Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104022851/ga1081sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104022851/ga1081FIsup2.hkl |
CCDC reference: 257019
The title compound was obtained from Bachem. Crystals were grown by fast evaporation of an aqueous solution at elevated temperature (333 K), the same technique used for crystallizing compounds in the FF-class (Görbitz, 2001, 2004b).
Heavy atoms other than the low-occupancy water atoms O3W and O4W were refined anisotropically. Positional parameters were refined for H atoms involved in short hydrogen bonds (H···O < 2.50 Å), with water-molecule geometries being constrained by DFIX 0.85 0.01 commands for the O—H distances and DFIX 1.35 0.01 commands for the H···H distances (giving H—O—H angles close to 105°). H atoms bonded to O3W and O4W were introduced in positions giving the best possible hydrogen-bonding geometry (with O—H = 0.85 Å) and refined as riding. The remaining H atoms were positioned geometrically and refined with constraints to keep all C—H distances and C—C—H angles on one C atom the same. Uiso(H) values were 1.2Ueq of the carrier atom, or 1.5Ueq for amino and methyl groups and water molecules. In the absence of significant anomalous scattering effects, 1585 Friedel pairs were merged. The absolute configuration was known for the purchased material.
Data collection: SMART (Bruker, 1998); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C15H22N2O3·0.88H2O | F(000) = 635 |
Mr = 294.24 | Dx = 1.243 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.5634 (3) Å | Cell parameters from 6894 reflections |
b = 17.0558 (9) Å | θ = 1.7–27.1° |
c = 16.6859 (9) Å | µ = 0.09 mm−1 |
β = 96.744 (1)° | T = 105 K |
V = 1572.34 (15) Å3 | Needle, colourless |
Z = 4 | 0.75 × 0.15 × 0.12 mm |
Siemens SMART CCD area-detector diffractometer | 3570 independent reflections |
Radiation source: fine-focus sealed tube | 3378 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.025 |
Detector resolution: 8.3 pixels mm-1 | θmax = 27.1°, θmin = 1.7° |
Sets of exposures each taken over 0.3° ω rotation scans | h = −7→7 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −13→21 |
Tmin = 0.899, Tmax = 0.989 | l = −21→20 |
10060 measured reflections |
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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0431P)2 + 0.3167P] where P = (Fo2 + 2Fc2)/3 |
3570 reflections | (Δ/σ)max < 0.001 |
434 parameters | Δρmax = 0.27 e Å−3 |
8 restraints | Δρmin = −0.17 e Å−3 |
C15H22N2O3·0.88H2O | V = 1572.34 (15) Å3 |
Mr = 294.24 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 5.5634 (3) Å | µ = 0.09 mm−1 |
b = 17.0558 (9) Å | T = 105 K |
c = 16.6859 (9) Å | 0.75 × 0.15 × 0.12 mm |
β = 96.744 (1)° |
Siemens SMART CCD area-detector diffractometer | 3570 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3378 reflections with I > 2σ(I) |
Tmin = 0.899, Tmax = 0.989 | Rint = 0.025 |
10060 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 8 restraints |
wR(F2) = 0.077 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.00 | Δρmax = 0.27 e Å−3 |
3570 reflections | Δρmin = −0.17 e Å−3 |
434 parameters |
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 5.00 cm. Refinement of F2 against ALL reflections. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1A | 0.1472 (2) | 0.67637 (11) | 0.48728 (8) | 0.0344 (4) | |
O2A | 0.1077 (2) | 0.49230 (8) | 0.34428 (8) | 0.0237 (3) | |
O3A | −0.2329 (2) | 0.56164 (9) | 0.32458 (8) | 0.0263 (3) | |
N1A | 0.5293 (3) | 0.70646 (11) | 0.59045 (10) | 0.0229 (3) | |
