rac-3-Benzoyl-2-methyl­propionic acid and its organic salts: possibilities of Yang photocyclization in crystals

The analysis of the crystal structures of rac-3-benzoyl-2-methyl­propionic acid, C₁₁H₁₂O₃, (I), morpholinium rac-3-benzoyl-2-methyl­propionate monohydrate, C₄H₁₀NO⁺·C₁₁H₁₁O₃^-·H₂O, (II), pyridinium [hydrogen bis­(rac-3-benzoyl-2-methyl­propionate)], C₅H₆N⁺·(H⁺·2C₁₁H₁₁O₃^-), (III), and pyrrolidinium rac-3-benzoyl-2-methyl­propionate rac-3-benzoyl-2-methyl­propionic acid, C₄H₁₀N⁺·C₁₁H₁₁O₃^-·C₁₁H₁₂O₃, (IV), has enabled us to predict and understand the behaviour of these compounds in Yang photocyclization. Mol­ecules containing the Ar-CO-C-C-CH fragment can undergo Yang photocyclization in solvents but they can be photoinert in the crystalline state. In the case of the compounds studied here, the long distances between the O atom of the carbonyl group and the [gamma]-H atom, and between the C atom of the carbonyl group and the [gamma]-C atom preclude Yang photocyclization in the crystals. Mol­ecules of (I) are deprotonated in a different manner depending on the kind of organic base used. In the crystal structure of (III), strong centrosymmetric O...H...O hydrogen bonds are observed.

S1. Comment

Many chemists are interested in photochemical reactions in crystals. The reasons for this are of a practical and theoretical nature (Boldyreva, 1999). Such reactions are often highly selective and can serve as a source of pure products impossible to obtain in solutions. They are environmentally friendly because they are carried out without the use of solvents (green chemistry) (Tanaka, 2003). They are also applied in modern technologies (Balzani, 2003; Dürr & Bouas-Laurent, 1990; Irie, 2000).

Photochemical reactions in crystals are also the subject of our interest. Our studies concern the step-by-step monitoring of structural changes during `reactant crystal → product crystal' phototransformations. In particular, we study variations in the reaction centre and the positions of molecules. In the past, we have studied intermolecular photochemical reactions (Turowska-Tyrk, 2001, 2003; Turowska-Tyrk & Trzop, 2003). Our present interests are associated with intramolecular photochemical processes (Turowska-Tyrk, Bąkowicz, Scheffer & Xia, 2006; Turowska-Tyrk, Trzop, Scheffer & Chen, 2006a,b; Turowska-Tyrk, Bąkowicz, Scheffer, 2007; Turowska-Tyrk, Łabęcka, Scheffer & Xia, 2007; Trzop & Turowska-Tyrk, 2008), mainly Yang photocyclization.

A molecule containing a carbonyl group and a γ-H atom can create a 1,4-hydroxy-biradical in a Norrish type II photoreaction (see first scheme) (Braslavsky, 2007). In the next step, named Yang photocyclization, a cyclobutane ring can be formed from such a biradical (Braslavsky, 2007; Chen et al., 2004; Yang et al., 2005). For instance, Ph–CO–CH₂–CH₂–CH₂–CH₃, Ph–CO–CH₂–CH₂–CH(CH₃)–CH₂–CH₃ and other compounds of similar formulae undergo Yang photocyclization in solvents (Wagner, 1971). Compounds which are photoactive in solvents can be photoinert in the crystalline state. In this paper, we analyse the crystal structures of rac-3-benzoyl-2-methylpropionic acid, (I), morpholinium rac-3-benzoyl-2-methylpropionate monohydrate, (II), pyridinium [hydrogen bis(rac-3-benzoyl-2-methylpropionate)], (III), and pyrrolidinium rac-3-benzoyl-2-methylpropionate rac-3-benzoyl-2-methylpropionic acid, (IV), to predict and understand the behaviour of these compounds in Yang photocyclization in crystals and to check the influence of organic cations on it. The formulae of the studied compounds are shown in the second scheme. As can be seen, the compounds may be presented by the general formula given in the first scheme; potentially, they can form 1,4-hydroxy-biradicals and can undergo Yang photocyclization (Braga et al., 2004; Chen et al., 2004; Wagner, 1971).

Figs. 1–4 present views of the crystal lattice fragments and strong hydrogen bonds for compounds (I)–(IV), respectively. In the case of compound (I), molecules of the phenylbutyric acid form centrosymmetric dimers. The step between the planes of two carboxylic acid groups in the dimer is very small, 0.12 and 0.03 Å for symmetrically independent molecules A and B, respectively. In the crystal structure of compound (II), all molecules of the butyric acid are deprotonated. Anions, cations and water molecules are involved in strong N—H···O and O—H···O hydrogen bonds, forming ribbons along the b crystal axis. Cations are located inside these ribbons. A very interesting situation takes place in the crystal of compound (III), namely two symmetrically dependent anions have contacts with the same H atom located on an inversion centre and a cationic species lies on a two-fold axis. The distances between this H atom and two neighbouring O atoms are both 1.236 (2) Å. This short O···O distance and the linear O···H···O geometry indicate the existence of a strong hydrogen bond. Symmetric hydrogen bonds have also been observed in the crystal structures of several other carboxylic acids and pyridines (Bhogala et al., 2005; Wilson, 2001; Wilson et al., 2003). O···H···O and N—H···O hydrogen bonds form zigzags along the c crystal axis. In the crystal structure of compound (IV), only half of the molecules of the acid are dissociated (molecules A) but all molecules of the amine are protonated. N—H···O and O—H···O hydrogen bonds form ribbons along the c crystal axis. The geometry of the hydrogen bonds in compounds (I)–(IV) is presented in Table 1.

Fig. 5 shows a superposition of the molecules and anions of compounds (I)–(IV). As can be seen, the presence of organic cations in the crystal structures of compounds (II)–(IV) does not cause significant changes in the overall shape of the anions. The methyl group containing the γ-H atoms and the carbonyl group are situated on different sides of the chain. This arrangement has an impact on the reactivity of the compounds in a Norrish–Yang photoreaction. In general, the reactivity of compounds in a Norrish–Yang photoreaction in the crystalline state is influenced by several geometric parameters (Ihmels & Scheffer,1999; Natarajan et al., 2005). Fig. 6 presents a definition of these parameters, and Table 2 gives their ideal and average literature values for compounds undergoing this photoreaction (Natarajan et al., 2005; Xia et al., 2005) and additionally the values for compounds (I)–(IV). These data indicate that compounds (I)–(IV) will not undergo Yang photocyclization in the crystalline state. The distance between the carbonyl C atom and the γ-C atom, parameter D, is too large (ca 3.9 Å) in comparison with the average literature value (3.0 Å). Yang photocyclization was not observed in crystals where D was larger than 3.2 Å (Xia et al., 2005). The carbonyl O and the γ-H atoms are also too far from each other: parameter d is larger than 4.5 Å (average literature value is ca 2.6 Å). The values of these two parameters preclude the possibility of Yang photocyclization of compounds (I)–(IV) in the crystalline state.

S2. Experimental

Compound (I) was purchased from Sigma–Aldrich. Organic salts (II)–(IV) were prepared by us. Morpholine, C₄H₉NO (0.1 ml, 0.0011 mol), was added to compound (I) (0.192 g, 0.0010 mol) dissolved in toluene (10 ml). The mixture was left for evaporation at room temperature. After 1 d, colourless crystals were collected. Pyridine, C₅H₅N (0.0435 g, 0.00055 mol), and pyrrolidine, C₄H₉N (0.03912 g, 0.00055 mol), respectively, were added to compound (I) (0.100 g, 0.0005 mol) dissolved in toluene (10 ml). After several days, the colourless crystalline products were collected and recrystallized from toluene.

S3. Refinement

H atoms were positioned geometrically and treated as riding, with C—H = 0.93–0.98 Å and with U_iso(H) = 1.5U_eq(C) for –CH₃ groups or 1.2U_eq(C) for the remaining groups. H atoms in carboxylic acid groups, a water molecule and at an N atom in a pyrrolidinium cation were located in difference Fourier maps and refined without constraints. Bond lengths for these atoms are given in Table 1. Several geometric restraints for bond lengths and valence angles were applied for a pyridinium cation, owing to features of disorder.

Computing details

For all compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2003); cell refinement: CrysAlis CCD (Oxford Diffraction, 2003); data reduction: CrysAlis RED (Oxford Diffraction, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures

	Fig. 1. A view of the hydrogen-bonded dimers for compound (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 10% probability level. H atoms not taking part in hydrogen bonds have been omitted for clarity. See Table 1 for symmetry codes.
	Fig. 2. A view of the crystal lattice fragment for compound (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 10% probability level. H atoms not taking part in hydrogen bonds have been omitted for clarity. See Table 1 for symmetry codes.
	Fig. 3. A view of the crystal lattice fragment for compound (III), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 10% probability level. H atoms not taking part in hydrogen bonds have been omitted for clarity. See Table 1 for symmetry codes.
	Fig. 4. A view of the crystal lattice fragment for compound (IV), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 10% probability level. H atoms not taking part in hydrogen bonds have been omitted for clarity. See Table 1 for symmetry codes.
	Fig. 5. Superposition of the molecules and anions of compounds (I)–(IV).
	Fig. 6. Definition of the parameters influencing the reactivity of compounds in a Norrish–Yang photoreaction in the crystalline state.

