2-(2-Naphthyl­oxy)­acetate derivatives. II. A new class of antiamnesic agents

The title compounds, 4-(2-naphthyl­oxy­methyl­carbonyl)­morpholine, C₁₆H₁₇NO₃, (I), and 4-methyl-1-(2-naphthyl­oxy­methyl­carbonyl)­piper­azine, C₁₇H₂₀N₂O₂, (II), are potential antiamnesics. The morpholine ring in (I) and the piperazine ring in (II) adopt chair conformations. In (I), the mol­ecules are linked by weak intermolecular C-H...O interactions into chains that have a graph-set motif of C(10), while in (II), the mol­ecules are linked by weak intermolecular C-H...O interactions that generate two C(7) graph-set motifs. The dihedral angle between the naphthalene moiety and the best plane through the morpholine ring is 20.62 (4)° in (I), while the naphthalene moiety is oriented nearly perpendicular to the mean plane of the piperazine ring in (II).

S1. Comment

The conformation of molecules with antiamnesic activity has attracted considerable interest (Amato et al., 1991), and the present structure determinations are part of our research program on biologically active 2-(2-Naphthyloxy)acetate derivatives. We report here the preparation and the X-ray crystal structure of 4-(2-Naphthyloxymethylcarbonyl)morpholine, (I), and 1-(2-Naphthyloxymethylcarbonyl)-4-methylpiperazine, (II), both of which are important in the treatment of human cognitive disorders (Thamotharan et al., 2003, and references therein).

Views of the molecules of (I) and (II), with the atomic numbering schemes, are shown in Figs. 1 and 2, respectively. The corresponding bond lengths and angles in (I) and (II) are essentially equivalent and are comparable to those in the related structures N-(2-naphthyloxymethylcarbonyl)piperidine and 3-Methyl-N-(2-naphthyloxymethylcarbonyl)piperidine (Thamotharan et al., 2003). In the molecule of (I), the central C2—O11—C12—C13—N14 fragment is planar, with a maximum deviation of 0.023 (1) Å for atom C13. In contrast, only the O11—C12—C13—N14 segment is planar in compound (II). Atom C2 is twisted about the O11—C12 bond so that it lies almost perpendicular to the O11/C12/C13/N14 plane (Table 3). In (I), the central unit is almost coplanar with the naphthalene moiety, the angle between the planes being 3.67 (7)°, while the dihedral angle between the central unit and the naphthalene moiety in (II) is 76.94 (15)°. The central unit is twisted 27.79 (14)° out of the mean plane of the piperazine ring in (II), whereas it is twisted 21.73 (6)° out of the best plane passing through the morpholine ring in (I). The C2—O11—C12—C13 and O11—C12—C13—N14 torsion angles show that the central unit has an antiperiplanar conformation in (I), while the corresponding torsion angles in (II) represent synclinal and antiperiplanar conformations, respectively.

The morpholine ring in (I) has a chair conformation [Cremer & Pople (1975) puckering parameters Q = 0.550 (1) Å, q₂ = 0.045 (1) Å, q₃ = 0.548 (1) Å, θ = 4.7 (1)° and ϕ₂ = 345.8 (19)° for the atom sequence O17—C16—C15—N14—C19—C18]. The dihedral angle between the naphthalene moiety and the morpholine ring is 20.62 (4)°. In (II), the puckering parameters of the piperazine ring [Q = 0.5585 (3) Å, q₂ = 0.016 (3) Å, q₃ = 0.558 (3) Å, θ = 0.7 (3)° and ϕ₂ = 131 (10)° for the atom sequence N14—C15—C16—N17—C18—C19] are indicative of a chair conformation, and the methyl substituent at atom N17 is in an equatorial position. The sum of the angles around N17 is 331°, showing an essentially pyramidal geometry at atom N17. In contrast, atom N14 in (I) and (II) exhibits little pyramidal geometry becasue of the amide-type cojugation with carbonyl atom O13. The sum of the angles around atom N14 in (I) and (II) is 360° (Table 1 & 3). The naphthalene moiety is oriented nearly perpendicular to the mean plane of the piperazine ring.

The exocyclic C1—C2—O11 and C13—N14—C15 bond angles deviate significantly from the normal value of 120° (Tables 1 and 3) and this may be a result of steric repulsion [H1···H121 = 2.21 (2.10) Å, H121···H151 = 2.25 Å (H121···H152 = 2.26 Å) and H122···H151 = 2.17 Å (H122···H152 = 2.11 Å); the values in parentheses correspond to (II)].

