The crystal structures of the four dipeptides L-seryl-L-asparagine monohydrate, C7H13N3O5·H2O, L-seryl-L-tyrosine monohydrate, C12H16N2O5·H2O, L-tryptophanyl-L-serine monohydrate, C14H17N3O4·H2O, and L-tyrosyl-L-tryptophan monohydrate, C20H21N3O4·H2O, are dominated by extensive hydrogen-bonding networks that include cocrystallized solvent water molecules. Side-chain conformations are discussed on the basis of previous observations in dipeptides. These four dipeptide structures greatly expand our knowledge on dipeptides incorporating polar residues such as serine, asparagine, threonine, tyrosine and tryptophan.
Supporting information
CCDC references: 682834; 682835; 682836; 682837
The title compounds were obtained from Bachem. Crystals were obtained by slow
diffusion of acetonitrile into 30 µl of an aqueous solution containing about
0.2–2.0 mg of the peptide depending on the solubility.
Positional parameters were refined for all H atoms of SN. For the three other
structures, positional parameters were refined only for H atoms involved in
short hydrogen bonds. Other H atoms were positioned with idealized geometry
and fixed C—H distances in the range 0.95–1.00 Å. Uiso values
were set at 1.2Ueq of the carrier atom, or 1.5Ueq for the
amine and hydroxy groups as well as for cocrystallized water molecules. In the
absence of significant anomalous scattering effects, Friedel pairs were
merged.
For all compounds, data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Version 6.10; Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Version 6.10; Sheldrick, 2008); molecular graphics: SHELXTL (Version 6.10; Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Version 6.10; Sheldrick, 2008).
(SN)
L-Seryl-
L-asparagine monohydrate
top
Crystal data top
C7H13N3O5·H2O | Z = 1 |
Mr = 237.22 | F(000) = 126 |
Triclinic, P1 | Dx = 1.493 Mg m−3 |
a = 4.7547 (1) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.5121 (2) Å | Cell parameters from 2419 reflections |
c = 8.5626 (2) Å | θ = 2.7–28.3° |
α = 115.691 (1)° | µ = 0.13 mm−1 |
β = 90.266 (1)° | T = 105 K |
γ = 104.957 (1)° | Block, colourless |
V = 263.87 (1) Å3 | 0.30 × 0.25 × 0.20 mm |
Data collection top
Siemens SMART CCD diffractometer | 1289 independent reflections |
Radiation source: fine-focus sealed tube | 1281 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
Detector resolution: 8.3 pixels mm-1 | θmax = 28.3°, θmin = 2.7° |
Sets of exposures each taken over 0.3° ω rotation scans | h = −6→6 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −9→10 |
Tmin = 0.838, Tmax = 0.974 | l = −11→11 |
2522 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.067 | Only H-atom coordinates refined |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0446P)2 + 0.0335P] where P = (Fo2 + 2Fc2)/3 |
1289 reflections | (Δ/σ)max = 0.002 |
190 parameters | Δρmax = 0.29 e Å−3 |
3 restraints | Δρmin = −0.21 e Å−3 |
Crystal data top
C7H13N3O5·H2O | γ = 104.957 (1)° |
Mr = 237.22 | V = 263.87 (1) Å3 |
Triclinic, P1 | Z = 1 |
a = 4.7547 (1) Å | Mo Kα radiation |
b = 7.5121 (2) Å | µ = 0.13 mm−1 |
c = 8.5626 (2) Å | T = 105 K |
α = 115.691 (1)° | 0.30 × 0.25 × 0.20 mm |
β = 90.266 (1)° | |
Data collection top
Siemens SMART CCD diffractometer | 1289 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1281 reflections with I > 2σ(I) |
Tmin = 0.838, Tmax = 0.974 | Rint = 0.017 |
2522 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.025 | 3 restraints |
wR(F2) = 0.067 | Only H-atom coordinates refined |
S = 1.09 | Δρmax = 0.29 e Å−3 |
1289 reflections | Δρmin = −0.21 e Å−3 |
190 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Data were collected by measuring three sets of exposures with the detector set
at 2θ = 29°, crystal-to-detector distance 5.00 cm. Refinement of F2
against ALL reflections. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.8448 (3) | 1.22469 (17) | 0.81811 (16) | 0.0235 (3) | |
H5 | 0.928 (7) | 1.258 (5) | 0.915 (4) | 0.035* | |
O2 | 0.9515 (2) | 0.61709 (17) | 0.57196 (15) | 0.0203 (3) | |
O3 | 0.6661 (3) | −0.06442 (18) | 0.25320 (16) | 0.0209 (2) | |
O4 | 0.1441 (3) | 0.35031 (18) | 0.12595 (15) | 0.0227 (3) | |
O5 | 0.3046 (2) | 0.07138 (16) | 0.01594 (14) | 0.0159 (2) | |
N1 | 0.7140 (3) | 0.86205 (18) | 0.87460 (15) | 0.0124 (2) | |
H1 | 0.642 (5) | 0.742 (4) | 0.873 (3) | 0.019* | |
H2 | 0.618 (5) | 0.948 (4) | 0.949 (3) | 0.019* | |
H3 | 0.889 (6) | 0.908 (4) | 0.906 (3) | 0.019* | |
N2 | 0.4876 (3) | 0.52295 (18) | 0.43487 (15) | 0.0126 (2) | |
H4 | 0.322 (5) | 0.552 (3) | 0.446 (3) | 0.015* | |
N3 | 0.1800 (3) | −0.2081 (2) | 0.2418 (2) | 0.0210 (3) | |
H6 | 0.197 (6) | −0.326 (5) | 0.200 (4) | 0.025* | |
H7 | 0.007 (6) | −0.193 (4) | 0.248 (3) | 0.025* | |
C1 | 0.6593 (3) | 0.8486 (2) | 0.69714 (18) | 0.0123 (3) | |
H11 | 0.454 (5) | 0.844 (4) | 0.680 (3) | 0.015* | |
C2 | 0.8700 (3) | 1.0348 (2) | 0.68728 (19) | 0.0165 (3) | |
H21 | 1.071 (5) | 1.034 (4) | 0.705 (3) | 0.020* | |
H22 | 0.829 (5) | 1.025 (4) | 0.575 (3) | 0.020* | |
C3 | 0.7128 (3) | 0.6494 (2) | 0.56081 (18) | 0.0124 (3) | |
C4 | 0.4933 (3) | 0.3171 (2) | 0.30937 (17) | 0.0114 (3) | |
H41 | 0.685 (5) | 0.320 (3) | 0.288 (3) | 0.014* | |
C5 | 0.3727 (3) | 0.1646 (2) | 0.38577 (19) | 0.0148 (3) | |
H51 | 0.473 (5) | 0.216 (4) | 0.494 (3) | 0.018* | |
H52 | 0.163 (5) | 0.152 (4) | 0.394 (3) | 0.018* | |
C6 | 0.4173 (3) | −0.0465 (2) | 0.28399 (18) | 0.0147 (3) | |
C7 | 0.3016 (3) | 0.2442 (2) | 0.13613 (18) | 0.0131 (3) | |
O1W | 0.4833 (3) | 0.4668 (2) | 0.8323 (2) | 0.0290 (3) | |
H1W | 0.585 (8) | 0.384 (5) | 0.831 (5) | 0.044* | |
H2W | 0.317 (8) | 0.425 (5) | 0.842 (5) | 0.044* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0395 (7) | 0.0113 (5) | 0.0161 (5) | 0.0064 (5) | −0.0041 (5) | 0.0036 (4) |
O2 | 0.0120 (5) | 0.0189 (5) | 0.0203 (5) | 0.0066 (4) | −0.0009 (4) | −0.0010 (5) |
O3 | 0.0167 (5) | 0.0198 (5) | 0.0249 (6) | 0.0083 (4) | 0.0014 (4) | 0.0072 (5) |
O4 | 0.0278 (6) | 0.0184 (6) | 0.0173 (5) | 0.0123 (5) | −0.0065 (4) | 0.0008 (4) |
O5 | 0.0158 (5) | 0.0141 (5) | 0.0126 (4) | 0.0060 (4) | −0.0004 (4) | 0.0004 (4) |
N1 | 0.0122 (5) | 0.0108 (5) | 0.0119 (5) | 0.0023 (4) | 0.0018 (4) | 0.0036 (4) |
N2 | 0.0109 (5) | 0.0108 (5) | 0.0121 (5) | 0.0042 (4) | 0.0000 (4) | 0.0010 (5) |
N3 | 0.0189 (7) | 0.0128 (6) | 0.0297 (7) | 0.0051 (5) | 0.0033 (5) | 0.0080 (5) |
C1 | 0.0120 (6) | 0.0106 (6) | 0.0105 (6) | 0.0026 (5) | −0.0001 (5) | 0.0019 (5) |
C2 | 0.0223 (7) | 0.0118 (6) | 0.0122 (6) | 0.0018 (5) | −0.0001 (5) | 0.0043 (5) |
C3 | 0.0111 (6) | 0.0116 (6) | 0.0115 (6) | 0.0027 (5) | 0.0017 (5) | 0.0028 (5) |
C4 | 0.0111 (6) | 0.0088 (6) | 0.0107 (6) | 0.0028 (4) | 0.0001 (5) | 0.0012 (5) |
C5 | 0.0177 (7) | 0.0124 (6) | 0.0128 (6) | 0.0042 (5) | 0.0030 (5) | 0.0044 (5) |
C6 | 0.0172 (7) | 0.0140 (6) | 0.0129 (6) | 0.0057 (5) | −0.0003 (5) | 0.0056 (5) |
C7 | 0.0118 (6) | 0.0126 (6) | 0.0114 (6) | 0.0025 (5) | 0.0004 (5) | 0.0027 (5) |
