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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270108021380/sk3242sup1.cif
Contains datablocks I, II, III, IV, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108021380/sk3242Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108021380/sk3242IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108021380/sk3242IIIsup4.hkl
Contains datablock III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270108021380/sk3242IVsup5.hkl
Contains datablock IV

CCDC references: 700026; 700027; 700028; 700029

Comment top

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.

Experimental top

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.

Refinement top

H atoms were positioned geometrically and treated as riding, with C—H = 0.93–0.98 Å and with Uiso(H) = 1.5Ueq(C) for –CH3 groups or 1.2Ueq(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 top

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 top
[Figure 1] 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.
[Figure 2] 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.
[Figure 3] 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.
[Figure 4] 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.
[Figure 5] Fig. 5. Superposition of the molecules and anions of compounds (I)–(IV).
[Figure 6] 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 top
Crystal data top
C11H12O3F(000) = 816
Mr = 192.21Dx = 1.256 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1198 reflections
a = 14.951 (3) Åθ = 2.8–19.4°
b = 6.0452 (9) ŵ = 0.09 mm1
c = 22.935 (4) ÅT = 299 K
β = 101.201 (17)°Block, colourless
V = 2033.4 (6) Å30.40 × 0.20 × 0.20 mm
Z = 8
Data collection top
Kuma KM4 CCD
diffractometer
1715 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.056
Graphite monochromatorθmax = 25.0°, θmin = 3.5°
ω scansh = 1717
10560 measured reflectionsk = 75
3550 independent reflectionsl = 2727
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.139H atoms treated by a mixture of independent and constrained refinement
S = 0.95 w = 1/[σ2(Fo2) + (0.0544P)2]
where P = (Fo2 + 2Fc2)/3
3550 reflections(Δ/σ)max < 0.001
261 parametersΔρmax = 0.16 e Å3
0 restraintsΔρmin = 0.15 e Å3
Crystal data top
C11H12O3V = 2033.4 (6) Å3
Mr = 192.21Z = 8
Monoclinic, P21/cMo Kα radiation
a = 14.951 (3) ŵ = 0.09 mm1
b = 6.0452 (9) ÅT = 299 K
c = 22.935 (4) Å0.40 × 0.20 × 0.20 mm
β = 101.201 (17)°
Data collection top
Kuma KM4 CCD
diffractometer
1715 reflections with I > 2σ(I)
10560 measured reflectionsRint = 0.056
3550 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0530 restraints
wR(F2) = 0.139H atoms treated by a mixture of independent and constrained refinement
S = 0.95Δρmax = 0.16 e Å3
3550 reflectionsΔρmin = 0.15 e Å3
261 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C1A0.0712 (2)0.8098 (4)0.05848 (12)0.0519 (7)
C2A0.12409 (19)0.6402 (4)0.09788 (11)0.0549 (7)
H2A0.18920.67010.10070.066*
C3A0.1024 (2)0.4142 (4)0.06846 (14)0.0761 (10)
H3A10.13610.30160.09290.114*
H3A20.11920.41410.03010.114*
H3A30.03830.38510.06390.114*
C4A0.10342 (19)0.6439 (4)0.15994 (12)0.0593 (8)
H4A10.03800.63220.15720.071*
H4A20.13140.51600.18170.071*
C5A0.13717 (19)0.8506 (4)0.19428 (12)0.0571 (8)
C6A0.13644 (18)0.8613 (4)0.25875 (12)0.0533 (7)
C7A0.1766 (2)1.0390 (5)0.29134 (14)0.0699 (9)
H7A0.20021.15400.27200.084*
C8A0.1823 (2)1.0496 (6)0.35198 (15)0.0862 (10)
H8A0.20981.17060.37340.103*
C9A0.1475 (3)0.8811 (7)0.38050 (16)0.0953 (12)
H9A0.15210.88640.42150.114*
C10A0.1060 (3)0.7050 (7)0.34909 (17)0.0955 (12)
H10A0.08140.59240.36870.115*
C11A0.1003 (2)0.6934 (5)0.28834 (15)0.0765 (9)
H11A0.07210.57270.26720.092*
O1A0.11097 (14)0.8787 (3)0.01555 (10)0.0656 (6)
HO1A0.069 (3)0.960 (6)0.0122 (18)0.141 (16)*
O2A0.00586 (14)0.8674 (3)0.06251 (8)0.0599 (5)
O3A0.16580 (15)1.0048 (3)0.16909 (8)0.0785 (7)
C1B0.4161 (2)0.3102 (4)0.03135 (14)0.0589 (8)
C2B0.3511 (2)0.1532 (4)0.05184 (13)0.0633 (8)
H2B0.28920.21120.03920.076*
C3B0.3565 (3)0.0696 (5)0.02185 (15)0.0935 (12)
H3B10.31450.17080.03440.140*
H3B20.41740.12700.03280.140*
H3B30.34120.05150.02050.140*
C4B0.3706 (2)0.1314 (4)0.11937 (12)0.0627 (8)
H4B10.33020.02060.13060.075*
H4B20.43270.07950.13230.075*
C5B0.35891 (18)0.3422 (5)0.15101 (13)0.0548 (7)
C6B0.37212 (18)0.3447 (4)0.21688 (12)0.0525 (7)
C7B0.34663 (19)0.5302 (5)0.24508 (14)0.0637 (8)
H7B0.32210.65120.22240.076*
C8B0.3569 (2)0.5389 (6)0.30565 (16)0.0786 (10)
H8B0.33850.66400.32370.094*
C9B0.3944 (2)0.3632 (6)0.33973 (15)0.0813 (10)
H9B0.40160.36930.38090.098*
C10B0.4212 (2)0.1793 (6)0.31299 (15)0.0771 (10)
H10B0.44730.06100.33610.093*
