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The title compound, C24H28N2O6·0.825CH3NO2, is a member of the TIPP (i.e. Try–Tic–Phe–Phe) family of opioid ligands. The asymmetric unit contains one peptide mol­ecule and one nitro­methane mol­ecule. Unlike other members of this familiy, this dipeptide has an extended conformation [i.e. φ1 = −103.6 (6)°, ω1 = 168.1 (4)°, ψ1 = 152.4 (5)°]. This conformation was further ex­amined with the program CHEM3D. No significant energy difference was found between the energy-minimized conformation and a more tightly folded model conformation.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800020109/na6023sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536800020109/na6023Isup2.hkl
Contains datablock I

CCDC reference: 155902

Key indicators

  • Single-crystal X-ray study
  • T = 223 K
  • Mean [sigma](C-C) = 0.009 Å
  • Disorder in solvent or counterion
  • R factor = 0.075
  • wR factor = 0.195
  • Data-to-parameter ratio = 6.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Red Alert Alert Level A:
THETM_01 Alert A The value of sine(theta_max)/wavelength is less than 0.550 Calculated sin(theta_max)/wavelength = 0.5410
Yellow Alert Alert Level C:
CRYSC_01 Alert C There is an ordering error in _exptl_crystal_colour. It should be (QUALIFIER) (INTENSITY) (BASE_COLOUR). REFNR_01 Alert C Ratio of reflections to parameters is < 8 for a non-centrosymmetric structure, where ZMAX < 18 sine(theta)/lambda 0.5410 Proportion of unique data used 1.0000 Ratio reflections to parameters 6.8988 PLAT_302 Alert C Anion/Solvent disorder ....................... 82.00 Perc. PLAT_601 Alert C Structure contains solvent accessible VOIDS of 62.00 A   3 General Notes
REFLE_01 _reflns_observed_criterion is an old dataname which has been superseded by _reflns_threshold_expression REFLT_03 From the CIF: _diffrn_reflns_theta_max 56.53 From the CIF: _reflns_number_total 2249 Count of symmetry unique reflns 2117 Completeness (_total/calc) 106.24% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 132 Fraction of Friedel pairs measured 0.062 Are heavy atom types Z>Si present no WARNING: CuKa measured Friedel data can be used to determine absolute structure in a light-atom study only if the Friedel fraction is large.
1 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
4 Alert Level C = Please check

Comment top

There are at least four main opioid receptors (µ, δ, κ and σ), some of which also have distinct sub-types (Walker et al., 1990; Schiller, 1991). Most natural opioid peptides have a low receptor-site selectivity (Hruby & Gehrig, 1989). Diversity of the opioid receptors and low receptor-site selectivity of the natural opioid peptides have complicated the interpretation of binding and structural studies of these molecules.

The structural requirements for receptor-site selectivity and activity of the opioid peptides has been attributed to the composition and conformation of the peptide ligand and the net charge of the ligand (Hruby & Gehrig, 1989; Schiller, 1984; Temussi et al., 1989; Rapaka, 1986; Schwyzer, 1986). Of these structural parameters, the relative location and orientation of the aromatic side chains and the relationship of the N-terminal nitrogen to the phenolic oxygen have been identified as critical elements for biological activity (Hansen & Morgan, 1984). To overcome the limitations imposed by studies of natural opioids, several systematic approaches for the rational design of potent and selective analogues of the endogenous opioids have been developed. One approach places a tetrahydroisoquinoline-3-carboxylic acid (Tic) residue in the second position in order to constrain the conformation of the peptide backbone, which in turn constrains some of the structural parameters relevant to selectivity and activity. Peptides with the initial sequence Tyr–Tic–X are δ-selective antagonists. The tetrapeptide Tyr–Tic–Phe–Phe is one of the most potent and selective δ-antagonists known (Schiller et al., 1993). Antagonist activity has even been observed in the dipeptide Tyr–Tic–NH2 (Temussi et al., 1994).

