O—H...O, C—H...O and C—H...π_arene intermolecular interactions in (2S)-2-(1-oxo-1H-2,3-dihydroisoindol-2-yl)pentanoic acid and (2S)-3-methyl-2-(1-oxo-1H-2,3-dihydroisoindol-2-yl)butanoic acid

In the first of the title compounds, (2S)-2-(1-oxo-1H-2,3-di­hydro­isoindol-2-yl)­pentanoic acid, C₁₃H₁₅NO₃, prepared from L-norvaline, a hydrogen-bonded network is formed in the solid state through O—H...O=C, C—H...O=C and C—H...π_arene intermolecular interactions, with shortest O...O, C...O and C...centroid distances of 2.582 (13), 3.231 (11) and 3.466 (3) Å, respectively. In the L-valine derivative, (2S)-3-methyl-2-(1-oxo-1H-2,3-di­hydro­isoindol-2-yl)­butanoic acid, C₁₃H₁₅NO₃, O—H...O=C and C_arene—H...O=C intermolecular interactions generate a cyclic R(9) motif through cooperativity, with shortest O...O and C...O distances of 2.634 (3) and 3.529 (5) Å, respectively. Methyl­ene C—H...O=C_indole interactions complete the hydrogen bonding, with C...O distances ranging from 3.283 (4) to 3.477 (4) Å.

S1. Comment

Phthalimidines (isoindolin-1-ones) often display biological activity as potential antiinflammatory agents and antipsychotics (Mukherjee et al., 2000), and most of the structurally determined systems are either N-substituted or have a hydroxy substituent at the 3-position (McNab et al., 1997; Kundu et al., 1999). Amino acids constitute a fundamental building block in biological compounds and valine derivatives have been utilized in the formation of chiral host lattices (Weigand et al., 1998). The title compounds, (2S)-2-(1-oxo-1H-2,3-dihydroisoindol-2-yl)pentanoic acid, (I) and (2S)-3-methyl-2-(1-oxo-1H-2,3-dihydroisoindol-2-yl)butanoic acid, (II), derived from L-norvaline and L-valine, respectively, form part of a systematic study of hydrogen-bonding interactions in a series of amino acid derivatives (Brady et al., 1998; Dalton et al., 1999; Gallagher & Murphy, 1999; Gallagher et al., 2000). \sch

Compound (I) crystallizes in space group P2₁2₁2₁ with one molecule in the asymmetric unit and a view of (I) with the atomic numbering scheme is given in Fig. 1, with selected dimensions in Table 1. The bond lengths and angles in the heterocyclic ring are similar to those reported previously (McNab et al., 1997; Brady et al., 1998; Gallagher & Murphy, 1999) and are in agreement with expected values (Orpen et al., 1994). The carboxylic acid group exhibits rotational disorder, with site occupancies of 0.55 (4)/0.45 (4) for the major and minor orientations, respectively. The angle between the CO₂ planes is 31 (3)° and the major CO₂ orientation is at an angle of 67 (2)° to the C₄N ring plane, [87.1 (16)° for the minor site]. The angle between the five- and six-membered rings of the isoindole system is 1.37 (17)° and the maximum deviation from planarity for an atom in either ring plane is 0.0084 (16) Å for C9 (C₆ ring), with the carbonyl O3 atom 0.026 (3) Å from the C₄N ring plane. The n-propyl chain adopts two conformations, with site occupancies of 0.519 (11)/0.481 (11); details in the Experimental section.

The hydrogen-bonding in (I) is dominated by O—H···O=C, C—H···O=C and C_arene—H···π_arene intermolecular interactions (Table 2 and Fig. 2). Conventional O—H···O hydrogen bonding is not observed, either between pairs of carboxylic acid groups [graph set R₂²(8); Ferguson et al., 1995] or through interaction of the COOH group with a C—H/C=O pair from an isoindolin-1-one system [compound (III); graph set R₂²(9); Brady et al., 1998]. Carboxylic acid O—H···O=C hydrogen bonds are formed with the heterocyclic ring C=O group O1A/O1B···O3ⁱ = 2.582 (13)/2.640 (12) Å [symmetry code: (i) 1 - x, y - 1/2, 1/2 - z], where B/A are the major/minor carboxylate sites. A C_arene—H···O interaction involving the carboxylic acid C=O moiety as C7—H7···O2Aⁱⁱ/O2Bⁱⁱ, with C···O = 3.231 (11)/3.49 (2) Å [symmetry code: (ii) 1/2 + x, 1/2 - y, 1 - z], generates a chain of C_arene^iv-H···O=C—O—H···O=C_{isoindolin-1-one}ⁱ hydrogen bonds, thus preventing the formation of a cyclic R₂²(9) system [Brady et al., 1998; symmetry code: (iv) ?]. Further association of (I) through C8—H8···Cg1ⁱⁱ interactions [C8···Cg1ⁱⁱ = 3.466 (3) Å, where Cg1 is the C4/C5/C6/C7/C8/C9 ring centroid] and C10_methylene—H10A···O3ⁱⁱⁱ interactions [C···Oⁱⁱⁱ = 3.335 (3) Å], complete the hydrogen-bonding network [symmetry code: (iii) 1 + x, y, z]. The orientation of the isoindole ring defined by C3—N1—C2—C1A is -95.3 (9)°, which is greater than the values of -85.2 (2)° in a related 3-phenylpropanoic acid derivative, (III) (Brady et al., 1998), or -86.6 (2)° in a meta-tyrosine derivative, (IV) (Gallagher & Murphy, 1999), but smaller than the values of -104.5 (3) and -112.29 (14)° in the chiral, (V), and racemic forms, (VI), of related threonine structures (Refs?).

Compound (II) crystallizes in space group P1, with two independent molecules, A and B, in the asymmetric unit, which differ slightly in conformation but retain the same configuration (S) at the chiral centre. A view of the asymmetric unit with the atomic numbering scheme is given in Fig. 3 and selected dimensions are in Table 3. Bond lengths and angles are in accord with anticipated values (Orpen et al., 1994). The r.m.s. deviation for the superposition of the non-H atoms in both molecules is 0.39 Å (Spek, 1998). The angles between the five- and six-membered rings of the isoindole system are 1.0 (2) (A) and 1.7 (2)° (B), and the maximum deviation from planarity for an atom in either indole ring is 0.010 (3) Å for C7A, with the carbonyl O3 atom 0.039 (5) (A) and 0.036 (5) Å (B) from the C₄N ring plane. The angles between the CCO₂ group and the C₄N ring planes are 77.51 (11) and 79.28 (11)° in molecules A and B, respectively. Torsion angle differences are evident from N1—C2—C11—C12: -43.6 (4) (A) and -52.0 (3)° (B) (Table 3). The orientations of the isoindole rings defined by C3—N1—C2—C1 are 57.3 (4) (A) and 60.7 (4)° (B) and these values are opposite to those in structures (I)-(VI), presumably due to steric hindrance of the isopropyl group in (II) compared with the n-propyl group in (I).

The hydrogen bonding in (II) is dominated by O—H···O=C, C—H···O=C and Csp³—H···O intermolecular interactions (Table 4, Fig. 4). Hydrogen-bonded rings with graph set R₂²(9) are formed from the combination of acid O1_A/B—H1···O3_B/A interactions with the heterocyclic ring C=O group [2.642 (3) and 2.634 (3) Å, respectively] and arene C5_B/A—H5···O2_A/B contacts with the carboxylic acid C=O [3.529 (5) and 3.714 (5) Å, respectively]. The R₂²(9) motif is present in a related 3-phenylpropanoic acid system, (III) (Brady et al., 1998). This cooperativity generates a hydrogen-bonded zigzag chain in the direction of the a and b axes. The hydrogen-bonded network is completed with C10—H10···O3 interactions in which all four methylene H atoms, H10A and H10B in A, and H10C and H10D in B, participate. The C5—H5···O2 distances are longer in (II) as compared to (III), although the O···O distances are similar. This C···O difference may be due to the weak intramolecular C13—H13···O2 contacts present both in molecules A and B of (II).

The hydrogen bonding in (I) and (II) is similar in terms of hydrogen-bond numbers and associated distances per molecule, with one O—H···O, two C—H···O and a C—H···π_arene interaction in (I), comparable with the O—H···O and three C—H···O interactions per molecule in (II). The unit cell volumes of 1265.3 in (I) and 584.6 ų in (II) show a difference of 24 ų per molecule [316 in (I) and 292 ų in (II)], which can be accounted for by the carboxylic acid and n-propyl-group disorder in (I). The rotational disorder of the carboxylic acid group is assisted by the looser interactions involving the carboxylate O2 in (I). Examination of (II) and the major conformation of (I) with PLATON (Spek, 1998) showed that there were no solvent accessible voids in either crystal lattice. The hydrogen bonding in (II) can be compared with the two independent molecules which differ slightly in conformation in N,N'-dicyclohexyl-N-(3-pyridinylcarbonyl)urea (Gallagher et al., 1999). The overall crystal structure of (II) may be facilitated through hydrogen-bonded oligomeric units crystallizing from solution to produce the primary [A.·B..]_n hydrogen-bonded chain.