(I) rac-3-benzoyl-2-methylpropionic acid

Crystal data

C11H12O3	F(000) = 816
Mr = 192.21	Dx = 1.256 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1198 reflections
a = 14.951 (3) Å	θ = 2.8–19.4°
b = 6.0452 (9) Å	µ = 0.09 mm^−1
c = 22.935 (4) Å	T = 299 K
β = 101.201 (17)°	Block, colourless
V = 2033.4 (6) Å^3	0.40 × 0.20 × 0.20 mm
Z = 8

Data collection

Kuma KM4 CCD diffractometer	1715 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.056
Graphite monochromator	θmax = 25.0°, θmin = 3.5°
ω scans	h = −17→17
10560 measured reflections	k = −7→5
3550 independent reflections	l = −27→27

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)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.139	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	w = 1/[σ^2(Fo^2) + (0.0544P)^2] where P = (Fo^2 + 2Fc^2)/3
3550 reflections	(Δ/σ)max < 0.001
261 parameters	Δρmax = 0.16 e Å^−3
0 restraints	Δρmin = −0.15 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.

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

	x	y	z	Uiso*/Ueq
C1A	0.0712 (2)	0.8098 (4)	0.05848 (12)	0.0519 (7)
C2A	0.12409 (19)	0.6402 (4)	0.09788 (11)	0.0549 (7)
H2A	0.1892	0.6701	0.1007	0.066*
C3A	0.1024 (2)	0.4142 (4)	0.06846 (14)	0.0761 (10)
H3A1	0.1361	0.3016	0.0929	0.114*
H3A2	0.1192	0.4141	0.0301	0.114*
H3A3	0.0383	0.3851	0.0639	0.114*
C4A	0.10342 (19)	0.6439 (4)	0.15994 (12)	0.0593 (8)
H4A1	0.0380	0.6322	0.1572	0.071*
H4A2	0.1314	0.5160	0.1817	0.071*
C5A	0.13717 (19)	0.8506 (4)	0.19428 (12)	0.0571 (8)
C6A	0.13644 (18)	0.8613 (4)	0.25875 (12)	0.0533 (7)
C7A	0.1766 (2)	1.0390 (5)	0.29134 (14)	0.0699 (9)
H7A	0.2002	1.1540	0.2720	0.084*
C8A	0.1823 (2)	1.0496 (6)	0.35198 (15)	0.0862 (10)
H8A	0.2098	1.1706	0.3734	0.103*
C9A	0.1475 (3)	0.8811 (7)	0.38050 (16)	0.0953 (12)
H9A	0.1521	0.8864	0.4215	0.114*
C10A	0.1060 (3)	0.7050 (7)	0.34909 (17)	0.0955 (12)
H10A	0.0814	0.5924	0.3687	0.115*
C11A	0.1003 (2)	0.6934 (5)	0.28834 (15)	0.0765 (9)
H11A	0.0721	0.5727	0.2672	0.092*
O1A	0.11097 (14)	0.8787 (3)	0.01555 (10)	0.0656 (6)
HO1A	0.069 (3)	0.960 (6)	−0.0122 (18)	0.141 (16)*
O2A	−0.00586 (14)	0.8674 (3)	0.06251 (8)	0.0599 (5)
O3A	0.16580 (15)	1.0048 (3)	0.16909 (8)	0.0785 (7)
C1B	0.4161 (2)	0.3102 (4)	0.03135 (14)	0.0589 (8)
C2B	0.3511 (2)	0.1532 (4)	0.05184 (13)	0.0633 (8)
H2B	0.2892	0.2112	0.0392	0.076*
C3B	0.3565 (3)	−0.0696 (5)	0.02185 (15)	0.0935 (12)
H3B1	0.3145	−0.1708	0.0344	0.140*
H3B2	0.4174	−0.1270	0.0328	0.140*
H3B3	0.3412	−0.0515	−0.0205	0.140*
C4B	0.3706 (2)	0.1314 (4)	0.11937 (12)	0.0627 (8)
H4B1	0.3302	0.0206	0.1306	0.075*
H4B2	0.4327	0.0795	0.1323	0.075*
C5B	0.35891 (18)	0.3422 (5)	0.15101 (13)	0.0548 (7)
C6B	0.37212 (18)	0.3447 (4)	0.21688 (12)	0.0525 (7)
C7B	0.34663 (19)	0.5302 (5)	0.24508 (14)	0.0637 (8)
H7B	0.3221	0.6512	0.2224	0.076*
C8B	0.3569 (2)	0.5389 (6)	0.30565 (16)	0.0786 (10)
H8B	0.3385	0.6640	0.3237	0.094*
C9B	0.3944 (2)	0.3632 (6)	0.33973 (15)	0.0813 (10)
H9B	0.4016	0.3693	0.3809	0.098*
C10B	0.4212 (2)	0.1793 (6)	0.31299 (15)	0.0771 (10)
H10B	0.4473	0.0610	0.3361	0.093*
C11B	0.40969 (19)	0.1678 (5)	0.25147 (14)	0.0645 (8)
H11B	0.4272	0.0413	0.2335	0.077*
O1B	0.38452 (15)	0.3992 (4)	−0.02061 (9)	0.0739 (6)
HO1B	0.432 (3)	0.499 (7)	−0.0336 (19)	0.162 (17)*
O2B	0.49387 (15)	0.3447 (3)	0.05920 (9)	0.0697 (6)
O3B	0.33834 (14)	0.5132 (3)	0.12302 (9)	0.0733 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1A	0.064 (2)	0.0452 (16)	0.0457 (18)	0.0065 (15)	0.0079 (16)	−0.0023 (14)
C2A	0.0624 (19)	0.0498 (17)	0.0504 (18)	0.0061 (14)	0.0054 (14)	0.0022 (14)
C3A	0.106 (3)	0.0498 (17)	0.070 (2)	0.0130 (17)	0.0101 (19)	−0.0035 (16)
C4A	0.070 (2)	0.0513 (18)	0.0529 (18)	−0.0029 (14)	0.0019 (15)	0.0109 (14)
C5A	0.063 (2)	0.0546 (19)	0.0509 (18)	0.0013 (15)	0.0049 (15)	0.0119 (16)
C6A	0.0534 (18)	0.0591 (18)	0.0474 (17)	0.0004 (14)	0.0096 (14)	0.0061 (15)
C7A	0.083 (2)	0.075 (2)	0.053 (2)	−0.0102 (17)	0.0161 (17)	0.0009 (17)
C8A	0.101 (3)	0.101 (3)	0.058 (2)	−0.015 (2)	0.020 (2)	−0.017 (2)
C9A	0.112 (3)	0.123 (3)	0.058 (2)	−0.006 (3)	0.034 (2)	0.004 (2)
C10A	0.122 (3)	0.102 (3)	0.074 (3)	−0.022 (2)	0.045 (2)	0.011 (2)
C11A	0.089 (2)	0.080 (2)	0.065 (2)	−0.0136 (18)	0.0253 (18)	0.0058 (19)
O1A	0.0694 (14)	0.0729 (14)	0.0577 (14)	0.0166 (11)	0.0203 (12)	0.0157 (11)
O2A	0.0644 (13)	0.0652 (13)	0.0513 (12)	0.0161 (10)	0.0140 (10)	0.0076 (10)
O3A	0.1182 (19)	0.0639 (13)	0.0527 (13)	−0.0200 (12)	0.0152 (12)	0.0105 (11)
C1B	0.080 (2)	0.0509 (18)	0.051 (2)	−0.0021 (18)	0.0252 (18)	−0.0017 (16)
C2B	0.078 (2)	0.0569 (19)	0.061 (2)	−0.0026 (15)	0.0281 (17)	0.0002 (16)
C3B	0.143 (3)	0.067 (2)	0.080 (2)	−0.027 (2)	0.046 (2)	−0.0133 (19)
C4B	0.077 (2)	0.0589 (19)	0.0597 (19)	−0.0007 (15)	0.0323 (16)	0.0041 (15)
C5B	0.0520 (18)	0.059 (2)	0.0565 (19)	0.0016 (15)	0.0182 (14)	0.0072 (16)
C6B	0.0494 (17)	0.0545 (18)	0.0570 (19)	0.0014 (14)	0.0183 (14)	0.0062 (15)
C7B	0.068 (2)	0.064 (2)	0.063 (2)	0.0046 (16)	0.0207 (17)	0.0029 (16)
C8B	0.085 (3)	0.081 (2)	0.072 (3)	0.0000 (19)	0.020 (2)	−0.014 (2)
C9B	0.079 (2)	0.107 (3)	0.061 (2)	−0.016 (2)	0.0200 (19)	−0.002 (2)
C10B	0.077 (2)	0.088 (3)	0.066 (2)	0.0032 (19)	0.0133 (19)	0.020 (2)
C11B	0.067 (2)	0.065 (2)	0.065 (2)	0.0057 (16)	0.0203 (16)	0.0094 (17)
O1B	0.0887 (17)	0.0812 (15)	0.0519 (14)	−0.0158 (13)	0.0140 (12)	0.0108 (12)
O2B	0.0693 (15)	0.0835 (15)	0.0587 (14)	−0.0089 (12)	0.0186 (12)	0.0130 (11)
O3B	0.0897 (16)	0.0643 (13)	0.0676 (14)	0.0170 (11)	0.0197 (11)	0.0161 (11)

