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The present paper reports the crystal structures of two short phosphonotripeptides (one in two crystal forms) containing one
Phe (dehydrophenylalanine) residue, namely dimethyl (3-{[
tert-butoxycarbonylglycyl-
,
-(
Z)-dehydrophenylalanyl]amino}propyl)phosphonate, Boc
0-Gly
1-
(
Z)Phe
2-
-Abu
3PO
3Me
2, C
21H
32N
3O
7P, (I), and diethyl (4-{[
tert-butoxycarbonylglycyl-
,
-(
Z)-dehydrophenylalanyl]amino}butyl)phosphonate, Boc
0-Gly
1-
(
Z)Phe
2-
-Nva
3PO
3Et
2, as the propan-2-ol monosolvate 0.122-hydrate, C
24H
38N
3O
7P·C
3H
8O·0.122H
2O, (II), and the ethanol monosolvate 0.076-hydrate, C
24H
38N
3O
7P·C
2H
6O·0.076H
2O, (III). The crystals of (II) and (III) are isomorphous but differ in the type of solvent. The phosphono group is linked directly to the last C
atom in the main chain for all three peptides. All the amino acids are
trans linked in the main chains. The crystal structures exhibit no intramolecular hydrogen bonds and are stabilized by intermolecular hydrogen bonds only.
Supporting information
CCDC references: 934572; 934573; 934574
The syntheses of the title compounds were described by Latajka et al.
(2013). Crystals of (I) were recrystallized from ethanol at 293 K,
those of
(II) from propan-2-ol at 278 K and those of (III) from ethanol at 293 K.
All C-bound H atoms were introduced in positions calculated from geometry, with
C—H = 0.95–1.0 Å. The N- and O-bound H atoms were found from difference
Fourier maps; the O—H bonds were restrained with a distance of 0.84 Å; in
the final refinement step, AFIX3 was used (SHELXL97; Sheldrick,
2008).
For C- and N-bound H atoms, except for the methyl groups, Uiso(H) =
1.2Ueq(C,N); for the methyl groups, Uiso(H) =
1.5Ueq(C).
In the case of (I), it was found during refinement that the position of the
phosphonate group is slightly disordered. The disorder groups were modelled
using SAME restraints (SHELXL97). Additionally, the N3—C16 and
N31—C16 bonds were modelled using the SADI command (SHELXL97). Atoms
C16 and C161 were in the same position and therefore were modelled with
constraints EADP and EXYZ (SHELXL97). In the absence of significant
anomalous dispersion effects, Friedel pairs were merged and the absolute
structure was not determined.
In (II), disorder is present in the side-chain of the (1-aminobutyl)phosphonate
(C19 and C20) and two ethoxy groups (C21, C22, C23 and C24). In the side-chain
of (1-aminobutyl)phosphonate, the disorder was modelled for atoms C19 and C20
with the same occupancy of 0.876 (3). In one of the ethoxy groups, disordered
atom C21 was modelled over two positions. Atoms C22 and C22A were in
the same position, therefore EADP and EXYZ instructions were used. For the
second ethoxy group, disordered atoms C23 and C24 were each modelled over two
positions.
In (III), two ethoxy groups (C21, C22, C23 and C24) and the ethanol molecule
(C31, C32 and O31) are disordered. For atoms C21, C23, C24 and O31, disorder
was modelled for each over two positions. Atoms C22, C31 and C32 were in the
same position and were therefore modelled using EADP and EXYZ instructions.
After refinement of (II) and (III), additional peaks were found in the
difference Fourier maps, one peak in each case. In (II), the highest residual
electron density was 0.83 e Å-3 and this was modelled as a water O atom.
In the adopted model, the R factor decreases from 0.049 to 0.045. In
(III), the highest peak was 0.48 e Å-3 and this was modelled as in (II).
The R factor decreases from 0.045 to 0.044. In both (II) and (III), the
water molecules labelled O1W are cooperatively disordered with the
ethoxy groups (C21 and C22 atoms in both structures) and have partial
occupancies of 0.122 (3) and 0.076 (4), respectively. The water molecules
occupy a similar position as the disordered ethoxy groups. [Rather than use
software-specific terms such as AFIX3, please paraphrase their effect or
action.]
For all compounds, data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and publCIF (Westrip, 2010).
(I) Dimethyl (3-{[
tert-butoxycarbonylglycyl-
α,
β-(
Z)-dehydrophenylalanyl]amino}propyl)phosphonate
top
Crystal data top
C21H32N3O7P | F(000) = 1000 |
Mr = 469.47 | Dx = 1.270 Mg m−3 |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2c -2n | Cell parameters from 17556 reflections |
a = 8.597 (3) Å | θ = 3–29° |
b = 18.023 (4) Å | µ = 0.16 mm−1 |
c = 15.852 (4) Å | T = 100 K |
V = 2456.2 (12) Å3 | Needle, colourless |
Z = 4 | 0.30 × 0.15 × 0.08 mm |
Data collection top
Oxford Xcalibur PX κ-geometry diffractometer with CCD area detector | 3134 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.098 |
Graphite monochromator | θmax = 29.0°, θmin = 3.3° |
ω and ϕ scans | h = −11→11 |
30498 measured reflections | k = −24→23 |
3370 independent reflections | l = −21→19 |
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)] = 0.067 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.126 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.23 | w = 1/[σ2(Fo2) + (0.045P)2 + 1.3496P] where P = (Fo2 + 2Fc2)/3 |
3370 reflections | (Δ/σ)max < 0.001 |
334 parameters | Δρmax = 0.29 e Å−3 |
23 restraints | Δρmin = −0.25 e Å−3 |
Crystal data top
C21H32N3O7P | V = 2456.2 (12) Å3 |
Mr = 469.47 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 8.597 (3) Å | µ = 0.16 mm−1 |
b = 18.023 (4) Å | T = 100 K |
c = 15.852 (4) Å | 0.30 × 0.15 × 0.08 mm |
Data collection top
Oxford Xcalibur PX κ-geometry diffractometer with CCD area detector | 3134 reflections with I > 2σ(I) |
30498 measured reflections | Rint = 0.098 |
3370 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.067 | 23 restraints |
wR(F2) = 0.126 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.23 | Δρmax = 0.29 e Å−3 |
3370 reflections | Δρmin = −0.25 e Å−3 |
334 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R-factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.3576 (5) | 0.8746 (2) | 0.4021 (3) | 0.0215 (8) | |
C2 | 0.2514 (6) | 0.9355 (3) | 0.3688 (3) | 0.0378 (12) | |
H2A | 0.3061 | 0.9832 | 0.3709 | 0.057* | |
H2B | 0.1575 | 0.9382 | 0.4037 | 0.057* | |
H2C | 0.2223 | 0.9245 | 0.3104 | 0.057* | |
C3 | 0.5102 (5) | 0.8735 (3) | 0.3547 (3) | 0.0355 (11) | |
H3A | 0.5606 | 0.9221 | 0.3595 | 0.053* | |
H3B | 0.4907 | 0.8625 | 0.2951 | 0.053* | |
H3C | 0.5782 | 0.8354 | 0.3787 | 0.053* | |
C4 | 0.2758 (6) | 0.8000 (3) | 0.3997 (3) | 0.0396 (12) | |
H4A | 0.3444 | 0.7619 | 0.4232 | 0.059* | |
H4B | 0.2501 | 0.7874 | 0.3412 | 0.059* | |
H4C | 0.1801 | 0.8026 | 0.4332 | 0.059* | |
O1 | 0.3819 (3) | 0.89845 (15) | 0.48950 (18) | 0.0228 (6) | |
O2 | 0.5417 (3) | 0.80166 (17) | 0.52359 (19) | 0.0291 (7) | |
C5 | 0.4731 (4) | 0.8583 (2) | 0.5414 (3) | 0.0202 (8) | |
N1 | 0.4819 (4) | 0.8931 (2) | 0.6177 (2) | 0.0213 (7) | |
H1 | 0.415 (6) | 0.926 (3) | 0.634 (3) | 0.026* | |
C6 | 0.5601 (5) | 0.8588 (2) | 0.6866 (3) | 0.0223 (8) | |
H6A | 0.6062 | 0.8980 | 0.7226 | 0.027* | |
H6B | 0.6464 | 0.8282 | 0.6643 | 0.027* | |
C7 | 0.4562 (4) | 0.81006 (19) | 0.7409 (2) | 0.0172 (7) | |
O3 | 0.3254 (3) | 0.78945 (14) | 0.72015 (17) | 0.0198 (6) | |
N2 | 0.5227 (4) | 0.78868 (17) | 0.8150 (2) | 0.0162 (6) | |
H2 | 0.600 (5) | 0.805 (2) | 0.839 (3) | 0.019* | |
C8 | 0.4512 (4) | 0.73264 (19) | 0.8638 (2) | 0.0152 (7) | |
C9 | 0.4083 (4) | 0.7375 (2) | 0.9442 (2) | 0.0187 (8) | |
H9 | 0.3668 | 0.6932 | 0.9674 | 0.022* | |
C10 | 0.4148 (4) | 0.8005 (2) | 1.0029 (2) | 0.0192 (8) | |
C11 | 0.3090 (5) | 0.8015 (3) | 1.0697 (3) | 0.0284 (9) | |
H11 | 0.2386 | 0.7613 | 1.0764 | 0.034* | |
C12 | 0.3044 (6) | 0.8596 (3) | 1.1262 (3) | 0.0380 (12) | |
H12 | 0.2294 | 0.8595 | 1.1702 | 0.046* | |
C13 | 0.4078 (6) | 0.9181 (3) | 1.1194 (3) | 0.0336 (11) | |
H13 | 0.4060 | 0.9577 | 1.1590 | 0.040* | |
C14 | 0.5141 (5) | 0.9178 (2) | 1.0535 (3) | 0.0287 (9) | |
H14 | 0.5860 | 0.9576 | 1.0483 | 0.034* | |
C15 | 0.5175 (5) | 0.8606 (2) | 0.9954 (3) | 0.0216 (8) | |
H15 | 0.5898 | 0.8620 | 0.9501 | 0.026* | |
O4 | 0.3059 (3) | 0.62187 (14) | 0.83751 (18) | 0.0196 (6) | |
C16 | 0.4192 (4) | 0.6604 (2) | 0.8181 (2) | 0.0169 (7) | 0.943 (3) |
N3 | 0.5213 (4) | 0.64126 (18) | 0.7571 (2) | 0.0170 (7) | 0.943 (3) |
H3 | 0.595 (5) | 0.662 (3) | 0.754 (3) | 0.020* | 0.943 (3) |
C17 | 0.5075 (4) | 0.5730 (2) | 0.7082 (2) | 0.0159 (8) | 0.943 (3) |
H17 | 0.3990 | 0.5538 | 0.7148 | 0.019* | 0.943 (3) |
C18 | 0.5383 (5) | 0.5856 (3) | 0.6131 (3) | 0.0234 (9) | 0.943 (3) |
H18A | 0.6362 | 0.6139 | 0.6066 | 0.028* | 0.943 (3) |
H18B | 0.5528 | 0.5368 | 0.5854 | 0.028* | 0.943 (3) |
C19 | 0.4095 (5) | 0.6267 (3) | 0.5689 (3) | 0.0290 (10) | 0.943 (3) |
H19A | 0.4372 | 0.6338 | 0.5095 | 0.043* | 0.943 (3) |