S2. Experimental

The title compounds, (I) and (II), were prepared by the overnight reaction of o-phthalaldehyde with L-norvaline and L-valine, respectively, in refluxing CH₃CN under N₂ (Allin et al., 1996). Filtration of the hot solution and subsequent slow cooling of the filtrate allowed the isolation of large colourless crystals from CH₃CN. Spectroscopic analysis for (I), m.p. 467–468 K (uncorrected): IR (ν_C═O, cm^-1): 1730, 1649 (KBr); ¹H NMR (400 MHz, δ, d₆ DMSO): 0.89 (t, 3H, CH₃), 1.29 (br m, 2H, CH₂), 1.90 (br m, 2H, CH₂), 4.49 (q, 2H, CH₂), 4.77 (m, 1H, CH), 7.48–7.51, 7.69–7.72 (m, 4H, C₆H₄). Spectroscopic analysis for (II), m.p. 436–438 K (uncorrected): IR (ν_C═O cm^-1): 1734, 1647, 1634 (KBr); ¹H NMR (400 MHz, δ, d₆ DMSO): 0.84 (d, 3H, CH₃), 1.02 (d, 3H, CH₃), 2.29 (br m, 1H, CH), 4.53 (m, 2H, CH₂), 4.63 (m, 1H, CH), 7.30–7.37, 7.69–7.72 (m, 4H, C₆H₄).

S3. Refinement

For both compounds, all atoms bound to C were treated as riding, with the SHELXL97 (Sheldrick, 1997) defaults for C—H distances and with U_iso(H) = 1.5U_eq(C) for methyl H atoms and 1.2U_eq(C) for the remainder. For (I), the H atom sites of O—H were located from difference Fourier maps in the penultimate stages of refinement and included at these positions in the calculations, with O—H 1.07 and 0.98 Å, while for (II) the H atom bound to O was located from a difference Fourier map and subsequently treated as a rigid rotating group, with U_iso(H) = 1.5U_eq(O). The absolute structures of (I) and (II) were not reliably determined by our X-ray analysis, but they can be inferred from the known absolute configuration of the L-norvaline and L-valine used in the synthesis of (I) and (II), respectively.

Computing details

For both compounds, data collection: CAD-4-PC Software (Enraf-Nonius, 1992); cell refinement: CAD-4-PC Software; data reduction: NRCVAX96 (Gabe et al., 1989); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: NRCVAX96 and SHELXL97; molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEX (McArdle, 1995) and PLATON (Spek, 1998); software used to prepare material for publication: NRCVAX96, SHELXL97 and PREP8 (Ferguson, 1998).

Figures

	Fig. 1. A view of (I) with the atomic numbering scheme. Atom labels with the suffix A indicate one of the disordered conformations of the carboxylic acid and n-propyl groups. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A view of the intermolecular interactions of (I) with the major conformation only; symmetry codes are as given in Table 2.
	Fig. 3. A view of the two independent molecules in the asymmetric unit of (II) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 4. A view of the intermolecular interactions in (II); symmetry codes are as given in Table 4.

(I) (2S)-2-(1-oxo-1H-2,3-dihydroisoindol-2-yl)pentanoic acid

Crystal data

C13H15NO3	Dx = 1.224 Mg m^−3
Mr = 233.26	Melting point: 467 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.7107 Å
a = 5.9384 (4) Å	Cell parameters from 25 reflections
b = 12.3808 (9) Å	θ = 9.5–19.6°
c = 17.2097 (14) Å	µ = 0.09 mm^−1
V = 1265.29 (16) Å^3	T = 294 K
Z = 4	Block, colourless
F(000) = 496	0.48 × 0.20 × 0.18 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.011
Radiation source: X-ray tube	θmax = 25°, θmin = 2°
Graphite monochromator	h = 0→7
ω/2θ scans	k = −14→14
4433 measured reflections	l = −20→20
1313 independent reflections	3 standard reflections every 120 min
1001 reflections with I > 2σ(I)	intensity decay: <1%

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)] = 0.029	H-atom parameters constrained
wR(F^2) = 0.076	Calculated w = 1/[σ^2(Fo^2) + (0.0451P)^2 + 0.0395P] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
1313 reflections	Δρmax = 0.09 e Å^−3
202 parameters	Δρmin = −0.10 e Å^−3
56 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.047 (5)

Special details

Experimental. The phenyl ring centroid position used in the C—H···CgX (X = 1) distance calculations were obtained using PLATON (Spek, 1998). This is listed as follows: [this was for the original refinement with Friedels unmerged].

[Original calculations] Centroid Cg1: x,y,z 1.00702 (17) 0.38147 (7) 0.45195 (5) Friedels not merged

[Further details in additon to the experimental section - Original refinement]. Molecule (I) crystallized in the orthorhombic system; space group P2₁2₁2₁ from the systematic absences. H atoms were treated as riding atoms (C—H 0.93 to 0.98 Å); the hydroxyl H atom sites were located from a difference map in the penultimate stages of refinement and included at these positions in the structure factor calculations, O—H 1.07 Å, 0.98 Å. A full "Friedel" data set was collected for this structure although the anomalous dispersion terms for O, N and C are small. The absolute structure was not reliably determined [Flack parameter, 2.1 (14)] by our X-ray analysis but can be inferred from the known absolute configuration of the L-norvaline used in the synthesis.

It was evident during the penultimate stage of refinement {when R[F² > 2σ(F²)] was 0.06} that the carboxylic acid and n-propyl groups were disordered over two sites; coordinates for these positions were generated from analysis of the SHELXL97 output files. In subsequent refinement cycles a combination of DFIX and DELU/ISOR controls were used in the SHELXL97 (Sheldrick, 1997) calculations. The relevant part of the SHELXL97 instruction file (with details of the restraints used) is included in the CIF for (I). The atomic positions of the carboxylate and n-propyl groups were refined with anisotropic displacement parameters to final site occupancies of 0.52 (3)/0.48 (3) and 0.522 (9)/0.478 (9), respectively. A view of the disorder has been deposited as Fig. 5.

Molecule (II) crystallized in the triclinic system; space group P1 assumed and confirmed by the analysis. H atoms were treated as riding atoms (C—H 0.93 to 0.98 Å, O—H 0.82 Å). The absolute structure was not determined [Flack parameter, -1.0 (12)] by our X-ray analysis but can be inferred from the known absolute configuration of the L-valine used in the synthesis. A view of the superposition of molecules A, B has been deposited as Fig. 6.

[New refinement - with Friedels merged] The phenyl ring centroid position used in the C—H···CgX (X = 1) distance calculations were obtained using PLATON (Spek, 1998). This is listed as follows: [this was for the new refinement with Friedel pairs merged].

[With Friedel pairs merged] Centroid Cg1: x,y,z 1.0071 (2) 0.38147 (8) 0.45193 (6) Friedels merged

The data were merged in both structures using the MERG 3 command in SHELXL97. In (I), the H atoms were treated as previous with O—H 1.06 Å, 0.98 Å from the new calculations. The atomic positions of the carboxylate and n-propyl groups were refined with anisotropic displacement parameters to final site occupancies of 0.45 (4)/0.55 (4) and 0.52 (1)/0.48 (1), respectively.

The absolute structures were not reliably determined by our X-ray analysis for structures (I) and (II) but can be inferred from the known absolute configuration of the L-norvaline and L-valine used in the synthesis of (I) and (II), respectively.

Geometry. Centroid data for geometry calculations for the L-norvaline derivative (I) ##########################################################################

Centroid Cg(1): x,y,z 1.00702 (17) 0.38147 (7) 0.45195 (5) [Friedel refined]

X—H···Cg [ARU(I)] to Cg(J) [ARU(J)] H.·Cg X—H···Cg C(8)—H(8)···Cg(1) [1555.01] -> Cg(1) [2556.01] 2.74 136

The phenyl ring centroid position used in the C—H···CgX (X = 1) distance calculations were obtained using PLATON (Spek, 1998). This is listed as follows: [this was for the new refinement with Friedel pairs merged].