As can be seen from Table 2 for (I), atom C1 acts as a donor for a weak intermolecular C—H···O interaction with atom O17 of an adjacent molecule. This interaction links the molecules into chains, which run parallel to the c axis and have a graph-set motif of C(10) (Bernstein et al., 1995).

In (II), atom C1 acts as a donor for a weak intermolecular C—H···O interaction with carbonyl atom O13 of an adjacent molecule (Table 4). This interaction produces a continuous chain that runs parallel to the c axis and has a graph-set motif of C(7). In addition, atom C5 is involved in an intermolecular C—H···O interaction with atom O11 of a different molecule. This interaction links the molecules into a continuous chain, that runs parallel to the a axis and has a graph-set motif of C(7) (Bernstein et al., 1995).

S2. Experimental

For the preparation of (I), methyl 2-(2-naphthyloxy)acetate (0.5 g) was reacted with morpholine. The oily product obtained was treated with water, and the resulting precipitate was filtered off, dried and crystallized from acetone to afford crystals of (I) (yield 0.532 g, 84.8%; m.p. 416–418 K). For the preparation of (II), methyl 2-(2-naphthyloxy)acetate (0.5 g) was reacted with N-methylpiperazine. The oily product obtained was treated with water, and the resulting precipitate was filtered off, dried and crystallized from ethanol to afford crystals of (II) (yield 0.514 g, 78.17%; m.p. 383–385 K).

S3. Refinement

For compound (I), all H atoms were placed in idealized positions (C—H = 0.95–0.99 Å) and constrained to ride on their parent atoms, with U_iso(H) values of 1.2U_eq(C). For compound (II), methyl H atoms were constrained to an ideal geometry (C—H = 0.98 Å), with U_iso(H) values of 1.5U_eq(C), but were allowed to rotate freely about the C—C bond. All remaining H atoms were placed in idealized positions (C—H = 0.95–0.99 Å) and constrained to ride on their parent atoms with U_iso(H) values of 1.2U_eq(C). Although the molecule is achiral, the structure possesses a polar axis. Because of the absence of any significant anomalous scatterers in the compound, attempts to confirm the absolute structure by refinement of the Flack parameter (Flack, 1983) in the presence of 1099 sets of Friedel equivalents led to an inconclusive value (Flack & Bernardinelli, 2000) of −0.1 (15) for this parameter. Therefore, the absolute direction of the polar axis was assigned arbitrarily and the Friedel pairs were merged before the final refinement. Reflection 110 was partially obscured by the beam stop and was omitted.

Computing details

For both compounds, data collection: COLLECT (Nonius, 2000); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: PARST97 (Nardelli, 1995) and PLATON (Spek, 2003).

Figures

	Fig. 1. A view of the molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level, and H atoms are represented by circles of arbitrary radii.
	Fig. 2. A view of the molecule of (II), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by circles of arbitrary radii.

(I) 4-(2-Naphthyloxymethylcarbonyl)morpholine

Crystal data

C16H17NO3	F(000) = 576
Mr = 271.31	Dx = 1.378 Mg m^−3
Monoclinic, P21/n	Melting point: 416 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 10.5594 (2) Å	Cell parameters from 4035 reflections
b = 9.2956 (2) Å	θ = 2.0–30.0°
c = 14.1012 (3) Å	µ = 0.10 mm^−1
β = 109.0917 (9)°	T = 160 K
V = 1307.98 (5) Å^3	Prism, colourless
Z = 4	0.28 × 0.25 × 0.23 mm

Data collection

Nonius KappaCCD diffractometer	2574 reflections with I > 2σ(I)
Radiation source: Nonius FR591 sealed tube generator	Rint = 0.060
Horizontally mounted graphite crystal monochromator	θmax = 30.0°, θmin = 2.1°
Detector resolution: 9 pixels mm^-1	h = 0→14
ϕ and ω scans with κ offsets	k = 0→13
37467 measured reflections	l = −19→18
3815 independent reflections

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.148	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.089P)^2 + 0.0564P] where P = (Fo^2 + 2Fc^2)/3
3815 reflections	(Δ/σ)max < 0.001
181 parameters	Δρmax = 0.36 e Å^−3
0 restraints	Δρmin = −0.26 e Å^−3