O1W | 0.0294 (7) | 0.0166 (6) | 0.0409 (8) | 0.0049 (5) | 0.0140 (6) | 0.0137 (5) |
Geometric parameters (Å, º) top
O1—C2 | 1.4170 (19) | N3—H7 | 0.86 (3) |
O1—H5 | 0.82 (3) | C1—C2 | 1.5320 (19) |
O2—C3 | 1.2315 (18) | C1—C3 | 1.5336 (19) |
O3—C6 | 1.2413 (19) | C1—H11 | 0.98 (2) |
O4—C7 | 1.2539 (19) | C2—H21 | 0.97 (3) |
O5—C7 | 1.2631 (17) | C2—H22 | 0.94 (3) |
N1—C1 | 1.4955 (18) | C4—C7 | 1.5349 (19) |
N1—H1 | 0.87 (3) | C4—C5 | 1.5436 (19) |
N1—H2 | 0.91 (3) | C4—H41 | 0.93 (2) |
N1—H3 | 0.81 (3) | C5—C6 | 1.516 (2) |
N2—C3 | 1.3372 (18) | C5—H51 | 0.91 (3) |
N2—C4 | 1.4587 (16) | C5—H52 | 0.98 (2) |
N2—H4 | 0.86 (2) | O1W—H1W | 0.88 (4) |
N3—C6 | 1.336 (2) | O1W—H2W | 0.79 (4) |
N3—H6 | 0.83 (3) | | |
| | | |
C2—O1—H5 | 114 (2) | H21—C2—H22 | 110 (2) |
C1—N1—H1 | 110.8 (16) | O2—C3—N2 | 125.02 (13) |
C1—N1—H2 | 108.5 (15) | O2—C3—C1 | 119.83 (12) |
H1—N1—H2 | 107 (2) | N2—C3—C1 | 115.15 (12) |
C1—N1—H3 | 108.0 (17) | N2—C4—C7 | 111.01 (11) |
H1—N1—H3 | 112 (2) | N2—C4—C5 | 109.02 (11) |
H2—N1—H3 | 110 (2) | C7—C4—C5 | 108.53 (12) |
C3—N2—C4 | 121.07 (12) | N2—C4—H41 | 109.2 (14) |
C3—N2—H4 | 117.7 (15) | C7—C4—H41 | 109.1 (14) |
C4—N2—H4 | 119.2 (15) | C5—C4—H41 | 110.0 (14) |
C6—N3—H6 | 120.1 (19) | C6—C5—C4 | 114.41 (12) |
C6—N3—H7 | 121.1 (18) | C6—C5—H51 | 105.3 (15) |
H6—N3—H7 | 119 (3) | C4—C5—H51 | 108.2 (15) |
N1—C1—C2 | 109.67 (11) | C6—C5—H52 | 110.2 (14) |
N1—C1—C3 | 108.51 (12) | C4—C5—H52 | 108.7 (14) |
C2—C1—C3 | 109.56 (11) | H51—C5—H52 | 110 (2) |
N1—C1—H11 | 106.7 (13) | O3—C6—N3 | 123.02 (14) |
C2—C1—H11 | 112.0 (13) | O3—C6—C5 | 120.62 (13) |
C3—C1—H11 | 110.3 (14) | N3—C6—C5 | 116.19 (13) |
O1—C2—C1 | 112.28 (12) | O4—C7—O5 | 124.91 (13) |
O1—C2—H21 | 107.0 (14) | O4—C7—C4 | 119.34 (12) |
C1—C2—H21 | 109.6 (14) | O5—C7—C4 | 115.62 (12) |
O1—C2—H22 | 109.8 (15) | H1W—O1W—H2W | 112 (3) |
C1—C2—H22 | 108.5 (15) | | |
| | | |
N1—C1—C3—N2 | 124.40 (13) | C4—N2—C3—O2 | 8.5 (2) |
C1—C3—N2—C4 | −172.27 (12) | N1—C1—C3—O2 | −56.29 (18) |
C3—N2—C4—C7 | −153.03 (13) | C2—C1—C3—O2 | 63.42 (17) |
N2—C4—C7—O4 | −7.36 (19) | C2—C1—C3—N2 | −115.88 (14) |
N1—C1—C2—O1 | −57.08 (15) | C3—N2—C4—C5 | 87.47 (15) |
N2—C4—C5—C6 | −169.42 (11) | C7—C4—C5—C6 | 69.55 (15) |
C4—C5—C6—O3 | 54.70 (19) | C5—C4—C7—O4 | 112.43 (15) |
C4—C5—C6—N3 | −129.80 (14) | N2—C4—C7—O5 | 176.54 (12) |
C3—C1—C2—O1 | −176.08 (12) | C5—C4—C7—O5 | −63.66 (15) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1W | 0.88 (3) | 1.88 (3) | 2.7446 (18) | 171 (2) |
N1—H2···O5i | 0.91 (3) | 1.92 (3) | 2.7712 (16) | 156 (2) |
N1—H3···O5ii | 0.81 (3) | 2.03 (3) | 2.8037 (17) | 169 (2) |
N2—H4···O2iii | 0.86 (2) | 2.12 (2) | 2.9349 (16) | 156 (2) |
O1—H5···O4ii | 0.81 (3) | 1.82 (3) | 2.6418 (16) | 174 (3) |
C1—H11···O2iii | 0.98 (2) | 2.45 (2) | 3.2908 (18) | 144.5 (18) |
N3—H6···O4iv | 0.82 (3) | 2.17 (3) | 2.9784 (18) | 165 (3) |
N3—H7···O3iii | 0.86 (2) | 2.08 (3) | 2.9014 (19) | 160 (3) |
C5—H52···O3iii | 0.98 (2) | 2.44 (2) | 3.2899 (19) | 144.2 (19) |
O1W—H1W···O1iv | 0.88 (4) | 1.90 (4) | 2.775 (2) | 173 (3) |
O1W—H2W···O1v | 0.78 (4) | 2.31 (4) | 3.081 (2) | 165 (3) |
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y+1, z+1; (iii) x−1, y, z; (iv) x, y−1, z; (v) x−1, y−1, z. |
(SY)
L-Seryl-
L-tyrosine monohydrate
top
Crystal data top
C12H16N2O5·H2O | Dx = 1.452 Mg m−3 |
Mr = 286.28 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P21212 | Cell parameters from 8269 reflections |
a = 15.3480 (9) Å | θ = 1.8–28.4° |
b = 17.8805 (11) Å | µ = 0.12 mm−1 |
c = 4.7728 (3) Å | T = 105 K |
V = 1309.80 (14) Å3 | Block, colourless |
Z = 4 | 0.80 × 0.50 × 0.20 mm |
F(000) = 608 | |
Data collection top
Siemens SMART CCD diffractometer | 1932 independent reflections |
Radiation source: fine-focus sealed tube | 1655 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
Detector resolution: 8.3 pixels mm-1 | θmax = 28.4°, θmin = 1.8° |
Sets of exposures each taken over 0.3° ω rotation scans | h = −20→20 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −23→23 |
Tmin = 0.814, Tmax = 0.976 | l = −6→6 |
14151 measured reflections | |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.102 | w = 1/[σ2(Fo2) + (0.0385P)2 + 0.6547P] where P = (Fo2 + 2Fc2)/3 |
S = 1.14 | (Δ/σ)max = 0.001 |
1932 reflections | Δρmax = 0.24 e Å−3 |
206 parameters | Δρmin = −0.24 e Å−3 |
3 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.025 (3) |
Crystal data top
C12H16N2O5·H2O | V = 1309.80 (14) Å3 |
Mr = 286.28 | Z = 4 |
Orthorhombic, P21212 | Mo Kα radiation |
a = 15.3480 (9) Å | µ = 0.12 mm−1 |
b = 17.8805 (11) Å | T = 105 K |
c = 4.7728 (3) Å | 0.80 × 0.50 × 0.20 mm |
Data collection top
Siemens SMART CCD diffractometer | 1932 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1655 reflections with I > 2σ(I) |
Tmin = 0.814, Tmax = 0.976 | Rint = 0.040 |
14151 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.038 | 3 restraints |
wR(F2) = 0.102 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.14 | Δρmax = 0.24 e Å−3 |
1932 reflections | Δρmin = −0.24 e Å−3 |
206 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Data were collected by measuring three sets of exposures with the detector set
at 2θ = 29°, crystal-to-detector distance 5.00 cm. Refinement of F2
against ALL reflections. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.09778 (12) | 0.52864 (10) | 0.1718 (4) | 0.0313 (4) | |
H4 | 0.048 (2) | 0.5513 (18) | 0.090 (8) | 0.047* | |
O2 | 0.27723 (13) | 0.58953 (11) | 0.9110 (4) | 0.0322 (5) | |
O3 | 0.70144 (12) | 0.61764 (11) | −0.0543 (5) | 0.0393 (5) | |
H6 | 0.735 (2) | 0.655 (2) | −0.104 (9) | 0.059* | |
O4 | 0.30283 (12) | 0.77640 (10) | 0.2429 (4) | 0.0299 (4) | |
O5 | 0.38375 (11) | 0.84101 (9) | 0.5464 (4) | 0.0274 (4) | |
N1 | 0.19134 (15) | 0.47846 (12) | 0.6692 (5) | 0.0249 (4) | |
H1 | 0.154 (2) | 0.4957 (18) | 0.825 (7) | 0.037* | |
H2 | 0.159 (2) | 0.4404 (17) | 0.560 (7) | 0.037* | |
H3 | 0.241 (2) | 0.4547 (17) | 0.748 (7) | 0.037* | |
N2 | 0.31198 (14) | 0.64926 (12) | 0.5087 (4) | 0.0236 (4) | |
H5 | 0.3047 (18) | 0.6492 (17) | 0.337 (7) | 0.028* | |
C1 | 0.21854 (15) | 0.54057 (13) | 0.4828 (5) | 0.0227 (5) | |
H11 | 0.2549 | 0.5201 | 0.3268 | 0.027* | |
C2 | 0.13860 (16) | 0.57872 (13) | 0.3612 (6) | 0.0260 (5) | |
H21 | 0.0977 | 0.5923 | 0.5133 | 0.031* | |
H22 | 0.1559 | 0.6250 | 0.2621 | 0.031* | |
C3 | 0.27301 (16) | 0.59550 (14) | 0.6552 (5) | 0.0231 (5) | |
C4 | 0.35316 (16) | 0.71277 (13) | 0.6492 (5) | 0.0225 (5) | |
H41 | 0.3173 | 0.7235 | 0.8194 | 0.027* | |
C5 | 0.44587 (15) | 0.69475 (13) | 0.7543 (6) | 0.0240 (5) | |
H51 | 0.4679 | 0.7386 | 0.8592 | 0.029* | |
H52 | 0.4421 | 0.6525 | 0.8878 | 0.029* | |
C6 | 0.51152 (15) | 0.67495 (13) | 0.5316 (5) | 0.0234 (5) | |
C7 | 0.52259 (16) | 0.60151 (13) | 0.4421 (6) | 0.0278 (5) | |
H71 | 0.4866 | 0.5634 | 0.5183 | 0.033* | |
C8 | 0.58528 (16) | 0.58270 (14) | 0.2429 (7) | 0.0311 (6) | |
H81 | 0.5914 | 0.5324 | 0.1821 | 0.037* | |
C9 | 0.63865 (16) | 0.63806 (14) | 0.1344 (6) | 0.0273 (5) | |