H1A | 0.519 (5) | 0.7546 (18) | 0.5770 (16) | 0.034* | |
H2A | 0.385 (5) | 0.6950 (16) | 0.6051 (16) | 0.034* | |
H3A | 0.645 (5) | 0.7002 (16) | 0.6336 (16) | 0.034* | |
N2A | 0.3542 (3) | 0.63444 (9) | 0.38674 (9) | 0.0193 (3) | |
H4A | 0.495 (4) | 0.6188 (14) | 0.3709 (13) | 0.023* | |
C1A | 0.5770 (3) | 0.65925 (12) | 0.51901 (11) | 0.0225 (4) | |
H11A | 0.708 (4) | 0.6867 (15) | 0.4915 (14) | 0.027* | |
C2A | 0.6744 (4) | 0.57726 (13) | 0.54422 (12) | 0.0268 (4) | |
H21A | 0.6999 | 0.5473 | 0.4951 | 0.032* | |
H22A | 0.8336 | 0.5831 | 0.5770 | 0.032* | |
C3A | 0.5093 (4) | 0.53088 (12) | 0.59195 (12) | 0.0245 (4) | |
C4A | 0.3186 (4) | 0.48692 (15) | 0.55405 (14) | 0.0381 (5) | |
H41A | 0.2934 | 0.4846 | 0.4968 | 0.046* | |
C5A | 0.1642 (5) | 0.44627 (17) | 0.59918 (17) | 0.0482 (6) | |
H51A | 0.0358 | 0.4159 | 0.5725 | 0.058* | |
C6A | 0.1958 (5) | 0.44969 (15) | 0.68200 (16) | 0.0426 (6) | |
H61A | 0.0900 | 0.4217 | 0.7125 | 0.051* | |
C7A | 0.3818 (5) | 0.49398 (14) | 0.72061 (13) | 0.0399 (5) | |
H71A | 0.4022 | 0.4974 | 0.7778 | 0.048* | |
C8A | 0.5394 (4) | 0.53355 (13) | 0.67624 (12) | 0.0329 (5) | |
H81A | 0.6694 | 0.5628 | 0.7035 | 0.040* | |
C9A | 0.3382 (3) | 0.65728 (12) | 0.46259 (11) | 0.0213 (4) | |
C10A | 0.1391 (3) | 0.63225 (11) | 0.32760 (10) | 0.0189 (3) | |
H10A | 0.0327 | 0.6772 | 0.3388 | 0.023* | |
C11A | 0.2158 (3) | 0.64347 (11) | 0.24208 (10) | 0.0217 (4) | |
H12A | 0.3307 | 0.6001 | 0.2333 | 0.026* | |
C12A | −0.0005 (4) | 0.63564 (15) | 0.17682 (12) | 0.0325 (5) | |
H13A | 0.0538 | 0.6433 | 0.1236 | 0.049* | |
H14A | −0.1221 | 0.6753 | 0.1855 | 0.049* | |
H15A | −0.0714 | 0.5833 | 0.1796 | 0.049* | |
C13A | 0.3534 (4) | 0.72115 (12) | 0.23516 (12) | 0.0290 (4) | |
H16A | 0.5106 | 0.7176 | 0.2695 | 0.035* | |
H17A | 0.3881 | 0.7273 | 0.1787 | 0.035* | |
C14A | 0.2213 (5) | 0.79449 (14) | 0.25922 (16) | 0.0400 (5) | |
H18A | 0.3106 | 0.8413 | 0.2457 | 0.060* | |
H19A | 0.2106 | 0.7935 | 0.3174 | 0.060* | |
H20A | 0.0579 | 0.7957 | 0.2300 | 0.060* | |
C15A | −0.0061 (3) | 0.55595 (11) | 0.33324 (10) | 0.0191 (3) | |
O1B | 0.8668 (2) | 0.36151 (8) | 0.19460 (8) | 0.0229 (3) | |
O2B | 0.8959 (2) | 0.22315 (9) | 0.33220 (8) | 0.0267 (3) | |
O3B | 1.1946 (2) | 0.19973 (8) | 0.25828 (8) | 0.0233 (3) | |
N1B | 0.4997 (3) | 0.42731 (10) | 0.29077 (10) | 0.0215 (3) | |
H1B | 0.552 (5) | 0.3933 (17) | 0.3265 (16) | 0.032* | |
H2B | 0.617 (5) | 0.4630 (17) | 0.2965 (15) | 0.032* | |
H3B | 0.366 (5) | 0.4522 (16) | 0.3031 (15) | 0.032* | |
N2B | 0.6018 (3) | 0.25980 (9) | 0.19158 (9) | 0.0191 (3) | |
H4B | 0.464 (4) | 0.2467 (14) | 0.2049 (13) | 0.023* | |
C1B | 0.4502 (3) | 0.39037 (11) | 0.20891 (11) | 0.0191 (3) | |
H11B | 0.301 (4) | 0.3593 (14) | 0.2078 (13) | 0.023* | |
C2B | 0.4232 (4) | 0.45568 (11) | 0.14551 (11) | 0.0229 (4) | |
H21B | 0.2781 | 0.4873 | 0.1529 | 0.027* | |
H22B | 0.5658 | 0.4907 | 0.1542 | 0.027* | |
C3B | 0.4000 (3) | 0.42496 (11) | 0.05993 (11) | 0.0213 (4) | |
C4B | 0.2025 (3) | 0.37977 (11) | 0.02937 (11) | 0.0239 (4) | |
H41B | 0.0805 | 0.3676 | 0.0627 | 0.029* | |
C5B | 0.1816 (4) | 0.35209 (13) | −0.04984 (12) | 0.0277 (4) | |
H51B | 0.0459 | 0.3212 | −0.0702 | 0.033* | |
C6B | 0.3595 (4) | 0.36977 (12) | −0.09887 (12) | 0.0290 (4) | |
H61B | 0.3458 | 0.3508 | −0.1527 | 0.035* | |
C7B | 0.5565 (4) | 0.41501 (13) | −0.06920 (12) | 0.0294 (4) | |
H71B | 0.6773 | 0.4276 | −0.1029 | 0.035* | |
C8B | 0.5775 (4) | 0.44214 (12) | 0.00999 (12) | 0.0257 (4) | |
H81B | 0.7141 | 0.4727 | 0.0303 | 0.031* | |
C9B | 0.6624 (3) | 0.33557 (11) | 0.19751 (10) | 0.0177 (3) | |
