(S)-(Z)-Methyl 2-[2,3-bis­(benzyl­oxy­carbon­yl)guanidino]-4-methyl­penta­no­ate

Fronczek, C.F.; Kil, H.J.; McLaughlin, M.L.; Fronczek, F.R.

doi:10.1107/S1600536810050130

(S)-(Z)-Methyl 2-[2,3-bis(benzyloxycarbonyl)guanidino]-4-methylpentanoate

C. F. Fronczek, H. J. Kil, M. L. McLaughlin and F. R. Fronczek

The title molecule, C₂₄H₂₉N₃O₆, has a nearly planar ten-atom C₃N₃O₄ core, on account of both N—H groups forming six-membered-ring intramolecular hydrogen bonds to carbamate carbonyl O atoms. The absolute configuration was determined from resonant scattering of light atoms in Mo Kα radiation, agreeing with the configuration of starting materials.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536810050130/om2385sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536810050130/om2385Isup2.hkl Contains datablock I

CCDC reference: 807316

checkCIF report

Key indicators

Single-crystal X-ray study
T = 90 K
Mean (C-C) = 0.002 Å
R factor = 0.043
wR factor = 0.101
Data-to-parameter ratio = 33.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O4     --  C9      ..       5.42 su
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N2     --  C9      ..       5.09 su
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          3
PLAT024_ALERT_4_C Merging of Friedel Pairs is Indicated ..........          !
PLAT032_ALERT_4_C Std. Uncertainty in Flack Parameter too High ...       0.50
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600        263

Alert level G
REFLT03_ALERT_4_G  ALERT: MoKa measured Friedel data cannot be used to
                   determine absolute structure in a light-atom
                   study EXCEPT under VERY special conditions.
                   It is preferred that Friedel data is merged in such cases.
           From the CIF: _diffrn_reflns_theta_max           36.10
           From the CIF: _reflns_number_total              10411
           Count of symmetry unique reflns         6176
           Completeness (_total/calc)            168.57%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      4235
           Fraction of Friedel pairs measured     0.686
           Are heavy atom types Z>Si present         no
PLAT916_ALERT_2_G Hooft y and Flack x Parameter values differ by .       0.20
PLAT791_ALERT_4_G Note: The Model has Chirality at C3     (Verify)          S

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   5 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

Molecules used as drugs frequently contain heterocyclic subunits, and substituted guanidine or amidine compounds are very important intermediates in the synthesis of many heterocyclic compounds. However, substituted guanidines and amidine compounds themselves can be difficult to synthesize. Thus, synthesis of substituted guanidines is important and interesting. One possible route to these compounds is to use 1,3-bis(benzyloxycarbonyl)-2-methyl-2-thiopseudourea, which has a good leaving group and L-leucine methyl ester hydrochloride, which is a good nucleophile. Reaction of these starting materials led to successful synthesis of the chiral title compound, which was confirmed by crystal structure determination.

The structure, shown in Figure 1, has a guanidine at its core. The three C—N distances of the guanidine vary from 1.3225 (12) to 1.3864 (12) Å, with the shortest being the formal double bond to the unprotonated N atom N2 and the longest being to the other carbamate N atom N3. These values are in good agreement with those seen in 1,2-bis(methoxycarbonyl)-3-phenylguanidine, (Travlos & White, 1994), in which the length pattern is the same and the range of lengths is 1.309 (3) to 1.388 (4) Å. In N,N',N''-tris(t-butoxycarbonyl)guanidine (Feichtinger et al., 1998; space group corrected by Marsh, 2002), the C═N and C—NH groups are disordered, and the C—N distance is 1.343 Å. In the title compound, the two N—H groups form intramolecular hydrogen bonds with graph set (Etter, 1990) S(6). The hydrogen bonding leads to a fairly planar central C₃N₃O₄ portion of the molecule, which has a mean deviation 0.019 Å from coplanarity and a maximum deviation 0.0533 (10) Å for N3.