C10 | 0.62790 (15) | 0.71177 (14) | 0.2176 (6) | 0.0274 (5) | |
H101 | 0.6633 | 0.7500 | 0.1396 | 0.033* | |
C11 | 0.56504 (15) | 0.72919 (14) | 0.4154 (6) | 0.0260 (5) | |
H111 | 0.5584 | 0.7797 | 0.4731 | 0.031* | |
C12 | 0.34644 (15) | 0.78185 (13) | 0.4617 (5) | 0.0235 (5) | |
O1W | 0.47158 (13) | 0.88314 (12) | 1.0312 (4) | 0.0365 (5) | |
H1W | 0.452 (2) | 0.865 (2) | 1.181 (5) | 0.055* | |
H2W | 0.436 (2) | 0.868 (2) | 0.902 (5) | 0.055* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0277 (9) | 0.0286 (9) | 0.0375 (11) | −0.0001 (7) | −0.0083 (8) | −0.0052 (8) |
O2 | 0.0424 (10) | 0.0338 (10) | 0.0204 (9) | −0.0107 (9) | −0.0011 (8) | 0.0022 (8) |
O3 | 0.0364 (10) | 0.0276 (9) | 0.0539 (13) | −0.0026 (8) | 0.0198 (10) | −0.0065 (10) |
O4 | 0.0378 (9) | 0.0303 (9) | 0.0217 (8) | 0.0038 (8) | −0.0059 (8) | −0.0004 (8) |
O5 | 0.0317 (9) | 0.0229 (8) | 0.0276 (9) | −0.0036 (7) | −0.0024 (8) | 0.0014 (8) |
N1 | 0.0270 (10) | 0.0234 (10) | 0.0243 (10) | −0.0020 (9) | −0.0030 (9) | 0.0010 (9) |
N2 | 0.0285 (10) | 0.0262 (9) | 0.0162 (9) | −0.0054 (8) | −0.0016 (9) | 0.0007 (9) |
C1 | 0.0246 (10) | 0.0221 (10) | 0.0214 (11) | −0.0029 (9) | −0.0007 (10) | 0.0003 (9) |
C2 | 0.0274 (12) | 0.0227 (11) | 0.0279 (12) | 0.0024 (10) | −0.0026 (10) | −0.0020 (10) |
C3 | 0.0219 (11) | 0.0256 (11) | 0.0219 (10) | −0.0010 (10) | −0.0002 (9) | 0.0003 (10) |
C4 | 0.0244 (11) | 0.0239 (11) | 0.0193 (10) | −0.0027 (9) | −0.0001 (9) | −0.0006 (10) |
C5 | 0.0253 (11) | 0.0252 (11) | 0.0214 (10) | −0.0003 (9) | −0.0025 (10) | 0.0006 (10) |
C6 | 0.0214 (10) | 0.0240 (11) | 0.0247 (11) | 0.0019 (9) | −0.0011 (10) | 0.0002 (10) |
C7 | 0.0274 (12) | 0.0227 (11) | 0.0332 (13) | −0.0028 (9) | 0.0030 (11) | −0.0002 (11) |
C8 | 0.0304 (12) | 0.0241 (11) | 0.0388 (14) | −0.0012 (10) | 0.0049 (12) | −0.0028 (12) |
C9 | 0.0231 (11) | 0.0269 (12) | 0.0319 (13) | 0.0018 (9) | 0.0030 (10) | −0.0023 (11) |
C10 | 0.0223 (11) | 0.0246 (11) | 0.0352 (14) | −0.0032 (9) | 0.0013 (11) | −0.0002 (11) |
C11 | 0.0241 (11) | 0.0232 (11) | 0.0306 (13) | −0.0017 (9) | 0.0000 (11) | −0.0019 (10) |
C12 | 0.0234 (11) | 0.0244 (11) | 0.0226 (11) | 0.0011 (9) | 0.0016 (10) | −0.0027 (10) |
O1W | 0.0410 (11) | 0.0398 (11) | 0.0288 (10) | −0.0130 (9) | −0.0016 (9) | 0.0059 (9) |
Geometric parameters (Å, º) top
O1—C2 | 1.418 (3) | C4—C12 | 1.529 (3) |
O1—H4 | 0.95 (3) | C4—C5 | 1.543 (3) |
O2—C3 | 1.227 (3) | C4—H41 | 1.0000 |
O3—C9 | 1.369 (3) | C5—C6 | 1.507 (3) |
O3—H6 | 0.87 (4) | C5—H51 | 0.9900 |
O4—C12 | 1.244 (3) | C5—H52 | 0.9900 |
O5—C12 | 1.269 (3) | C6—C11 | 1.387 (3) |
N1—C1 | 1.483 (3) | C6—C7 | 1.391 (3) |
N1—H1 | 0.99 (3) | C7—C8 | 1.394 (4) |
N1—H2 | 0.99 (3) | C7—H71 | 0.9500 |
N1—H3 | 0.95 (3) | C8—C9 | 1.385 (4) |
N2—C3 | 1.331 (3) | C8—H81 | 0.9500 |
N2—C4 | 1.462 (3) | C9—C10 | 1.386 (3) |
N2—H5 | 0.82 (3) | C10—C11 | 1.385 (4) |
C1—C2 | 1.519 (3) | C10—H101 | 0.9500 |
C1—C3 | 1.530 (3) | C11—H111 | 0.9500 |
C1—H11 | 1.0000 | O1W—H1W | 0.846 (18) |
C2—H21 | 0.9900 | O1W—H2W | 0.864 (17) |
C2—H22 | 0.9900 | | |
| | | |
C2—O1—H4 | 110 (2) | C12—C4—H41 | 106.5 |
C9—O3—H6 | 113 (3) | C5—C4—H41 | 106.5 |
C1—N1—H1 | 112.4 (19) | C6—C5—C4 | 115.9 (2) |
C1—N1—H2 | 110.0 (19) | C6—C5—H51 | 108.3 |
H1—N1—H2 | 109 (2) | C4—C5—H51 | 108.3 |
C1—N1—H3 | 110.2 (19) | C6—C5—H52 | 108.3 |
H1—N1—H3 | 108 (3) | C4—C5—H52 | 108.3 |
H2—N1—H3 | 108 (2) | H51—C5—H52 | 107.4 |
C3—N2—C4 | 120.9 (2) | C11—C6—C7 | 117.7 (2) |
C3—N2—H5 | 117 (2) | C11—C6—C5 | 120.9 (2) |
C4—N2—H5 | 121 (2) | C7—C6—C5 | 121.3 (2) |
N1—C1—C2 | 109.77 (19) | C6—C7—C8 | 121.4 (2) |
N1—C1—C3 | 108.2 (2) | C6—C7—H71 | 119.3 |
C2—C1—C3 | 111.01 (19) | C8—C7—H71 | 119.3 |
N1—C1—H11 | 109.3 | C9—C8—C7 | 119.4 (2) |
C2—C1—H11 | 109.3 | C9—C8—H81 | 120.3 |
C3—C1—H11 | 109.3 | C7—C8—H81 | 120.3 |
O1—C2—C1 | 108.47 (19) | O3—C9—C8 | 118.1 (2) |
O1—C2—H21 | 110.0 | O3—C9—C10 | 121.7 (2) |
C1—C2—H21 | 110.0 | C8—C9—C10 | 120.1 (2) |
O1—C2—H22 | 110.0 | C11—C10—C9 | 119.5 (2) |
C1—C2—H22 | 110.0 | C11—C10—H101 | 120.3 |
H21—C2—H22 | 108.4 | C9—C10—H101 | 120.3 |
O2—C3—N2 | 124.2 (2) | C10—C11—C6 | 121.9 (2) |
O2—C3—C1 | 120.5 (2) | C10—C11—H111 | 119.1 |
N2—C3—C1 | 115.3 (2) | C6—C11—H111 | 119.1 |
N2—C4—C12 | 109.3 (2) | O4—C12—O5 | 125.1 (2) |
N2—C4—C5 | 112.7 (2) | O4—C12—C4 | 117.7 (2) |
C12—C4—C5 | 114.92 (19) | O5—C12—C4 | 117.1 (2) |
N2—C4—H41 | 106.5 | H1W—O1W—H2W | 105 (2) |
| | | |
N1—C1—C3—N2 | 171.4 (2) | C4—C5—C6—C11 | 93.4 (3) |
C1—C3—N2—C4 | 169.2 (2) | C11—C6—C7—C8 | 0.1 (4) |
C3—N2—C4—C12 | −148.6 (2) | C5—C6—C7—C8 | −177.8 (2) |
N2—C4—C12—O4 | 6.1 (3) | C6—C7—C8—C9 | 0.9 (4) |
N1—C1—C2—O1 | −68.9 (3) | C7—C8—C9—O3 | 178.0 (3) |
N2—C4—C5—C6 | 62.4 (3) | C7—C8—C9—C10 | −1.9 (4) |
C4—C5—C6—C7 | −88.7 (3) | O3—C9—C10—C11 | −178.1 (2) |
C3—C1—C2—O1 | 171.6 (2) | C8—C9—C10—C11 | 1.8 (4) |
C4—N2—C3—O2 | −9.2 (4) | C9—C10—C11—C6 | −0.7 (4) |
N1—C1—C3—O2 | −10.1 (3) | C7—C6—C11—C10 | −0.2 (4) |
C2—C1—C3—O2 | 110.4 (3) | C5—C6—C11—C10 | 177.7 (2) |
C2—C1—C3—N2 | −68.1 (3) | C5—C4—C12—O4 | 133.9 (2) |
C3—N2—C4—C5 | 82.3 (3) | N2—C4—C12—O5 | −176.0 (2) |
C12—C4—C5—C6 | −63.7 (3) | C5—C4—C12—O5 | −48.2 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.99 (3) | 1.96 (3) | 2.936 (3) | 171 (3) |
N1—H2···O5ii | 0.99 (3) | 1.96 (3) | 2.903 (3) | 158 (3) |
N1—H3···O3iii | 0.95 (3) | 1.83 (3) | 2.721 (3) | 155 (3) |
O1—H4···O1Wiv | 0.95 (3) | 1.76 (3) | 2.679 (3) | 163 (3) |
N2—H5···O2v | 0.82 (3) | 2.34 (3) | 3.092 (3) | 153 (3) |
O3—H6···O4vi | 0.87 (4) | 1.74 (4) | 2.612 (3) | 173 (4) |
C1—H11···O2v | 1.00 | 2.37 | 3.004 (3) | 121 |
O1W—H1W···O5i | 0.85 (2) | 2.07 (2) | 2.904 (3) | 167 (4) |
O1W—H2W···O5 | 0.85 (2) | 1.94 (2) | 2.782 (3) | 164 (3) |
Symmetry codes: (i) x, y, z+1; (ii) −x+1/2, y−1/2, −z+1; (iii) −x+1, −y+1, z+1; (iv) x−1/2, −y+3/2, −z+1; (v) x, y, z−1; (vi) x+1/2, −y+3/2, −z. |
(WS)
L-Tryptophanyl-
L-serine monohydrate
top
Crystal data top
C14H17N3O4·H2O | F(000) = 328 |
Mr = 309.32 | Dx = 1.399 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.5613 (5) Å | Cell parameters from 3410 reflections |
b = 9.1474 (7) Å | θ = 1.7–27.9° |
c = 12.5052 (9) Å | µ = 0.11 mm−1 |
β = 101.973 (1)° | T = 105 K |
V = 734.22 (10) Å3 | Plate, colourless |
Z = 2 | 0.40 × 0.25 × 0.08 mm |
Data collection top
Siemens SMART CCD diffractometer | 1827 independent reflections |
Radiation source: fine-focus sealed tube | 1623 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.073 |
Detector resolution: 8.3 pixels mm-1 | θmax = 27.9°, θmin = 1.7° |
Sets of exposures each taken over 0.3° ω rotation scans | h = −8→8 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −7→12 |
Tmin = 0.893, Tmax = 0.991 | l = −14→16 |
4829 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0493P)2 + 0.0424P] where P = (Fo2 + 2Fc2)/3 |
1827 reflections | (Δ/σ)max = 0.004 |
225 parameters | Δρmax = 0.21 e Å−3 |
1 restraint | Δρmin = −0.25 e Å−3 |
Crystal data top
C14H17N3O4·H2O | V = 734.22 (10) Å3 |