C10B | 0.7828 (3) | 0.19743 (10) | 0.19162 (11) | 0.0187 (3) | |
H10B | 0.6965 | 0.1473 | 0.2005 | 0.022* | |
C11B | 0.8952 (3) | 0.18705 (11) | 0.11129 (11) | 0.0224 (4) | |
H12B | 1.0448 | 0.2200 | 0.1153 | 0.027* | |
C12B | 0.9752 (4) | 0.10118 (12) | 0.10482 (13) | 0.0298 (4) | |
H13B | 1.0444 | 0.0936 | 0.0540 | 0.045* | |
H14B | 0.8350 | 0.0666 | 0.1061 | 0.045* | |
H15B | 1.0973 | 0.0887 | 0.1503 | 0.045* | |
C13B | 0.7320 (4) | 0.21370 (13) | 0.03549 (11) | 0.0281 (4) | |
H16B | 0.6846 | 0.2689 | 0.0430 | 0.034* | |
H17B | 0.8271 | 0.2120 | −0.0110 | 0.034* | |
C14B | 0.5037 (4) | 0.16519 (16) | 0.01515 (15) | 0.0401 (5) | |
H18B | 0.4052 | 0.1883 | −0.0315 | 0.060* | |
H19B | 0.4108 | 0.1646 | 0.0615 | 0.060* | |
H20B | 0.5480 | 0.1114 | 0.0023 | 0.060* | |
C15B | 0.9752 (3) | 0.20827 (10) | 0.26656 (10) | 0.0184 (3) | |
O1W | 0.0678 (6) | 0.34683 (16) | 0.42164 (15) | 0.0502 (8) | 0.709 (4) |
H11W | 0.013 (9) | 0.3108 (18) | 0.389 (2) | 0.075* | 0.709 (4) |
H12W | 0.060 (10) | 0.3885 (15) | 0.394 (2) | 0.075* | 0.709 (4) |
O2W | 0.6045 (5) | 0.35782 (14) | 0.45431 (13) | 0.0390 (7) | 0.709 (4) |
H21W | 0.757 (2) | 0.364 (3) | 0.457 (2) | 0.058* | 0.709 (4) |
H22W | 0.561 (6) | 0.386 (2) | 0.492 (2) | 0.058* | 0.709 (4) |
O3W | −0.1496 (9) | 0.3674 (3) | 0.4048 (3) | 0.0292 (14)* | 0.291 (4) |
H31W | −0.1526 | 0.3246 | 0.3787 | 0.044* | 0.291 (4) |
H32W | −0.0559 | 0.3970 | 0.3818 | 0.044* | 0.291 (4) |
O4W | 0.563 (6) | 0.328 (2) | 0.516 (2) | 0.044* | 0.054 (4) |
H41W | 0.6547 | 0.3404 | 0.4806 | 0.044* | 0.054 (4) |
H42W | 0.4949 | 0.3703 | 0.5300 | 0.044* | 0.054 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1A | 0.0169 (6) | 0.0644 (11) | 0.0215 (7) | 0.0029 (7) | 0.0004 (5) | −0.0096 (7) |
O2A | 0.0210 (6) | 0.0230 (6) | 0.0273 (7) | 0.0010 (5) | 0.0042 (5) | 0.0007 (6) |
O3A | 0.0167 (6) | 0.0319 (7) | 0.0299 (7) | 0.0007 (5) | 0.0012 (5) | −0.0077 (6) |
N1A | 0.0180 (8) | 0.0323 (9) | 0.0177 (7) | −0.0016 (7) | −0.0013 (6) | −0.0011 (7) |
N2A | 0.0146 (7) | 0.0246 (8) | 0.0182 (7) | 0.0016 (6) | 0.0005 (6) | −0.0031 (6) |
C1A | 0.0168 (8) | 0.0327 (10) | 0.0178 (8) | −0.0013 (7) | 0.0006 (7) | −0.0018 (7) |
C2A | 0.0173 (9) | 0.0359 (11) | 0.0260 (10) | 0.0044 (8) | −0.0016 (7) | −0.0022 (8) |
C3A | 0.0246 (9) | 0.0253 (9) | 0.0230 (9) | 0.0042 (7) | 0.0004 (7) | −0.0021 (7) |
C4A | 0.0385 (12) | 0.0438 (13) | 0.0306 (11) | −0.0096 (10) | −0.0020 (9) | −0.0049 (10) |
C5A | 0.0427 (14) | 0.0465 (15) | 0.0530 (16) | −0.0165 (12) | −0.0039 (12) | 0.0038 (12) |
C6A | 0.0433 (13) | 0.0354 (12) | 0.0506 (14) | −0.0002 (10) | 0.0115 (11) | 0.0157 (11) |
C7A | 0.0660 (16) | 0.0274 (10) | 0.0273 (10) | 0.0012 (11) | 0.0099 (10) | 0.0054 (9) |
C8A | 0.0477 (13) | 0.0263 (10) | 0.0228 (10) | −0.0050 (9) | −0.0040 (9) | −0.0005 (8) |
C9A | 0.0165 (8) | 0.0281 (10) | 0.0188 (8) | −0.0008 (7) | 0.0003 (6) | −0.0009 (7) |
C10A | 0.0168 (8) | 0.0215 (9) | 0.0178 (8) | 0.0034 (7) | −0.0009 (6) | −0.0024 (7) |
C11A | 0.0250 (9) | 0.0225 (9) | 0.0174 (8) | 0.0019 (7) | 0.0015 (7) | −0.0004 (7) |
C12A | 0.0342 (11) | 0.0439 (13) | 0.0181 (9) | −0.0005 (9) | −0.0024 (8) | 0.0014 (8) |
C13A | 0.0333 (11) | 0.0265 (10) | 0.0278 (10) | 0.0002 (8) | 0.0067 (8) | 0.0030 (8) |
C14A | 0.0520 (15) | 0.0237 (11) | 0.0455 (13) | 0.0027 (10) | 0.0101 (11) | 0.0021 (9) |
C15A | 0.0191 (8) | 0.0252 (9) | 0.0130 (8) | −0.0004 (7) | 0.0026 (6) | −0.0033 (7) |
O1B | 0.0160 (6) | 0.0219 (6) | 0.0309 (7) | −0.0006 (5) | 0.0029 (5) | −0.0012 (5) |
O2B | 0.0273 (7) | 0.0338 (8) | 0.0195 (6) | −0.0044 (6) | 0.0042 (5) | −0.0021 (6) |