C11B0.40969 (19)0.1678 (5)0.25147 (14)0.0645 (8)
H11B0.42720.04130.23350.077*
O1B0.38452 (15)0.3992 (4)0.02061 (9)0.0739 (6)
HO1B0.432 (3)0.499 (7)0.0336 (19)0.162 (17)*
O2B0.49387 (15)0.3447 (3)0.05920 (9)0.0697 (6)
O3B0.33834 (14)0.5132 (3)0.12302 (9)0.0733 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C1A0.064 (2)0.0452 (16)0.0457 (18)0.0065 (15)0.0079 (16)0.0023 (14)
C2A0.0624 (19)0.0498 (17)0.0504 (18)0.0061 (14)0.0054 (14)0.0022 (14)
C3A0.106 (3)0.0498 (17)0.070 (2)0.0130 (17)0.0101 (19)0.0035 (16)
C4A0.070 (2)0.0513 (18)0.0529 (18)0.0029 (14)0.0019 (15)0.0109 (14)
C5A0.063 (2)0.0546 (19)0.0509 (18)0.0013 (15)0.0049 (15)0.0119 (16)
C6A0.0534 (18)0.0591 (18)0.0474 (17)0.0004 (14)0.0096 (14)0.0061 (15)
C7A0.083 (2)0.075 (2)0.053 (2)0.0102 (17)0.0161 (17)0.0009 (17)
C8A0.101 (3)0.101 (3)0.058 (2)0.015 (2)0.020 (2)0.017 (2)
C9A0.112 (3)0.123 (3)0.058 (2)0.006 (3)0.034 (2)0.004 (2)
C10A0.122 (3)0.102 (3)0.074 (3)0.022 (2)0.045 (2)0.011 (2)
C11A0.089 (2)0.080 (2)0.065 (2)0.0136 (18)0.0253 (18)0.0058 (19)
O1A0.0694 (14)0.0729 (14)0.0577 (14)0.0166 (11)0.0203 (12)0.0157 (11)
O2A0.0644 (13)0.0652 (13)0.0513 (12)0.0161 (10)0.0140 (10)0.0076 (10)
O3A0.1182 (19)0.0639 (13)0.0527 (13)0.0200 (12)0.0152 (12)0.0105 (11)
C1B0.080 (2)0.0509 (18)0.051 (2)0.0021 (18)0.0252 (18)0.0017 (16)
C2B0.078 (2)0.0569 (19)0.061 (2)0.0026 (15)0.0281 (17)0.0002 (16)
C3B0.143 (3)0.067 (2)0.080 (2)0.027 (2)0.046 (2)0.0133 (19)
C4B0.077 (2)0.0589 (19)0.0597 (19)0.0007 (15)0.0323 (16)0.0041 (15)
C5B0.0520 (18)0.059 (2)0.0565 (19)0.0016 (15)0.0182 (14)0.0072 (16)
C6B0.0494 (17)0.0545 (18)0.0570 (19)0.0014 (14)0.0183 (14)0.0062 (15)
C7B0.068 (2)0.064 (2)0.063 (2)0.0046 (16)0.0207 (17)0.0029 (16)
C8B0.085 (3)0.081 (2)0.072 (3)0.0000 (19)0.020 (2)0.014 (2)
C9B0.079 (2)0.107 (3)0.061 (2)0.016 (2)0.0200 (19)0.002 (2)
C10B0.077 (2)0.088 (3)0.066 (2)0.0032 (19)0.0133 (19)0.020 (2)
C11B0.067 (2)0.065 (2)0.065 (2)0.0057 (16)0.0203 (16)0.0094 (17)
O1B0.0887 (17)0.0812 (15)0.0519 (14)0.0158 (13)0.0140 (12)0.0108 (12)
O2B0.0693 (15)0.0835 (15)0.0587 (14)0.0089 (12)0.0186 (12)0.0130 (11)
O3B0.0897 (16)0.0643 (13)0.0676 (14)0.0170 (11)0.0197 (11)0.0161 (11)
Geometric parameters (Å, º) top
C1A—O2A1.224 (3)C1B—O2B1.231 (3)
C1A—O1A1.313 (3)C1B—O1B1.309 (3)
C1A—C2A1.488 (3)C1B—C2B1.498 (4)
C2A—C4A1.514 (3)C2B—C3B1.521 (3)
C2A—C3A1.530 (3)C2B—C4B1.525 (4)
C2A—H2A0.9800C2B—H2B0.9800
C3A—H3A10.9600C3B—H3B10.9600
C3A—H3A20.9600C3B—H3B20.9600
C3A—H3A30.9600C3B—H3B30.9600
C4A—C5A1.511 (3)C4B—C5B1.493 (3)
C4A—H4A10.9700C4B—H4B10.9700
C4A—H4A20.9700C4B—H4B20.9700
C5A—O3A1.217 (3)C5B—O3B1.224 (3)
C5A—C6A1.482 (4)C5B—C6B1.485 (4)
C6A—C7A1.378 (4)C6B—C11B1.384 (3)
C6A—C11A1.388 (4)C6B—C7B1.385 (3)
C7A—C8A1.378 (4)C7B—C8B1.369 (4)
C7A—H7A0.9300C7B—H7B0.9300
C8A—C9A1.367 (4)C8B—C9B1.372 (4)
C8A—H8A0.9300C8B—H8B0.9300
C9A—C10A1.365 (4)C9B—C10B1.367 (4)
C9A—H9A0.9300C9B—H9B0.9300
C10A—C11A1.381 (4)C10B—C11B1.390 (4)
C10A—H10A0.9300C10B—H10B0.9300
C11A—H11A0.9300C11B—H11B0.9300
O1A—HO1A0.94 (4)O1B—HO1B1.02 (5)
O2A—C1A—O1A122.4 (2)O2B—C1B—O1B122.7 (3)
O2A—C1A—C2A123.1 (3)O2B—C1B—C2B123.3 (3)
O1A—C1A—C2A114.2 (3)O1B—C1B—C2B113.9 (3)
C1A—C2A—C4A112.3 (2)C1B—C2B—C3B108.9 (2)
C1A—C2A—C3A107.8 (2)C1B—C2B—C4B111.4 (3)
C4A—C2A—C3A111.3 (2)C3B—C2B—C4B111.5 (2)
C1A—C2A—H2A108.5C1B—C2B—H2B108.3
C4A—C2A—H2A108.5C3B—C2B—H2B108.3
C3A—C2A—H2A108.5C4B—C2B—H2B108.3
C2A—C3A—H3A1109.5C2B—C3B—H3B1109.5
C2A—C3A—H3A2109.5C2B—C3B—H3B2109.5
H3A1—C3A—H3A2109.5H3B1—C3B—H3B2109.5
C2A—C3A—H3A3109.5C2B—C3B—H3B3109.5
H3A1—C3A—H3A3109.5H3B1—C3B—H3B3109.5
H3A2—C3A—H3A3109.5H3B2—C3B—H3B3109.5
C5A—C4A—C2A113.2 (2)C5B—C4B—C2B113.7 (2)
C5A—C4A—H4A1108.9C5B—C4B—H4B1108.8
C2A—C4A—H4A1108.9C2B—C4B—H4B1108.8
C5A—C4A—H4A2108.9C5B—C4B—H4B2108.8
C2A—C4A—H4A2108.9C2B—C4B—H4B2108.8
H4A1—C4A—H4A2107.8H4B1—C4B—H4B2107.7
O3A—C5A—C6A120.8 (3)O3B—C5B—C6B119.7 (3)
O3A—C5A—C4A119.9 (3)O3B—C5B—C4B120.5 (3)
C6A—C5A—C4A119.3 (2)C6B—C5B—C4B119.9 (2)
C7A—C6A—C11A118.3 (3)C11B—C6B—C7B118.4 (3)
C7A—C6A—C5A119.2 (3)C11B—C6B—C5B122.3 (3)
C11A—C6A—C5A122.3 (3)C7B—C6B—C5B119.3 (3)
C6A—C7A—C8A121.3 (3)C8B—C7B—C6B121.2 (3)
C6A—C7A—H7A119.4C8B—C7B—H7B119.4
C8A—C7A—H7A119.4C6B—C7B—H7B119.4
C9A—C8A—C7A119.5 (3)C7B—C8B—C9B120.1 (3)
C9A—C8A—H8A120.2C7B—C8B—H8B119.9
C7A—C8A—H8A120.2C9B—C8B—H8B119.9
C10A—C9A—C8A120.3 (3)C10B—C9B—C8B119.8 (3)
C10A—C9A—H9A119.8C10B—C9B—H9B120.1
C8A—C9A—H9A119.8C8B—C9B—H9B120.1
C9A—C10A—C11A120.3 (3)C9B—C10B—C11B120.5 (3)
C9A—C10A—H10A119.8C9B—C10B—H10B119.8
C11A—C10A—H10A119.8C11B—C10B—H10B119.8
C10A—C11A—C6A120.2 (3)C6B—C11B—C10B120.0 (3)
C10A—C11A—H11A119.9C6B—C11B—H11B120.0
C6A—C11A—H11A119.9C10B—C11B—H11B120.0
