The analysis of the crystal structures of
rac-3-benzoyl-2-methylpropionic acid, C
11H
12O
3, (I), morpholinium
rac-3-benzoyl-2-methylpropionate monohydrate, C
4H
10NO
+·C
11H
11O
3-·H
2O, (II), pyridinium [hydrogen bis(
rac-3-benzoyl-2-methylpropionate)], C
5H
6N
+·(H
+·2C
11H
11O
3-), (III), and pyrrolidinium
rac-3-benzoyl-2-methylpropionate
rac-3-benzoyl-2-methylpropionic acid, C
4H
10N
+·C
11H
11O
3-·C
11H
12O
3, (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
-H atom, and between the C atom of the carbonyl group and the
-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
CCDC references: 700026; 700027; 700028; 700029
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.
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.
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).
(I)
rac-3-benzoyl-2-methylpropionic acid
top
Crystal data top
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) Å3 | 0.40 × 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 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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.053 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.139 | H 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 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.15 e Å−3 |
Crystal data top
C11H12O3 | V = 2033.4 (6) Å3 |
Mr = 192.21 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 14.951 (3) Å | µ = 0.09 mm−1 |
b = 6.0452 (9) Å | T = 299 K |
c = 22.935 (4) Å | 0.40 × 0.20 × 0.20 mm |
β = 101.201 (17)° | |
Data collection top
Kuma KM4 CCD diffractometer | 1715 reflections with I > 2σ(I) |
10560 measured reflections | Rint = 0.056 |
3550 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.053 | 0 restraints |
wR(F2) = 0.139 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.95 | Δρmax = 0.16 e Å−3 |
3550 reflections | Δρmin = −0.15 e Å−3 |
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 | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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
top
Crystal data top
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) Å3 | 0.50 × 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 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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.128 | H 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 parameters | Δρmax = 0.12 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
Crystal data top
C4H10NO+·C11H11O3−·H2O | V = 1589.3 (9) Å3 |
Mr = 297.34 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 15.010 (5) Å | µ = 0.09 mm−1 |
b = 6.697 (2) Å | T = 299 K |
c = 16.017 (5) Å | 0.50 × 0.20 × 0.10 mm |
β = 99.21 (3)° | |
Data collection top
Kuma KM4 CCD diffractometer | 1366 reflections with I > 2σ(I) |
8314 measured reflections | Rint = 0.060 |
2746 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.128 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | Δρmax = 0.12 e Å−3 |
2746 reflections | Δρmin = −0.18 e Å−3 |
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 | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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)]
top
Crystal data top
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) Å3 | 0.60 × 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 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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.210 | H-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 parameters | Δρmax = 0.22 e Å−3 |
7 restraints | Δρmin = −0.21 e Å−3 |
Crystal data top
C5H6N+·H+·2C11H11O3− | V = 2545.8 (9) Å3 |
Mr = 463.51 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 25.759 (6) Å | µ = 0.09 mm−1 |
b = 10.172 (2) Å | T = 299 K |
c = 9.776 (2) Å | 0.60 × 0.30 × 0.15 mm |
β = 96.34 (2)° | |
Data collection top
Kuma KM4 CCD diffractometer | 1454 reflections with I > 2σ(I) |
6670 measured reflections | Rint = 0.040 |
2199 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.063 | 7 restraints |
wR(F2) = 0.210 | H-atom parameters constrained |
S = 1.11 | Δρmax = 0.22 e Å−3 |
2199 reflections | Δρmin = −0.21 e Å−3 |
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 | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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—C12i | 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—C13i | 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—C12i | 119.2 (3) |
