A combinatorial chemistry approach to new materials for non-linear optics. II. 4-(Dimethylamino)cinnamaldehyde and a molecular complex of ­4-­methoxycinnamaldehyde with 2,4-­dinitroaniline

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.

S1. Comment

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.

S2. Experimental

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.

S3. Refinement

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

Computing details

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

	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.
	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

Crystal data

C10H10O2·C6H5N3O4	Z = 2
Mr = 345.31	F(000) = 360
Triclinic, P1	Dx = 1.426 Mg m^−3
a = 7.3490 (15) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.2520 (19) Å	Cell parameters from 24 reflections
c = 12.523 (3) Å	θ = 11–12°
α = 108.01 (3)°	µ = 0.11 mm^−1
β = 93.48 (3)°	T = 298 K
γ = 94.40 (3)°	Parallelepiped prism, yellow
V = 804.2 (3) Å^3	0.50 × 0.35 × 0.25 mm

Data collection

Enraf-Nonius CAD4 diffractometer	Rint = 0.042
Radiation source: fine-focus sealed tube	θmax = 28.0°, θmin = 1.7°
Graphite monochromator	h = 0→9
θ/2θ scan	k = −12→12
4088 measured reflections	l = −16→16
3786 independent reflections	3 standard reflections every 97 reflections
2370 reflections with I > 2σ(I)	intensity decay: 5%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.047	Hydrogen site location: difference Fourier map
wR(F^2) = 0.156	All H-atom parameters refined
S = 1.02	w = 1/[σ^2(Fo^2) + (0.08P)^2 + 0.152P] where P = (Fo^2 + 2Fc^2)/3
3786 reflections	(Δ/σ)max = 0.001
286 parameters	Δρmax = 0.21 e Å^−3
0 restraints	Δρmin = −0.25 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. All H atoms were located from a difference Fourier map and were refined isotropically.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	−0.3360 (3)	0.9726 (2)	−0.10703 (16)	0.0932 (6)
O2	−0.0914 (2)	0.25456 (18)	0.20034 (14)	0.0710 (5)
C1	−0.1500 (2)	0.6433 (2)	0.10727 (14)	0.0457 (4)
C2	−0.2401 (3)	0.5005 (2)	0.04665 (16)	0.0520 (5)
C3	−0.2182 (3)	0.3745 (2)	0.07944 (18)	0.0574 (5)
C4	−0.1038 (3)	0.3862 (2)	0.17518 (16)	0.0508 (5)
C5	−0.0134 (3)	0.5267 (2)	0.23743 (17)	0.0542 (5)
C6	−0.0375 (3)	0.6526 (2)	0.20332 (16)	0.0529 (5)
C7	−0.1699 (3)	0.7791 (2)	0.07555 (18)	0.0546 (5)
C8	−0.2626 (3)	0.7951 (2)	−0.01365 (18)	0.0575 (5)
C9	−0.2629 (4)	0.9426 (3)	−0.0289 (2)	0.0716 (6)
