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The amino acid
L-phenylalanine has been cocrystallized with
D-2-aminobutyric acid, C
9H
11NO
2·C
4H
9NO
2,
D-norvaline, C
9H
11NO
2·C
5H
11NO
2, and
D-methionine, C
9H
11NO
2·C
5H
11NO
2S, with linear side chains, as well as with
D-leucine, C
9H
11NO
2·C
6H
13NO
2,
D-isoleucine, C
9H
11NO
2·C
6H
13NO
2, and
D-
allo-isoleucine, C
9H
11NO
2·C
6H
13NO
2, with branched side chains. The structures of these 1:1 complexes fall into two classes based on the observed hydrogen-bonding pattern. From a comparison with other
L:
D complexes involving hydrophobic amino acids and regular racemates, it is shown that the structure-directing properties of phenylalanine closely parallel those of valine and isoleucine but not those of leucine, which shares side-chain branching at C
with phenylalanine and is normally considered to be the most closely related non-aromatic amino acid.
Supporting information
CCDC references: 742169; 742170; 742171; 742172; 742173; 742174
Aqueous solutions of the selected complexes were prepared by dissolving
equimolar amounts (typically 1 mg of each) of the two selected amino acids in
90 µl of deionized water. The mixture was distributed into three 30 × 5 mm test tubes and sealed with Parafilm, in which a couple of small holes were
then pricked with a needle. Usable crystals emerged for five complexes as
acetonitrile diffused into the solutions at room temperature. For the sixth,
L-Phe:D-Abu, additional crystallizations had to be carried out. These
employed, rather than pure water as the solvent, a mixture of water (80 µl)
and tetramethoxysilane (20 µl). After vigorous stirring for about 1 min, the
mixture was left to polymerize into a gel (1 h). Equilibration against
acetonitrile subsequently proceeded as above, producing in the gel larger
crystals of good quality.
H atoms bonded to C atoms were positioned with idealized geometry and C—H
distances fixed in the range 0.93–0.98 Å. Positional parameters were
refined for H atoms bonded to N atoms, but with a mild SHELXTL
restraint for the N—H distances, which accordingly varied between 0.88 (2)
and 0.95 (3) Å. Uiso(H) values were 1.2Ueq of the carrier
atom, or 1.5Ueq for amino and methyl groups. Friedel pairs were
merged for all data sets except L-Phe:D-Met, for which the anomalous
scattering effects of 1082 Friedel pairs were used to confirm the known
absolute configurations of the complex components.
For all compounds, data collection: APEX2 (Bruker, 2007); cell refinement: SAINT-Plus (Bruker, 2007); data reduction: SAINT-Plus (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008a); program(s) used to refine structure: SHELXTL (Sheldrick, 2008a); molecular graphics: SHELXTL (Sheldrick, 2008a); software used to prepare material for publication: SHELXTL (Sheldrick, 2008a).
(I) L-Phenylalanine–D-2-ammoniobutyrate (1/1)
top
Crystal data top
C9H11NO2·C4H9NO2 | F(000) = 576 |
Mr = 268.31 | Dx = 1.316 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: p 2ac 2ab | Cell parameters from 3167 reflections |
a = 4.7869 (7) Å | θ = 2.2–25.0° |
b = 9.9558 (15) Å | µ = 0.10 mm−1 |
c = 28.423 (4) Å | T = 296 K |
V = 1354.6 (3) Å3 | Flat needle, colourless |
Z = 4 | 0.80 × 0.12 × 0.04 mm |
Data collection top
Bruker APEXII CCD diffractometer | 1443 independent reflections |
Radiation source: fine-focus sealed tube | 1284 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
Detector resolution: 8.3 pixels mm-1 | θmax = 25.0°, θmin = 2.2° |
Sets of exposures each taken over 0.5° ω rotation scans | h = −5→5 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008b) | k = −11→11 |
Tmin = 0.770, Tmax = 0.996 | l = −33→33 |
10082 measured reflections | |
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)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.120 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0794P)2 + 0.2457P] where P = (Fo2 + 2Fc2)/3 |
1443 reflections | (Δ/σ)max = 0.001 |
191 parameters | Δρmax = 0.24 e Å−3 |
6 restraints | Δρmin = −0.18 e Å−3 |
Crystal data top
C9H11NO2·C4H9NO2 | V = 1354.6 (3) Å3 |
Mr = 268.31 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 4.7869 (7) Å | µ = 0.10 mm−1 |
b = 9.9558 (15) Å | T = 296 K |
c = 28.423 (4) Å | 0.80 × 0.12 × 0.04 mm |
Data collection top
Bruker APEXII CCD diffractometer | 1443 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008b) | 1284 reflections with I > 2σ(I) |
Tmin = 0.770, Tmax = 0.996 | Rint = 0.037 |
10082 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.042 | 6 restraints |
wR(F2) = 0.120 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.24 e Å−3 |
1443 reflections | Δρmin = −0.18 e Å−3 |
191 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. Data were collected by measuring four sets of exposures with the detector set at
2θ = 29°, crystal-to-detector distance 6.00 cm. Refinement of F2
against ALL reflections. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1A | 0.0384 (4) | 0.19658 (19) | 0.03353 (6) | 0.0342 (5) | |
O2A | 0.3090 (5) | 0.03509 (18) | 0.06282 (8) | 0.0401 (6) | |
N1A | 0.4115 (5) | 0.3904 (2) | 0.05721 (8) | 0.0285 (5) | |
H1A | 0.540 (7) | 0.452 (3) | 0.0682 (11) | 0.043* | |
H2A | 0.233 (6) | 0.430 (3) | 0.0596 (12) | 0.043* | |
H3A | 0.442 (7) | 0.368 (3) | 0.0262 (8) | 0.043* | |
C1A | 0.4154 (6) | 0.2600 (3) | 0.08330 (9) | 0.0253 (6) | |
H11A | 0.6083 | 0.2280 | 0.0862 | 0.030* | |
C2A | 0.2871 (7) | 0.2747 (3) | 0.13221 (9) | 0.0349 (7) | |
H21A | 0.0991 | 0.3095 | 0.1285 | 0.042* | |
H22A | 0.2713 | 0.1858 | 0.1459 | 0.042* | |
C3A | 0.4397 (7) | 0.3634 (3) | 0.16678 (9) | 0.0329 (7) | |
C4A | 0.3735 (8) | 0.4988 (3) | 0.17116 (12) | 0.0467 (9) | |
H41A | 0.2388 | 0.5367 | 0.1517 | 0.056* | |
C5A | 0.5066 (11) | 0.5772 (4) | 0.20426 (12) | 0.0601 (11) | |
H51A | 0.4599 | 0.6675 | 0.2070 | 0.072* | |
C6A | 0.7070 (10) | 0.5239 (4) | 0.23330 (13) | 0.0623 (12) | |
H61A | 0.7954 | 0.5777 | 0.2555 | 0.075* | |
C7A | 0.7760 (9) | 0.3906 (4) | 0.22931 (12) | 0.0568 (10) | |
H71A | 0.9121 | 0.3536 | 0.2487 | 0.068* | |
C8A | 0.6419 (8) | 0.3117 (4) | 0.19620 (10) | 0.0439 (8) | |
H81A | 0.6893 | 0.2213 | 0.1937 | 0.053* | |
C9A | 0.2417 (6) | 0.1562 (2) | 0.05665 (9) | 0.0253 (6) | |
O1B | 1.1859 (5) | 0.6907 (2) | 0.04024 (7) | 0.0371 (5) | |
O2B | 0.9078 (5) | 0.54024 (18) | 0.07490 (8) | 0.0403 (6) | |
N1B | 0.8067 (6) | 0.8884 (2) | 0.05042 (9) | 0.0301 (5) | |
H1B | 0.671 (7) | 0.952 (3) | 0.0583 (11) | 0.045* | |
H2B | 0.796 (8) | 0.859 (3) | 0.0191 (8) | 0.045* | |
H3B | 0.978 (6) | 0.930 (3) | 0.0506 (12) | 0.045* | |
C1B | 0.7978 (6) | 0.7720 (3) | 0.08327 (9) | 0.0285 (6) | |
H11B | 0.6043 | 0.7412 | 0.0866 | 0.034* | |
C2B | 0.9099 (7) | 0.8129 (3) | 0.13141 (9) | 0.0362 (7) | |
H21B | 1.1051 | 0.8373 | 0.1282 | 0.043* | |
H22B | 0.8998 | 0.7360 | 0.1523 | 0.043* | |
C3B | 0.7520 (9) | 0.9307 (3) | 0.15403 (11) | 0.0536 (10) | |
H31B | 0.8297 | 0.9492 | 0.1845 | 0.080* | |
H32B | 0.5582 | 0.9077 | 0.1573 | 0.080* | |
H33B | 0.7695 | 1.0089 | 0.1345 | 0.080* | |
C4B | 0.9755 (6) | 0.6582 (3) | 0.06374 (9) | 0.0275 (6) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1A | 0.0319 (11) | 0.0294 (10) | 0.0412 (11) | 0.0014 (9) | −0.0079 (9) | −0.0022 (9) |
O2A | 0.0329 (12) | 0.0193 (10) | 0.0681 (15) | 0.0007 (9) | −0.0057 (12) | −0.0021 (9) |
N1A | 0.0306 (13) | 0.0212 (12) | 0.0337 (13) | −0.0047 (11) | 0.0008 (12) | −0.0020 (10) |
C1A | 0.0219 (13) | 0.0194 (12) | 0.0346 (14) | 0.0016 (11) | −0.0016 (12) | −0.0005 (10) |
C2A | 0.0375 (17) | 0.0335 (15) | 0.0338 (14) | −0.0065 (14) | 0.0011 (13) | 0.0002 (12) |
C3A | 0.0398 (17) | 0.0333 (15) | 0.0256 (13) | −0.0036 (15) | 0.0047 (13) | −0.0022 (11) |
C4A | 0.058 (2) | 0.0351 (17) | 0.0465 (18) | 0.0059 (18) | −0.0011 (17) | −0.0008 (14) |
C5A | 0.090 (3) | 0.0378 (19) | 0.053 (2) | −0.006 (2) | 0.010 (2) | −0.0126 (16) |
C6A | 0.074 (3) | 0.069 (3) | 0.044 (2) | −0.024 (2) | 0.000 (2) | −0.0215 (19) |
C7A | 0.054 (2) | 0.072 (3) | 0.0449 (19) | −0.003 (2) | −0.0095 (18) | −0.0059 (18) |
C8A | 0.052 (2) | 0.0397 (17) | 0.0401 (16) | 0.0054 (18) | −0.0016 (15) | −0.0031 (14) |
C9A | 0.0226 (13) | 0.0224 (14) | 0.0310 (13) | −0.0009 (12) | 0.0045 (12) | −0.0026 (11) |
O1B | 0.0325 (12) | 0.0341 (11) | 0.0445 (11) | 0.0042 (10) | 0.0053 (10) | −0.0047 (9) |
O2B | 0.0367 (12) | 0.0182 (10) | 0.0660 (14) | −0.0005 (9) | −0.0011 (11) | −0.0028 (9) |
N1B | 0.0306 (13) | 0.0221 (12) | 0.0377 (13) | 0.0020 (11) | −0.0031 (12) | −0.0022 (10) |
C1B | 0.0258 (14) | 0.0209 (13) | 0.0387 (15) | −0.0006 (12) | 0.0013 (13) | 0.0000 (11) |
C2B | 0.0396 (17) | 0.0310 (15) | 0.0379 (15) | 0.0060 (15) | −0.0029 (14) | −0.0033 (12) |
C3B | 0.069 (3) | 0.047 (2) | 0.0444 (18) | 0.017 (2) | −0.0087 (19) | −0.0152 (16) |
C4B | 0.0237 (14) | 0.0237 (14) | 0.0350 (14) | −0.0007 (12) | −0.0055 (12) | −0.0045 (11) |
Geometric parameters (Å, º) top
O1A—C9A | 1.241 (3) | C6A—H61A | 0.9300 |
O2A—C9A | 1.260 (3) | C7A—C8A | 1.384 (5) |
N1A—C1A | 1.496 (3) | C7A—H71A | 0.9300 |
N1A—H1A | 0.92 (2) | C8A—H81A | 0.9300 |
N1A—H2A | 0.95 (3) | O1B—C4B | 1.251 (4) |
N1A—H3A | 0.92 (2) | O2B—C4B | 1.259 (3) |
C1A—C2A | 1.527 (4) | N1B—C1B | 1.488 (3) |
C1A—C9A | 1.527 (4) | N1B—H1B | 0.94 (2) |
C1A—H11A | 0.9800 | N1B—H2B | 0.94 (2) |
C2A—C3A | 1.510 (4) | N1B—H3B | 0.92 (3) |
C2A—H21A | 0.9700 | C1B—C4B | 1.522 (4) |
C2A—H22A | 0.9700 | C1B—C2B | 1.525 (4) |
C3A—C8A | 1.379 (5) | C1B—H11B | 0.9800 |
C3A—C4A | 1.390 (4) | C2B—C3B | 1.537 (4) |
C4A—C5A | 1.378 (5) | C2B—H21B | 0.9700 |
C4A—H41A | 0.9300 | C2B—H22B | 0.9700 |
C5A—C6A | 1.372 (6) | C3B—H31B | 0.9600 |
C5A—H51A | 0.9300 | C3B—H32B | 0.9600 |
C6A—C7A | 1.372 (6) | C3B—H33B | 0.9600 |
| | | |
C1A—N1A—H1A | 113 (2) | C3A—C8A—C7A | 121.7 (3) |
C1A—N1A—H2A | 110 (2) | C3A—C8A—H81A | 119.2 |
H1A—N1A—H2A | 108 (3) | C7A—C8A—H81A | 119.2 |
C1A—N1A—H3A | 105 (2) | O1A—C9A—O2A | 125.8 (3) |
H1A—N1A—H3A | 112 (3) | O1A—C9A—C1A | 118.0 (2) |