[With Friedel pairs merged] Centroid Cg1: x,y,z 1.0071 (2) 0.38147 (8) 0.45193 (6) Friedels merged

Mean plane data ex SHELXL97 for (I) ###################################

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

4.7233(0.1424)x - 7.5041(0.3892)y + 0.0230(0.4001)z = 2.7318(0.1100)

* 0.0000 (0.0000) O1A_a * 0.0000 (0.0000) O2A_a * 0.0000 (0.0000) C1A_a -0.3171 (0.0811) C2 0.6997 (0.1163) C11 - 0.4409 (0.1009) N1

Rms deviation of fitted atoms = 0.0000

4.8513(0.0884)x - 4.2288(0.4870)y - 7.9974(0.2750)z = 1.2475(0.1020)

Angle to previous plane (with approximate e.s.d.) = 31 (3)

* 0.0000 (0.0000) O1B_b * 0.0000 (0.0000) O2B_b * 0.0000 (0.0000) C1B_b 0.2058 (0.0825) C2 1.6560 (0.0964) C11 - 0.2760 (0.1096) N1

Rms deviation of fitted atoms = 0.0000

2.8054(0.0054)x + 9.0704(0.0088)y - 8.4327(0.0161)z = 2.4744(0.0112)

Angle to previous plane (with approximate e.s.d.) = 69 (2)

* 0.0032 (0.0015) C4 * 0.0040 (0.0017) C5 * -0.0060 (0.0019) C6 * 0.0009 (0.0019) C7 * 0.0063 (0.0018) C8 * -0.0084 (0.0016) C9 - 0.0373 (0.0041) N1

Rms deviation of fitted atoms = 0.0054

4.7233(0.1424)x - 7.5041(0.3892)y + 0.0230(0.4001)z = 2.7318(0.1100)

Angle to previous plane (with approximate e.s.d.) = 86.1 (16)

* 0.0000 (0.0000) O1A_a * 0.0000 (0.0000) O2A_a * 0.0000 (0.0000) C1A_a -0.3171 (0.0811) C2 0.6997 (0.1163) C11 - 0.4409 (0.1009) N1

Rms deviation of fitted atoms = 0.0000

2.8652(0.0063)x + 8.8669(0.0105)y - 8.6783(0.0168)z = 2.3635(0.0097)

Angle to previous plane (with approximate e.s.d.) = 87.1 (16)

* 0.0051 (0.0014) N1 * -0.0011 (0.0013) C3 * 0.0066 (0.0014) C9 * -0.0037 (0.0014) C4 * -0.0068 (0.0013) C10 - 0.0260 (0.0034) O3 - 1.5718 (0.0132) C1A_a -1.4792 (0.0166) C1B_b -0.0931 (0.0039) C2

Rms deviation of fitted atoms = 0.0051

2.8054(0.0054)x + 9.0704(0.0088)y - 8.4327(0.0161)z = 2.4744(0.0112)

Angle to previous plane (with approximate e.s.d.) = 1.37 (17)

* 0.0032 (0.0015) C4 * 0.0040 (0.0017) C5 * -0.0060 (0.0019) C6 * 0.0009 (0.0019) C7 * 0.0063 (0.0018) C8 * -0.0084 (0.0016) C9 - 0.0373 (0.0041) N1

Rms deviation of fitted atoms = 0.0054

# For site B calculations

* 0.0000 (0.0000) O1B_b * 0.0000 (0.0000) O2B_b * 0.0000 (0.0000) C1B_b 0.2058 (0.0825) C2 1.6560 (0.0964) C11 - 0.2760 (0.1096) N1

Rms deviation of fitted atoms = 0.0000

2.8652(0.0063)x + 8.8669(0.0105)y - 8.6783(0.0168)z = 2.3635(0.0097)

Angle to previous plane (with approximate e.s.d.) = 67 (2)

* 0.0051 (0.0014) N1 * -0.0011 (0.0013) C3 * 0.0066 (0.0014) C9 * -0.0037 (0.0014) C4 * -0.0068 (0.0013) C10 - 0.0260 (0.0034) O3 - 1.5718 (0.0132) C1A_a -1.4792 (0.0166) C1B_b -0.0931 (0.0039) C2

Rms deviation of fitted atoms = 0.0051

Refinement. Details of how the disorder of the carboxylic acid and n-propyl groups were handled. The relevant portion of the SHELXL.ins file is as follows:-

TITL 97–48 for L-norv. derv. with MERGED data [25–2-00] CELL 0.7093 5.9384 12.3808 17.2097 90.00 90.00 90.00 ZERR 4 0.0004 0.0009 0.0014 0.00 0.00 0.00 L A T T -1 SYMM 0.5+X, 0.5-Y, –Z SYMM –X, 0.5+Y, 0.5-Z SYMM 0.5-X, –Y, 0.5+Z SFAC C H N O UNIT 52 60 4 12

# Thermal parameter restraints for the carboxylic acid and n-propyl groups

DELU 0.020 O1A O1B ISOR 0.020 O1A O1B DELU 0.015 O2A O2B ISOR 0.015 O2A O2B DELU 0.005 C13A C13B ISOR 0.005 C13A C13B

# Intermolecular hydrogen-bond calculations for GD1085 cif file

CONF EQIV $1 X, Y, Z EQIV $2 1-X, -1/2+Y, 1/2-Z EQIV $3 1/2+X, 1/2-Y, 1-Z EQIV $4 1+X, Y, Z

HTAB C2 O3_$1 HTAB C10 O2A_$1 HTAB O1A O3_$2 HTAB O1B O3_$2 HTAB C7 O2A_$3 HTAB C7 O2B_$3 HTAB C7 N1_$3 HTAB C7 C9_$3 HTAB C7 C10_$3 HTAB C8 C4_$3 HTAB C8 C5_$3 HTAB C8 C6_$3 HTAB C8 C7_$3 HTAB C8 C8_$3 HTAB C8 C9_$3 HTAB C10 O3_$4

PLAN 5

# Mean plane angle input data, weighting scheme

MPLA 3 O1A O2A C1A C2 C11 N1 MPLA 3 O1B O2B C1B C2 C11 N1 MPLA 6 C4 C5 C6 C7 C8 C9 N1 MPLA 3 O1A O2A C1A C2 C11 N1 MPLA 5 N1 C3 C9 C4 C10 O3 C1A C1B C2 MPLA 6 C4 C5 C6 C7 C8 C9 N1 MPLA 3 O1B O2B C1B C2 C11 N1 MPLA 5 N1 C3 C9 C4 C10 O3 C1A C1B C2 WGHT 0.045100 0.039500 EXTI 0.047498

# Fvar for scale and major site occupancies of the COOH and n-propyl groups

FVAR 1.47971 0.44645 0.51941 PART 1 O1A 4 0.63733 0.03767 0.17740 21.00000 0.10213 0.06179 = 0.04501 - 0.00200 0.00547 - 0.02736

etc ···..