C1A—O1A—HO1A109 (2)C1B—O1B—HO1B111 (2)
O2A—C1A—C2A—C4A33.1 (4)O2B—C1B—C2B—C3B95.7 (3)
O1A—C1A—C2A—C4A152.7 (2)O1B—C1B—C2B—C3B80.8 (3)
O2A—C1A—C2A—C3A89.9 (3)O2B—C1B—C2B—C4B27.7 (4)
O1A—C1A—C2A—C3A84.4 (3)O1B—C1B—C2B—C4B155.8 (2)
C1A—C2A—C4A—C5A68.0 (3)C1B—C2B—C4B—C5B62.7 (3)
C3A—C2A—C4A—C5A171.1 (2)C3B—C2B—C4B—C5B175.4 (2)
C2A—C4A—C5A—O3A9.5 (4)C2B—C4B—C5B—O3B2.2 (4)
C2A—C4A—C5A—C6A169.5 (2)C2B—C4B—C5B—C6B177.7 (2)
O3A—C5A—C6A—C7A6.2 (4)O3B—C5B—C6B—C11B169.1 (3)
C4A—C5A—C6A—C7A172.7 (3)C4B—C5B—C6B—C11B11.0 (4)
O3A—C5A—C6A—C11A176.8 (3)O3B—C5B—C6B—C7B10.5 (4)
C4A—C5A—C6A—C11A4.3 (4)C4B—C5B—C6B—C7B169.4 (2)
C11A—C6A—C7A—C8A1.1 (4)C11B—C6B—C7B—C8B0.9 (4)
C5A—C6A—C7A—C8A176.1 (3)C5B—C6B—C7B—C8B179.5 (3)
C6A—C7A—C8A—C9A0.1 (5)C6B—C7B—C8B—C9B1.1 (5)
C7A—C8A—C9A—C10A1.0 (6)C7B—C8B—C9B—C10B0.2 (5)
C8A—C9A—C10A—C11A1.2 (6)C8B—C9B—C10B—C11B0.8 (5)
C9A—C10A—C11A—C6A0.3 (5)C7B—C6B—C11B—C10B0.1 (4)
C7A—C6A—C11A—C10A0.9 (5)C5B—C6B—C11B—C10B179.5 (3)
C5A—C6A—C11A—C10A176.2 (3)C9B—C10B—C11B—C6B0.9 (5)
(II) morpholinium rac-3-benzoyl-2-methylpropionate monohydrate top
Crystal data top
C4H10NO+·C11H11O3·H2OF(000) = 640
Mr = 297.34Dx = 1.243 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 946 reflections
a = 15.010 (5) Åθ = 2.7–18.5°
b = 6.697 (2) ŵ = 0.09 mm1
c = 16.017 (5) ÅT = 299 K
β = 99.21 (3)°Block, colourless
V = 1589.3 (9) Å30.50 × 0.20 × 0.10 mm
Z = 4
Data collection top
Kuma KM4 CCD
diffractometer
1366 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.060
Graphite monochromatorθmax = 25.0°, θmin = 3.3°
ω scansh = 1617
8314 measured reflectionsk = 75
2746 independent reflectionsl = 1818
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128H atoms treated by a mixture of independent and constrained refinement
S = 0.96 w = 1/[σ2(Fo2) + (0.0479P)2]
where P = (Fo2 + 2Fc2)/3
2746 reflections(Δ/σ)max < 0.001
198 parametersΔρmax = 0.12 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C4H10NO+·C11H11O3·H2OV = 1589.3 (9) Å3
Mr = 297.34Z = 4
Monoclinic, P21/nMo Kα radiation
a = 15.010 (5) ŵ = 0.09 mm1
b = 6.697 (2) ÅT = 299 K
c = 16.017 (5) Å0.50 × 0.20 × 0.10 mm
β = 99.21 (3)°
Data collection top
Kuma KM4 CCD
diffractometer
1366 reflections with I > 2σ(I)
8314 measured reflectionsRint = 0.060
2746 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0550 restraints
wR(F2) = 0.128H atoms treated by a mixture of independent and constrained refinement
S = 0.96Δρmax = 0.12 e Å3
2746 reflectionsΔρmin = 0.18 e Å3
198 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.63835 (18)0.3001 (5)0.35558 (15)0.0457 (7)
C20.55508 (18)0.3153 (4)0.39719 (16)0.0500 (7)
H20.52870.44820.38520.060*
C30.5824 (2)0.2954 (4)0.49276 (17)0.0657 (9)
H3A0.62730.39400.51260.099*
H3B0.60670.16450.50600.099*
H3C0.53050.31530.51980.099*
C40.48522 (19)0.1631 (4)0.36415 (17)0.0567 (8)
H4A0.43290.18220.39190.068*
H4B0.50930.03120.37920.068*
C50.4554 (2)0.1711 (5)0.27033 (19)0.0581 (8)
C60.39609 (19)0.0119 (4)0.22858 (19)0.0535 (8)
C70.3609 (2)0.0309 (5)0.1435 (2)0.0703 (9)
H70.37400.14390.11390.084*
C80.3068 (2)0.1153 (6)0.1025 (2)0.0852 (11)
H80.28330.10030.04550.102*
C90.2874 (2)0.2819 (6)0.1444 (3)0.0841 (11)
H90.25090.38080.11600.101*
C100.3212 (2)0.3042 (5)0.2279 (3)0.0790 (10)
H100.30780.41850.25640.095*
C110.3754 (2)0.1585 (5)0.2708 (2)0.0647 (9)
H110.39810.17470.32790.078*
O10.67893 (13)0.4583 (3)0.34239 (11)0.0595 (6)
O20.66569 (12)0.1310 (3)0.33849 (12)0.0597 (6)
O30.47971 (15)0.3070 (3)0.22875 (14)0.0829 (7)
C120.5972 (2)0.7779 (4)0.17666 (18)0.0578 (8)
H12A0.62050.87410.22000.069*
H12B0.53810.73500.18680.069*
C130.5891 (2)0.8731 (4)0.09166 (19)0.0661 (9)
H13A0.54730.98430.08860.079*
H13B0.64740.92500.08360.079*
C140.6188 (2)0.5741 (5)0.02879 (19)0.0691 (9)
H14A0.67740.62370.02060.083*
H14B0.59750.48290.01720.083*
C150.6280 (2)0.4640 (4)0.11092 (19)0.0621 (9)
H15A0.57040.40580.11780.075*
H15B0.67160.35690.11140.075*
N10.65827 (14)0.6046 (3)0.18126 (13)0.0511 (6)
H1A0.65920.54170.23100.061*
H1B0.71470.64660.17830.061*
O40.55822 (14)0.7352 (3)0.02660 (13)0.0692 (6)
O50.6530 (2)0.7933 (5)0.44136 (17)0.0928 (9)
HO5A0.657 (3)0.882 (6)0.412 (3)0.14 (2)*
HO5B0.669 (3)0.687 (6)0.409 (3)0.136 (18)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0459 (18)0.0575 (18)0.0334 (16)0.0032 (16)0.0055 (13)0.0074 (15)
C20.0487 (18)0.0547 (18)0.0498 (18)0.0023 (14)0.0179 (15)0.0022 (14)
C30.078 (2)0.073 (2)0.049 (2)0.0087 (17)0.0210 (17)0.0052 (16)
C40.0509 (19)0.074 (2)0.0483 (18)0.0019 (16)0.0160 (15)0.0088 (15)
C50.0455 (19)0.070 (2)0.060 (2)0.0048 (16)0.0121 (16)0.0142 (18)
C60.0417 (18)0.072 (2)0.0486 (19)0.0043 (15)0.0133 (15)0.0059 (16)