The lone stereocenter is carbon C3, with (S) configuration, as known from starting material L-leucine. Absolute configuration determination based on resonant scattering of the light atoms in Mo Kα radiation was possible for this structure, on account of the excellent quality of the crystal, the fact that it is relatively rich in O and N, the high resolution of the data, and the completeness of the set of 4545 Bijvoet pairs, which were kept separate in the refinement. While the Flack (1983) parameter is unconvincing, with a value of 0.2 (5), the Hooft et al. (2008) parameter y = 0.0 (2) has a much smaller uncertainty, and the Hooft P2(true) value is 1.000. A number of oxygen-rich compounds producing Mo data sets of similar high quality have been shown to yield similarly reliable absolute-structure results, agreeing with the known configurations (Fronczek, 2010; Lutz & van Krieken, 2010; Thompson et al., 2008).

Related literature top

For related structures, see: Travlos & White (1994); Feichtinger et al. (1998); Marsh (2002). For graph sets, see: Etter (1990). For absolute configuration based on resonant scattering from light atoms, see: Hooft et al. (2008); Fronczek (2010); Lutz & van Krieken (2010); Thompson et al. (2008).

Experimental top

A mixture of 1,3-bis(benzyloxycarbonyl)-2-methyl-2-thiopseudourea (2.79 mmol, 1 g), L-leucine methyl ester hydrochloride (2.79 mmol, 0.51 g), and triethylamine (2.79 mmole, 0.4 ml) in THF (absolute, 10 mL) was stirred at 338 K. The mixture was brought to room temperature, and the precipitate was filtered by vacuum. After evaporation of all solvents from the filtrate, the product was purified by chromatography (EtOAc/hexane, 1:4). The product was isolated as colorless crystals in 46% yield. ¹H NMR (Methanol, 400 MHz): δ 0.85–0.88 (dd, 6H), 1.58–1.60 (m, 2H), 1.67–1.74 (m, 1H), 3.63 (s, 3H), 4.54–4.59 (m, 1H), 7.28–7.43 (m, 10H), 8.53–8.55 (d, 1H), 11.47 (s, 1H). ¹³C NMR (Methanol, 400 MHz): δ 22.12, 24.95, 67.08, 68.47, 128.44, 128.54, 128.93, 129.01, 129.13, 155.36, 163.12, 172.39. MS m/z 456.21 [M+H]⁺, 478.19 [M+Na]⁺.

Structure description top

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. Ellipsoids at the 50% level, with H atoms having arbitrary radius.

(S)-(Z)-Methyl 2-[2,3-bis(benzyloxycarbonyl)guanidino]-4-methylpentanoate top

Crystal data top

C₂₄H₂₉N₃O₆	F(000) = 968
M_r = 455.50	D_x = 1.297 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 5760 reflections
a = 7.7203 (5) Å	θ = 2.5–36.1°
b = 14.2043 (10) Å	µ = 0.09 mm⁻¹
c = 21.280 (2) Å	T = 90 K
V = 2333.6 (3) Å³	Fragment, colourless
Z = 4	0.30 × 0.28 × 0.15 mm

Data collection top

Nonius KappaCCD (with an Oxford Cryosystems Cryostream cooler) diffractometer	9219 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.056
Graphite monochromator	θ_max = 36.1°, θ_min = 2.8°
ω and φ scans	h = −12→12
43001 measured reflections	k = −22→22
10411 independent reflections	l = −34→34

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)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.101	w = 1/[σ²(F_o²) + (0.0473P)² + 0.6349P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
10411 reflections	Δρ_max = 0.33 e Å⁻³
307 parameters	Δρ_min = −0.28 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 4545 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.2 (5)

Crystal data top

C₂₄H₂₉N₃O₆	V = 2333.6 (3) Å³
M_r = 455.50	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 7.7203 (5) Å	µ = 0.09 mm⁻¹
b = 14.2043 (10) Å	T = 90 K
c = 21.280 (2) Å	0.30 × 0.28 × 0.15 mm