To better understand the structural elements required for selectivity and potency, detailed structural studies have been completed on many of the natural opioids and their synthetic analogues (Deschamps et al., 1996). As part of this effort, the structure of boc–Tyr–Tic, (I), where boc is tert-butoxycarbonyl, was determined by X-ray diffraction.

There are three intermolecular hydrogen bonds (Table 2) which link the dipeptide in an infinite three-dimensional network. Each of the hydroxyls and the N-terminal nitrogen form hydrogen bonds to carbonyl-O atoms in neighboring molecules. The nitromethane solvent does not form any hydrogen bonds. Its closest approach to the dipeptide is at van der Waals separation.

The torsion angles that define the conformation of this peptide are reported in Table 1. The conformation of this dipeptide is more open than that of the tetrapeptide TIPP (Flippen-Anderson et al., 1994) or any other Tic-containing peptide reported to date. This could be due, in part, to the presence of the bulky boc moiety.

Molecular modeling was used to increase our understanding of the conformational differences between boc–Tyr–Tic and TIPP. In TIPP, ω1 (C1A—C1'—N2—C2A) is cis, but in boc–Tyr–Tic, ω1 is trans. The closely related agonists Tyr–D-Tic–Phe–Phe (D-TIPP) and Tyr–D-Tic (Flippen-Anderson et al., 1997; Deschamps et al., 1997) also have a trans conformation at ω1, but are more tightly folded than boc–Tyr–Tic. These differences in folding result in variations in the the separation of the aromatic rings. In boc–Tyr–Tic, the distance between the rings (reported as the distance between the centroids of the rings) is 8.4 (1) Å. In the other Tic-containing peptides, the rings are closer together, with separations ranging from 6.6–6.7 Å in D-TIPP, to 5.93 Å in TIPP, and to 3.9–4.1 Å in the D-Tic dipeptides (Deschamps et al., 1998).

Using TIPP (the only L-Tic-containing peptide whose solid-state X-ray structure has been reported) as a template, an alternate conformation for boc–Tyr–Tic was constructed. Using MIDAS, the torsion angles in boc–Tyr–Tic were changed to more closely resemble those in TIPP. A comparison of the steric energy (after energy minimization) of the observed X-ray structure and this `rotated' model reveals only a 1.8 kcal difference. This small difference can not account for the rather large conformational differences between TIPP and boc–Tyr–Tic. Thus, in solution, boc–Tyr–Tic could have a conformation like that of TIPP which could account for the observed antagonist activity of the dipeptide Tyr–Tic–NH2 (Temussi et al., 1994). In the rotated conformation, the distance between the rings is 4.4 Å before energy minimization and 4.7 Å after minimization. These distances are longer than the separation of the aromatic rings observed in the D-Tic dipeptides and shorter than the distance observed in TIPP. Since a conformation similar to that observed in TIPP (i.e. the rotated model) is not energetically unfavored and since the unblocked dipeptides have biologic activity similar to longer peptides of the same series, the differences in the conformation of TIPP and boc–Tyr–Tic are most likely due to the presence of the boc moiety.

Experimental top

Crystallization: the dipeptide, boc-tyrosyl-tetrahydroisoquinoline-3-carboxylic acid, was obtained from Research Triangle Institute (RTI). Crystals were grown by evaporation from methanol–nitromethane (2:1). Attempts to produce higher quality crystals out of aqueous solutions were not successful. Modeling: using MIDAS (Ferrin et al., 1988), the torsion angles of the dipeptide were rotated until a good match with residues 1 and 2 of Tyr–Tic–Phe–Phe (TIPP; Flippen-Anderson et al., 1994) was achieved. The steric energy of the energy-minimized X-ray structure and the `rotated' model were then calculated using MM2 parameters as implemented in the program CHEM3D plus (Version 3.1; Cambridge Scientific Computing, Inc., Cambridge, MA 02139, USA). Several missing torsional parameters were approximated by the substitution of a similar atom into the atomic sequence. The values for the optimal bond lengths for the atoms in the ring systems were taken from the median values listed for those ring systems in International Tables for Crystallography, Vol. C.