Mr = 309.32 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.5613 (5) Å | µ = 0.11 mm−1 |
b = 9.1474 (7) Å | T = 105 K |
c = 12.5052 (9) Å | 0.40 × 0.25 × 0.08 mm |
β = 101.973 (1)° | |
Data collection top
Siemens SMART CCD diffractometer | 1827 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1623 reflections with I > 2σ(I) |
Tmin = 0.893, Tmax = 0.991 | Rint = 0.073 |
4829 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.036 | 1 restraint |
wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | Δρmax = 0.21 e Å−3 |
1827 reflections | Δρmin = −0.25 e Å−3 |
225 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Data were collected by measuring three sets of exposures with the detector set
at 2θ = 29°, crystal-to-detector distance 5.00 cm. Refinement of F2
against ALL reflections. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.4006 (3) | 0.57631 (17) | 0.26300 (12) | 0.0216 (4) | |
O2 | 0.0728 (3) | 0.78297 (18) | −0.01045 (13) | 0.0229 (4) | |
H6 | 0.166 (5) | 0.713 (3) | −0.021 (2) | 0.034* | |
O3 | −0.3112 (3) | 0.56471 (17) | 0.07650 (14) | 0.0228 (4) | |
O4 | −0.3174 (3) | 0.80483 (17) | 0.10278 (13) | 0.0230 (4) | |
N1 | 0.5801 (3) | 0.3416 (2) | 0.19792 (16) | 0.0195 (4) | |
H1 | 0.625 (5) | 0.351 (3) | 0.271 (2) | 0.029* | |
H2 | 0.630 (5) | 0.410 (3) | 0.162 (2) | 0.029* | |
H3 | 0.634 (5) | 0.253 (4) | 0.177 (2) | 0.029* | |
N2 | 0.4865 (4) | 0.2155 (2) | 0.53366 (17) | 0.0290 (5) | |
H4 | 0.563 (5) | 0.171 (4) | 0.590 (3) | 0.035* | |
N3 | 0.0926 (3) | 0.53940 (19) | 0.14458 (15) | 0.0167 (4) | |
H5 | 0.018 (5) | 0.481 (3) | 0.101 (2) | 0.020* | |
C1 | 0.3489 (3) | 0.3458 (2) | 0.17062 (16) | 0.0165 (4) | |
H11 | 0.2991 | 0.3260 | 0.0908 | 0.020* | |
C2 | 0.2631 (4) | 0.2273 (2) | 0.23731 (18) | 0.0195 (5) | |
H21 | 0.1092 | 0.2270 | 0.2154 | 0.023* | |
H22 | 0.3132 | 0.1307 | 0.2181 | 0.023* | |
C3 | 0.3227 (4) | 0.2460 (2) | 0.35877 (18) | 0.0202 (5) | |
C4 | 0.4870 (4) | 0.1794 (3) | 0.42754 (19) | 0.0254 (5) | |
H41 | 0.5862 | 0.1175 | 0.4048 | 0.030* | |
C5 | 0.2135 (4) | 0.3274 (2) | 0.42683 (18) | 0.0201 (4) | |
C6 | 0.3178 (4) | 0.3028 (2) | 0.53607 (19) | 0.0242 (5) | |
C7 | 0.2445 (5) | 0.3570 (3) | 0.6254 (2) | 0.0329 (6) | |
H71 | 0.3154 | 0.3380 | 0.6983 | 0.039* | |
C8 | 0.0648 (5) | 0.4393 (3) | 0.6031 (2) | 0.0386 (7) | |
H81 | 0.0096 | 0.4764 | 0.6621 | 0.046* | |
C9 | −0.0384 (5) | 0.4696 (3) | 0.4960 (3) | 0.0371 (7) | |
H91 | −0.1605 | 0.5282 | 0.4836 | 0.044* | |
C10 | 0.0348 (4) | 0.4153 (3) | 0.4078 (2) | 0.0270 (6) | |
H101 | −0.0352 | 0.4375 | 0.3353 | 0.032* | |
C11 | 0.2825 (4) | 0.4997 (2) | 0.19674 (16) | 0.0162 (4) | |
C12 | 0.0082 (4) | 0.6832 (2) | 0.15927 (17) | 0.0182 (5) | |
H121 | 0.0299 | 0.7043 | 0.2393 | 0.022* | |
C13 | 0.1183 (4) | 0.8015 (2) | 0.10535 (18) | 0.0207 (5) | |
H131 | 0.0712 | 0.8993 | 0.1240 | 0.025* | |
H132 | 0.2707 | 0.7951 | 0.1334 | 0.025* | |
C14 | −0.2266 (4) | 0.6854 (2) | 0.10997 (17) | 0.0176 (4) | |
O1W | 0.6546 (3) | 0.09657 (19) | 0.08266 (15) | 0.0237 (4) | |
H1W | 0.684 (6) | 0.009 (5) | 0.099 (3) | 0.050 (11)* | |
H2W | 0.545 (6) | 0.096 (4) | 0.030 (3) | 0.048 (10)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0246 (9) | 0.0180 (8) | 0.0197 (7) | 0.0008 (7) | −0.0009 (6) | −0.0045 (6) |
O2 | 0.0251 (9) | 0.0205 (8) | 0.0229 (8) | 0.0047 (7) | 0.0047 (7) | 0.0066 (6) |
O3 | 0.0208 (9) | 0.0166 (8) | 0.0295 (8) | −0.0021 (7) | 0.0018 (7) | 0.0002 (6) |
O4 | 0.0243 (9) | 0.0161 (8) | 0.0283 (8) | 0.0054 (7) | 0.0047 (7) | 0.0024 (6) |
N1 | 0.0206 (10) | 0.0150 (9) | 0.0229 (9) | 0.0014 (8) | 0.0042 (8) | 0.0001 (8) |
N2 | 0.0296 (13) | 0.0306 (12) | 0.0241 (10) | 0.0023 (10) | −0.0007 (9) | 0.0121 (9) |
N3 | 0.0192 (10) | 0.0118 (9) | 0.0179 (9) | 0.0002 (7) | 0.0010 (7) | −0.0004 (7) |
C1 | 0.0195 (11) | 0.0124 (9) | 0.0164 (9) | 0.0011 (9) | 0.0004 (8) | 0.0002 (8) |
C2 | 0.0226 (12) | 0.0140 (10) | 0.0215 (10) | −0.0007 (9) | 0.0033 (9) | 0.0010 (8) |
C3 | 0.0225 (12) | 0.0147 (10) | 0.0232 (11) | 0.0000 (9) | 0.0046 (9) | 0.0060 (9) |
C4 | 0.0254 (13) | 0.0237 (11) | 0.0276 (12) | 0.0058 (11) | 0.0067 (10) | 0.0082 (10) |
C5 | 0.0229 (11) | 0.0150 (9) | 0.0223 (10) | −0.0027 (9) | 0.0047 (9) | 0.0018 (8) |
C6 | 0.0308 (13) | 0.0186 (11) | 0.0230 (11) | −0.0069 (10) | 0.0051 (10) | 0.0038 (8) |
C7 | 0.0519 (18) | 0.0265 (13) | 0.0223 (11) | −0.0105 (13) | 0.0126 (11) | 0.0002 (10) |
C8 | 0.059 (2) | 0.0255 (13) | 0.0400 (16) | −0.0023 (14) | 0.0305 (14) | −0.0032 (11) |
C9 | 0.0411 (17) | 0.0257 (14) | 0.0514 (16) | 0.0069 (12) | 0.0256 (14) | 0.0030 (12) |
C10 | 0.0281 (14) | 0.0224 (12) | 0.0317 (13) | 0.0011 (10) | 0.0091 (10) | 0.0052 (10) |
C11 | 0.0210 (11) | 0.0131 (10) | 0.0142 (9) | 0.0001 (9) | 0.0027 (8) | 0.0007 (8) |
C12 | 0.0224 (12) | 0.0126 (9) | 0.0187 (10) | 0.0015 (9) | 0.0017 (9) | 0.0001 (8) |
C13 | 0.0205 (11) | 0.0136 (10) | 0.0265 (11) | −0.0008 (9) | 0.0014 (9) | 0.0005 (8) |
C14 | 0.0204 (11) | 0.0152 (9) | 0.0176 (10) | 0.0011 (9) | 0.0047 (8) | 0.0024 (8) |
O1W | 0.0258 (10) | 0.0156 (8) | 0.0284 (9) | 0.0019 (7) | 0.0025 (8) | −0.0011 (7) |
Geometric parameters (Å, º) top
O1—C11 | 1.229 (3) | C3—C4 | 1.374 (3) |
O2—C13 | 1.427 (3) | C3—C5 | 1.430 (3) |
O2—H6 | 0.91 (3) | C4—H41 | 0.9500 |
O3—C14 | 1.268 (3) | C5—C10 | 1.401 (4) |
O4—C14 | 1.238 (3) | C5—C6 | 1.413 (3) |
N1—C1 | 1.485 (3) | C6—C7 | 1.395 (4) |
N1—H1 | 0.90 (3) | C7—C8 | 1.378 (5) |
N1—H2 | 0.87 (3) | C7—H71 | 0.9500 |
N1—H3 | 0.94 (4) | C8—C9 | 1.397 (4) |
N2—C4 | 1.368 (3) | C8—H81 | 0.9500 |
N2—C6 | 1.370 (3) | C9—C10 | 1.383 (4) |
N2—H4 | 0.87 (3) | C9—H91 | 0.9500 |
N3—C11 | 1.331 (3) | C10—H101 | 0.9500 |
N3—C12 | 1.454 (3) | C12—C13 | 1.532 (3) |
N3—H5 | 0.84 (3) | C12—C14 | 1.536 (3) |
C1—C11 | 1.529 (3) | C12—H121 | 1.0000 |
C1—C2 | 1.543 (3) | C13—H131 | 0.9900 |
C1—H11 | 1.0000 | C13—H132 | 0.9900 |
C2—C3 | 1.497 (3) | O1W—H1W | 0.84 (4) |
C2—H21 | 0.9900 | O1W—H2W | 0.87 (4) |
C2—H22 | 0.9900 | | |
| | | |
C13—O2—H6 | 103.2 (19) | N2—C6—C7 | 129.7 (2) |
C1—N1—H1 | 109.5 (19) | N2—C6—C5 | 107.6 (2) |
C1—N1—H2 | 110 (2) | C7—C6—C5 | 122.6 (2) |
H1—N1—H2 | 112 (3) | C8—C7—C6 | 117.1 (2) |
C1—N1—H3 | 112.4 (19) | C8—C7—H71 | 121.5 |
H1—N1—H3 | 107 (3) | C6—C7—H71 | 121.5 |
H2—N1—H3 | 106 (2) | C7—C8—C9 | 121.7 (3) |
C4—N2—C6 | 109.0 (2) | C7—C8—H81 | 119.1 |
C4—N2—H4 | 123 (2) | C9—C8—H81 | 119.1 |
C6—N2—H4 | 126 (2) | C10—C9—C8 | 120.9 (3) |
C11—N3—C12 | 121.82 (19) | C10—C9—H91 | 119.5 |
C11—N3—H5 | 120.2 (19) | C8—C9—H91 | 119.5 |
C12—N3—H5 | 117.9 (19) | C9—C10—C5 | 119.2 (2) |
N1—C1—C11 | 107.31 (18) | C9—C10—H101 | 120.4 |
N1—C1—C2 | 109.11 (17) | C5—C10—H101 | 120.4 |
C11—C1—C2 | 112.27 (18) | O1—C11—N3 | 124.7 (2) |
N1—C1—H11 | 109.4 | O1—C11—C1 | 120.07 (19) |
C11—C1—H11 | 109.4 | N3—C11—C1 | 115.18 (18) |
C2—C1—H11 | 109.4 | N3—C12—C13 | 110.88 (19) |
C3—C2—C1 | 114.85 (18) | N3—C12—C14 | 109.74 (18) |
C3—C2—H21 | 108.6 | C13—C12—C14 | 109.83 (17) |
C1—C2—H21 | 108.6 | N3—C12—H121 | 108.8 |
C3—C2—H22 | 108.6 | C13—C12—H121 | 108.8 |