Special details

Experimental. Solvent used: acetone Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.507 (2) Frames collected: 355 Seconds exposure per frame: 20 Degrees rotation per frame: 2.0 Crystal-Detector distance (mm): 28.0

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 (Ų)

	x	y	z	Uiso*/Ueq
O11	0.32333 (9)	0.03996 (9)	0.58744 (6)	0.0279 (2)
O13	0.49043 (10)	0.24018 (11)	0.57496 (7)	0.0360 (3)
O17	0.40547 (10)	0.38343 (11)	0.22620 (7)	0.0359 (3)
N14	0.43256 (11)	0.23332 (11)	0.40585 (8)	0.0276 (3)
C1	0.13279 (12)	−0.12066 (13)	0.51817 (9)	0.0243 (3)
H1	0.1241	−0.0959	0.4510	0.029*
C2	0.23104 (12)	−0.05858 (13)	0.59661 (9)	0.0241 (3)
C3	0.24569 (13)	−0.09515 (14)	0.69741 (9)	0.0272 (3)
H3	0.3142	−0.0513	0.7510	0.033*
C4	0.16191 (13)	−0.19275 (14)	0.71757 (9)	0.0263 (3)
H4	0.1732	−0.2171	0.7853	0.032*
C5	−0.03142 (13)	−0.35885 (14)	0.65827 (10)	0.0277 (3)
H5	−0.0236	−0.3821	0.7256	0.033*
C6	−0.12947 (13)	−0.42270 (14)	0.58034 (10)	0.0296 (3)
H6	−0.1884	−0.4908	0.5939	0.035*
C7	−0.14292 (13)	−0.38752 (14)	0.48035 (10)	0.0295 (3)
H7	−0.2108	−0.4324	0.4269	0.035*
C8	−0.05911 (13)	−0.28928 (14)	0.45942 (10)	0.0274 (3)
H8	−0.0702	−0.2658	0.3916	0.033*
C9	0.04402 (12)	−0.22226 (13)	0.53796 (9)	0.0230 (3)
C10	0.05781 (12)	−0.25888 (13)	0.63888 (9)	0.0232 (3)
C12	0.31701 (12)	0.07438 (13)	0.48810 (9)	0.0251 (3)
H121	0.2266	0.1105	0.4495	0.030*
H122	0.3356	−0.0122	0.4539	0.030*
C13	0.42171 (12)	0.18958 (13)	0.49442 (9)	0.0247 (3)
C15	0.36503 (14)	0.16693 (14)	0.30831 (9)	0.0320 (3)
H151	0.2926	0.1029	0.3134	0.038*
H152	0.4298	0.1079	0.2879	0.038*
C16	0.30662 (14)	0.28181 (15)	0.23035 (10)	0.0308 (3)
H161	0.2675	0.2360	0.1637	0.037*
H162	0.2337	0.3323	0.2465	0.037*
C18	0.46241 (14)	0.45207 (15)	0.32142 (10)	0.0324 (3)
H181	0.3910	0.5031	0.3393	0.039*
H182	0.5291	0.5242	0.3169	0.039*
C19	0.52943 (13)	0.34431 (14)	0.40266 (10)	0.0298 (3)
H191	0.6065	0.2996	0.3887	0.036*
H192	0.5632	0.3936	0.4684	0.036*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O11	0.0318 (5)	0.0310 (5)	0.0193 (4)	−0.0051 (4)	0.0060 (3)	0.0010 (4)
O13	0.0376 (6)	0.0438 (6)	0.0228 (5)	−0.0110 (4)	0.0049 (4)	−0.0043 (4)
O17	0.0471 (6)	0.0369 (5)	0.0235 (5)	−0.0126 (4)	0.0115 (4)	−0.0011 (4)
N14	0.0336 (6)	0.0264 (6)	0.0206 (5)	−0.0061 (5)	0.0058 (4)	−0.0011 (4)
C1	0.0279 (6)	0.0265 (6)	0.0181 (6)	0.0044 (5)	0.0071 (5)	0.0018 (5)
C2	0.0260 (6)	0.0231 (6)	0.0229 (6)	0.0022 (5)	0.0076 (5)	0.0010 (5)
C3	0.0294 (7)	0.0299 (7)	0.0197 (6)	0.0008 (5)	0.0045 (5)	−0.0017 (5)
C4	0.0313 (7)	0.0298 (7)	0.0176 (6)	0.0040 (5)	0.0075 (5)	0.0017 (5)
C5	0.0303 (7)	0.0298 (7)	0.0240 (6)	0.0049 (5)	0.0103 (5)	0.0046 (5)
C6	0.0287 (7)	0.0290 (7)	0.0308 (7)	0.0004 (5)	0.0096 (5)	0.0035 (5)
C7	0.0272 (6)	0.0307 (7)	0.0271 (7)	0.0006 (5)	0.0043 (5)	−0.0019 (5)
C8	0.0289 (6)	0.0307 (7)	0.0213 (6)	0.0020 (5)	0.0062 (5)	0.0003 (5)
C9	0.0241 (6)	0.0240 (6)	0.0196 (6)	0.0054 (5)	0.0054 (4)	0.0004 (5)
C10	0.0259 (6)	0.0244 (6)	0.0187 (6)	0.0049 (5)	0.0064 (5)	0.0013 (5)
C12	0.0290 (6)	0.0251 (6)	0.0194 (6)	0.0003 (5)	0.0057 (5)	0.0015 (5)
C13	0.0258 (6)	0.0242 (6)	0.0226 (6)	0.0034 (5)	0.0059 (5)	−0.0003 (5)
C15	0.0443 (8)	0.0281 (7)	0.0214 (6)	−0.0076 (6)	0.0076 (5)	−0.0043 (5)
C16	0.0352 (7)	0.0324 (7)	0.0232 (6)	−0.0058 (6)	0.0075 (5)	−0.0017 (5)
C18	0.0385 (7)	0.0309 (7)	0.0264 (6)	−0.0098 (6)	0.0086 (5)	−0.0031 (5)
C19	0.0279 (7)	0.0324 (7)	0.0283 (7)	−0.0050 (5)	0.0081 (5)	−0.0016 (5)