H19B | 0.3944 | 0.6751 | 0.5958 | 0.043* | 0.943 (3) |
H19C | 0.3131 | 0.5979 | 0.5727 | 0.043* | 0.943 (3) |
P1 | 0.64018 (11) | 0.50407 (5) | 0.74984 (7) | 0.0169 (2) | 0.943 (3) |
O5 | 0.8040 (3) | 0.51538 (16) | 0.7261 (2) | 0.0239 (7) | 0.943 (3) |
O6 | 0.6126 (4) | 0.4998 (2) | 0.8477 (2) | 0.0244 (9) | 0.943 (3) |
C20 | 0.7098 (7) | 0.5403 (3) | 0.9062 (3) | 0.0386 (12) | 0.943 (3) |
H20A | 0.7388 | 0.5078 | 0.9532 | 0.058* | 0.943 (3) |
H20B | 0.6526 | 0.5832 | 0.9279 | 0.058* | 0.943 (3) |
H20C | 0.8040 | 0.5572 | 0.8771 | 0.058* | 0.943 (3) |
O7 | 0.5615 (4) | 0.43075 (15) | 0.7172 (2) | 0.0247 (7) | 0.943 (3) |
C21 | 0.6347 (6) | 0.3600 (2) | 0.7311 (4) | 0.0462 (16) | 0.943 (3) |
H21A | 0.5784 | 0.3215 | 0.7000 | 0.069* | 0.943 (3) |
H21B | 0.6330 | 0.3484 | 0.7915 | 0.069* | 0.943 (3) |
H21C | 0.7427 | 0.3620 | 0.7114 | 0.069* | 0.943 (3) |
C161 | 0.4192 (4) | 0.6604 (2) | 0.8181 (2) | 0.0169 (7) | 0.057 (3) |
N31 | 0.550 (4) | 0.628 (3) | 0.791 (4) | 0.050* | 0.057 (3) |
H31 | 0.6374 | 0.6518 | 0.7806 | 0.060* | 0.057 (3) |
C171 | 0.530 (7) | 0.548 (3) | 0.7828 (19) | 0.050* | 0.057 (3) |
H171 | 0.4197 | 0.5361 | 0.7978 | 0.060* | 0.057 (3) |
C181 | 0.637 (17) | 0.505 (5) | 0.844 (4) | 0.050* | 0.057 (3) |
H18C | 0.6043 | 0.4529 | 0.8465 | 0.060* | 0.057 (3) |
H18D | 0.7452 | 0.5070 | 0.8226 | 0.060* | 0.057 (3) |
C191 | 0.633 (14) | 0.538 (6) | 0.932 (3) | 0.050* | 0.057 (3) |
H19D | 0.7077 | 0.5114 | 0.9682 | 0.075* | 0.057 (3) |
H19E | 0.5284 | 0.5328 | 0.9558 | 0.075* | 0.057 (3) |
H19F | 0.6615 | 0.5906 | 0.9300 | 0.075* | 0.057 (3) |
P11 | 0.560 (3) | 0.5220 (13) | 0.6736 (15) | 0.050* | 0.057 (3) |
O51 | 0.721 (4) | 0.532 (3) | 0.643 (3) | 0.050* | 0.057 (3) |
O61 | 0.434 (5) | 0.562 (3) | 0.619 (3) | 0.050* | 0.057 (3) |
C201 | 0.401 (11) | 0.537 (5) | 0.534 (3) | 0.050* | 0.057 (3) |
H20D | 0.3193 | 0.5685 | 0.5093 | 0.075* | 0.057 (3) |
H20E | 0.3666 | 0.4857 | 0.5349 | 0.075* | 0.057 (3) |
H20F | 0.4957 | 0.5415 | 0.4994 | 0.075* | 0.057 (3) |
O71 | 0.505 (6) | 0.4385 (17) | 0.678 (3) | 0.050* | 0.057 (3) |
C211 | 0.551 (12) | 0.391 (3) | 0.609 (5) | 0.050* | 0.057 (3) |
H21D | 0.5119 | 0.3406 | 0.6188 | 0.075* | 0.057 (3) |
H21E | 0.6651 | 0.3896 | 0.6050 | 0.075* | 0.057 (3) |
H21F | 0.5082 | 0.4101 | 0.5559 | 0.075* | 0.057 (3) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0227 (19) | 0.022 (2) | 0.0198 (18) | 0.0023 (16) | −0.0030 (16) | −0.0037 (16) |
C2 | 0.046 (3) | 0.041 (3) | 0.026 (2) | 0.021 (2) | −0.010 (2) | −0.005 (2) |
C3 | 0.025 (2) | 0.054 (3) | 0.027 (2) | 0.001 (2) | 0.0027 (18) | 0.011 (2) |
C4 | 0.046 (3) | 0.037 (3) | 0.036 (3) | −0.017 (2) | 0.002 (2) | −0.002 (2) |
O1 | 0.0244 (15) | 0.0210 (14) | 0.0229 (14) | 0.0072 (11) | −0.0005 (12) | −0.0010 (11) |
O2 | 0.0272 (16) | 0.0299 (17) | 0.0301 (16) | 0.0098 (13) | 0.0020 (12) | 0.0023 (13) |
C5 | 0.0152 (18) | 0.022 (2) | 0.023 (2) | 0.0005 (15) | 0.0039 (15) | 0.0048 (15) |
N1 | 0.0218 (17) | 0.0253 (18) | 0.0168 (16) | 0.0045 (14) | 0.0010 (14) | 0.0063 (14) |
C6 | 0.0170 (18) | 0.026 (2) | 0.024 (2) | −0.0017 (16) | −0.0003 (15) | 0.0072 (16) |
C7 | 0.0161 (16) | 0.0170 (16) | 0.0186 (19) | 0.0051 (13) | 0.0044 (15) | −0.0003 (14) |
O3 | 0.0155 (13) | 0.0201 (13) | 0.0237 (13) | 0.0002 (10) | −0.0016 (10) | −0.0006 (11) |
N2 | 0.0125 (14) | 0.0162 (15) | 0.0199 (16) | −0.0028 (12) | 0.0015 (12) | −0.0004 (13) |
C8 | 0.0134 (17) | 0.0128 (17) | 0.0193 (18) | 0.0016 (13) | −0.0025 (14) | 0.0022 (14) |
C9 | 0.0157 (18) | 0.020 (2) | 0.0199 (18) | −0.0007 (15) | −0.0001 (14) | 0.0058 (15) |
C10 | 0.0186 (17) | 0.020 (2) | 0.0186 (19) | −0.0001 (14) | −0.0037 (15) | 0.0063 (15) |
C11 | 0.034 (2) | 0.029 (2) | 0.022 (2) | −0.0122 (19) | 0.0037 (18) | −0.0002 (17) |
C12 | 0.039 (3) | 0.049 (3) | 0.026 (2) | −0.011 (2) | 0.014 (2) | −0.008 (2) |
C13 | 0.046 (3) | 0.030 (2) | 0.025 (2) | −0.010 (2) | 0.002 (2) | −0.006 (2) |
C14 | 0.032 (2) | 0.026 (2) | 0.028 (2) | −0.0089 (18) | −0.0033 (19) | −0.0006 (19) |
C15 | 0.024 (2) | 0.0209 (19) | 0.0203 (19) | −0.0033 (16) | 0.0013 (16) | −0.0011 (16) |
O4 | 0.0139 (12) | 0.0174 (13) | 0.0275 (14) | −0.0030 (10) | 0.0016 (11) | 0.0009 (11) |
C16 | 0.0144 (16) | 0.0143 (17) | 0.0219 (19) | 0.0035 (13) | −0.0022 (14) | 0.0028 (14) |
N3 | 0.0110 (14) | 0.0151 (15) | 0.0248 (18) | −0.0024 (11) | 0.0031 (15) | −0.0016 (15) |
C17 | 0.0141 (17) | 0.0156 (18) | 0.0181 (19) | 0.0000 (15) | 0.0027 (15) | 0.0009 (15) |
C18 | 0.023 (2) | 0.029 (2) | 0.019 (2) | 0.0019 (17) | 0.0003 (17) | 0.0048 (18) |
C19 | 0.028 (2) | 0.039 (3) | 0.020 (2) | 0.009 (2) | 0.0017 (18) | 0.0046 (19) |
P1 | 0.0157 (4) | 0.0155 (4) | 0.0194 (4) | 0.0003 (4) | 0.0014 (5) | 0.0002 (4) |
O5 | 0.0169 (14) | 0.0237 (14) | 0.0311 (17) | 0.0030 (11) | 0.0026 (12) | 0.0060 (12) |
O6 | 0.024 (2) | 0.0282 (17) | 0.0211 (15) | 0.0019 (14) | −0.0013 (13) | 0.0021 (13) |
C20 | 0.050 (3) | 0.040 (3) | 0.027 (2) | 0.005 (3) | −0.010 (2) | −0.010 (2) |
O7 | 0.0268 (16) | 0.0139 (14) | 0.0335 (17) | 0.0002 (12) | −0.0072 (14) | −0.0032 (13) |
C21 | 0.042 (3) | 0.015 (2) | 0.081 (5) | 0.003 (2) | −0.017 (3) | −0.011 (3) |
C161 | 0.0144 (16) | 0.0143 (17) | 0.0219 (19) | 0.0035 (13) | −0.0022 (14) | 0.0028 (14) |
Geometric parameters (Å, º) top
C1—O1 | 1.466 (5) | N3—H3 | 0.74 (5) |
C1—C3 | 1.512 (6) | C17—C18 | 1.548 (6) |
C1—C4 | 1.517 (6) | C17—P1 | 1.811 (4) |
C1—C2 | 1.523 (6) | C17—H17 | 1.0000 |
C2—H2A | 0.9800 | C18—C19 | 1.505 (6) |
C2—H2B | 0.9800 | C18—H18A | 0.9900 |
C2—H2C | 0.9800 | C18—H18B | 0.9900 |
C3—H3A | 0.9800 | C19—H19A | 0.9800 |
C3—H3B | 0.9800 | C19—H19B | 0.9800 |
C3—H3C | 0.9800 | C19—H19C | 0.9800 |
C4—H4A | 0.9800 | P1—O5 | 1.472 (3) |
C4—H4B | 0.9800 | P1—O6 | 1.571 (3) |
C4—H4C | 0.9800 | P1—O7 | 1.572 (3) |
O1—C5 | 1.347 (5) | O6—C20 | 1.446 (6) |
O2—C5 | 1.212 (5) | C20—H20A | 0.9800 |
C5—N1 | 1.366 (5) | C20—H20B | 0.9800 |
N1—C6 | 1.424 (5) | C20—H20C | 0.9800 |
N1—H1 | 0.87 (5) | O7—C21 | 1.439 (5) |
C6—C7 | 1.519 (5) | C21—H21A | 0.9800 |
C6—H6A | 0.9900 | C21—H21B | 0.9800 |
C6—H6B | 0.9900 | C21—H21C | 0.9800 |
C7—O3 | 1.229 (4) | N31—C171 | 1.46 (2) |
C7—N2 | 1.362 (5) | N31—H31 | 0.8800 |
N2—C8 | 1.413 (5) | C171—C181 | 1.55 (2) |
N2—H2 | 0.81 (5) | C171—P11 | 1.813 (19) |
C8—C9 | 1.329 (5) | C171—H171 | 1.0000 |
C8—C16 | 1.515 (5) | C181—C191 | 1.51 (2) |
C9—C10 | 1.468 (6) | C181—H18C | 0.9900 |
C9—H9 | 0.9500 | C181—H18D | 0.9900 |
C10—C11 | 1.397 (6) | C191—H19D | 0.9800 |
C10—C15 | 1.403 (5) | C191—H19E | 0.9800 |
C11—C12 | 1.378 (7) | C191—H19F | 0.9800 |
C11—H11 | 0.9500 | P11—O51 | 1.475 (19) |
C12—C13 | 1.384 (7) | P11—O61 | 1.566 (19) |
C12—H12 | 0.9500 | P11—O71 | 1.578 (19) |
C13—C14 | 1.388 (7) | O61—C201 | 1.45 (2) |
C13—H13 | 0.9500 | C201—H20D | 0.9800 |
C14—C15 | 1.383 (6) | C201—H20E | 0.9800 |
C14—H14 | 0.9500 | C201—H20F | 0.9800 |
C15—H15 | 0.9500 | O71—C211 | 1.44 (2) |
O4—C16 | 1.235 (4) | C211—H21D | 0.9800 |
C16—N3 | 1.352 (5) | C211—H21E | 0.9800 |
N3—C17 | 1.459 (5) | C211—H21F | 0.9800 |
| | | |
O1—C1—C3 | 110.5 (3) | P1—C17—H17 | 108.2 |
O1—C1—C4 | 110.4 (4) | C19—C18—C17 | 113.6 (4) |
C3—C1—C4 | 112.3 (4) | C19—C18—H18A | 108.9 |
O1—C1—C2 | 101.6 (3) | C17—C18—H18A | 108.9 |
C3—C1—C2 | 110.9 (4) | C19—C18—H18B | 108.9 |
C4—C1—C2 | 110.6 (4) | C17—C18—H18B | 108.9 |
C5—O1—C1 | 120.1 (3) | H18A—C18—H18B | 107.7 |
O2—C5—O1 | 126.4 (4) | C18—C19—H19A | 109.5 |
O2—C5—N1 | 124.5 (4) | C18—C19—H19B | 109.5 |
O1—C5—N1 | 109.0 (3) | H19A—C19—H19B | 109.5 |
C5—N1—C6 | 120.4 (4) | C18—C19—H19C | 109.5 |
C5—N1—H1 | 123 (3) | H19A—C19—H19C | 109.5 |
C6—N1—H1 | 112 (3) | H19B—C19—H19C | 109.5 |
N1—C6—C7 | 114.1 (3) | O5—P1—O6 | 113.8 (2) |
N1—C6—H6A | 108.7 | O5—P1—O7 | 116.35 (17) |
C7—C6—H6A | 108.7 | O6—P1—O7 | 102.7 (2) |
N1—C6—H6B | 108.7 | O5—P1—C17 | 114.50 (17) |
C7—C6—H6B | 108.7 | O6—P1—C17 | 107.35 (18) |
H6A—C6—H6B | 107.6 | O7—P1—C17 | 100.68 (18) |
O3—C7—N2 | 122.0 (3) | C20—O6—P1 | 121.4 (4) |
O3—C7—C6 | 124.1 (3) | C21—O7—P1 | 120.4 (3) |
N2—C7—C6 | 113.9 (3) | C171—N31—H31 | 124.5 |
C7—N2—C8 | 119.5 (3) | N31—C171—C181 | 111 (3) |
C7—N2—H2 | 130 (3) | N31—C171—P11 | 109 (2) |
C8—N2—H2 | 110 (3) | C181—C171—P11 | 113 (3) |
C9—C8—N2 | 126.8 (3) | N31—C171—H171 | 107.9 |
C9—C8—C16 | 117.7 (3) | C181—C171—H171 | 107.9 |
N2—C8—C16 | 115.5 (3) | P11—C171—H171 | 107.9 |
C8—C9—C10 | 130.4 (4) | C191—C181—C171 | 112 (3) |
C8—C9—H9 | 114.8 | C191—C181—H18C | 109.2 |
C10—C9—H9 | 114.8 | C171—C181—H18C | 109.2 |
C11—C10—C15 | 117.6 (4) | C191—C181—H18D | 109.2 |
C11—C10—C9 | 117.8 (4) | C171—C181—H18D | 109.2 |
C15—C10—C9 | 124.5 (4) | H18C—C181—H18D | 109.2 |
C12—C11—C10 | 121.4 (4) | C181—C191—H19D | 109.5 |
C12—C11—H11 | 119.3 | C181—C191—H19E | 109.5 |