Geometric parameters (Å, º)

C1A—O2A	1.224 (3)	C1B—O2B	1.231 (3)
C1A—O1A	1.313 (3)	C1B—O1B	1.309 (3)
C1A—C2A	1.488 (3)	C1B—C2B	1.498 (4)
C2A—C4A	1.514 (3)	C2B—C3B	1.521 (3)
C2A—C3A	1.530 (3)	C2B—C4B	1.525 (4)
C2A—H2A	0.9800	C2B—H2B	0.9800
C3A—H3A1	0.9600	C3B—H3B1	0.9600
C3A—H3A2	0.9600	C3B—H3B2	0.9600
C3A—H3A3	0.9600	C3B—H3B3	0.9600
C4A—C5A	1.511 (3)	C4B—C5B	1.493 (3)
C4A—H4A1	0.9700	C4B—H4B1	0.9700
C4A—H4A2	0.9700	C4B—H4B2	0.9700
C5A—O3A	1.217 (3)	C5B—O3B	1.224 (3)
C5A—C6A	1.482 (4)	C5B—C6B	1.485 (4)
C6A—C7A	1.378 (4)	C6B—C11B	1.384 (3)
C6A—C11A	1.388 (4)	C6B—C7B	1.385 (3)
C7A—C8A	1.378 (4)	C7B—C8B	1.369 (4)
C7A—H7A	0.9300	C7B—H7B	0.9300
C8A—C9A	1.367 (4)	C8B—C9B	1.372 (4)
C8A—H8A	0.9300	C8B—H8B	0.9300
C9A—C10A	1.365 (4)	C9B—C10B	1.367 (4)
C9A—H9A	0.9300	C9B—H9B	0.9300
C10A—C11A	1.381 (4)	C10B—C11B	1.390 (4)
C10A—H10A	0.9300	C10B—H10B	0.9300
C11A—H11A	0.9300	C11B—H11B	0.9300
O1A—HO1A	0.94 (4)	O1B—HO1B	1.02 (5)
O2A—C1A—O1A	122.4 (2)	O2B—C1B—O1B	122.7 (3)
O2A—C1A—C2A	123.1 (3)	O2B—C1B—C2B	123.3 (3)
O1A—C1A—C2A	114.2 (3)	O1B—C1B—C2B	113.9 (3)
C1A—C2A—C4A	112.3 (2)	C1B—C2B—C3B	108.9 (2)
C1A—C2A—C3A	107.8 (2)	C1B—C2B—C4B	111.4 (3)
C4A—C2A—C3A	111.3 (2)	C3B—C2B—C4B	111.5 (2)
C1A—C2A—H2A	108.5	C1B—C2B—H2B	108.3
C4A—C2A—H2A	108.5	C3B—C2B—H2B	108.3
C3A—C2A—H2A	108.5	C4B—C2B—H2B	108.3
C2A—C3A—H3A1	109.5	C2B—C3B—H3B1	109.5
C2A—C3A—H3A2	109.5	C2B—C3B—H3B2	109.5
H3A1—C3A—H3A2	109.5	H3B1—C3B—H3B2	109.5
C2A—C3A—H3A3	109.5	C2B—C3B—H3B3	109.5
H3A1—C3A—H3A3	109.5	H3B1—C3B—H3B3	109.5
H3A2—C3A—H3A3	109.5	H3B2—C3B—H3B3	109.5
C5A—C4A—C2A	113.2 (2)	C5B—C4B—C2B	113.7 (2)
C5A—C4A—H4A1	108.9	C5B—C4B—H4B1	108.8
C2A—C4A—H4A1	108.9	C2B—C4B—H4B1	108.8
C5A—C4A—H4A2	108.9	C5B—C4B—H4B2	108.8
C2A—C4A—H4A2	108.9	C2B—C4B—H4B2	108.8
H4A1—C4A—H4A2	107.8	H4B1—C4B—H4B2	107.7
O3A—C5A—C6A	120.8 (3)	O3B—C5B—C6B	119.7 (3)
O3A—C5A—C4A	119.9 (3)	O3B—C5B—C4B	120.5 (3)
C6A—C5A—C4A	119.3 (2)	C6B—C5B—C4B	119.9 (2)
C7A—C6A—C11A	118.3 (3)	C11B—C6B—C7B	118.4 (3)
C7A—C6A—C5A	119.2 (3)	C11B—C6B—C5B	122.3 (3)
C11A—C6A—C5A	122.3 (3)	C7B—C6B—C5B	119.3 (3)
C6A—C7A—C8A	121.3 (3)	C8B—C7B—C6B	121.2 (3)
C6A—C7A—H7A	119.4	C8B—C7B—H7B	119.4
C8A—C7A—H7A	119.4	C6B—C7B—H7B	119.4
C9A—C8A—C7A	119.5 (3)	C7B—C8B—C9B	120.1 (3)
C9A—C8A—H8A	120.2	C7B—C8B—H8B	119.9
C7A—C8A—H8A	120.2	C9B—C8B—H8B	119.9
C10A—C9A—C8A	120.3 (3)	C10B—C9B—C8B	119.8 (3)
C10A—C9A—H9A	119.8	C10B—C9B—H9B	120.1
C8A—C9A—H9A	119.8	C8B—C9B—H9B	120.1
C9A—C10A—C11A	120.3 (3)	C9B—C10B—C11B	120.5 (3)
C9A—C10A—H10A	119.8	C9B—C10B—H10B	119.8
C11A—C10A—H10A	119.8	C11B—C10B—H10B	119.8
C10A—C11A—C6A	120.2 (3)	C6B—C11B—C10B	120.0 (3)
C10A—C11A—H11A	119.9	C6B—C11B—H11B	120.0
C6A—C11A—H11A	119.9	C10B—C11B—H11B	120.0
C1A—O1A—HO1A	109 (2)	C1B—O1B—HO1B	111 (2)
O2A—C1A—C2A—C4A	−33.1 (4)	O2B—C1B—C2B—C3B	−95.7 (3)
O1A—C1A—C2A—C4A	152.7 (2)	O1B—C1B—C2B—C3B	80.8 (3)
O2A—C1A—C2A—C3A	89.9 (3)	O2B—C1B—C2B—C4B	27.7 (4)
O1A—C1A—C2A—C3A	−84.4 (3)	O1B—C1B—C2B—C4B	−155.8 (2)
C1A—C2A—C4A—C5A	−68.0 (3)	C1B—C2B—C4B—C5B	62.7 (3)
C3A—C2A—C4A—C5A	171.1 (2)	C3B—C2B—C4B—C5B	−175.4 (2)
C2A—C4A—C5A—O3A	9.5 (4)	C2B—C4B—C5B—O3B	−2.2 (4)
C2A—C4A—C5A—C6A	−169.5 (2)	C2B—C4B—C5B—C6B	177.7 (2)
O3A—C5A—C6A—C7A	−6.2 (4)	O3B—C5B—C6B—C11B	−169.1 (3)
C4A—C5A—C6A—C7A	172.7 (3)	C4B—C5B—C6B—C11B	11.0 (4)
O3A—C5A—C6A—C11A	176.8 (3)	O3B—C5B—C6B—C7B	10.5 (4)
C4A—C5A—C6A—C11A	−4.3 (4)	C4B—C5B—C6B—C7B	−169.4 (2)
C11A—C6A—C7A—C8A	1.1 (4)	C11B—C6B—C7B—C8B	−0.9 (4)
C5A—C6A—C7A—C8A	−176.1 (3)	C5B—C6B—C7B—C8B	179.5 (3)
C6A—C7A—C8A—C9A	−0.1 (5)	C6B—C7B—C8B—C9B	1.1 (5)
C7A—C8A—C9A—C10A	−1.0 (6)	C7B—C8B—C9B—C10B	−0.2 (5)
C8A—C9A—C10A—C11A	1.2 (6)	C8B—C9B—C10B—C11B	−0.8 (5)
C9A—C10A—C11A—C6A	−0.3 (5)	C7B—C6B—C11B—C10B	−0.1 (4)
C7A—C6A—C11A—C10A	−0.9 (5)	C5B—C6B—C11B—C10B	179.5 (3)
C5A—C6A—C11A—C10A	176.2 (3)	C9B—C10B—C11B—C6B	0.9 (5)

(II) morpholinium rac-3-benzoyl-2-methylpropionate monohydrate

Crystal data

C4H10NO^+·C11H11O3^−·H2O	F(000) = 640
Mr = 297.34	Dx = 1.243 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 946 reflections
a = 15.010 (5) Å	θ = 2.7–18.5°
b = 6.697 (2) Å	µ = 0.09 mm^−1
c = 16.017 (5) Å	T = 299 K
β = 99.21 (3)°	Block, colourless
V = 1589.3 (9) Å^3	0.50 × 0.20 × 0.10 mm
Z = 4

Data collection

Kuma KM4 CCD diffractometer	1366 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.060
Graphite monochromator	θmax = 25.0°, θmin = 3.3°
ω scans	h = −16→17
8314 measured reflections	k = −7→5
2746 independent reflections	l = −18→18

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.128	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0479P)^2] where P = (Fo^2 + 2Fc^2)/3
2746 reflections	(Δ/σ)max < 0.001
198 parameters	Δρmax = 0.12 e Å^−3
0 restraints	Δρmin = −0.18 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.