C70.062 (2)0.094 (2)0.056 (2)0.000 (2)0.0108 (18)0.009 (2)
C80.073 (3)0.120 (3)0.062 (2)0.009 (2)0.009 (2)0.006 (2)
C90.064 (2)0.101 (3)0.089 (3)0.014 (2)0.019 (2)0.034 (3)
C100.068 (2)0.083 (2)0.089 (3)0.010 (2)0.020 (2)0.004 (2)
C110.053 (2)0.083 (2)0.058 (2)0.0019 (18)0.0120 (17)0.0066 (19)
O10.0673 (14)0.0552 (12)0.0583 (13)0.0111 (11)0.0167 (11)0.0105 (10)
O20.0583 (14)0.0512 (12)0.0734 (14)0.0036 (10)0.0227 (11)0.0042 (10)
O30.0900 (17)0.0867 (16)0.0693 (15)0.0188 (13)0.0040 (13)0.0266 (13)
C120.055 (2)0.0631 (19)0.055 (2)0.0059 (16)0.0109 (15)0.0038 (16)
C130.070 (2)0.062 (2)0.065 (2)0.0071 (17)0.0059 (18)0.0054 (18)
C140.067 (2)0.087 (2)0.054 (2)0.006 (2)0.0113 (17)0.0118 (19)
C150.058 (2)0.0526 (18)0.079 (2)0.0045 (15)0.0185 (18)0.0086 (18)
N10.0463 (15)0.0606 (15)0.0478 (14)0.0028 (12)0.0121 (12)0.0143 (12)
O40.0602 (14)0.0887 (16)0.0551 (13)0.0061 (12)0.0017 (11)0.0017 (12)
O50.134 (2)0.0627 (17)0.0805 (19)0.0028 (17)0.0148 (17)0.0079 (17)
Geometric parameters (Å, º) top
C1—O21.249 (3)C10—C111.380 (4)
C1—O11.257 (3)C10—H100.9300
C1—C21.511 (3)C11—H110.9300
C2—C41.497 (4)C12—N11.474 (3)
C2—C31.526 (3)C12—C131.491 (4)
C2—H20.9800C12—H12A0.9700
C3—H3A0.9600C12—H12B0.9700
C3—H3B0.9600C13—O41.414 (3)
C3—H3C0.9600C13—H13A0.9700
C4—C51.499 (4)C13—H13B0.9700
C4—H4A0.9700C14—O41.408 (3)
C4—H4B0.9700C14—C151.495 (4)
C5—O31.218 (3)C14—H14A0.9700
C5—C61.478 (4)C14—H14B0.9700
C6—C111.387 (4)C15—N11.483 (3)
C6—C71.387 (4)C15—H15A0.9700
C7—C81.370 (4)C15—H15B0.9700
C7—H70.9300N1—H1A0.9000
C8—C91.358 (4)N1—H1B0.9000
C8—H80.9300O5—HO5A0.77 (4)
C9—C101.361 (4)O5—HO5B0.93 (4)
C9—H90.9300
O2—C1—O1122.8 (3)C9—C10—H10119.7
O2—C1—C2118.8 (3)C11—C10—H10119.7
O1—C1—C2118.3 (3)C10—C11—C6120.0 (3)
C4—C2—C1112.3 (2)C10—C11—H11120.0
C4—C2—C3110.8 (2)C6—C11—H11120.0
C1—C2—C3109.1 (2)N1—C12—C13110.0 (2)
C4—C2—H2108.1N1—C12—H12A109.7
C1—C2—H2108.1C13—C12—H12A109.7
C3—C2—H2108.1N1—C12—H12B109.7
C2—C3—H3A109.5C13—C12—H12B109.7
C2—C3—H3B109.5H12A—C12—H12B108.2
H3A—C3—H3B109.5O4—C13—C12111.3 (2)
C2—C3—H3C109.5O4—C13—H13A109.4
H3A—C3—H3C109.5C12—C13—H13A109.4
H3B—C3—H3C109.5O4—C13—H13B109.4
C2—C4—C5114.2 (2)C12—C13—H13B109.4
C2—C4—H4A108.7H13A—C13—H13B108.0
C5—C4—H4A108.7O4—C14—C15111.6 (2)
C2—C4—H4B108.7O4—C14—H14A109.3
C5—C4—H4B108.7C15—C14—H14A109.3
H4A—C4—H4B107.6O4—C14—H14B109.3
O3—C5—C6120.2 (3)C15—C14—H14B109.3
O3—C5—C4120.5 (3)H14A—C14—H14B108.0
C6—C5—C4119.3 (3)N1—C15—C14109.2 (2)
C11—C6—C7118.3 (3)N1—C15—H15A109.8
C11—C6—C5122.6 (3)C14—C15—H15A109.8
C7—C6—C5119.1 (3)N1—C15—H15B109.8
C8—C7—C6120.6 (3)C14—C15—H15B109.8
C8—C7—H7119.7H15A—C15—H15B108.3
C6—C7—H7119.7C12—N1—C15110.4 (2)
C9—C8—C7120.6 (3)C12—N1—H1A109.6
C9—C8—H8119.7C15—N1—H1A109.6
C7—C8—H8119.7C12—N1—H1B109.6
C8—C9—C10120.0 (4)C15—N1—H1B109.6
C8—C9—H9120.0H1A—N1—H1B108.1
C10—C9—H9120.0C14—O4—C13110.4 (2)
C9—C10—C11120.6 (3)HO5A—O5—HO5B101 (4)
O2—C1—C2—C437.7 (3)C5—C6—C7—C8179.0 (3)
O1—C1—C2—C4144.8 (2)C6—C7—C8—C90.5 (5)
O2—C1—C2—C385.7 (3)C7—C8—C9—C100.4 (5)
O1—C1—C2—C391.8 (3)C8—C9—C10—C110.0 (5)
C1—C2—C4—C556.9 (3)C9—C10—C11—C60.3 (5)
C3—C2—C4—C5179.3 (2)C7—C6—C11—C100.2 (4)
C2—C4—C5—O38.1 (4)C5—C6—C11—C10178.6 (3)
C2—C4—C5—C6171.8 (2)N1—C12—C13—O457.2 (3)
O3—C5—C6—C11171.8 (3)O4—C14—C15—N157.5 (3)
C4—C5—C6—C118.1 (4)C13—C12—N1—C1554.5 (3)
O3—C5—C6—C76.9 (4)C14—C15—N1—C1254.3 (3)
C4—C5—C6—C7173.2 (3)C15—C14—O4—C1360.6 (3)
C11—C6—C7—C80.2 (4)C12—C13—O4—C1460.1 (3)
(III) pyridinium [hydrogen bis(rac-3-benzoyl-2-methylpropionate)] top
Crystal data top
C5H6N+·H+·2C11H11O3F(000) = 984
Mr = 463.51Dx = 1.209 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 1115 reflections
a = 25.759 (6) Åθ = 3.0–18.9°
b = 10.172 (2) ŵ = 0.09 mm1
c = 9.776 (2) ÅT = 299 K
β = 96.34 (2)°Block, colourless
V = 2545.8 (9) Å30.60 × 0.30 × 0.15 mm
Z = 4
Data collection top
Kuma KM4 CCD
diffractometer
1454 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.040
Graphite monochromatorθmax = 25.0°, θmin = 3.6°
ω scansh = 2830
6670 measured reflectionsk = 1112
2199 independent reflectionsl = 116
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.063Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.210H-atom parameters constrained
S = 1.11 w = 1/[σ2(Fo2) + (0.1206P)2 + 0.2239P]
where P = (Fo2 + 2Fc2)/3
2199 reflections(Δ/σ)max < 0.001
156 parametersΔρmax = 0.22 e Å3
7 restraintsΔρmin = 0.21 e Å3
Crystal data top
C5H6N+·H+·2C11H11O3V = 2545.8 (9) Å3
Mr = 463.51Z = 4
Monoclinic, C2/cMo Kα radiation
a = 25.759 (6) ŵ = 0.09 mm1
b = 10.172 (2) ÅT = 299 K
c = 9.776 (2) Å0.60 × 0.30 × 0.15 mm
β = 96.34 (2)°
Data collection top
Kuma KM4 CCD
diffractometer
1454 reflections with I > 2σ(I)
6670 measured reflectionsRint = 0.040