O3B | 0.0159 (6) | 0.0297 (7) | 0.0236 (6) | 0.0018 (5) | −0.0004 (5) | 0.0033 (5) |
N1B | 0.0196 (8) | 0.0246 (8) | 0.0199 (8) | 0.0030 (7) | 0.0004 (6) | −0.0032 (6) |
N2B | 0.0137 (7) | 0.0198 (7) | 0.0233 (7) | 0.0015 (6) | 0.0006 (6) | 0.0003 (6) |
C1B | 0.0157 (8) | 0.0203 (8) | 0.0212 (8) | 0.0009 (6) | 0.0010 (6) | −0.0036 (7) |
C2B | 0.0239 (9) | 0.0195 (9) | 0.0241 (9) | 0.0035 (7) | −0.0021 (7) | −0.0011 (7) |
C3B | 0.0218 (9) | 0.0187 (8) | 0.0223 (9) | 0.0051 (7) | −0.0023 (7) | 0.0011 (7) |
C4B | 0.0217 (9) | 0.0256 (10) | 0.0244 (9) | 0.0008 (7) | 0.0020 (7) | 0.0014 (7) |
C5B | 0.0270 (10) | 0.0284 (10) | 0.0260 (9) | −0.0008 (8) | −0.0036 (7) | −0.0009 (8) |
C6B | 0.0351 (11) | 0.0312 (11) | 0.0202 (8) | 0.0058 (9) | 0.0013 (8) | 0.0004 (8) |
C7B | 0.0254 (10) | 0.0361 (11) | 0.0276 (10) | 0.0041 (8) | 0.0063 (8) | 0.0073 (8) |
C8B | 0.0221 (9) | 0.0246 (10) | 0.0293 (10) | −0.0001 (7) | −0.0016 (8) | 0.0046 (8) |
C9B | 0.0154 (8) | 0.0204 (8) | 0.0166 (8) | 0.0026 (6) | −0.0016 (6) | −0.0009 (6) |
C10B | 0.0154 (8) | 0.0169 (8) | 0.0231 (9) | 0.0014 (6) | −0.0001 (6) | 0.0005 (6) |
C11B | 0.0244 (9) | 0.0218 (9) | 0.0202 (9) | 0.0015 (7) | 0.0001 (7) | −0.0035 (7) |
C12B | 0.0305 (11) | 0.0256 (10) | 0.0333 (11) | 0.0055 (8) | 0.0039 (8) | −0.0062 (8) |
C13B | 0.0327 (10) | 0.0300 (10) | 0.0211 (9) | 0.0017 (8) | 0.0010 (8) | −0.0016 (8) |
C14B | 0.0375 (12) | 0.0395 (13) | 0.0402 (13) | −0.0025 (10) | −0.0084 (10) | −0.0061 (10) |
C15B | 0.0197 (8) | 0.0156 (8) | 0.0195 (8) | −0.0013 (6) | −0.0003 (6) | 0.0040 (6) |
O1W | 0.079 (2) | 0.0310 (13) | 0.0356 (13) | −0.0189 (13) | −0.0143 (12) | 0.0026 (10) |
O2W | 0.0631 (16) | 0.0278 (12) | 0.0256 (11) | 0.0059 (11) | 0.0032 (10) | −0.0036 (9) |
O1A—C9A | 1.228 (2) | N1B—H2B | 0.89 (3) |
O2A—C15A | 1.259 (2) | N1B—H3B | 0.90 (3) |
O3A—C15A | 1.257 (2) | N2B—C9B | 1.336 (2) |
N1A—C1A | 1.488 (2) | N2B—C10B | 1.465 (2) |
N1A—H1A | 0.85 (3) | N2B—H4B | 0.85 (2) |
N1A—H2A | 0.89 (3) | C1B—C2B | 1.531 (3) |
N1A—H3A | 0.91 (3) | C1B—C9B | 1.535 (2) |
N2A—C9A | 1.337 (2) | C1B—H11B | 0.98 (2) |
N2A—C10A | 1.460 (2) | C2B—C3B | 1.512 (3) |
N2A—H4A | 0.90 (2) | C2B—H21B | 0.9900 |
C1A—C9A | 1.536 (3) | C2B—H22B | 0.9900 |
C1A—C2A | 1.540 (3) | C3B—C4B | 1.389 (3) |
C1A—H11A | 1.02 (2) | C3B—C8B | 1.396 (3) |
C2A—C3A | 1.509 (3) | C4B—C5B | 1.395 (3) |
C2A—H21A | 0.9900 | C4B—H41B | 0.9500 |
C2A—H22A | 0.9900 | C5B—C6B | 1.389 (3) |
C3A—C4A | 1.389 (3) | C5B—H51B | 0.9500 |
C3A—C8A | 1.397 (3) | C6B—C7B | 1.383 (3) |
C4A—C5A | 1.392 (4) | C6B—H61B | 0.9500 |
C4A—H41A | 0.9500 | C7B—C8B | 1.392 (3) |
C5A—C6A | 1.374 (4) | C7B—H71B | 0.9500 |
C5A—H51A | 0.9500 | C8B—H81B | 0.9500 |
C6A—C7A | 1.379 (4) | C10B—C11B | 1.554 (3) |
C6A—H61A | 0.9500 | C10B—C15B | 1.559 (2) |
C7A—C8A | 1.387 (3) | C10B—H10B | 1.0000 |
C7A—H71A | 0.9500 | C11B—C13B | 1.537 (3) |
C8A—H81A | 0.9500 | C11B—C12B | 1.538 (3) |
C10A—C15A | 1.540 (3) | C11B—H12B | 1.0000 |
C10A—C11A | 1.548 (2) | C12B—H13B | 0.9800 |
C10A—H10A | 1.0000 | C12B—H14B | 0.9800 |
C11A—C12A | 1.531 (3) | C12B—H15B | 0.9800 |
C11A—C13A | 1.541 (3) | C13B—C14B | 1.520 (3) |
C11A—H12A | 1.0000 | C13B—H16B | 0.9900 |
C12A—H13A | 0.9800 | C13B—H17B | 0.9900 |
C12A—H14A | 0.9800 | C14B—H18B | 0.9800 |
C12A—H15A | 0.9800 | C14B—H19B | 0.9800 |
C13A—C14A | 1.528 (3) | C14B—H20B | 0.9800 |
C13A—H16A | 0.9900 | O1W—H11W | 0.849 (10) |
C13A—H17A | 0.9900 | O1W—H12W | 0.848 (10) |
C14A—H18A | 0.9800 | O2W—H21W | 0.852 (10) |
C14A—H19A | 0.9800 | O2W—H22W | 0.847 (10) |