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

	x	y	z	Uiso*/Ueq
C1	0.63835 (18)	0.3001 (5)	0.35558 (15)	0.0457 (7)
C2	0.55508 (18)	0.3153 (4)	0.39719 (16)	0.0500 (7)
H2	0.5287	0.4482	0.3852	0.060*
C3	0.5824 (2)	0.2954 (4)	0.49276 (17)	0.0657 (9)
H3A	0.6273	0.3940	0.5126	0.099*
H3B	0.6067	0.1645	0.5060	0.099*
H3C	0.5305	0.3153	0.5198	0.099*
C4	0.48522 (19)	0.1631 (4)	0.36415 (17)	0.0567 (8)
H4A	0.4329	0.1822	0.3919	0.068*
H4B	0.5093	0.0312	0.3792	0.068*
C5	0.4554 (2)	0.1711 (5)	0.27033 (19)	0.0581 (8)
C6	0.39609 (19)	0.0119 (4)	0.22858 (19)	0.0535 (8)
C7	0.3609 (2)	0.0309 (5)	0.1435 (2)	0.0703 (9)
H7	0.3740	0.1439	0.1139	0.084*
C8	0.3068 (2)	−0.1153 (6)	0.1025 (2)	0.0852 (11)
H8	0.2833	−0.1003	0.0455	0.102*
C9	0.2874 (2)	−0.2819 (6)	0.1444 (3)	0.0841 (11)
H9	0.2509	−0.3808	0.1160	0.101*
C10	0.3212 (2)	−0.3042 (5)	0.2279 (3)	0.0790 (10)
H10	0.3078	−0.4185	0.2564	0.095*
C11	0.3754 (2)	−0.1585 (5)	0.2708 (2)	0.0647 (9)
H11	0.3981	−0.1747	0.3279	0.078*
O1	0.67893 (13)	0.4583 (3)	0.34239 (11)	0.0595 (6)
O2	0.66569 (12)	0.1310 (3)	0.33849 (12)	0.0597 (6)
O3	0.47971 (15)	0.3070 (3)	0.22875 (14)	0.0829 (7)
C12	0.5972 (2)	0.7779 (4)	0.17666 (18)	0.0578 (8)
H12A	0.6205	0.8741	0.2200	0.069*
H12B	0.5381	0.7350	0.1868	0.069*
C13	0.5891 (2)	0.8731 (4)	0.09166 (19)	0.0661 (9)
H13A	0.5473	0.9843	0.0886	0.079*
H13B	0.6474	0.9250	0.0836	0.079*
C14	0.6188 (2)	0.5741 (5)	0.02879 (19)	0.0691 (9)
H14A	0.6774	0.6237	0.0206	0.083*
H14B	0.5975	0.4829	−0.0172	0.083*
C15	0.6280 (2)	0.4640 (4)	0.11092 (19)	0.0621 (9)
H15A	0.5704	0.4058	0.1178	0.075*
H15B	0.6716	0.3569	0.1114	0.075*
N1	0.65827 (14)	0.6046 (3)	0.18126 (13)	0.0511 (6)
H1A	0.6592	0.5417	0.2310	0.061*
H1B	0.7147	0.6466	0.1783	0.061*
O4	0.55822 (14)	0.7352 (3)	0.02660 (13)	0.0692 (6)
O5	0.6530 (2)	0.7933 (5)	0.44136 (17)	0.0928 (9)
HO5A	0.657 (3)	0.882 (6)	0.412 (3)	0.14 (2)*
HO5B	0.669 (3)	0.687 (6)	0.409 (3)	0.136 (18)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0459 (18)	0.0575 (18)	0.0334 (16)	0.0032 (16)	0.0055 (13)	0.0074 (15)
C2	0.0487 (18)	0.0547 (18)	0.0498 (18)	0.0023 (14)	0.0179 (15)	0.0022 (14)
C3	0.078 (2)	0.073 (2)	0.049 (2)	−0.0087 (17)	0.0210 (17)	−0.0052 (16)
C4	0.0509 (19)	0.074 (2)	0.0483 (18)	−0.0019 (16)	0.0160 (15)	0.0088 (15)
C5	0.0455 (19)	0.070 (2)	0.060 (2)	0.0048 (16)	0.0121 (16)	0.0142 (18)
C6	0.0417 (18)	0.072 (2)	0.0486 (19)	0.0043 (15)	0.0133 (15)	0.0059 (16)
C7	0.062 (2)	0.094 (2)	0.056 (2)	0.000 (2)	0.0108 (18)	0.009 (2)
C8	0.073 (3)	0.120 (3)	0.062 (2)	−0.009 (2)	0.009 (2)	−0.006 (2)
C9	0.064 (2)	0.101 (3)	0.089 (3)	−0.014 (2)	0.019 (2)	−0.034 (3)
C10	0.068 (2)	0.083 (2)	0.089 (3)	−0.010 (2)	0.020 (2)	−0.004 (2)
C11	0.053 (2)	0.083 (2)	0.058 (2)	−0.0019 (18)	0.0120 (17)	0.0066 (19)
O1	0.0673 (14)	0.0552 (12)	0.0583 (13)	−0.0111 (11)	0.0167 (11)	0.0105 (10)
O2	0.0583 (14)	0.0512 (12)	0.0734 (14)	0.0036 (10)	0.0227 (11)	−0.0042 (10)
O3	0.0900 (17)	0.0867 (16)	0.0693 (15)	−0.0188 (13)	0.0040 (13)	0.0266 (13)
C12	0.055 (2)	0.0631 (19)	0.055 (2)	0.0059 (16)	0.0109 (15)	−0.0038 (16)
C13	0.070 (2)	0.062 (2)	0.065 (2)	0.0071 (17)	0.0059 (18)	0.0054 (18)
C14	0.067 (2)	0.087 (2)	0.054 (2)	−0.006 (2)	0.0113 (17)	−0.0118 (19)
C15	0.058 (2)	0.0526 (18)	0.079 (2)	−0.0045 (15)	0.0185 (18)	−0.0086 (18)
N1	0.0463 (15)	0.0606 (15)	0.0478 (14)	−0.0028 (12)	0.0121 (12)	0.0143 (12)
O4	0.0602 (14)	0.0887 (16)	0.0551 (13)	0.0061 (12)	−0.0017 (11)	0.0017 (12)
O5	0.134 (2)	0.0627 (17)	0.0805 (19)	0.0028 (17)	0.0148 (17)	0.0079 (17)

Geometric parameters (Å, º)