HKLF 4 END

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
O3	0.5760 (3)	0.36156 (13)	0.29023 (11)	0.0706 (6)
N1	0.8913 (3)	0.25660 (14)	0.28351 (12)	0.0558 (5)
C2	0.8260 (4)	0.19881 (19)	0.21423 (14)	0.0580 (6)
C3	0.7597 (4)	0.33137 (16)	0.31716 (14)	0.0529 (6)
C4	0.8708 (4)	0.36562 (17)	0.38915 (13)	0.0541 (6)
C5	0.8034 (5)	0.43876 (17)	0.44531 (15)	0.0698 (7)
C6	0.9429 (6)	0.4532 (2)	0.50842 (17)	0.0821 (9)
C7	1.1440 (6)	0.3973 (2)	0.51439 (17)	0.0835 (9)
C8	1.2111 (5)	0.3252 (2)	0.45849 (16)	0.0717 (8)
C9	1.0705 (4)	0.30875 (19)	0.39579 (14)	0.0564 (6)
C10	1.0943 (4)	0.23375 (19)	0.32858 (15)	0.0624 (7)
C11	1.0185 (6)	0.1843 (2)	0.15734 (17)	0.0838 (10)
O1A	0.637 (3)	0.0377 (14)	0.1774 (5)	0.070 (3)	0.45 (4)
C1A	0.718 (4)	0.0886 (10)	0.2364 (10)	0.042 (5)	0.45 (4)
O2A	0.680 (4)	0.0648 (16)	0.3003 (6)	0.099 (5)	0.45 (4)
O1B	0.598 (3)	0.0530 (11)	0.1790 (7)	0.095 (4)	0.55 (4)
C1B	0.726 (4)	0.0946 (13)	0.2344 (11)	0.082 (7)	0.55 (4)
O2B	0.776 (4)	0.0408 (10)	0.2929 (10)	0.107 (4)	0.55 (4)
C12A	1.148 (2)	0.2795 (11)	0.1298 (6)	0.088 (4)	0.519 (11)
C13A	0.998 (2)	0.3488 (8)	0.0780 (7)	0.177 (6)	0.519 (11)
C12B	1.065 (3)	0.3037 (14)	0.1234 (11)	0.124 (6)	0.481 (11)
C13B	1.250 (2)	0.2894 (9)	0.0624 (6)	0.163 (5)	0.481 (11)
H2	0.7099	0.2418	0.1881	0.070*
H5	0.6690	0.4768	0.4406	0.084*
H6	0.9014	0.5011	0.5475	0.098*
H7	1.2359	0.4089	0.5573	0.100*
H8	1.3472	0.2885	0.4627	0.086*
H10A	1.2293	0.2494	0.2989	0.075*
H10B	1.0982	0.1590	0.3455	0.075*
H11A	1.1252	0.1348	0.1809	0.101*
H11B	0.9581	0.1484	0.1118	0.101*
H1A	0.5683	−0.0404	0.1853	0.084*	0.45 (4)
H1B	0.5563	−0.0136	0.2058	0.114*	0.55 (4)
H12A	1.2789	0.2558	0.1008	0.105*	0.519 (11)
H12B	1.1992	0.3215	0.1739	0.105*	0.519 (11)
H13A	1.0759	0.4139	0.0642	0.265*	0.519 (11)
H13B	0.8620	0.3669	0.1056	0.265*	0.519 (11)
H13C	0.9601	0.3094	0.0318	0.265*	0.519 (11)
H12C	0.9293	0.3330	0.1000	0.149*	0.481 (11)
H12D	1.1141	0.3520	0.1644	0.149*	0.481 (11)
H13D	1.2823	0.3579	0.0388	0.244*	0.481 (11)
H13E	1.1997	0.2396	0.0233	0.244*	0.481 (11)
H13F	1.3832	0.2618	0.0868	0.244*	0.481 (11)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O3	0.0592 (11)	0.0578 (9)	0.0948 (12)	0.0123 (9)	−0.0146 (11)	−0.0086 (9)
N1	0.0516 (12)	0.0472 (9)	0.0687 (11)	0.0027 (10)	−0.0042 (10)	−0.0074 (9)
C2	0.0648 (16)	0.0442 (12)	0.0649 (15)	−0.0025 (12)	−0.0047 (13)	−0.0035 (12)
C3	0.0491 (14)	0.0371 (11)	0.0725 (15)	−0.0018 (10)	−0.0009 (13)	0.0010 (10)
C4	0.0563 (15)	0.0418 (10)	0.0641 (13)	−0.0070 (12)	−0.0020 (13)	0.0018 (11)
C5	0.0811 (19)	0.0496 (13)	0.0786 (17)	−0.0004 (13)	0.0040 (17)	−0.0069 (13)
C6	0.113 (3)	0.0621 (15)	0.0710 (18)	−0.014 (2)	0.000 (2)	−0.0095 (14)
C7	0.101 (2)	0.0780 (18)	0.0719 (17)	−0.021 (2)	−0.0204 (18)	0.0064 (16)
C8	0.0667 (18)	0.0688 (16)	0.0795 (17)	−0.0086 (15)	−0.0113 (15)	0.0067 (14)
C9	0.0513 (15)	0.0525 (12)	0.0654 (14)	−0.0075 (13)	−0.0028 (13)	0.0039 (12)
C10	0.0478 (14)	0.0597 (14)	0.0796 (15)	0.0027 (13)	−0.0035 (14)	−0.0035 (12)
C11	0.103 (2)	0.0722 (18)	0.0757 (18)	−0.0236 (18)	0.0229 (18)	−0.0136 (15)
O1A	0.102 (7)	0.062 (5)	0.045 (5)	−0.027 (5)	0.005 (5)	−0.002 (3)
C1A	0.049 (9)	0.023 (5)	0.055 (10)	−0.013 (6)	−0.006 (7)	0.014 (5)
O2A	0.143 (10)	0.105 (7)	0.048 (5)	−0.056 (7)	0.005 (5)	0.000 (4)
O1B	0.098 (5)	0.054 (4)	0.132 (8)	−0.021 (4)	−0.057 (6)	0.012 (3)
C1B	0.083 (12)	0.093 (12)	0.071 (11)	0.004 (10)	0.003 (9)	−0.020 (8)
O2B	0.140 (9)	0.074 (4)	0.109 (6)	−0.041 (5)	−0.047 (6)	0.028 (4)
C12A	0.088 (7)	0.104 (8)	0.071 (5)	−0.027 (5)	0.021 (4)	−0.010 (5)
C13A	0.185 (10)	0.147 (7)	0.197 (9)	−0.059 (7)	−0.046 (7)	0.091 (7)
C12B	0.140 (14)	0.085 (8)	0.148 (11)	−0.041 (10)	0.031 (10)	0.021 (7)
C13B	0.185 (9)	0.162 (7)	0.141 (7)	−0.052 (7)	0.058 (7)	0.021 (6)

Geometric parameters (Å, º)

O3—C3	1.243 (3)	C9—C10	1.490 (3)
N1—C3	1.343 (3)	C11—C12A	1.484 (14)
N1—C2	1.444 (3)	C11—C12B	1.613 (16)
N1—C10	1.461 (3)	O1A—C1A	1.288 (16)
C2—C11	1.516 (4)	C1A—O2A	1.160 (17)
C3—C4	1.467 (3)	C1A—C2	1.555 (11)
C4—C5	1.384 (3)	O1B—C1B	1.322 (18)
C4—C9	1.384 (4)	C1B—O2B	1.242 (17)
C5—C6	1.378 (4)	C1B—C2	1.463 (15)
C6—C7	1.384 (4)	C12A—C13A	1.526 (10)
C7—C8	1.372 (4)	C12B—C13B	1.530 (10)
C8—C9	1.379 (3)
C2—N1—C3	122.8 (2)	C8—C9—C10	129.9 (2)
C2—N1—C10	124.3 (2)	N1—C10—C9	102.30 (19)
C3—N1—C10	112.6 (2)	C2—C11—C12A	120.1 (5)
N1—C2—C11	112.9 (2)	C2—C11—C12B	104.7 (5)
O3—C3—N1	123.9 (2)	O1A—C1A—O2A	123.3 (13)
O3—C3—C4	128.5 (2)	O1A—C1A—C2	112.9 (12)
N1—C3—C4	107.5 (2)	O2A—C1A—C2	122.5 (14)
C3—C4—C5	130.5 (2)	N1—C2—C1A	110.1 (7)
C3—C4—C9	108.0 (2)	C1A—C2—C11	111.4 (8)
C5—C4—C9	121.6 (2)	C11—C12A—C13A	109.3 (9)
C4—C5—C6	117.5 (3)	O1B—C1B—O2B	120.8 (14)
C5—C6—C7	120.8 (3)	O1B—C1B—C2	113.9 (14)
C6—C7—C8	121.6 (3)	O2B—C1B—C2	124.7 (16)
C7—C8—C9	118.0 (3)	N1—C2—C1B	110.5 (8)
C4—C9—C8	120.5 (2)	C1B—C2—C11	110.8 (9)
C4—C9—C10	109.5 (2)	C11—C12B—C13B	105.4 (10)
C3—N1—C2—C11	139.4 (2)	C2—N1—C10—C9	−175.6 (2)
C10—N1—C2—C11	−46.6 (3)	C8—C9—C10—N1	−179.6 (2)
C2—N1—C3—O3	−3.6 (3)	C4—C9—C10—N1	1.2 (2)
C10—N1—C3—O3	−178.2 (2)	O2B—C1B—C2—N1	−30 (3)
C2—N1—C3—C4	175.2 (2)	O1B—C1B—C2—N1	159.2 (15)
C10—N1—C3—C4	0.6 (2)	O2B—C1B—C2—C11	96 (2)
O3—C3—C4—C5	0.1 (4)	O1B—C1B—C2—C11	−75 (2)
N1—C3—C4—C5	−178.6 (2)	O2A—C1A—C2—N1	7 (3)
O3—C3—C4—C9	178.9 (2)	O1A—C1A—C2—N1	174.0 (15)
N1—C3—C4—C9	0.2 (2)	O2A—C1A—C2—C11	133 (2)
C9—C4—C5—C6	0.1 (3)	O1A—C1A—C2—C11	−59.9 (18)
C3—C4—C5—C6	178.8 (2)	N1—C2—C11—C12A	−54.3 (6)
C4—C5—C6—C7	0.8 (4)	C1A—C2—C11—C12A	−178.8 (9)
C5—C6—C7—C8	−0.6 (4)	N1—C2—C11—C12B	−70.3 (9)
C6—C7—C8—C9	−0.6 (4)	C1B—C2—C11—C12B	165.0 (13)
C7—C8—C9—C4	1.5 (4)	C2—C11—C12A—C13A	−68.7 (11)
C7—C8—C9—C10	−177.6 (2)	C12B—C11—C12A—C13A	−21 (2)
C5—C4—C9—C8	−1.3 (3)	C2—C11—C12B—C13B	−176.9 (10)
C3—C4—C9—C8	179.8 (2)	C3—N1—C2—C1A	−95.3 (9)
C5—C4—C9—C10	178.0 (2)	C10—N1—C2—C1A	78.6 (9)
C3—C4—C9—C10	−0.9 (2)	C3—N1—C2—C1B	−95.8 (11)
C3—N1—C10—C9	−1.1 (2)	C10—N1—C2—C1B	78.1 (11)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1A—H1A···O3^i	1.06	1.54	2.582 (13)	165
O1B—H1B···O3^i	0.98	1.74	2.640 (12)	152
C7—H7···O2A^ii	0.93	2.49	3.231 (11)	136
C7—H7···O2B^ii	0.93	2.66	3.49 (2)	149
C8—H8···Cg1^ii	0.93	2.74	3.466 (3)	136
C10—H10A···O3^iii	0.97	2.49	3.335 (3)	146