Geometric parameters (Å, º)

O17—C16	1.4230 (16)	C6—H6	0.9500
O17—C18	1.4294 (16)	C7—C8	1.3693 (18)
O11—C2	1.3740 (15)	C7—H7	0.9500
O11—C12	1.4170 (14)	C8—C9	1.4183 (18)
O13—C13	1.2242 (15)	C8—H8	0.9500
N14—C13	1.3534 (16)	C9—C10	1.4237 (17)
N14—C15	1.4628 (16)	C12—C13	1.5207 (17)
N14—C19	1.4638 (16)	C12—H121	0.9900
C1—C2	1.3719 (17)	C12—H122	0.9900
C1—C9	1.4211 (17)	C15—C16	1.5118 (19)
C1—H1	0.9500	C15—H151	0.9900
C2—C3	1.4198 (17)	C15—H152	0.9900
C3—C4	1.3606 (18)	C16—H161	0.9900
C3—H3	0.9500	C16—H162	0.9900
C4—C10	1.4211 (17)	C18—C19	1.5121 (19)
C4—H4	0.9500	C18—H181	0.9900
C5—C6	1.3739 (18)	C18—H182	0.9900
C5—C10	1.4122 (18)	C19—H191	0.9900
C5—H5	0.9500	C19—H192	0.9900
C6—C7	1.4086 (18)
C16—O17—C18	110.28 (10)	C4—C10—C9	118.50 (11)
C2—O11—C12	115.98 (9)	O11—C12—C13	107.63 (9)
C13—N14—C15	125.35 (11)	O11—C12—H121	110.2
C13—N14—C19	120.73 (10)	C13—C12—H121	110.2
C15—N14—C19	113.52 (10)	O11—C12—H122	110.2
C2—C1—C9	119.64 (11)	C13—C12—H122	110.2
C2—C1—H1	120.2	H121—C12—H122	108.5
C9—C1—H1	120.2	O13—C13—N14	122.50 (12)
C1—C2—O11	125.24 (11)	O13—C13—C12	121.59 (11)
C1—C2—C3	120.83 (12)	N14—C13—C12	115.90 (10)
O11—C2—C3	113.92 (10)	N14—C15—C16	110.07 (11)
C4—C3—C2	120.23 (11)	N14—C15—H151	109.6
C4—C3—H3	119.9	C16—C15—H151	109.6
C2—C3—H3	119.9	N14—C15—H152	109.6
C3—C4—C10	121.00 (11)	C16—C15—H152	109.6
C3—C4—H4	119.5	H151—C15—H152	108.2
C10—C4—H4	119.5	O17—C16—C15	111.62 (11)
C6—C5—C10	120.36 (12)	O17—C16—H161	109.3
C6—C5—H5	119.8	C15—C16—H161	109.3
C10—C5—H5	119.8	O17—C16—H162	109.3
C5—C6—C7	120.21 (12)	C15—C16—H162	109.3
C5—C6—H6	119.9	H161—C16—H162	108.0
C7—C6—H6	119.9	O17—C18—C19	111.39 (11)
C8—C7—C6	120.66 (12)	O17—C18—H181	109.3
C8—C7—H7	119.7	C19—C18—H181	109.3
C6—C7—H7	119.7	O17—C18—H182	109.3
C7—C8—C9	120.66 (12)	C19—C18—H182	109.3
C7—C8—H8	119.7	H181—C18—H182	108.0
C9—C8—H8	119.7	N14—C19—C18	109.36 (10)
C8—C9—C1	121.73 (11)	N14—C19—H191	109.8
C8—C9—C10	118.48 (12)	C18—C19—H191	109.8
C1—C9—C10	119.79 (11)	N14—C19—H192	109.8
C5—C10—C4	121.88 (11)	C18—C19—H192	109.8
C5—C10—C9	119.62 (11)	H191—C19—H192	108.2
C9—C1—C2—O11	179.52 (10)	C1—C9—C10—C5	179.39 (11)