Refinement top

Despite low-temperature data collection, the crystals suffered almost a 7% loss of intensity during data collection. This, in combination with restrictions caused by the low-temperature device itself, limited the data collection range. The solvent (nitromethane) does not interact with any other molecule and it is likely that solvent was lost from the crystal during data collection. The loss of solvent during data collection would explain both the partial occupancy of the solvent and the final R value of aproximately 7% even though Rinternal and Rsigma are 4.9 and 3.8, respectivly. The nitromethane molecule also has larger displacement parameters than the peptide. The correct configuration was set by comparison to TIPP, a related peptide whose absolute configuration is known.

Computing details top

Data collection: XSCANS (Bruker, 1994); cell refinement: XSCANS; data reduction: XPREP (Bruker, 1994); program(s) used to solve structure: SHELXS (Sheldrick, 1990); program(s) used to refine structure: SHELXTL (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. View of (I) showing the labeling of all non-H atoms in the dipeptide. The nitromethane molecule, which does not interact with the peptide, has been omitted for clarity. Displacement elipsoids are shown at 30% probability level; H atoms are drawn as small circles of arbitrary radii.
boc-tyrosyl-tetrahydroisoquinoline-3-carboxylic acid nitromethane solvate top
Crystal data top
C24H28N2O6·0.825CH3NO2Dx = 1.166 Mg m3
Mr = 490.85Cu Kα radiation, λ = 1.54178 Å
Orthorhombic, P212121Cell parameters from 35 reflections
a = 11.464 (3) Åθ = 8.0–55.0°
b = 14.827 (2) ŵ = 0.73 mm1
c = 16.444 (2) ÅT = 223 K
V = 2795.1 (9) Å3Prism, clear colourless
Z = 40.52 × 0.50 × 0.46 mm
F(000) = 1064
Data collection top
Siemens P4
diffractometer
2080 reflections with I > 2σ(I)
Radiation source: sealed tubeRint = 0.049
Graphite monochromatorθmax = 56.5°, θmin = 4.0°
2θ/ω scansh = 012
Absorption correction: analytical
(XPREP; Siemens, 1994)
k = 016
Tmin = 0.723, Tmax = 0.807l = 217
2366 measured reflections3 standard reflections every 97 reflections
2249 independent reflections intensity decay: 6.8%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.075Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.195H-atom parameters constrained
S = 1.08 w = 1/[σ2(Fo2) + (0.1436P)2 + 1.0149P]
where P = (Fo2 + 2Fc2)/3
2249 reflections(Δ/σ)max = 0.002
326 parametersΔρmax = 0.42 e Å3
12 restraintsΔρmin = 0.36 e Å3
Crystal data top
C24H28N2O6·0.825CH3NO2V = 2795.1 (9) Å3
Mr = 490.85Z = 4
Orthorhombic, P212121Cu Kα radiation
a = 11.464 (3) ŵ = 0.73 mm1
b = 14.827 (2) ÅT = 223 K
c = 16.444 (2) Å0.52 × 0.50 × 0.46 mm
Data collection top
Siemens P4
diffractometer
2080 reflections with I > 2σ(I)
Absorption correction: analytical
(XPREP; Siemens, 1994)
Rint = 0.049
Tmin = 0.723, Tmax = 0.807θmax = 56.5°
2366 measured reflections3 standard reflections every 97 reflections
2249 independent reflections intensity decay: 6.8%
Refinement top
R[F2 > 2σ(F2)] = 0.07512 restraints
wR(F2) = 0.195H-atom parameters constrained
S = 1.08Δρmax = 0.42 e Å3
2249 reflectionsΔρmin = 0.36 e Å3
326 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. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating R-factor (obs) 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.