C10—C11—H11 | 119.3 | H19D—C191—H19E | 109.5 |
C11—C12—C13 | 120.7 (4) | C181—C191—H19F | 109.5 |
C11—C12—H12 | 119.7 | H19D—C191—H19F | 109.5 |
C13—C12—H12 | 119.7 | H19E—C191—H19F | 109.5 |
C12—C13—C14 | 118.6 (4) | O51—P11—O61 | 114 (2) |
C12—C13—H13 | 120.7 | O51—P11—O71 | 114 (2) |
C14—C13—H13 | 120.7 | O61—P11—O71 | 105 (2) |
C15—C14—C13 | 121.2 (4) | O51—P11—C171 | 115 (2) |
C15—C14—H14 | 119.4 | O61—P11—C171 | 108 (2) |
C13—C14—H14 | 119.4 | O71—P11—C171 | 99.5 (19) |
C14—C15—C10 | 120.4 (4) | C201—O61—P11 | 121 (3) |
C14—C15—H15 | 119.8 | O61—C201—H20D | 109.5 |
C10—C15—H15 | 119.8 | O61—C201—H20E | 109.5 |
O4—C16—N3 | 123.1 (3) | H20D—C201—H20E | 109.5 |
O4—C16—C8 | 120.5 (3) | O61—C201—H20F | 109.5 |
N3—C16—C8 | 116.4 (3) | H20D—C201—H20F | 109.5 |
C16—N3—C17 | 122.9 (3) | H20E—C201—H20F | 109.5 |
C16—N3—H3 | 118 (4) | C211—O71—P11 | 117 (3) |
C17—N3—H3 | 118 (4) | O71—C211—H21D | 109.5 |
N3—C17—C18 | 112.3 (3) | O71—C211—H21E | 109.5 |
N3—C17—P1 | 109.5 (3) | H21D—C211—H21E | 109.5 |
C18—C17—P1 | 110.4 (3) | O71—C211—H21F | 109.5 |
N3—C17—H17 | 108.2 | H21D—C211—H21F | 109.5 |
C18—C17—H17 | 108.2 | H21E—C211—H21F | 109.5 |
| | | |
C3—C1—O1—C5 | −61.7 (5) | C8—C16—N3—C17 | 179.2 (3) |
C4—C1—O1—C5 | 63.1 (5) | C16—N3—C17—C18 | 136.7 (4) |
C2—C1—O1—C5 | −179.5 (4) | C16—N3—C17—P1 | −100.4 (4) |
C1—O1—C5—O2 | 0.1 (6) | N3—C17—C18—C19 | −72.2 (5) |
C1—O1—C5—N1 | 177.8 (3) | P1—C17—C18—C19 | 165.3 (3) |
O2—C5—N1—C6 | −7.9 (6) | N3—C17—P1—O5 | −76.7 (3) |
O1—C5—N1—C6 | 174.3 (3) | C18—C17—P1—O5 | 47.4 (3) |
C5—N1—C6—C7 | −89.8 (4) | N3—C17—P1—O6 | 50.7 (3) |
N1—C6—C7—O3 | 13.6 (6) | C18—C17—P1—O6 | 174.8 (3) |
N1—C6—C7—N2 | −168.3 (3) | N3—C17—P1—O7 | 157.7 (3) |
O3—C7—N2—C8 | 9.8 (5) | C18—C17—P1—O7 | −78.2 (3) |
C6—C7—N2—C8 | −168.4 (3) | O5—P1—O6—C20 | 31.0 (4) |
C7—N2—C8—C9 | −124.7 (4) | O7—P1—O6—C20 | 157.6 (4) |
C7—N2—C8—C16 | 54.3 (4) | C17—P1—O6—C20 | −96.8 (4) |
N2—C8—C9—C10 | 3.1 (7) | O5—P1—O7—C21 | 51.5 (5) |
C16—C8—C9—C10 | −175.9 (4) | O6—P1—O7—C21 | −73.4 (4) |
C8—C9—C10—C11 | 154.2 (4) | C17—P1—O7—C21 | 175.9 (4) |
C8—C9—C10—C15 | −24.2 (7) | N31—C171—C181—C191 | 46 (12) |
C15—C10—C11—C12 | 0.4 (7) | P11—C171—C181—C191 | 169 (9) |
C9—C10—C11—C12 | −178.1 (4) | N31—C171—P11—O51 | 67 (4) |
C10—C11—C12—C13 | −1.6 (8) | C181—C171—P11—O51 | −57 (6) |
C11—C12—C13—C14 | 1.3 (8) | N31—C171—P11—O61 | −62 (4) |
C12—C13—C14—C15 | 0.2 (7) | C181—C171—P11—O61 | 174 (6) |
C13—C14—C15—C10 | −1.4 (7) | N31—C171—P11—O71 | −171 (4) |
C11—C10—C15—C14 | 1.1 (6) | C181—C171—P11—O71 | 65 (6) |
C9—C10—C15—C14 | 179.4 (4) | O51—P11—O61—C201 | 68 (7) |
C9—C8—C16—O4 | 30.7 (5) | O71—P11—O61—C201 | −58 (7) |
N2—C8—C16—O4 | −148.4 (3) | C171—P11—O61—C201 | −163 (6) |
C9—C8—C16—N3 | −148.6 (4) | O51—P11—O71—C211 | −41 (7) |
N2—C8—C16—N3 | 32.3 (5) | O61—P11—O71—C211 | 85 (6) |
O4—C16—N3—C17 | 0.0 (6) | C171—P11—O71—C211 | −163 (6) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O5i | 0.87 (5) | 2.04 (5) | 2.830 (5) | 152 (4) |
N2—H2···O4ii | 0.81 (5) | 2.21 (5) | 2.942 (4) | 149 (4) |
N3—H3···O3ii | 0.74 (5) | 2.23 (5) | 2.955 (4) | 168 (5) |
C3—H3C···O2 | 0.98 | 2.40 | 2.987 (6) | 118 |
C6—H6A···O4ii | 0.99 | 2.53 | 3.210 (5) | 126 |
C9—H9···O4 | 0.95 | 2.48 | 2.825 (5) | 101 |
C15—H15···O4ii | 0.95 | 2.59 | 3.537 (5) | 173 |
C17—H17···O4 | 1.00 | 2.44 | 2.825 (5) | 103 |
C20—H20C···O5 | 0.98 | 2.51 | 3.001 (7) | 111 |
Symmetry codes: (i) x−1/2, −y+3/2, z; (ii) x+1/2, −y+3/2, z. |
(II) Diethyl (4-{[
tert-butoxycarbonylglycyl-
α,
β-(
Z)-dehydrophenylalanyl]amino}butyl)phosphonate
propan-2-ol monosolvate 0.122-hydrate
top
Crystal data top
C24H38N3O7P·C3H8O·0.122H2O | Z = 2 |
Mr = 573.80 | F(000) = 618.4 |
Triclinic, P1 | Dx = 1.209 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.131 (4) Å | Cell parameters from 12025 reflections |
b = 12.866 (5) Å | θ = 2–32° |
c = 13.368 (5) Å | µ = 0.14 mm−1 |
α = 68.90 (4)° | T = 110 K |
β = 75.94 (4)° | Needle, colourless |
γ = 84.11 (4)° | 0.44 × 0.08 × 0.07 mm |
V = 1576.7 (11) Å3 | |
Data collection top
Oxford Xcalibur PX κ-geometry diffractometer with CCD area detector | 5951 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.034 |
Graphite monochromator | θmax = 32.6°, θmin = 2.5° |
ω and ϕ scans | h = −15→14 |
23109 measured reflections | k = −15→19 |
10752 independent reflections | l = −18→20 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | w = 1/[σ2(Fo2) + (0.031P)2] where P = (Fo2 + 2Fc2)/3 |
10752 reflections | (Δ/σ)max < 0.001 |
406 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.45 e Å−3 |
Crystal data top
C24H38N3O7P·C3H8O·0.122H2O | γ = 84.11 (4)° |
Mr = 573.80 | V = 1576.7 (11) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.131 (4) Å | Mo Kα radiation |
b = 12.866 (5) Å | µ = 0.14 mm−1 |
c = 13.368 (5) Å | T = 110 K |
α = 68.90 (4)° | 0.44 × 0.08 × 0.07 mm |
β = 75.94 (4)° | |
Data collection top
Oxford Xcalibur PX κ-geometry diffractometer with CCD area detector | 5951 reflections with I > 2σ(I) |
23109 measured reflections | Rint = 0.034 |
10752 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.35 e Å−3 |
10752 reflections | Δρmin = −0.45 e Å−3 |
406 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R-factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.88289 (12) | 0.83953 (9) | 0.49438 (10) | 0.0223 (3) | |
C2 | 0.78410 (14) | 0.89598 (10) | 0.56612 (11) | 0.0315 (3) | |
H2A | 0.7632 | 0.8444 | 0.6423 | 0.047* | |
H2B | 0.7000 | 0.9168 | 0.5392 | 0.047* | |
H2C | 0.8258 | 0.9629 | 0.5629 | 0.047* | |
C3 | 1.00949 (13) | 0.79835 (10) | 0.53939 (11) | 0.0284 (3) | |
H3A | 1.0730 | 0.7649 | 0.4909 | 0.043* | |
H3B | 0.9844 | 0.7424 | 0.6132 | 0.043* | |
H3C | 1.0529 | 0.8611 | 0.5432 | 0.043* | |
C4 | 0.91378 (15) | 0.91661 (10) | 0.37548 (11) | 0.0321 (3) | |
H4A | 0.9774 | 0.8793 | 0.3306 | 0.048* | |
H4B | 0.9547 | 0.9848 | 0.3699 | 0.048* | |
H4C | 0.8292 | 0.9355 | 0.3490 | 0.048* | |
O1 | 0.80483 (8) | 0.74312 (6) | 0.50807 (7) | 0.02299 (19) | |
O2 | 0.96637 (9) | 0.68231 (7) | 0.38784 (7) | 0.0276 (2) | |
C5 | 0.86125 (12) | 0.66988 (9) | 0.45724 (10) | 0.0204 (3) | |
N1 | 0.78111 (11) | 0.58026 (8) | 0.49455 (9) | 0.0231 (2) | |
H1 | 0.7129 (14) | 0.5793 (11) | 0.5424 (11) | 0.028* | |
C6 | 0.82078 (14) | 0.48688 (10) | 0.45732 (10) | 0.0269 (3) | |
H6A | 0.7880 | 0.4179 | 0.5192 | 0.032* | |
H6B | 0.9214 | 0.4821 | 0.4391 | 0.032* | |
C7 | 0.77005 (13) | 0.48942 (10) | 0.35906 (10) | 0.0226 (3) | |
O3 | 0.80630 (9) | 0.41841 (7) | 0.31670 (7) | 0.0312 (2) | |
N2 | 0.68531 (11) | 0.57523 (8) | 0.31986 (8) | 0.0204 (2) | |
H2 | 0.6524 (13) | 0.6169 (10) | 0.3554 (10) | 0.024* | |
C8 | 0.61936 (12) | 0.57743 (9) | 0.23755 (9) | 0.0193 (2) | |
C9 | 0.61443 (12) | 0.66722 (10) | 0.14831 (9) | 0.0221 (3) | |
H9 | 0.5612 | 0.6595 | 0.1019 | 0.027* | |
C10 | 0.67873 (13) | 0.77603 (10) | 0.11089 (10) | 0.0241 (3) | |
C11 | 0.63240 (14) | 0.86320 (10) | 0.02841 (11) | 0.0317 (3) | |
H11 | 0.5612 | 0.8501 | −0.0003 | 0.038* | |
C12 | 0.68754 (16) | 0.96818 (11) | −0.01250 (12) | 0.0408 (4) | |
H12 | 0.6544 | 1.0260 | −0.0689 | 0.049* | |
C13 | 0.79096 (16) | 0.98913 (12) | 0.02853 (12) | 0.0425 (4) | |
H13 | 0.8284 | 1.0614 | 0.0012 | 0.051* | |
C14 | 0.83930 (15) | 0.90385 (12) | 0.10965 (12) | 0.0399 (4) | |
H14 | 0.9112 | 0.9176 | 0.1373 | 0.048* | |
C15 | 0.78402 (14) | 0.79865 (11) | 0.15108 (11) | 0.0310 (3) | |
H15 | 0.8178 | 0.7412 | 0.2073 | 0.037* | |
C16 | 0.53710 (12) | 0.47600 (9) | 0.26615 (10) | 0.0210 (3) | |
O4 | 0.48435 (9) | 0.42379 (7) | 0.36352 (6) | 0.0252 (2) | |
N3 | 0.52032 (11) | 0.44868 (8) | 0.18258 (8) | 0.0251 (2) | |
H3 | 0.5651 (14) | 0.4803 (11) | 0.1194 (11) | 0.030* | |
C17 | 0.43626 (13) | 0.35517 (10) | 0.19976 (10) | 0.0265 (3) | |
H17 | 0.4060 | 0.3148 | 0.2806 | 0.032* | |
C18 | 0.51460 (14) | 0.27329 (11) | 0.14702 (12) | 0.0338 (3) | |
H18A | 0.5296 | 0.3088 | 0.0661 | 0.041* | |
H18B | 0.4578 | 0.2071 | 0.1693 | 0.041* | |
C19 | 0.65442 (19) | 0.23403 (14) | 0.17748 (16) | 0.0320 (4) | 0.876 (3) |
H19A | 0.6967 | 0.1802 | 0.1411 | 0.038* | 0.876 (3) |
H19B | 0.7148 | 0.2990 | 0.1485 | 0.038* | 0.876 (3) |
C20 | 0.64482 (18) | 0.18009 (13) | 0.29977 (14) | 0.0402 (5) | 0.876 (3) |
H20A | 0.7357 | 0.1556 | 0.3133 | 0.060* | 0.876 (3) |
H20B | 0.5851 | 0.1157 | 0.3292 | 0.060* | 0.876 (3) |
H20C | 0.6074 | 0.2341 | 0.3361 | 0.060* | 0.876 (3) |
C19A | 0.5932 (18) | 0.2156 (12) | 0.2239 (13) | 0.046 (4)* | 0.124 (3) |
H19C | 0.5358 | 0.1741 | 0.2964 | 0.055* | 0.124 (3) |
H19D | 0.6534 | 0.2660 | 0.2328 | 0.055* | 0.124 (3) |
C20A | 0.6698 (13) | 0.1412 (11) | 0.1703 (10) | 0.045 (4)* | 0.124 (3) |
H20D | 0.7522 | 0.1149 | 0.1988 | 0.068* | 0.124 (3) |
H20E | 0.6953 | 0.1812 | 0.0908 | 0.068* | 0.124 (3) |