C1—C2—H22 | 108.6 | C14—C12—H121 | 108.8 |
H21—C2—H22 | 107.5 | O2—C13—C12 | 110.14 (17) |
C4—C3—C5 | 106.4 (2) | O2—C13—H131 | 109.6 |
C4—C3—C2 | 126.2 (2) | C12—C13—H131 | 109.6 |
C5—C3—C2 | 127.2 (2) | O2—C13—H132 | 109.6 |
N2—C4—C3 | 109.9 (2) | C12—C13—H132 | 109.6 |
N2—C4—H41 | 125.0 | H131—C13—H132 | 108.1 |
C3—C4—H41 | 125.0 | O4—C14—O3 | 125.0 (2) |
C10—C5—C6 | 118.4 (2) | O4—C14—C12 | 117.9 (2) |
C10—C5—C3 | 134.7 (2) | O3—C14—C12 | 117.1 (2) |
C6—C5—C3 | 106.9 (2) | H1W—O1W—H2W | 107 (3) |
| | | |
N1—C1—C11—N3 | 157.96 (19) | C3—C5—C6—N2 | 2.3 (3) |
C1—C11—N3—C12 | −178.97 (19) | C10—C5—C6—C7 | 3.0 (4) |
C11—N3—C12—C14 | −167.49 (19) | C3—C5—C6—C7 | −175.2 (2) |
N3—C12—C14—O3 | 7.1 (3) | N2—C6—C7—C8 | −177.9 (3) |
N1—C1—C2—C3 | 61.6 (3) | C5—C6—C7—C8 | −1.1 (4) |
C1—C2—C3—C4 | −95.8 (3) | C6—C7—C8—C9 | −1.0 (4) |
N3—C12—C13—O2 | 66.3 (2) | C7—C8—C9—C10 | 1.2 (5) |
C11—C1—C2—C3 | −57.2 (3) | C8—C9—C10—C5 | 0.8 (4) |
C1—C2—C3—C5 | 88.9 (3) | C6—C5—C10—C9 | −2.8 (4) |
C6—N2—C4—C3 | 1.8 (3) | C3—C5—C10—C9 | 174.7 (3) |
C5—C3—C4—N2 | −0.4 (3) | C12—N3—C11—O1 | 2.1 (3) |
C2—C3—C4—N2 | −176.5 (2) | N1—C1—C11—O1 | −23.0 (3) |
C4—C3—C5—C10 | −178.9 (3) | C2—C1—C11—O1 | 96.9 (2) |
C2—C3—C5—C10 | −2.8 (4) | C2—C1—C11—N3 | −82.2 (2) |
C4—C3—C5—C6 | −1.2 (3) | C11—N3—C12—C13 | 71.0 (3) |
C2—C3—C5—C6 | 174.9 (2) | C14—C12—C13—O2 | −55.2 (2) |
C4—N2—C6—C7 | 174.6 (2) | N3—C12—C14—O4 | −170.76 (19) |
C4—N2—C6—C5 | −2.5 (3) | C13—C12—C14—O4 | −48.6 (3) |
C10—C5—C6—N2 | −179.6 (2) | C13—C12—C14—O3 | 129.2 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···C3 | 0.90 (3) | 2.64 (3) | 3.012 (3) | 106 (2) |
N1—H2···O3i | 0.87 (3) | 1.86 (3) | 2.726 (3) | 170 (3) |
N1—H3···O1W | 0.94 (4) | 1.88 (3) | 2.762 (3) | 156 (3) |
N2—H4···O1ii | 0.87 (3) | 2.01 (3) | 2.802 (3) | 151 (3) |
N3—H5···O2iii | 0.84 (3) | 2.16 (3) | 2.956 (2) | 159 (3) |
O2—H6···O1Wiv | 0.91 (3) | 1.87 (3) | 2.756 (3) | 164 (3) |
C1—H11···O2iii | 1.00 | 2.47 | 3.114 (3) | 122 |
C1—H11···O4iii | 1.00 | 2.46 | 3.403 (3) | 158 |
C9—H91···C6v | 0.95 | 2.71 | 3.537 (4) | 146 |
O1W—H1W···O4vi | 0.84 (4) | 1.87 (4) | 2.683 (2) | 164 (4) |
O1W—H2W···O3iii | 0.87 (4) | 1.83 (4) | 2.694 (2) | 171 (4) |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, y−1/2, −z+1; (iii) −x, y−1/2, −z; (iv) −x+1, y+1/2, −z; (v) −x, y+1/2, −z+1; (vi) x+1, y−1, z. |
(YW)
L-tyrosyl-
L-tryptophane monohydrate
top
Crystal data top
C20H21N3O4·H2O | F(000) = 408 |
Mr = 385.41 | Dx = 1.428 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.7309 (3) Å | Cell parameters from 3908 reflections |
b = 8.1960 (4) Å | θ = 2.1–27.9° |
c = 19.0952 (9) Å | µ = 0.10 mm−1 |
β = 91.694 (1)° | T = 105 K |
V = 896.52 (8) Å3 | Block, yellow |
Z = 2 | 0.36 × 0.20 × 0.14 mm |
Data collection top
Siemens SMART CCD diffractometer | 2245 independent reflections |
Radiation source: fine-focus sealed tube | 2089 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
Detector resolution: 8.3 pixels mm-1 | θmax = 27.9°, θmin = 2.1° |
Sets of exposures each taken over 0.3° ω rotation scans | h = −6→7 |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | k = −6→10 |
Tmin = 0.882, Tmax = 0.986 | l = −25→22 |
5858 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.080 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0483P)2 + 0.1067P] where P = (Fo2 + 2Fc2)/3 |
2245 reflections | (Δ/σ)max = 0.002 |
284 parameters | Δρmax = 0.22 e Å−3 |
4 restraints | Δρmin = −0.17 e Å−3 |
Crystal data top
C20H21N3O4·H2O | V = 896.52 (8) Å3 |
Mr = 385.41 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 5.7309 (3) Å | µ = 0.10 mm−1 |
b = 8.1960 (4) Å | T = 105 K |
c = 19.0952 (9) Å | 0.36 × 0.20 × 0.14 mm |
β = 91.694 (1)° | |
Data collection top
Siemens SMART CCD diffractometer | 2245 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2089 reflections with I > 2σ(I) |
Tmin = 0.882, Tmax = 0.986 | Rint = 0.045 |
5858 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.031 | 4 restraints |
wR(F2) = 0.080 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.22 e Å−3 |
2245 reflections | Δρmin = −0.17 e Å−3 |
284 parameters | |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Refinement. Data were collected by measuring three sets of exposures with the detector set
at 2θ = 29°, crystal-to-detector distance 5.00 cm. Refinement of F2
against ALL reflections. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
O1 | 0.4999 (3) | 0.4479 (2) | 0.38676 (8) | 0.0250 (3) | |
H4 | 0.451 (5) | 0.513 (4) | 0.3542 (14) | 0.038* | |
O2 | 0.4612 (2) | 0.60015 (18) | 0.70704 (7) | 0.0198 (3) | |
O3 | 0.8189 (2) | 0.25717 (19) | 0.77450 (7) | 0.0194 (3) | |
O4 | 0.5038 (2) | 0.17317 (19) | 0.71301 (7) | 0.0199 (3) | |
N1 | 0.0973 (3) | 0.7550 (2) | 0.65267 (9) | 0.0196 (3) | |
H1 | 0.256 (5) | 0.760 (4) | 0.6403 (13) | 0.029* | |
H2 | 0.084 (5) | 0.847 (4) | 0.6856 (13) | 0.029* | |
H3 | 0.015 (4) | 0.771 (4) | 0.6140 (14) | 0.029* | |
N2 | 0.2481 (3) | 0.4263 (2) | 0.77238 (8) | 0.0147 (3) | |
H5 | 0.114 (4) | 0.379 (3) | 0.7782 (11) | 0.018* | |
N3 | −0.0105 (3) | 0.4665 (2) | 0.99236 (9) | 0.0246 (4) | |
H6 | −0.134 (5) | 0.527 (4) | 0.9999 (13) | 0.030* | |
C1 | 0.0442 (3) | 0.5953 (2) | 0.68609 (9) | 0.0157 (3) | |
H11 | −0.0778 | 0.6118 | 0.7218 | 0.019* | |
C2 | −0.0460 (3) | 0.4717 (2) | 0.63084 (9) | 0.0175 (4) | |
H21 | −0.0493 | 0.3620 | 0.6525 | 0.021* | |
H22 | −0.2083 | 0.5008 | 0.6167 | 0.021* | |
C3 | 0.0991 (3) | 0.4636 (2) | 0.56578 (9) | 0.0154 (4) | |
C4 | 0.3102 (3) | 0.3784 (2) | 0.56479 (9) | 0.0168 (4) | |
H41 | 0.3648 | 0.3227 | 0.6057 | 0.020* | |
C5 | 0.4418 (3) | 0.3741 (2) | 0.50454 (10) | 0.0183 (4) | |
H51 | 0.5841 | 0.3146 | 0.5044 | 0.022* | |
C6 | 0.3644 (3) | 0.4572 (2) | 0.44429 (9) | 0.0174 (4) | |
C7 | 0.1542 (3) | 0.5420 (2) | 0.44429 (9) | 0.0177 (4) | |
H71 | 0.1001 | 0.5982 | 0.4035 | 0.021* | |
C8 | 0.0235 (3) | 0.5438 (2) | 0.50473 (10) | 0.0175 (4) | |
H81 | −0.1207 | 0.6010 | 0.5043 | 0.021* | |
C9 | 0.2728 (3) | 0.5405 (2) | 0.72320 (9) | 0.0146 (3) | |
C10 | 0.4526 (3) | 0.3582 (2) | 0.80947 (9) | 0.0150 (4) | |
H101 | 0.5493 | 0.4499 | 0.8291 | 0.018* | |
C11 | 0.3781 (3) | 0.2478 (3) | 0.87026 (9) | 0.0174 (4) | |
H111 | 0.528 (4) | 0.198 (3) | 0.8893 (12) | 0.021* | |
H112 | 0.285 (4) | 0.158 (4) | 0.8493 (13) | 0.026 (6)* | |
C12 | 0.2526 (3) | 0.3307 (2) | 0.92882 (9) | 0.0181 (4) | |
C13 | 0.0498 (3) | 0.4194 (3) | 0.92593 (10) | 0.0233 (4) | |
H131 | −0.0369 | 0.4448 | 0.8842 | 0.028* | |
C14 | 0.3228 (3) | 0.3214 (2) | 1.00197 (9) | 0.0169 (4) | |
C15 | 0.5110 (3) | 0.2497 (3) | 1.03895 (10) | 0.0205 (4) | |
H151 | 0.6287 | 0.1929 | 1.0148 | 0.025* | |
C16 | 0.5227 (4) | 0.2632 (3) | 1.11160 (10) | 0.0244 (4) | |
H161 | 0.6512 | 0.2165 | 1.1370 | 0.029* | |
C17 | 0.3480 (4) | 0.3444 (3) | 1.14817 (10) | 0.0259 (4) | |
H171 | 0.3589 | 0.3496 | 1.1979 | 0.031* | |
C18 | 0.1606 (4) | 0.4170 (3) | 1.11315 (10) | 0.0241 (4) | |
H181 | 0.0427 | 0.4723 | 1.1378 | 0.029* | |