Data collection top

Nonius KappaCCD (with an Oxford Cryosystems Cryostream cooler) diffractometer	9219 reflections with I > 2σ(I)
43001 measured reflections	R_int = 0.056
10411 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.101	Δρ_max = 0.33 e Å⁻³
S = 1.02	Δρ_min = −0.28 e Å⁻³
10411 reflections	Absolute structure: Flack (1983), 4545 Friedel pairs
307 parameters	Absolute structure parameter: 0.2 (5)
0 restraints

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. 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	U_iso*/U_eq
O1	0.58734 (12)	0.48105 (6)	0.79229 (4)	0.01853 (16)
O2	0.69349 (11)	0.37173 (6)	0.72588 (4)	0.01797 (15)
O3	0.66892 (11)	0.75163 (5)	0.55412 (3)	0.01520 (14)
O4	0.70303 (12)	0.64048 (5)	0.47943 (4)	0.01833 (15)
O5	0.57441 (13)	0.31412 (5)	0.54332 (4)	0.02052 (17)
O6	0.65667 (11)	0.35908 (5)	0.44569 (3)	0.01435 (13)
N1	0.55713 (12)	0.46022 (6)	0.62459 (4)	0.01239 (14)
H1N	0.555 (2)	0.4008 (11)	0.6200 (7)	0.015*
N2	0.62092 (12)	0.60509 (5)	0.58336 (4)	0.01166 (14)
N3	0.63981 (13)	0.46856 (6)	0.51925 (4)	0.01316 (15)
H3N	0.665 (2)	0.5094 (11)	0.4900 (7)	0.016*
C1	0.66331 (18)	0.43149 (9)	0.84503 (5)	0.0225 (2)
H1A	0.6032	0.3714	0.8511	0.034*
H1B	0.6519	0.4699	0.8831	0.034*
H1C	0.7862	0.4197	0.8366	0.034*
C2	0.61124 (13)	0.44220 (7)	0.73573 (4)	0.01164 (15)
C3	0.51657 (13)	0.49959 (7)	0.68598 (4)	0.01065 (15)
H3	0.5592	0.5660	0.6876	0.013*
C4	0.32033 (13)	0.49892 (7)	0.69888 (4)	0.01355 (16)
H4A	0.2779	0.4334	0.6954	0.016*
H4B	0.3005	0.5198	0.7427	0.016*
C5	0.21252 (14)	0.56144 (7)	0.65481 (5)	0.01525 (17)
H5	0.2404	0.5437	0.6105	0.018*
C6	0.01921 (16)	0.54251 (9)	0.66614 (7)	0.0256 (2)
H6A	−0.0103	0.5586	0.7096	0.038*
H6B	−0.0055	0.4758	0.6587	0.038*
H6C	−0.0499	0.5811	0.6374	0.038*
C7	0.25316 (14)	0.66599 (7)	0.66332 (5)	0.01623 (18)
H7A	0.1775	0.7033	0.6360	0.024*
H7B	0.3744	0.6778	0.6522	0.024*
H7C	0.2336	0.6839	0.7072	0.024*
C8	0.60582 (13)	0.51301 (6)	0.57593 (4)	0.01072 (15)
C9	0.66760 (13)	0.66107 (7)	0.53418 (4)	0.01203 (15)
C10	0.70649 (16)	0.82125 (7)	0.50644 (5)	0.01594 (18)
H10A	0.6129	0.8227	0.4747	0.019*
H10B	0.8168	0.8061	0.4850	0.019*
C11	0.71972 (14)	0.91503 (7)	0.53912 (5)	0.01436 (17)
