)
C20.7997 (5)0.1853 (7)0.2850 (2)0.0586 (14)
H2A0.73360.14330.26300.070*
C30.7908 (5)0.1528 (7)0.3379 (2)0.0606 (14)
H3A0.71960.08940.35090.073*
C40.8901 (6)0.2157 (7)0.3722 (2)0.0590 (14)
C50.9951 (5)0.3109 (7)0.3507 (2)0.0634 (15)
H5A1.06200.35290.37230.076*
C61.0006 (6)0.3431 (7)0.2979 (2)0.0613 (15)
H6A1.07040.40920.28490.074*
C70.9181 (6)0.3140 (7)0.2075 (2)0.0667 (16)
H7A0.98400.39270.19820.080*
C80.8492 (6)0.2487 (8)0.1683 (2)0.0660 (15)
H8A0.77780.17560.17520.079*
C90.8824 (7)0.2885 (10)0.1153 (2)0.091 (2)
H9A0.95030.36850.11010.110*
C100.9896 (7)0.2453 (9)0.4593 (2)0.091 (2)
H10A0.99770.36850.45590.136*
H10B1.07240.19160.44990.136*
H10C0.96800.21670.49480.136*
C110.7728 (7)0.0906 (9)0.4478 (2)0.088 (2)
H11A0.69110.14700.43840.132*
H11B0.78180.08980.48510.132*
H11C0.77190.02620.43510.132*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.140 (5)0.197 (7)0.059 (3)0.004 (5)0.005 (3)0.009 (4)
N10.080 (3)0.076 (3)0.057 (3)0.007 (3)0.009 (3)0.004 (2)
C10.061 (3)0.040 (3)0.068 (3)0.003 (3)0.003 (3)0.000 (2)
C20.057 (3)0.051 (3)0.068 (3)0.001 (3)0.006 (3)0.007 (3)
C30.064 (4)0.053 (3)0.065 (3)0.004 (3)0.008 (3)0.001 (3)
C40.068 (4)0.047 (3)0.061 (3)0.002 (3)0.002 (3)0.009 (3)
C50.059 (3)0.061 (3)0.071 (4)0.009 (3)0.006 (3)0.012 (3)
C60.064 (3)0.046 (3)0.074 (4)0.008 (3)0.006 (3)0.000 (3)
C70.078 (4)0.052 (3)0.070 (4)0.002 (3)0.001 (3)0.006 (3)
C80.068 (3)0.071 (4)0.059 (3)0.002 (3)0.005 (3)0.010 (3)
C90.103 (5)0.108 (6)0.063 (4)0.013 (5)0.002 (4)0.021 (4)
C100.101 (5)0.110 (5)0.062 (4)0.005 (5)0.015 (4)0.012 (4)
C110.120 (6)0.077 (4)0.067 (4)0.012 (4)0.015 (4)0.008 (3)
Geometric parameters (Å, º) top
O1—C91.204 (8)C2—C31.379 (7)
N1—C41.374 (6)C3—C41.415 (7)
N1—C101.457 (7)C4—C51.399 (7)
N1—C111.455 (7)C5—C61.375 (7)
C1—C61.387 (7)C7—C81.320 (7)
C1—C21.404 (7)C8—C91.430 (8)
C1—C71.466 (7)
C4—N1—C10120.3 (5)N1—C4—C5120.9 (5)
C4—N1—C11121.3 (5)N1—C4—C3121.2 (5)
C10—N1—C11118.4 (5)C5—C4—C3117.8 (5)
C6—C1—C2117.1 (5)C6—C5—C4120.8 (5)
C6—C1—C7120.1 (5)C5—C6—C1122.2 (5)
C2—C1—C7122.8 (5)C8—C7—C1129.3 (6)
C3—C2—C1121.9 (5)C7—C8—C9121.2 (6)
C2—C3—C4120.1 (5)O1—C9—C8126.3 (8)
C6—C1—C2—C31.2 (8)N1—C4—C5—C6179.9 (5)
C7—C1—C2—C3179.0 (5)C3—C4—C5—C60.5 (8)
C1—C2—C3—C40.1 (8)C4—C5—C6—C11.6 (8)
C10—N1—C4—C51.0 (8)C2—C1—C6—C51.9 (8)
C11—N1—C4—C5177.4 (5)C7—C1—C6—C5178.3 (5)
C10—N1—C4—C3178.3 (5)C6—C1—C7—C8170.6 (6)
C11—N1—C4—C33.2 (8)C2—C1—C7—C89.6 (9)
C2—C3—C4—N1179.2 (5)C1—C7—C8—C9175.5 (6)
C2—C3—C4—C50.2 (8)C7—C8—C9—O1175.5 (7)