C19 | 0.1514 (3) | 0.4058 (2) | 1.04015 (10) | 0.0194 (4) | |
C20 | 0.6037 (3) | 0.2555 (2) | 0.76074 (9) | 0.0147 (3) | |
O1W | 0.0885 (3) | 0.0181 (2) | 0.72966 (9) | 0.0277 (3) | |
H1W | 0.215 (3) | 0.070 (4) | 0.7244 (15) | 0.042* | |
H2W | −0.011 (4) | 0.090 (3) | 0.7413 (15) | 0.042* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0322 (8) | 0.0244 (8) | 0.0191 (7) | 0.0070 (7) | 0.0115 (6) | 0.0060 (6) |
O2 | 0.0167 (6) | 0.0223 (7) | 0.0206 (7) | −0.0022 (6) | 0.0023 (5) | 0.0017 (6) |
O3 | 0.0144 (6) | 0.0213 (6) | 0.0226 (6) | −0.0009 (6) | 0.0024 (5) | −0.0008 (6) |
O4 | 0.0192 (6) | 0.0242 (7) | 0.0163 (6) | 0.0000 (6) | 0.0011 (5) | −0.0046 (6) |
N1 | 0.0240 (8) | 0.0179 (8) | 0.0168 (7) | 0.0015 (8) | 0.0002 (6) | 0.0008 (7) |
N2 | 0.0128 (7) | 0.0158 (7) | 0.0156 (7) | 0.0001 (6) | 0.0007 (5) | 0.0007 (6) |
N3 | 0.0209 (8) | 0.0332 (10) | 0.0201 (8) | 0.0072 (8) | 0.0047 (6) | −0.0018 (8) |
C1 | 0.0160 (8) | 0.0176 (8) | 0.0136 (8) | 0.0015 (7) | 0.0022 (6) | 0.0007 (7) |
C2 | 0.0165 (8) | 0.0206 (9) | 0.0154 (8) | −0.0029 (7) | 0.0015 (7) | −0.0005 (8) |
C3 | 0.0168 (8) | 0.0155 (8) | 0.0139 (8) | −0.0023 (7) | −0.0001 (6) | −0.0020 (7) |
C4 | 0.0192 (8) | 0.0171 (9) | 0.0139 (8) | −0.0015 (8) | −0.0013 (7) | 0.0013 (7) |
C5 | 0.0182 (9) | 0.0165 (8) | 0.0202 (9) | 0.0010 (7) | 0.0015 (7) | −0.0008 (7) |
C6 | 0.0212 (9) | 0.0150 (8) | 0.0162 (8) | −0.0029 (7) | 0.0041 (7) | −0.0011 (7) |
C7 | 0.0224 (9) | 0.0173 (9) | 0.0132 (8) | −0.0004 (7) | −0.0011 (7) | 0.0018 (7) |
C8 | 0.0168 (8) | 0.0173 (9) | 0.0182 (8) | 0.0001 (7) | −0.0016 (7) | −0.0010 (8) |
C9 | 0.0165 (8) | 0.0151 (8) | 0.0123 (8) | 0.0011 (7) | 0.0017 (6) | −0.0033 (7) |
C10 | 0.0145 (8) | 0.0161 (9) | 0.0144 (8) | 0.0005 (7) | 0.0009 (6) | −0.0013 (7) |
C11 | 0.0203 (8) | 0.0196 (9) | 0.0125 (8) | 0.0013 (8) | 0.0021 (6) | 0.0009 (8) |
C12 | 0.0198 (9) | 0.0188 (9) | 0.0160 (8) | −0.0012 (8) | 0.0033 (7) | 0.0009 (8) |
C13 | 0.0209 (9) | 0.0323 (11) | 0.0166 (9) | 0.0040 (9) | 0.0014 (7) | −0.0025 (8) |
C14 | 0.0205 (9) | 0.0156 (8) | 0.0150 (8) | −0.0033 (7) | 0.0047 (7) | −0.0002 (7) |
C15 | 0.0243 (9) | 0.0167 (8) | 0.0207 (9) | 0.0019 (9) | 0.0029 (7) | 0.0020 (8) |
C16 | 0.0298 (10) | 0.0233 (9) | 0.0198 (9) | 0.0020 (9) | −0.0026 (8) | 0.0030 (8) |
C17 | 0.0379 (12) | 0.0260 (11) | 0.0140 (9) | −0.0038 (10) | 0.0027 (8) | −0.0003 (8) |
C18 | 0.0297 (10) | 0.0237 (10) | 0.0192 (9) | −0.0001 (9) | 0.0067 (8) | −0.0030 (8) |
C19 | 0.0205 (9) | 0.0189 (9) | 0.0189 (9) | −0.0004 (8) | 0.0037 (7) | −0.0004 (7) |
C20 | 0.0156 (8) | 0.0154 (8) | 0.0130 (8) | −0.0008 (8) | 0.0027 (6) | 0.0025 (7) |
O1W | 0.0216 (7) | 0.0275 (8) | 0.0345 (8) | −0.0031 (6) | 0.0074 (6) | −0.0126 (7) |
Geometric parameters (Å, º) top
O1—C6 | 1.366 (2) | C5—H51 | 0.9500 |
O1—H4 | 0.86 (3) | C6—C7 | 1.391 (3) |
O2—C9 | 1.233 (2) | C7—C8 | 1.394 (3) |
O3—C20 | 1.253 (2) | C7—H71 | 0.9500 |
O4—C20 | 1.258 (2) | C8—H81 | 0.9500 |
N1—C1 | 1.492 (3) | C10—C20 | 1.540 (2) |
N1—H1 | 0.95 (3) | C10—C11 | 1.542 (2) |
N1—H2 | 0.99 (3) | C10—H101 | 1.0000 |
N1—H3 | 0.87 (3) | C11—C12 | 1.509 (3) |
N2—C9 | 1.337 (2) | C11—H111 | 1.01 (2) |
N2—C10 | 1.462 (2) | C11—H112 | 0.99 (3) |
N2—H5 | 0.87 (3) | C12—C13 | 1.371 (3) |
N3—C19 | 1.375 (3) | C12—C14 | 1.444 (3) |
N3—C13 | 1.380 (3) | C13—H131 | 0.9500 |
N3—H6 | 0.88 (3) | C14—C15 | 1.401 (3) |
C1—C9 | 1.538 (2) | C14—C19 | 1.420 (3) |
C1—C2 | 1.541 (3) | C15—C16 | 1.391 (3) |
C1—H11 | 1.0000 | C15—H151 | 0.9500 |
C2—C3 | 1.517 (2) | C16—C17 | 1.405 (3) |
C2—H21 | 0.9900 | C16—H161 | 0.9500 |
C2—H22 | 0.9900 | C17—C18 | 1.383 (3) |
C3—C8 | 1.396 (3) | C17—H171 | 0.9500 |
C3—C4 | 1.398 (3) | C18—C19 | 1.396 (3) |
C4—C5 | 1.395 (2) | C18—H181 | 0.9500 |
C4—H41 | 0.9500 | O1W—H1W | 0.850 (18) |
C5—C6 | 1.398 (3) | O1W—H2W | 0.857 (18) |
| | | |
C6—O1—H4 | 111.7 (18) | O2—C9—N2 | 124.43 (17) |
C1—N1—H1 | 110.7 (18) | O2—C9—C1 | 120.62 (17) |
C1—N1—H2 | 112.3 (15) | N2—C9—C1 | 114.95 (15) |
H1—N1—H2 | 103 (2) | N2—C10—C20 | 111.90 (14) |
C1—N1—H3 | 112 (2) | N2—C10—C11 | 110.67 (14) |
H1—N1—H3 | 106 (2) | C20—C10—C11 | 107.91 (15) |
H2—N1—H3 | 112 (3) | N2—C10—H101 | 108.8 |
C9—N2—C10 | 120.51 (15) | C20—C10—H101 | 108.8 |
C9—N2—H5 | 120.8 (16) | C11—C10—H101 | 108.8 |
C10—N2—H5 | 117.9 (16) | C12—C11—C10 | 116.26 (17) |
C19—N3—C13 | 109.06 (17) | C12—C11—H111 | 109.5 (14) |
C19—N3—H6 | 128.7 (16) | C10—C11—H111 | 104.9 (14) |
C13—N3—H6 | 122.3 (17) | C12—C11—H112 | 111.9 (14) |
N1—C1—C9 | 105.76 (15) | C10—C11—H112 | 106.9 (15) |
N1—C1—C2 | 110.65 (14) | H111—C11—H112 | 107 (2) |
C9—C1—C2 | 112.77 (16) | C13—C12—C14 | 106.15 (17) |
N1—C1—H11 | 109.2 | C13—C12—C11 | 129.14 (18) |
C9—C1—H11 | 109.2 | C14—C12—C11 | 124.62 (17) |
C2—C1—H11 | 109.2 | C12—C13—N3 | 110.28 (18) |
C3—C2—C1 | 114.12 (15) | C12—C13—H131 | 124.9 |
C3—C2—H21 | 108.7 | N3—C13—H131 | 124.9 |
C1—C2—H21 | 108.7 | C15—C14—C19 | 118.66 (17) |
C3—C2—H22 | 108.7 | C15—C14—C12 | 134.25 (18) |
C1—C2—H22 | 108.7 | C19—C14—C12 | 107.09 (17) |
H21—C2—H22 | 107.6 | C16—C15—C14 | 118.88 (18) |
C8—C3—C4 | 118.13 (16) | C16—C15—H151 | 120.6 |
C8—C3—C2 | 119.97 (16) | C14—C15—H151 | 120.6 |
C4—C3—C2 | 121.91 (17) | C15—C16—C17 | 121.27 (19) |
C5—C4—C3 | 120.88 (17) | C15—C16—H161 | 119.4 |
C5—C4—H41 | 119.6 | C17—C16—H161 | 119.4 |
C3—C4—H41 | 119.6 | C18—C17—C16 | 121.21 (18) |
C4—C5—C6 | 120.04 (17) | C18—C17—H171 | 119.4 |
C4—C5—H51 | 120.0 | C16—C17—H171 | 119.4 |
C6—C5—H51 | 120.0 | C17—C18—C19 | 117.42 (19) |
O1—C6—C7 | 122.73 (17) | C17—C18—H181 | 121.3 |
O1—C6—C5 | 117.45 (17) | C19—C18—H181 | 121.3 |
C7—C6—C5 | 119.80 (16) | N3—C19—C18 | 130.07 (18) |
C6—C7—C8 | 119.47 (17) | N3—C19—C14 | 107.39 (16) |
C6—C7—H71 | 120.3 | C18—C19—C14 | 122.54 (18) |
C8—C7—H71 | 120.3 | O3—C20—O4 | 125.55 (17) |
C7—C8—C3 | 121.67 (17) | O3—C20—C10 | 115.78 (16) |
C7—C8—H81 | 119.2 | O4—C20—C10 | 118.60 (15) |
C3—C8—H81 | 119.2 | H1W—O1W—H2W | 105 (2) |
| | | |
N1—C1—C9—N2 | 161.60 (15) | C20—C10—C11—C12 | 172.80 (16) |
C1—C9—N2—C10 | 177.26 (15) | C10—C11—C12—C14 | −125.9 (2) |
C9—N2—C10—C20 | −67.6 (2) | C14—C12—C13—N3 | 0.2 (2) |
N2—C10—C20—O3 | 147.54 (16) | C11—C12—C13—N3 | 176.8 (2) |
N1—C1—C2—C3 | 47.2 (2) | C19—N3—C13—C12 | −1.2 (3) |
C1—C2—C3—C4 | 78.8 (2) | C13—C12—C14—C15 | −179.8 (2) |
N2—C10—C11—C12 | −64.5 (2) | C11—C12—C14—C15 | 3.4 (4) |
C10—C11—C12—C13 | 58.1 (3) | C13—C12—C14—C19 | 0.8 (2) |
C9—C1—C2—C3 | −71.0 (2) | C11—C12—C14—C19 | −176.03 (18) |
C1—C2—C3—C8 | −100.8 (2) | C19—C14—C15—C16 | 0.3 (3) |
C8—C3—C4—C5 | 0.2 (3) | C12—C14—C15—C16 | −179.1 (2) |
C2—C3—C4—C5 | −179.36 (18) | C14—C15—C16—C17 | 1.1 (3) |
C3—C4—C5—C6 | 0.7 (3) | C15—C16—C17—C18 | −1.4 (3) |
C4—C5—C6—O1 | −179.68 (18) | C16—C17—C18—C19 | 0.2 (3) |
C4—C5—C6—C7 | −1.0 (3) | C13—N3—C19—C18 | −177.9 (2) |
O1—C6—C7—C8 | 178.95 (19) | C13—N3—C19—C14 | 1.7 (2) |
C5—C6—C7—C8 | 0.3 (3) | C17—C18—C19—N3 | −179.4 (2) |
C6—C7—C8—C3 | 0.6 (3) | C17—C18—C19—C14 | 1.2 (3) |
C4—C3—C8—C7 | −0.9 (3) | C15—C14—C19—N3 | 179.01 (18) |