C1—O2	1.249 (3)	C10—C11	1.380 (4)
C1—O1	1.257 (3)	C10—H10	0.9300
C1—C2	1.511 (3)	C11—H11	0.9300
C2—C4	1.497 (4)	C12—N1	1.474 (3)
C2—C3	1.526 (3)	C12—C13	1.491 (4)
C2—H2	0.9800	C12—H12A	0.9700
C3—H3A	0.9600	C12—H12B	0.9700
C3—H3B	0.9600	C13—O4	1.414 (3)
C3—H3C	0.9600	C13—H13A	0.9700
C4—C5	1.499 (4)	C13—H13B	0.9700
C4—H4A	0.9700	C14—O4	1.408 (3)
C4—H4B	0.9700	C14—C15	1.495 (4)
C5—O3	1.218 (3)	C14—H14A	0.9700
C5—C6	1.478 (4)	C14—H14B	0.9700
C6—C11	1.387 (4)	C15—N1	1.483 (3)
C6—C7	1.387 (4)	C15—H15A	0.9700
C7—C8	1.370 (4)	C15—H15B	0.9700
C7—H7	0.9300	N1—H1A	0.9000
C8—C9	1.358 (4)	N1—H1B	0.9000
C8—H8	0.9300	O5—HO5A	0.77 (4)
C9—C10	1.361 (4)	O5—HO5B	0.93 (4)
C9—H9	0.9300
O2—C1—O1	122.8 (3)	C9—C10—H10	119.7
O2—C1—C2	118.8 (3)	C11—C10—H10	119.7
O1—C1—C2	118.3 (3)	C10—C11—C6	120.0 (3)
C4—C2—C1	112.3 (2)	C10—C11—H11	120.0
C4—C2—C3	110.8 (2)	C6—C11—H11	120.0
C1—C2—C3	109.1 (2)	N1—C12—C13	110.0 (2)
C4—C2—H2	108.1	N1—C12—H12A	109.7
C1—C2—H2	108.1	C13—C12—H12A	109.7
C3—C2—H2	108.1	N1—C12—H12B	109.7
C2—C3—H3A	109.5	C13—C12—H12B	109.7
C2—C3—H3B	109.5	H12A—C12—H12B	108.2
H3A—C3—H3B	109.5	O4—C13—C12	111.3 (2)
C2—C3—H3C	109.5	O4—C13—H13A	109.4
H3A—C3—H3C	109.5	C12—C13—H13A	109.4
H3B—C3—H3C	109.5	O4—C13—H13B	109.4
C2—C4—C5	114.2 (2)	C12—C13—H13B	109.4
C2—C4—H4A	108.7	H13A—C13—H13B	108.0
C5—C4—H4A	108.7	O4—C14—C15	111.6 (2)
C2—C4—H4B	108.7	O4—C14—H14A	109.3
C5—C4—H4B	108.7	C15—C14—H14A	109.3
H4A—C4—H4B	107.6	O4—C14—H14B	109.3
O3—C5—C6	120.2 (3)	C15—C14—H14B	109.3
O3—C5—C4	120.5 (3)	H14A—C14—H14B	108.0
C6—C5—C4	119.3 (3)	N1—C15—C14	109.2 (2)
C11—C6—C7	118.3 (3)	N1—C15—H15A	109.8
C11—C6—C5	122.6 (3)	C14—C15—H15A	109.8
C7—C6—C5	119.1 (3)	N1—C15—H15B	109.8
C8—C7—C6	120.6 (3)	C14—C15—H15B	109.8
C8—C7—H7	119.7	H15A—C15—H15B	108.3
C6—C7—H7	119.7	C12—N1—C15	110.4 (2)
C9—C8—C7	120.6 (3)	C12—N1—H1A	109.6
C9—C8—H8	119.7	C15—N1—H1A	109.6
C7—C8—H8	119.7	C12—N1—H1B	109.6
C8—C9—C10	120.0 (4)	C15—N1—H1B	109.6
C8—C9—H9	120.0	H1A—N1—H1B	108.1
C10—C9—H9	120.0	C14—O4—C13	110.4 (2)
C9—C10—C11	120.6 (3)	HO5A—O5—HO5B	101 (4)
O2—C1—C2—C4	−37.7 (3)	C5—C6—C7—C8	179.0 (3)
O1—C1—C2—C4	144.8 (2)	C6—C7—C8—C9	−0.5 (5)
O2—C1—C2—C3	85.7 (3)	C7—C8—C9—C10	0.4 (5)
O1—C1—C2—C3	−91.8 (3)	C8—C9—C10—C11	0.0 (5)
C1—C2—C4—C5	−56.9 (3)	C9—C10—C11—C6	−0.3 (5)
C3—C2—C4—C5	−179.3 (2)	C7—C6—C11—C10	0.2 (4)
C2—C4—C5—O3	−8.1 (4)	C5—C6—C11—C10	−178.6 (3)
C2—C4—C5—C6	171.8 (2)	N1—C12—C13—O4	57.2 (3)
O3—C5—C6—C11	171.8 (3)	O4—C14—C15—N1	−57.5 (3)
C4—C5—C6—C11	−8.1 (4)	C13—C12—N1—C15	−54.5 (3)
O3—C5—C6—C7	−6.9 (4)	C14—C15—N1—C12	54.3 (3)
C4—C5—C6—C7	173.2 (3)	C15—C14—O4—C13	60.6 (3)
C11—C6—C7—C8	0.2 (4)	C12—C13—O4—C14	−60.1 (3)

(III) pyridinium [hydrogen bis(rac-3-benzoyl-2-methylpropionate)]

Crystal data

C5H6N^+·H^+·2C11H11O3^−	F(000) = 984
Mr = 463.51	Dx = 1.209 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1115 reflections
a = 25.759 (6) Å	θ = 3.0–18.9°
b = 10.172 (2) Å	µ = 0.09 mm^−1
c = 9.776 (2) Å	T = 299 K
β = 96.34 (2)°	Block, colourless
V = 2545.8 (9) Å^3	0.60 × 0.30 × 0.15 mm
Z = 4

Data collection

Kuma KM4 CCD diffractometer	1454 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.040
Graphite monochromator	θmax = 25.0°, θmin = 3.6°
ω scans	h = −28→30
6670 measured reflections	k = −11→12
2199 independent reflections	l = −11→6

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.210	H-atom parameters constrained
S = 1.11	w = 1/[σ^2(Fo^2) + (0.1206P)^2 + 0.2239P] where P = (Fo^2 + 2Fc^2)/3
2199 reflections	(Δ/σ)max < 0.001
156 parameters	Δρmax = 0.22 e Å^−3
7 restraints	Δρmin = −0.21 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.

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

	x	y	z	Uiso*/Ueq
C1	0.06840 (9)	0.4104 (2)	0.1105 (3)	0.0666 (7)
C2	0.10296 (9)	0.4036 (3)	0.2455 (3)	0.0678 (7)
H2	0.1011	0.4883	0.2925	0.081*
C3	0.08289 (12)	0.2977 (3)	0.3353 (3)	0.0901 (9)
H3A	0.1049	0.2933	0.4212	0.135*
H3B	0.0833	0.2144	0.2893	0.135*
H3C	0.0478	0.3184	0.3525	0.135*
C4	0.15940 (9)	0.3771 (3)	0.2249 (3)	0.0703 (7)
H4A	0.1787	0.3609	0.3142	0.084*
H4B	0.1609	0.2975	0.1709	0.084*
C5	0.18602 (10)	0.4843 (3)	0.1557 (3)	0.0704 (7)
C6	0.23955 (9)	0.4621 (3)	0.1171 (2)	0.0667 (7)
C7	0.26233 (11)	0.5590 (3)	0.0451 (3)	0.0890 (9)
H7	0.2446	0.6375	0.0248	0.107*
C8	0.31145 (13)	0.5401 (4)	0.0029 (3)	0.1031 (11)
H8	0.3265	0.6058	−0.0458	0.124*
C9	0.33768 (12)	0.4251 (4)	0.0327 (3)	0.1006 (10)
H9	0.3704	0.4124	0.0032	0.121*
C10	0.31636 (11)	0.3299 (3)	0.1048 (3)	0.0877 (9)
H10	0.3347	0.2524	0.1260	0.105*
C11	0.26728 (10)	0.3474 (3)	0.1471 (3)	0.0779 (8)
H11	0.2528	0.2811	0.1962	0.093*
O1	0.03023 (7)	0.49029 (17)	0.10689 (17)	0.0788 (6)
HO1	0.0000	0.5000	0.0000	0.18 (2)*
O2	0.07553 (8)	0.3375 (2)	0.01525 (19)	0.1040 (8)
O3	0.16416 (8)	0.5889 (2)	0.1291 (3)	0.1052 (8)
N1	0.0000	0.7117 (3)	0.2500	0.0989 (12)
H1	0.0000	0.6271	0.2500	0.119*
C12	0.04013 (11)	0.7802 (3)	0.2005 (4)	0.1218 (14)
H12	0.0676	0.7340	0.1691	0.146*
C13	0.04039 (15)	0.9176 (3)	0.1963 (5)	0.153 (2)
H13	0.0670	0.9617	0.1584	0.184*
C14	0.0000	0.9898 (4)	0.2500	0.1227 (19)
H14	0.0000	1.0812	0.2500	0.147*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0576 (14)	0.0653 (15)	0.0794 (15)	−0.0005 (12)	0.0189 (12)	−0.0142 (12)
C2	0.0615 (15)	0.0679 (15)	0.0755 (15)	0.0046 (11)	0.0139 (12)	−0.0098 (11)
C3	0.0734 (18)	0.097 (2)	0.104 (2)	0.0057 (16)	0.0269 (15)	0.0111 (16)
C4	0.0552 (14)	0.0730 (16)	0.0833 (15)	0.0013 (11)	0.0107 (12)	−0.0011 (13)
C5	0.0620 (15)	0.0666 (16)	0.0812 (16)	−0.0004 (12)	0.0012 (12)	−0.0017 (12)
C6	0.0563 (14)	0.0727 (16)	0.0701 (14)	−0.0093 (12)	0.0022 (11)	−0.0039 (12)
C7	0.0722 (19)	0.089 (2)	0.104 (2)	−0.0149 (15)	0.0022 (15)	0.0155 (16)
C8	0.077 (2)	0.124 (3)	0.110 (2)	−0.027 (2)	0.0154 (17)	0.022 (2)
C9	0.0643 (18)	0.137 (3)	0.102 (2)	−0.011 (2)	0.0147 (16)	−0.001 (2)
C10	0.0617 (16)	0.099 (2)	0.104 (2)	0.0079 (15)	0.0135 (15)	−0.0027 (17)
C11	0.0622 (16)	0.0840 (18)	0.0880 (17)	0.0003 (14)	0.0111 (13)	0.0060 (14)
O1	0.0604 (11)	0.0836 (12)	0.0933 (13)	0.0149 (9)	0.0118 (9)	−0.0203 (10)
O2	0.0976 (16)	0.1232 (17)	0.0888 (13)	0.0431 (13)	−0.0011 (11)	−0.0344 (12)
O3	0.0846 (14)	0.0802 (14)	0.1524 (19)	0.0127 (11)	0.0210 (13)	0.0157 (13)
N1	0.164 (4)	0.0566 (18)	0.086 (2)	0.000	0.057 (2)	0.000
C12	0.078 (2)	0.090 (2)	0.202 (4)	−0.0010 (18)	0.034 (2)	−0.038 (3)
C13	0.127 (3)	0.093 (3)	0.257 (6)	0.019 (2)	0.096 (4)	0.068 (3)
C14	0.119 (4)	0.055 (2)	0.198 (6)	0.000	0.032 (4)	0.000