C9—C1—C2—C3	0.36 (19)	C8—C9—C10—C4	179.43 (11)
C12—O11—C2—C1	−2.29 (17)	C1—C9—C10—C4	−0.53 (17)
C12—O11—C2—C3	176.92 (10)	C2—O11—C12—C13	177.19 (10)
C1—C2—C3—C4	−0.04 (19)	C15—N14—C13—O13	172.73 (12)
O11—C2—C3—C4	−179.29 (11)	C19—N14—C13—O13	0.45 (19)
C2—C3—C4—C10	−0.58 (19)	C15—N14—C13—C12	−8.07 (18)
C10—C5—C6—C7	−0.83 (19)	C19—N14—C13—C12	179.65 (10)
C5—C6—C7—C8	−0.2 (2)	O11—C12—C13—O13	−2.51 (17)
C6—C7—C8—C9	0.79 (19)	O11—C12—C13—N14	178.29 (10)
C7—C8—C9—C1	179.60 (11)	C13—N14—C15—C16	135.57 (13)
C7—C8—C9—C10	−0.35 (18)	C19—N14—C15—C16	−51.66 (15)
C2—C1—C9—C8	179.98 (11)	C18—O17—C16—C15	−59.57 (14)
C2—C1—C9—C10	−0.06 (18)	N14—C15—C16—O17	54.55 (15)
C6—C5—C10—C4	−178.84 (12)	C16—O17—C18—C19	60.55 (14)
C6—C5—C10—C9	1.24 (18)	C13—N14—C19—C18	−134.54 (13)
C3—C4—C10—C5	−179.06 (12)	C15—N14—C19—C18	52.33 (15)
C3—C4—C10—C9	0.86 (18)	O17—C18—C19—N14	−56.08 (15)
C8—C9—C10—C5	−0.65 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O17^i	0.95	2.42	3.3359 (15)	161

Symmetry code: (i) −x+1/2, y−1/2, −z+1/2.

(II) 1-(2-Naphthyloxymethylcarbonyl)-4-methylpiperazine

Crystal data

C17H20N2O2	Dx = 1.268 Mg m^−3
Mr = 284.35	Melting point: 383 K
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 1547 reflections
a = 13.7560 (3) Å	θ = 2.0–25.0°
b = 12.7389 (2) Å	µ = 0.08 mm^−1
c = 8.5031 (2) Å	T = 160 K
V = 1490.05 (5) Å^3	Plate, colourless
Z = 4	0.23 × 0.13 × 0.07 mm
F(000) = 608

Data collection

Nonius KappaCCD diffractometer	1169 reflections with I > 2σ(I)
Radiation source: Nonius FR591 sealed tube generator	Rint = 0.079
Horizontally mounted graphite crystal monochromator	θmax = 25.0°, θmin = 3.0°
Detector resolution: 9 pixels mm^-1	h = −16→16
ω scans with κ offsets	k = −15→15
17668 measured reflections	l = −10→10
1414 independent reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.039	H-atom parameters constrained
wR(F^2) = 0.095	w = 1/[σ^2(Fo^2) + (0.0575P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max < 0.001
1414 reflections	Δρmax = 0.18 e Å^−3
192 parameters	Δρmin = −0.16 e Å^−3
1 restraint	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.014 (3)