H2A—N1A—H3A | 108 (3) | O2A—C9A—C1A | 116.0 (2) |
N1A—C1A—C2A | 111.3 (2) | C1B—N1B—H1B | 111 (2) |
N1A—C1A—C9A | 109.6 (2) | C1B—N1B—H2B | 110 (2) |
C2A—C1A—C9A | 107.3 (2) | H1B—N1B—H2B | 114 (3) |
N1A—C1A—H11A | 109.6 | C1B—N1B—H3B | 112 (2) |
C2A—C1A—H11A | 109.6 | H1B—N1B—H3B | 108 (3) |
C9A—C1A—H11A | 109.6 | H2B—N1B—H3B | 101 (3) |
C3A—C2A—C1A | 117.0 (2) | N1B—C1B—C4B | 109.5 (2) |
C3A—C2A—H21A | 108.0 | N1B—C1B—C2B | 110.2 (2) |
C1A—C2A—H21A | 108.0 | C4B—C1B—C2B | 109.2 (2) |
C3A—C2A—H22A | 108.0 | N1B—C1B—H11B | 109.3 |
C1A—C2A—H22A | 108.0 | C4B—C1B—H11B | 109.3 |
H21A—C2A—H22A | 107.3 | C2B—C1B—H11B | 109.3 |
C8A—C3A—C4A | 117.9 (3) | C1B—C2B—C3B | 114.0 (3) |
C8A—C3A—C2A | 121.0 (3) | C1B—C2B—H21B | 108.8 |
C4A—C3A—C2A | 121.0 (3) | C3B—C2B—H21B | 108.8 |
C5A—C4A—C3A | 120.3 (4) | C1B—C2B—H22B | 108.8 |
C5A—C4A—H41A | 119.9 | C3B—C2B—H22B | 108.8 |
C3A—C4A—H41A | 119.9 | H21B—C2B—H22B | 107.7 |
C6A—C5A—C4A | 121.0 (4) | C2B—C3B—H31B | 109.5 |
C6A—C5A—H51A | 119.5 | C2B—C3B—H32B | 109.5 |
C4A—C5A—H51A | 119.5 | H31B—C3B—H32B | 109.5 |
C7A—C6A—C5A | 119.5 (3) | C2B—C3B—H33B | 109.5 |
C7A—C6A—H61A | 120.2 | H31B—C3B—H33B | 109.5 |
C5A—C6A—H61A | 120.2 | H32B—C3B—H33B | 109.5 |
C6A—C7A—C8A | 119.6 (4) | O1B—C4B—O2B | 125.7 (3) |
C6A—C7A—H71A | 120.2 | O1B—C4B—C1B | 116.9 (2) |
C8A—C7A—H71A | 120.2 | O2B—C4B—C1B | 117.3 (2) |
| | | |
N1A—C1A—C2A—C3A | −65.5 (3) | C6A—C7A—C8A—C3A | 0.2 (6) |
C9A—C1A—C2A—C3A | 174.6 (2) | N1A—C1A—C9A—O1A | −31.2 (3) |
C1A—C2A—C3A—C8A | −90.0 (3) | C2A—C1A—C9A—O1A | 89.7 (3) |
C1A—C2A—C3A—C4A | 92.4 (4) | N1A—C1A—C9A—O2A | 153.2 (2) |
C8A—C3A—C4A—C5A | −0.4 (5) | C2A—C1A—C9A—O2A | −85.8 (3) |
C2A—C3A—C4A—C5A | 177.3 (3) | N1B—C1B—C2B—C3B | 57.7 (3) |
C3A—C4A—C5A—C6A | 0.3 (6) | C4B—C1B—C2B—C3B | 178.1 (3) |
C4A—C5A—C6A—C7A | 0.0 (6) | N1B—C1B—C4B—O1B | 32.3 (3) |
C5A—C6A—C7A—C8A | −0.3 (6) | C2B—C1B—C4B—O1B | −88.5 (3) |
C4A—C3A—C8A—C7A | 0.2 (5) | N1B—C1B—C4B—O2B | −151.8 (3) |
C2A—C3A—C8A—C7A | −177.5 (3) | C2B—C1B—C4B—O2B | 87.4 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O2B | 0.92 (2) | 1.98 (3) | 2.850 (3) | 157 (3) |
N1A—H2A···O2Bi | 0.95 (3) | 1.95 (3) | 2.879 (3) | 167 (3) |
N1A—H3A···O1Aii | 0.92 (2) | 1.87 (2) | 2.788 (3) | 172 (3) |
N1B—H1B···O2Aiii | 0.94 (2) | 1.92 (3) | 2.817 (3) | 159 (3) |
N1B—H2B···O1Biv | 0.94 (2) | 1.83 (2) | 2.756 (3) | 166 (3) |
N1B—H3B···O2Av | 0.92 (3) | 1.93 (3) | 2.835 (3) | 168 (3) |
Symmetry codes: (i) x−1, y, z; (ii) x+1/2, −y+1/2, −z; (iii) x, y+1, z; (iv) x−1/2, −y+3/2, −z; (v) x+1, y+1, z. |
(II) L-Phenylalanine–D-norvaline (1/1)
top
Crystal data top
C9H11NO2·C5H11NO2 | F(000) = 608 |
Mr = 282.34 | Dx = 1.278 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 10916 reflections |
a = 4.7624 (8) Å | θ = 2.2–25.0° |
b = 9.9569 (17) Å | µ = 0.09 mm−1 |
c = 30.935 (6) Å | T = 296 K |
V = 1466.9 (5) Å3 | Flat needle, colourless |
Z = 4 | 0.48 × 0.14 × 0.05 mm |
Data collection top
Bruker APEXII CCD diffractometer | 1564 independent reflections |
Radiation source: fine-focus sealed tube | 1395 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
Detector resolution: 8.3 pixels mm-1 | θmax = 25.0°, θmin = 2.2° |
Sets of exposures each taken over 0.5° ω rotation scans | h = −5→5 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008b) | k = −11→11 |
Tmin = 0.862, Tmax = 0.995 | l = −36→36 |
14224 measured reflections | |
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)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0318P)2 + 0.7814P] where P = (Fo2 + 2Fc2)/3 |
1564 reflections | (Δ/σ)max < 0.001 |
200 parameters | Δρmax = 0.20 e Å−3 |
6 restraints | Δρmin = −0.15 e Å−3 |
Crystal data top
C9H11NO2·C5H11NO2 | V = 1466.9 (5) Å3 |
Mr = 282.34 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 4.7624 (8) Å | µ = 0.09 mm−1 |
b = 9.9569 (17) Å | T = 296 K |
c = 30.935 (6) Å | 0.48 × 0.14 × 0.05 mm |
Data collection top
Bruker APEXII CCD diffractometer | 1564 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008b) | 1395 reflections with I > 2σ(I) |
Tmin = 0.862, Tmax = 0.995 | Rint = 0.037 |
14224 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.040 | 6 restraints |
wR(F2) = 0.093 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.20 e Å−3 |
1564 reflections | Δρmin = −0.15 e Å−3 |
200 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. Data were collected by measuring four sets of exposures with the detector set at
2θ = 29°, crystal-to-detector distance 6.00 cm. Refinement of F2
against ALL reflections. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1A | −0.0266 (4) | 0.19410 (19) | 0.03104 (6) | 0.0361 (5) | |
O2A | 0.2466 (5) | 0.03710 (18) | 0.05989 (7) | 0.0422 (6) | |
N1A | 0.3413 (6) | 0.3907 (2) | 0.05212 (8) | 0.0297 (5) | |
H1A | 0.481 (6) | 0.446 (3) | 0.0620 (10) | 0.045* | |
H2A | 0.374 (7) | 0.367 (3) | 0.0234 (7) | 0.045* | |
H3A | 0.177 (6) | 0.435 (3) | 0.0547 (10) | 0.045* | |
C1A | 0.3439 (6) | 0.2630 (2) | 0.07710 (8) | 0.0277 (6) | |
H11A | 0.5379 | 0.2322 | 0.0806 | 0.033* | |
C2A | 0.2084 (7) | 0.2805 (3) | 0.12154 (8) | 0.0389 (7) | |
H21A | 0.0217 | 0.3171 | 0.1173 | 0.047* | |
H22A | 0.1864 | 0.1922 | 0.1343 | 0.047* | |
C3A | 0.3587 (7) | 0.3680 (3) | 0.15365 (8) | 0.0362 (7) | |
C4A | 0.2970 (9) | 0.5025 (3) | 0.15766 (10) | 0.0534 (9) | |
H41A | 0.1653 | 0.5412 | 0.1393 | 0.064* | |
C5A | 0.4275 (11) | 0.5808 (4) | 0.18850 (12) | 0.0695 (13) | |
H51A | 0.3819 | 0.6713 | 0.1909 | 0.083* | |
C6A | 0.6217 (11) | 0.5265 (5) | 0.21529 (12) | 0.0741 (13) | |
H61A | 0.7085 | 0.5793 | 0.2362 | 0.089* | |
C7A | 0.6892 (11) | 0.3940 (5) | 0.21153 (12) | 0.0801 (14) | |
H71A | 0.8238 | 0.3566 | 0.2297 | 0.096* | |
C8A | 0.5582 (9) | 0.3157 (4) | 0.18092 (11) | 0.0589 (10) | |
H81A | 0.6059 | 0.2254 | 0.1787 | 0.071* | |
C9A | 0.1753 (6) | 0.1564 (3) | 0.05297 (8) | 0.0273 (6) | |
O1B | 1.1154 (4) | 0.69071 (19) | 0.03545 (6) | 0.0368 (5) | |
O2B | 0.8361 (5) | 0.54126 (18) | 0.06687 (7) | 0.0408 (5) | |
N1B | 0.7435 (6) | 0.8904 (2) | 0.04696 (8) | 0.0302 (5) | |
H1B | 0.613 (6) | 0.954 (3) | 0.0539 (10) | 0.045* | |
H2B | 0.917 (6) | 0.928 (3) | 0.0489 (10) | 0.045* | |
H3B | 0.719 (7) | 0.858 (3) | 0.0184 (8) | 0.045* | |
C1B | 0.7330 (6) | 0.7718 (2) | 0.07604 (8) | 0.0288 (6) | |
H11B | 0.5379 | 0.7423 | 0.0795 | 0.035* | |
C2B | 0.8568 (7) | 0.8073 (3) | 0.12044 (8) | 0.0367 (7) | |
H21B | 0.8467 | 0.7281 | 0.1386 | 0.044* | |
H22B | 1.0540 | 0.8286 | 0.1166 | 0.044* | |
C3B | 0.7200 (9) | 0.9225 (3) | 0.14436 (9) | 0.0498 (9) | |
H31B | 0.5210 | 0.9045 | 0.1477 | 0.060* | |
H32B | 0.7405 | 1.0044 | 0.1277 | 0.060* | |
C4B | 0.8527 (11) | 0.9412 (4) | 0.18845 (10) | 0.0644 (12) | |
H41B | 0.7472 | 1.0063 | 0.2046 | 0.097* | |
H42B | 1.0424 | 0.9721 | 0.1850 | 0.097* | |
H43B | 0.8526 | 0.8572 | 0.2036 | 0.097* | |
C5B | 0.9062 (6) | 0.6585 (3) | 0.05702 (8) | 0.0269 (6) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1A | 0.0328 (12) | 0.0312 (11) | 0.0442 (11) | −0.0006 (10) | −0.0099 (10) | −0.0034 (9) |
O2A | 0.0337 (12) | 0.0227 (10) | 0.0701 (14) | 0.0012 (9) | −0.0045 (12) | −0.0033 (10) |
N1A | 0.0289 (13) | 0.0251 (12) | 0.0350 (13) | −0.0011 (11) | 0.0018 (12) | −0.0032 (10) |
C1A | 0.0246 (14) | 0.0232 (13) | 0.0353 (14) | 0.0021 (12) | −0.0015 (13) | −0.0012 (11) |
C2A | 0.0419 (19) | 0.0379 (16) | 0.0369 (15) | −0.0063 (16) | 0.0028 (15) | 0.0011 (13) |
C3A | 0.0391 (18) | 0.0395 (16) | 0.0299 (14) | −0.0018 (16) | 0.0037 (14) | −0.0010 (12) |
C4A | 0.070 (3) | 0.0435 (18) | 0.0470 (18) | 0.003 (2) | −0.007 (2) | −0.0039 (15) |
C5A | 0.096 (4) | 0.053 (2) | 0.060 (2) | −0.014 (3) | 0.009 (3) | −0.0164 (19) |
C6A | 0.078 (3) | 0.095 (3) | 0.049 (2) | −0.030 (3) | 0.000 (2) | −0.025 (2) |
C7A | 0.074 (3) | 0.121 (4) | 0.045 (2) | 0.009 (3) | −0.023 (2) | −0.010 (2) |
C8A | 0.066 (3) | 0.065 (2) | 0.0457 (19) | 0.017 (2) | −0.0104 (19) | −0.0037 (18) |
C9A | 0.0206 (14) | 0.0276 (15) | 0.0337 (14) | 0.0008 (12) | 0.0040 (13) | −0.0020 (11) |
O1B | 0.0332 (12) | 0.0358 (11) | 0.0413 (11) | 0.0032 (10) | 0.0065 (10) | −0.0043 (9) |
O2B | 0.0340 (12) | 0.0215 (10) | 0.0669 (14) | −0.0005 (9) | −0.0007 (11) | −0.0031 (9) |
N1B | 0.0290 (13) | 0.0263 (13) | 0.0353 (12) | 0.0036 (11) | −0.0039 (12) | −0.0038 (10) |
C1B | 0.0240 (14) | 0.0244 (13) | 0.0379 (14) | −0.0001 (12) | 0.0022 (13) | −0.0014 (11) |
C2B | 0.0385 (17) | 0.0359 (15) | 0.0357 (15) | 0.0058 (16) | 0.0015 (14) | 0.0026 (13) |
C3B | 0.054 (2) | 0.0521 (19) | 0.0431 (17) | 0.0094 (19) | −0.0017 (18) | −0.0112 (15) |
C4B | 0.086 (3) | 0.065 (2) | 0.0424 (18) | 0.009 (3) | −0.006 (2) | −0.0136 (17) |
C5B | 0.0223 (15) | 0.0278 (15) | 0.0307 (14) | −0.0007 (12) | −0.0075 (13) | −0.0046 (11) |
Geometric parameters (Å, º) top
O1A—C9A | 1.235 (3) | C7A—H71A | 0.9300 |
O2A—C9A | 1.254 (3) | C8A—H81A | 0.9300 |
N1A—C1A | 1.488 (3) | O1B—C5B | 1.241 (3) |
N1A—H1A | 0.92 (2) | O2B—C5B | 1.252 (3) |
N1A—H2A | 0.93 (2) | N1B—C1B | 1.486 (3) |
N1A—H3A | 0.90 (2) | N1B—H1B | 0.91 (2) |
C1A—C9A | 1.526 (4) | N1B—H2B | 0.91 (2) |
C1A—C2A | 1.528 (4) | N1B—H3B | 0.95 (2) |
C1A—H11A | 0.9800 | C1B—C5B | 1.516 (4) |
C2A—C3A | 1.503 (4) | C1B—C2B | 1.536 (4) |
C2A—H21A | 0.9700 | C1B—H11B | 0.9800 |
C2A—H22A | 0.9700 | C2B—C3B | 1.512 (4) |
C3A—C8A | 1.374 (5) | C2B—H21B | 0.9700 |
C3A—C4A | 1.376 (4) | C2B—H22B | 0.9700 |
C4A—C5A | 1.380 (5) | C3B—C4B | 1.515 (4) |
C4A—H41A | 0.9300 | C3B—H31B | 0.9700 |
C5A—C6A | 1.354 (6) | C3B—H32B | 0.9700 |
C5A—H51A | 0.9300 | C4B—H41B | 0.9600 |
C6A—C7A | 1.362 (6) | C4B—H42B | 0.9600 |
C6A—H61A | 0.9300 | C4B—H43B | 0.9600 |
C7A—C8A | 1.376 (5) | | |
| | | |
C1A—N1A—H1A | 110 (2) | O1A—C9A—O2A | 126.3 (3) |
C1A—N1A—H2A | 105.9 (18) | O1A—C9A—C1A | 117.8 (2) |
H1A—N1A—H2A | 111 (3) | O2A—C9A—C1A | 115.7 (2) |
C1A—N1A—H3A | 112 (2) | C1B—N1B—H1B | 113 (2) |
H1A—N1A—H3A | 108 (3) | C1B—N1B—H2B | 108 (2) |
H2A—N1A—H3A | 111 (3) | H1B—N1B—H2B | 109 (3) |
N1A—C1A—C9A | 109.6 (2) | C1B—N1B—H3B | 107.0 (17) |
N1A—C1A—C2A | 111.5 (2) | H1B—N1B—H3B | 112 (3) |