Geometric parameters (Å, º)

C1—O2	1.220 (3)	C8—C9	1.366 (4)
C1—O1	1.273 (3)	C8—H8	0.9300
C1—C2	1.509 (4)	C9—C10	1.349 (4)
C2—C4	1.514 (3)	C9—H9	0.9300
C2—C3	1.517 (4)	C10—C11	1.384 (4)
C2—H2	0.9800	C10—H10	0.9300
C3—H3A	0.9600	C11—H11	0.9300
C3—H3B	0.9600	O1—HO1	1.24
C3—H3C	0.9600	N1—C12	1.378 (3)
C4—C5	1.490 (4)	N1—C12^i	1.378 (3)
C4—H4A	0.9700	N1—H1	0.8600
C4—H4B	0.9700	C12—C13	1.399 (3)
C5—O3	1.219 (3)	C12—H12	0.9300
C5—C6	1.486 (4)	C13—C14	1.420 (3)
C6—C7	1.380 (4)	C13—H13	0.9300
C6—C11	1.382 (4)	C14—C13^i	1.420 (3)
C7—C8	1.387 (4)	C14—H14	0.9300
C7—H7	0.9300
O2—C1—O1	123.2 (2)	C6—C7—H7	119.8
O2—C1—C2	121.0 (2)	C8—C7—H7	119.8
O1—C1—C2	115.7 (2)	C9—C8—C7	120.1 (3)
C1—C2—C4	112.0 (2)	C9—C8—H8	120.0
C1—C2—C3	109.5 (2)	C7—C8—H8	120.0
C4—C2—C3	110.1 (2)	C10—C9—C8	120.4 (3)
C1—C2—H2	108.4	C10—C9—H9	119.8
C4—C2—H2	108.4	C8—C9—H9	119.8
C3—C2—H2	108.4	C9—C10—C11	120.1 (3)
C2—C3—H3A	109.5	C9—C10—H10	120.0
C2—C3—H3B	109.5	C11—C10—H10	120.0
H3A—C3—H3B	109.5	C6—C11—C10	120.9 (3)
C2—C3—H3C	109.5	C6—C11—H11	119.6
H3A—C3—H3C	109.5	C10—C11—H11	119.6
H3B—C3—H3C	109.5	C1—O1—HO1	119
C5—C4—C2	115.3 (2)	C12—N1—C12^i	119.2 (3)
C5—C4—H4A	108.5	C12—N1—H1	120.4
C2—C4—H4A	108.5	C12^i—N1—H1	120.4
C5—C4—H4B	108.5	N1—C12—C13	121.5 (2)
C2—C4—H4B	108.5	N1—C12—H12	119.3
H4A—C4—H4B	107.5	C13—C12—H12	119.3
O3—C5—C6	119.9 (2)	C12—C13—C14	120.0 (3)
O3—C5—C4	120.7 (2)	C12—C13—H13	120.0
C6—C5—C4	119.4 (2)	C14—C13—H13	120.0
C7—C6—C11	118.2 (2)	C13^i—C14—C13	117.8 (3)
C7—C6—C5	118.7 (2)	C13^i—C14—H14	121.1
C11—C6—C5	123.2 (2)	C13—C14—H14	121.1
C6—C7—C8	120.4 (3)
O2—C1—C2—C4	37.5 (3)	C11—C6—C7—C8	0.8 (4)
O1—C1—C2—C4	−146.6 (2)	C5—C6—C7—C8	−177.6 (3)
O2—C1—C2—C3	−84.9 (3)	C6—C7—C8—C9	−0.1 (5)
O1—C1—C2—C3	90.9 (3)	C7—C8—C9—C10	−0.8 (5)
C1—C2—C4—C5	66.5 (3)	C8—C9—C10—C11	1.0 (5)
C3—C2—C4—C5	−171.4 (2)	C7—C6—C11—C10	−0.6 (4)
C2—C4—C5—O3	5.7 (4)	C5—C6—C11—C10	177.8 (2)
C2—C4—C5—C6	−173.4 (2)	C9—C10—C11—C6	−0.3 (4)
O3—C5—C6—C7	−3.3 (4)	C12^i—N1—C12—C13	−1.6 (4)
C4—C5—C6—C7	175.8 (2)	N1—C12—C13—C14	3.1 (7)
O3—C5—C6—C11	178.3 (3)	C12—C13—C14—C13^i	−1.5 (4)
C4—C5—C6—C11	−2.6 (4)

Symmetry code: (i) −x, y, −z+1/2.

(IV) pyrrolidinium rac-3-benzoyl-2-methylpropionate rac-3-benzoyl-2-methylpropionic acid

Crystal data

C4H10N^+·C11H11O3^+·C11H12O3	F(000) = 976
Mr = 455.53	Dx = 1.228 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 852 reflections
a = 26.249 (9) Å	θ = 3.0–18.2°
b = 9.556 (3) Å	µ = 0.09 mm^−1
c = 9.869 (3) Å	T = 299 K
β = 95.32 (3)°	Block, colourless
V = 2464.8 (14) Å^3	0.35 × 0.25 × 0.20 mm
Z = 4

Data collection

Kuma KM4 CCD diffractometer	1733 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.062
Graphite monochromator	θmax = 25.0°, θmin = 2.6°
ω scans	h = −31→31
12988 measured reflections	k = −11→11
4295 independent reflections	l = −5→11

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)] = 0.063	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.199	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	w = 1/[σ^2(Fo^2) + (0.0827P)^2] where P = (Fo^2 + 2Fc^2)/3
4295 reflections	(Δ/σ)max < 0.001
310 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.18 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.