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

(II) (2S)-3-methyl-2-(1-oxo-1H-2,3-dihydroisoindol-2-yl)butanoic acid

Crystal data

C13H15NO3	F(000) = 248
Mr = 233.26	CELL REDUCTION USING CREDUC - NRCVAX CELL REDUCTION PROGRAM Input Cell: 5.877 9.904 10.482 103.332 99.759 89.792 Lattice Type P The Shortest Non-coplanar Translations 5.877 9.904 10.482 76.668 80.241 89.792 The Old-to-New Cell Matrix -1.0 0.0 0.0 0.0 -1.0 0.0 0.0 0.0 1.0 Possible 2-fold Axes: Rows Products Kind Direct Reciprocal Dot Vector of Axis NONE OBSERVED Metrically Triclinic P Max Delta 0.00 a -1.0 0.0 0.0 5.8767 Alpha 76.668 a* -1.00 0.00 0.00 0.0 -1.0 0.0 9.9036 Beta 80.241 b* 0.00 -1.00 0.00 c 0.0 0.0 1.0 10.4818 Gamma 89.792 c* 0.00 0.00 1.00 *** No Obvious Extra Crystallographic Symmetry was Detected *** Solution and subsequent refinement were undertaken in space group P1
Triclinic, P1	Dx = 1.325 Mg m^−3
a = 5.8767 (6) Å	Melting point: 437 K
b = 9.9036 (13) Å	Mo Kα radiation, λ = 0.7107 Å
c = 10.4818 (15) Å	Cell parameters from 25 reflections
α = 103.332 (13)°	θ = 9.5–19.9°
β = 99.759 (11)°	µ = 0.09 mm^−1
γ = 89.792 (11)°	T = 294 K
V = 584.62 (13) Å^3	Plate, colourless
Z = 2	0.45 × 0.35 × 0.14 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	Rint = 0.014
Radiation source: X-ray tube	θmax = 27°, θmin = 2°
Graphite monochromator	h = −7→7
ω/2θ scans	k = −12→12
5259 measured reflections	l = −13→13
2575 independent reflections	3 standard reflections every 120 min
2059 reflections with I > 2σ(I)	intensity decay: <1%

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)] = 0.048	H-atom parameters constrained
wR(F^2) = 0.112	Calculated w = 1/[σ^2(Fo^2) + (0.0711P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.02	(Δ/σ)max < 0.001
2575 reflections	Δρmax = 0.36 e Å^−3
310 parameters	Δρmin = −0.31 e Å^−3
3 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.022 (8)

Special details

Experimental. [original refinement with Friedels] Molecule (II) crystallized in the triclinic system (space group P1 assumed and confirmed by the analysis). H atoms were treated as riding atoms (C—H 0.93 to 0.98 Å, O—H 0.82 Å). The absolute structure was not determined [Flack parameter, -1.0 (12)] by our X-ray analysis but can be inferred from the known absolute configuration of the L-valine used in the synthesis.

[New refinement with Friedel pairs merged] Molecule (II) crystallized in the triclinic system (space group P1 assumed and confirmed by the analysis). H atoms were treated as riding atoms (C—H 0.93 to 0.98 Å, O—H 0.82 Å). The absolute structure was not determined [Flack parameter, 0.6 (14)] by our X-ray analysis but can be inferred from the known absolute configuration of the L-valine used in the synthesis. Only small changes in the bond lengths and angles are observed on merging the data.

Geometry. Fitting routine used for comparing molecules A and B in (II) ex-PLATON ###################################################################### Molfit with Quaternion Transformation Method (see A. L. Mackay (1984). Acta Cryst. A40, 165–166) ======================================================================

Determinant = 0.215E+04, THETA = 175.8 Direction Cosines with Orth. Cell: L,M,N = -0.010036 - 0.999832 0.015302 Components in crystal system -0.006281 - 1.000000 0.015144

Transf. Orthog. Coord. Mol1 Orth. Coord. Mol2 with Resp. to CG Dist(A) —————————————————————————- O(1 A) -1.444 2.201 - 0.868 O(1B) -1.444 2.232 - 0.875 0.032 O(2 A) -2.461 1.118 - 2.517 O(2B) -2.381 1.236 - 2.611 0.171 O(3 A) -1.670 - 0.996 0.152 O(3B) -1.678 - 0.985 0.109 0.045 N(1 A) 0.196 0.143 - 0.485 N(1B) 0.184 0.199 - 0.468 0.060 C(1 A) -1.519 1.272 - 1.798 C(1B) -1.468 1.337 - 1.834 0.090 C(2 A) -0.220 0.450 - 1.852 C(2B) -0.197 0.495 - 1.842 0.052 C(3 A) -0.572 - 0.504 0.407 C(3B) -0.586 - 0.485 0.402 0.024 C(4 A) 0.153 - 0.459 1.689 C(4B) 0.110 - 0.478 1.689 0.047 C(5 A) -0.206 - 0.991 2.919 C(5B) -0.232 - 1.090 2.894 0.105 C(6 A) 0.655 - 0.777 3.975 C(6B) 0.644 - 0.938 3.945 0.165 C(7 A) 1.813 - 0.067 3.814 C(7B) 1.811 - 0.212 3.815 0.145 C(8 A) 2.190 0.442 2.576 C(8B) 2.146 0.387 2.617 0.082 C(9 A) 1.318 0.227 1.513 C(9B) 1.293 0.239 1.551 0.047 C(10 A) 1.424 0.669 0.087 C(10B) 1.402 0.729 0.149 0.089 C(11 A) -0.276 - 0.768 - 2.788 C(11B) -0.220 - 0.756 - 2.736 0.077 C(12 A) 0.957 - 1.650 - 2.589 C(12B) 1.093 - 1.506 - 2.614 0.199 C(13 A) -0.337 - 0.309 - 4.234 C(13B) -0.477 - 0.403 - 4.192 0.173

RMS = 0.39 Å for fitting molecules A and B using PLATON.

Mean plane data for (II) ex SHELXL97 ####################################

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

-2.4773(0.0097)x + 6.6240(0.0130)y + 5.2668(0.0167)z = 2.5536(0.0016)

* 0.0022 (0.0009) O1A * 0.0028 (0.0011) O2A * -0.0070 (0.0027) C1A * 0.0019 (0.0007) C2A -0.1831 (0.0059) C11A -0.9349 (0.0050) N1A

Rms deviation of fitted atoms = 0.0041

-3.0037(0.0081)x - 8.2819(0.0088)y + 4.9909(0.0155)z = 1.1109(0.0068)

Angle to previous plane (with approximate e.s.d.) = 77.41 (11)

* -0.0074 (0.0023) C4A * 0.0047 (0.0026) C5A * 0.0041 (0.0030) C6A * -0.0101 (0.0032) C7A * 0.0073 (0.0030) C8A * 0.0014 (0.0024) C9A -0.0321 (0.0059) N1A

Rms deviation of fitted atoms = 0.0065

-2.9403(0.0081)x - 8.3119(0.0091)y + 5.1156(0.0140)z = 1.0480(0.0045)

Angle to previous plane (with approximate e.s.d.) = 1.0 (2)

* 0.0040 (0.0019) N1A * -0.0047 (0.0017) C3A * 0.0036 (0.0018) C4A * -0.0014 (0.0020) C9A * -0.0015 (0.0018) C10A -0.0388 (0.0045) O3A -1.4593 (0.0056) C1A -0.1362 (0.0051) C2A 1.0920 (0.0060) C11A

Rms deviation of fitted atoms = 0.0033

-2.9724(0.0242)x + 7.9991(0.0185)y - 4.0466(0.0531)z = 0.1185(0.0236)

Angle to previous plane (with approximate e.s.d.) = 60.6 (2)

* 0.0000 (0.0000) C11A * 0.0000 (0.0000) C12A * 0.0000 (0.0000) C13A 1.2055 (0.0148) C1A 1.2306 (0.0088) C2A

Rms deviation of fitted atoms = 0.0000

-2.5787(0.0094)x - 6.5154(0.0128)y + 8.5271(0.0118)z = 0.7135(0.0067)

Angle to previous plane (with approximate e.s.d.) = 60.5 (3)