2199 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0637 restraints
wR(F2) = 0.210H-atom parameters constrained
S = 1.11Δρmax = 0.22 e Å3
2199 reflectionsΔρmin = 0.21 e Å3
156 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.06840 (9)0.4104 (2)0.1105 (3)0.0666 (7)
C20.10296 (9)0.4036 (3)0.2455 (3)0.0678 (7)
H20.10110.48830.29250.081*
C30.08289 (12)0.2977 (3)0.3353 (3)0.0901 (9)
H3A0.10490.29330.42120.135*
H3B0.08330.21440.28930.135*
H3C0.04780.31840.35250.135*
C40.15940 (9)0.3771 (3)0.2249 (3)0.0703 (7)
H4A0.17870.36090.31420.084*
H4B0.16090.29750.17090.084*
C50.18602 (10)0.4843 (3)0.1557 (3)0.0704 (7)
C60.23955 (9)0.4621 (3)0.1171 (2)0.0667 (7)
C70.26233 (11)0.5590 (3)0.0451 (3)0.0890 (9)
H70.24460.63750.02480.107*
C80.31145 (13)0.5401 (4)0.0029 (3)0.1031 (11)
H80.32650.60580.04580.124*
C90.33768 (12)0.4251 (4)0.0327 (3)0.1006 (10)
H90.37040.41240.00320.121*
C100.31636 (11)0.3299 (3)0.1048 (3)0.0877 (9)
H100.33470.25240.12600.105*
C110.26728 (10)0.3474 (3)0.1471 (3)0.0779 (8)
H110.25280.28110.19620.093*
O10.03023 (7)0.49029 (17)0.10689 (17)0.0788 (6)
HO10.00000.50000.00000.18 (2)*
O20.07553 (8)0.3375 (2)0.01525 (19)0.1040 (8)
O30.16416 (8)0.5889 (2)0.1291 (3)0.1052 (8)
N10.00000.7117 (3)0.25000.0989 (12)
H10.00000.62710.25000.119*
C120.04013 (11)0.7802 (3)0.2005 (4)0.1218 (14)
H120.06760.73400.16910.146*
C130.04039 (15)0.9176 (3)0.1963 (5)0.153 (2)
H130.06700.96170.15840.184*
C140.00000.9898 (4)0.25000.1227 (19)
H140.00001.08120.25000.147*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0576 (14)0.0653 (15)0.0794 (15)0.0005 (12)0.0189 (12)0.0142 (12)
C20.0615 (15)0.0679 (15)0.0755 (15)0.0046 (11)0.0139 (12)0.0098 (11)
C30.0734 (18)0.097 (2)0.104 (2)0.0057 (16)0.0269 (15)0.0111 (16)
C40.0552 (14)0.0730 (16)0.0833 (15)0.0013 (11)0.0107 (12)0.0011 (13)
C50.0620 (15)0.0666 (16)0.0812 (16)0.0004 (12)0.0012 (12)0.0017 (12)
C60.0563 (14)0.0727 (16)0.0701 (14)0.0093 (12)0.0022 (11)0.0039 (12)
C70.0722 (19)0.089 (2)0.104 (2)0.0149 (15)0.0022 (15)0.0155 (16)
C80.077 (2)0.124 (3)0.110 (2)0.027 (2)0.0154 (17)0.022 (2)
C90.0643 (18)0.137 (3)0.102 (2)0.011 (2)0.0147 (16)0.001 (2)
C100.0617 (16)0.099 (2)0.104 (2)0.0079 (15)0.0135 (15)0.0027 (17)
C110.0622 (16)0.0840 (18)0.0880 (17)0.0003 (14)0.0111 (13)0.0060 (14)
O10.0604 (11)0.0836 (12)0.0933 (13)0.0149 (9)0.0118 (9)0.0203 (10)
O20.0976 (16)0.1232 (17)0.0888 (13)0.0431 (13)0.0011 (11)0.0344 (12)
O30.0846 (14)0.0802 (14)0.1524 (19)0.0127 (11)0.0210 (13)0.0157 (13)
N10.164 (4)0.0566 (18)0.086 (2)0.0000.057 (2)0.000
C120.078 (2)0.090 (2)0.202 (4)0.0010 (18)0.034 (2)0.038 (3)
C130.127 (3)0.093 (3)0.257 (6)0.019 (2)0.096 (4)0.068 (3)
C140.119 (4)0.055 (2)0.198 (6)0.0000.032 (4)0.000
Geometric parameters (Å, º) top
C1—O21.220 (3)C8—C91.366 (4)
C1—O11.273 (3)C8—H80.9300
C1—C21.509 (4)C9—C101.349 (4)
C2—C41.514 (3)C9—H90.9300
C2—C31.517 (4)C10—C111.384 (4)
C2—H20.9800C10—H100.9300
C3—H3A0.9600C11—H110.9300
C3—H3B0.9600O1—HO11.24
C3—H3C0.9600N1—C121.378 (3)
C4—C51.490 (4)N1—C12i1.378 (3)
C4—H4A0.9700N1—H10.8600
C4—H4B0.9700C12—C131.399 (3)
C5—O31.219 (3)C12—H120.9300
C5—C61.486 (4)C13—C141.420 (3)
C6—C71.380 (4)C13—H130.9300
C6—C111.382 (4)C14—C13i1.420 (3)
C7—C81.387 (4)C14—H140.9300
C7—H70.9300
O2—C1—O1123.2 (2)C6—C7—H7119.8
O2—C1—C2121.0 (2)C8—C7—H7119.8
O1—C1—C2115.7 (2)C9—C8—C7120.1 (3)
C1—C2—C4112.0 (2)C9—C8—H8120.0
C1—C2—C3109.5 (2)C7—C8—H8120.0
C4—C2—C3110.1 (2)C10—C9—C8120.4 (3)
C1—C2—H2108.4C10—C9—H9119.8
C4—C2—H2108.4C8—C9—H9119.8
C3—C2—H2108.4C9—C10—C11120.1 (3)
C2—C3—H3A109.5C9—C10—H10120.0
C2—C3—H3B109.5C11—C10—H10120.0
H3A—C3—H3B109.5C6—C11—C10120.9 (3)
C2—C3—H3C109.5C6—C11—H11119.6
H3A—C3—H3C109.5C10—C11—H11119.6
H3B—C3—H3C109.5C1—O1—HO1119
C5—C4—C2115.3 (2)C12—N1—C12i119.2 (3)
C5—C4—H4A108.5C12—N1—H1120.4
C2—C4—H4A108.5C12i—N1—H1120.4
C5—C4—H4B108.5N1—C12—C13121.5 (2)
C2—C4—H4B108.5N1—C12—H12119.3
H4A—C4—H4B107.5C13—C12—H12119.3
O3—C5—C6119.9 (2)C12—C13—C14120.0 (3)
O3—C5—C4120.7 (2)C12—C13—H13120.0
C6—C5—C4119.4 (2)C14—C13—H13120.0
C7—C6—C11118.2 (2)C13i—C14—C13117.8 (3)
C7—C6—C5118.7 (2)C13i—C14—H14121.1
C11—C6—C5123.2 (2)C13—C14—H14121.1
C6—C7—C8120.4 (3)
O2—C1—C2—C437.5 (3)C11—C6—C7—C80.8 (4)
O1—C1—C2—C4146.6 (2)C5—C6—C7—C8177.6 (3)
O2—C1—C2—C384.9 (3)C6—C7—C8—C90.1 (5)
O1—C1—C2—C390.9 (3)C7—C8—C9—C100.8 (5)
C1—C2—C4—C566.5 (3)C8—C9—C10—C111.0 (5)
C3—C2—C4—C5171.4 (2)C7—C6—C11—C100.6 (4)
C2—C4—C5—O35.7 (4)C5—C6—C11—C10177.8 (2)
C2—C4—C5—C6173.4 (2)C9—C10—C11—C60.3 (4)
O3—C5—C6—C73.3 (4)C12i—N1—C12—C131.6 (4)
C4—C5—C6—C7175.8 (2)N1—C12—C13—C143.1 (7)
O3—C5—C6—C11178.3 (3)C12—C13—C14—C13i1.5 (4)
C4—C5—C6—C112.6 (4)
Symmetry code: (i) x, y, z+1/2.