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

	x	y	z	Uiso*/Ueq
O1A	0.28045 (9)	0.7542 (3)	0.5961 (2)	0.0645 (7)
O2A	0.32287 (9)	0.9303 (3)	0.5131 (2)	0.0800 (8)
O3A	0.40829 (10)	0.6636 (3)	0.6097 (3)	0.0908 (9)
C1A	0.31566 (13)	0.8453 (4)	0.6039 (3)	0.0566 (9)
C2A	0.34824 (12)	0.8547 (4)	0.7375 (3)	0.0584 (10)
H2A	0.3462	0.7654	0.7854	0.070*
C3A	0.32717 (13)	0.9688 (4)	0.8229 (3)	0.0863 (13)
H3A1	0.3475	0.9750	0.9087	0.129*
H3A2	0.2925	0.9471	0.8382	0.129*
H3A3	0.3282	1.0567	0.7760	0.129*
C4A	0.40406 (12)	0.8833 (4)	0.7169 (3)	0.0613 (10)
H4A1	0.4059	0.9699	0.6664	0.074*
H4A2	0.4227	0.8971	0.8054	0.074*
C5A	0.43012 (13)	0.7710 (4)	0.6438 (3)	0.0598 (10)
C6A	0.48399 (13)	0.7931 (4)	0.6127 (3)	0.0573 (9)
C7A	0.50683 (15)	0.6928 (4)	0.5367 (4)	0.0748 (11)
H7A	0.4883	0.6136	0.5077	0.090*
C8A	0.55613 (16)	0.7077 (5)	0.5032 (4)	0.0863 (13)
H8A	0.5707	0.6389	0.4525	0.104*
C9A	0.58376 (15)	0.8242 (5)	0.5445 (4)	0.0834 (13)
H9A	0.6172	0.8348	0.5219	0.100*
C10A	0.56217 (15)	0.9245 (5)	0.6189 (4)	0.0777 (12)
H10A	0.5809	1.0038	0.6463	0.093*
C11A	0.51275 (14)	0.9097 (4)	0.6539 (3)	0.0703 (11)
H11A	0.4986	0.9786	0.7056	0.084*
O1B	0.21790 (9)	0.7438 (3)	0.3864 (2)	0.0690 (8)
HO1B	0.2468 (17)	0.752 (4)	0.478 (5)	0.16 (2)*
O2B	0.17327 (10)	0.5833 (3)	0.4829 (3)	0.0986 (10)
O3B	0.08743 (10)	0.8328 (3)	0.3909 (3)	0.0961 (9)
C1B	0.18005 (14)	0.6571 (4)	0.3868 (3)	0.0605 (10)
C2B	0.14712 (12)	0.6511 (4)	0.2546 (3)	0.0621 (10)
H2B	0.1484	0.7425	0.2099	0.074*
C3B	0.16874 (14)	0.5419 (4)	0.1636 (4)	0.0854 (12)
H3B1	0.1478	0.5372	0.0786	0.128*
H3B2	0.1690	0.4523	0.2076	0.128*
H3B3	0.2030	0.5673	0.1472	0.128*
C4B	0.09170 (12)	0.6186 (4)	0.2758 (3)	0.0655 (10)
H4B1	0.0728	0.6072	0.1873	0.079*
H4B2	0.0907	0.5297	0.3230	0.079*
C5B	0.06507 (14)	0.7252 (4)	0.3537 (4)	0.0648 (10)
C6B	0.01132 (13)	0.7043 (4)	0.3847 (3)	0.0611 (10)
C7B	−0.01178 (16)	0.8023 (4)	0.4619 (4)	0.0795 (12)
H7B	0.0066	0.8813	0.4918	0.095*
C8B	−0.06096 (18)	0.7869 (5)	0.4958 (4)	0.0948 (14)
H8B	−0.0756	0.8550	0.5473	0.114*
C9B	−0.08833 (17)	0.6706 (5)	0.4534 (5)	0.0912 (13)
H9B	−0.1217	0.6590	0.4756	0.109*
C10B	−0.06627 (16)	0.5721 (5)	0.3783 (4)	0.0889 (13)
H10B	−0.0848	0.4928	0.3499	0.107*
C11B	−0.01663 (15)	0.5878 (4)	0.3432 (4)	0.0762 (12)
H11B	−0.0022	0.5195	0.2916	0.091*
N1	0.27156 (13)	0.5286 (4)	0.7683 (3)	0.0672 (9)
H1A	0.2609 (15)	0.612 (5)	0.717 (4)	0.117 (17)*
H1B	0.2911 (17)	0.561 (5)	0.864 (5)	0.143 (17)*
C12	0.30435 (17)	0.4319 (5)	0.6978 (4)	0.0943 (14)
H12A	0.3233	0.4826	0.6337	0.113*
H12B	0.3285	0.3846	0.7629	0.113*
C13	0.2698 (3)	0.3319 (6)	0.6272 (6)	0.153 (2)
H13A	0.2868	0.2437	0.6135	0.184*
H13B	0.2556	0.3680	0.5399	0.184*
C14	0.2287 (2)	0.3158 (6)	0.7252 (7)	0.149 (3)
H14A	0.1969	0.2830	0.6777	0.179*
H14B	0.2394	0.2499	0.7969	0.179*
C15	0.22207 (16)	0.4582 (5)	0.7823 (4)	0.0908 (13)
H15A	0.1942	0.5075	0.7315	0.109*
H15B	0.2152	0.4530	0.8771	0.109*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1A	0.0538 (15)	0.0858 (19)	0.0519 (13)	−0.0148 (14)	−0.0065 (11)	0.0060 (13)
O2A	0.0815 (18)	0.101 (2)	0.0540 (14)	−0.0266 (16)	−0.0119 (13)	0.0249 (14)
O3A	0.0673 (18)	0.072 (2)	0.132 (2)	−0.0204 (16)	0.0066 (16)	−0.0186 (18)
C1A	0.046 (2)	0.075 (3)	0.048 (2)	−0.007 (2)	−0.0008 (17)	0.001 (2)
C2A	0.052 (2)	0.078 (3)	0.0439 (18)	−0.0153 (19)	−0.0042 (16)	0.0055 (19)
C3A	0.067 (3)	0.131 (4)	0.062 (2)	−0.018 (3)	0.0104 (19)	−0.024 (2)
C4A	0.050 (2)	0.079 (3)	0.0533 (19)	−0.011 (2)	−0.0023 (16)	0.0000 (19)
C5A	0.051 (2)	0.065 (3)	0.061 (2)	−0.005 (2)	−0.0097 (18)	0.008 (2)
C6A	0.053 (2)	0.062 (3)	0.055 (2)	−0.001 (2)	−0.0074 (17)	0.0016 (18)
C7A	0.057 (3)	0.069 (3)	0.096 (3)	0.000 (2)	−0.007 (2)	−0.008 (2)
C8A	0.065 (3)	0.101 (4)	0.092 (3)	0.014 (3)	−0.001 (2)	−0.020 (3)
C9A	0.056 (3)	0.116 (4)	0.078 (3)	−0.004 (3)	0.005 (2)	0.001 (3)
C10A	0.056 (3)	0.089 (3)	0.086 (3)	−0.017 (2)	0.000 (2)	−0.003 (2)
C11A	0.058 (3)	0.084 (3)	0.069 (2)	−0.010 (2)	0.0027 (19)	−0.015 (2)
O1B	0.0551 (15)	0.093 (2)	0.0572 (14)	−0.0244 (15)	−0.0055 (12)	0.0111 (14)
O2B	0.095 (2)	0.115 (2)	0.0809 (18)	−0.0416 (18)	−0.0203 (16)	0.0409 (17)
O3B	0.0738 (19)	0.075 (2)	0.139 (2)	−0.0201 (16)	0.0061 (16)	−0.0231 (18)
C1B	0.057 (2)	0.066 (3)	0.058 (2)	−0.004 (2)	−0.0003 (19)	0.012 (2)
C2B	0.053 (2)	0.071 (3)	0.060 (2)	−0.0052 (19)	−0.0070 (18)	0.002 (2)
C3B	0.067 (3)	0.109 (3)	0.079 (3)	−0.004 (3)	0.000 (2)	−0.015 (3)
C4B	0.057 (2)	0.072 (3)	0.065 (2)	−0.009 (2)	−0.0051 (18)	−0.002 (2)
C5B	0.064 (3)	0.057 (3)	0.070 (2)	−0.008 (2)	−0.010 (2)	0.002 (2)
C6B	0.053 (2)	0.065 (3)	0.063 (2)	−0.004 (2)	−0.0063 (18)	0.009 (2)
C7B	0.068 (3)	0.073 (3)	0.095 (3)	0.004 (2)	−0.008 (2)	−0.006 (2)
C8B	0.071 (3)	0.106 (4)	0.107 (3)	0.018 (3)	0.007 (3)	−0.009 (3)
C9B	0.067 (3)	0.103 (4)	0.103 (3)	0.002 (3)	0.002 (3)	0.012 (3)
C10B	0.062 (3)	0.097 (4)	0.107 (3)	−0.021 (3)	0.001 (2)	−0.002 (3)
C11B	0.067 (3)	0.078 (3)	0.082 (3)	−0.019 (2)	0.002 (2)	−0.012 (2)
N1	0.079 (2)	0.068 (2)	0.0543 (18)	−0.005 (2)	0.0023 (17)	−0.0063 (19)
C12	0.109 (3)	0.107 (4)	0.067 (2)	0.004 (3)	0.012 (2)	−0.022 (3)
C13	0.207 (7)	0.113 (5)	0.131 (5)	0.016 (5)	−0.036 (5)	−0.041 (4)
C14	0.140 (5)	0.076 (4)	0.220 (7)	−0.036 (4)	−0.043 (5)	0.014 (5)
C15	0.084 (3)	0.089 (3)	0.097 (3)	−0.024 (3)	−0.003 (2)	0.000 (3)

Geometric parameters (Å, º)