* -0.0023 (0.0008) O1B * -0.0029 (0.0010) O2B * 0.0073 (0.0026) C1B * -0.0021 (0.0007) C2B 0.2806 (0.0056) C11B 0.8685 (0.0047) N1B

Rms deviation of fitted atoms = 0.0042

2.8301(0.0078)x - 8.2103(0.0086)y - 1.6565(0.0163)z = 5.0700(0.0071)

Angle to previous plane (with approximate e.s.d.) = 80.64 (11)

* -0.0038 (0.0024) C4B * -0.0008 (0.0027) C5B * 0.0022 (0.0030) C6B * 0.0009 (0.0030) C7B * -0.0055 (0.0028) C8B * 0.0069 (0.0025) C9B 0.0685 (0.0059) N1B

Rms deviation of fitted atoms = 0.0041

2.8257(0.0087)x - 8.3020(0.0095)y - 1.3535(0.0171)z = 5.1606(0.0038)

Angle to previous plane (with approximate e.s.d.) = 1.7 (2)

* 0.0088 (0.0020) N1B * -0.0073 (0.0018) C3B * 0.0028 (0.0019) C4B * 0.0021 (0.0021) C9B * -0.0063 (0.0020) C10B -0.0360 (0.0048) O3B -1.4005 (0.0059) C1B -0.0753 (0.0054) C2B 1.1869 (0.0063) C11B

Rms deviation of fitted atoms = 0.0061

-2.8288(0.0199)x - 8.6084(0.0152)y + 1.6846(0.0501)z = 3.9647(0.0267)

Angle to previous plane (with approximate e.s.d.) = 58.07 (18)

* 0.0000 (0.0000) C11B * 0.0000 (0.0000) C12B * 0.0000 (0.0000) C13B -1.3300 (0.0131) C1B -1.2091 (0.0081) C2B

Rms deviation of fitted atoms = 0.0000

-2.5787(0.0094)x - 6.5154(0.0128)y + 8.5271(0.0118)z = 0.7135(0.0067)

Angle to previous plane (with approximate e.s.d.) = 45.3 (3)

* -0.0023 (0.0008) O1B * -0.0029 (0.0010) O2B * 0.0073 (0.0026) C1B * -0.0021 (0.0007) C2B 0.2806 (0.0056) C11B 0.8685 (0.0047) N1B

Rms deviation of fitted atoms = 0.0042

-2.4773(0.0097)x + 6.6240(0.0130)y + 5.2668(0.0167)z = 2.5536(0.0016)

Angle to previous plane (with approximate e.s.d.) = 83.12 (12)

* 0.0022 (0.0009) O1A * 0.0028 (0.0011) O2A * -0.0070 (0.0027) C1A * 0.0019 (0.0007) C2A -0.1831 (0.0059) C11A -0.9349 (0.0050) N1A

Rms deviation of fitted atoms = 0.0041

-3.0037(0.0081)x - 8.2819(0.0088)y + 4.9909(0.0155)z = 1.1109(0.0068)

Angle to previous plane (with approximate e.s.d.) = 77.41 (11)

* -0.0074 (0.0023) C4A * 0.0047 (0.0026) C5A * 0.0041 (0.0030) C6A * -0.0101 (0.0032) C7A * 0.0073 (0.0030) C8A * 0.0014 (0.0024) C9A -0.0321 (0.0059) N1A

Rms deviation of fitted atoms = 0.0065

-2.5787(0.0094)x - 6.5154(0.0128)y + 8.5271(0.0118)z = 0.7135(0.0067)

Angle to previous plane (with approximate e.s.d.) = 26.0 (2)

* -0.0023 (0.0008) O1B * -0.0029 (0.0010) O2B * 0.0073 (0.0026) C1B * -0.0021 (0.0007) C2B 0.2806 (0.0056) C11B 0.8685 (0.0047) N1B

Rms deviation of fitted atoms = 0.0042

2.8301(0.0078)x - 8.2103(0.0086)y - 1.6565(0.0163)z = 5.0700(0.0071)

Angle to previous plane (with approximate e.s.d.) = 80.64 (11)

* -0.0038 (0.0024) C4B * -0.0008 (0.0027) C5B * 0.0022 (0.0030) C6B * 0.0009 (0.0030) C7B * -0.0055 (0.0028) C8B * 0.0069 (0.0025) C9B 0.0685 (0.0059) N1B

Rms deviation of fitted atoms = 0.0041

-2.4773(0.0097)x + 6.6240(0.0130)y + 5.2668(0.0167)z = 2.5536(0.0016)

Angle to previous plane (with approximate e.s.d.) = 21.5 (2)

* 0.0022 (0.0009) O1A * 0.0028 (0.0011) O2A * -0.0070 (0.0027) C1A * 0.0019 (0.0007) C2A -0.1831 (0.0059) C11A -0.9349 (0.0050) N1A

Rms deviation of fitted atoms = 0.0041

-2.4773(0.0097)x + 6.6240(0.0130)y + 5.2668(0.0167)z = 2.5536(0.0016)

Angle to previous plane (with approximate e.s.d.) = 0.0 (3)

* 0.0022 (0.0009) O1A * 0.0028 (0.0011) O2A * -0.0070 (0.0027) C1A * 0.0019 (0.0007) C2A -0.1831 (0.0059) C11A -0.9349 (0.0050) N1A

Rms deviation of fitted atoms = 0.0041

-2.9403(0.0081)x - 8.3119(0.0091)y + 5.1156(0.0140)z = 1.0480(0.0045)

Angle to previous plane (with approximate e.s.d.) = 77.51 (11)

* 0.0040 (0.0019) N1A * -0.0047 (0.0017) C3A * 0.0036 (0.0018) C4A * -0.0014 (0.0020) C9A * -0.0015 (0.0018) C10A -0.0388 (0.0045) O3A -1.4593 (0.0056) C1A -0.1362 (0.0051) C2A 1.0920 (0.0060) C11A

Rms deviation of fitted atoms = 0.0033

-2.5787(0.0094)x - 6.5154(0.0128)y + 8.5271(0.0118)z = 0.7135(0.0067)

Angle to previous plane (with approximate e.s.d.) = 25.3 (2)

* -0.0023 (0.0008) O1B * -0.0029 (0.0010) O2B * 0.0073 (0.0026) C1B * -0.0021 (0.0007) C2B 0.2806 (0.0056) C11B 0.8685 (0.0047) N1B

Rms deviation of fitted atoms = 0.0042

2.8257(0.0087)x - 8.3020(0.0095)y - 1.3535(0.0171)z = 5.1606(0.0038)

Angle to previous plane (with approximate e.s.d.) = 79.28 (11)

* 0.0088 (0.0020) N1B * -0.0073 (0.0018) C3B * 0.0028 (0.0019) C4B * 0.0021 (0.0021) C9B * -0.0063 (0.0020) C10B -0.0360 (0.0048) O3B -1.4005 (0.0059) C1B -0.0753 (0.0054) C2B 1.1869 (0.0063) C11B