Special details

Experimental. Solvent used: EtOH Cooling Device: Oxford Cryosystems Cryostream 700 Crystal mount: glued on a glass fibre Mosaicity (°.): 0.404 (2) Frames collected: 329 Seconds exposure per frame: 60 Degrees rotation per frame: 1.0 Crystal-Detector distance (mm): 28.0

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 (Ų)

	x	y	z	Uiso*/Ueq
O11	0.25055 (15)	0.39224 (13)	0.8553 (2)	0.0350 (5)
O13	0.22566 (14)	0.18626 (13)	0.9209 (2)	0.0380 (5)
N14	0.11364 (16)	0.16057 (17)	0.7278 (3)	0.0320 (6)
N17	−0.06198 (16)	0.05552 (19)	0.6436 (3)	0.0350 (6)
C1	0.3922 (2)	0.3208 (2)	0.7204 (3)	0.0301 (7)
H1	0.3536	0.2762	0.6562	0.036*
C2	0.3491 (2)	0.38717 (19)	0.8255 (3)	0.0294 (7)
C3	0.4050 (2)	0.4571 (2)	0.9184 (3)	0.0351 (7)
H3	0.3738	0.5055	0.9867	0.042*
C4	0.5042 (2)	0.4543 (2)	0.9090 (4)	0.0349 (7)
H4	0.5416	0.4999	0.9734	0.042*
C5	0.6550 (2)	0.3793 (2)	0.7946 (4)	0.0412 (8)
H5	0.6940	0.4220	0.8609	0.049*
C6	0.6981 (2)	0.3127 (2)	0.6894 (4)	0.0481 (9)
H6	0.7670	0.3098	0.6826	0.058*
C7	0.6414 (2)	0.2488 (3)	0.5914 (4)	0.0490 (9)
H7	0.6721	0.2033	0.5181	0.059*
C8	0.5425 (2)	0.2515 (2)	0.6006 (4)	0.0391 (7)
H8	0.5051	0.2074	0.5338	0.047*
C9	0.4944 (2)	0.3188 (2)	0.7080 (3)	0.0303 (6)
C10	0.5521 (2)	0.3847 (2)	0.8052 (4)	0.0343 (7)
C12	0.18678 (19)	0.3337 (2)	0.7559 (4)	0.0337 (7)
H121	0.2116	0.3358	0.6466	0.040*
H122	0.1216	0.3668	0.7567	0.040*
C13	0.17791 (19)	0.2196 (2)	0.8090 (3)	0.0298 (6)
C15	0.0576 (2)	0.1944 (2)	0.5913 (3)	0.0372 (7)
H151	0.0823	0.1590	0.4957	0.045*
H152	0.0649	0.2711	0.5768	0.045*
C16	−0.0486 (2)	0.1676 (2)	0.6151 (4)	0.0369 (7)
H161	−0.0743	0.2078	0.7057	0.044*
H162	−0.0860	0.1884	0.5206	0.044*
C18	−0.0054 (2)	0.0230 (2)	0.7801 (4)	0.0352 (7)
H181	−0.0129	−0.0536	0.7956	0.042*
H182	−0.0308	0.0588	0.8750	0.042*
C19	0.1014 (2)	0.0488 (2)	0.7611 (4)	0.0351 (7)
H191	0.1367	0.0305	0.8587	0.042*