C9A—C1A—C2A | 107.3 (2) | H2B—N1B—H3B | 108 (3) |
N1A—C1A—H11A | 109.5 | N1B—C1B—C5B | 109.8 (2) |
C9A—C1A—H11A | 109.5 | N1B—C1B—C2B | 110.2 (2) |
C2A—C1A—H11A | 109.5 | C5B—C1B—C2B | 108.0 (2) |
C3A—C2A—C1A | 117.4 (3) | N1B—C1B—H11B | 109.6 |
C3A—C2A—H21A | 108.0 | C5B—C1B—H11B | 109.6 |
C1A—C2A—H21A | 108.0 | C2B—C1B—H11B | 109.6 |
C3A—C2A—H22A | 108.0 | C3B—C2B—C1B | 116.5 (3) |
C1A—C2A—H22A | 108.0 | C3B—C2B—H21B | 108.2 |
H21A—C2A—H22A | 107.2 | C1B—C2B—H21B | 108.2 |
C8A—C3A—C4A | 117.5 (3) | C3B—C2B—H22B | 108.2 |
C8A—C3A—C2A | 121.0 (3) | C1B—C2B—H22B | 108.2 |
C4A—C3A—C2A | 121.5 (3) | H21B—C2B—H22B | 107.3 |
C3A—C4A—C5A | 121.0 (4) | C2B—C3B—C4B | 110.8 (3) |
C3A—C4A—H41A | 119.5 | C2B—C3B—H31B | 109.5 |
C5A—C4A—H41A | 119.5 | C4B—C3B—H31B | 109.5 |
C6A—C5A—C4A | 120.3 (4) | C2B—C3B—H32B | 109.5 |
C6A—C5A—H51A | 119.8 | C4B—C3B—H32B | 109.5 |
C4A—C5A—H51A | 119.8 | H31B—C3B—H32B | 108.1 |
C5A—C6A—C7A | 119.7 (4) | C3B—C4B—H41B | 109.5 |
C5A—C6A—H61A | 120.1 | C3B—C4B—H42B | 109.5 |
C7A—C6A—H61A | 120.1 | H41B—C4B—H42B | 109.5 |
C6A—C7A—C8A | 120.0 (4) | C3B—C4B—H43B | 109.5 |
C6A—C7A—H71A | 120.0 | H41B—C4B—H43B | 109.5 |
C8A—C7A—H71A | 120.0 | H42B—C4B—H43B | 109.5 |
C3A—C8A—C7A | 121.4 (4) | O1B—C5B—O2B | 125.8 (3) |
C3A—C8A—H81A | 119.3 | O1B—C5B—C1B | 117.0 (2) |
C7A—C8A—H81A | 119.3 | O2B—C5B—C1B | 117.0 (3) |
| | | |
N1A—C1A—C2A—C3A | −67.5 (3) | N1A—C1A—C9A—O1A | −31.8 (3) |
C9A—C1A—C2A—C3A | 172.5 (2) | C2A—C1A—C9A—O1A | 89.4 (3) |
C1A—C2A—C3A—C8A | −88.5 (4) | N1A—C1A—C9A—O2A | 152.8 (2) |
C1A—C2A—C3A—C4A | 93.2 (4) | C2A—C1A—C9A—O2A | −86.0 (3) |
C8A—C3A—C4A—C5A | −1.2 (6) | N1B—C1B—C2B—C3B | 57.9 (3) |
C2A—C3A—C4A—C5A | 177.2 (3) | C5B—C1B—C2B—C3B | 177.8 (3) |
C3A—C4A—C5A—C6A | 0.6 (6) | C1B—C2B—C3B—C4B | 176.9 (3) |
C4A—C5A—C6A—C7A | 0.4 (7) | N1B—C1B—C5B—O1B | 32.0 (3) |
C5A—C6A—C7A—C8A | −0.7 (7) | C2B—C1B—C5B—O1B | −88.1 (3) |
C4A—C3A—C8A—C7A | 0.9 (6) | N1B—C1B—C5B—O2B | −152.6 (2) |
C2A—C3A—C8A—C7A | −177.5 (4) | C2B—C1B—C5B—O2B | 87.2 (3) |
C6A—C7A—C8A—C3A | 0.0 (7) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O2B | 0.92 (2) | 1.95 (3) | 2.830 (3) | 162 (3) |
N1A—H3A···O2Bi | 0.90 (2) | 1.97 (3) | 2.871 (3) | 173 (3) |
N1A—H2A···O1Aii | 0.93 (2) | 1.85 (2) | 2.780 (3) | 173 (3) |
N1B—H1B···O2Aiii | 0.91 (2) | 1.94 (3) | 2.809 (3) | 159 (3) |
N1B—H3B···O1Biv | 0.95 (2) | 1.80 (2) | 2.743 (3) | 171 (3) |
N1B—H2B···O2Av | 0.91 (2) | 1.94 (3) | 2.835 (3) | 168 (3) |
Symmetry codes: (i) x−1, y, z; (ii) x+1/2, −y+1/2, −z; (iii) x, y+1, z; (iv) x−1/2, −y+3/2, −z; (v) x+1, y+1, z. |
(III) L-Phenylalanine–D-methionine (1/1)
top
Crystal data top
C9H11NO2·C5H11NO2S | F(000) = 336 |
Mr = 314.40 | Dx = 1.368 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 4140 reflections |
a = 10.110 (2) Å | θ = 2.1–25.0° |
b = 4.7064 (9) Å | µ = 0.23 mm−1 |
c = 16.686 (3) Å | T = 296 K |
β = 106.663 (2)° | Flat needle, colourless |
V = 760.6 (3) Å3 | 1.24 × 0.1 × 0.02 mm |
Z = 2 | |
Data collection top
Bruker APEXII CCD diffractometer | 2580 independent reflections |
Radiation source: fine-focus sealed tube | 2406 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.022 |
Detector resolution: 8.3 pixels mm-1 | θmax = 25.0°, θmin = 2.1° |
Sets of exposures each taken over 0.5° ω rotation scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008b) | k = −5→5 |
Tmin = 0.800, Tmax = 0.995 | l = −19→19 |
5312 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.099 | w = 1/[σ2(Fo2) + (0.0482P)2 + 0.0887P] where P = (Fo2 + 2Fc2)/3 |
S = 1.18 | (Δ/σ)max < 0.001 |
2580 reflections | Δρmax = 0.24 e Å−3 |
208 parameters | Δρmin = −0.22 e Å−3 |
7 restraints | Absolute structure: Flack (1983), 1082 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.00 (10) |
Crystal data top
C9H11NO2·C5H11NO2S | V = 760.6 (3) Å3 |
Mr = 314.40 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 10.110 (2) Å | µ = 0.23 mm−1 |
b = 4.7064 (9) Å | T = 296 K |
c = 16.686 (3) Å | 1.24 × 0.1 × 0.02 mm |
β = 106.663 (2)° | |
Data collection top
Bruker APEXII CCD diffractometer | 2580 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008b) | 2406 reflections with I > 2σ(I) |
Tmin = 0.800, Tmax = 0.995 | Rint = 0.022 |
5312 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.099 | Δρmax = 0.24 e Å−3 |
S = 1.18 | Δρmin = −0.22 e Å−3 |
2580 reflections | Absolute structure: Flack (1983), 1082 Friedel pairs |
208 parameters | Absolute structure parameter: 0.00 (10) |
7 restraints | |
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. Data were collected by measuring three sets of exposures with the detector set
at 2θ = 29°, crystal-to-detector distance 6.00 cm. Refinement of F2
against ALL reflections. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1A | 1.02662 (17) | 0.6111 (5) | 0.94043 (11) | 0.0328 (4) | |
O2A | 1.15498 (18) | 0.3254 (4) | 0.88695 (13) | 0.0372 (5) | |
N1A | 0.8114 (2) | 0.2392 (5) | 0.90004 (14) | 0.0259 (5) | |
H1A | 0.744 (3) | 0.100 (6) | 0.8811 (17) | 0.039* | |
H2A | 0.772 (3) | 0.416 (6) | 0.8981 (18) | 0.039* | |
H3A | 0.858 (3) | 0.204 (7) | 0.9544 (14) | 0.039* | |
C1A | 0.9139 (2) | 0.2362 (6) | 0.85202 (15) | 0.0243 (6) | |
H11A | 0.9395 | 0.0394 | 0.8443 | 0.029* | |
C2A | 0.8565 (3) | 0.3771 (7) | 0.76664 (16) | 0.0335 (7) | |
H21A | 0.8235 | 0.5649 | 0.7752 | 0.040* | |
H22A | 0.9317 | 0.4016 | 0.7419 | 0.040* | |
C3A | 0.7421 (3) | 0.2220 (6) | 0.70527 (16) | 0.0294 (6) | |
C4A | 0.6054 (3) | 0.2728 (7) | 0.69934 (18) | 0.0383 (7) | |
H41A | 0.5827 | 0.4032 | 0.7351 | 0.046* | |
C5A | 0.5017 (3) | 0.1316 (9) | 0.64071 (19) | 0.0461 (7) | |
H51A | 0.4099 | 0.1693 | 0.6372 | 0.055* | |
C6A | 0.5325 (3) | −0.0625 (7) | 0.58788 (19) | 0.0454 (8) | |
H61A | 0.4621 | −0.1572 | 0.5487 | 0.054* | |
C7A | 0.6677 (4) | −0.1165 (7) | 0.59309 (19) | 0.0469 (8) | |
H71A | 0.6895 | −0.2485 | 0.5574 | 0.056* | |
C8A | 0.7717 (3) | 0.0247 (6) | 0.65126 (18) | 0.0390 (7) | |
H81A | 0.8632 | −0.0133 | 0.6542 | 0.047* | |
C9A | 1.0433 (2) | 0.4028 (6) | 0.89916 (15) | 0.0235 (6) | |
S1B | 0.08623 (7) | 0.6219 (2) | 0.63320 (4) | 0.0437 (2) | |
O1B | 0.52388 (19) | 0.4513 (4) | 0.93063 (12) | 0.0347 (5) | |
O2B | 0.64088 (17) | 0.7423 (4) | 0.87050 (13) | 0.0365 (5) | |
N1B | 0.3166 (2) | 0.8280 (5) | 0.90972 (15) | 0.0264 (5) | |
H1B | 0.366 (3) | 0.867 (7) | 0.9627 (14) | 0.040* | |
H2B | 0.274 (3) | 0.666 (6) | 0.9100 (18) | 0.040* | |
H3B | 0.252 (3) | 0.963 (6) | 0.8966 (19) | 0.040* | |
C1B | 0.4016 (2) | 0.8308 (6) | 0.85007 (16) | 0.0244 (6) | |
H11B | 0.4241 | 1.0273 | 0.8396 | 0.029* | |
C2B | 0.3229 (2) | 0.6906 (6) | 0.76771 (15) | 0.0285 (6) | |
H21B | 0.3794 | 0.7005 | 0.7296 | 0.034* | |
H22B | 0.3101 | 0.4913 | 0.7783 | 0.034* | |
C3B | 0.1827 (3) | 0.8196 (7) | 0.72479 (17) | 0.0357 (7) | |
H31B | 0.1958 | 1.0127 | 0.7082 | 0.043* | |
H32B | 0.1290 | 0.8280 | 0.7645 | 0.043* | |
C4B | 0.1662 (4) | 0.7323 (12) | 0.5567 (2) | 0.0769 (13) | |
H41B | 0.1226 | 0.6396 | 0.5045 | 0.115* | |
H42B | 0.2623 | 0.6827 | 0.5746 | 0.115* | |
H43B | 0.1570 | 0.9344 | 0.5494 | 0.115* | |
C5B | 0.5345 (2) | 0.6651 (6) | 0.88800 (15) | 0.0247 (6) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1A | 0.0323 (9) | 0.0284 (10) | 0.0356 (10) | −0.0043 (9) | 0.0065 (8) | −0.0093 (10) |
O2A | 0.0206 (9) | 0.0328 (11) | 0.0586 (13) | −0.0004 (8) | 0.0124 (9) | −0.0036 (10) |
N1A | 0.0227 (11) | 0.0249 (12) | 0.0286 (12) | −0.0018 (10) | 0.0049 (9) | 0.0036 (11) |
C1A | 0.0224 (12) | 0.0223 (13) | 0.0283 (13) | −0.0003 (11) | 0.0076 (10) | −0.0003 (12) |
C2A | 0.0341 (15) | 0.0375 (18) | 0.0285 (14) | −0.0065 (13) | 0.0082 (12) | 0.0024 (13) |
C3A | 0.0322 (14) | 0.0313 (15) | 0.0225 (13) | −0.0009 (12) | 0.0047 (11) | 0.0059 (12) |
C4A | 0.0356 (15) | 0.0421 (18) | 0.0350 (16) | 0.0055 (14) | 0.0066 (13) | −0.0051 (14) |
C5A | 0.0282 (14) | 0.059 (2) | 0.0451 (16) | −0.0018 (17) | 0.0015 (12) | 0.001 (2) |
C6A | 0.0464 (19) | 0.047 (2) | 0.0327 (16) | −0.0135 (16) | −0.0044 (14) | 0.0005 (16) |
C7A | 0.064 (2) | 0.0405 (19) | 0.0343 (16) | 0.0017 (16) | 0.0115 (15) | −0.0094 (15) |
C8A | 0.0352 (15) | 0.047 (2) | 0.0326 (15) | 0.0033 (14) | 0.0070 (13) | −0.0019 (14) |
C9A | 0.0246 (13) | 0.0192 (15) | 0.0245 (13) | 0.0001 (11) | 0.0033 (11) | 0.0063 (12) |
S1B | 0.0360 (4) | 0.0576 (5) | 0.0332 (4) | −0.0070 (4) | 0.0032 (3) | −0.0072 (4) |
O1B | 0.0334 (10) | 0.0318 (12) | 0.0360 (11) | 0.0047 (9) | 0.0052 (9) | 0.0064 (10) |
O2B | 0.0215 (9) | 0.0330 (11) | 0.0557 (13) | −0.0019 (8) | 0.0123 (9) | −0.0010 (10) |
N1B | 0.0248 (12) | 0.0248 (13) | 0.0284 (12) | 0.0007 (10) | 0.0057 (10) | −0.0049 (11) |
C1B | 0.0252 (13) | 0.0168 (13) | 0.0318 (14) | 0.0016 (11) | 0.0093 (11) | 0.0030 (12) |
C2B | 0.0288 (13) | 0.0272 (18) | 0.0278 (13) | 0.0043 (11) | 0.0054 (11) | 0.0007 (12) |
C3B | 0.0302 (15) | 0.0418 (18) | 0.0310 (15) | 0.0037 (13) | 0.0022 (12) | −0.0097 (14) |
C4B | 0.066 (2) | 0.125 (4) | 0.0393 (19) | −0.019 (3) | 0.0147 (17) | −0.001 (2) |
C5B | 0.0235 (12) | 0.0217 (17) | 0.0261 (13) | −0.0007 (12) | 0.0025 (10) | −0.0045 (12) |
Geometric parameters (Å, º) top
O1A—C9A | 1.237 (3) | C7A—H71A | 0.9300 |
O2A—C9A | 1.257 (3) | C8A—H81A | 0.9300 |
N1A—C1A | 1.481 (3) | S1B—C4B | 1.774 (4) |
N1A—H1A | 0.93 (2) | S1B—C3B | 1.816 (3) |
N1A—H2A | 0.92 (2) | O1B—C5B | 1.254 (3) |
N1A—H3A | 0.91 (2) | O2B—C5B | 1.247 (3) |
C1A—C2A | 1.527 (4) | N1B—C1B | 1.491 (3) |
C1A—C9A | 1.535 (4) | N1B—H1B | 0.90 (2) |
C1A—H11A | 0.9800 | N1B—H2B | 0.88 (2) |
C2A—C3A | 1.497 (4) | N1B—H3B | 0.89 (2) |
C2A—H21A | 0.9700 | C1B—C5B | 1.525 (3) |
C2A—H22A | 0.9700 | C1B—C2B | 1.526 (3) |
C3A—C4A | 1.378 (4) | C1B—H11B | 0.9800 |
C3A—C8A | 1.385 (4) | C2B—C3B | 1.519 (4) |
C4A—C5A | 1.381 (4) | C2B—H21B | 0.9700 |
C4A—H41A | 0.9300 | C2B—H22B | 0.9700 |
C5A—C6A | 1.366 (5) | C3B—H31B | 0.9700 |
C5A—H51A | 0.9300 | C3B—H32B | 0.9700 |
C6A—C7A | 1.368 (5) | C4B—H41B | 0.9600 |
C6A—H61A | 0.9300 | C4B—H42B | 0.9600 |
C7A—C8A | 1.380 (4) | C4B—H43B | 0.9600 |