O1A—C1A	1.267 (4)	C3B—H3B1	0.9600
O1A—HO1B	1.39 (5)	C3B—H3B2	0.9600
O2A—C1A	1.237 (4)	C3B—H3B3	0.9600
O3A—C5A	1.208 (4)	C4B—C5B	1.489 (5)
C1A—C2A	1.506 (4)	C4B—H4B1	0.9700
C2A—C3A	1.514 (4)	C4B—H4B2	0.9700
C2A—C4A	1.522 (4)	C5B—C6B	1.485 (5)
C2A—H2A	0.9800	C6B—C11B	1.374 (5)
C3A—H3A1	0.9600	C6B—C7B	1.382 (5)
C3A—H3A2	0.9600	C7B—C8B	1.371 (5)
C3A—H3A3	0.9600	C7B—H7B	0.9300
C4A—C5A	1.494 (5)	C8B—C9B	1.368 (5)
C4A—H4A1	0.9700	C8B—H8B	0.9300
C4A—H4A2	0.9700	C9B—C10B	1.360 (5)
C5A—C6A	1.489 (5)	C9B—H9B	0.9300
C6A—C11A	1.386 (5)	C10B—C11B	1.387 (5)
C6A—C7A	1.387 (5)	C10B—H10B	0.9300
C7A—C8A	1.372 (5)	C11B—H11B	0.9300
C7A—H7A	0.9300	N1—C12	1.480 (5)
C8A—C9A	1.370 (5)	N1—C15	1.481 (5)
C8A—H8A	0.9300	N1—H1A	0.97 (4)
C9A—C10A	1.362 (5)	N1—H1B	1.07 (5)
C9A—H9A	0.9300	C12—C13	1.451 (6)
C10A—C11A	1.380 (5)	C12—H12A	0.9700
C10A—H10A	0.9300	C12—H12B	0.9700
C11A—H11A	0.9300	C13—C14	1.523 (7)
O1B—C1B	1.294 (4)	C13—H13A	0.9700
O1B—HO1B	1.13 (5)	C13—H13B	0.9700
O2B—C1B	1.208 (4)	C14—C15	1.489 (6)
O3B—C5B	1.223 (4)	C14—H14A	0.9700
C1B—C2B	1.499 (4)	C14—H14B	0.9700
C2B—C3B	1.520 (4)	C15—H15A	0.9700
C2B—C4B	1.521 (4)	C15—H15B	0.9700
C2B—H2B	0.9800
C1A—O1A—HO1B	117.5 (17)	H3B2—C3B—H3B3	109.5
O2A—C1A—O1A	124.6 (3)	C5B—C4B—C2B	115.6 (3)
O2A—C1A—C2A	118.8 (3)	C5B—C4B—H4B1	108.4
O1A—C1A—C2A	116.5 (3)	C2B—C4B—H4B1	108.4
C1A—C2A—C3A	108.9 (3)	C5B—C4B—H4B2	108.4
C1A—C2A—C4A	111.7 (3)	C2B—C4B—H4B2	108.4
C3A—C2A—C4A	110.5 (3)	H4B1—C4B—H4B2	107.4
C1A—C2A—H2A	108.6	O3B—C5B—C6B	119.3 (4)
C3A—C2A—H2A	108.6	O3B—C5B—C4B	119.7 (4)
C4A—C2A—H2A	108.6	C6B—C5B—C4B	121.0 (3)
C2A—C3A—H3A1	109.5	C11B—C6B—C7B	117.6 (4)
C2A—C3A—H3A2	109.5	C11B—C6B—C5B	122.6 (4)
H3A1—C3A—H3A2	109.5	C7B—C6B—C5B	119.8 (4)
C2A—C3A—H3A3	109.5	C8B—C7B—C6B	122.2 (4)
H3A1—C3A—H3A3	109.5	C8B—C7B—H7B	118.9
H3A2—C3A—H3A3	109.5	C6B—C7B—H7B	118.9
C5A—C4A—C2A	115.2 (3)	C9B—C8B—C7B	119.5 (4)
C5A—C4A—H4A1	108.5	C9B—C8B—H8B	120.3
C2A—C4A—H4A1	108.5	C7B—C8B—H8B	120.3
C5A—C4A—H4A2	108.5	C10B—C9B—C8B	119.4 (4)
C2A—C4A—H4A2	108.5	C10B—C9B—H9B	120.3
H4A1—C4A—H4A2	107.5	C8B—C9B—H9B	120.3
O3A—C5A—C6A	119.9 (4)	C9B—C10B—C11B	121.2 (4)
O3A—C5A—C4A	121.2 (3)	C9B—C10B—H10B	119.4
C6A—C5A—C4A	118.9 (3)	C11B—C10B—H10B	119.4
C11A—C6A—C7A	117.6 (3)	C6B—C11B—C10B	120.1 (4)
C11A—C6A—C5A	123.8 (4)	C6B—C11B—H11B	120.0
C7A—C6A—C5A	118.6 (4)	C10B—C11B—H11B	120.0
C8A—C7A—C6A	121.5 (4)	C12—N1—C15	108.3 (3)
C8A—C7A—H7A	119.2	C12—N1—H1A	115 (2)
C6A—C7A—H7A	119.2	C15—N1—H1A	102 (2)
C9A—C8A—C7A	119.8 (4)	C12—N1—H1B	110 (2)
C9A—C8A—H8A	120.1	C15—N1—H1B	114 (2)
C7A—C8A—H8A	120.1	H1A—N1—H1B	108 (3)
C10A—C9A—C8A	119.8 (4)	C13—C12—N1	105.8 (4)
C10A—C9A—H9A	120.1	C13—C12—H12A	110.6
C8A—C9A—H9A	120.1	N1—C12—H12A	110.6
C9A—C10A—C11A	120.7 (4)	C13—C12—H12B	110.6
C9A—C10A—H10A	119.7	N1—C12—H12B	110.6
C11A—C10A—H10A	119.7	H12A—C12—H12B	108.7
C10A—C11A—C6A	120.5 (4)	C12—C13—C14	102.1 (4)
C10A—C11A—H11A	119.7	C12—C13—H13A	111.3
C6A—C11A—H11A	119.7	C14—C13—H13A	111.3
C1B—O1B—HO1B	120 (2)	C12—C13—H13B	111.3
O2B—C1B—O1B	123.0 (3)	C14—C13—H13B	111.3
O2B—C1B—C2B	123.1 (3)	H13A—C13—H13B	109.2
O1B—C1B—C2B	113.7 (3)	C15—C14—C13	105.2 (4)
C1B—C2B—C3B	108.9 (3)	C15—C14—H14A	110.7
C1B—C2B—C4B	111.7 (3)	C13—C14—H14A	110.7
C3B—C2B—C4B	110.8 (3)	C15—C14—H14B	110.7
C1B—C2B—H2B	108.5	C13—C14—H14B	110.7
C3B—C2B—H2B	108.5	H14A—C14—H14B	108.8
C4B—C2B—H2B	108.5	N1—C15—C14	104.2 (4)
C2B—C3B—H3B1	109.5	N1—C15—H15A	110.9
C2B—C3B—H3B2	109.5	C14—C15—H15A	110.9
H3B1—C3B—H3B2	109.5	N1—C15—H15B	110.9
C2B—C3B—H3B3	109.5	C14—C15—H15B	110.9
H3B1—C3B—H3B3	109.5	H15A—C15—H15B	108.9
O2A—C1A—C2A—C3A	80.5 (4)	O1B—C1B—C2B—C4B	−148.7 (3)
O1A—C1A—C2A—C3A	−95.6 (4)	C1B—C2B—C4B—C5B	63.4 (4)
O2A—C1A—C2A—C4A	−41.9 (5)	C3B—C2B—C4B—C5B	−175.0 (3)
O1A—C1A—C2A—C4A	142.1 (3)	C2B—C4B—C5B—O3B	2.8 (5)
C1A—C2A—C4A—C5A	−63.6 (4)	C2B—C4B—C5B—C6B	−178.3 (3)
C3A—C2A—C4A—C5A	175.1 (3)	O3B—C5B—C6B—C11B	178.3 (3)
C2A—C4A—C5A—O3A	−3.1 (5)	C4B—C5B—C6B—C11B	−0.5 (5)
C2A—C4A—C5A—C6A	176.9 (3)	O3B—C5B—C6B—C7B	−3.8 (5)
O3A—C5A—C6A—C11A	−176.6 (3)	C4B—C5B—C6B—C7B	177.4 (3)
C4A—C5A—C6A—C11A	3.4 (5)	C11B—C6B—C7B—C8B	−0.7 (6)
O3A—C5A—C6A—C7A	4.3 (5)	C5B—C6B—C7B—C8B	−178.7 (3)
C4A—C5A—C6A—C7A	−175.6 (3)	C6B—C7B—C8B—C9B	0.5 (6)
C11A—C6A—C7A—C8A	0.1 (5)	C7B—C8B—C9B—C10B	0.1 (6)
C5A—C6A—C7A—C8A	179.2 (3)	C8B—C9B—C10B—C11B	−0.4 (6)
C6A—C7A—C8A—C9A	−0.4 (6)	C7B—C6B—C11B—C10B	0.4 (5)
C7A—C8A—C9A—C10A	0.1 (6)	C5B—C6B—C11B—C10B	178.3 (3)
C8A—C9A—C10A—C11A	0.4 (6)	C9B—C10B—C11B—C6B	0.2 (6)
C9A—C10A—C11A—C6A	−0.7 (6)	C15—N1—C12—C13	20.7 (5)
C7A—C6A—C11A—C10A	0.4 (5)	N1—C12—C13—C14	−35.0 (5)
C5A—C6A—C11A—C10A	−178.6 (3)	C12—C13—C14—C15	37.4 (6)
O2B—C1B—C2B—C3B	−88.2 (4)	C12—N1—C15—C14	3.2 (5)
O1B—C1B—C2B—C3B	88.6 (4)	C13—C14—C15—N1	−24.7 (6)
O2B—C1B—C2B—C4B	34.4 (5)