Rms deviation of fitted atoms = 0.0061

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

	x	y	z	Uiso*/Ueq
O1A	−0.1617 (4)	0.2679 (3)	0.0722 (3)	0.0452 (6)
O2A	0.0393 (4)	0.2045 (3)	0.2467 (3)	0.0575 (7)
O3A	−0.1475 (4)	−0.0801 (2)	−0.0177 (2)	0.0389 (5)
N1A	−0.4545 (4)	0.0517 (3)	0.0285 (2)	0.0320 (6)
C1A	−0.1346 (5)	0.2005 (3)	0.1680 (3)	0.0352 (7)
C2A	−0.3586 (5)	0.1195 (3)	0.1662 (3)	0.0333 (7)
C3A	−0.3395 (5)	−0.0377 (3)	−0.0525 (3)	0.0300 (6)
C4A	−0.4863 (5)	−0.0683 (3)	−0.1850 (3)	0.0348 (7)
C5A	−0.4475 (6)	−0.1551 (4)	−0.3031 (3)	0.0431 (8)
C6A	−0.6128 (8)	−0.1623 (5)	−0.4148 (4)	0.0575 (11)
C7A	−0.8079 (8)	−0.0867 (5)	−0.4096 (4)	0.0655 (12)
C8A	−0.8502 (7)	−0.0019 (4)	−0.2907 (4)	0.0546 (10)
C9A	−0.6822 (5)	0.0056 (3)	−0.1783 (3)	0.0376 (7)
C10A	−0.6750 (6)	0.0889 (4)	−0.0389 (3)	0.0380 (7)
C11A	−0.3356 (6)	0.0232 (4)	0.2631 (3)	0.0400 (8)
C12A	−0.5522 (7)	−0.0705 (4)	0.2369 (4)	0.0549 (10)
C13A	−0.2990 (9)	0.1089 (5)	0.4056 (4)	0.0688 (13)
O1B	0.1621 (4)	−0.2680 (3)	−0.0723 (3)	0.0466 (6)
O2B	−0.0487 (5)	−0.4107 (3)	−0.2452 (3)	0.0582 (7)
O3B	0.1539 (3)	−0.5691 (3)	0.0256 (2)	0.0386 (5)
N1B	0.4526 (4)	−0.4634 (3)	−0.0317 (2)	0.0299 (6)
C1B	0.1296 (5)	−0.3815 (3)	−0.1678 (3)	0.0347 (7)
C2B	0.3467 (5)	−0.4670 (3)	−0.1686 (3)	0.0314 (6)
C3B	0.3478 (5)	−0.5113 (3)	0.0548 (3)	0.0288 (6)
C4B	0.5053 (5)	−0.4798 (3)	0.1830 (3)	0.0314 (6)
C5B	0.4829 (6)	−0.5120 (4)	0.3027 (4)	0.0435 (8)
C6B	0.6637 (7)	−0.4712 (4)	0.4076 (4)	0.0502 (9)
C7B	0.8584 (7)	−0.4013 (5)	0.3946 (4)	0.0555 (10)
C8B	0.8788 (6)	−0.3695 (4)	0.2753 (4)	0.0484 (9)
C9B	0.7017 (5)	−0.4106 (3)	0.1691 (3)	0.0350 (7)
C10B	0.6777 (5)	−0.3950 (4)	0.0296 (3)	0.0378 (7)
C11B	0.3163 (6)	−0.6149 (4)	−0.2576 (3)	0.0390 (7)
C12B	0.5440 (7)	−0.6873 (4)	−0.2454 (4)	0.0514 (9)
C13B	0.2288 (8)	−0.6145 (6)	−0.4026 (4)	0.0629 (11)
H1A	−0.0348	0.2877	0.0575	0.068*
H2A	−0.4689	0.1893	0.1959	0.040*
H5A	−0.3149	−0.2063	−0.3067	0.052*
H6A	−0.5916	−0.2197	−0.4953	0.069*
H7A	−0.9146	−0.0921	−0.4871	0.079*
H8A	−0.9847	0.0475	−0.2868	0.066*
H10A	−0.6782	0.1876	−0.0353	0.046*
H10B	−0.8026	0.0625	−0.0008	0.046*
H11A	−0.2020	−0.0348	0.2504	0.048*
H12A	−0.5756	−0.1246	0.1468	0.082*
H12B	−0.6835	−0.0145	0.2506	0.082*
H12C	−0.5337	−0.1314	0.2968	0.082*
H13A	−0.1627	0.1678	0.4222	0.103*
H13B	−0.2809	0.0481	0.4657	0.103*
H13C	−0.4303	0.1650	0.4191	0.103*
H1B	0.0511	−0.2184	−0.0809	0.070*
H2B	0.4558	−0.4175	−0.2043	0.038*
H5B	0.3519	−0.5590	0.3117	0.052*
H6B	0.6543	−0.4913	0.4890	0.060*
H7B	0.9775	−0.3754	0.4672	0.067*
H8B	1.0092	−0.3214	0.2671	0.058*
H10C	0.6791	−0.2979	0.0263	0.045*
H10D	0.8001	−0.4406	−0.0137	0.045*
H11B	0.2032	−0.6668	−0.2269	0.047*
H12D	0.5986	−0.6873	−0.1538	0.077*
H12E	0.6555	−0.6393	−0.2777	0.077*
H12F	0.5220	−0.7813	−0.2972	0.077*
H13D	0.0848	−0.5685	−0.4099	0.094*
H13E	0.2063	−0.7084	−0.4545	0.094*
H13F	0.3401	−0.5665	−0.4350	0.094*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1A	0.0353 (13)	0.0482 (15)	0.0563 (15)	−0.0097 (11)	0.0054 (11)	0.0222 (12)
O2A	0.0449 (15)	0.0696 (19)	0.0558 (16)	−0.0142 (13)	−0.0041 (13)	0.0193 (14)
O3A	0.0331 (12)	0.0395 (13)	0.0418 (12)	0.0042 (10)	0.0073 (9)	0.0042 (10)
N1A	0.0302 (13)	0.0292 (13)	0.0374 (14)	−0.0023 (10)	0.0085 (11)	0.0074 (11)
C1A	0.0321 (16)	0.0340 (17)	0.0377 (16)	−0.0013 (13)	0.0078 (13)	0.0031 (13)
C2A	0.0322 (15)	0.0314 (16)	0.0358 (16)	−0.0004 (12)	0.0104 (13)	0.0038 (13)
C3A	0.0284 (15)	0.0280 (15)	0.0339 (15)	−0.0040 (12)	0.0072 (12)	0.0066 (12)
C4A	0.0352 (16)	0.0341 (17)	0.0374 (16)	−0.0070 (13)	0.0085 (13)	0.0114 (14)
C5A	0.0489 (19)	0.0399 (19)	0.0398 (18)	−0.0001 (15)	0.0093 (15)	0.0067 (15)
C6A	0.074 (3)	0.056 (3)	0.037 (2)	−0.003 (2)	0.0021 (19)	0.0052 (18)
C7A	0.072 (3)	0.066 (3)	0.048 (2)	−0.011 (2)	−0.017 (2)	0.010 (2)
C8A	0.047 (2)	0.050 (2)	0.061 (2)	0.0024 (17)	−0.0067 (18)	0.013 (2)
C9A	0.0355 (16)	0.0345 (18)	0.0412 (17)	−0.0054 (13)	0.0030 (13)	0.0081 (14)
C10A	0.0303 (15)	0.0364 (17)	0.0455 (18)	0.0008 (12)	0.0045 (13)	0.0071 (14)
C11A	0.0468 (19)	0.0383 (19)	0.0366 (17)	−0.0015 (14)	0.0099 (14)	0.0103 (14)
C12A	0.065 (2)	0.050 (2)	0.056 (2)	−0.0112 (19)	0.0160 (19)	0.0208 (19)
C13A	0.093 (3)	0.074 (3)	0.040 (2)	−0.013 (3)	0.014 (2)	0.011 (2)
O1B	0.0366 (13)	0.0393 (13)	0.0578 (15)	0.0033 (10)	0.0034 (11)	0.0023 (12)
O2B	0.0446 (15)	0.0643 (18)	0.0545 (16)	0.0087 (13)	−0.0067 (12)	0.0025 (14)
O3B	0.0297 (11)	0.0484 (14)	0.0394 (12)	−0.0100 (10)	0.0052 (9)	0.0138 (11)
N1B	0.0249 (12)	0.0338 (14)	0.0328 (13)	−0.0037 (10)	0.0066 (10)	0.0100 (11)
C1B	0.0329 (16)	0.0380 (18)	0.0357 (16)	−0.0005 (13)	0.0056 (13)	0.0138 (14)
C2B	0.0285 (14)	0.0349 (16)	0.0332 (15)	−0.0008 (12)	0.0073 (12)	0.0116 (13)
C3B	0.0241 (14)	0.0306 (15)	0.0328 (14)	0.0033 (11)	0.0065 (11)	0.0083 (12)
C4B	0.0287 (14)	0.0302 (15)	0.0344 (15)	0.0023 (11)	0.0059 (12)	0.0054 (12)
C5B	0.0447 (18)	0.048 (2)	0.0415 (19)	0.0033 (15)	0.0099 (15)	0.0170 (16)
C6B	0.056 (2)	0.060 (2)	0.0323 (18)	0.0018 (19)	0.0014 (15)	0.0107 (17)
C7B	0.052 (2)	0.060 (3)	0.044 (2)	−0.0005 (19)	−0.0119 (17)	0.0066 (18)
C8B	0.0385 (18)	0.045 (2)	0.055 (2)	−0.0061 (15)	−0.0062 (16)	0.0095 (18)
C9B	0.0305 (16)	0.0325 (17)	0.0418 (17)	−0.0007 (13)	0.0036 (13)	0.0101 (14)
C10B	0.0272 (14)	0.0411 (18)	0.0454 (17)	−0.0075 (13)	0.0043 (13)	0.0120 (15)
C11B	0.0422 (18)	0.0374 (18)	0.0364 (17)	−0.0026 (14)	0.0081 (14)	0.0057 (14)
C12B	0.052 (2)	0.045 (2)	0.052 (2)	0.0053 (17)	0.0102 (17)	0.0021 (17)
C13B	0.071 (3)	0.072 (3)	0.040 (2)	0.008 (2)	0.0079 (19)	0.005 (2)

Geometric parameters (Å, º)