C2—C3—C8—C7 | 178.70 (17) | C12—C14—C19—N3 | −1.5 (2) |
C10—N2—C9—O2 | −2.5 (3) | C15—C14—C19—C18 | −1.4 (3) |
N1—C1—C9—O2 | −18.6 (2) | C12—C14—C19—C18 | 178.07 (19) |
C2—C1—C9—O2 | 102.4 (2) | C11—C10—C20—O3 | −90.47 (19) |
C2—C1—C9—N2 | −77.34 (19) | N2—C10—C20—O4 | −35.2 (2) |
C9—N2—C10—C11 | 172.00 (16) | C11—C10—C20—O4 | 86.8 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.95 (3) | 2.16 (3) | 2.915 (2) | 137 (2) |
N1—H2···O1Wii | 0.99 (3) | 1.63 (3) | 2.611 (2) | 170 (2) |
N1—H3···C7iii | 0.87 (3) | 2.66 (3) | 3.298 (3) | 131 (2) |
O1—H4···O4i | 0.86 (3) | 1.86 (3) | 2.653 (2) | 153 (3) |
N2—H5···O3iv | 0.87 (3) | 1.96 (3) | 2.825 (2) | 170 (2) |
N3—H6···C14v | 0.88 (3) | 2.65 (3) | 3.419 (3) | 147 (2) |
O1W—H1W···O4 | 0.85 (2) | 1.88 (2) | 2.725 (2) | 177 (3) |
O1W—H2W···O3iv | 0.86 (2) | 1.81 (2) | 2.653 (2) | 170 (3) |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) x, y+1, z; (iii) −x, y+1/2, −z+1; (iv) x−1, y, z; (v) −x, y+1/2, −z+2. |
Experimental details
| (SN) | (SY) | (WS) | (YW) |
Crystal data |
Chemical formula | C7H13N3O5·H2O | C12H16N2O5·H2O | C14H17N3O4·H2O | C20H21N3O4·H2O |
Mr | 237.22 | 286.28 | 309.32 | 385.41 |
Crystal system, space group | Triclinic, P1 | Orthorhombic, P21212 | Monoclinic, P21 | Monoclinic, P21 |
Temperature (K) | 105 | 105 | 105 | 105 |
a, b, c (Å) | 4.7547 (1), 7.5121 (2), 8.5626 (2) | 15.3480 (9), 17.8805 (11), 4.7728 (3) | 6.5613 (5), 9.1474 (7), 12.5052 (9) | 5.7309 (3), 8.1960 (4), 19.0952 (9) |
α, β, γ (°) | 115.691 (1), 90.266 (1), 104.957 (1) | 90, 90, 90 | 90, 101.973 (1), 90 | 90, 91.694 (1), 90 |
V (Å3) | 263.87 (1) | 1309.80 (14) | 734.22 (10) | 896.52 (8) |
Z | 1 | 4 | 2 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.13 | 0.12 | 0.11 | 0.10 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 | 0.80 × 0.50 × 0.20 | 0.40 × 0.25 × 0.08 | 0.36 × 0.20 × 0.14 |
|
Data collection |
Diffractometer | Siemens SMART CCD diffractometer | Siemens SMART CCD diffractometer | Siemens SMART CCD diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.838, 0.974 | 0.814, 0.976 | 0.893, 0.991 | 0.882, 0.986 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2522, 1289, 1281 | 14151, 1932, 1655 | 4829, 1827, 1623 | 5858, 2245, 2089 |
Rint | 0.017 | 0.040 | 0.073 | 0.045 |
(sin θ/λ)max (Å−1) | 0.667 | 0.669 | 0.658 | 0.658 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.025, 0.067, 1.09 | 0.038, 0.102, 1.14 | 0.036, 0.091, 1.04 | 0.031, 0.080, 1.02 |
No. of reflections | 1289 | 1932 | 1827 | 2245 |
No. of parameters | 190 | 206 | 225 | 284 |
No. of restraints | 3 | 3 | 1 | 4 |
H-atom treatment | Only H-atom coordinates refined | 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, −0.21 | 0.24, −0.24 | 0.21, −0.25 | 0.22, −0.17 |
Selected torsion angles (º) for (SN) topN1—C1—C3—N2 | 124.40 (13) | N1—C1—C2—O1 | −57.08 (15) |
C1—C3—N2—C4 | −172.27 (12) | N2—C4—C5—C6 | −169.42 (11) |
C3—N2—C4—C7 | −153.03 (13) | C4—C5—C6—O3 | 54.70 (19) |
N2—C4—C7—O4 | −7.36 (19) | C4—C5—C6—N3 | −129.80 (14) |
Hydrogen-bond geometry (Å, º) for (SN) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1W | 0.88 (3) | 1.88 (3) | 2.7446 (18) | 171 (2) |
N1—H2···O5i | 0.91 (3) | 1.92 (3) | 2.7712 (16) | 156 (2) |
N1—H3···O5ii | 0.81 (3) | 2.03 (3) | 2.8037 (17) | 169 (2) |
N2—H4···O2iii | 0.86 (2) | 2.12 (2) | 2.9349 (16) | 156 (2) |
O1—H5···O4ii | 0.81 (3) | 1.82 (3) | 2.6418 (16) | 174 (3) |
C1—H11···O2iii | 0.98 (2) | 2.45 (2) | 3.2908 (18) | 144.5 (18) |
N3—H6···O4iv | 0.82 (3) | 2.17 (3) | 2.9784 (18) | 165 (3) |
N3—H7···O3iii | 0.86 (2) | 2.08 (3) | 2.9014 (19) | 160 (3) |
C5—H52···O3iii | 0.98 (2) | 2.44 (2) | 3.2899 (19) | 144.2 (19) |
O1W—H1W···O1iv | 0.88 (4) | 1.90 (4) | 2.7750 (21) | 173 (3) |
O1W—H2W···O1v | 0.78 (4) | 2.31 (4) | 3.0814 (20) | 165 (3) |
Symmetry codes: (i) x, y+1, z+1; (ii) x+1, y+1, z+1; (iii) x−1, y, z; (iv) x, y−1, z; (v) x−1, y−1, z. |
Selected torsion angles (º) for (SY) topN1—C1—C3—N2 | 171.4 (2) | N1—C1—C2—O1 | −68.9 (3) |
C1—C3—N2—C4 | 169.2 (2) | N2—C4—C5—C6 | 62.4 (3) |
C3—N2—C4—C12 | −148.6 (2) | C4—C5—C6—C7 | −88.7 (3) |
N2—C4—C12—O4 | 6.1 (3) | | |
Hydrogen-bond geometry (Å, º) for (SY) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.99 (3) | 1.96 (3) | 2.936 (3) | 171 (3) |
N1—H2···O5ii | 0.99 (3) | 1.96 (3) | 2.903 (3) | 158 (3) |
N1—H3···O3iii | 0.95 (3) | 1.83 (3) | 2.721 (3) | 155 (3) |
O1—H4···O1Wiv | 0.95 (3) | 1.76 (3) | 2.679 (3) | 163 (3) |
N2—H5···O2v | 0.82 (3) | 2.34 (3) | 3.092 (3) | 153 (3) |
O3—H6···O4vi | 0.87 (4) | 1.74 (4) | 2.612 (3) | 173 (4) |
C1—H11···O2v | 1.00 | 2.37 | 3.004 (3) | 121 |
O1W—H1W···O5i | 0.846 (17) | 2.07 (2) | 2.904 (3) | 167 (4) |
O1W—H2W···O5 | 0.846 (17) | 1.940 (18) | 2.782 (3) | 164 (3) |
Symmetry codes: (i) x, y, z+1; (ii) −x+1/2, y−1/2, −z+1; (iii) −x+1, −y+1, z+1; (iv) x−1/2, −y+3/2, −z+1; (v) x, y, z−1; (vi) x+1/2, −y+3/2, −z. |
Selected torsion angles (º) for (WS) topN1—C1—C11—N3 | 157.96 (19) | N1—C1—C2—C3 | 61.6 (3) |
C1—C11—N3—C12 | −178.97 (19) | C1—C2—C3—C4 | −95.8 (3) |
C11—N3—C12—C14 | −167.49 (19) | N3—C12—C13—O2 | 66.3 (2) |
N3—C12—C14—O3 | 7.1 (3) | | |
Hydrogen-bond geometry (Å, º) for (WS) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···C3 | 0.90 (3) | 2.64 (3) | 3.012 (3) | 106 (2) |
N1—H2···O3i | 0.87 (3) | 1.86 (3) | 2.726 (3) | 170 (3) |
N1—H3···O1W | 0.94 (4) | 1.88 (3) | 2.762 (3) | 156 (3) |
N2—H4···O1ii | 0.87 (3) | 2.01 (3) | 2.802 (3) | 151 (3) |
N3—H5···O2iii | 0.84 (3) | 2.16 (3) | 2.956 (2) | 159 (3) |
O2—H6···O1Wiv | 0.91 (3) | 1.87 (3) | 2.756 (3) | 164 (3) |
C1—H11···O2iii | 1.00 | 2.47 | 3.114 (3) | 122 |
C1—H11···O4iii | 1.00 | 2.46 | 3.403 (3) | 158 |
C9—H91···C6v | 0.95 | 2.71 | 3.537 (4) | 146 |
O1W—H1W···O4vi | 0.84 (4) | 1.87 (4) | 2.683 (2) | 164 (4) |
O1W—H2W···O3iii | 0.87 (4) | 1.83 (4) | 2.694 (2) | 171 (4) |
Symmetry codes: (i) x+1, y, z; (ii) −x+1, y−1/2, −z+1; (iii) −x, y−1/2, −z; (iv) −x+1, y+1/2, −z; (v) −x, y+1/2, −z+1; (vi) x+1, y−1, z. |
Selected torsion angles (º) for (YW) topN1—C1—C9—N2 | 161.60 (15) | N1—C1—C2—C3 | 47.2 (2) |
C1—C9—N2—C10 | 177.26 (15) | C1—C2—C3—C4 | 78.8 (2) |
C9—N2—C10—C20 | −67.6 (2) | N2—C10—C11—C12 | −64.5 (2) |
N2—C10—C20—O3 | 147.54 (16) | C10—C11—C12—C13 | 58.1 (3) |
Hydrogen-bond geometry (Å, º) for (YW) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1i | 0.95 (3) | 2.16 (3) | 2.915 (2) | 137 (2) |
N1—H2···O1Wii | 0.99 (3) | 1.63 (3) | 2.611 (2) | 170 (2) |
N1—H3···C7iii | 0.87 (3) | 2.66 (3) | 3.298 (3) | 131 (2) |
O1—H4···O4i | 0.86 (3) | 1.86 (3) | 2.653 (2) | 153 (3) |
N2—H5···O3iv | 0.87 (3) | 1.96 (3) | 2.825 (2) | 170 (2) |
N3—H6···C14v | 0.88 (3) | 2.65 (3) | 3.419 (3) | 147 (2) |
O1W—H1W···O4 | 0.850 (18) | 1.877 (17) | 2.725 (2) | 177 (3) |
O1W—H2W···O3iv | 0.857 (18) | 1.805 (19) | 2.653 (2) | 170 (3) |
Symmetry codes: (i) −x+1, y+1/2, −z+1; (ii) x, y+1, z; (iii) −x, y+1/2, −z+1; (iv) x−1, y, z; (v) −x, y+1/2, −z+2. |