(IV) pyrrolidinium rac-3-benzoyl-2-methylpropionate rac-3-benzoyl-2-methylpropionic acid top
Crystal data top
C4H10N+·C11H11O3+·C11H12O3F(000) = 976
Mr = 455.53Dx = 1.228 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 852 reflections
a = 26.249 (9) Åθ = 3.0–18.2°
b = 9.556 (3) ŵ = 0.09 mm1
c = 9.869 (3) ÅT = 299 K
β = 95.32 (3)°Block, colourless
V = 2464.8 (14) Å30.35 × 0.25 × 0.20 mm
Z = 4
Data collection top
Kuma KM4 CCD
diffractometer
1733 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.062
Graphite monochromatorθmax = 25.0°, θmin = 2.6°
ω scansh = 3131
12988 measured reflectionsk = 1111
4295 independent reflectionsl = 511
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.063Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.199H atoms treated by a mixture of independent and constrained refinement
S = 0.96 w = 1/[σ2(Fo2) + (0.0827P)2]
where P = (Fo2 + 2Fc2)/3
4295 reflections(Δ/σ)max < 0.001
310 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C4H10N+·C11H11O3+·C11H12O3V = 2464.8 (14) Å3
Mr = 455.53Z = 4
Monoclinic, P21/cMo Kα radiation
a = 26.249 (9) ŵ = 0.09 mm1
b = 9.556 (3) ÅT = 299 K
c = 9.869 (3) Å0.35 × 0.25 × 0.20 mm
β = 95.32 (3)°
Data collection top
Kuma KM4 CCD
diffractometer
1733 reflections with I > 2σ(I)
12988 measured reflectionsRint = 0.062
4295 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0630 restraints
wR(F2) = 0.199H atoms treated by a mixture of independent and constrained refinement
S = 0.96Δρmax = 0.22 e Å3
4295 reflectionsΔρmin = 0.18 e Å3
310 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O1A0.28045 (9)0.7542 (3)0.5961 (2)0.0645 (7)
O2A0.32287 (9)0.9303 (3)0.5131 (2)0.0800 (8)
O3A0.40829 (10)0.6636 (3)0.6097 (3)0.0908 (9)
C1A0.31566 (13)0.8453 (4)0.6039 (3)0.0566 (9)
C2A0.34824 (12)0.8547 (4)0.7375 (3)0.0584 (10)
H2A0.34620.76540.78540.070*
C3A0.32717 (13)0.9688 (4)0.8229 (3)0.0863 (13)
H3A10.34750.97500.90870.129*
H3A20.29250.94710.83820.129*
H3A30.32821.05670.77600.129*
C4A0.40406 (12)0.8833 (4)0.7169 (3)0.0613 (10)
H4A10.40590.96990.66640.074*
H4A20.42270.89710.80540.074*
C5A0.43012 (13)0.7710 (4)0.6438 (3)0.0598 (10)
C6A0.48399 (13)0.7931 (4)0.6127 (3)0.0573 (9)
C7A0.50683 (15)0.6928 (4)0.5367 (4)0.0748 (11)
H7A0.48830.61360.50770.090*
C8A0.55613 (16)0.7077 (5)0.5032 (4)0.0863 (13)
H8A0.57070.63890.45250.104*
C9A0.58376 (15)0.8242 (5)0.5445 (4)0.0834 (13)
H9A0.61720.83480.52190.100*
C10A0.56217 (15)0.9245 (5)0.6189 (4)0.0777 (12)
H10A0.58091.00380.64630.093*
C11A0.51275 (14)0.9097 (4)0.6539 (3)0.0703 (11)
H11A0.49860.97860.70560.084*
O1B0.21790 (9)0.7438 (3)0.3864 (2)0.0690 (8)
HO1B0.2468 (17)0.752 (4)0.478 (5)0.16 (2)*
O2B0.17327 (10)0.5833 (3)0.4829 (3)0.0986 (10)
O3B0.08743 (10)0.8328 (3)0.3909 (3)0.0961 (9)
C1B0.18005 (14)0.6571 (4)0.3868 (3)0.0605 (10)
C2B0.14712 (12)0.6511 (4)0.2546 (3)0.0621 (10)
H2B0.14840.74250.20990.074*
C3B0.16874 (14)0.5419 (4)0.1636 (4)0.0854 (12)
H3B10.14780.53720.07860.128*
H3B20.16900.45230.20760.128*
H3B30.20300.56730.14720.128*
C4B0.09170 (12)0.6186 (4)0.2758 (3)0.0655 (10)
H4B10.07280.60720.18730.079*
H4B20.09070.52970.32300.079*
C5B0.06507 (14)0.7252 (4)0.3537 (4)0.0648 (10)
C6B0.01132 (13)0.7043 (4)0.3847 (3)0.0611 (10)
C7B0.01178 (16)0.8023 (4)0.4619 (4)0.0795 (12)
H7B0.00660.88130.49180.095*
C8B0.06096 (18)0.7869 (5)0.4958 (4)0.0948 (14)
H8B0.07560.85500.54730.114*
C9B0.08833 (17)0.6706 (5)0.4534 (5)0.0912 (13)
H9B0.12170.65900.47560.109*
C10B0.06627 (16)0.5721 (5)0.3783 (4)0.0889 (13)
H10B0.08480.49280.34990.107*
C11B0.01663 (15)0.5878 (4)0.3432 (4)0.0762 (12)
H11B0.00220.51950.29160.091*
N10.27156 (13)0.5286 (4)0.7683 (3)0.0672 (9)
H1A0.2609 (15)0.612 (5)0.717 (4)0.117 (17)*
H1B0.2911 (17)0.561 (5)0.864 (5)0.143 (17)*
C120.30435 (17)0.4319 (5)0.6978 (4)0.0943 (14)
H12A0.32330.48260.63370.113*
H12B0.32850.38460.76290.113*
C130.2698 (3)0.3319 (6)0.6272 (6)0.153 (2)
H13A0.28680.24370.61350.184*
H13B0.25560.36800.53990.184*
C140.2287 (2)0.3158 (6)0.7252 (7)0.149 (3)
H14A0.19690.28300.67770.179*
H14B0.23940.24990.79690.179*
C150.22207 (16)0.4582 (5)0.7823 (4)0.0908 (13)
H15A0.19420.50750.73150.109*
H15B0.21520.45300.87710.109*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O1A0.0538 (15)0.0858 (19)0.0519 (13)0.0148 (14)0.0065 (11)0.0060 (13)
O2A0.0815 (18)0.101 (2)0.0540 (14)0.0266 (16)0.0119 (13)0.0249 (14)
O3A0.0673 (18)0.072 (2)0.132 (2)0.0204 (16)0.0066 (16)0.0186 (18)
C1A0.046 (2)0.075 (3)0.048 (2)0.007 (2)0.0008 (17)0.001 (2)
C2A0.052 (2)0.078 (3)0.0439 (18)0.0153 (19)0.0042 (16)0.0055 (19)