O1A—C1A	1.317 (4)	O1B—C1B	1.311 (4)
O2A—C1A	1.194 (4)	O2B—C1B	1.202 (4)
O3A—C3A	1.229 (4)	O3B—C3B	1.235 (3)
N1A—C2A	1.460 (4)	N1B—C2B	1.456 (4)
N1A—C3A	1.344 (4)	N1B—C3B	1.348 (4)
N1A—C10A	1.456 (4)	N1B—C10B	1.463 (4)
C1A—C2A	1.540 (4)	C1B—C2B	1.530 (4)
C2A—C11A	1.535 (5)	C2B—C11B	1.537 (4)
C3A—C4A	1.472 (4)	C3B—C4B	1.465 (4)
C4A—C5A	1.388 (5)	C4B—C5B	1.392 (5)
C4A—C9A	1.365 (5)	C4B—C9B	1.389 (4)
C5A—C6A	1.377 (6)	C5B—C6B	1.379 (5)
C6A—C7A	1.369 (7)	C6B—C7B	1.382 (6)
C7A—C8A	1.393 (6)	C7B—C8B	1.382 (6)
C8A—C9A	1.391 (5)	C8B—C9B	1.375 (5)
C9A—C10A	1.497 (5)	C9B—C10B	1.489 (5)
C11A—C12A	1.526 (5)	C11B—C12B	1.516 (5)
C11A—C13A	1.519 (5)	C11B—C13B	1.521 (5)
C2A—N1A—C3A	124.0 (3)	C2B—N1B—C3B	124.2 (2)
C2A—N1A—C10A	122.3 (3)	C2B—N1B—C10B	122.7 (2)
C3A—N1A—C10A	113.3 (3)	C3B—N1B—C10B	112.8 (2)
O1A—C1A—O2A	124.2 (3)	O1B—C1B—O2B	123.1 (3)
O1A—C1A—C2A	110.7 (3)	O1B—C1B—C2B	111.4 (3)
O2A—C1A—C2A	125.1 (3)	O2B—C1B—C2B	125.5 (3)
N1A—C2A—C1A	108.6 (2)	N1B—C2B—C1B	108.9 (2)
N1A—C2A—C11A	114.5 (3)	N1B—C2B—C11B	112.9 (3)
C1A—C2A—C11A	114.6 (3)	C1B—C2B—C11B	116.0 (3)
O3A—C3A—N1A	124.4 (3)	O3B—C3B—N1B	123.9 (3)
O3A—C3A—C4A	129.2 (3)	O3B—C3B—C4B	129.1 (3)
N1A—C3A—C4A	106.4 (3)	N1B—C3B—C4B	107.0 (2)
C3A—C4A—C5A	129.4 (3)	C3B—C4B—C5B	129.8 (3)
C3A—C4A—C9A	108.9 (3)	C3B—C4B—C9B	108.6 (3)
C5A—C4A—C9A	121.7 (3)	C5B—C4B—C9B	121.6 (3)
C4A—C5A—C6A	117.5 (4)	C4B—C5B—C6B	117.0 (3)
C5A—C6A—C7A	121.2 (4)	C5B—C6B—C7B	121.6 (4)
C6A—C7A—C8A	121.5 (4)	C6B—C7B—C8B	120.9 (4)
C7A—C8A—C9A	117.0 (4)	C7B—C8B—C9B	118.4 (3)
C4A—C9A—C8A	121.0 (3)	C4B—C9B—C8B	120.4 (3)
C4A—C9A—C10A	109.4 (3)	C4B—C9B—C10B	109.1 (3)
C8A—C9A—C10A	129.6 (3)	C8B—C9B—C10B	130.5 (3)
N1A—C10A—C9A	102.0 (3)	N1B—C10B—C9B	102.5 (2)
C2A—C11A—C12A	110.5 (3)	C2B—C11B—C12B	109.8 (3)
C2A—C11A—C13A	109.9 (3)	C2B—C11B—C13B	111.8 (3)
C12A—C11A—C13A	109.4 (3)	C12B—C11B—C13B	109.7 (3)
O1A—C1A—C2A—C11A	172.8 (3)	O1B—C1B—C2B—C11B	168.6 (3)
N1A—C2A—C11A—C12A	−43.6 (4)	N1B—C2B—C11B—C12B	−52.0 (3)
C1A—C2A—C11A—C13A	69.1 (4)	C1B—C2B—C11B—C13B	59.2 (4)
C3A—N1A—C2A—C1A	57.3 (4)	C3B—N1B—C2B—C1B	60.7 (4)
C3A—N1A—C2A—C11A	−72.2 (3)	C3B—N1B—C2B—C11B	−69.6 (4)
C10A—N1A—C2A—C1A	−114.8 (3)	C10B—N1B—C2B—C1B	−113.3 (3)
C10A—N1A—C2A—C11A	115.7 (3)	C10B—N1B—C2B—C11B	116.3 (3)
O2A—C1A—C2A—N1A	−138.1 (4)	O2B—C1B—C2B—N1B	−141.5 (3)
O1A—C1A—C2A—N1A	43.3 (3)	O1B—C1B—C2B—N1B	39.9 (3)
O2A—C1A—C2A—C11A	−8.6 (5)	O2B—C1B—C2B—C11B	−12.8 (5)
C2A—N1A—C3A—O3A	5.2 (5)	C2B—N1B—C3B—O3B	3.3 (5)
C10A—N1A—C3A—O3A	177.9 (3)	C10B—N1B—C3B—O3B	177.9 (3)
C2A—N1A—C3A—C4A	−173.5 (3)	C2B—N1B—C3B—C4B	−176.1 (3)
C10A—N1A—C3A—C4A	−0.8 (3)	C10B—N1B—C3B—C4B	−1.6 (3)
O3A—C3A—C4A—C9A	−177.9 (3)	O3B—C3B—C4B—C9B	−178.4 (3)
N1A—C3A—C4A—C9A	0.8 (3)	N1B—C3B—C4B—C9B	1.0 (3)
O3A—C3A—C4A—C5A	1.7 (5)	O3B—C3B—C4B—C5B	3.3 (6)
N1A—C3A—C4A—C5A	−179.6 (3)	N1B—C3B—C4B—C5B	−177.2 (3)
C9A—C4A—C5A—C6A	1.0 (5)	C9B—C4B—C5B—C6B	0.5 (5)
C3A—C4A—C5A—C6A	−178.4 (3)	C3B—C4B—C5B—C6B	178.5 (3)
C4A—C5A—C6A—C7A	0.1 (6)	C4B—C5B—C6B—C7B	0.1 (6)
C5A—C6A—C7A—C8A	−1.5 (7)	C5B—C6B—C7B—C8B	0.1 (7)
C6A—C7A—C8A—C9A	1.8 (7)	C6B—C7B—C8B—C9B	−0.8 (6)
C5A—C4A—C9A—C8A	−0.8 (5)	C5B—C4B—C9B—C8B	−1.3 (5)
C3A—C4A—C9A—C8A	178.8 (3)	C3B—C4B—C9B—C8B	−179.7 (3)
C5A—C4A—C9A—C10A	179.9 (3)	C5B—C4B—C9B—C10B	178.3 (3)
C3A—C4A—C9A—C10A	−0.5 (3)	C3B—C4B—C9B—C10B	−0.1 (4)
C7A—C8A—C9A—C4A	−0.6 (6)	C7B—C8B—C9B—C4B	1.4 (5)
C7A—C8A—C9A—C10A	178.5 (4)	C7B—C8B—C9B—C10B	−178.1 (4)
C3A—N1A—C10A—C9A	0.5 (3)	C3B—N1B—C10B—C9B	1.5 (4)
C2A—N1A—C10A—C9A	173.4 (3)	C2B—N1B—C10B—C9B	176.1 (3)
C4A—C9A—C10A—N1A	0.0 (3)	C4B—C9B—C10B—N1B	−0.8 (4)
C8A—C9A—C10A—N1A	−179.2 (3)	C8B—C9B—C10B—N1B	178.8 (4)
N1A—C2A—C11A—C13A	−164.4 (3)	C1B—C2B—C11B—C12B	−178.7 (3)
C1A—C2A—C11A—C12A	−170.1 (3)	N1B—C2B—C11B—C13B	−174.1 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1A—H1A···O3B^i	0.82	1.93	2.642 (3)	145
C5A—H5A···O2B	0.93	2.68	3.529 (5)	152
C10A—H10B···O3A^ii	0.97	2.43	3.314 (4)	151
C10A—H10A···O3B^iii	0.97	2.58	3.477 (4)	153
O1B—H1B···O3A	0.82	1.87	2.634 (3)	154
C5B—H5B···O2A^iv	0.93	2.86	3.714 (5)	153
C10B—H10C···O3A^v	0.97	2.56	3.455 (4)	154
C10B—H10D···O3B^v	0.97	2.46	3.283 (4)	143

Symmetry codes: (i) x, y+1, z; (ii) x−1, y, z; (iii) x−1, y+1, z; (iv) x, y−1, z; (v) x+1, y, z.