| | | |
C1A—N1A—H1A | 111.4 (18) | O1A—C9A—C1A | 117.2 (2) |
C1A—N1A—H2A | 110.5 (19) | O2A—C9A—C1A | 116.2 (2) |
H1A—N1A—H2A | 111 (3) | C4B—S1B—C3B | 102.12 (17) |
C1A—N1A—H3A | 107.2 (17) | C1B—N1B—H1B | 113.2 (18) |
H1A—N1A—H3A | 109 (3) | C1B—N1B—H2B | 113 (2) |
H2A—N1A—H3A | 107 (3) | H1B—N1B—H2B | 108 (3) |
N1A—C1A—C2A | 111.3 (2) | C1B—N1B—H3B | 111 (2) |
N1A—C1A—C9A | 110.1 (2) | H1B—N1B—H3B | 105 (3) |
C2A—C1A—C9A | 107.2 (2) | H2B—N1B—H3B | 107 (3) |
N1A—C1A—H11A | 109.4 | N1B—C1B—C5B | 109.1 (2) |
C2A—C1A—H11A | 109.4 | N1B—C1B—C2B | 110.2 (2) |
C9A—C1A—H11A | 109.4 | C5B—C1B—C2B | 108.8 (2) |
C3A—C2A—C1A | 116.0 (2) | N1B—C1B—H11B | 109.6 |
C3A—C2A—H21A | 108.3 | C5B—C1B—H11B | 109.6 |
C1A—C2A—H21A | 108.3 | C2B—C1B—H11B | 109.6 |
C3A—C2A—H22A | 108.3 | C3B—C2B—C1B | 115.3 (2) |
C1A—C2A—H22A | 108.3 | C3B—C2B—H21B | 108.5 |
H21A—C2A—H22A | 107.4 | C1B—C2B—H21B | 108.5 |
C4A—C3A—C8A | 117.9 (3) | C3B—C2B—H22B | 108.5 |
C4A—C3A—C2A | 121.8 (3) | C1B—C2B—H22B | 108.5 |
C8A—C3A—C2A | 120.2 (3) | H21B—C2B—H22B | 107.5 |
C3A—C4A—C5A | 120.6 (3) | C2B—C3B—S1B | 113.29 (19) |
C3A—C4A—H41A | 119.7 | C2B—C3B—H31B | 108.9 |
C5A—C4A—H41A | 119.7 | S1B—C3B—H31B | 108.9 |
C6A—C5A—C4A | 120.8 (3) | C2B—C3B—H32B | 108.9 |
C6A—C5A—H51A | 119.6 | S1B—C3B—H32B | 108.9 |
C4A—C5A—H51A | 119.6 | H31B—C3B—H32B | 107.7 |
C5A—C6A—C7A | 119.4 (3) | S1B—C4B—H41B | 109.5 |
C5A—C6A—H61A | 120.3 | S1B—C4B—H42B | 109.5 |
C7A—C6A—H61A | 120.3 | H41B—C4B—H42B | 109.5 |
C6A—C7A—C8A | 120.1 (3) | S1B—C4B—H43B | 109.5 |
C6A—C7A—H71A | 120.0 | H41B—C4B—H43B | 109.5 |
C8A—C7A—H71A | 120.0 | H42B—C4B—H43B | 109.5 |
C7A—C8A—C3A | 121.2 (3) | O2B—C5B—O1B | 125.9 (2) |
C7A—C8A—H81A | 119.4 | O2B—C5B—C1B | 118.0 (2) |
C3A—C8A—H81A | 119.4 | O1B—C5B—C1B | 115.9 (2) |
O1A—C9A—O2A | 126.3 (2) | | |
| | | |
N1A—C1A—C2A—C3A | −68.4 (3) | N1A—C1A—C9A—O1A | −33.7 (3) |
C9A—C1A—C2A—C3A | 171.1 (2) | C2A—C1A—C9A—O1A | 87.5 (3) |
C1A—C2A—C3A—C4A | 91.2 (3) | N1A—C1A—C9A—O2A | 151.3 (2) |
C1A—C2A—C3A—C8A | −90.0 (3) | C2A—C1A—C9A—O2A | −87.5 (3) |
C8A—C3A—C4A—C5A | −0.5 (5) | N1B—C1B—C2B—C3B | 56.5 (3) |
C2A—C3A—C4A—C5A | 178.4 (3) | C5B—C1B—C2B—C3B | 176.1 (2) |
C3A—C4A—C5A—C6A | 0.5 (5) | C1B—C2B—C3B—S1B | −173.88 (19) |
C4A—C5A—C6A—C7A | −0.2 (5) | C4B—S1B—C3B—C2B | −78.3 (3) |
C5A—C6A—C7A—C8A | −0.1 (5) | N1B—C1B—C5B—O2B | −148.0 (2) |
C6A—C7A—C8A—C3A | 0.1 (5) | C2B—C1B—C5B—O2B | 91.8 (3) |
C4A—C3A—C8A—C7A | 0.2 (4) | N1B—C1B—C5B—O1B | 36.0 (3) |
C2A—C3A—C8A—C7A | −178.7 (3) | C2B—C1B—C5B—O1B | −84.3 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O2Bi | 0.93 (2) | 1.96 (3) | 2.863 (3) | 162 (3) |
N1A—H2A···O2B | 0.92 (2) | 2.00 (2) | 2.887 (3) | 163 (3) |
N1A—H3A···O1Aii | 0.91 (2) | 1.86 (2) | 2.762 (3) | 172 (3) |
N1B—H1B···O1Biii | 0.90 (2) | 1.85 (2) | 2.752 (3) | 176 (3) |
N1B—H2B···O2Aiv | 0.88 (2) | 1.98 (2) | 2.838 (3) | 168 (3) |
N1B—H3B···O2Av | 0.89 (2) | 1.95 (2) | 2.817 (3) | 163 (3) |
Symmetry codes: (i) x, y−1, z; (ii) −x+2, y−1/2, −z+2; (iii) −x+1, y+1/2, −z+2; (iv) x−1, y, z; (v) x−1, y+1, z. |
(IV) L-Phenylalanine–D-leucine (1/1)
top
Crystal data top
C9H11NO2·C6H13NO2 | F(000) = 320 |
Mr = 296.36 | Dx = 1.259 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 2870 reflections |
a = 5.1861 (5) Å | θ = 2.7–25.0° |
b = 29.698 (3) Å | µ = 0.09 mm−1 |
c = 5.4158 (5) Å | T = 296 K |
β = 110.372 (1)° | Plate, colourless |
V = 781.95 (13) Å3 | 0.3 × 0.2 × 0.06 mm |
Z = 2 | |
Data collection top
Bruker APEXII CCD diffractometer | 1411 independent reflections |
Radiation source: fine-focus sealed tube | 1269 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
Detector resolution: 8.3 pixels mm-1 | θmax = 25.0°, θmin = 2.7° |
Sets of exposures each taken over 0.5° ω rotation scans | h = −6→6 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008b) | k = −35→35 |
Tmin = 0.909, Tmax = 0.995 | l = −6→6 |
7778 measured reflections | |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.089 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | w = 1/[σ2(Fo2) + (0.0438P)2 + 0.1739P] where P = (Fo2 + 2Fc2)/3 |
1411 reflections | (Δ/σ)max < 0.001 |
208 parameters | Δρmax = 0.14 e Å−3 |
12 restraints | Δρmin = −0.16 e Å−3 |
Crystal data top
C9H11NO2·C6H13NO2 | V = 781.95 (13) Å3 |
Mr = 296.36 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 5.1861 (5) Å | µ = 0.09 mm−1 |
b = 29.698 (3) Å | T = 296 K |
c = 5.4158 (5) Å | 0.3 × 0.2 × 0.06 mm |
β = 110.372 (1)° | |
Data collection top
Bruker APEXII CCD diffractometer | 1411 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008b) | 1269 reflections with I > 2σ(I) |
Tmin = 0.909, Tmax = 0.995 | Rint = 0.024 |
7778 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | 12 restraints |
wR(F2) = 0.089 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.14 e Å−3 |
1411 reflections | Δρmin = −0.16 e Å−3 |
208 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. Data were collected by measuring four sets of exposures with the detector set at
2θ = 29°, crystal-to-detector distance 6.00 cm. Refinement of F2
against ALL reflections. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1A | 0.1937 (4) | 0.65841 (9) | 0.6354 (4) | 0.0413 (7) | |
O2A | 0.6475 (4) | 0.65012 (8) | 0.7847 (4) | 0.0356 (5) | |
N1A | 0.2052 (5) | 0.67014 (10) | 1.1385 (5) | 0.0303 (6) | |
H1A | 0.240 (7) | 0.7000 (9) | 1.111 (7) | 0.045* | |
H2A | 0.210 (7) | 0.6659 (12) | 1.307 (5) | 0.045* | |
H3A | 0.034 (5) | 0.6623 (12) | 1.038 (6) | 0.045* | |
C1A | 0.4093 (5) | 0.63963 (10) | 1.0854 (5) | 0.0275 (6) | |
H11A | 0.5913 | 0.6446 | 1.2189 | 0.033* | |
C2A | 0.3164 (7) | 0.59156 (11) | 1.1079 (7) | 0.0416 (8) | |
H21A | 0.3074 | 0.5877 | 1.2825 | 0.050* | |
H22A | 0.1314 | 0.5878 | 0.9823 | 0.050* | |
C3A | 0.4919 (7) | 0.55507 (11) | 1.0625 (6) | 0.0425 (8) | |
C4A | 0.7301 (9) | 0.54142 (17) | 1.2477 (11) | 0.0857 (16) | |
H41A | 0.7924 | 0.5561 | 1.4096 | 0.103* | |
C5A | 0.8839 (10) | 0.50614 (19) | 1.2023 (12) | 0.107 (2) | |
H51A | 1.0491 | 0.4982 | 1.3320 | 0.128* | |
C6A | 0.7980 (10) | 0.48372 (15) | 0.9764 (10) | 0.0826 (15) | |
H61A | 0.8957 | 0.4590 | 0.9504 | 0.099* | |
C7A | 0.5713 (14) | 0.4972 (2) | 0.7897 (12) | 0.122 (2) | |
H71A | 0.5134 | 0.4826 | 0.6274 | 0.147* | |
C8A | 0.4192 (12) | 0.53240 (18) | 0.8317 (9) | 0.1005 (19) | |
H81A | 0.2601 | 0.5410 | 0.6958 | 0.121* | |
C9A | 0.4199 (5) | 0.65037 (10) | 0.8121 (5) | 0.0254 (6) | |
O1B | 0.8063 (4) | 0.74386 (8) | 1.1112 (4) | 0.0380 (6) | |
O2B | 0.3534 (4) | 0.75444 (7) | 0.9634 (4) | 0.0351 (5) | |
N1B | 0.8026 (5) | 0.73490 (10) | 0.6116 (5) | 0.0288 (6) | |
H1B | 0.767 (7) | 0.7060 (9) | 0.641 (7) | 0.043* | |
H2B | 0.979 (5) | 0.7419 (12) | 0.712 (6) | 0.043* | |
H3B | 0.808 (7) | 0.7377 (12) | 0.441 (5) | 0.043* | |
C1B | 0.5946 (6) | 0.76440 (10) | 0.6625 (5) | 0.0264 (6) | |
H11B | 0.4140 | 0.7592 | 0.5273 | 0.032* | |
C2B | 0.6793 (7) | 0.81324 (11) | 0.6502 (7) | 0.0382 (8) | |
H21B | 0.7254 | 0.8172 | 0.4926 | 0.046* | |
H22B | 0.8447 | 0.8190 | 0.8004 | 0.046* | |
C3B | 0.4638 (8) | 0.84833 (12) | 0.6484 (8) | 0.0508 (9) | |
H31B | 0.3792 | 0.8392 | 0.7765 | 0.061* | |
C4B | 0.2403 (9) | 0.85166 (17) | 0.3812 (9) | 0.0764 (13) | |
H41B | 0.1094 | 0.8742 | 0.3861 | 0.115* | |
H42B | 0.1493 | 0.8231 | 0.3356 | 0.115* | |
H43B | 0.3202 | 0.8598 | 0.2519 | 0.115* | |
C5B | 0.6026 (13) | 0.89361 (16) | 0.7332 (12) | 0.0970 (18) | |
H51B | 0.4668 | 0.9157 | 0.7310 | 0.145* | |
H52B | 0.6938 | 0.9025 | 0.6142 | 0.145* | |
H53B | 0.7351 | 0.8912 | 0.9082 | 0.145* | |
C6B | 0.5822 (5) | 0.75299 (9) | 0.9353 (5) | 0.0250 (6) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1A | 0.0333 (13) | 0.0715 (18) | 0.0207 (11) | 0.0090 (11) | 0.0113 (9) | 0.0068 (11) |
O2A | 0.0303 (11) | 0.0483 (13) | 0.0349 (11) | −0.0014 (10) | 0.0198 (8) | 0.0022 (10) |
N1A | 0.0336 (15) | 0.0400 (15) | 0.0189 (13) | 0.0047 (12) | 0.0112 (11) | 0.0025 (11) |
C1A | 0.0251 (14) | 0.0379 (16) | 0.0210 (14) | 0.0035 (12) | 0.0099 (11) | 0.0029 (12) |
C2A | 0.0513 (19) | 0.0409 (19) | 0.0432 (18) | 0.0043 (15) | 0.0297 (16) | 0.0083 (15) |
C3A | 0.0499 (19) | 0.0365 (17) | 0.0487 (19) | 0.0022 (14) | 0.0268 (16) | 0.0094 (16) |
C4A | 0.062 (3) | 0.075 (3) | 0.098 (4) | 0.014 (2) | 0.000 (2) | −0.033 (3) |
C5A | 0.065 (3) | 0.086 (4) | 0.139 (5) | 0.034 (3) | −0.004 (3) | −0.023 (4) |
C6A | 0.090 (3) | 0.050 (3) | 0.123 (4) | 0.013 (2) | 0.057 (3) | −0.010 (3) |
C7A | 0.153 (6) | 0.108 (5) | 0.091 (4) | 0.059 (4) | 0.024 (4) | −0.032 (3) |
C8A | 0.122 (4) | 0.103 (4) | 0.064 (3) | 0.060 (4) | 0.015 (3) | −0.013 (3) |
C9A | 0.0295 (14) | 0.0279 (14) | 0.0222 (14) | −0.0008 (12) | 0.0132 (11) | −0.0004 (12) |
O1B | 0.0335 (12) | 0.0623 (17) | 0.0215 (11) | 0.0088 (11) | 0.0137 (10) | 0.0058 (10) |
O2B | 0.0292 (11) | 0.0488 (13) | 0.0323 (11) | −0.0022 (9) | 0.0169 (9) | 0.0010 (10) |
N1B | 0.0318 (15) | 0.0390 (15) | 0.0197 (13) | 0.0043 (12) | 0.0141 (12) | 0.0031 (12) |
C1B | 0.0269 (14) | 0.0334 (15) | 0.0195 (14) | 0.0013 (12) | 0.0087 (11) | 0.0025 (12) |
C2B | 0.0405 (17) | 0.0400 (19) | 0.0372 (17) | −0.0025 (13) | 0.0174 (14) | 0.0065 (14) |
C3B | 0.066 (2) | 0.0402 (19) | 0.055 (2) | 0.0086 (18) | 0.0311 (19) | 0.0106 (17) |
C4B | 0.065 (3) | 0.072 (3) | 0.084 (3) | 0.023 (2) | 0.016 (2) | 0.018 (2) |
C5B | 0.120 (4) | 0.045 (2) | 0.116 (4) | 0.003 (3) | 0.027 (4) | −0.006 (3) |
C6B | 0.0275 (14) | 0.0265 (14) | 0.0232 (14) | −0.0002 (11) | 0.0118 (11) | −0.0022 (11) |
Geometric parameters (Å, º) top
O1A—C9A | 1.252 (3) | C8A—H81A | 0.9300 |
O2A—C9A | 1.240 (3) | O1B—C6B | 1.250 (3) |
N1A—C1A | 1.495 (4) | O2B—C6B | 1.248 (3) |
N1A—H1A | 0.93 (3) | N1B—C1B | 1.488 (4) |
N1A—H2A | 0.91 (2) | N1B—H1B | 0.90 (3) |
N1A—H3A | 0.90 (2) | N1B—H2B | 0.91 (2) |
C1A—C2A | 1.525 (4) | N1B—H3B | 0.94 (2) |
C1A—C9A | 1.534 (3) | C1B—C2B | 1.524 (4) |
C1A—H11A | 0.9800 | C1B—C6B | 1.539 (4) |
C2A—C3A | 1.490 (4) | C1B—H11B | 0.9800 |
C2A—H21A | 0.9700 | C2B—C3B | 1.526 (5) |