H20F | 0.6138 | 0.0774 | 0.1851 | 0.068* | 0.124 (3) |
P1 | 0.28819 (4) | 0.41540 (3) | 0.14543 (3) | 0.02698 (9) | |
O5 | 0.31962 (9) | 0.49069 (7) | 0.03001 (7) | 0.0318 (2) | |
O6 | 0.20563 (9) | 0.30975 (7) | 0.16752 (8) | 0.0358 (2) | |
C21 | 0.0785 (2) | 0.32298 (16) | 0.12818 (17) | 0.0359 (5) | 0.878 (3) |
H21A | 0.0938 | 0.3694 | 0.0492 | 0.043* | 0.878 (3) |
H21B | 0.0065 | 0.3589 | 0.1702 | 0.043* | 0.878 (3) |
C22 | 0.03778 (15) | 0.20675 (13) | 0.14607 (13) | 0.0433 (4) | 0.878 (3) |
H22A | −0.0465 | 0.2107 | 0.1212 | 0.065* | 0.878 (3) |
H22B | 0.0233 | 0.1619 | 0.2245 | 0.065* | 0.878 (3) |
H22C | 0.1102 | 0.1723 | 0.1042 | 0.065* | 0.878 (3) |
C21A | 0.1268 (18) | 0.3010 (14) | 0.1041 (15) | 0.044 (5)* | 0.122 (3) |
H21C | 0.1869 | 0.2997 | 0.0340 | 0.052* | 0.122 (3) |
H21D | 0.0697 | 0.3695 | 0.0864 | 0.052* | 0.122 (3) |
C22A | 0.03778 (15) | 0.20675 (13) | 0.14607 (13) | 0.0433 (4) | 0.122 (3) |
H22D | −0.0139 | 0.2112 | 0.0914 | 0.065* | 0.122 (3) |
H22E | −0.0254 | 0.2075 | 0.2142 | 0.065* | 0.122 (3) |
H22F | 0.0922 | 0.1376 | 0.1611 | 0.065* | 0.122 (3) |
O7 | 0.20462 (10) | 0.47239 (8) | 0.22701 (7) | 0.0373 (2) | |
C23 | 0.1966 (4) | 0.5895 (3) | 0.2029 (3) | 0.0407 (7) | 0.55331 |
H23A | 0.2866 | 0.6223 | 0.1615 | 0.049* | 0.55341 |
H23B | 0.1725 | 0.6053 | 0.2724 | 0.049* | 0.55341 |
C24 | 0.0926 (4) | 0.6419 (3) | 0.1366 (3) | 0.0600 (10) | 0.55341 |
H24A | 0.0886 | 0.7224 | 0.1213 | 0.090* | 0.55341 |
H24B | 0.0034 | 0.6100 | 0.1779 | 0.090* | 0.55341 |
H24C | 0.1174 | 0.6275 | 0.0672 | 0.090* | 0.55341 |
C23A | 0.1238 (5) | 0.5781 (4) | 0.1930 (4) | 0.0488 (11) | 0.44659 |
H23C | 0.0902 | 0.5835 | 0.1276 | 0.059* | 0.44659 |
H23D | 0.0438 | 0.5767 | 0.2532 | 0.059* | 0.44659 |
C24A | 0.2058 (5) | 0.6767 (4) | 0.1669 (5) | 0.0849 (17) | 0.44659 |
H24D | 0.1500 | 0.7444 | 0.1447 | 0.127* | 0.44659 |
H24E | 0.2844 | 0.6789 | 0.1066 | 0.127* | 0.44659 |
H24F | 0.2376 | 0.6724 | 0.2320 | 0.127* | 0.44659 |
C31 | 0.59945 (14) | 0.21126 (11) | 0.58563 (12) | 0.0336 (3) | |
H31A | 0.6728 | 0.2132 | 0.5197 | 0.040* | |
C32 | 0.66023 (17) | 0.17570 (14) | 0.68502 (12) | 0.0535 (5) | |
H32A | 0.7357 | 0.2246 | 0.6711 | 0.080* | |
H32B | 0.6941 | 0.0987 | 0.7003 | 0.080* | |
H32C | 0.5906 | 0.1806 | 0.7485 | 0.080* | |
C33 | 0.48880 (16) | 0.13581 (13) | 0.59736 (17) | 0.0589 (5) | |
H33A | 0.4507 | 0.1642 | 0.5316 | 0.088* | |
H33B | 0.4169 | 0.1334 | 0.6622 | 0.088* | |
H33C | 0.5265 | 0.0606 | 0.6060 | 0.088* | |
O31 | 0.54430 (10) | 0.32157 (7) | 0.57126 (7) | 0.0340 (2) | |
H31 | 0.5353 | 0.3528 | 0.5062 | 0.051* | |
O1W | 0.8669 (12) | 0.4473 (9) | 0.1058 (10) | 0.082 (5)* | 0.122 (3) |
H1W | 0.8100 | 0.4655 | 0.0647 | 0.124* | 0.122 (3) |
H2W | 0.8428 | 0.4771 | 0.1540 | 0.124* | 0.122 (3) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0260 (7) | 0.0164 (6) | 0.0258 (7) | −0.0055 (5) | −0.0051 (5) | −0.0077 (5) |
C2 | 0.0331 (8) | 0.0259 (7) | 0.0391 (8) | −0.0033 (6) | −0.0042 (6) | −0.0173 (6) |
C3 | 0.0292 (8) | 0.0282 (7) | 0.0315 (7) | −0.0054 (5) | −0.0074 (6) | −0.0131 (6) |
C4 | 0.0428 (9) | 0.0220 (7) | 0.0289 (7) | −0.0050 (6) | −0.0087 (6) | −0.0041 (6) |
O1 | 0.0233 (5) | 0.0206 (4) | 0.0283 (5) | −0.0042 (3) | −0.0038 (4) | −0.0125 (4) |
O2 | 0.0257 (5) | 0.0287 (5) | 0.0302 (5) | −0.0017 (4) | −0.0016 (4) | −0.0150 (4) |
C5 | 0.0251 (7) | 0.0195 (6) | 0.0198 (6) | 0.0011 (5) | −0.0120 (5) | −0.0063 (5) |
N1 | 0.0295 (6) | 0.0211 (5) | 0.0205 (5) | −0.0056 (5) | −0.0067 (4) | −0.0070 (4) |
C6 | 0.0398 (8) | 0.0177 (6) | 0.0287 (7) | −0.0006 (5) | −0.0198 (6) | −0.0065 (5) |
C7 | 0.0274 (7) | 0.0177 (6) | 0.0230 (6) | −0.0042 (5) | −0.0087 (5) | −0.0044 (5) |
O3 | 0.0388 (6) | 0.0274 (5) | 0.0362 (5) | 0.0071 (4) | −0.0168 (4) | −0.0180 (4) |
N2 | 0.0282 (6) | 0.0185 (5) | 0.0175 (5) | −0.0015 (4) | −0.0093 (4) | −0.0068 (4) |
C8 | 0.0213 (6) | 0.0217 (6) | 0.0164 (6) | −0.0022 (5) | −0.0048 (5) | −0.0073 (5) |
C9 | 0.0233 (7) | 0.0265 (7) | 0.0179 (6) | −0.0028 (5) | −0.0076 (5) | −0.0069 (5) |
C10 | 0.0283 (7) | 0.0233 (6) | 0.0190 (6) | −0.0033 (5) | −0.0037 (5) | −0.0055 (5) |
C11 | 0.0357 (8) | 0.0268 (7) | 0.0290 (7) | −0.0025 (6) | −0.0078 (6) | −0.0044 (6) |
C12 | 0.0524 (10) | 0.0253 (7) | 0.0356 (8) | −0.0016 (7) | −0.0085 (7) | −0.0005 (6) |
C13 | 0.0551 (10) | 0.0270 (8) | 0.0384 (9) | −0.0152 (7) | 0.0015 (7) | −0.0069 (7) |
C14 | 0.0464 (9) | 0.0411 (9) | 0.0311 (8) | −0.0227 (7) | −0.0043 (7) | −0.0080 (7) |
C15 | 0.0347 (8) | 0.0318 (7) | 0.0234 (7) | −0.0114 (6) | −0.0058 (6) | −0.0035 (6) |
C16 | 0.0231 (7) | 0.0216 (6) | 0.0187 (6) | −0.0008 (5) | −0.0066 (5) | −0.0060 (5) |
O4 | 0.0328 (5) | 0.0266 (5) | 0.0150 (4) | −0.0084 (4) | −0.0056 (4) | −0.0036 (4) |
N3 | 0.0332 (7) | 0.0279 (6) | 0.0150 (5) | −0.0139 (5) | −0.0040 (5) | −0.0056 (4) |
C17 | 0.0338 (8) | 0.0270 (7) | 0.0189 (6) | −0.0127 (5) | −0.0051 (5) | −0.0055 (5) |
C18 | 0.0428 (9) | 0.0320 (7) | 0.0322 (8) | −0.0083 (6) | −0.0110 (6) | −0.0139 (6) |
C19 | 0.0315 (10) | 0.0305 (9) | 0.0365 (10) | 0.0015 (7) | −0.0069 (8) | −0.0155 (8) |
C20 | 0.0415 (11) | 0.0338 (9) | 0.0441 (11) | 0.0060 (7) | −0.0157 (8) | −0.0099 (8) |
P1 | 0.0316 (2) | 0.03067 (19) | 0.01837 (17) | −0.01066 (15) | −0.00276 (14) | −0.00730 (14) |
O5 | 0.0370 (6) | 0.0356 (5) | 0.0189 (5) | −0.0083 (4) | −0.0009 (4) | −0.0063 (4) |
O6 | 0.0382 (6) | 0.0365 (5) | 0.0338 (5) | −0.0163 (4) | −0.0143 (4) | −0.0051 (4) |
C21 | 0.0274 (11) | 0.0446 (11) | 0.0392 (11) | −0.0054 (9) | −0.0124 (9) | −0.0142 (9) |
C22 | 0.0361 (9) | 0.0550 (10) | 0.0447 (9) | −0.0180 (7) | −0.0050 (7) | −0.0221 (8) |
C22A | 0.0361 (9) | 0.0550 (10) | 0.0447 (9) | −0.0180 (7) | −0.0050 (7) | −0.0221 (8) |
O7 | 0.0439 (6) | 0.0421 (6) | 0.0235 (5) | −0.0004 (5) | −0.0016 (4) | −0.0126 (4) |
C23 | 0.040 (2) | 0.0353 (19) | 0.0457 (19) | −0.0001 (16) | 0.0016 (17) | −0.0208 (14) |
C24 | 0.057 (2) | 0.056 (2) | 0.045 (2) | 0.0245 (18) | −0.0035 (17) | −0.0044 (17) |
C23A | 0.037 (3) | 0.071 (3) | 0.045 (3) | −0.006 (3) | 0.002 (2) | −0.034 (2) |
C24A | 0.078 (4) | 0.058 (3) | 0.097 (4) | −0.017 (3) | 0.031 (3) | −0.030 (3) |
C31 | 0.0298 (8) | 0.0356 (8) | 0.0332 (8) | 0.0028 (6) | −0.0030 (6) | −0.0128 (6) |
C32 | 0.0494 (11) | 0.0645 (11) | 0.0314 (9) | 0.0207 (8) | −0.0101 (7) | −0.0037 (8) |
C33 | 0.0382 (10) | 0.0448 (10) | 0.0931 (15) | −0.0039 (8) | −0.0012 (10) | −0.0312 (10) |
O31 | 0.0476 (6) | 0.0310 (5) | 0.0226 (5) | 0.0060 (4) | −0.0108 (4) | −0.0082 (4) |
Geometric parameters (Å, º) top
C1—O1 | 1.4715 (14) | C19—H19A | 0.9900 |
C1—C3 | 1.5145 (18) | C19—H19B | 0.9900 |
C1—C4 | 1.5149 (19) | C20—H20A | 0.9800 |
C1—C2 | 1.5279 (18) | C20—H20B | 0.9800 |
C2—H2A | 0.9800 | C20—H20C | 0.9800 |
C2—H2B | 0.9800 | C19A—C20A | 1.449 (19) |
C2—H2C | 0.9800 | C19A—H19C | 0.9900 |
C3—H3A | 0.9800 | C19A—H19D | 0.9900 |
C3—H3B | 0.9800 | C20A—H20D | 0.9800 |
C3—H3C | 0.9800 | C20A—H20E | 0.9800 |
C4—H4A | 0.9800 | C20A—H20F | 0.9800 |
C4—H4B | 0.9800 | P1—O5 | 1.4727 (12) |
C4—H4C | 0.9800 | P1—O7 | 1.5632 (12) |
O1—C5 | 1.3558 (15) | P1—O6 | 1.5681 (12) |
O2—C5 | 1.2118 (15) | O6—C21A | 1.336 (18) |
C5—N1 | 1.3486 (17) | O6—C21 | 1.478 (2) |
N1—C6 | 1.4447 (16) | C21—C22 | 1.511 (2) |
N1—H1 | 0.817 (13) | C21—H21A | 0.9900 |
C6—C7 | 1.5114 (17) | C21—H21B | 0.9900 |
C6—H6A | 0.9900 | C22—H22A | 0.9800 |
C6—H6B | 0.9900 | C22—H22B | 0.9800 |
C7—O3 | 1.2218 (14) | C22—H22C | 0.9800 |
C7—N2 | 1.3557 (17) | C21A—H21C | 0.9900 |
N2—C8 | 1.4103 (15) | C21A—H21D | 0.9900 |
N2—H2 | 0.833 (12) | O7—C23 | 1.421 (3) |
C8—C9 | 1.3360 (18) | O7—C23A | 1.494 (5) |
C8—C16 | 1.5009 (17) | C23—C24 | 1.493 (5) |
C9—C10 | 1.4694 (18) | C23—H23A | 0.9900 |
C9—H9 | 0.9500 | C23—H23B | 0.9900 |
C10—C11 | 1.3954 (19) | C24—H24A | 0.9800 |
C10—C15 | 1.4021 (18) | C24—H24B | 0.9800 |
C11—C12 | 1.3822 (19) | C24—H24C | 0.9800 |
C11—H11 | 0.9500 | C23A—C24A | 1.477 (6) |
C12—C13 | 1.384 (2) | C23A—H23C | 0.9900 |
C12—H12 | 0.9500 | C23A—H23D | 0.9900 |
C13—C14 | 1.382 (2) | C24A—H24D | 0.9800 |
C13—H13 | 0.9500 | C24A—H24E | 0.9800 |
C14—C15 | 1.3847 (19) | C24A—H24F | 0.9800 |
C14—H14 | 0.9500 | C31—O31 | 1.4340 (17) |
C15—H15 | 0.9500 | C31—C33 | 1.501 (2) |
C16—O4 | 1.2399 (15) | C31—C32 | 1.502 (2) |
C16—N3 | 1.3371 (15) | C31—H31A | 1.0000 |
N3—C17 | 1.4635 (16) | C32—H32A | 0.9800 |
N3—H3 | 0.830 (13) | C32—H32B | 0.9800 |
C17—C18 | 1.5257 (19) | C32—H32C | 0.9800 |
C17—P1 | 1.8066 (16) | C33—H33A | 0.9800 |
C17—H17 | 1.0000 | C33—H33B | 0.9800 |
C18—C19A | 1.403 (15) | C33—H33C | 0.9800 |
C18—C19 | 1.553 (2) | O31—H31 | 0.8400 |
C18—H18A | 0.9900 | O1W—H1W | 0.8497 |
C18—H18B | 0.9900 | O1W—H2W | 0.8400 |
C19—C20 | 1.511 (3) | | |
| | | |