Since the Flack parameter refined to 0.2 (6) the absolute configuration was set by comparison to a related peptide whose absolute configuration was known.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
C1N0.8397 (5)0.9496 (5)0.0963 (4)0.0529 (18)
C2N0.8443 (7)1.0444 (5)0.1288 (6)0.077 (2)
H1NA0.85161.04280.18690.115*
H1NB0.77401.07570.11420.115*
H1NC0.91031.07520.10590.115*
C3N0.7467 (6)0.8936 (6)0.1373 (5)0.068 (2)
H1ND0.75500.89830.19520.101*
H1NE0.75490.83170.12110.101*
H1NF0.67110.91530.12150.101*
C4N0.8264 (8)0.9435 (7)0.0035 (4)0.084 (3)
H1NG0.75720.97510.01290.125*
H1NH0.82040.88130.01230.125*
H1NI0.89320.97020.02220.125*
O2N0.9474 (3)0.8996 (3)0.1202 (2)0.0415 (10)
C5N1.0536 (5)0.9298 (4)0.1003 (3)0.0362 (14)
O1N1.0733 (4)0.9969 (3)0.0596 (3)0.0554 (12)
N11.1361 (4)0.8777 (3)0.1333 (3)0.0334 (11)
H1N1.11690.83550.16660.040*
C1A1.2567 (5)0.8916 (4)0.1134 (3)0.0306 (12)
H1A1.27940.95410.12490.037*
C1'1.2778 (5)0.8692 (4)0.0227 (3)0.0351 (13)
O11.2209 (4)0.8082 (3)0.0098 (2)0.0440 (11)
C1B1.3340 (5)0.8252 (4)0.1628 (3)0.0386 (14)
H1B11.31170.76380.14990.046*
H1B21.41490.83320.14710.046*
C1G1.3226 (5)0.8399 (4)0.2540 (3)0.0380 (14)
C1D11.3792 (5)0.9110 (4)0.2922 (4)0.0415 (14)
H1D11.42630.94950.26190.050*
C1E11.3660 (5)0.9253 (4)0.3761 (3)0.0394 (14)
H1E11.40400.97320.40130.047*
C1Z1.2959 (5)0.8676 (4)0.4210 (3)0.0373 (14)
O1Z1.2772 (4)0.8792 (3)0.5026 (2)0.0461 (11)
H1Z1.32630.91380.52110.069*
C1E21.2407 (6)0.7965 (4)0.3838 (4)0.0423 (15)
H1E21.19470.75740.41420.051*
C1D21.2537 (6)0.7830 (4)0.3006 (4)0.0445 (15)
H1D21.21550.73500.27570.053*
N21.3648 (4)0.9107 (3)0.0169 (3)0.0308 (10)
C2A1.4002 (5)0.8771 (4)0.0972 (3)0.0332 (13)
H2A1.33910.83610.11660.040*
C2'1.5136 (5)0.8236 (4)0.0916 (3)0.0381 (14)
O2'1.5346 (4)0.7912 (3)0.0187 (2)0.0456 (11)
H2'1.59540.76210.01950.068*
O21.5738 (4)0.8109 (3)0.1510 (3)0.0557 (13)
C2B1.4091 (5)0.9544 (4)0.1572 (3)0.0375 (13)
H2B11.44550.93290.20680.045*
H2B21.33130.97520.17080.045*
C2G1.4789 (5)1.0327 (4)0.1243 (3)0.0360 (13)
C2D1.4925 (5)1.0430 (4)0.0410 (3)0.0343 (13)
C2E1.4412 (5)0.9787 (4)0.0208 (3)0.0346 (13)
H2E11.50410.94840.04930.042*
H2E21.39681.01290.06040.042*
C2G11.5256 (6)1.0966 (5)0.1759 (4)0.0472 (16)
H2G11.51651.08950.23170.057*
C2G21.5852 (7)1.1704 (5)0.1471 (4)0.0594 (19)
H2G21.61521.21310.18300.071*
C2G31.6002 (6)1.1804 (5)0.0633 (5)0.0589 (18)
H2G31.64001.22990.04250.071*
C2G41.5557 (5)1.1162 (4)0.0121 (4)0.0442 (15)