C2A—H22A | 0.9700 | C2B—H21B | 0.9700 |
C3A—C8A | 1.353 (5) | C2B—H22B | 0.9700 |
C3A—C4A | 1.354 (5) | C3B—C4B | 1.510 (6) |
C4A—C5A | 1.389 (6) | C3B—C5B | 1.519 (6) |
C4A—H41A | 0.9300 | C3B—H31B | 0.9800 |
C5A—C6A | 1.326 (6) | C4B—H41B | 0.9600 |
C5A—H51A | 0.9300 | C4B—H42B | 0.9600 |
C6A—C7A | 1.318 (6) | C4B—H43B | 0.9600 |
C6A—H61A | 0.9300 | C5B—H51B | 0.9600 |
C7A—C8A | 1.376 (6) | C5B—H52B | 0.9600 |
C7A—H71A | 0.9300 | C5B—H53B | 0.9600 |
| | | |
C1A—N1A—H1A | 111 (2) | C1B—N1B—H1B | 109 (2) |
C1A—N1A—H2A | 110 (2) | C1B—N1B—H2B | 113 (2) |
H1A—N1A—H2A | 111 (3) | H1B—N1B—H2B | 110 (3) |
C1A—N1A—H3A | 110 (2) | C1B—N1B—H3B | 114 (2) |
H1A—N1A—H3A | 111 (3) | H1B—N1B—H3B | 110 (3) |
H2A—N1A—H3A | 104 (3) | H2B—N1B—H3B | 102 (3) |
N1A—C1A—C2A | 106.7 (2) | N1B—C1B—C2B | 108.3 (2) |
N1A—C1A—C9A | 109.0 (2) | N1B—C1B—C6B | 108.9 (2) |
C2A—C1A—C9A | 113.0 (2) | C2B—C1B—C6B | 111.1 (2) |
N1A—C1A—H11A | 109.4 | N1B—C1B—H11B | 109.5 |
C2A—C1A—H11A | 109.4 | C2B—C1B—H11B | 109.5 |
C9A—C1A—H11A | 109.4 | C6B—C1B—H11B | 109.5 |
C3A—C2A—C1A | 116.1 (2) | C1B—C2B—C3B | 115.4 (3) |
C3A—C2A—H21A | 108.3 | C1B—C2B—H21B | 108.4 |
C1A—C2A—H21A | 108.3 | C3B—C2B—H21B | 108.4 |
C3A—C2A—H22A | 108.3 | C1B—C2B—H22B | 108.4 |
C1A—C2A—H22A | 108.3 | C3B—C2B—H22B | 108.4 |
H21A—C2A—H22A | 107.4 | H21B—C2B—H22B | 107.5 |
C8A—C3A—C4A | 115.1 (4) | C4B—C3B—C5B | 110.9 (4) |
C8A—C3A—C2A | 121.7 (3) | C4B—C3B—C2B | 111.5 (3) |
C4A—C3A—C2A | 123.2 (3) | C5B—C3B—C2B | 109.5 (4) |
C3A—C4A—C5A | 121.8 (4) | C4B—C3B—H31B | 108.3 |
C3A—C4A—H41A | 119.1 | C5B—C3B—H31B | 108.3 |
C5A—C4A—H41A | 119.1 | C2B—C3B—H31B | 108.3 |
C6A—C5A—C4A | 120.8 (4) | C3B—C4B—H41B | 109.5 |
C6A—C5A—H51A | 119.6 | C3B—C4B—H42B | 109.5 |
C4A—C5A—H51A | 119.6 | H41B—C4B—H42B | 109.5 |
C7A—C6A—C5A | 118.6 (5) | C3B—C4B—H43B | 109.5 |
C7A—C6A—H61A | 120.7 | H41B—C4B—H43B | 109.5 |
C5A—C6A—H61A | 120.7 | H42B—C4B—H43B | 109.5 |
C6A—C7A—C8A | 120.9 (5) | C3B—C5B—H51B | 109.5 |
C6A—C7A—H71A | 119.6 | C3B—C5B—H52B | 109.5 |
C8A—C7A—H71A | 119.6 | H51B—C5B—H52B | 109.5 |
C3A—C8A—C7A | 122.7 (5) | C3B—C5B—H53B | 109.5 |
C3A—C8A—H81A | 118.7 | H51B—C5B—H53B | 109.5 |
C7A—C8A—H81A | 118.7 | H52B—C5B—H53B | 109.5 |
O2A—C9A—O1A | 126.0 (2) | O2B—C6B—O1B | 125.9 (2) |
O2A—C9A—C1A | 118.0 (2) | O2B—C6B—C1B | 118.0 (2) |
O1A—C9A—C1A | 116.0 (2) | O1B—C6B—C1B | 116.2 (2) |
| | | |
N1A—C1A—C2A—C3A | −179.9 (3) | N1A—C1A—C9A—O2A | 140.2 (3) |
C9A—C1A—C2A—C3A | 60.4 (3) | C2A—C1A—C9A—O2A | −101.4 (3) |
C1A—C2A—C3A—C8A | −101.7 (5) | N1A—C1A—C9A—O1A | −40.2 (3) |
C1A—C2A—C3A—C4A | 79.8 (5) | C2A—C1A—C9A—O1A | 78.2 (3) |
C8A—C3A—C4A—C5A | −1.0 (8) | N1B—C1B—C2B—C3B | 169.4 (3) |
C2A—C3A—C4A—C5A | 177.6 (5) | C6B—C1B—C2B—C3B | −71.1 (3) |
C3A—C4A—C5A—C6A | −1.7 (10) | C1B—C2B—C3B—C4B | −76.9 (4) |
C4A—C5A—C6A—C7A | 3.8 (10) | C1B—C2B—C3B—C5B | 159.9 (4) |
C5A—C6A—C7A—C8A | −3.0 (11) | N1B—C1B—C6B—O2B | −143.5 (3) |
C4A—C3A—C8A—C7A | 1.8 (9) | C2B—C1B—C6B—O2B | 97.3 (3) |
C2A—C3A—C8A—C7A | −176.8 (6) | N1B—C1B—C6B—O1B | 37.8 (3) |
C6A—C7A—C8A—C3A | 0.2 (11) | C2B—C1B—C6B—O1B | −81.4 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O2B | 0.93 (3) | 1.98 (3) | 2.875 (4) | 161 (3) |
N1A—H2A···O1Ai | 0.91 (2) | 1.82 (3) | 2.735 (3) | 176 (3) |
N1A—H3A···O2Aii | 0.90 (2) | 2.03 (3) | 2.921 (3) | 174 (3) |
N1B—H1B···O2A | 0.90 (3) | 2.02 (3) | 2.896 (4) | 163 (3) |
N1B—H2B···O2Biii | 0.91 (2) | 1.98 (3) | 2.887 (3) | 174 (3) |
N1B—H3B···O1Biv | 0.94 (2) | 1.79 (2) | 2.729 (3) | 178 (3) |
Symmetry codes: (i) x, y, z+1; (ii) x−1, y, z; (iii) x+1, y, z; (iv) x, y, z−1. |
(V) L-Phenylalanine–D-isoleucine (1/1)
top
Crystal data top
C9H11NO2·C6H13NO2 | Z = 1 |
Mr = 296.36 | F(000) = 160 |
Triclinic, P1 | Dx = 1.279 Mg m−3 |
Hall symbol: P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.2317 (12) Å | Cell parameters from 3065 reflections |
b = 5.4232 (12) Å | θ = 2.8–25.0° |
c = 14.459 (3) Å | µ = 0.09 mm−1 |
α = 85.936 (3)° | T = 296 K |
β = 85.343 (3)° | Plate, colourless |
γ = 70.424 (2)° | 0.32 × 0.18 × 0.03 mm |
V = 384.83 (15) Å3 | |
Data collection top
Bruker APEXII CCD diffractometer | 1359 independent reflections |
Radiation source: fine-focus sealed tube | 1054 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.028 |
Detector resolution: 8.3 pixels mm-1 | θmax = 25.0°, θmin = 2.8° |
Sets of exposures each taken over 0.5° ω rotation scans | h = −6→6 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008b) | k = −6→6 |
Tmin = 0.762, Tmax = 0.997 | l = −17→17 |
2821 measured reflections | |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.099 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0544P)2 + 0.0052P] where P = (Fo2 + 2Fc2)/3 |
1359 reflections | (Δ/σ)max < 0.001 |
210 parameters | Δρmax = 0.17 e Å−3 |
9 restraints | Δρmin = −0.16 e Å−3 |
Crystal data top
C9H11NO2·C6H13NO2 | γ = 70.424 (2)° |
Mr = 296.36 | V = 384.83 (15) Å3 |
Triclinic, P1 | Z = 1 |
a = 5.2317 (12) Å | Mo Kα radiation |
b = 5.4232 (12) Å | µ = 0.09 mm−1 |
c = 14.459 (3) Å | T = 296 K |
α = 85.936 (3)° | 0.32 × 0.18 × 0.03 mm |
β = 85.343 (3)° | |
Data collection top
Bruker APEXII CCD diffractometer | 1359 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008b) | 1054 reflections with I > 2σ(I) |
Tmin = 0.762, Tmax = 0.997 | Rint = 0.028 |
2821 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 9 restraints |
wR(F2) = 0.099 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.17 e Å−3 |
1359 reflections | Δρmin = −0.16 e Å−3 |
210 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. Data were collected by measuring three sets of exposures with the detector set
at 2θ = 29°, crystal-to-detector distance 6.00 cm. Refinement of F2
against ALL reflections. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1A | 0.5376 (5) | −0.0492 (5) | 0.5393 (2) | 0.0421 (9) | |
O2A | 0.0926 (5) | 0.0988 (6) | 0.5197 (2) | 0.0382 (8) | |
N1A | 0.5316 (7) | 0.4467 (7) | 0.5611 (3) | 0.0314 (9) | |
H1A | 0.496 (9) | 0.404 (9) | 0.622 (2) | 0.047* | |
H2A | 0.529 (10) | 0.615 (6) | 0.552 (3) | 0.047* | |
H3A | 0.712 (6) | 0.340 (8) | 0.546 (3) | 0.047* | |
C1A | 0.3369 (9) | 0.4021 (8) | 0.5000 (3) | 0.0323 (11) | |
H11A | 0.1569 | 0.5330 | 0.5112 | 0.039* | |
C2A | 0.4435 (9) | 0.4386 (9) | 0.4000 (3) | 0.0431 (13) | |
H21A | 0.4543 | 0.6140 | 0.3917 | 0.052* | |
H22A | 0.6271 | 0.3165 | 0.3918 | 0.052* | |
C3A | 0.2821 (9) | 0.4015 (9) | 0.3247 (3) | 0.0449 (11) | |
C4A | 0.0499 (11) | 0.5901 (14) | 0.2978 (4) | 0.0789 (19) | |
H41A | −0.0151 | 0.7472 | 0.3279 | 0.095* | |
C5A | −0.0921 (13) | 0.5497 (17) | 0.2251 (5) | 0.097 (2) | |
H51A | −0.2523 | 0.6782 | 0.2083 | 0.116* | |
C6A | 0.0020 (14) | 0.3276 (16) | 0.1800 (4) | 0.085 (2) | |
H61A | −0.0884 | 0.3055 | 0.1301 | 0.102* | |
C7A | 0.225 (2) | 0.1373 (17) | 0.2061 (6) | 0.121 (3) | |
H71A | 0.2872 | −0.0195 | 0.1758 | 0.146* | |
C8A | 0.3632 (15) | 0.1757 (13) | 0.2794 (5) | 0.101 (2) | |
H81A | 0.5170 | 0.0410 | 0.2977 | 0.121* | |
C9A | 0.3195 (8) | 0.1261 (8) | 0.5215 (3) | 0.0277 (10) | |
O1B | −0.0869 (5) | 0.3990 (5) | 0.7093 (2) | 0.0371 (8) | |
O2B | 0.3513 (5) | 0.2610 (6) | 0.7389 (2) | 0.0355 (8) | |
N1B | −0.1008 (7) | −0.0869 (7) | 0.6984 (3) | 0.0304 (9) | |
H1B | −0.075 (9) | −0.043 (9) | 0.635 (2) | 0.046* | |
H2B | −0.273 (6) | 0.019 (8) | 0.720 (3) | 0.046* | |
H3B | −0.101 (10) | −0.256 (6) | 0.706 (3) | 0.046* | |
C1B | 0.1225 (7) | −0.0544 (8) | 0.7494 (3) | 0.0255 (10) | |
H11B | 0.2948 | −0.1748 | 0.7239 | 0.031* | |
C2B | 0.0936 (8) | −0.1298 (9) | 0.8528 (3) | 0.0338 (10) | |
H21B | 0.0230 | −0.2766 | 0.8575 | 0.041* | |
C3B | 0.3671 (9) | −0.2258 (10) | 0.8952 (3) | 0.0501 (12) | |
H31B | 0.4938 | −0.3550 | 0.8556 | 0.060* | |
H32B | 0.4343 | −0.0796 | 0.8960 | 0.060* | |
C4B | 0.3637 (13) | −0.3460 (13) | 0.9926 (4) | 0.084 (2) | |
H41B | 0.5466 | −0.4210 | 1.0116 | 0.127* | |
H42B | 0.2817 | −0.4803 | 0.9939 | 0.127* | |
H43B | 0.2609 | −0.2130 | 1.0343 | 0.127* | |
C5B | −0.1114 (9) | 0.0922 (9) | 0.9064 (3) | 0.0453 (11) | |
H51B | −0.2767 | 0.1580 | 0.8746 | 0.068* | |
H52B | −0.0376 | 0.2307 | 0.9107 | 0.068* | |
H53B | −0.1488 | 0.0274 | 0.9678 | 0.068* | |
C6B | 0.1290 (8) | 0.2251 (9) | 0.7304 (3) | 0.0268 (10) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1A | 0.0362 (18) | 0.0201 (18) | 0.072 (2) | −0.0120 (16) | −0.0090 (16) | 0.0022 (16) |
O2A | 0.0310 (17) | 0.0360 (18) | 0.0525 (19) | −0.0183 (15) | 0.0000 (14) | −0.0017 (15) |
N1A | 0.037 (2) | 0.024 (2) | 0.037 (2) | −0.0160 (19) | −0.0069 (17) | 0.0036 (19) |
C1A | 0.032 (2) | 0.029 (3) | 0.041 (3) | −0.017 (2) | −0.008 (2) | 0.002 (2) |
C2A | 0.053 (3) | 0.047 (3) | 0.039 (3) | −0.030 (2) | −0.010 (2) | 0.008 (2) |
C3A | 0.055 (3) | 0.051 (3) | 0.036 (2) | −0.029 (2) | −0.004 (2) | 0.006 (2) |
C4A | 0.061 (4) | 0.095 (5) | 0.065 (4) | 0.001 (3) | −0.016 (3) | −0.024 (4) |
C5A | 0.065 (4) | 0.142 (7) | 0.068 (4) | −0.007 (4) | −0.030 (3) | −0.013 (4) |
C6A | 0.080 (4) | 0.134 (7) | 0.060 (4) | −0.056 (5) | −0.017 (3) | −0.007 (4) |
C7A | 0.156 (8) | 0.104 (6) | 0.110 (6) | −0.034 (6) | −0.063 (6) | −0.030 (5) |
C8A | 0.134 (6) | 0.066 (4) | 0.092 (5) | −0.005 (4) | −0.066 (5) | −0.015 (4) |
C9A | 0.031 (2) | 0.021 (3) | 0.032 (2) | −0.009 (2) | 0.0037 (19) | −0.006 (2) |
O1B | 0.0338 (19) | 0.0224 (18) | 0.057 (2) | −0.0098 (16) | −0.0133 (15) | 0.0021 (15) |
O2B | 0.0307 (17) | 0.0350 (18) | 0.0482 (18) | −0.0205 (15) | −0.0036 (13) | 0.0002 (15) |
N1B | 0.032 (2) | 0.022 (2) | 0.041 (2) | −0.0128 (19) | −0.0084 (18) | −0.0009 (19) |
C1B | 0.021 (2) | 0.022 (2) | 0.033 (2) | −0.0058 (19) | −0.0039 (17) | −0.004 (2) |
C2B | 0.034 (2) | 0.031 (2) | 0.040 (3) | −0.0162 (19) | −0.0051 (19) | 0.0036 (19) |
C3B | 0.050 (3) | 0.051 (3) | 0.047 (3) | −0.013 (2) | −0.013 (2) | 0.006 (2) |
C4B | 0.089 (4) | 0.091 (5) | 0.049 (3) | 0.002 (4) | −0.016 (3) | 0.011 (3) |
C5B | 0.048 (3) | 0.045 (3) | 0.045 (3) | −0.017 (2) | 0.001 (2) | −0.004 (2) |
C6B | 0.029 (2) | 0.028 (3) | 0.028 (2) | −0.016 (2) | 0.0008 (19) | −0.004 (2) |