O1—C1—C3 | 109.10 (10) | C17—C18—H18B | 108.6 |
O1—C1—C4 | 110.88 (10) | C19—C18—H18B | 108.6 |
C3—C1—C4 | 113.06 (11) | H18A—C18—H18B | 107.6 |
O1—C1—C2 | 102.19 (10) | C20—C19—C18 | 113.52 (16) |
C3—C1—C2 | 110.61 (11) | C20—C19—H19A | 108.9 |
C4—C1—C2 | 110.48 (11) | C18—C19—H19A | 108.9 |
C1—C2—H2A | 109.5 | C20—C19—H19B | 108.9 |
C1—C2—H2B | 109.5 | C18—C19—H19B | 108.9 |
H2A—C2—H2B | 109.5 | H19A—C19—H19B | 107.7 |
C1—C2—H2C | 109.5 | C18—C19A—C20A | 99.9 (10) |
H2A—C2—H2C | 109.5 | C18—C19A—H19C | 111.8 |
H2B—C2—H2C | 109.5 | C20A—C19A—H19C | 111.8 |
C1—C3—H3A | 109.5 | C18—C19A—H19D | 111.8 |
C1—C3—H3B | 109.5 | C20A—C19A—H19D | 111.8 |
H3A—C3—H3B | 109.5 | H19C—C19A—H19D | 109.5 |
C1—C3—H3C | 109.5 | C19A—C20A—H20D | 109.5 |
H3A—C3—H3C | 109.5 | C19A—C20A—H20E | 109.5 |
H3B—C3—H3C | 109.5 | H20D—C20A—H20E | 109.5 |
C1—C4—H4A | 109.5 | C19A—C20A—H20F | 109.5 |
C1—C4—H4B | 109.5 | H20D—C20A—H20F | 109.5 |
H4A—C4—H4B | 109.5 | H20E—C20A—H20F | 109.5 |
C1—C4—H4C | 109.5 | O5—P1—O7 | 113.76 (6) |
H4A—C4—H4C | 109.5 | O5—P1—O6 | 114.89 (6) |
H4B—C4—H4C | 109.5 | O7—P1—O6 | 105.36 (7) |
C5—O1—C1 | 119.87 (10) | O5—P1—C17 | 114.24 (7) |
O2—C5—N1 | 124.49 (12) | O7—P1—C17 | 104.99 (7) |
O2—C5—O1 | 126.00 (11) | O6—P1—C17 | 102.38 (6) |
N1—C5—O1 | 109.50 (11) | C21A—O6—P1 | 125.3 (7) |
C5—N1—C6 | 120.92 (12) | C21—O6—P1 | 119.62 (10) |
C5—N1—H1 | 117.0 (9) | O6—C21—C22 | 106.03 (15) |
C6—N1—H1 | 122.0 (9) | O6—C21—H21A | 110.5 |
N1—C6—C7 | 116.34 (11) | C22—C21—H21A | 110.5 |
N1—C6—H6A | 108.2 | O6—C21—H21B | 110.5 |
C7—C6—H6A | 108.2 | C22—C21—H21B | 110.5 |
N1—C6—H6B | 108.2 | H21A—C21—H21B | 108.7 |
C7—C6—H6B | 108.2 | O6—C21A—H21C | 107.7 |
H6A—C6—H6B | 107.4 | O6—C21A—H21D | 107.7 |
O3—C7—N2 | 122.36 (11) | H21C—C21A—H21D | 107.1 |
O3—C7—C6 | 121.08 (11) | C23—O7—P1 | 123.81 (15) |
N2—C7—C6 | 116.54 (11) | C23A—O7—P1 | 123.98 (19) |
C7—N2—C8 | 120.66 (10) | O7—C23—C24 | 110.9 (3) |
C7—N2—H2 | 120.6 (9) | O7—C23—H23A | 109.5 |
C8—N2—H2 | 116.2 (9) | C24—C23—H23A | 109.5 |
C9—C8—N2 | 123.38 (11) | O7—C23—H23B | 109.5 |
C9—C8—C16 | 121.84 (11) | C24—C23—H23B | 109.5 |
N2—C8—C16 | 114.20 (10) | H23A—C23—H23B | 108.0 |
C8—C9—C10 | 129.91 (11) | C23—C24—H24A | 109.5 |
C8—C9—H9 | 115.0 | C23—C24—H24B | 109.5 |
C10—C9—H9 | 115.0 | H24A—C24—H24B | 109.5 |
C11—C10—C15 | 117.50 (12) | C23—C24—H24C | 109.5 |
C11—C10—C9 | 117.55 (12) | H24A—C24—H24C | 109.5 |
C15—C10—C9 | 124.95 (12) | H24B—C24—H24C | 109.5 |
C12—C11—C10 | 121.60 (13) | C24A—C23A—O7 | 111.6 (5) |
C12—C11—H11 | 119.2 | C24A—C23A—H23C | 109.3 |
C10—C11—H11 | 119.2 | O7—C23A—H23C | 109.3 |
C11—C12—C13 | 120.10 (14) | C24A—C23A—H23D | 109.3 |
C11—C12—H12 | 120.0 | O7—C23A—H23D | 109.3 |
C13—C12—H12 | 120.0 | H23C—C23A—H23D | 108.0 |
C14—C13—C12 | 119.35 (14) | C23A—C24A—H24D | 109.5 |
C14—C13—H13 | 120.3 | C23A—C24A—H24E | 109.5 |
C12—C13—H13 | 120.3 | H24D—C24A—H24E | 109.5 |
C13—C14—C15 | 120.72 (14) | C23A—C24A—H24F | 109.5 |
C13—C14—H14 | 119.6 | H24D—C24A—H24F | 109.5 |
C15—C14—H14 | 119.6 | H24E—C24A—H24F | 109.5 |
C14—C15—C10 | 120.73 (13) | O31—C31—C33 | 109.29 (12) |
C14—C15—H15 | 119.6 | O31—C31—C32 | 107.05 (12) |
C10—C15—H15 | 119.6 | C33—C31—C32 | 112.84 (14) |
O4—C16—N3 | 122.86 (11) | O31—C31—H31A | 109.2 |
O4—C16—C8 | 120.04 (11) | C33—C31—H31A | 109.2 |
N3—C16—C8 | 117.06 (11) | C32—C31—H31A | 109.2 |
C16—N3—C17 | 122.08 (11) | C31—C32—H32A | 109.5 |
C16—N3—H3 | 120.0 (9) | C31—C32—H32B | 109.5 |
C17—N3—H3 | 117.6 (9) | H32A—C32—H32B | 109.5 |
N3—C17—C18 | 111.88 (11) | C31—C32—H32C | 109.5 |
N3—C17—P1 | 106.27 (9) | H32A—C32—H32C | 109.5 |
C18—C17—P1 | 112.93 (9) | H32B—C32—H32C | 109.5 |
N3—C17—H17 | 108.5 | C31—C33—H33A | 109.5 |
C18—C17—H17 | 108.5 | C31—C33—H33B | 109.5 |
P1—C17—H17 | 108.5 | H33A—C33—H33B | 109.5 |
C19A—C18—C17 | 100.9 (6) | C31—C33—H33C | 109.5 |
C17—C18—C19 | 114.55 (11) | H33A—C33—H33C | 109.5 |
C19A—C18—H18A | 137.1 | H33B—C33—H33C | 109.5 |
C17—C18—H18A | 108.6 | C31—O31—H31 | 109.5 |
C19—C18—H18A | 108.6 | H1W—O1W—H2W | 109.0 |
C19A—C18—H18B | 91.1 | | |
| | | |
C3—C1—O1—C5 | −61.59 (13) | C16—N3—C17—P1 | 110.64 (12) |
C4—C1—O1—C5 | 63.55 (14) | N3—C17—C18—C19A | 77.6 (7) |
C2—C1—O1—C5 | −178.71 (10) | P1—C17—C18—C19A | −162.5 (7) |
C1—O1—C5—O2 | −10.36 (17) | N3—C17—C18—C19 | 50.86 (16) |
C1—O1—C5—N1 | 170.52 (10) | P1—C17—C18—C19 | 170.72 (11) |
O2—C5—N1—C6 | 3.66 (18) | C19A—C18—C19—C20 | −9.2 (12) |
O1—C5—N1—C6 | −177.20 (10) | C17—C18—C19—C20 | 57.30 (17) |
C5—N1—C6—C7 | −92.40 (15) | C17—C18—C19A—C20A | −178.1 (8) |
N1—C6—C7—O3 | 174.63 (11) | C19—C18—C19A—C20A | −56.3 (11) |
N1—C6—C7—N2 | −4.09 (17) | N3—C17—P1—O5 | 55.17 (10) |
O3—C7—N2—C8 | 9.25 (18) | C18—C17—P1—O5 | −67.86 (10) |
C6—C7—N2—C8 | −172.05 (10) | N3—C17—P1—O7 | −70.14 (10) |
C7—N2—C8—C9 | −133.21 (13) | C18—C17—P1—O7 | 166.83 (9) |
C7—N2—C8—C16 | 55.42 (15) | N3—C17—P1—O6 | −179.99 (8) |
N2—C8—C9—C10 | 4.5 (2) | C18—C17—P1—O6 | 56.98 (10) |
C16—C8—C9—C10 | 175.19 (12) | O5—P1—O6—C21A | −23.1 (10) |
C8—C9—C10—C11 | −165.79 (13) | O7—P1—O6—C21A | 102.9 (10) |
C8—C9—C10—C15 | 14.8 (2) | C17—P1—O6—C21A | −147.5 (10) |
C15—C10—C11—C12 | −0.1 (2) | O5—P1—O6—C21 | −51.83 (14) |
C9—C10—C11—C12 | −179.50 (12) | O7—P1—O6—C21 | 74.19 (13) |
C10—C11—C12—C13 | −0.2 (2) | C17—P1—O6—C21 | −176.24 (12) |
C11—C12—C13—C14 | 0.7 (2) | C21A—O6—C21—C22 | 60.4 (18) |
C12—C13—C14—C15 | −0.9 (2) | P1—O6—C21—C22 | 171.12 (11) |
C13—C14—C15—C10 | 0.6 (2) | O5—P1—O7—C23 | −19.8 (2) |
C11—C10—C15—C14 | −0.1 (2) | O6—P1—O7—C23 | −146.5 (2) |
C9—C10—C15—C14 | 179.25 (13) | C17—P1—O7—C23 | 105.9 (2) |
C9—C8—C16—O4 | −141.68 (12) | O5—P1—O7—C23A | 19.6 (2) |
N2—C8—C16—O4 | 29.85 (16) | O6—P1—O7—C23A | −107.1 (2) |
C9—C8—C16—N3 | 35.90 (17) | C17—P1—O7—C23A | 145.2 (2) |
N2—C8—C16—N3 | −152.57 (11) | C23A—O7—C23—C24 | −19.4 (4) |
O4—C16—N3—C17 | 0.82 (19) | P1—O7—C23—C24 | 82.1 (3) |
C8—C16—N3—C17 | −176.69 (11) | C23—O7—C23A—C24A | 10.3 (4) |
C16—N3—C17—C18 | −125.68 (13) | P1—O7—C23A—C24A | −90.7 (4) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O4i | 0.817 (13) | 2.083 (14) | 2.883 (2) | 166.5 (13) |
N2—H2···O31i | 0.833 (12) | 2.201 (13) | 2.8991 (19) | 141.3 (11) |
N3—H3···O5ii | 0.830 (13) | 1.978 (14) | 2.782 (2) | 162.8 (12) |
O31—H31···O4 | 0.84 | 1.97 | 2.7993 (18) | 171 |
O1W—H2W···O3 | 0.84 | 1.98 | 2.630 (12) | 134 |
O1W—H1W···O5ii | 0.85 | 1.95 | 2.795 (12) | 179 |
C3—H3A···O2 | 0.98 | 2.49 | 3.0440 (18) | 115 |
C4—H4A···O2 | 0.98 | 2.38 | 2.9585 (19) | 118 |
C15—H15···N2 | 0.95 | 2.43 | 3.029 (2) | 121 |
C17—H17···O4 | 1.00 | 2.37 | 2.7943 (17) | 105 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z. |
(III)
tert-butoxycarbonylglycyl-
α,
β-(
Z)-
dehydrophenylalanyl-˘1-aminobutyl)phosphonic acid diethyl ester ethanol water
solvate
top
Crystal data top
C24H38N3O7P·C2H6O·0.076H2O | Z = 2 |
Mr = 558.97 | F(000) = 601.5 |
Triclinic, P1 | Dx = 1.189 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.047 (3) Å | Cell parameters from 16877 reflections |
b = 12.667 (4) Å | θ = 2–35° |
c = 13.499 (4) Å | µ = 0.14 mm−1 |
α = 69.16 (4)° | T = 180 K |
β = 76.54 (4)° | Parallelepiped, colourless |
γ = 83.89 (4)° | 0.47 × 0.22 × 0.21 mm |
V = 1560.9 (10) Å3 | |
Data collection top
Oxford Xcalibur PX κ-geometry diffractometer with CCD area detector | 7581 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.017 |
Graphite monochromator | θmax = 35.0°, θmin = 2.7° |
ω and ϕ scans | h = −13→14 |
21697 measured reflections | k = −17→20 |
11597 independent reflections | l = −21→19 |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.131 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.072P)2] where P = (Fo2 + 2Fc2)/3 |
11597 reflections | (Δ/σ)max < 0.001 |
380 parameters | Δρmax = 0.42 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
Crystal data top
C24H38N3O7P·C2H6O·0.076H2O | γ = 83.89 (4)° |
Mr = 558.97 | V = 1560.9 (10) Å3 |
Triclinic, P1 | Z = 2 |
a = 10.047 (3) Å | Mo Kα radiation |
b = 12.667 (4) Å | µ = 0.14 mm−1 |
c = 13.499 (4) Å | T = 180 K |
α = 69.16 (4)° | 0.47 × 0.22 × 0.21 mm |
β = 76.54 (4)° | |
Data collection top
Oxford Xcalibur PX κ-geometry diffractometer with CCD area detector | 7581 reflections with I > 2σ(I) |
21697 measured reflections | Rint = 0.017 |
11597 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.131 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.42 e Å−3 |
11597 reflections | Δρmin = −0.25 e Å−3 |
380 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor
wR and goodness of fit S are based on F2, conventional
R-factors R are based on F, with F set to zero for
negative F2. The threshold expression of F2 >
σ(F2) is used only for calculating R-factors(gt) etc.
and is not relevant to the choice of reflections for refinement.