C3A0.067 (3)0.131 (4)0.062 (2)0.018 (3)0.0104 (19)0.024 (2)
C4A0.050 (2)0.079 (3)0.0533 (19)0.011 (2)0.0023 (16)0.0000 (19)
C5A0.051 (2)0.065 (3)0.061 (2)0.005 (2)0.0097 (18)0.008 (2)
C6A0.053 (2)0.062 (3)0.055 (2)0.001 (2)0.0074 (17)0.0016 (18)
C7A0.057 (3)0.069 (3)0.096 (3)0.000 (2)0.007 (2)0.008 (2)
C8A0.065 (3)0.101 (4)0.092 (3)0.014 (3)0.001 (2)0.020 (3)
C9A0.056 (3)0.116 (4)0.078 (3)0.004 (3)0.005 (2)0.001 (3)
C10A0.056 (3)0.089 (3)0.086 (3)0.017 (2)0.000 (2)0.003 (2)
C11A0.058 (3)0.084 (3)0.069 (2)0.010 (2)0.0027 (19)0.015 (2)
O1B0.0551 (15)0.093 (2)0.0572 (14)0.0244 (15)0.0055 (12)0.0111 (14)
O2B0.095 (2)0.115 (2)0.0809 (18)0.0416 (18)0.0203 (16)0.0409 (17)
O3B0.0738 (19)0.075 (2)0.139 (2)0.0201 (16)0.0061 (16)0.0231 (18)
C1B0.057 (2)0.066 (3)0.058 (2)0.004 (2)0.0003 (19)0.012 (2)
C2B0.053 (2)0.071 (3)0.060 (2)0.0052 (19)0.0070 (18)0.002 (2)
C3B0.067 (3)0.109 (3)0.079 (3)0.004 (3)0.000 (2)0.015 (3)
C4B0.057 (2)0.072 (3)0.065 (2)0.009 (2)0.0051 (18)0.002 (2)
C5B0.064 (3)0.057 (3)0.070 (2)0.008 (2)0.010 (2)0.002 (2)
C6B0.053 (2)0.065 (3)0.063 (2)0.004 (2)0.0063 (18)0.009 (2)
C7B0.068 (3)0.073 (3)0.095 (3)0.004 (2)0.008 (2)0.006 (2)
C8B0.071 (3)0.106 (4)0.107 (3)0.018 (3)0.007 (3)0.009 (3)
C9B0.067 (3)0.103 (4)0.103 (3)0.002 (3)0.002 (3)0.012 (3)
C10B0.062 (3)0.097 (4)0.107 (3)0.021 (3)0.001 (2)0.002 (3)
C11B0.067 (3)0.078 (3)0.082 (3)0.019 (2)0.002 (2)0.012 (2)
N10.079 (2)0.068 (2)0.0543 (18)0.005 (2)0.0023 (17)0.0063 (19)
C120.109 (3)0.107 (4)0.067 (2)0.004 (3)0.012 (2)0.022 (3)
C130.207 (7)0.113 (5)0.131 (5)0.016 (5)0.036 (5)0.041 (4)
C140.140 (5)0.076 (4)0.220 (7)0.036 (4)0.043 (5)0.014 (5)
C150.084 (3)0.089 (3)0.097 (3)0.024 (3)0.003 (2)0.000 (3)
Geometric parameters (Å, º) top
O1A—C1A1.267 (4)C3B—H3B10.9600
O1A—HO1B1.39 (5)C3B—H3B20.9600
O2A—C1A1.237 (4)C3B—H3B30.9600
O3A—C5A1.208 (4)C4B—C5B1.489 (5)
C1A—C2A1.506 (4)C4B—H4B10.9700
C2A—C3A1.514 (4)C4B—H4B20.9700
C2A—C4A1.522 (4)C5B—C6B1.485 (5)
C2A—H2A0.9800C6B—C11B1.374 (5)
C3A—H3A10.9600C6B—C7B1.382 (5)
C3A—H3A20.9600C7B—C8B1.371 (5)
C3A—H3A30.9600C7B—H7B0.9300
C4A—C5A1.494 (5)C8B—C9B1.368 (5)
C4A—H4A10.9700C8B—H8B0.9300
C4A—H4A20.9700C9B—C10B1.360 (5)
C5A—C6A1.489 (5)C9B—H9B0.9300
C6A—C11A1.386 (5)C10B—C11B1.387 (5)
C6A—C7A1.387 (5)C10B—H10B0.9300
C7A—C8A1.372 (5)C11B—H11B0.9300
C7A—H7A0.9300N1—C121.480 (5)
C8A—C9A1.370 (5)N1—C151.481 (5)
C8A—H8A0.9300N1—H1A0.97 (4)
C9A—C10A1.362 (5)N1—H1B1.07 (5)
C9A—H9A0.9300C12—C131.451 (6)
C10A—C11A1.380 (5)C12—H12A0.9700
C10A—H10A0.9300C12—H12B0.9700
C11A—H11A0.9300C13—C141.523 (7)
O1B—C1B1.294 (4)C13—H13A0.9700
O1B—HO1B1.13 (5)C13—H13B0.9700
O2B—C1B1.208 (4)C14—C151.489 (6)
O3B—C5B1.223 (4)C14—H14A0.9700
C1B—C2B1.499 (4)C14—H14B0.9700
C2B—C3B1.520 (4)C15—H15A0.9700
C2B—C4B1.521 (4)C15—H15B0.9700
C2B—H2B0.9800
C1A—O1A—HO1B117.5 (17)H3B2—C3B—H3B3109.5
O2A—C1A—O1A124.6 (3)C5B—C4B—C2B115.6 (3)
O2A—C1A—C2A118.8 (3)C5B—C4B—H4B1108.4
O1A—C1A—C2A116.5 (3)C2B—C4B—H4B1108.4
C1A—C2A—C3A108.9 (3)C5B—C4B—H4B2108.4
C1A—C2A—C4A111.7 (3)C2B—C4B—H4B2108.4
C3A—C2A—C4A110.5 (3)H4B1—C4B—H4B2107.4
C1A—C2A—H2A108.6O3B—C5B—C6B119.3 (4)
C3A—C2A—H2A108.6O3B—C5B—C4B119.7 (4)
C4A—C2A—H2A108.6C6B—C5B—C4B121.0 (3)
C2A—C3A—H3A1109.5C11B—C6B—C7B117.6 (4)
C2A—C3A—H3A2109.5C11B—C6B—C5B122.6 (4)
H3A1—C3A—H3A2109.5C7B—C6B—C5B119.8 (4)
C2A—C3A—H3A3109.5C8B—C7B—C6B122.2 (4)
H3A1—C3A—H3A3109.5C8B—C7B—H7B118.9
H3A2—C3A—H3A3109.5C6B—C7B—H7B118.9
C5A—C4A—C2A115.2 (3)C9B—C8B—C7B119.5 (4)
C5A—C4A—H4A1108.5C9B—C8B—H8B120.3
C2A—C4A—H4A1108.5C7B—C8B—H8B120.3
C5A—C4A—H4A2108.5C10B—C9B—C8B119.4 (4)
C2A—C4A—H4A2108.5C10B—C9B—H9B120.3
H4A1—C4A—H4A2107.5C8B—C9B—H9B120.3
O3A—C5A—C6A119.9 (4)C9B—C10B—C11B121.2 (4)
O3A—C5A—C4A121.2 (3)C9B—C10B—H10B119.4
C6A—C5A—C4A118.9 (3)C11B—C10B—H10B119.4
C11A—C6A—C7A117.6 (3)C6B—C11B—C10B120.1 (4)
C11A—C6A—C5A123.8 (4)C6B—C11B—H11B120.0
C7A—C6A—C5A118.6 (4)C10B—C11B—H11B120.0
C8A—C7A—C6A121.5 (4)C12—N1—C15108.3 (3)
C8A—C7A—H7A119.2C12—N1—H1A115 (2)
C6A—C7A—H7A119.2C15—N1—H1A102 (2)
C9A—C8A—C7A119.8 (4)C12—N1—H1B110 (2)
C9A—C8A—H8A120.1C15—N1—H1B114 (2)
C7A—C8A—H8A120.1H1A—N1—H1B108 (3)
C10A—C9A—C8A119.8 (4)C13—C12—N1105.8 (4)
C10A—C9A—H9A120.1C13—C12—H12A110.6
C8A—C9A—H9A120.1N1—C12—H12A110.6
C9A—C10A—C11A120.7 (4)C13—C12—H12B110.6
C9A—C10A—H10A119.7N1—C12—H12B110.6
C11A—C10A—H10A119.7H12A—C12—H12B108.7
C10A—C11A—C6A120.5 (4)C12—C13—C14102.1 (4)
C10A—C11A—H11A119.7C12—C13—H13A111.3
C6A—C11A—H11A119.7C14—C13—H13A111.3
C1B—O1B—HO1B120 (2)C12—C13—H13B111.3
O2B—C1B—O1B123.0 (3)C14—C13—H13B111.3
O2B—C1B—C2B123.1 (3)H13A—C13—H13B109.2