H192	0.1290	0.0069	0.6739	0.042*
C20	−0.1646 (2)	0.0311 (3)	0.6685 (4)	0.0451 (8)
H201	−0.1725	−0.0447	0.6824	0.068*
H202	−0.2024	0.0542	0.5770	0.068*
H203	−0.1879	0.0677	0.7627	0.068*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O11	0.0359 (11)	0.0336 (10)	0.0355 (10)	−0.0012 (9)	−0.0020 (9)	−0.0044 (9)
O13	0.0375 (12)	0.0397 (10)	0.0367 (12)	−0.0002 (9)	−0.0051 (11)	0.0040 (10)
N14	0.0307 (13)	0.0337 (12)	0.0314 (14)	−0.0041 (10)	−0.0018 (12)	0.0044 (10)
N17	0.0275 (13)	0.0400 (13)	0.0374 (14)	−0.0044 (10)	0.0026 (11)	−0.0015 (11)
C1	0.0335 (15)	0.0297 (14)	0.0272 (16)	−0.0040 (12)	−0.0029 (13)	0.0006 (12)
C2	0.0307 (16)	0.0264 (13)	0.0312 (16)	0.0007 (12)	−0.0014 (13)	0.0036 (12)
C3	0.0428 (18)	0.0285 (14)	0.0340 (15)	−0.0016 (12)	0.0000 (15)	−0.0009 (13)
C4	0.0409 (18)	0.0296 (14)	0.0342 (16)	−0.0076 (12)	−0.0044 (15)	0.0016 (13)
C5	0.0368 (17)	0.0337 (15)	0.053 (2)	−0.0035 (13)	−0.0071 (17)	0.0102 (15)
C6	0.0319 (17)	0.0461 (17)	0.066 (2)	0.0075 (15)	0.0012 (18)	0.0067 (17)
C7	0.0450 (19)	0.0457 (18)	0.056 (2)	0.0106 (16)	0.0072 (18)	−0.0012 (16)
C8	0.0397 (18)	0.0375 (15)	0.0402 (16)	0.0030 (13)	−0.0017 (16)	−0.0040 (14)
C9	0.0363 (16)	0.0267 (13)	0.0280 (14)	−0.0004 (12)	−0.0024 (13)	0.0044 (11)
C10	0.0385 (17)	0.0274 (14)	0.0370 (16)	−0.0044 (12)	−0.0058 (15)	0.0061 (13)
C12	0.0294 (15)	0.0363 (15)	0.0354 (16)	−0.0008 (12)	−0.0022 (15)	0.0005 (13)
C13	0.0248 (14)	0.0347 (14)	0.0298 (15)	0.0024 (12)	0.0034 (13)	−0.0020 (12)
C15	0.0381 (17)	0.0424 (17)	0.0311 (16)	−0.0059 (12)	−0.0050 (14)	0.0050 (14)
C16	0.0341 (17)	0.0399 (16)	0.0368 (16)	0.0011 (12)	−0.0041 (15)	0.0032 (14)
C18	0.0361 (16)	0.0325 (14)	0.0371 (17)	−0.0009 (12)	0.0029 (14)	0.0001 (13)
C19	0.0334 (16)	0.0304 (14)	0.0414 (17)	0.0006 (12)	−0.0041 (15)	0.0021 (14)
C20	0.0347 (16)	0.0509 (18)	0.050 (2)	−0.0072 (15)	0.0050 (16)	−0.0074 (15)