C10	0.0271 (4)	0.2591 (4)	0.2959 (3)	0.0782 (8)
O21	−0.7915 (2)	0.82378 (16)	−0.50985 (13)	0.0676 (4)
O22	−0.8674 (2)	0.98320 (17)	−0.59450 (12)	0.0659 (4)
O31	−0.6885 (2)	1.51358 (18)	−0.44630 (15)	0.0761 (5)
O32	−0.4914 (3)	1.60099 (16)	−0.30196 (16)	0.0818 (5)
N1	−0.5672 (3)	0.9164 (2)	−0.32234 (17)	0.0600 (5)
N2	−0.7861 (2)	0.95381 (18)	−0.51607 (13)	0.0499 (4)
N3	−0.5879 (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)
H1.1	−0.494 (3)	0.914 (3)	−0.262 (2)	0.076 (7)*
H1.2	−0.628 (3)	0.839 (3)	−0.371 (2)	0.066 (7)*
H2	−0.317 (3)	0.485 (2)	−0.0231 (19)	0.062 (6)*
H3	−0.276 (3)	0.278 (3)	0.036 (2)	0.065 (6)*
H5	0.064 (3)	0.544 (2)	0.3071 (19)	0.060 (6)*
H6	0.021 (3)	0.751 (3)	0.2456 (19)	0.060 (6)*
H7	−0.112 (3)	0.874 (3)	0.130 (2)	0.075 (7)*
H8	−0.327 (3)	0.720 (3)	−0.072 (2)	0.067 (6)*
H9	−0.190 (4)	1.023 (4)	0.031 (3)	0.110 (10)*
H101	0.160 (4)	0.292 (3)	0.285 (2)	0.089 (8)*
H102	−0.004 (4)	0.325 (3)	0.364 (3)	0.087 (9)*
H103	0.019 (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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.1303 (16)	0.0711 (11)	0.0865 (12)	0.0144 (10)	−0.0271 (11)	0.0426 (9)
O2	0.0831 (11)	0.0626 (9)	0.0774 (10)	0.0048 (8)	−0.0121 (8)	0.0411 (8)
C1	0.0490 (10)	0.0459 (9)	0.0436 (9)	0.0048 (7)	0.0006 (7)	0.0169 (7)
C2	0.0606 (12)	0.0506 (10)	0.0433 (9)	0.0063 (8)	−0.0091 (8)	0.0152 (8)
C3	0.0666 (13)	0.0455 (10)	0.0571 (12)	−0.0002 (9)	−0.0119 (10)	0.0165 (9)
C4	0.0533 (11)	0.0543 (11)	0.0514 (10)	0.0086 (8)	0.0017 (8)	0.0261 (9)
C5	0.0536 (11)	0.0605 (12)	0.0486 (10)	0.0016 (9)	−0.0081 (8)	0.0209 (9)
C6	0.0566 (11)	0.0495 (11)	0.0487 (10)	−0.0025 (9)	−0.0065 (8)	0.0137 (8)
C7	0.0628 (12)	0.0455 (10)	0.0549 (11)	0.0058 (9)	−0.0022 (9)	0.0163 (9)
C8	0.0683 (13)	0.0472 (11)	0.0566 (12)	0.0077 (9)	−0.0059 (10)	0.0175 (9)
C9	0.0904 (17)	0.0535 (12)	0.0730 (15)	0.0115 (11)	−0.0131 (13)	0.0259 (11)
C10	0.088 (2)	0.0847 (19)	0.0802 (18)	0.0144 (15)	−0.0038 (14)	0.0531 (16)
O21	0.0805 (10)	0.0417 (7)	0.0761 (10)	−0.0035 (7)	−0.0065 (8)	0.0167 (7)
O22	0.0706 (10)	0.0633 (9)	0.0574 (8)	0.0025 (7)	−0.0176 (7)	0.0153 (7)
O31	0.0930 (12)	0.0611 (10)	0.0901 (12)	0.0205 (8)	0.0049 (9)	0.0443 (9)
O32	0.1037 (13)	0.0384 (8)	0.0972 (13)	−0.0049 (8)	0.0008 (10)	0.0170 (8)
N1	0.0728 (12)	0.0486 (10)	0.0642 (11)	0.0057 (9)	−0.0076 (10)	0.0282 (9)
N2	0.0485 (9)	0.0464 (9)	0.0520 (9)	0.0033 (6)	−0.0001 (7)	0.0128 (7)
N3	0.0678 (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)