C5—C4—H4A | 108.5 | C12—N1—H1 | 120.4 |
C2—C4—H4A | 108.5 | C12i—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) | C13i—C14—C13 | 117.8 (3) |
C7—C6—C5 | 118.7 (2) | C13i—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) | C12i—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—C13i | −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
top
Crystal data top
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) Å3 | 0.35 × 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 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 top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.063 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.199 | H 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 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
Crystal data top
C4H10N+·C11H11O3+·C11H12O3 | V = 2464.8 (14) Å3 |
Mr = 455.53 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 26.249 (9) Å | µ = 0.09 mm−1 |
b = 9.556 (3) Å | T = 299 K |
c = 9.869 (3) Å | 0.35 × 0.25 × 0.20 mm |
β = 95.32 (3)° | |
Data collection top
Kuma KM4 CCD diffractometer | 1733 reflections with I > 2σ(I) |
12988 measured reflections | Rint = 0.062 |
4295 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
wR(F2) = 0.199 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.96 | Δρmax = 0.22 e Å−3 |
4295 reflections | Δρmin = −0.18 e Å−3 |
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 | 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 (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
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) top
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) | | |
Experimental details
| (I) | (II) | (III) | (IV) |
Crystal data |
Chemical formula | C11H12O3 | C4H10NO+·C11H11O3−·H2O | C5H6N+·H+·2C11H11O3− | C4H10N+·C11H11O3+·C11H12O3 |
Mr | 192.21 | 297.34 | 463.51 | 455.53 |
Crystal system, space group | Monoclinic, P21/c | Monoclinic, P21/n | Monoclinic, C2/c | Monoclinic, P21/c |
Temperature (K) | 299 | 299 | 299 | 299 |
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) |
V (Å3) | 2033.4 (6) | 1589.3 (9) | 2545.8 (9) | 2464.8 (14) |
Z | 8 | 4 | 4 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.09 | 0.09 | 0.09 |
Crystal size (mm) | 0.40 × 0.20 × 0.20 | 0.50 × 0.20 × 0.10 | 0.60 × 0.30 × 0.15 | 0.35 × 0.25 × 0.20 |
|
Data collection |
Diffractometer | Kuma 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 |
Rint | 0.056 | 0.060 | 0.040 | 0.062 |
(sin θ/λ)max (Å−1) | 0.595 | 0.594 | 0.595 | 0.595 |
|
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 reflections | 3550 | 2746 | 2199 | 4295 |
No. of parameters | 261 | 198 | 156 | 310 |
No. of restraints | 0 | 0 | 7 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H-atom parameters constrained | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.16, −0.15 | 0.12, −0.18 | 0.22, −0.21 | 0.22, −0.18 |
Geometry of strong hydrogen bonds in the crystal structures of compounds
(I)–(IV) (Å, °) topCompound/bonda | D—H | H···A | D···A | D—H···A |
(I) | | | | |
O1A—HO1A···O2Ai | 0.94 (4) | 1.70 (4) | 2.634 (3) | 172 (4) |
O1B—HO1B···O2Bii | 1.02 (5) | 1.65 (5) | 2.667 (3) | 176 (4) |
(II) | | | | |
N1—H1A···O1 | 0.90 | 1.85 | 2.732 (3) | 167 |
N1—H1B···O2i | 0.90 | 1.86 | 2.717 (3) | 158 |
O5—HO5B···O1 | 0.93 (4) | 1.89 (4) | 2.810 (4) | 170 (4) |
O5—HO5A···O2ii | 0.77 (4) | 2.06 (4) | 2.823 (4) | 177 (4) |
(III) | | | | |
N1—H1···O1 | 0.86 | 2.18 | 2.807 (3) | 130 |
N1—H1···O1i | 0.86 | 2.18 | 2.806 (3) | 130 |
O1···HO1···O1ii | 1.24 | 1.24 | 2.473 (4) | 180 |
(IV) | | | | |
N1—H1A···O1A | 0.97 (4) | 1.91 (4) | 2.768 (4) | 146 (3) |
N1—H1B···O2Ai | 1.08 (5) | 1.63 (5) | 2.684 (4) | 166 (4) |
O1B—HO1B···O1A | 1.13 (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 | <2.7 | | 0 | 90–120 | 180 |
Average literature valuea | 2.64 (8) | 3.00 (9) | 54 (10) | 82 (8) | 116 (3) |
(IA) | 4.58 | 3.87 | -17.8 | 56.9 | 64.3 |
(IB) | 4.59 | 3.86 | 14.1 | 57.4 | 63.9 |
(II) | 4.60 | 3.85 | -9.5 | 58.0 | 63.6 |
(III) | 5.31 | 3.85 | 14.3 | 57.7 | 68.0 |
(IVA) | 4.58 | 3.86 | 13.3 | 56.9 | 65.8 |
(IVB) | 4.57 | 3.86 | 13.2 | 57.7 | 65.7 |
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). |
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.