Geometric parameters (Å, º) top
O1A—C9A | 1.248 (5) | C8A—H81A | 0.9300 |
O2A—C9A | 1.247 (5) | O1B—C6B | 1.249 (5) |
N1A—C1A | 1.489 (6) | O2B—C6B | 1.258 (5) |
N1A—H1A | 0.91 (3) | N1B—C1B | 1.495 (5) |
N1A—H2A | 0.91 (3) | N1B—H1B | 0.94 (3) |
N1A—H3A | 0.94 (3) | N1B—H2B | 0.93 (3) |
C1A—C2A | 1.532 (6) | N1B—H3B | 0.92 (3) |
C1A—C9A | 1.538 (6) | C1B—C2B | 1.531 (6) |
C1A—H11A | 0.9800 | C1B—C6B | 1.533 (6) |
C2A—C3A | 1.494 (6) | C1B—H11B | 0.9800 |
C2A—H21A | 0.9700 | C2B—C3B | 1.514 (6) |
C2A—H22A | 0.9700 | C2B—C5B | 1.527 (6) |
C3A—C8A | 1.353 (8) | C2B—H21B | 0.9800 |
C3A—C4A | 1.364 (7) | C3B—C4B | 1.511 (7) |
C4A—C5A | 1.405 (9) | C3B—H31B | 0.9700 |
C4A—H41A | 0.9300 | C3B—H32B | 0.9700 |
C5A—C6A | 1.333 (10) | C4B—H41B | 0.9600 |
C5A—H51A | 0.9300 | C4B—H42B | 0.9600 |
C6A—C7A | 1.332 (9) | C4B—H43B | 0.9600 |
C6A—H61A | 0.9300 | C5B—H51B | 0.9600 |
C7A—C8A | 1.396 (9) | C5B—H52B | 0.9600 |
C7A—H71A | 0.9300 | C5B—H53B | 0.9600 |
| | | |
C1A—N1A—H1A | 111 (3) | C1B—N1B—H1B | 109 (3) |
C1A—N1A—H2A | 109 (3) | C1B—N1B—H2B | 113 (3) |
H1A—N1A—H2A | 112 (5) | H1B—N1B—H2B | 108 (4) |
C1A—N1A—H3A | 112 (3) | C1B—N1B—H3B | 110 (3) |
H1A—N1A—H3A | 106 (4) | H1B—N1B—H3B | 110 (5) |
H2A—N1A—H3A | 107 (4) | H2B—N1B—H3B | 106 (4) |
N1A—C1A—C2A | 106.3 (3) | N1B—C1B—C2B | 110.8 (3) |
N1A—C1A—C9A | 109.6 (3) | N1B—C1B—C6B | 109.2 (3) |
C2A—C1A—C9A | 112.5 (4) | C2B—C1B—C6B | 113.6 (3) |
N1A—C1A—H11A | 109.5 | N1B—C1B—H11B | 107.7 |
C2A—C1A—H11A | 109.5 | C2B—C1B—H11B | 107.7 |
C9A—C1A—H11A | 109.5 | C6B—C1B—H11B | 107.7 |
C3A—C2A—C1A | 116.6 (3) | C3B—C2B—C5B | 111.9 (4) |
C3A—C2A—H21A | 108.1 | C3B—C2B—C1B | 111.1 (3) |
C1A—C2A—H21A | 108.1 | C5B—C2B—C1B | 112.1 (4) |
C3A—C2A—H22A | 108.1 | C3B—C2B—H21B | 107.1 |
C1A—C2A—H22A | 108.1 | C5B—C2B—H21B | 107.1 |
H21A—C2A—H22A | 107.3 | C1B—C2B—H21B | 107.1 |
C8A—C3A—C4A | 116.7 (5) | C4B—C3B—C2B | 114.5 (4) |
C8A—C3A—C2A | 120.7 (5) | C4B—C3B—H31B | 108.6 |
C4A—C3A—C2A | 122.6 (4) | C2B—C3B—H31B | 108.6 |
C3A—C4A—C5A | 120.7 (6) | C4B—C3B—H32B | 108.6 |
C3A—C4A—H41A | 119.6 | C2B—C3B—H32B | 108.6 |
C5A—C4A—H41A | 119.6 | H31B—C3B—H32B | 107.6 |
C6A—C5A—C4A | 120.2 (6) | C3B—C4B—H41B | 109.5 |
C6A—C5A—H51A | 119.9 | C3B—C4B—H42B | 109.5 |
C4A—C5A—H51A | 119.9 | H41B—C4B—H42B | 109.5 |
C7A—C6A—C5A | 120.4 (6) | C3B—C4B—H43B | 109.5 |
C7A—C6A—H61A | 119.8 | H41B—C4B—H43B | 109.5 |
C5A—C6A—H61A | 119.8 | H42B—C4B—H43B | 109.5 |
C6A—C7A—C8A | 119.3 (7) | C2B—C5B—H51B | 109.5 |
C6A—C7A—H71A | 120.4 | C2B—C5B—H52B | 109.5 |
C8A—C7A—H71A | 120.4 | H51B—C5B—H52B | 109.5 |
C3A—C8A—C7A | 122.5 (6) | C2B—C5B—H53B | 109.5 |
C3A—C8A—H81A | 118.8 | H51B—C5B—H53B | 109.5 |
C7A—C8A—H81A | 118.8 | H52B—C5B—H53B | 109.5 |
O2A—C9A—O1A | 126.5 (4) | O1B—C6B—O2B | 125.4 (4) |
O2A—C9A—C1A | 117.7 (4) | O1B—C6B—C1B | 117.5 (3) |
O1A—C9A—C1A | 115.8 (4) | O2B—C6B—C1B | 117.1 (4) |
| | | |
N1A—C1A—C2A—C3A | 179.5 (4) | C2A—C1A—C9A—O2A | −99.9 (5) |
C9A—C1A—C2A—C3A | 59.6 (5) | N1A—C1A—C9A—O1A | −37.8 (5) |
C1A—C2A—C3A—C8A | −101.1 (6) | C2A—C1A—C9A—O1A | 80.2 (4) |
C1A—C2A—C3A—C4A | 79.4 (6) | N1B—C1B—C2B—C3B | 152.2 (4) |
C8A—C3A—C4A—C5A | −1.2 (9) | C6B—C1B—C2B—C3B | −84.4 (4) |
C2A—C3A—C4A—C5A | 178.4 (6) | N1B—C1B—C2B—C5B | −81.7 (4) |
C3A—C4A—C5A—C6A | −1.4 (11) | C6B—C1B—C2B—C5B | 41.7 (4) |
C4A—C5A—C6A—C7A | 3.0 (11) | C5B—C2B—C3B—C4B | 63.4 (6) |
C5A—C6A—C7A—C8A | −1.9 (13) | C1B—C2B—C3B—C4B | −170.4 (5) |
C4A—C3A—C8A—C7A | 2.3 (10) | N1B—C1B—C6B—O1B | 25.6 (5) |
C2A—C3A—C8A—C7A | −177.2 (7) | C2B—C1B—C6B—O1B | −98.7 (4) |
C6A—C7A—C8A—C3A | −0.9 (13) | N1B—C1B—C6B—O2B | −155.5 (4) |
N1A—C1A—C9A—O2A | 142.1 (4) | C2B—C1B—C6B—O2B | 80.2 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O2B | 0.91 (3) | 2.01 (3) | 2.896 (5) | 163 (4) |
N1A—H2A···O1Ai | 0.91 (3) | 1.83 (3) | 2.740 (5) | 177 (5) |
N1A—H3A···O2Aii | 0.94 (3) | 2.01 (3) | 2.949 (5) | 177 (4) |
N1B—H1B···O2A | 0.94 (3) | 2.04 (3) | 2.933 (5) | 157 (4) |
N1B—H2B···O2Biii | 0.93 (3) | 1.98 (3) | 2.895 (5) | 169 (4) |
N1B—H3B···O1Biv | 0.92 (3) | 1.84 (3) | 2.758 (5) | 174 (5) |
Symmetry codes: (i) x, y+1, z; (ii) x+1, y, z; (iii) x−1, y, z; (iv) x, y−1, z. |
(VI) L-Phenylalanine–D-alloisoleucine (1/1)
top
Crystal data top
C9H11NO2·C6H13NO2 | F(000) = 320 |
Mr = 296.36 | Dx = 1.274 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 5224 reflections |
a = 5.2436 (5) Å | θ = 2.8–26.7° |
b = 28.949 (3) Å | µ = 0.09 mm−1 |
c = 5.4069 (5) Å | T = 296 K |
β = 109.747 (1)° | Plate, colourless |
V = 772.49 (13) Å3 | 0.58 × 0.16 × 0.1 mm |
Z = 2 | |
Data collection top
Bruker APEXII CCD diffractometer | 1668 independent reflections |
Radiation source: fine-focus sealed tube | 1605 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
Detector resolution: 8.3 pixels mm-1 | θmax = 26.7°, θmin = 2.8° |
Sets of exposures each taken over 0.5° ω rotation scans | h = −6→6 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008b) | k = −36→36 |
Tmin = 0.903, Tmax = 0.991 | l = −6→6 |
8740 measured reflections | |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0479P)2 + 0.1517P] where P = (Fo2 + 2Fc2)/3 |
1668 reflections | (Δ/σ)max < 0.001 |
210 parameters | Δρmax = 0.16 e Å−3 |
7 restraints | Δρmin = −0.16 e Å−3 |
Crystal data top
C9H11NO2·C6H13NO2 | V = 772.49 (13) Å3 |
Mr = 296.36 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 5.2436 (5) Å | µ = 0.09 mm−1 |
b = 28.949 (3) Å | T = 296 K |
c = 5.4069 (5) Å | 0.58 × 0.16 × 0.1 mm |
β = 109.747 (1)° | |
Data collection top
Bruker APEXII CCD diffractometer | 1668 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2008b) | 1605 reflections with I > 2σ(I) |
Tmin = 0.903, Tmax = 0.991 | Rint = 0.017 |
8740 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.034 | 7 restraints |
wR(F2) = 0.088 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.16 e Å−3 |
1668 reflections | Δρmin = −0.16 e Å−3 |
210 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. Data were collected by measuring four sets of exposures with the detector set at
2θ = 29°, crystal-to-detector distance 6.00 cm. Refinement of F2
against ALL reflections. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1A | 0.9385 (3) | 0.65069 (7) | 0.8930 (3) | 0.0390 (4) | |
O2A | 0.4907 (3) | 0.64146 (6) | 0.7469 (3) | 0.0346 (4) | |
N1A | 0.9341 (4) | 0.66153 (7) | 0.3916 (3) | 0.0279 (4) | |
H1A | 0.905 (6) | 0.6919 (9) | 0.421 (5) | 0.042* | |
H2A | 0.934 (6) | 0.6593 (11) | 0.225 (5) | 0.042* | |
H3A | 1.107 (5) | 0.6560 (11) | 0.496 (5) | 0.042* | |
C1A | 0.7295 (4) | 0.63103 (7) | 0.4456 (4) | 0.0271 (4) | |
H11A | 0.5513 | 0.6364 | 0.3125 | 0.033* | |
C2A | 0.8191 (5) | 0.58148 (8) | 0.4237 (5) | 0.0405 (6) | |
H21A | 0.8277 | 0.5771 | 0.2489 | 0.049* | |
H22A | 1.0011 | 0.5775 | 0.5477 | 0.049* | |
C3A | 0.6425 (6) | 0.54422 (8) | 0.4730 (5) | 0.0412 (6) | |
C4A | 0.4052 (8) | 0.53073 (14) | 0.2926 (9) | 0.0765 (11) | |
H41A | 0.3421 | 0.5455 | 0.1304 | 0.092* | |
C5A | 0.2547 (8) | 0.49501 (16) | 0.3472 (11) | 0.0918 (14) | |
H51A | 0.0895 | 0.4870 | 0.2224 | 0.110* | |
C6A | 0.3409 (9) | 0.47226 (13) | 0.5724 (10) | 0.0787 (12) | |
H61A | 0.2446 | 0.4471 | 0.6017 | 0.094* | |
C7A | 0.5692 (12) | 0.48621 (18) | 0.7568 (10) | 0.1055 (18) | |
H71A | 0.6269 | 0.4718 | 0.9201 | 0.127* | |
C8A | 0.7201 (11) | 0.52176 (16) | 0.7079 (8) | 0.0890 (14) | |
H81A | 0.8793 | 0.5306 | 0.8388 | 0.107* | |
C9A | 0.7166 (4) | 0.64203 (7) | 0.7192 (4) | 0.0259 (4) | |
O1B | 0.3408 (3) | 0.73557 (6) | 0.4192 (3) | 0.0342 (4) | |
O2B | 0.7839 (3) | 0.74939 (6) | 0.5546 (3) | 0.0334 (4) | |
N1B | 0.3259 (4) | 0.73038 (7) | 0.9067 (3) | 0.0269 (4) | |
H1B | 0.328 (6) | 0.7331 (11) | 1.075 (5) | 0.040* | |
H2B | 0.342 (6) | 0.7006 (8) | 0.879 (6) | 0.040* | |
H3B | 0.170 (5) | 0.7409 (10) | 0.798 (5) | 0.040* | |
C1B | 0.5597 (4) | 0.75489 (7) | 0.8694 (4) | 0.0251 (4) | |
H11B | 0.7262 | 0.7418 | 0.9936 | 0.030* | |
C2B | 0.5533 (5) | 0.80673 (8) | 0.9319 (4) | 0.0344 (5) | |
H21B | 0.4817 | 0.8096 | 1.0768 | 0.041* | |
C3B | 0.3685 (7) | 0.83414 (9) | 0.7024 (6) | 0.0505 (7) | |
H31B | 0.1936 | 0.8189 | 0.6378 | 0.061* | |
H32B | 0.4442 | 0.8340 | 0.5617 | 0.061* | |
C4B | 0.3273 (10) | 0.88379 (12) | 0.7704 (11) | 0.0881 (13) | |
H41B | 0.1837 | 0.8974 | 0.6284 | 0.132* | |
H42B | 0.4915 | 0.9009 | 0.7983 | 0.132* | |
H43B | 0.2807 | 0.8845 | 0.9274 | 0.132* | |
C5B | 0.8413 (7) | 0.82552 (13) | 1.0286 (8) | 0.0667 (9) | |
H51B | 0.9535 | 0.8060 | 1.1661 | 0.100* | |
H52B | 0.8411 | 0.8563 | 1.0949 | 0.100* | |
H53B | 0.9110 | 0.8261 | 0.8857 | 0.100* | |
C6B | 0.5614 (4) | 0.74567 (7) | 0.5903 (4) | 0.0242 (4) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1A | 0.0334 (8) | 0.0643 (12) | 0.0210 (7) | −0.0068 (8) | 0.0113 (6) | −0.0047 (7) |
O2A | 0.0312 (7) | 0.0442 (9) | 0.0348 (8) | 0.0015 (7) | 0.0193 (7) | −0.0005 (7) |
N1A | 0.0301 (9) | 0.0371 (10) | 0.0185 (8) | −0.0041 (8) | 0.0107 (7) | −0.0032 (7) |
C1A | 0.0257 (9) | 0.0344 (10) | 0.0229 (9) | −0.0025 (8) | 0.0104 (8) | −0.0026 (8) |
C2A | 0.0512 (14) | 0.0360 (12) | 0.0450 (13) | −0.0035 (11) | 0.0303 (11) | −0.0083 (11) |
C3A | 0.0505 (14) | 0.0308 (11) | 0.0517 (15) | −0.0017 (10) | 0.0296 (12) | −0.0082 (10) |
C4A | 0.063 (2) | 0.063 (2) | 0.089 (3) | −0.0087 (17) | 0.0055 (19) | 0.0200 (19) |
C5A | 0.053 (2) | 0.075 (3) | 0.130 (4) | −0.0192 (19) | 0.009 (2) | 0.011 (3) |
C6A | 0.081 (3) | 0.0498 (18) | 0.121 (4) | −0.0141 (18) | 0.055 (3) | 0.007 (2) |
C7A | 0.135 (4) | 0.090 (3) | 0.088 (3) | −0.047 (3) | 0.033 (3) | 0.022 (3) |
C8A | 0.114 (3) | 0.084 (3) | 0.058 (2) | −0.047 (3) | 0.015 (2) | 0.0106 (19) |
C9A | 0.0312 (10) | 0.0273 (10) | 0.0228 (10) | 0.0010 (8) | 0.0139 (8) | 0.0012 (8) |
O1B | 0.0330 (8) | 0.0512 (10) | 0.0200 (7) | −0.0069 (7) | 0.0113 (6) | −0.0050 (7) |
O2B | 0.0292 (7) | 0.0462 (9) | 0.0295 (7) | 0.0022 (7) | 0.0159 (6) | −0.0004 (7) |
N1B | 0.0304 (9) | 0.0336 (9) | 0.0191 (8) | −0.0025 (8) | 0.0115 (7) | −0.0013 (7) |