R-factors based on F2 are statistically about twice as large
as those based on F, and R-factors based on ALL data will be
even larger. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.87156 (12) | 0.83991 (8) | 0.49273 (9) | 0.0337 (2) | |
C2 | 0.77336 (15) | 0.89573 (10) | 0.56450 (11) | 0.0499 (3) | |
H2A | 0.7592 | 0.8447 | 0.6400 | 0.075* | |
H2B | 0.6855 | 0.9122 | 0.5416 | 0.075* | |
H2C | 0.8120 | 0.9663 | 0.5582 | 0.075* | |
C3 | 1.00486 (15) | 0.80511 (11) | 0.53146 (12) | 0.0511 (3) | |
H3A | 1.0714 | 0.7796 | 0.4784 | 0.077* | |
H3B | 0.9885 | 0.7434 | 0.6015 | 0.077* | |
H3C | 1.0409 | 0.8698 | 0.5396 | 0.077* | |
C4 | 0.89389 (18) | 0.91542 (11) | 0.37463 (11) | 0.0572 (4) | |
H4A | 0.9599 | 0.8787 | 0.3304 | 0.086* | |
H4B | 0.9294 | 0.9878 | 0.3665 | 0.086* | |
H4C | 0.8068 | 0.9285 | 0.3507 | 0.086* | |
O1 | 0.79888 (8) | 0.73782 (6) | 0.51125 (6) | 0.03548 (17) | |
O2 | 0.95622 (8) | 0.67825 (7) | 0.38888 (6) | 0.03872 (19) | |
C5 | 0.85424 (11) | 0.66428 (8) | 0.46007 (8) | 0.0282 (2) | |
N1 | 0.77711 (10) | 0.57145 (7) | 0.49982 (7) | 0.03015 (18) | |
H1 | 0.7089 (14) | 0.5656 (10) | 0.5508 (10) | 0.036* | |
C6 | 0.81542 (13) | 0.47790 (8) | 0.46094 (8) | 0.0340 (2) | |
H6A | 0.7783 | 0.4082 | 0.5195 | 0.041* | |
H6B | 0.9165 | 0.4694 | 0.4467 | 0.041* | |
C7 | 0.76828 (11) | 0.48629 (8) | 0.35917 (8) | 0.0286 (2) | |
O3 | 0.80442 (10) | 0.41511 (7) | 0.31631 (7) | 0.0440 (2) | |
N2 | 0.68664 (9) | 0.57629 (7) | 0.31933 (6) | 0.02612 (17) | |
H2 | 0.6517 (13) | 0.6174 (10) | 0.3563 (9) | 0.031* | |
C8 | 0.62200 (10) | 0.57979 (8) | 0.23573 (7) | 0.02560 (19) | |
C9 | 0.61901 (11) | 0.67056 (9) | 0.14653 (7) | 0.0298 (2) | |
H9 | 0.5659 | 0.6630 | 0.0998 | 0.036* | |
C10 | 0.68509 (12) | 0.77982 (9) | 0.10977 (8) | 0.0319 (2) | |
C11 | 0.63968 (14) | 0.86821 (9) | 0.02642 (9) | 0.0409 (3) | |
H11 | 0.5691 | 0.8551 | −0.0037 | 0.049* | |
C12 | 0.69563 (16) | 0.97443 (10) | −0.01303 (11) | 0.0518 (3) | |
H12 | 0.6630 | 1.0333 | −0.0694 | 0.062* | |
C13 | 0.79850 (16) | 0.99482 (11) | 0.02932 (10) | 0.0516 (3) | |
H13 | 0.8365 | 1.0677 | 0.0028 | 0.062* | |
C14 | 0.84601 (16) | 0.90831 (11) | 0.11084 (10) | 0.0503 (3) | |
H14 | 0.9177 | 0.9220 | 0.1395 | 0.060* | |
C15 | 0.79046 (13) | 0.80187 (10) | 0.15127 (9) | 0.0409 (3) | |
H15 | 0.8240 | 0.7435 | 0.2075 | 0.049* | |
C16 | 0.53736 (10) | 0.47875 (8) | 0.26216 (7) | 0.02578 (19) | |
O4 | 0.48229 (8) | 0.42769 (6) | 0.35797 (5) | 0.03334 (17) | |
N3 | 0.52000 (9) | 0.45069 (7) | 0.17953 (6) | 0.02808 (18) | |
H3 | 0.5669 (13) | 0.4798 (10) | 0.1182 (10) | 0.034* | |
C17 | 0.43245 (11) | 0.35834 (8) | 0.19640 (7) | 0.0286 (2) | |
H17 | 0.4026 | 0.3182 | 0.2761 | 0.034* | |
C18 | 0.50870 (13) | 0.27315 (10) | 0.14465 (9) | 0.0384 (2) | |
H18A | 0.4486 | 0.2088 | 0.1636 | 0.046* | |
H18B | 0.5278 | 0.3098 | 0.0648 | 0.046* | |
C19 | 0.64300 (15) | 0.22817 (12) | 0.18016 (12) | 0.0503 (3) | |
H19A | 0.6865 | 0.1751 | 0.1424 | 0.060* | |
H19B | 0.7052 | 0.2921 | 0.1569 | 0.060* | |
C20 | 0.6282 (2) | 0.16846 (15) | 0.30059 (14) | 0.0712 (5) | |
H20A | 0.7185 | 0.1416 | 0.3169 | 0.107* | |
H20B | 0.5684 | 0.1040 | 0.3244 | 0.107* | |
H20C | 0.5883 | 0.2210 | 0.3388 | 0.107* | |
P1 | 0.28278 (3) | 0.42088 (2) | 0.142084 (19) | 0.02960 (7) | |
O5 | 0.31129 (8) | 0.49481 (7) | 0.02755 (5) | 0.03827 (19) | |
O6 | 0.19809 (9) | 0.31408 (7) | 0.16625 (7) | 0.0457 (2) | |
C21 | 0.07167 (19) | 0.32449 (16) | 0.12762 (16) | 0.0550 (4) | 0.924 (4) |
H21A | 0.0866 | 0.3699 | 0.0494 | 0.066* | 0.924 (4) |
H21B | −0.0009 | 0.3624 | 0.1676 | 0.066* | 0.924 (4) |
C22 | 0.03020 (17) | 0.20850 (15) | 0.14626 (15) | 0.0719 (5) | |
H22A | −0.0522 | 0.2130 | 0.1177 | 0.108* | |
H22B | 0.0111 | 0.1656 | 0.2242 | 0.108* | |
H22C | 0.1044 | 0.1705 | 0.1091 | 0.108* | |
C21A | 0.120 (3) | 0.292 (2) | 0.105 (2) | 0.056 (6)* | 0.076 (4) |
H21C | 0.0674 | 0.3630 | 0.0749 | 0.067* | 0.076 (4) |
H21D | 0.1839 | 0.2790 | 0.0424 | 0.067* | 0.076 (4) |
O7 | 0.20497 (10) | 0.48232 (7) | 0.22160 (6) | 0.0465 (2) | |
C23 | 0.1316 (2) | 0.58995 (16) | 0.18940 (15) | 0.0527 (5) | 0.868 (5) |
H23A | 0.0438 | 0.5867 | 0.2421 | 0.063* | 0.868 (5) |
H23B | 0.1106 | 0.6050 | 0.1174 | 0.063* | 0.868 (5) |
C24 | 0.2141 (2) | 0.68300 (18) | 0.1844 (2) | 0.0857 (9) | 0.868 (5) |
H24A | 0.1629 | 0.7549 | 0.1621 | 0.129* | 0.868 (5) |
H24B | 0.3006 | 0.6866 | 0.1317 | 0.129* | 0.868 (5) |
H24C | 0.2332 | 0.6689 | 0.2561 | 0.129* | 0.868 (5) |
C23A | 0.195 (2) | 0.5981 (14) | 0.1979 (13) | 0.069 (5)* | 0.132 (5) |
H23C | 0.2849 | 0.6311 | 0.1568 | 0.082* | 0.132 (5) |
H23D | 0.1729 | 0.6143 | 0.2665 | 0.082* | 0.132 (5) |
C24A | 0.0929 (19) | 0.6520 (15) | 0.1359 (14) | 0.087 (6)* | 0.132 (5) |
H24D | 0.0909 | 0.7336 | 0.1216 | 0.131* | 0.132 (5) |
H24E | 0.0030 | 0.6214 | 0.1769 | 0.131* | 0.132 (5) |
H24F | 0.1150 | 0.6379 | 0.0670 | 0.131* | 0.132 (5) |
O31 | 0.5212 (2) | 0.30183 (13) | 0.56798 (8) | 0.0519 (6) | 0.924 (6) |
H31 | 0.5121 | 0.3358 | 0.5039 | 0.078* | 0.924 (6) |
C31 | 0.56670 (19) | 0.18897 (13) | 0.58014 (12) | 0.0635 (4) | 0.924 (6) |
H31B | 0.6520 | 0.1888 | 0.5258 | 0.076* | 0.924 (6) |
H31C | 0.4965 | 0.1489 | 0.5674 | 0.076* | 0.924 (6) |
C32 | 0.5921 (2) | 0.13020 (15) | 0.68955 (13) | 0.0864 (7) | |
H32A | 0.6230 | 0.0522 | 0.6970 | 0.130* | |
H32B | 0.5074 | 0.1299 | 0.7432 | 0.130* | |
H32C | 0.6628 | 0.1692 | 0.7015 | 0.130* | |
O31A | 0.4590 (18) | 0.2669 (12) | 0.5744 (9) | 0.036 (4)* | 0.076 (6) |
H31A | 0.4900 | 0.3250 | 0.5228 | 0.054* | 0.076 (6) |
C31B | 0.56670 (19) | 0.18897 (13) | 0.58014 (12) | 0.0635 (4) | 0.076 (6) |
H31D | 0.6509 | 0.2282 | 0.5332 | 0.076* | 0.076 (6) |
H31F | 0.5484 | 0.1320 | 0.5507 | 0.076* | 0.076 (6) |
O1W | 0.889 (2) | 0.4733 (16) | 0.0989 (17) | 0.102 (8)* | 0.076 (4) |
H1W | 0.8628 | 0.4547 | 0.1673 | 0.153* | 0.076 (4) |
H2W | 0.8293 | 0.4826 | 0.0611 | 0.153* | 0.076 (4) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0395 (6) | 0.0257 (5) | 0.0367 (5) | −0.0054 (4) | −0.0049 (4) | −0.0122 (4) |
C2 | 0.0576 (9) | 0.0380 (6) | 0.0576 (7) | −0.0055 (6) | 0.0006 (6) | −0.0272 (6) |
C3 | 0.0509 (9) | 0.0454 (7) | 0.0692 (9) | −0.0054 (6) | −0.0234 (7) | −0.0261 (6) |
C4 | 0.0867 (12) | 0.0342 (6) | 0.0421 (7) | 0.0011 (6) | −0.0099 (7) | −0.0060 (5) |
O1 | 0.0348 (4) | 0.0347 (4) | 0.0413 (4) | −0.0079 (3) | 0.0004 (3) | −0.0215 (3) |
O2 | 0.0343 (5) | 0.0421 (4) | 0.0415 (4) | −0.0030 (3) | 0.0003 (3) | −0.0210 (3) |
C5 | 0.0308 (6) | 0.0298 (5) | 0.0281 (4) | 0.0013 (4) | −0.0110 (4) | −0.0123 (4) |
N1 | 0.0363 (5) | 0.0309 (4) | 0.0263 (4) | −0.0045 (4) | −0.0082 (3) | −0.0115 (3) |
C6 | 0.0479 (7) | 0.0263 (5) | 0.0338 (5) | 0.0030 (4) | −0.0216 (5) | −0.0105 (4) |
C7 | 0.0321 (6) | 0.0278 (5) | 0.0290 (4) | −0.0014 (4) | −0.0104 (4) | −0.0110 (4) |
O3 | 0.0522 (6) | 0.0446 (5) | 0.0492 (5) | 0.0145 (4) | −0.0226 (4) | −0.0298 (4) |
N2 | 0.0323 (5) | 0.0270 (4) | 0.0226 (3) | −0.0003 (3) | −0.0096 (3) | −0.0105 (3) |
C8 | 0.0264 (5) | 0.0307 (5) | 0.0214 (4) | −0.0016 (4) | −0.0059 (3) | −0.0101 (3) |
C9 | 0.0315 (6) | 0.0347 (5) | 0.0245 (4) | −0.0037 (4) | −0.0086 (4) | −0.0090 (4) |
C10 | 0.0370 (6) | 0.0320 (5) | 0.0247 (4) | −0.0039 (4) | −0.0055 (4) | −0.0071 (4) |
C11 | 0.0493 (8) | 0.0359 (6) | 0.0353 (5) | −0.0010 (5) | −0.0144 (5) | −0.0062 (4) |
C12 | 0.0668 (10) | 0.0351 (6) | 0.0437 (6) | 0.0000 (6) | −0.0103 (6) | −0.0029 (5) |
C13 | 0.0674 (10) | 0.0369 (6) | 0.0446 (7) | −0.0163 (6) | −0.0005 (6) | −0.0095 (5) |
C14 | 0.0576 (9) | 0.0519 (7) | 0.0401 (6) | −0.0242 (6) | −0.0076 (6) | −0.0093 (5) |
C15 | 0.0448 (7) | 0.0434 (6) | 0.0303 (5) | −0.0145 (5) | −0.0093 (5) | −0.0027 (4) |
C16 | 0.0268 (5) | 0.0305 (4) | 0.0212 (4) | −0.0024 (4) | −0.0051 (3) | −0.0098 (3) |
O4 | 0.0387 (4) | 0.0404 (4) | 0.0197 (3) | −0.0106 (3) | −0.0017 (3) | −0.0089 (3) |
N3 | 0.0303 (5) | 0.0362 (4) | 0.0189 (3) | −0.0095 (3) | −0.0018 (3) | −0.0105 (3) |
C17 | 0.0298 (5) | 0.0334 (5) | 0.0245 (4) | −0.0060 (4) | −0.0043 (4) | −0.0118 (4) |
C18 | 0.0407 (7) | 0.0404 (6) | 0.0408 (6) | −0.0010 (5) | −0.0078 (5) | −0.0226 (5) |
C19 | 0.0444 (8) | 0.0503 (7) | 0.0628 (8) | 0.0093 (6) | −0.0132 (6) | −0.0290 (6) |
C20 | 0.0671 (12) | 0.0713 (10) | 0.0716 (10) | 0.0286 (9) | −0.0263 (9) | −0.0212 (8) |
P1 | 0.02777 (15) | 0.03788 (14) | 0.02264 (11) | −0.00503 (10) | −0.00243 (9) | −0.01036 (10) |
O5 | 0.0358 (5) | 0.0519 (5) | 0.0220 (3) | −0.0024 (3) | −0.0018 (3) | −0.0088 (3) |
O6 | 0.0386 (5) | 0.0484 (5) | 0.0510 (5) | −0.0146 (4) | −0.0179 (4) | −0.0089 (4) |
C21 | 0.0339 (9) | 0.0702 (11) | 0.0725 (11) | −0.0054 (8) | −0.0195 (8) | −0.0320 (9) |
C22 | 0.0459 (9) | 0.0940 (13) | 0.0903 (12) | −0.0261 (8) | −0.0039 (8) | −0.0487 (10) |
C22A | 0.0459 (9) | 0.0940 (13) | 0.0903 (12) | −0.0261 (8) | −0.0039 (8) | −0.0487 (10) |
O7 | 0.0529 (6) | 0.0524 (5) | 0.0282 (4) | 0.0117 (4) | −0.0004 (3) | −0.0152 (3) |
C23 | 0.0475 (12) | 0.0611 (11) | 0.0508 (9) | 0.0169 (9) | −0.0087 (8) | −0.0271 (8) |
C24 | 0.0759 (16) | 0.0537 (12) | 0.1023 (17) | −0.0077 (10) | 0.0188 (12) | −0.0185 (11) |
O31 | 0.0659 (11) | 0.0550 (8) | 0.0320 (5) | 0.0163 (7) | −0.0118 (5) | −0.0157 (4) |
C31 | 0.0810 (12) | 0.0622 (9) | 0.0529 (8) | 0.0185 (8) | −0.0195 (8) | −0.0288 (7) |
C32 | 0.1257 (18) | 0.0748 (12) | 0.0534 (9) | 0.0465 (12) | −0.0269 (10) | −0.0240 (8) |
C31B | 0.0810 (12) | 0.0622 (9) | 0.0529 (8) | 0.0185 (8) | −0.0195 (8) | −0.0288 (7) |
C32B | 0.1257 (18) | 0.0748 (12) | 0.0534 (9) | 0.0465 (12) | −0.0269 (10) | −0.0240 (8) |
Geometric parameters (Å, º) top
C1—O1 | 1.4676 (13) | C18—H18A | 0.9900 |
C1—C3 | 1.5159 (19) | C18—H18B | 0.9900 |
C1—C4 | 1.5168 (18) | C19—C20 | 1.508 (2) |
C1—C2 | 1.5185 (17) | C19—H19A | 0.9900 |
C2—H2A | 0.9800 | C19—H19B | 0.9900 |
C2—H2B | 0.9800 | C20—H20A | 0.9800 |
C2—H2C | 0.9800 | C20—H20B | 0.9800 |
C3—H3A | 0.9800 | C20—H20C | 0.9800 |
C3—H3B | 0.9800 | P1—O5 | 1.4731 (11) |
C3—H3C | 0.9800 | P1—O7 | 1.5631 (11) |
C4—H4A | 0.9800 | P1—O6 | 1.5692 (11) |
C4—H4B | 0.9800 | O6—C21A | 1.38 (2) |
C4—H4C | 0.9800 | O6—C21 | 1.4582 (18) |
O1—C5 | 1.3502 (13) | C21—C22 | 1.488 (2) |
O2—C5 | 1.2098 (14) | C21—H21A | 0.9900 |
C5—N1 | 1.3501 (14) | C21—H21B | 0.9900 |
N1—C6 | 1.4420 (14) | C22—H22A | 0.9800 |