O1—C9	1.204 (3)	C10—H102	0.93 (3)
O2—C4	1.357 (2)	C10—H103	0.86 (3)
O2—C10	1.424 (3)	O21—N2	1.227 (2)
C1—C6	1.394 (3)	O22—N2	1.231 (2)
C1—C2	1.395 (3)	O31—N3	1.221 (2)
C1—C7	1.445 (3)	O32—N3	1.225 (2)
C2—C3	1.367 (3)	N1—C1'	1.333 (2)
C2—H2	0.98 (2)	N1—H1.1	0.91 (3)
C3—C4	1.393 (3)	N1—H1.2	0.85 (3)
C3—H3	0.94 (2)	N2—C2'	1.443 (2)
C4—C5	1.384 (3)	N3—C4'	1.456 (2)
C5—C6	1.379 (3)	C1'—C6'	1.421 (3)
C5—H5	0.97 (2)	C1'—C2'	1.424 (2)
C6—H6	0.95 (2)	C2'—C3'	1.389 (2)
C7—C8	1.326 (3)	C3'—C4'	1.363 (3)
C7—H7	0.98 (3)	C3'—H3'	0.90 (2)
C8—C9	1.435 (3)	C4'—C5'	1.391 (3)
C8—H8	0.91 (3)	C5'—C6'	1.351 (3)
C9—H9	0.98 (3)	C5'—H5'	0.93 (2)
C10—H101	1.03 (3)	C6'—H6'	0.98 (2)
C4—O2—C10	118.1 (2)	O2—C10—H103	107 (2)
C6—C1—C2	117.19 (17)	H101—C10—H103	110 (3)
C6—C1—C7	119.62 (17)	H102—C10—H103	108 (3)
C2—C1—C7	123.19 (17)	C1'—N1—H1.1	117.4 (16)
C3—C2—C1	121.53 (18)	C1'—N1—H1.2	117.3 (16)
C3—C2—H2	116.8 (13)	H1.1—N1—H1.2	125 (2)
C1—C2—H2	121.6 (13)	O21—N2—O22	122.24 (16)
C2—C3—C4	120.28 (19)	O21—N2—C2'	119.52 (15)
C2—C3—H3	120.8 (14)	O22—N2—C2'	118.24 (15)
C4—C3—H3	118.9 (14)	O31—N3—O32	122.96 (17)
O2—C4—C5	124.86 (17)	O31—N3—C4'	118.96 (18)
O2—C4—C3	115.64 (17)	O32—N3—C4'	118.08 (17)
C5—C4—C3	119.50 (17)	N1—C1'—C6'	119.12 (17)
C6—C5—C4	119.45 (18)	N1—C1'—C2'	125.32 (18)
C6—C5—H5	116.8 (13)	C6'—C1'—C2'	115.54 (15)
C4—C5—H5	123.7 (13)	C3'—C2'—C1'	121.72 (16)
C5—C6—C1	122.05 (18)	C3'—C2'—N2	116.72 (15)
C5—C6—H6	121.3 (13)	C1'—C2'—N2	121.56 (15)
C1—C6—H6	116.7 (13)	C4'—C3'—C2'	119.24 (16)
C8—C7—C1	129.6 (2)	C4'—C3'—H3'	120.6 (14)
C8—C7—H7	115.0 (14)	C2'—C3'—H3'	120.2 (14)
C1—C7—H7	115.3 (14)	C3'—C4'—C5'	121.27 (16)
C7—C8—C9	120.3 (2)	C3'—C4'—N3	119.57 (16)
C7—C8—H8	127.4 (15)	C5'—C4'—N3	119.16 (17)
C9—C8—H8	112.3 (15)	C6'—C5'—C4'	119.77 (18)
O1—C9—C8	127.2 (2)	C6'—C5'—H5'	118.6 (14)
O1—C9—H9	119.6 (19)	C4'—C5'—H5'	121.6 (14)
C8—C9—H9	113.1 (19)	C5'—C6'—C1'	122.42 (17)
O2—C10—H101	109.7 (15)	C5'—C6'—H6'	117.4 (14)
O2—C10—H102	113.8 (18)	C1'—C6'—H6'	120.2 (14)
H101—C10—H102	109 (2)
C6—C1—C2—C3	−0.4 (3)	C6'—C1'—C2'—N2	178.24 (16)
C7—C1—C2—C3	−179.8 (2)	O21—N2—C2'—C3'	−178.41 (17)
C1—C2—C3—C4	−0.1 (3)	O22—N2—C2'—C3'	2.2 (2)
C10—O2—C4—C5	−1.9 (3)	O21—N2—C2'—C1'	1.7 (3)
C10—O2—C4—C3	178.6 (2)	O22—N2—C2'—C1'	−177.70 (16)
C2—C3—C4—O2	−179.92 (19)	C1'—C2'—C3'—C4'	1.1 (3)
C2—C3—C4—C5	0.5 (3)	N2—C2'—C3'—C4'	−178.82 (16)
O2—C4—C5—C6	−179.85 (19)	C2'—C3'—C4'—C5'	0.6 (3)
C3—C4—C5—C6	−0.3 (3)	C2'—C3'—C4'—N3	−178.90 (16)
C4—C5—C6—C1	−0.3 (3)	O31—N3—C4'—C3'	3.0 (3)
C2—C1—C6—C5	0.6 (3)	O32—N3—C4'—C3'	−177.58 (18)
C7—C1—C6—C5	−180.0 (2)	O31—N3—C4'—C5'	−176.57 (18)
C6—C1—C7—C8	177.0 (2)	O32—N3—C4'—C5'	2.9 (3)
C2—C1—C7—C8	−3.6 (4)	C3'—C4'—C5'—C6'	−1.7 (3)
C1—C7—C8—C9	−179.7 (2)	N3—C4'—C5'—C6'	177.86 (18)
C7—C8—C9—O1	177.6 (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'—N2	−0.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1.2···O21	0.85 (3)	2.02 (2)	2.652 (2)	130 (1)
N1—H1.1···O1	0.91 (3)	2.09 (3)	2.978 (2)	164 (1)
C6′—H6′···O1	0.98 (2)	2.51 (2)	3.308 (2)	138 (1)