H2G41.56811.12190.04350.053*
N1S1.1140 (10)0.8247 (8)0.6963 (6)0.097 (4)0.825 (14)
C1S1.1003 (8)0.7499 (6)0.6474 (7)0.070 (3)0.825 (14)
H1S1.15830.70570.66100.105*0.825 (14)
H2S1.10910.76710.59140.105*0.825 (14)
H3S1.02400.72470.65560.105*0.825 (14)
O1S1.0480 (12)0.8892 (6)0.6892 (5)0.126 (4)0.825 (14)
O2S1.1947 (19)0.8304 (12)0.7369 (13)0.250 (9)0.825 (14)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C1N0.032 (3)0.079 (5)0.048 (4)0.013 (3)0.010 (3)0.004 (4)
C2N0.050 (4)0.065 (5)0.115 (7)0.016 (4)0.003 (5)0.007 (5)
C3N0.032 (3)0.099 (6)0.072 (5)0.005 (4)0.005 (4)0.013 (5)
C4N0.073 (5)0.133 (8)0.045 (4)0.024 (5)0.019 (4)0.016 (5)
O2N0.030 (2)0.061 (3)0.034 (2)0.0068 (19)0.0036 (18)0.003 (2)
C5N0.032 (3)0.058 (4)0.019 (3)0.009 (3)0.003 (3)0.003 (3)
O1N0.054 (3)0.065 (3)0.047 (2)0.005 (2)0.000 (2)0.027 (2)
N10.033 (3)0.047 (3)0.019 (2)0.002 (2)0.002 (2)0.004 (2)
C1A0.032 (3)0.041 (3)0.019 (3)0.003 (2)0.000 (2)0.002 (2)
C1'0.037 (3)0.048 (3)0.021 (3)0.000 (3)0.001 (3)0.005 (3)
O10.043 (2)0.062 (3)0.027 (2)0.015 (2)0.0058 (19)0.013 (2)
C1B0.032 (3)0.060 (4)0.024 (3)0.009 (3)0.003 (2)0.001 (3)
C1G0.035 (3)0.056 (3)0.024 (3)0.005 (3)0.004 (3)0.003 (3)
C1D10.041 (3)0.052 (3)0.032 (3)0.005 (3)0.001 (3)0.004 (3)
C1E10.051 (4)0.036 (3)0.031 (3)0.006 (3)0.006 (3)0.006 (3)
C1Z0.050 (3)0.041 (3)0.022 (3)0.009 (3)0.004 (3)0.001 (3)
O1Z0.063 (3)0.053 (2)0.022 (2)0.001 (2)0.002 (2)0.0066 (18)
C1E20.049 (4)0.050 (3)0.028 (3)0.002 (3)0.003 (3)0.008 (3)
C1D20.056 (4)0.049 (3)0.029 (3)0.008 (3)0.009 (3)0.003 (3)
N20.025 (2)0.047 (3)0.021 (2)0.001 (2)0.0007 (19)0.008 (2)
C2A0.028 (3)0.053 (3)0.019 (3)0.000 (3)0.002 (2)0.010 (2)
C2'0.041 (3)0.046 (3)0.027 (3)0.004 (3)0.005 (3)0.003 (3)
O2'0.040 (2)0.065 (3)0.031 (2)0.017 (2)0.0001 (19)0.004 (2)
O20.064 (3)0.060 (3)0.043 (3)0.019 (2)0.024 (3)0.008 (2)
C2B0.037 (3)0.055 (3)0.021 (3)0.005 (3)0.000 (2)0.001 (3)
C2G0.028 (3)0.054 (3)0.026 (3)0.008 (3)0.003 (2)0.003 (3)
C2D0.032 (3)0.045 (3)0.027 (3)0.005 (3)0.002 (2)0.001 (3)
C2E0.037 (3)0.043 (3)0.024 (3)0.002 (3)0.004 (3)0.004 (2)
C2G10.051 (4)0.062 (4)0.028 (3)0.006 (3)0.003 (3)0.009 (3)
C2G20.067 (5)0.063 (4)0.048 (4)0.013 (4)0.012 (4)0.009 (4)
C2G30.055 (4)0.059 (4)0.063 (4)0.014 (4)0.003 (4)0.004 (4)
C2G40.044 (3)0.053 (3)0.035 (3)0.005 (3)0.001 (3)0.002 (3)
N1S0.118 (9)0.099 (7)0.075 (7)0.002 (6)0.052 (6)0.005 (6)
C1S0.056 (5)0.065 (5)0.089 (8)0.011 (4)0.001 (5)0.001 (5)