N1—H1 | 0.839 (13) | C22—H22B | 0.9800 |
C6—C7 | 1.5202 (14) | C22—H22C | 0.9800 |
C6—H6A | 0.9900 | C21A—H21C | 0.9900 |
C6—H6B | 0.9900 | C21A—H21D | 0.9900 |
C7—O3 | 1.2179 (13) | O7—C23A | 1.384 (17) |
C7—N2 | 1.3534 (15) | O7—C23 | 1.451 (2) |
N2—C8 | 1.4130 (12) | C23—C24 | 1.485 (3) |
N2—H2 | 0.841 (13) | C23—H23A | 0.9900 |
C8—C9 | 1.3405 (15) | C23—H23B | 0.9900 |
C8—C16 | 1.5014 (15) | C24—H24A | 0.9800 |
C9—C10 | 1.4683 (16) | C24—H24B | 0.9800 |
C9—H9 | 0.9500 | C24—H24C | 0.9800 |
C10—C11 | 1.4006 (17) | C23A—C24A | 1.44 (3) |
C10—C15 | 1.4011 (16) | C23A—H23C | 0.9900 |
C11—C12 | 1.3863 (18) | C23A—H23D | 0.9900 |
C11—H11 | 0.9500 | C24A—H24D | 0.9800 |
C12—C13 | 1.378 (2) | C24A—H24E | 0.9800 |
C12—H12 | 0.9500 | C24A—H24F | 0.9800 |
C13—C14 | 1.384 (2) | O31—C31 | 1.4171 (19) |
C13—H13 | 0.9500 | O31—H31 | 0.8400 |
C14—C15 | 1.3863 (17) | O31—H31A | 0.7065 |
C14—H14 | 0.9500 | C31—C32 | 1.467 (2) |
C15—H15 | 0.9500 | C31—H31B | 0.9900 |
C16—O4 | 1.2430 (13) | C31—H31C | 0.9900 |
C16—N3 | 1.3367 (12) | C32—H32A | 0.9800 |
N3—C17 | 1.4595 (14) | C32—H32B | 0.9800 |
N3—H3 | 0.826 (12) | C32—H32C | 0.9800 |
C17—C18 | 1.5332 (16) | O31A—H31 | 1.1058 |
C17—P1 | 1.8091 (13) | O31A—H31A | 0.8400 |
C17—H17 | 1.0000 | O1W—H1W | 0.8498 |
C18—C19 | 1.523 (2) | O1W—H2W | 0.8508 |
| | | |
O1—C1—C3 | 108.83 (9) | P1—C17—H17 | 108.5 |
O1—C1—C4 | 111.12 (10) | C19—C18—C17 | 113.63 (10) |
C3—C1—C4 | 112.25 (12) | C19—C18—H18A | 108.8 |
O1—C1—C2 | 102.33 (10) | C17—C18—H18A | 108.8 |
C3—C1—C2 | 110.81 (11) | C19—C18—H18B | 108.8 |
C4—C1—C2 | 111.06 (11) | C17—C18—H18B | 108.8 |
C1—C2—H2A | 109.5 | H18A—C18—H18B | 107.7 |
C1—C2—H2B | 109.5 | C20—C19—C18 | 114.33 (13) |
H2A—C2—H2B | 109.5 | C20—C19—H19A | 108.7 |
C1—C2—H2C | 109.5 | C18—C19—H19A | 108.7 |
H2A—C2—H2C | 109.5 | C20—C19—H19B | 108.7 |
H2B—C2—H2C | 109.5 | C18—C19—H19B | 108.7 |
C1—C3—H3A | 109.5 | H19A—C19—H19B | 107.6 |
C1—C3—H3B | 109.5 | C19—C20—H20A | 109.5 |
H3A—C3—H3B | 109.5 | C19—C20—H20B | 109.5 |
C1—C3—H3C | 109.5 | H20A—C20—H20B | 109.5 |
H3A—C3—H3C | 109.5 | C19—C20—H20C | 109.5 |
H3B—C3—H3C | 109.5 | H20A—C20—H20C | 109.5 |
C1—C4—H4A | 109.5 | H20B—C20—H20C | 109.5 |
C1—C4—H4B | 109.5 | O5—P1—O7 | 113.72 (6) |
H4A—C4—H4B | 109.5 | O5—P1—O6 | 114.54 (6) |
C1—C4—H4C | 109.5 | O7—P1—O6 | 106.43 (6) |
H4A—C4—H4C | 109.5 | O5—P1—C17 | 115.12 (6) |
H4B—C4—H4C | 109.5 | O7—P1—C17 | 103.74 (6) |
C5—O1—C1 | 120.52 (9) | O6—P1—C17 | 101.98 (6) |
O2—C5—N1 | 124.43 (10) | C21A—O6—P1 | 129.8 (9) |
O2—C5—O1 | 126.15 (10) | C21—O6—P1 | 120.94 (10) |
N1—C5—O1 | 109.42 (9) | O6—C21—C22 | 107.64 (15) |
C5—N1—C6 | 120.88 (10) | O6—C21—H21A | 110.2 |
C5—N1—H1 | 120.1 (9) | C22—C21—H21A | 110.2 |
C6—N1—H1 | 118.9 (9) | O6—C21—H21B | 110.2 |
N1—C6—C7 | 116.29 (9) | C22—C21—H21B | 110.2 |
N1—C6—H6A | 108.2 | H21A—C21—H21B | 108.5 |
C7—C6—H6A | 108.2 | O6—C21A—H21C | 106.8 |
N1—C6—H6B | 108.2 | O6—C21A—H21D | 106.8 |
C7—C6—H6B | 108.2 | H21C—C21A—H21D | 106.6 |
H6A—C6—H6B | 107.4 | C23A—O7—P1 | 125.3 (7) |
O3—C7—N2 | 122.63 (9) | C23—O7—P1 | 124.72 (9) |
O3—C7—C6 | 120.62 (10) | O7—C23—C24 | 110.81 (19) |
N2—C7—C6 | 116.75 (9) | O7—C23—H23A | 109.5 |
C7—N2—C8 | 119.38 (9) | C24—C23—H23A | 109.5 |
C7—N2—H2 | 120.4 (8) | O7—C23—H23B | 109.5 |
C8—N2—H2 | 116.7 (8) | C24—C23—H23B | 109.5 |
C9—C8—N2 | 123.99 (9) | H23A—C23—H23B | 108.1 |
C9—C8—C16 | 121.30 (9) | C23—C24—H24A | 109.5 |
N2—C8—C16 | 114.09 (8) | C23—C24—H24B | 109.5 |
C8—C9—C10 | 130.07 (10) | H24A—C24—H24B | 109.5 |
C8—C9—H9 | 115.0 | C23—C24—H24C | 109.5 |
C10—C9—H9 | 115.0 | H24A—C24—H24C | 109.5 |
C11—C10—C15 | 117.74 (11) | H24B—C24—H24C | 109.5 |
C11—C10—C9 | 117.33 (10) | O7—C23A—C24A | 113.3 (14) |
C15—C10—C9 | 124.93 (10) | O7—C23A—H23C | 108.9 |
C12—C11—C10 | 121.33 (12) | C24A—C23A—H23C | 108.9 |
C12—C11—H11 | 119.3 | O7—C23A—H23D | 108.9 |
C10—C11—H11 | 119.3 | C24A—C23A—H23D | 108.9 |
C13—C12—C11 | 120.13 (12) | H23C—C23A—H23D | 107.7 |
C13—C12—H12 | 119.9 | C23A—C24A—H24D | 109.5 |
C11—C12—H12 | 119.9 | C23A—C24A—H24E | 109.5 |
C12—C13—C14 | 119.48 (12) | H24D—C24A—H24E | 109.5 |
C12—C13—H13 | 120.3 | C23A—C24A—H24F | 109.5 |
C14—C13—H13 | 120.3 | H24D—C24A—H24F | 109.5 |
C13—C14—C15 | 120.90 (13) | H24E—C24A—H24F | 109.5 |
C13—C14—H14 | 119.5 | C31—O31—H31 | 109.4 |
C15—C14—H14 | 119.5 | C31—O31—H31A | 110.5 |
C14—C15—C10 | 120.40 (11) | O31—C31—C32 | 110.27 (13) |
C14—C15—H15 | 119.8 | O31—C31—H31B | 109.6 |
C10—C15—H15 | 119.8 | C32—C31—H31B | 109.6 |
O4—C16—N3 | 122.75 (9) | O31—C31—H31C | 109.6 |
O4—C16—C8 | 119.57 (9) | C32—C31—H31C | 109.6 |
N3—C16—C8 | 117.62 (8) | H31B—C31—H31C | 108.1 |
C16—N3—C17 | 121.69 (8) | C31—C32—H32A | 109.5 |
C16—N3—H3 | 120.2 (9) | C31—C32—H32B | 109.5 |
C17—N3—H3 | 117.6 (9) | H32A—C32—H32B | 109.5 |
N3—C17—C18 | 111.55 (9) | C31—C32—H32C | 109.5 |
N3—C17—P1 | 107.22 (7) | H32A—C32—H32C | 109.5 |
C18—C17—P1 | 112.44 (7) | H32B—C32—H32C | 109.5 |
N3—C17—H17 | 108.5 | H1W—O1W—H2W | 118.3 |
C18—C17—H17 | 108.5 | | |
| | | |
C3—C1—O1—C5 | −62.98 (13) | C8—C16—N3—C17 | −176.06 (9) |
C4—C1—O1—C5 | 61.12 (14) | C16—N3—C17—C18 | −126.77 (11) |
C2—C1—O1—C5 | 179.72 (9) | C16—N3—C17—P1 | 109.72 (10) |
C1—O1—C5—O2 | −8.00 (16) | N3—C17—C18—C19 | 53.53 (13) |
C1—O1—C5—N1 | 172.61 (8) | P1—C17—C18—C19 | 174.04 (9) |
O2—C5—N1—C6 | 2.15 (15) | C17—C18—C19—C20 | 59.42 (16) |
O1—C5—N1—C6 | −178.44 (8) | N3—C17—P1—O5 | 55.92 (9) |
C5—N1—C6—C7 | −85.37 (13) | C18—C17—P1—O5 | −67.05 (9) |
N1—C6—C7—O3 | 174.65 (10) | N3—C17—P1—O7 | −68.98 (8) |
N1—C6—C7—N2 | −4.71 (15) | C18—C17—P1—O7 | 168.05 (8) |
O3—C7—N2—C8 | 10.60 (16) | N3—C17—P1—O6 | −179.44 (6) |
C6—C7—N2—C8 | −170.05 (9) | C18—C17—P1—O6 | 57.59 (9) |
C7—N2—C8—C9 | −133.76 (11) | O5—P1—O6—C21A | −17.4 (15) |
C7—N2—C8—C16 | 55.14 (13) | O7—P1—O6—C21A | 109.2 (15) |
N2—C8—C9—C10 | 4.74 (18) | C17—P1—O6—C21A | −142.4 (15) |
C16—C8—C9—C10 | 175.23 (10) | O5—P1—O6—C21 | −49.97 (14) |
C8—C9—C10—C11 | −165.79 (12) | O7—P1—O6—C21 | 76.60 (13) |
C8—C9—C10—C15 | 14.66 (19) | C17—P1—O6—C21 | −175.00 (12) |
C15—C10—C11—C12 | −0.76 (19) | C21A—O6—C21—C22 | 53 (2) |
C9—C10—C11—C12 | 179.66 (11) | P1—O6—C21—C22 | 170.15 (11) |
C10—C11—C12—C13 | 0.3 (2) | O5—P1—O7—C23A | −17.6 (10) |
C11—C12—C13—C14 | 0.5 (2) | O6—P1—O7—C23A | −144.7 (9) |
C12—C13—C14—C15 | −0.7 (2) | C17—P1—O7—C23A | 108.1 (10) |
C13—C14—C15—C10 | 0.3 (2) | O5—P1—O7—C23 | 17.13 (16) |
C11—C10—C15—C14 | 0.49 (18) | O6—P1—O7—C23 | −109.93 (15) |
C9—C10—C15—C14 | −179.97 (12) | C17—P1—O7—C23 | 142.92 (15) |
C9—C8—C16—O4 | −141.62 (11) | C23A—O7—C23—C24 | 0.1 (15) |
N2—C8—C16—O4 | 29.75 (13) | P1—O7—C23—C24 | −101.27 (17) |
C9—C8—C16—N3 | 35.57 (15) | C23—O7—C23A—C24A | −19.1 (9) |
N2—C8—C16—N3 | −153.06 (10) | P1—O7—C23A—C24A | 79.9 (16) |
O4—C16—N3—C17 | 1.03 (16) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O4i | 0.839 (13) | 2.038 (14) | 2.8561 (18) | 165.0 (12) |
N2—H2···O31Ai | 0.841 (13) | 2.099 (18) | 2.928 (12) | 168.8 (12) |
N2—H2···O31i | 0.841 (13) | 2.156 (13) | 2.9267 (19) | 152.2 (11) |
N3—H3···O5ii | 0.826 (12) | 1.996 (13) | 2.7990 (18) | 164.0 (12) |
O31—H31···O4 | 0.84 | 1.97 | 2.8106 (17) | 175 |
O31A—H31A···O4 | 0.84 | 2.16 | 2.879 (12) | 144 |
O1W—H1W···O3 | 0.85 | 1.85 | 2.70 (2) | 180 |
O1W—H2W···O5ii | 0.85 | 1.99 | 2.84 (2) | 180 |
C3—H3A···O2 | 0.98 | 2.55 | 3.0548 (18) | 112 |
C4—H4A···O2 | 0.98 | 2.38 | 2.9494 (19) | 117 |
C15—H15···N2 | 0.95 | 2.46 | 3.053 (2) | 120 |
C17—H17···O4 | 1.00 | 2.35 | 2.7829 (14) | 105 |
C23—H23A···O2iii | 0.99 | 2.58 | 3.335 (2) | 133 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z; (iii) x−1, y, z. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C21H32N3O7P | C24H38N3O7P·C3H8O·0.122H2O | C24H38N3O7P·C2H6O·0.076H2O |
Mr | 469.47 | 573.80 | 558.97 |
Crystal system, space group | Orthorhombic, Pna21 | Triclinic, P1 | Triclinic, P1 |
Temperature (K) | 100 | 110 | 180 |
a, b, c (Å) | 8.597 (3), 18.023 (4), 15.852 (4) | 10.131 (4), 12.866 (5), 13.368 (5) | 10.047 (3), 12.667 (4), 13.499 (4) |
α, β, γ (°) | 90, 90, 90 | 68.90 (4), 75.94 (4), 84.11 (4) | 69.16 (4), 76.54 (4), 83.89 (4) |
V (Å3) | 2456.2 (12) | 1576.7 (11) | 1560.9 (10) |
Z | 4 | 2 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.16 | 0.14 | 0.14 |
Crystal size (mm) | 0.30 × 0.15 × 0.08 | 0.44 × 0.08 × 0.07 | 0.47 × 0.22 × 0.21 |
|
Data collection |
Diffractometer | Oxford Xcalibur PX κ-geometry diffractometer with CCD area detector | Oxford Xcalibur PX κ-geometry diffractometer with CCD area detector | Oxford Xcalibur PX κ-geometry diffractometer with CCD area detector |
Absorption correction | – | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 30498, 3370, 3134 | 23109, 10752, 5951 | 21697, 11597, 7581 |
Rint | 0.098 | 0.034 | 0.017 |
(sin θ/λ)max (Å−1) | 0.682 | 0.757 | 0.807 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.067, 0.126, 1.23 | 0.045, 0.091, 1.01 | 0.044, 0.131, 1.04 |
No. of reflections | 3370 | 10752 | 11597 |
No. of parameters | 334 | 406 | 380 |
No. of restraints | 23 | 0 | 0 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.29, −0.25 | 0.35, −0.45 | 0.42, −0.25 |
Selected geometric parameters (Å, º) for (I) topN2—C8 | 1.413 (5) | C9—C10 | 1.468 (6) |
C8—C9 | 1.329 (5) | C17—P1 | 1.811 (4) |
C8—C16 | 1.515 (5) | | |
| | | |
C9—C8—N2 | 126.8 (3) | O5—P1—O6 | 113.8 (2) |
N2—C8—C16 | 115.5 (3) | O5—P1—O7 | 116.35 (17) |
C8—C9—C10 | 130.4 (4) | O6—P1—O7 | 102.7 (2) |
| | | |
C6—C7—N2—C8 | −168.4 (3) | C8—C9—C10—C15 | −24.2 (7) |
N2—C8—C9—C10 | 3.1 (7) | C8—C16—N3—C17 | 179.2 (3) |
C8—C9—C10—C11 | 154.2 (4) | | |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O5i | 0.87 (5) | 2.04 (5) | 2.830 (5) | 152 (4) |
N2—H2···O4ii | 0.81 (5) | 2.21 (5) | 2.942 (4) | 149 (4) |
N3—H3···O3ii | 0.74 (5) | 2.23 (5) | 2.955 (4) | 168 (5) |
C3—H3C···O2 | 0.98 | 2.40 | 2.987 (6) | 118 |
C6—H6A···O4ii | 0.99 | 2.53 | 3.210 (5) | 126 |
C9—H9···O4 | 0.95 | 2.48 | 2.825 (5) | 101 |
C15—H15···O4ii | 0.95 | 2.59 | 3.537 (5) | 173 |
C17—H17···O4 | 1.00 | 2.44 | 2.825 (5) | 103 |
C20—H20C···O5 | 0.98 | 2.51 | 3.001 (7) | 111 |
Symmetry codes: (i) x−1/2, −y+3/2, z; (ii) x+1/2, −y+3/2, z. |
Selected geometric parameters (Å, º) for (II) topN2—C8 | 1.4103 (15) | C9—C10 | 1.4694 (18) |
C8—C9 | 1.3360 (18) | C17—P1 | 1.8066 (16) |