C14A—H20A | 0.9800 | O2W—H41W | 0.5746 |
O1B—C9B | 1.227 (2) | O3W—H31W | 0.8493 |
O2B—C15B | 1.254 (2) | O3W—H32W | 0.8489 |
O3B—C15B | 1.253 (2) | O4W—H41W | 0.8495 |
N1B—C1B | 1.500 (2) | O4W—H42W | 0.8624 |
N1B—H1B | 0.86 (3) | ||
C1A—N1A—H1A | 108.9 (18) | H1B—N1B—H2B | 102 (2) |
C1A—N1A—H2A | 110.7 (18) | C1B—N1B—H3B | 109.7 (16) |
H1A—N1A—H2A | 104 (3) | H1B—N1B—H3B | 112 (2) |
C1A—N1A—H3A | 113.0 (17) | H2B—N1B—H3B | 106 (2) |
H1A—N1A—H3A | 110 (3) | C9B—N2B—C10B | 122.33 (15) |
H2A—N1A—H3A | 109 (2) | C9B—N2B—H4B | 117.5 (16) |
C9A—N2A—C10A | 120.45 (15) | C10B—N2B—H4B | 116.6 (16) |
C9A—N2A—H4A | 121.6 (14) | N1B—C1B—C2B | 108.43 (15) |
C10A—N2A—H4A | 117.9 (14) | N1B—C1B—C9B | 107.86 (14) |
N1A—C1A—C9A | 106.27 (15) | C2B—C1B—C9B | 111.82 (15) |
N1A—C1A—C2A | 111.26 (16) | N1B—C1B—H11B | 108.0 (13) |
C9A—C1A—C2A | 113.50 (16) | C2B—C1B—H11B | 111.5 (14) |
N1A—C1A—H11A | 108.4 (14) | C9B—C1B—H11B | 109.2 (14) |
C9A—C1A—H11A | 110.4 (13) | C3B—C2B—C1B | 113.01 (15) |
C2A—C1A—H11A | 107.0 (14) | C3B—C2B—H21B | 109.0 |
C3A—C2A—C1A | 113.81 (16) | C1B—C2B—H21B | 109.0 |
C3A—C2A—H21A | 108.8 | C3B—C2B—H22B | 109.0 |
C1A—C2A—H21A | 108.8 | C1B—C2B—H22B | 109.0 |
C3A—C2A—H22A | 108.8 | H21B—C2B—H22B | 107.8 |
C1A—C2A—H22A | 108.8 | C4B—C3B—C8B | 118.81 (17) |
H21A—C2A—H22A | 107.7 | C4B—C3B—C2B | 120.98 (17) |
C4A—C3A—C8A | 118.1 (2) | C8B—C3B—C2B | 120.22 (17) |
C4A—C3A—C2A | 121.49 (18) | C3B—C4B—C5B | 120.65 (18) |
C8A—C3A—C2A | 120.38 (19) | C3B—C4B—H41B | 119.7 |
C3A—C4A—C5A | 120.6 (2) | C5B—C4B—H41B | 119.7 |
C3A—C4A—H41A | 119.7 | C6B—C5B—C4B | 119.90 (19) |
C5A—C4A—H41A | 119.7 | C6B—C5B—H51B | 120.1 |
C6A—C5A—C4A | 120.6 (2) | C4B—C5B—H51B | 120.1 |
C6A—C5A—H51A | 119.7 | C7B—C6B—C5B | 119.97 (18) |
C4A—C5A—H51A | 119.7 | C7B—C6B—H61B | 120.0 |
C5A—C6A—C7A | 119.6 (2) | C5B—C6B—H61B | 120.0 |
C5A—C6A—H61A | 120.2 | C6B—C7B—C8B | 119.99 (19) |
C7A—C6A—H61A | 120.2 | C6B—C7B—H71B | 120.0 |
C6A—C7A—C8A | 120.3 (2) | C8B—C7B—H71B | 120.0 |
C6A—C7A—H71A | 119.9 | C7B—C8B—C3B | 120.69 (18) |
C8A—C7A—H71A | 119.9 | C7B—C8B—H81B | 119.7 |
C7A—C8A—C3A | 120.8 (2) | C3B—C8B—H81B | 119.7 |
C7A—C8A—H81A | 119.6 | O1B—C9B—N2B | 124.96 (17) |
C3A—C8A—H81A | 119.6 | O1B—C9B—C1B | 121.03 (16) |
O1A—C9A—N2A | 123.46 (17) | N2B—C9B—C1B | 114.00 (15) |
O1A—C9A—C1A | 120.59 (16) | N2B—C10B—C11B | 115.37 (14) |
N2A—C9A—C1A | 115.94 (16) | N2B—C10B—C15B | 108.76 (14) |
N2A—C10A—C15A | 112.00 (15) | C11B—C10B—C15B | 113.42 (14) |
N2A—C10A—C11A | 109.09 (14) | N2B—C10B—H10B | 106.2 |
C15A—C10A—C11A | 111.34 (14) | C11B—C10B—H10B | 106.2 |
N2A—C10A—H10A | 108.1 | C15B—C10B—H10B | 106.2 |
C15A—C10A—H10A | 108.1 | C13B—C11B—C12B | 111.83 (16) |
C11A—C10A—H10A | 108.1 | C13B—C11B—C10B | 114.67 (15) |
C12A—C11A—C13A | 112.17 (16) | C12B—C11B—C10B | 108.54 (16) |
C12A—C11A—C10A | 111.48 (16) | C13B—C11B—H12B | 107.1 |
C13A—C11A—C10A | 111.62 (15) | C12B—C11B—H12B | 107.1 |
C12A—C11A—H12A | 107.1 | C10B—C11B—H12B | 107.1 |
C13A—C11A—H12A | 107.1 | C11B—C12B—H13B | 109.5 |
C10A—C11A—H12A | 107.1 | C11B—C12B—H14B | 109.5 |
C11A—C12A—H13A | 109.5 | H13B—C12B—H14B | 109.5 |
C11A—C12A—H14A | 109.5 | C11B—C12B—H15B | 109.5 |
H13A—C12A—H14A | 109.5 | H13B—C12B—H15B | 109.5 |
C11A—C12A—H15A | 109.5 | H14B—C12B—H15B | 109.5 |
H13A—C12A—H15A | 109.5 | C14B—C13B—C11B | 114.84 (18) |
H14A—C12A—H15A | 109.5 | C14B—C13B—H16B | 108.6 |
C14A—C13A—C11A | 115.19 (17) | C11B—C13B—H16B | 108.6 |
C14A—C13A—H16A | 108.5 | C14B—C13B—H17B | 108.6 |
C11A—C13A—H16A | 108.5 | C11B—C13B—H17B | 108.6 |
C14A—C13A—H17A | 108.5 | H16B—C13B—H17B | 107.5 |