(b) 4,4-dimethylaminocinnamaldehyde

Crystal data

C11H13NO	F(000) = 752
Mr = 175.22	Dx = 1.170 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 24 reflections
a = 10.040 (6) Å	θ = 10–11°
b = 7.733 (3) Å	µ = 0.08 mm^−1
c = 25.620 (13) Å	T = 298 K
V = 1989.1 (17) Å^3	Plate, light green
Z = 8	0.5 × 0.4 × 0.1 mm

Data collection

Siemens P3/PC diffractometer	Rint = 0.000
Radiation source: fine-focus sealed tube	θmax = 25.1°, θmin = 1.6°
Graphite monochromator	h = 0→11
θ/2θ scan	k = 0→9
1755 measured reflections	l = −30→0
1755 independent reflections	2 standard reflections every 98 reflections
1070 reflections with I > 2σ(I)	intensity decay: 5%

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.123	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.257	H-atom parameters constrained
S = 1.14	w = 1/[σ^2(Fo^2) + (0.038P)^2 + 5.11P] where P = (Fo^2 + 2Fc^2)/3
1755 reflections	(Δ/σ)max = 0.014
120 parameters	Δρmax = 0.26 e Å^−3
0 restraints	Δρmin = −0.25 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. All H atoms were positioned geometrically and thereafter refined using a riding model.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.8310 (6)	0.2284 (9)	0.07694 (18)	0.132 (2)
N1	0.8845 (5)	0.1833 (7)	0.42486 (17)	0.0711 (14)
C1	0.9056 (5)	0.2802 (6)	0.2636 (2)	0.0563 (14)
C2	0.7997 (5)	0.1853 (7)	0.2850 (2)	0.0586 (14)
H2A	0.7336	0.1433	0.2630	0.070*
C3	0.7908 (5)	0.1528 (7)	0.3379 (2)	0.0606 (14)
H3A	0.7196	0.0894	0.3509	0.073*
C4	0.8901 (6)	0.2157 (7)	0.3722 (2)	0.0590 (14)
C5	0.9951 (5)	0.3109 (7)	0.3507 (2)	0.0634 (15)
H5A	1.0620	0.3529	0.3723	0.076*
C6	1.0006 (6)	0.3431 (7)	0.2979 (2)	0.0613 (15)
H6A	1.0704	0.4092	0.2849	0.074*
C7	0.9181 (6)	0.3140 (7)	0.2075 (2)	0.0667 (16)
H7A	0.9840	0.3927	0.1982	0.080*
C8	0.8492 (6)	0.2487 (8)	0.1683 (2)	0.0660 (15)
H8A	0.7778	0.1756	0.1752	0.079*
C9	0.8824 (7)	0.2885 (10)	0.1153 (2)	0.091 (2)
H9A	0.9503	0.3685	0.1101	0.110*
C10	0.9896 (7)	0.2453 (9)	0.4593 (2)	0.091 (2)
H10A	0.9977	0.3685	0.4559	0.136*
H10B	1.0724	0.1916	0.4499	0.136*
H10C	0.9680	0.2167	0.4948	0.136*
C11	0.7728 (7)	0.0906 (9)	0.4478 (2)	0.088 (2)
H11A	0.6911	0.1470	0.4384	0.132*
H11B	0.7818	0.0898	0.4851	0.132*
H11C	0.7719	−0.0262	0.4351	0.132*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.140 (5)	0.197 (7)	0.059 (3)	−0.004 (5)	−0.005 (3)	0.009 (4)
N1	0.080 (3)	0.076 (3)	0.057 (3)	−0.007 (3)	0.009 (3)	−0.004 (2)
C1	0.061 (3)	0.040 (3)	0.068 (3)	−0.003 (3)	0.003 (3)	0.000 (2)
C2	0.057 (3)	0.051 (3)	0.068 (3)	0.001 (3)	−0.006 (3)	−0.007 (3)
C3	0.064 (4)	0.053 (3)	0.065 (3)	−0.004 (3)	0.008 (3)	0.001 (3)
C4	0.068 (4)	0.047 (3)	0.061 (3)	−0.002 (3)	0.002 (3)	−0.009 (3)
C5	0.059 (3)	0.061 (3)	0.071 (4)	−0.009 (3)	−0.006 (3)	−0.012 (3)
C6	0.064 (3)	0.046 (3)	0.074 (4)	−0.008 (3)	0.006 (3)	0.000 (3)
C7	0.078 (4)	0.052 (3)	0.070 (4)	0.002 (3)	0.001 (3)	0.006 (3)
C8	0.068 (3)	0.071 (4)	0.059 (3)	0.002 (3)	−0.005 (3)	0.010 (3)
C9	0.103 (5)	0.108 (6)	0.063 (4)	0.013 (5)	0.002 (4)	0.021 (4)
C10	0.101 (5)	0.110 (5)	0.062 (4)	−0.005 (5)	−0.015 (4)	−0.012 (4)
C11	0.120 (6)	0.077 (4)	0.067 (4)	−0.012 (4)	0.015 (4)	0.008 (3)