C1B | 0.0222 (9) | 0.0346 (10) | 0.0191 (8) | 0.0004 (8) | 0.0078 (7) | −0.0009 (8) |
C2B | 0.0392 (12) | 0.0376 (12) | 0.0309 (11) | −0.0080 (10) | 0.0178 (9) | −0.0108 (9) |
C3B | 0.0592 (17) | 0.0371 (13) | 0.0561 (16) | 0.0057 (12) | 0.0206 (13) | 0.0029 (12) |
C4B | 0.104 (3) | 0.0377 (17) | 0.135 (4) | 0.0096 (18) | 0.057 (3) | 0.002 (2) |
C5B | 0.0501 (16) | 0.0620 (19) | 0.083 (2) | −0.0231 (14) | 0.0165 (16) | −0.0276 (17) |
C6B | 0.0273 (9) | 0.0271 (10) | 0.0203 (9) | 0.0034 (8) | 0.0108 (7) | 0.0019 (7) |
Geometric parameters (Å, º) top
O1A—C9A | 1.249 (3) | C8A—H81A | 0.9300 |
O2A—C9A | 1.243 (2) | O1B—C6B | 1.248 (2) |
N1A—C1A | 1.493 (3) | O2B—C6B | 1.250 (2) |
N1A—H1A | 0.91 (2) | N1B—C1B | 1.488 (3) |
N1A—H2A | 0.90 (2) | N1B—H1B | 0.91 (2) |
N1A—H3A | 0.90 (2) | N1B—H2B | 0.88 (2) |
C1A—C2A | 1.526 (3) | N1B—H3B | 0.88 (2) |
C1A—C9A | 1.537 (3) | C1B—C6B | 1.536 (3) |
C1A—H11A | 0.9800 | C1B—C2B | 1.541 (3) |
C2A—C3A | 1.503 (3) | C1B—H11B | 0.9800 |
C2A—H21A | 0.9700 | C2B—C3B | 1.515 (4) |
C2A—H22A | 0.9700 | C2B—C5B | 1.522 (4) |
C3A—C4A | 1.353 (5) | C2B—H21B | 0.9800 |
C3A—C8A | 1.361 (5) | C3B—C4B | 1.517 (5) |
C4A—C5A | 1.392 (6) | C3B—H31B | 0.9700 |
C4A—H41A | 0.9300 | C3B—H32B | 0.9700 |
C5A—C6A | 1.322 (7) | C4B—H41B | 0.9600 |
C5A—H51A | 0.9300 | C4B—H42B | 0.9600 |
C6A—C7A | 1.336 (7) | C4B—H43B | 0.9600 |
C6A—H61A | 0.9300 | C5B—H51B | 0.9600 |
C7A—C8A | 1.377 (6) | C5B—H52B | 0.9600 |
C7A—H71A | 0.9300 | C5B—H53B | 0.9600 |
| | | |
C1A—N1A—H1A | 111.3 (19) | C1B—N1B—H1B | 111.3 (18) |
C1A—N1A—H2A | 113.2 (19) | C1B—N1B—H2B | 108 (2) |
H1A—N1A—H2A | 107 (3) | H1B—N1B—H2B | 107 (3) |
C1A—N1A—H3A | 113.9 (19) | C1B—N1B—H3B | 111.5 (19) |
H1A—N1A—H3A | 105 (3) | H1B—N1B—H3B | 109 (3) |
H2A—N1A—H3A | 106 (3) | H2B—N1B—H3B | 110 (3) |
N1A—C1A—C2A | 106.29 (18) | N1B—C1B—C6B | 109.21 (16) |
N1A—C1A—C9A | 109.50 (17) | N1B—C1B—C2B | 110.78 (17) |
C2A—C1A—C9A | 112.59 (18) | C6B—C1B—C2B | 113.10 (17) |
N1A—C1A—H11A | 109.5 | N1B—C1B—H11B | 107.9 |
C2A—C1A—H11A | 109.5 | C6B—C1B—H11B | 107.9 |
C9A—C1A—H11A | 109.5 | C2B—C1B—H11B | 107.9 |
C3A—C2A—C1A | 115.90 (19) | C3B—C2B—C5B | 112.3 (3) |
C3A—C2A—H21A | 108.3 | C3B—C2B—C1B | 112.68 (19) |
C1A—C2A—H21A | 108.3 | C5B—C2B—C1B | 109.3 (2) |
C3A—C2A—H22A | 108.3 | C3B—C2B—H21B | 107.4 |
C1A—C2A—H22A | 108.3 | C5B—C2B—H21B | 107.4 |
H21A—C2A—H22A | 107.4 | C1B—C2B—H21B | 107.4 |
C4A—C3A—C8A | 116.5 (3) | C2B—C3B—C4B | 113.7 (3) |
C4A—C3A—C2A | 123.4 (3) | C2B—C3B—H31B | 108.8 |
C8A—C3A—C2A | 120.0 (3) | C4B—C3B—H31B | 108.8 |
C3A—C4A—C5A | 120.7 (4) | C2B—C3B—H32B | 108.8 |
C3A—C4A—H41A | 119.6 | C4B—C3B—H32B | 108.8 |
C5A—C4A—H41A | 119.6 | H31B—C3B—H32B | 107.7 |
C6A—C5A—C4A | 121.6 (4) | C3B—C4B—H41B | 109.5 |
C6A—C5A—H51A | 119.2 | C3B—C4B—H42B | 109.5 |
C4A—C5A—H51A | 119.2 | H41B—C4B—H42B | 109.5 |
C5A—C6A—C7A | 118.6 (4) | C3B—C4B—H43B | 109.5 |
C5A—C6A—H61A | 120.7 | H41B—C4B—H43B | 109.5 |
C7A—C6A—H61A | 120.7 | H42B—C4B—H43B | 109.5 |
C6A—C7A—C8A | 120.7 (4) | C2B—C5B—H51B | 109.5 |
C6A—C7A—H71A | 119.6 | C2B—C5B—H52B | 109.5 |
C8A—C7A—H71A | 119.6 | H51B—C5B—H52B | 109.5 |
C3A—C8A—C7A | 121.8 (4) | C2B—C5B—H53B | 109.5 |
C3A—C8A—H81A | 119.1 | H51B—C5B—H53B | 109.5 |
C7A—C8A—H81A | 119.1 | H52B—C5B—H53B | 109.5 |
O2A—C9A—O1A | 126.50 (19) | O1B—C6B—O2B | 125.84 (17) |
O2A—C9A—C1A | 117.82 (18) | O1B—C6B—C1B | 117.25 (17) |
O1A—C9A—C1A | 115.67 (17) | O2B—C6B—C1B | 116.91 (17) |
| | | |
N1A—C1A—C2A—C3A | 179.6 (2) | C2A—C1A—C9A—O2A | −100.4 (2) |
C9A—C1A—C2A—C3A | 59.7 (3) | N1A—C1A—C9A—O1A | −38.6 (3) |
C1A—C2A—C3A—C4A | 78.8 (4) | C2A—C1A—C9A—O1A | 79.4 (2) |
C1A—C2A—C3A—C8A | −101.9 (4) | N1B—C1B—C2B—C3B | −83.0 (2) |
C8A—C3A—C4A—C5A | −1.2 (6) | C6B—C1B—C2B—C3B | 39.9 (3) |
C2A—C3A—C4A—C5A | 178.0 (4) | N1B—C1B—C2B—C5B | 151.3 (2) |
C3A—C4A—C5A—C6A | −2.0 (8) | C6B—C1B—C2B—C5B | −85.7 (3) |
C4A—C5A—C6A—C7A | 4.5 (8) | C5B—C2B—C3B—C4B | −64.2 (4) |
C5A—C6A—C7A—C8A | −3.8 (9) | C1B—C2B—C3B—C4B | 171.8 (3) |
C4A—C3A—C8A—C7A | 1.9 (7) | N1B—C1B—C6B—O1B | 24.8 (3) |
C2A—C3A—C8A—C7A | −177.4 (5) | C2B—C1B—C6B—O1B | −99.0 (2) |
C6A—C7A—C8A—C3A | 0.6 (9) | N1B—C1B—C6B—O2B | −155.76 (18) |
N1A—C1A—C9A—O2A | 141.5 (2) | C2B—C1B—C6B—O2B | 80.4 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O2B | 0.91 (2) | 2.00 (2) | 2.887 (3) | 162 (3) |
N1A—H2A···O1Ai | 0.90 (2) | 1.82 (2) | 2.722 (2) | 176 (3) |
N1A—H3A···O2Aii | 0.90 (2) | 2.06 (2) | 2.959 (3) | 177 (3) |
N1B—H1B···O1Biii | 0.91 (2) | 1.84 (2) | 2.750 (2) | 177 (3) |
N1B—H2B···O2A | 0.88 (2) | 2.10 (2) | 2.937 (3) | 157 (3) |
N1B—H3B···O2Biv | 0.88 (2) | 2.02 (2) | 2.890 (2) | 166 (3) |
Symmetry codes: (i) x, y, z−1; (ii) x+1, y, z; (iii) x, y, z+1; (iv) x−1, y, z. |
Experimental details
| (I) | (II) | (III) | (IV) |
Crystal data |
Chemical formula | C9H11NO2·C4H9NO2 | C9H11NO2·C5H11NO2 | C9H11NO2·C5H11NO2S | C9H11NO2·C6H13NO2 |
Mr | 268.31 | 282.34 | 314.40 | 296.36 |
Crystal system, space group | Orthorhombic, P212121 | Orthorhombic, P212121 | Monoclinic, P21 | Monoclinic, P21 |
Temperature (K) | 296 | 296 | 296 | 296 |
a, b, c (Å) | 4.7869 (7), 9.9558 (15), 28.423 (4) | 4.7624 (8), 9.9569 (17), 30.935 (6) | 10.110 (2), 4.7064 (9), 16.686 (3) | 5.1861 (5), 29.698 (3), 5.4158 (5) |
α, β, γ (°) | 90, 90, 90 | 90, 90, 90 | 90, 106.663 (2), 90 | 90, 110.372 (1), 90 |
V (Å3) | 1354.6 (3) | 1466.9 (5) | 760.6 (3) | 781.95 (13) |
Z | 4 | 4 | 2 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 0.09 | 0.23 | 0.09 |
Crystal size (mm) | 0.80 × 0.12 × 0.04 | 0.48 × 0.14 × 0.05 | 1.24 × 0.1 × 0.02 | 0.3 × 0.2 × 0.06 |
|
Data collection |
Diffractometer | Bruker APEXII CCD diffractometer | Bruker APEXII CCD diffractometer | Bruker APEXII CCD diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2008b) | Multi-scan (SADABS; Sheldrick, 2008b) | Multi-scan (SADABS; Sheldrick, 2008b) | Multi-scan (SADABS; Sheldrick, 2008b) |
Tmin, Tmax | 0.770, 0.996 | 0.862, 0.995 | 0.800, 0.995 | 0.909, 0.995 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10082, 1443, 1284 | 14224, 1564, 1395 | 5312, 2580, 2406 | 7778, 1411, 1269 |
Rint | 0.037 | 0.037 | 0.022 | 0.024 |
(sin θ/λ)max (Å−1) | 0.595 | 0.595 | 0.595 | 0.595 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.042, 0.120, 1.07 | 0.040, 0.093, 1.07 | 0.037, 0.099, 1.18 | 0.036, 0.089, 1.10 |
No. of reflections | 1443 | 1564 | 2580 | 1411 |
No. of parameters | 191 | 200 | 208 | 208 |
No. of restraints | 6 | 6 | 7 | 12 |
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 atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.18 | 0.20, −0.15 | 0.24, −0.22 | 0.14, −0.16 |
Absolute structure | ? | ? | Flack (1983), 1082 Friedel pairs | ? |
Absolute structure parameter | ? | ? | 0.00 (10) | ? |
| (V) | (VI) |
Crystal data |
Chemical formula | C9H11NO2·C6H13NO2 | C9H11NO2·C6H13NO2 |
Mr | 296.36 | 296.36 |
Crystal system, space group | Triclinic, P1 | Monoclinic, P21 |
Temperature (K) | 296 | 296 |
a, b, c (Å) | 5.2317 (12), 5.4232 (12), 14.459 (3) | 5.2436 (5), 28.949 (3), 5.4069 (5) |
α, β, γ (°) | 85.936 (3), 85.343 (3), 70.424 (2) | 90, 109.747 (1), 90 |
V (Å3) | 384.83 (15) | 772.49 (13) |
Z | 1 | 2 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.09 |
Crystal size (mm) | 0.32 × 0.18 × 0.03 | 0.58 × 0.16 × 0.1 |
|
Data collection |
Diffractometer | Bruker APEXII CCD diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2008b) | Multi-scan (SADABS; Sheldrick, 2008b) |
Tmin, Tmax | 0.762, 0.997 | 0.903, 0.991 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2821, 1359, 1054 | 8740, 1668, 1605 |
Rint | 0.028 | 0.017 |
(sin θ/λ)max (Å−1) | 0.595 | 0.633 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.099, 1.06 | 0.034, 0.088, 1.07 |
No. of reflections | 1359 | 1668 |
No. of parameters | 210 | 210 |
No. of restraints | 9 | 7 |
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 |
Δρmax, Δρmin (e Å−3) | 0.17, −0.16 | 0.16, −0.16 |
Absolute structure | ? | ? |
Absolute structure parameter | ? | ? |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O2B | 0.92 (2) | 1.98 (3) | 2.850 (3) | 157 (3) |
N1A—H2A···O2Bi | 0.95 (3) | 1.95 (3) | 2.879 (3) | 167 (3) |
N1A—H3A···O1Aii | 0.92 (2) | 1.87 (2) | 2.788 (3) | 172 (3) |
N1B—H1B···O2Aiii | 0.94 (2) | 1.92 (3) | 2.817 (3) | 159 (3) |
N1B—H2B···O1Biv | 0.94 (2) | 1.83 (2) | 2.756 (3) | 166 (3) |
N1B—H3B···O2Av | 0.92 (3) | 1.93 (3) | 2.835 (3) | 168 (3) |
Symmetry codes: (i) x−1, y, z; (ii) x+1/2, −y+1/2, −z; (iii) x, y+1, z; (iv) x−1/2, −y+3/2, −z; (v) x+1, y+1, z. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O2B | 0.92 (2) | 1.95 (3) | 2.830 (3) | 162 (3) |
N1A—H3A···O2Bi | 0.90 (2) | 1.97 (3) | 2.871 (3) | 173 (3) |
N1A—H2A···O1Aii | 0.93 (2) | 1.85 (2) | 2.780 (3) | 173 (3) |
N1B—H1B···O2Aiii | 0.91 (2) | 1.94 (3) | 2.809 (3) | 159 (3) |
N1B—H3B···O1Biv | 0.95 (2) | 1.80 (2) | 2.743 (3) | 171 (3) |
N1B—H2B···O2Av | 0.91 (2) | 1.94 (3) | 2.835 (3) | 168 (3) |
Symmetry codes: (i) x−1, y, z; (ii) x+1/2, −y+1/2, −z; (iii) x, y+1, z; (iv) x−1/2, −y+3/2, −z; (v) x+1, y+1, z. |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O2Bi | 0.93 (2) | 1.96 (3) | 2.863 (3) | 162 (3) |
N1A—H2A···O2B | 0.92 (2) | 2.00 (2) | 2.887 (3) | 163 (3) |
N1A—H3A···O1Aii | 0.91 (2) | 1.86 (2) | 2.762 (3) | 172 (3) |
N1B—H1B···O1Biii | 0.90 (2) | 1.85 (2) | 2.752 (3) | 176 (3) |
N1B—H2B···O2Aiv | 0.88 (2) | 1.98 (2) | 2.838 (3) | 168 (3) |
N1B—H3B···O2Av | 0.89 (2) | 1.95 (2) | 2.817 (3) | 163 (3) |
Symmetry codes: (i) x, y−1, z; (ii) −x+2, y−1/2, −z+2; (iii) −x+1, y+1/2, −z+2; (iv) x−1, y, z; (v) x−1, y+1, z. |
Hydrogen-bond geometry (Å, º) for (IV) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O2B | 0.93 (3) | 1.98 (3) | 2.875 (4) | 161 (3) |
N1A—H2A···O1Ai | 0.91 (2) | 1.82 (3) | 2.735 (3) | 176 (3) |
N1A—H3A···O2Aii | 0.90 (2) | 2.03 (3) | 2.921 (3) | 174 (3) |
N1B—H1B···O2A | 0.90 (3) | 2.02 (3) | 2.896 (4) | 163 (3) |
N1B—H2B···O2Biii | 0.91 (2) | 1.98 (3) | 2.887 (3) | 174 (3) |
N1B—H3B···O1Biv | 0.94 (2) | 1.79 (2) | 2.729 (3) | 178 (3) |