C11A—C13A—H17A | 108.5 | C13B—C14B—H18B | 109.5 |
H16A—C13A—H17A | 107.5 | C13B—C14B—H19B | 109.5 |
C13A—C14A—H18A | 109.5 | H18B—C14B—H19B | 109.5 |
C13A—C14A—H19A | 109.5 | C13B—C14B—H20B | 109.5 |
H18A—C14A—H19A | 109.5 | H18B—C14B—H20B | 109.5 |
C13A—C14A—H20A | 109.5 | H19B—C14B—H20B | 109.5 |
H18A—C14A—H20A | 109.5 | O3B—C15B—O2B | 124.55 (16) |
H19A—C14A—H20A | 109.5 | O3B—C15B—C10B | 118.94 (15) |
O3A—C15A—O2A | 124.33 (17) | O2B—C15B—C10B | 116.49 (15) |
O3A—C15A—C10A | 117.02 (16) | H11W—O1W—H12W | 105.6 (17) |
O2A—C15A—C10A | 118.63 (15) | H21W—O2W—H22W | 105.6 (17) |
C1B—N1B—H1B | 111.1 (18) | H31W—O3W—H32W | 104.9 |
C1B—N1B—H2B | 116.1 (17) | H41W—O4W—H42W | 107.3 |
N1A—C1A—C9A—N2A | 164.38 (17) | N1B—C1B—C9B—N2B | 114.94 (17) |
C1A—C9A—N2A—C10A | −178.54 (16) | C1B—C9B—N2B—C10B | −171.42 (15) |
C9A—N2A—C10A—C15A | −83.2 (2) | C9B—N2B—C10B—C15B | 52.3 (2) |
N2A—C10A—C15A—O2A | −41.0 (2) | N2B—C10B—C15B—O2B | 44.7 (2) |
N1A—C1A—C2A—C3A | 57.2 (2) | N1B—C1B—C2B—C3B | 173.66 (15) |
C1A—C2A—C3A—C4A | 84.8 (2) | C1B—C2B—C3B—C4B | 64.3 (2) |
C1A—C2A—C3A—C8A | −92.7 (2) | C1B—C2B—C3B—C8B | −116.06 (19) |
N2A—C10A—C11A—C12A | 175.79 (16) | N2B—C10B—C11B—C12B | −152.49 (16) |
N2A—C10A—C11A—C13A | −57.9 (2) | N2B—C10B—C11B—C13B | −26.6 (2) |
C10A—C11A—C13A—C14A | −54.3 (2) | C10B—C11B—C13B—C14B | −66.3 (2) |
C9A—C1A—C2A—C3A | −62.7 (2) | C9B—C1B—C2B—C3B | 54.9 (2) |
C8A—C3A—C4A—C5A | −0.6 (4) | C8B—C3B—C4B—C5B | −0.1 (3) |
C2A—C3A—C4A—C5A | −178.2 (2) | C2B—C3B—C4B—C5B | 179.56 (18) |
C3A—C4A—C5A—C6A | 0.8 (4) | C3B—C4B—C5B—C6B | 0.0 (3) |
C4A—C5A—C6A—C7A | 0.2 (4) | C4B—C5B—C6B—C7B | −0.2 (3) |
C5A—C6A—C7A—C8A | −1.3 (4) | C5B—C6B—C7B—C8B | 0.6 (3) |
C6A—C7A—C8A—C3A | 1.6 (4) | C6B—C7B—C8B—C3B | −0.7 (3) |
C4A—C3A—C8A—C7A | −0.6 (3) | C4B—C3B—C8B—C7B | 0.5 (3) |
C2A—C3A—C8A—C7A | 177.0 (2) | C2B—C3B—C8B—C7B | −179.18 (18) |
C10A—N2A—C9A—O1A | 1.0 (3) | C10B—N2B—C9B—O1B | 8.4 (3) |
N1A—C1A—C9A—O1A | −15.2 (3) | N1B—C1B—C9B—O1B | −64.9 (2) |
C2A—C1A—C9A—O1A | 107.4 (2) | C2B—C1B—C9B—O1B | 54.2 (2) |
C2A—C1A—C9A—N2A | −73.0 (2) | C2B—C1B—C9B—N2B | −125.93 (17) |
C9A—N2A—C10A—C11A | 153.13 (16) | C9B—N2B—C10B—C11B | −76.5 (2) |
C15A—C10A—C11A—C12A | 51.7 (2) | C15B—C10B—C11B—C13B | −153.03 (16) |
C15A—C10A—C11A—C13A | 177.99 (15) | C15B—C10B—C11B—C12B | 81.12 (19) |
C12A—C11A—C13A—C14A | 71.6 (2) | C12B—C11B—C13B—C14B | 57.8 (2) |
N2A—C10A—C15A—O3A | 140.58 (16) | N2B—C10B—C15B—O3B | −137.13 (16) |
C11A—C10A—C15A—O3A | −96.97 (18) | C11B—C10B—C15B—O3B | −7.3 (2) |
C11A—C10A—C15A—O2A | 81.47 (19) | C11B—C10B—C15B—O2B | 174.52 (16) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O2Wi | 0.85 (3) | 1.94 (3) | 2.765 (3) | 163 (3) |
N1A—H2A···O2Bi | 0.89 (2) | 2.04 (3) | 2.839 (2) | 150 (2) |
N1A—H3A···O3Bii | 0.91 (3) | 1.92 (3) | 2.799 (2) | 162 (2) |
N2A—H4A···O3Aiii | 0.90 (2) | 2.03 (3) | 2.908 (2) | 167 (2) |
C1A—H11A···O1Aiii | 1.02 (2) | 2.46 (2) | 3.290 (2) | 138.3 (18) |
C4A—H41A···O2A | 0.95 | 2.64 | 3.560 (3) | 165 |
C8A—H81A···O3Bii | 0.95 | 2.51 | 3.322 (3) | 143 |
N1B—H1B···O2W | 0.86 (3) | 2.20 (3) | 2.969 (3) | 149 (2) |
N1B—H2B···O3Aiii | 0.89 (2) | 1.91 (3) | 2.754 (2) | 157 (2) |
N1B—H3B···O2A | 0.90 (3) | 1.80 (3) | 2.691 (2) | 170 (2) |
N2B—H4B···O3Biv | 0.85 (2) | 2.00 (3) | 2.831 (2) | 165 (2) |
C1B—H11B···O1Biv | 0.98 (2) | 2.40 (2) | 3.263 (2) | 146.2 (19) |
C4B—H41B···O1Biv | 0.95 | 2.62 | 3.521 (2) | 158 |
O1W—H11W···O2Biv | 0.85 (3) | 1.85 (3) | 2.694 (3) | 172 (4) |
O1W—H12W···O2A | 0.85 (3) | 1.98 (3) | 2.818 (3) | 167 (5) |
O2W—H21W···O1Wiii | 0.85 (3) | 1.91 (3) | 2.703 (4) | 154 (3) |