A total of 36 dipeptides can be constructed from the six polar residues Asn, Gln, Ser, Thr, Tyr and Trp, but the structure of only one, Tyr–Tyr hydrate (Cotrait et al., 1984), has been investigated previously by single-crystal X-ray diffraction. The title molecules, Ser–Asn hydrate (SN), Ser–Tyr hydrate (SY), Trp–Ser hydrate (WS) and Tyr–Trp hydrate (YW), were studied as part of an effort to increase our knowledge of such dipeptides. The asymmetric units of the four dipeptides are shown in Fig. 1, while essential torsion angles are listed in Tables 1, 3, 5 and 7. The molecules occur in unconstrained, extended conformations with close to planar peptide bonds and deviations from a perfectly staggered orientation of the amine group reaching a maximum value of 25° for YW.
The side-chain conformations for the title compounds were compared with those of related dipeptides in the Cambridge Structural Database (CSD; Version 5.29 of November 2007; Allen 2002). It is noted that the side chains of N-terminal Ser residues in the CSD are always in a gauche- orientation (the gauche+/trans/gauche- distribution is 0:0:5), while C-terminal Ser on the other hand displays a 7:5:1 distribution. An opposite trend is found for Trp, with distributions of 3:0:0 and 1:0:5 for N-terminal and C-terminal residues, respectively. Tyr has the same preference as Trp for gauche+ at the N-terminus (5:2:1), but uniquely has trans as the most favoured C-terminal orientation (1:3:1). There are only two other dipeptides with a C-terminal Asn residue in the CSD, one each in a gauche+ and gauche- orientation. The side-chain conformations found for the four title dipeptides (Tables 1, 3, 5 and 7) agree with the CSD statistics; only for the Tyr residue of SY do we find a conformation (gauche+) that is not also the most frequently observed among dipeptides in the CSD (trans).
It is noteworthy that all four polar dipeptides have been obtained as hydrates. This observation is of particular interest for WS and YW, as all seven dipeptides with a Trp residue in the CSD are also hydrates, indicating a very high propensity for cocrystallization with water molecules for this particular residue. In contrast, SN is the first Ser–Xaa (Xaa = any amino acid) dipeptide to crystallize as a hydrate.
Among the four dipeptides studied, SN has the smallest hydrophobic units in the side chains, which generate inconspicuous hydrophobic columns along the short (4.75 Å) a axis (Fig. 2). Accordingly, the hydrogen-bonding network is three-dimensional, and as in all N-terminal Ser-residue dipeptide crystal structures, the hydroxy H atom hydrogen bonds to a carboxylate acceptor (Table 2). This group also accepts two of the amino H atoms, but the third amino H atom, which is usually donated to the Ser hydroxy group, is instead accepted by the cocrystallized water molecule that acts as a bridge between the two groups.
Unlike SN, the crystal packing of SY (Fig. 3) is clearly divided into layers. There is, however, only one head-to-tail chain involving the charged N– and C-terminal groups (Table 4). The remaining two amine H atoms are accepted by the hydroxy groups of the Ser and Tyr side chains. Adding to the three-dimensional hydrogen-bonding pattern, the hydroxy groups also act as donors and span the main chain layers by interacting with the carboxylate groups in a direct fashion for the Tyr OH group and in an indirect fashion, using the cocrystallized water as a bridging molecule, for the Ser OH group sitting on a shorter side chain. The extra OH group of Tyr compared with Phe means that SY has a completely different structure from Ser–Phe (Helle et al., 2004). Glu–Glu (Eggleston & Hodgson, 1982), on the other hand, shows some of the same traits, with the N-terminal Glu replacing the Ser residue as well as the cocrystallized water molecule in SY.
The structure of WS adds to a series of structures of dipeptides with a C-terminal Ser residue studied previously, including Gly–Ser (Görbitz, 1999), Leu–Ser (Görbitz et al., 2005), Val–Ser trihydrate (Johansen et al., 2005), Val–Ser trifluoroethanol solvate (Görbitz, 2005), Ile–Ser hydrate, Met–Ser hydrate and Phe–Ser (Görbitz et al., 2006), Ala–Ser hydrate (Jones et al., 1978), Arg–Ser acetate hydrate (Verdaguer et al., 1991), and His–Ser in complex with Gly–Glu (Suresh & Vijayan, 1985). In this group, Ile–Ser and Met–Ser have rather similar structures, while all other compounds have individually unique crystal packing arrangements. This is also true for WS, shown in Fig. 4, which, as expected from a dipeptide with large hydrophobic entities, is clearly divided into layers. The hydrogen-bonding pattern (Table 6) is nevertheless completely different even from that of its presumably closest relative Phe–Ser (Görbitz et al., 2006). The most unusual feature is the amine H atom that is not involved in a strong hydrogen bond to an O-atom acceptor, but instead is squeezed in between two Trp side chains where it acts as a donor in weak inter- and intramolecular interactions with C-atom acceptors (Desiraju & Steiner, 1999; Fig. 5).
The structure of YW (Fig. 6) has a `Big Mac' construction, with two different types of hydrophobic layers, one generated from Tyr side chains and one from Trp side chains, separated by the same type of hydrophilic layers constituted by the peptide main chains. The same pattern was found for the related compounds Tyr–Val (Ramakrishnan et al., 1984), Tyr–Leu (Ramakrishnan & Viswamitra, 1988) and Tyr–Phe (Murali & Subramanian, 1987). It follows that the NεH donor of the Trp side chain is involved only in a comparatively weak interaction, with the C atom (C14) of a neighbouring Trp side chain as the acceptor (Table 8). The hydrogen-bonding pattern of this group of dipeptides is furthermore interesting in that, as for WS, one of the amine H atoms does not participate in a strong N—H···O interaction. Instead it is sandwiched between two aromatic rings, where it is involved in weaker intermolecular and intramolecular N—H···C contacts (Fig. 7). The complete absence of direct head-to-tail interactions between the charged N-terminal and C-terminal groups in YW is a very rare phenomenon for dipeptide structures.
In summary, all four dipeptides display extensive hydrogen-bonding networks, but the gradual increase in the size of hydrophobic units in the side chains from SN through SY and WS to YW shifts the hydrophobic aggregation pattern from columns to layers and the dimensionality of the hydrogen-bonding pattern from three- to two-dimensional when only strong N—H···O and O—H···O interactions are considered. The presence of a large number of hydrogen-bonding donors and acceptors, including those present in cocrystallized water molecules, makes it possible for polar dipeptides to fulfil their hydrogen-bonding requirements while retaining peptide main chains and side chains in unconstrained conformations, but in both dipeptides with a Trp residue, WS and YW, unusual (amine)N—H···C(π) interactions are observed.