Symmetry codes: (i) x, y, z+1; (ii) x−1, y, z; (iii) x+1, y, z; (iv) x, y, z−1. |
Hydrogen-bond geometry (Å, º) for (V) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O2B | 0.91 (3) | 2.01 (3) | 2.896 (5) | 163 (4) |
N1A—H2A···O1Ai | 0.91 (3) | 1.83 (3) | 2.740 (5) | 177 (5) |
N1A—H3A···O2Aii | 0.94 (3) | 2.01 (3) | 2.949 (5) | 177 (4) |
N1B—H1B···O2A | 0.94 (3) | 2.04 (3) | 2.933 (5) | 157 (4) |
N1B—H2B···O2Biii | 0.93 (3) | 1.98 (3) | 2.895 (5) | 169 (4) |
N1B—H3B···O1Biv | 0.92 (3) | 1.84 (3) | 2.758 (5) | 174 (5) |
Symmetry codes: (i) x, y+1, z; (ii) x+1, y, z; (iii) x−1, y, z; (iv) x, y−1, z. |
Hydrogen-bond geometry (Å, º) for (VI) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O2B | 0.91 (2) | 2.00 (2) | 2.887 (3) | 162 (3) |
N1A—H2A···O1Ai | 0.90 (2) | 1.82 (2) | 2.722 (2) | 176 (3) |
N1A—H3A···O2Aii | 0.90 (2) | 2.06 (2) | 2.959 (3) | 177 (3) |
N1B—H1B···O1Biii | 0.91 (2) | 1.84 (2) | 2.750 (2) | 177 (3) |
N1B—H2B···O2A | 0.88 (2) | 2.10 (2) | 2.937 (3) | 157 (3) |
N1B—H3B···O2Biv | 0.88 (2) | 2.02 (2) | 2.890 (2) | 166 (3) |
Symmetry codes: (i) x, y, z−1; (ii) x+1, y, z; (iii) x, y, z+1; (iv) x−1, y, z. |
Observed N—Cα—Cβ—Cγ rotamers (χ1) in amino acid
complexes (after inversion to the L enantiomer if the D enantiomer was
crystallized in the complex) topAmino acid | Class I (LD–LD) | Class II (L1–D1) |
L-Abu / L-Nva / L-Phe | gauche- | trans |
L-Met | gauche-, trans | trans |
L-Val / L-Ile / L-aIle | trans/gauche-a | gauche+/transa |
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In three papers, we have presented the structures of various complexes between hydrophobic L- and D-amino acids (Dalhus & Görbitz, 1999a,b,c). All of these crystals are divided into hydrophilic and hydrophobic layers, with the former incorporating the same hydrogen-bonding patterns as found in the crystal structures of regular amino acid racemates. The mixed L:D complexes are thus often referred to as pseudo-racemates, the difference from normal racemates being confined to the hydrophobic regions of the crystal structures. A closer look at the hydrophilic layers shows that they are generated from two distinct sheets, shown schematically in Fig. 1. Hydrogen bonding within a sheet engages two of the amino H atoms, while the third serves as a sheet connector. Only two types of sheets have been found for (pseudo)racemates. The first is called LD and incorporates a mixture of L- and D-enantiomers, while the second arrangement involves amino acids of one hand only and is called L1 when constructed from L-amino acids and D1 when constructed from D-amino acids (Fig. 2). The sheets give rise to two types of layers: LD–LD, characterized by the presence of (pseudo)glide planes, and L1–D1 in which adjacent sheets are related by (pseudo)inversion. Theoretical ab initio calculations have indicated that the LD–LD layer, occurring in what has been referred to as class I crystal structures, is inherently preferred over L1–D1 (class II) as far as the hydrogen-bonding energy is concerned (Dalhus & Görbitz, 2004; Görbitz et al., 2009). Steric conflict may nevertheless lead to L1–D1 structures, and Dalhus (2000) gave the following empirical rules for the effect of the side chain: (i) Complexes with two linear amino acids crystallize in class I. (ii) Complexes with two branched amino acids crystallize in class II. (iii) Complexes with one linear and one branched amino acid crystallize in both class I and class II; branching at Cβ(Ile/Val) gives class I structures, while branching at Cγ(Leu) gives class II structures.
Our previous investigations included Ala, 2-aminobutyric acid (Abu), norvaline (Nva), norleucine (Nle) and Met with linear side chains, as well as Val, Ile, allo-isoleucine (aIle) and Leu with branched side chains, but not Phe. The only known structure of a 1:1 amino acid complex with this aromatic amino acid is L-Phe:D-Val (Prasad & Vijayan, 1991), which, in accordance with the observations of Dalhus (2000), forms a class II structure. Apart from this, the structure-directing properties of Phe in such complexes are unknown. In the structures of various peptides Phe can often be replaced by Leu, both with branching at Cγ, without major structure modifications, while isostructural peptides with Phe substituted for Ile or Val are less common. We thus anticipated that amino acid complexes with Phe would mimic the equivalent complexes with Leu. In order to verify this hypothesis, attempts were made to crystallize L-Phe with the D-enantiomer of all other hydrophobic amino acids listed above (except D-Val, but including D-Phe). Three complexes, L-Phe:D-Ala, L-Phe:D-Nle and DL-Phe, failed to give diffraction quality crystals, meaning that the present investigation deals with L-Phe in complex with the three linear amino acids D-Abu, D-Nva and D-Met as well as the three branched amino acids D-Leu, D-Ile and D-aIle (see scheme).
The asymmetric units of complexes between L-Phe and D-amino acids with linear and branched side chains are shown in Figs. 3 and 4, respectively. All structures are well ordered, but extensive thermal vibrations for certain side chains are evident, causing a significant artificial shortening of some covalent bond lengths such as C6A—C7A = 1.318 (6) Å for L-Phe:D-Leu. Packing diagrams are shown in Figs. 5 and 6. The hydrogen bonds observed in the six structures (Tables 1–6) follow closely the observed patterns for other LD—LD (class I) and L1—D1 (class II) structures. There is always a `knots-in-holes' fit at the hydrophobic interface (Fig. 1), but this is much more pronounced for class I structures than for class II structures owing to the involvement of two different amino acids in the formation of each hydrogen-bonded sheet, as illustrated for L-Phe:D-Abu in Fig. 5 and L-Phe:D-Leu in Fig. 6.
Dalhus (2000) previously noted that complexes between aIle and other amino acids, if formed at all, invariably yielded crystals of poor quality, in marked contrast to the corresponding complexes with Ile and Leu. A comparison of the unit-cell dimensions of complexes with Nva, Nle and Met (Dalhus & Görbitz, 1999a,b,c; Dalhus, 2000) shows that incorporation of aIle leads to a 6–18 Å3 increase in the volumes of the asymmetric unit compared with Ile or Leu, clearly indicating a less efficient packing of the hydrophobic side chains. In the present study, aIle shows no such deviating crystallization habit, and the asymmetric unit volume of L-Phe:D-aIle (386.2 Å3) is midway between the values of 384.8 Å3 for L-Phe:D-Ile and 391.0 Å3 for L-Phe:D-Leu. The 6.2 Å3 range is dwarfed by the 22.7 Å3 difference between L-Leu:D-Abu (310.5 Å3) and DL-Val (287.8 Å3 for the LD pair; Flaig et al., 2002), the more compact hydrophobic layer for the latter being easily recognized in Fig. 6 (note that the total number of side-chain C atoms remains unchanged).
Class I structures usually distribute evenly between the monoclinic space groups C2 and P21, as exemplified in Fig. 5 by L-Ile:D-Nva (Dalhus & Görbitz, 1999a) and D-Nle:L-Met (Dalhus & Görbitz, 1999b), respectively. L-Phe:D-Met is isostructural to D-Nle:L-Met (disregarding the shifts in chirality) and about five other complexes. The orthorhombic P212121 structures of L-Phe:D-Abu and L-Phe:D-Nva, on the other hand, have been preceded only by the structure of L-Val:D-Met (Dalhus & Görbitz, 1999c) (Fig. 5). For the pseudosymmetric class II complexes there is also an even distribution between two space groups, in this case P1 and P21. The monoclinic system has been chosen for L-Phe:D-Leu and L-Phe:D-aIle, and the triclinic for L-Phe:D-Ile, which is strikingly similar to the structure of D-Leu:L-Ile (Dalhus & Görbitz, 1999a) (Fig. 6). This example serves to illustrate that as long as the partner molecule has a branched side chain, Phe behaves similarly to Leu, or indeed similarly to any other amino acid with a branched side chain, in producing class II structures. Included in this group are also true racemates such as DL-Val (Fig. 6; Flaig et al., 2002). The difference between Leu and Phe becomes apparent when a comparison in made between L-Phe:D-Abu (Fig. 5) and L-Leu:D-Abu (Fig. 6). Even when paired with Abu, with a relatively small ethyl side chain, Leu is unable to form a class I complex, while Phe forms class I complexes with any amino acid with a linear side chain. The origin of this important difference between Leu and Phe can be derived from an analysis of amino acid side-chain rotamers (Table 7). The table shows that Met is the only amino acid to display any conformational variation within class I. In fact, it occurs with three different side-chain conformations for χ1,χ2,χ3 (L enantiomer): gauche-,trans,trans, gauche-,trans,gauche+ and finally trans,trans,gauche-, which is also observed in the class II complex with Leu (Dalhus & Görbitz, 1999c). More important is that Table 7 reveals systematic conformational shifts upon change of class, which is evidently a requirement for proper stacking of side chains in the hydrophobic layers. It is then essential that Leu, as the only amino acid, is unable to undergo such a shift as it is restricted to the trans, gauche+/trans conformation for χ1,χ2,1/χ2,2 (L enantiomer; Görbitz, 2006).
In summary, in complexes with other hydrophobic amino acids, L-Phe displays the same structure-directing properties as the Cβ-branched amino acids Val, Ile and aIle. This means that complexes with linear amino acids form class I (LD–LD) structures, while complexes with branched side chains from class II (L1–D1) structures. The ability of Phe to form the tightly packed LD sheets required for formation of an LD–LD class I layer stems from the availability of more than one possible conformation upon rotation around the Cα—Cβ bond. In contrast, Leu, which like Phe is branched at Cγ, has only a single viable side-chain conformation and is consequently limited to class II structures with L1–D1 hydrogen-bonded layers.