O2W—H22W···C4A | 0.85 (3) | 2.49 (3) | 3.282 (4) | 156 (4) |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) −x+2, y+1/2, −z+1; (iii) x+1, y, z; (iv) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C15H22N2O3·0.88H2O |
Mr | 294.24 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 105 |
a, b, c (Å) | 5.5634 (3), 17.0558 (9), 16.6859 (9) |
β (°) | 96.744 (1) |
V (Å3) | 1572.34 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.75 × 0.15 × 0.12 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.899, 0.989 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10060, 3570, 3378 |
Rint | 0.025 |
(sin θ/λ)max (Å−1) | 0.641 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.077, 1.00 |
No. of reflections | 3570 |
No. of parameters | 434 |
No. of restraints | 8 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.27, −0.17 |
Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 2001), SAINT-Plus, SHELXTL (Bruker, 2000), SHELXTL.
N1A—C1A—C9A—N2A | 164.38 (17) | N1B—C1B—C9B—N2B | 114.94 (17) |
C1A—C9A—N2A—C10A | −178.54 (16) | C1B—C9B—N2B—C10B | −171.42 (15) |
C9A—N2A—C10A—C15A | −83.2 (2) | C9B—N2B—C10B—C15B | 52.3 (2) |
N2A—C10A—C15A—O2A | −41.0 (2) | N2B—C10B—C15B—O2B | 44.7 (2) |
N1A—C1A—C2A—C3A | 57.2 (2) | N1B—C1B—C2B—C3B | 173.66 (15) |
C1A—C2A—C3A—C4A | 84.8 (2) | C1B—C2B—C3B—C4B | 64.3 (2) |
C1A—C2A—C3A—C8A | −92.7 (2) | C1B—C2B—C3B—C8B | −116.06 (19) |
N2A—C10A—C11A—C12A | 175.79 (16) | N2B—C10B—C11B—C12B | −152.49 (16) |
N2A—C10A—C11A—C13A | −57.9 (2) | N2B—C10B—C11B—C13B | −26.6 (2) |
C10A—C11A—C13A—C14A | −54.3 (2) | C10B—C11B—C13B—C14B | −66.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1A—H1A···O2Wi | 0.85 (3) | 1.94 (3) | 2.765 (3) | 163 (3) |
N1A—H2A···O2Bi | 0.89 (2) | 2.04 (3) | 2.839 (2) | 150 (2) |
N1A—H3A···O3Bii | 0.91 (3) | 1.92 (3) | 2.799 (2) | 162 (2) |
N2A—H4A···O3Aiii | 0.90 (2) | 2.03 (3) | 2.908 (2) | 167 (2) |
C1A—H11A···O1Aiii | 1.02 (2) | 2.46 (2) | 3.290 (2) | 138.3 (18) |
C4A—H41A···O2A | 0.95 | 2.64 | 3.560 (3) | 165 |
C8A—H81A···O3Bii | 0.95 | 2.51 | 3.322 (3) | 143 |
N1B—H1B···O2W | 0.86 (3) | 2.20 (3) | 2.969 (3) | 149 (2) |
N1B—H2B···O3Aiii | 0.89 (2) | 1.91 (3) | 2.754 (2) | 157 (2) |
N1B—H3B···O2A | 0.90 (3) | 1.80 (3) | 2.691 (2) | 170 (2) |
N2B—H4B···O3Biv | 0.85 (2) | 2.00 (3) | 2.831 (2) | 165 (2) |
C1B—H11B···O1Biv | 0.98 (2) | 2.40 (2) | 3.263 (2) | 146.2 (19) |
C4B—H41B···O1Biv | 0.95 | 2.62 | 3.521 (2) | 158 |
O1W—H11W···O2Biv | 0.85 (3) | 1.85 (3) | 2.694 (3) | 172 (4) |
O1W—H12W···O2A | 0.85 (3) | 1.98 (3) | 2.818 (3) | 167 (5) |
O2W—H21W···O1Wiii | 0.85 (3) | 1.91 (3) | 2.703 (4) | 154 (3) |
O2W—H22W···C4A | 0.85 (3) | 2.49 (3) | 3.282 (4) | 156 (4) |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) −x+2, y+1/2, −z+1; (iii) x+1, y, z; (iv) x−1, y, z. |
A systematic survey has revealed that dipeptides constructed from two amino acid residues with large hydrophobic side chains may give porous structures with hydrophilic inner surfaces. This structural family has been referred to as the FF-class, after L-phenylalanyl-L-phenylalanine (FF; Görbitz, 2001), and includes L-leucyl-L-leucine (LL), L-leucyl-L-phenylalanine (LF), L-phenylalanyl-L-leucine (FL; Görbitz, 2001) and L-isoleucyl-L-leucine (IL; Görbitz, 2004b), as well as L-tryptophylglycine (WG; Emge et al., 2000; Birkedal et al., 2002). Channel size ranges from a rectangular 2.5 × 6.0 Å for LL, LF and IL, to circular with diameter 10 Å for FF. All peptide molecules which form this type of nanotube occur in unusual folded conformations that bring both side