Geometric parameters (Å, º)

O1—C9	1.204 (8)	C2—C3	1.379 (7)
N1—C4	1.374 (6)	C3—C4	1.415 (7)
N1—C10	1.457 (7)	C4—C5	1.399 (7)
N1—C11	1.455 (7)	C5—C6	1.375 (7)
C1—C6	1.387 (7)	C7—C8	1.320 (7)
C1—C2	1.404 (7)	C8—C9	1.430 (8)
C1—C7	1.466 (7)
C4—N1—C10	120.3 (5)	N1—C4—C5	120.9 (5)
C4—N1—C11	121.3 (5)	N1—C4—C3	121.2 (5)
C10—N1—C11	118.4 (5)	C5—C4—C3	117.8 (5)
C6—C1—C2	117.1 (5)	C6—C5—C4	120.8 (5)
C6—C1—C7	120.1 (5)	C5—C6—C1	122.2 (5)
C2—C1—C7	122.8 (5)	C8—C7—C1	129.3 (6)
C3—C2—C1	121.9 (5)	C7—C8—C9	121.2 (6)
C2—C3—C4	120.1 (5)	O1—C9—C8	126.3 (8)
C6—C1—C2—C3	−1.2 (8)	N1—C4—C5—C6	179.9 (5)
C7—C1—C2—C3	179.0 (5)	C3—C4—C5—C6	0.5 (8)
C1—C2—C3—C4	0.1 (8)	C4—C5—C6—C1	−1.6 (8)
C10—N1—C4—C5	−1.0 (8)	C2—C1—C6—C5	1.9 (8)
C11—N1—C4—C5	177.4 (5)	C7—C1—C6—C5	−178.3 (5)
C10—N1—C4—C3	178.3 (5)	C6—C1—C7—C8	170.6 (6)
C11—N1—C4—C3	−3.2 (8)	C2—C1—C7—C8	−9.6 (9)
C2—C3—C4—N1	−179.2 (5)	C1—C7—C8—C9	−175.5 (6)
C2—C3—C4—C5	0.2 (8)	C7—C8—C9—O1	175.5 (7)