O1S0.225 (11)0.073 (5)0.079 (6)0.013 (7)0.044 (7)0.006 (4)
O2S0.274 (16)0.230 (14)0.245 (16)0.019 (12)0.105 (14)0.121 (12)
Geometric parameters (Å, º) top
C1N—O2N1.493 (7)C1E2—C1D21.391 (9)
C1N—C2N1.505 (11)N2—C2A1.469 (7)
C1N—C3N1.510 (11)N2—C2E1.473 (7)
C1N—C4N1.535 (10)C2A—C2B1.517 (8)
O2N—C5N1.337 (7)C2A—C2'1.526 (8)
C5N—O1N1.221 (7)C2'—O21.212 (7)
C5N—N11.336 (7)C2'—O2'1.312 (7)
N1—C1A1.436 (7)C2B—C2G1.509 (8)
C1A—C1'1.547 (7)C2G—C2G11.380 (9)
C1A—C1B1.554 (8)C2G—C2D1.388 (8)
C1'—O11.237 (7)C2D—C2G41.389 (8)
C1'—N21.340 (7)C2D—C2E1.511 (8)
C1B—C1G1.520 (8)C2G1—C2G21.374 (10)
C1G—C1D21.386 (9)C2G2—C2G31.397 (11)
C1G—C1D11.387 (8)C2G3—C2G41.369 (9)
C1D1—C1E11.404 (8)N1S—O2S1.145 (18)
C1E1—C1Z1.388 (8)N1S—O1S1.225 (13)
C1Z—O1Z1.370 (7)N1S—C1S1.380 (14)
C1Z—C1E21.373 (9)
O2N—C1N—C2N109.9 (5)C1Z—C1E2—C1D2120.0 (6)
O2N—C1N—C3N101.1 (5)C1G—C1D2—C1E2121.1 (6)
C2N—C1N—C3N112.3 (6)C1'—N2—C2A119.1 (5)
O2N—C1N—C4N108.4 (6)C1'—N2—C2E123.6 (4)
C2N—C1N—C4N114.3 (8)C2A—N2—C2E116.5 (4)
C3N—C1N—C4N109.9 (7)N2—C2A—C2B110.3 (5)
C5N—O2N—C1N121.5 (5)N2—C2A—C2'110.9 (5)
O1N—C5N—O2N125.2 (5)C2B—C2A—C2'112.0 (5)
O1N—C5N—N1124.2 (5)O2—C2'—O2'125.1 (5)
O2N—C5N—N1110.6 (5)O2—C2'—C2A121.1 (5)
C5N—N1—C1A120.4 (5)O2'—C2'—C2A113.7 (5)
N1—C1A—C1'109.8 (4)C2G—C2B—C2A112.6 (4)
N1—C1A—C1B109.8 (4)C2G1—C2G—C2D119.1 (6)
C1'—C1A—C1B106.3 (4)C2G1—C2G—C2B120.9 (5)
O1—C1'—N2121.2 (5)C2D—C2G—C2B119.9 (5)
O1—C1'—C1A119.4 (5)C2G—C2D—C2G4118.9 (5)
N2—C1'—C1A119.1 (5)C2G—C2D—C2E123.4 (5)
C1G—C1B—C1A112.1 (5)C2G4—C2D—C2E117.8 (5)
C1D2—C1G—C1D1118.6 (5)N2—C2E—C2D112.4 (4)
C1D2—C1G—C1B120.4 (5)C2G2—C2G1—C2G121.9 (6)
C1D1—C1G—C1B121.0 (5)C2G1—C2G2—C2G3119.0 (6)
C1G—C1D1—C1E1120.6 (6)C2G4—C2G3—C2G2119.2 (7)
C1Z—C1E1—C1D1119.5 (5)C2G3—C2G4—C2D121.8 (6)
O1Z—C1Z—C1E2117.5 (6)O2S—N1S—O1S119.8 (14)
O1Z—C1Z—C1E1122.3 (5)O2S—N1S—C1S119.5 (14)
C1E2—C1Z—C1E1120.2 (5)O1S—N1S—C1S120.2 (9)
N1—C1A—C1'—N2152.4 (5)C2A—C2B—C2G—C2G1160.8 (5)
C1'—N2—C2A—C2'103.6 (6)C2A—C2B—C2G—C2D21.9 (7)
N1—C1A—C1B—C1G61.6 (6)C2B—C2G—C2D—C2E0.4 (8)
C1A—C1'—N2—C2A168.1 (4)C2G—C2D—C2E—N26.5 (8)
C1A—C1B—C1G—C1D177.6 (7)C2D—C2E—N2—C2A36.2 (6)
C1A—C1B—C1G—C1D2101.5 (6)C2E—N2—C2A—C2B58.4 (6)
N2—C2A—C2B—C2G48.8 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1Z—H1Z···O1Ni0.821.872.682 (6)173
O2—H2···O1ii0.821.842.637 (6)163
N1—H1N···O2iii0.862.242.901 (6)133
Symmetry codes: (i) x+5/2, y+2, z+1/2; (ii) x+1/2, y+3/2, z; (iii) x1/2, y+3/2, z.