C8—C16 | 1.5009 (17) | | |
| | | |
C9—C8—N2 | 123.38 (11) | O5—P1—O7 | 113.76 (6) |
N2—C8—C16 | 114.20 (10) | O5—P1—O6 | 114.89 (6) |
C8—C9—C10 | 129.91 (11) | O7—P1—O6 | 105.36 (7) |
| | | |
C6—C7—N2—C8 | −172.05 (10) | C8—C9—C10—C15 | 14.8 (2) |
N2—C8—C9—C10 | 4.5 (2) | C8—C16—N3—C17 | −176.69 (11) |
C8—C9—C10—C11 | −165.79 (13) | | |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O4i | 0.817 (13) | 2.083 (14) | 2.883 (2) | 166.5 (13) |
N2—H2···O31i | 0.833 (12) | 2.201 (13) | 2.8991 (19) | 141.3 (11) |
N3—H3···O5ii | 0.830 (13) | 1.978 (14) | 2.782 (2) | 162.8 (12) |
O31—H31···O4 | 0.84 | 1.97 | 2.7993 (18) | 171 |
O1W—H2W···O3 | 0.84 | 1.98 | 2.630 (12) | 134 |
O1W—H1W···O5ii | 0.85 | 1.95 | 2.795 (12) | 179 |
C3—H3A···O2 | 0.98 | 2.49 | 3.0440 (18) | 115 |
C4—H4A···O2 | 0.98 | 2.38 | 2.9585 (19) | 118 |
C15—H15···N2 | 0.95 | 2.43 | 3.029 (2) | 121 |
C17—H17···O4 | 1.00 | 2.37 | 2.7943 (17) | 105 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z. |
Selected geometric parameters (Å, º) for (III) topN2—C8 | 1.4130 (12) | C9—C10 | 1.4683 (16) |
C8—C9 | 1.3405 (15) | C17—P1 | 1.8091 (13) |
C8—C16 | 1.5014 (15) | | |
| | | |
C9—C8—N2 | 123.99 (9) | O5—P1—O7 | 113.72 (6) |
N2—C8—C16 | 114.09 (8) | O5—P1—O6 | 114.54 (6) |
C8—C9—C10 | 130.07 (10) | O7—P1—O6 | 106.43 (6) |
| | | |
C6—C7—N2—C8 | −170.05 (9) | C8—C9—C10—C15 | 14.66 (19) |
N2—C8—C9—C10 | 4.74 (18) | C8—C16—N3—C17 | −176.06 (9) |
C8—C9—C10—C11 | −165.79 (12) | | |
Hydrogen-bond geometry (Å, º) for (III) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O4i | 0.839 (13) | 2.038 (14) | 2.8561 (18) | 165.0 (12) |
N2—H2···O31Ai | 0.841 (13) | 2.099 (18) | 2.928 (12) | 168.8 (12) |
N2—H2···O31i | 0.841 (13) | 2.156 (13) | 2.9267 (19) | 152.2 (11) |
N3—H3···O5ii | 0.826 (12) | 1.996 (13) | 2.7990 (18) | 164.0 (12) |
O31—H31···O4 | 0.84 | 1.97 | 2.8106 (17) | 175 |
O31A—H31A···O4 | 0.84 | 2.16 | 2.879 (12) | 144 |
O1W—H1W···O3 | 0.85 | 1.85 | 2.70 (2) | 180 |
O1W—H2W···O5ii | 0.85 | 1.99 | 2.84 (2) | 180 |
C3—H3A···O2 | 0.98 | 2.55 | 3.0548 (18) | 112 |
C4—H4A···O2 | 0.98 | 2.38 | 2.9494 (19) | 117 |
C15—H15···N2 | 0.95 | 2.46 | 3.053 (2) | 120 |
C17—H17···O4 | 1.00 | 2.35 | 2.7829 (14) | 105 |
C23—H23A···O2iii | 0.99 | 2.58 | 3.335 (2) | 133 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z; (iii) x−1, y, z. |
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In previous reports we have described the crystal structures of dehydropeptides containing two α,β-dehydroamino acid residues (with a double bond between the Cα and Cβ atoms) (Makowski et al., 2005, 2006, 2010; Lisowski et al., 2007). In short peptides, the presence of one or more ΔPhe residues causes an α,β-turn conformation (Główka et al., 1987; Główka, 1988) and a 310 helical conformation in longer peptides (Rajashankar et al., 1992; Padmanabhan & Singh, 1993; Rajashankar, Ramakumar, Jain & Chauhan, 1995; Rajashankar, Ramakumar, Mal et al., 1995). In this paper, we describe peptides with only one ΔPhe residue and, additionally, a phosphono group linked to the last Cα atom in the main chain. These phosphonodehydropeptides are a new class of peptide derivatives and their activity against cathepsin C was examined (Latajka et al., 2013).
Tripeptide (I), Boc0-Gly1-Δ(Z)Phe2-α-Abu3PO3Me2, contains one dehydrophenylalanyl residue with a Z configuration (the aromatic ring is located cis to the N atom). There is one molecule in the asymmetric unit (Fig. 1). Important bond lengths, bond angles and torsion angles are presented in Table 1. The Cα═Cβ (C8═C9) distance for the ΔPhe residue of (I) is 1.329 (5) Å, which agrees with other structures containing ΔPhe (Główka et al., 1987; Makowski et al., 2005, 2010) and also with the classical value of a double C═ C bond (Allen et al., 1987). Because of the unsaturated character of the bond between Cα and Cβ, the side-chain atoms of the ΔPhe residue are closer to the main chain than in the saturated form. This causes a shortening of the N—Cα (N2—C8), Cβ—Cγ (C9—C10) and Cα—C (C8—C16) bonds, which is similar to the previous data. The values of the angles also deviate from standard data, e.g. the N—Cα—C angle is smaller [115.5 (3)°] than the value of 120° for a standard trigonal bond angle, while the angles for N—Cα═Cβ and Cα═Cβ—Cγ are larger [126.8 (3) and 130.4 (4)°, respectively]. The values of the torsion angles of ΔPhe [χ2 = 3.1 (7)°, χ2,1 = 154.2 (4)° and χ2,2 = -24.2 (7)°] indicate that the side chain is almost planar. All amino acids in (I) are located trans to each other in the main chain. The value of the torsion angle between Gly–ΔPhe is ω1 = -168.4 (3)° and that between ΔPhe–AbuP is ω2 = 179.2 (3)°; the deviations from the ideal value of ±180° are 11.6 and 0.8°, respectively. The Boc group is located trans to the main chain. The phosphono group is linked directly to chiral atom C17. The bond length between Cα17 and atom P1 is 1.811 (4) Å, which is similar to the standard organic phosphonic bond length of 1.800 Å (Allen et al., 1987) and previous results obtained for organic compounds containing a C—P bond (Hong et al., 2009; Cheng et al., 2011). The O5—P1—O6 [113.8 (2)°] and O5—P1—O7 [116.35 (17)°] angles are larger than the O6—P1—O7 angle [102.7 (2)°], suggesting that the phosphono group has a distorted tetrahedral shape. Atoms C16, N31, C17, P1, O5, O7, C18, C19, C20 and C21 in (I) are slightly disordered, with an occupancy of 0.943 (3). The crystal structure of (I) is stabilized by nine intermolecular hydrogen bonds (Table 2). There are no intramolecular stabilizing hydrogen bonds, which corresponds to the spectroscopic studies of this peptide (Latajka et al., 2013). Thus, tripeptide (I) cannot adopt the ordered structure containing turns.
The structure of tripeptide (II), Boc0-Gly1-Δ(Z)Phe2-α-Nva3PO3Et2, contains three different species in the asymmetric unit, namely (II), propan-2-ol and water. The atom-numbering scheme is shown in Fig. 2 and selected bond lengths and angles are given in Table 3. Compound (II) also contains one dehydrophenylalanyl residue and has the same configuration as (I), i.e. Z. The C8═C9 bond is 1.3360 (18) Å and this raises the possibility of steric contacts between the side and main chains. Because of this there is also a shortening of the nearest bonds, viz. N—Cα (N2—C8), Cβ–Cγ (C9—C10) and Cα–C (C8—C16). The torsion angles of the ΔPhe residue [χ2 = 4.5 (2)°, χ2,1 = -165.79 (13)° and χ2,2 = 14.8 (2)°] indicate the almost planar conformation of its side chain. All amino acids in (II) are located trans to each other, with torsion angles Gly–ΔPhe ω1 = -172.05 (10)° and ΔPhe–NvaP ω2 = -176.69 (11)°; the deviations from the ideal values are 7.95 and 3.31°, respectively. The torsion angles of the Boc group correspond to a trans–trans conformation. The phosphono group is linked to chiral atom C17. The C17—P1 bond is 1.8066 (16) Å, similar to the value in (I). Like in peptide (I), the phosphono group displays a distorted tetrahedral shape, with O5—P1—O6 = 114.89 (6)°, O5—P1—O7 = 113.76 (6)° and O6—P1—O7 105.36 (7)°. This shows that the type of group [methoxy in (I) or ethoxy in (II)] linked directly to the P atom has almost no effect on the angles of the phosphono group. In (II), there are some disordered atoms, two ethoxy groups and the side chain of the (1-aminobutyl)phosphonate. In the side chain of Nva, atoms C19 and C20 are in two positions. Both ethoxy groups connected to the P atom are also disordered. The crystal structure of (II) is stabilized by ten intermolecular hydrogen bonds of different types, namely N—H···O, O—H···O, C—H···O and C—H···N (Table 4). The O atom of the propan-2-ol molecule takes part in two different hydrogen bonds, once as a proton-acceptor atom [N2—H2···O31i; symmetry code: (i) -x + 1, -y + 1, -z + 1] and once as a proton-donor atom (O31—H31···O4 [Symmetry code?]). This propan-2-ol molecule links two molecules of the tripeptide. A water molecule also plays the same linking role between neighbouring peptides, taking part in two hydrogen bonds [O1W—H2W···O3 and O1W—H1W···O5ii; symmetry code: (ii) -x + 1, -y + 1, -z]. Because of the presence of water and propan-2-ol molecules, there is no possibility of the formation of an intramolecular hydrogen-bond network which could stabilize the conformation of (II).
Tripeptide (III) is a second form of (II). The dehydrophenylalanyl residue has the Z configuration. There are three types of species in the asymmetric unit, namely the tripeptide, ethanol and water. The atom-numbering scheme is shown in Fig. 3 and selected bond lengths and angles are given in Table 5. The C8═C9 double bond in the ΔPhe residue is 1.3405 (15) Å, which is the longest in the structures presented in this paper. Compared with (I) and (II), the double-bond elongations are 0.0115 and 0.0045 Å, respectively. Because of the presence of a double bond, there is a shortening of the C8—N2 and C9—C10 bonds, which causes a closer positioning of the side chain of ΔPhe. The ΔPhe torsion angles are χ2 = 4.74 (18)°, χ2,1 = -165.79 (12)° and χ2,2 = 14.66 (19)°, and they indicate near-planarity, like in (I) and (II). The amino acids in the main chain are located trans to each other, with Gly–ΔPhe and ΔPhe–NvaP torsion angles of -170.05 (9) and 176.06 (9)°, respectively. The Boc group is also trans to the main chain. Atom C17 is chiral and connected directly to atom P1. The C17—P1 bond length is 1.8091 (13) Å. The phosphono group adopts the same shape as in (I) and (II), with O5—P1—O6 = 114.54 (6)°, O5—P1—O7 = 113.72 (6)° and O6—P1—O7 = 106.43 (6)°. Two disordered ethoxy groups are linked to atom P1. In (II), where the solvent is propan-2-ol, the disorder occurs in the (1-aminobutyl)phosphonate residue. Compared with (II), the side chain of this residue in (III) is ordered, while the ethanol solvent molecule is disordered. The crystal structure of (III) is stabilized by 13 intermolecular hydrogen bonds, namely N—H···O, C—H···N, O—H···O and C—H···O (Table 6). The ethanol and water molecules link two neighbouring phosphonopeptide molecules via hydrogen bonds. There is no turn in the secondary structure of (III); it cannot be stabilized because of the lack of intramolecular hydrogen bonds.