O1B—C1B—C2B113.7 (3)C15—C14—C13105.2 (4)
C1B—C2B—C3B108.9 (3)C15—C14—H14A110.7
C1B—C2B—C4B111.7 (3)C13—C14—H14A110.7
C3B—C2B—C4B110.8 (3)C15—C14—H14B110.7
C1B—C2B—H2B108.5C13—C14—H14B110.7
C3B—C2B—H2B108.5H14A—C14—H14B108.8
C4B—C2B—H2B108.5N1—C15—C14104.2 (4)
C2B—C3B—H3B1109.5N1—C15—H15A110.9
C2B—C3B—H3B2109.5C14—C15—H15A110.9
H3B1—C3B—H3B2109.5N1—C15—H15B110.9
C2B—C3B—H3B3109.5C14—C15—H15B110.9
H3B1—C3B—H3B3109.5H15A—C15—H15B108.9
O2A—C1A—C2A—C3A80.5 (4)O1B—C1B—C2B—C4B148.7 (3)
O1A—C1A—C2A—C3A95.6 (4)C1B—C2B—C4B—C5B63.4 (4)
O2A—C1A—C2A—C4A41.9 (5)C3B—C2B—C4B—C5B175.0 (3)
O1A—C1A—C2A—C4A142.1 (3)C2B—C4B—C5B—O3B2.8 (5)
C1A—C2A—C4A—C5A63.6 (4)C2B—C4B—C5B—C6B178.3 (3)
C3A—C2A—C4A—C5A175.1 (3)O3B—C5B—C6B—C11B178.3 (3)
C2A—C4A—C5A—O3A3.1 (5)C4B—C5B—C6B—C11B0.5 (5)
C2A—C4A—C5A—C6A176.9 (3)O3B—C5B—C6B—C7B3.8 (5)
O3A—C5A—C6A—C11A176.6 (3)C4B—C5B—C6B—C7B177.4 (3)
C4A—C5A—C6A—C11A3.4 (5)C11B—C6B—C7B—C8B0.7 (6)
O3A—C5A—C6A—C7A4.3 (5)C5B—C6B—C7B—C8B178.7 (3)
C4A—C5A—C6A—C7A175.6 (3)C6B—C7B—C8B—C9B0.5 (6)
C11A—C6A—C7A—C8A0.1 (5)C7B—C8B—C9B—C10B0.1 (6)
C5A—C6A—C7A—C8A179.2 (3)C8B—C9B—C10B—C11B0.4 (6)
C6A—C7A—C8A—C9A0.4 (6)C7B—C6B—C11B—C10B0.4 (5)
C7A—C8A—C9A—C10A0.1 (6)C5B—C6B—C11B—C10B178.3 (3)
C8A—C9A—C10A—C11A0.4 (6)C9B—C10B—C11B—C6B0.2 (6)
C9A—C10A—C11A—C6A0.7 (6)C15—N1—C12—C1320.7 (5)
C7A—C6A—C11A—C10A0.4 (5)N1—C12—C13—C1435.0 (5)
C5A—C6A—C11A—C10A178.6 (3)C12—C13—C14—C1537.4 (6)
O2B—C1B—C2B—C3B88.2 (4)C12—N1—C15—C143.2 (5)
O1B—C1B—C2B—C3B88.6 (4)C13—C14—C15—N124.7 (6)
O2B—C1B—C2B—C4B34.4 (5)

Experimental details

(I)(II)(III)(IV)
Crystal data
Chemical formulaC11H12O3C4H10NO+·C11H11O3·H2OC5H6N+·H+·2C11H11O3C4H10N+·C11H11O3+·C11H12O3
Mr192.21297.34463.51455.53
Crystal system, space groupMonoclinic, P21/cMonoclinic, P21/nMonoclinic, C2/cMonoclinic, P21/c
Temperature (K)299299299299
a, b, c (Å)14.951 (3), 6.0452 (9), 22.935 (4)15.010 (5), 6.697 (2), 16.017 (5)25.759 (6), 10.172 (2), 9.776 (2)26.249 (9), 9.556 (3), 9.869 (3)
β (°) 101.201 (17) 99.21 (3) 96.34 (2) 95.32 (3)
V3)2033.4 (6)1589.3 (9)2545.8 (9)2464.8 (14)
Z8444
Radiation typeMo KαMo KαMo KαMo Kα
µ (mm1)0.090.090.090.09
Crystal size (mm)0.40 × 0.20 × 0.200.50 × 0.20 × 0.100.60 × 0.30 × 0.150.35 × 0.25 × 0.20
Data collection
DiffractometerKuma KM4 CCD
diffractometer
Kuma KM4 CCD
diffractometer
Kuma KM4 CCD
diffractometer
Kuma KM4 CCD
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
10560, 3550, 1715 8314, 2746, 1366 6670, 2199, 1454 12988, 4295, 1733
Rint0.0560.0600.0400.062
(sin θ/λ)max1)0.5950.5940.5950.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.053, 0.139, 0.95 0.055, 0.128, 0.96 0.063, 0.210, 1.11 0.063, 0.199, 0.96
No. of reflections3550274621994295
No. of parameters261198156310
No. of restraints0070
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH-atom parameters constrainedH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.16, 0.150.12, 0.180.22, 0.210.22, 0.18

Computer programs: CrysAlis CCD (Oxford Diffraction, 2003), CrysAlis RED (Oxford Diffraction, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Geometry of strong hydrogen bonds in the crystal structures of compounds (I)–(IV) (Å, °) top
Compound/bondaD—HH···AD···AD—H···A
(I)
O1A—HO1A···O2Ai0.94 (4)1.70 (4)2.634 (3)172 (4)
O1B—HO1B···O2Bii1.02 (5)1.65 (5)2.667 (3)176 (4)
(II)
N1—H1A···O10.901.852.732 (3)167
N1—H1B···O2i0.901.862.717 (3)158
O5—HO5B···O10.93 (4)1.89 (4)2.810 (4)170 (4)
O5—HO5A···O2ii0.77 (4)2.06 (4)2.823 (4)177 (4)
(III)
N1—H1···O10.862.182.807 (3)130
N1—H1···O1i0.862.182.806 (3)130
O1···HO1···O1ii1.241.242.473 (4)180
(IV)
N1—H1A···O1A0.97 (4)1.91 (4)2.768 (4)146 (3)
N1—H1B···O2Ai1.08 (5)1.63 (5)2.684 (4)166 (4)
O1B—HO1B···O1A1.13 (5)1.39 (5)2.521 (3)176 (4)
Symmetry codes for (I): (i) -x, -y+2, -z; (ii) -x+1, -y+1, -z. Symmetry codes for (II): (i) -x+3/2, y+1/2, -z+1/2; (ii) x, y+1, z. Symmetry codes for (III): (i) -x, y, -z+1/2; (ii) -x, -y+1, -z. Symmetry codes for (IV): (i) x, -y+3/2, z+1/2.
Values of geometric parameters influencing Yang photocyclization top
d (Å)D (Å)ω (°)Δ (°)Θ (°)
Ideal value<2.7090–120180
Average literature valuea2.64 (8)3.00 (9)54 (10)82 (8)116 (3)
(IA)4.583.87-17.856.964.3
(IB)4.593.8614.157.463.9
(II)4.603.85-9.558.063.6
(III)5.313.8514.357.768.0
(IVA)4.583.8613.356.965.8
(IVB)4.573.8613.257.765.7
Notes: (a) the mean values of d, ω, Δ and Θ are given for 54 aromatic ketones undergoing Yang photocyclization (Natarajan et al., 2005) and D for 53 structures (Xia et al., 2005).
 

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