Experimental details

Crystal data
Chemical formulaC24H28N2O6·0.825CH3NO2
Mr490.85
Crystal system, space groupOrthorhombic, P212121
Temperature (K)223
a, b, c (Å)11.464 (3), 14.827 (2), 16.444 (2)
V3)2795.1 (9)
Z4
Radiation typeCu Kα
µ (mm1)0.73
Crystal size (mm)0.52 × 0.50 × 0.46
Data collection
DiffractometerSiemens P4
diffractometer
Absorption correctionAnalytical
(XPREP; Siemens, 1994)
Tmin, Tmax0.723, 0.807
No. of measured, independent and
observed [I > 2σ(I)] reflections
2366, 2249, 2080
Rint0.049
θmax (°)56.5
(sin θ/λ)max1)0.541
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.075, 0.195, 1.08
No. of reflections2249
No. of parameters326
No. of restraints12
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.42, 0.36

Computer programs: XSCANS (Bruker, 1994), XSCANS, XPREP (Bruker, 1994), SHELXS (Sheldrick, 1990), SHELXTL (Sheldrick, 1997), SHELXTL.

Selected torsion angles (º) top
N1—C1A—C1'—N2152.4 (5)C2A—C2B—C2G—C2G1160.8 (5)
C1'—N2—C2A—C2'103.6 (6)C2A—C2B—C2G—C2D21.9 (7)
N1—C1A—C1B—C1G61.6 (6)C2B—C2G—C2D—C2E0.4 (8)
C1A—C1'—N2—C2A168.1 (4)C2G—C2D—C2E—N26.5 (8)
C1A—C1B—C1G—C1D177.6 (7)C2D—C2E—N2—C2A36.2 (6)
C1A—C1B—C1G—C1D2101.5 (6)C2E—N2—C2A—C2B58.4 (6)
N2—C2A—C2B—C2G48.8 (6)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1Z—H1Z···O1Ni0.821.8652.682 (6)173.4
O2'—H2'···O1ii0.821.8412.637 (6)163.3
N1—H1N···O2iii0.862.2412.901 (6)133.4
Symmetry codes: (i) x+5/2, y+2, z+1/2; (ii) x+1/2, y+3/2, z; (iii) x1/2, y+3/2, z.
 

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