Geometric parameters (Å, º)

O11—C2	1.380 (3)	C7—C8	1.363 (4)
O11—C12	1.428 (3)	C7—H7	0.9500
O13—C13	1.232 (3)	C8—C9	1.417 (4)
N14—C13	1.350 (3)	C8—H8	0.9500
N14—C15	1.458 (4)	C9—C10	1.421 (4)
N14—C19	1.461 (3)	C12—C13	1.528 (4)
N17—C18	1.458 (4)	C12—H121	0.9900
N17—C16	1.460 (4)	C12—H122	0.9900
N17—C20	1.461 (4)	C15—C16	1.515 (4)
C1—C2	1.366 (4)	C15—H151	0.9900
C1—C9	1.410 (4)	C15—H152	0.9900
C1—H1	0.9500	C16—H161	0.9900
C2—C3	1.417 (4)	C16—H162	0.9900
C3—C4	1.367 (4)	C18—C19	1.513 (4)
C3—H3	0.9500	C18—H181	0.9900
C4—C10	1.413 (4)	C18—H182	0.9900
C4—H4	0.9500	C19—H191	0.9900
C5—C6	1.368 (4)	C19—H192	0.9900
C5—C10	1.420 (4)	C20—H201	0.9800
C5—H5	0.9500	C20—H202	0.9800
C6—C7	1.402 (5)	C20—H203	0.9800
C6—H6	0.9500
C2—O11—C12	118.1 (2)	O11—C12—H121	109.3
C13—N14—C15	126.0 (2)	C13—C12—H121	109.3
C13—N14—C19	121.2 (2)	O11—C12—H122	109.3
C15—N14—C19	112.4 (2)	C13—C12—H122	109.3
C18—N17—C16	110.0 (2)	H121—C12—H122	107.9
C18—N17—C20	109.9 (2)	O13—C13—N14	123.5 (3)
C16—N17—C20	110.7 (2)	O13—C13—C12	120.9 (2)
C2—C1—C9	119.5 (2)	N14—C13—C12	115.5 (2)
C2—C1—H1	120.2	N14—C15—C16	109.7 (2)
C9—C1—H1	120.2	N14—C15—H151	109.7
C1—C2—O11	125.1 (2)	C16—C15—H151	109.7
C1—C2—C3	121.2 (3)	N14—C15—H152	109.7
O11—C2—C3	113.7 (2)	C16—C15—H152	109.7
C4—C3—C2	119.6 (3)	H151—C15—H152	108.2
C4—C3—H3	120.2	N17—C16—C15	111.4 (2)
C2—C3—H3	120.2	N17—C16—H161	109.4
C3—C4—C10	121.2 (3)	C15—C16—H161	109.4
C3—C4—H4	119.4	N17—C16—H162	109.4
C10—C4—H4	119.4	C15—C16—H162	109.4
C6—C5—C10	120.3 (3)	H161—C16—H162	108.0
C6—C5—H5	119.8	N17—C18—C19	111.8 (2)
C10—C5—H5	119.8	N17—C18—H181	109.3
C5—C6—C7	120.4 (3)	C19—C18—H181	109.3
C5—C6—H6	119.8	N17—C18—H182	109.3
C7—C6—H6	119.8	C19—C18—H182	109.3
C8—C7—C6	120.5 (3)	H181—C18—H182	107.9
C8—C7—H7	119.8	N14—C19—C18	110.2 (2)
C6—C7—H7	119.8	N14—C19—H191	109.6
C7—C8—C9	121.2 (3)	C18—C19—H191	109.6
C7—C8—H8	119.4	N14—C19—H192	109.6
C9—C8—H8	119.4	C18—C19—H192	109.6
C1—C9—C8	121.7 (2)	H191—C19—H192	108.1
C1—C9—C10	120.2 (3)	N17—C20—H201	109.5
C8—C9—C10	118.1 (2)	N17—C20—H202	109.5
C4—C10—C5	122.3 (3)	H201—C20—H202	109.5
C4—C10—C9	118.3 (3)	N17—C20—H203	109.5
C5—C10—C9	119.4 (3)	H201—C20—H203	109.5
O11—C12—C13	111.8 (2)	H202—C20—H203	109.5
C9—C1—C2—O11	−176.1 (2)	C1—C9—C10—C5	178.0 (3)
C9—C1—C2—C3	2.3 (4)	C8—C9—C10—C5	−1.5 (4)
C12—O11—C2—C1	−8.4 (4)	C2—O11—C12—C13	84.0 (3)
C12—O11—C2—C3	173.1 (2)	C15—N14—C13—O13	−177.8 (3)
C1—C2—C3—C4	−3.5 (4)	C19—N14—C13—O13	−4.5 (4)
O11—C2—C3—C4	175.1 (2)	C15—N14—C13—C12	3.7 (4)
C2—C3—C4—C10	1.7 (4)	C19—N14—C13—C12	177.0 (2)
C10—C5—C6—C7	−0.3 (5)	O11—C12—C13—O13	−3.0 (4)
C5—C6—C7—C8	−0.5 (5)	O11—C12—C13—N14	175.6 (2)
C6—C7—C8—C9	0.3 (5)	C13—N14—C15—C16	−130.2 (3)
C2—C1—C9—C8	−179.9 (3)	C19—N14—C15—C16	56.1 (3)
C2—C1—C9—C10	0.7 (4)	C18—N17—C16—C15	57.5 (3)
C7—C8—C9—C1	−178.8 (3)	C20—N17—C16—C15	179.2 (3)
C7—C8—C9—C10	0.7 (4)	N14—C15—C16—N17	−57.0 (3)
C3—C4—C10—C5	−179.2 (3)	C16—N17—C18—C19	−56.6 (3)
C3—C4—C10—C9	1.3 (4)	C20—N17—C18—C19	−178.8 (2)
C6—C5—C10—C4	−178.2 (3)	C13—N14—C19—C18	130.7 (3)
C6—C5—C10—C9	1.3 (4)	C15—N14—C19—C18	−55.2 (3)
C1—C9—C10—C4	−2.5 (4)	N17—C18—C19—N14	55.2 (3)
C8—C9—C10—C4	178.1 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O13^i	0.95	2.55	3.471 (3)	163
C5—H5···O11^ii	0.95	2.49	3.236 (3)	135

Symmetry codes: (i) −x+1/2, y, z−1/2; (ii) x+1/2, −y+1, z.