chains onto the same side of the plane defined by the peptide bond. The associated absolute values for the torsion angle θ (C1β-C1α···C2α-C2β) are thus close to 0°. Conformations with low θ values are also observed for L-Ile-L-Phe (IF; Görbitz, 2004a), L-valyl-L-phenylalanine (VF, orthorhombic modification; Görbitz, 2002), and L-alanyl-L-trpyptophane (AW; Emge et al., 2000), but these three structures are divided into hydrophobic and hydrophilic layers, the latter including one (AW) or two (IF and VF) water molecules per peptide molecule. Against this background, the crystal structure of L-phenylalanyl-L-isoleucine, FI, is presented. \sch
The crystal structure of FI is depicted in Fig. 1 and Table 1. Just as for LL, LF, FL and IL, there are two peptide molecules in the asymmetric unit, but unlike the other four peptide structures the two molecules appear completely different. Molecule B has the typical `nanotube conformation', with θ (C2B—C1B···C10B—C11B) −0.65 (19)° and C9B—N2B—C10B—C15B 52.3 (2)°, while molecule A has a more elongated conformation, with θ (C2A—C1A···C10A—C11A) −95.83 (17)° and C9A—N2A—C10A—C15A −83.2 (2)°, which is stabilized by a weak intramolecular C4A—H41A···O2A hydrogen bond between the phenyl ring and the carboxylate group (Table 2). The resulting structure (Fig. 2) is divided into wave-shaped hydrophobic and hydrophilic layers, but nevertheless incorporates obvious water-filled channels, although these are significantly reduced in size (to 1.8 × 4.0 Å) compared with the FF-class. The channels have partly hydrophilic and partly hydrophobic inner surfaces.
The L-Phe side chain in FI is in a gauche+ orientation for molecule A and a trans orientation for molecule B. Both Ile side chains have the common gauche-/trans,gauche- conformation (for N2—C10—C11—C13/C12 and C10—C11—C13—C14), but twisted about 30° away from the ideal staggered orientation at C10—C11 for molecule B, to relieve what would have been a very close contact with the neighbouring molecule B along the b axis, to which it is related by the twofold screw (Fig. 2). The resulting intermolecular C14B—H20B···C8B(1 − x, y − 1/2, −z) interaction has a normal 2.97 Å H···C distance. The twist also leads to additional intra- and intermolecular contacts (H···C ≥ 3.01 Å) involving the peptide B molecules.
Hydrogen bonds with O acceptors are listed in Table 2, including three with C(π)-H donors (one intramolecular, see above). There are several similarities with the set of interactions found in the structures of the FF-class, and in particular with LL, LF (Görbitz, 2001) and IL (Görbitz, 2004b), including the presence of a hydrogen bond between the two water molecules in the asymmetric unit, with atom O2W as the donor. The only major difference concerns the second H atom of O2W, which is donated to a carboxylate group in the three FF-class structures. In the FI structure, access to the corresponding carboxylate group (of molecule B) is blocked by the amino group of molecule A (2 in Fig. 2), and the pertinent H22W atom (3 in Fig. 2) is instead pointing in the opposite direction, where it is accepted by the aromatic ring of the molecule A L-Phe side chain.
An L-leucine residue in a dipeptide can often be interchanged with an L-phenylalanine residue without major modifications to the crystal structure. An equivalent observation has been made for L-valine and L-isoleucine residues (Görbitz, 2004c). The FI structure, however, is not related to either L-leucyl-L-isoleucine (Görbitz, 2004c) or L-phenylalanyl-L-valine (Görbitz, 2000).