Experimental details

(4a)(b)
Crystal data
Chemical formulaC10H10O2·C6H5N3O4C11H13NO
Mr345.31175.22
Crystal system, space groupTriclinic, P1Orthorhombic, Pbca
Temperature (K)298298
a, b, c (Å)7.3490 (15), 9.2520 (19), 12.523 (3)10.040 (6), 7.733 (3), 25.620 (13)
α, β, γ (°)108.01 (3), 93.48 (3), 94.40 (3)90, 90, 90
V3)804.2 (3)1989.1 (17)
Z28
Radiation typeMo KαMo Kα
µ (mm1)0.110.08
Crystal size (mm)0.50 × 0.35 × 0.250.5 × 0.4 × 0.1
Data collection
DiffractometerEnraf-Nonius CAD4
diffractometer
Siemens P3/PC
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4088, 3786, 2370 1755, 1755, 1070
Rint0.0420.000
(sin θ/λ)max1)0.6600.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.156, 1.02 0.123, 0.257, 1.14
No. of reflections37861755
No. of parameters286120
H-atom treatmentAll H-atom parameters refinedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.21, 0.250.26, 0.25

Computer programs: CAD-4 Software (Enraf-Nonius, 1989), P3/PC Diffractometer Program (Siemens, 1989), CAD-4 Software, P3/PC Diffractometer Program, SHELXTL-Plus (Sheldrick, 1994), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), SHELXTL-Plus, SHELXL97.

Selected geometric parameters (Å, º) for (4a) top
O1—C91.204 (3)O31—N31.221 (2)
C1—C71.445 (3)O32—N31.225 (2)
C7—C81.326 (3)N1—C1'1.333 (2)
C8—C91.435 (3)N2—C2'1.443 (2)
O21—N21.227 (2)N3—C4'1.456 (2)
O22—N21.231 (2)C1'—C2'1.424 (2)
C8—C7—C1129.6 (2)O22—N2—C2'118.24 (15)
C7—C8—C9120.3 (2)O31—N3—O32122.96 (17)
O1—C9—C8127.2 (2)O31—N3—C4'118.96 (18)
O21—N2—O22122.24 (16)O32—N3—C4'118.08 (17)
O21—N2—C2'119.52 (15)
C10—O2—C4—C3178.6 (2)O21—N2—C2'—C1'1.7 (3)
C2—C1—C7—C83.6 (4)O22—N2—C2'—C1'177.70 (16)
C1—C7—C8—C9179.7 (2)O31—N3—C4'—C3'3.0 (3)
C7—C8—C9—O1177.6 (3)O32—N3—C4'—C3'177.58 (18)
Hydrogen-bond geometry (Å, º) for (4a) top
D—H···AD—HH···AD···AD—H···A
N1—H1.2···O210.85 (3)2.02 (2)2.652 (2)130 (1)
N1—H1.1···O10.91 (3)2.09 (3)2.978 (2)164 (1)
C6'—H6'···O10.98 (2)2.51 (2)3.308 (2)138 (1)
Selected geometric parameters (Å, º) for (b) top
O1—C91.204 (8)C7—C81.320 (7)
N1—C41.374 (6)C8—C91.430 (8)
C1—C71.466 (7)
C8—C7—C1129.3 (6)O1—C9—C8126.3 (8)
C7—C8—C9121.2 (6)
C2—C1—C7—C89.6 (9)C7—C8—C9—O1175.5 (7)
C1—C7—C8—C9175.5 (6)
 

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