C12	0.83270 (16)	0.92721 (8)	0.58972 (5)	0.01901 (19)
H12	0.9022	0.8761	0.6036	0.023*
C13	0.84373 (17)	1.01415 (9)	0.61988 (6)	0.0235 (2)
H13	0.9205	1.0221	0.6544	0.028*
C14	0.74245 (17)	1.08929 (8)	0.59950 (6)	0.0243 (2)
H14	0.7502	1.1485	0.6201	0.029*
C15	0.63033 (17)	1.07768 (7)	0.54924 (6)	0.0220 (2)
H15	0.5616	1.1290	0.5353	0.026*
C16	0.61826 (16)	0.99065 (7)	0.51914 (5)	0.01785 (18)
H16	0.5406	0.9828	0.4849	0.021*
C17	0.61893 (14)	0.37440 (7)	0.50618 (5)	0.01343 (16)
C18	0.63343 (15)	0.26163 (7)	0.42515 (5)	0.01528 (18)
H18A	0.5126	0.2412	0.4326	0.018*
H18B	0.7119	0.2194	0.4489	0.018*
C19	0.67470 (14)	0.25779 (6)	0.35627 (4)	0.01216 (15)
C20	0.55057 (14)	0.22770 (7)	0.31311 (5)	0.01544 (17)
H20	0.4373	0.2120	0.3270	0.019*
C21	0.59258 (16)	0.22057 (8)	0.24956 (5)	0.0188 (2)
H21	0.5084	0.1988	0.2204	0.023*
C22	0.75696 (16)	0.24510 (8)	0.22862 (5)	0.0190 (2)
H22	0.7849	0.2410	0.1852	0.023*
C23	0.88041 (15)	0.27570 (7)	0.27170 (5)	0.01767 (18)
H23	0.9928	0.2928	0.2576	0.021*
C24	0.84025 (14)	0.28140 (7)	0.33530 (5)	0.01503 (17)
H24	0.9257	0.3014	0.3645	0.018*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0276 (4)	0.0184 (3)	0.0095 (3)	0.0087 (3)	−0.0024 (3)	−0.0005 (3)
O2	0.0190 (4)	0.0179 (3)	0.0170 (3)	0.0076 (3)	0.0007 (3)	0.0004 (3)
O3	0.0251 (4)	0.0083 (3)	0.0122 (3)	−0.0017 (3)	0.0044 (3)	0.0002 (2)
O4	0.0303 (4)	0.0128 (3)	0.0120 (3)	−0.0029 (3)	0.0067 (3)	−0.0006 (2)
O5	0.0370 (5)	0.0108 (3)	0.0137 (3)	−0.0018 (3)	0.0072 (3)	−0.0001 (3)
O6	0.0222 (4)	0.0101 (3)	0.0107 (3)	−0.0015 (3)	0.0039 (3)	−0.0022 (2)
N1	0.0194 (4)	0.0083 (3)	0.0095 (3)	−0.0002 (3)	0.0026 (3)	−0.0005 (2)
N2	0.0163 (4)	0.0084 (3)	0.0103 (3)	−0.0011 (3)	0.0016 (3)	0.0001 (2)
N3	0.0209 (4)	0.0087 (3)	0.0099 (3)	−0.0009 (3)	0.0035 (3)	−0.0003 (2)
C1	0.0282 (6)	0.0277 (5)	0.0115 (4)	0.0081 (5)	−0.0040 (4)	0.0028 (4)
C2	0.0121 (4)	0.0126 (4)	0.0103 (3)	−0.0008 (3)	0.0002 (3)	0.0011 (3)
C3	0.0141 (4)	0.0096 (3)	0.0083 (3)	0.0009 (3)	0.0012 (3)	0.0000 (3)
C4	0.0127 (4)	0.0144 (4)	0.0136 (4)	0.0011 (3)	0.0005 (3)	0.0016 (3)
C5	0.0156 (4)	0.0147 (4)	0.0154 (4)	0.0030 (3)	−0.0035 (3)	−0.0015 (3)
C6	0.0152 (5)	0.0239 (5)	0.0377 (7)	0.0013 (4)	−0.0054 (5)	−0.0014 (5)
C7	0.0177 (5)	0.0139 (4)	0.0171 (4)	0.0043 (3)	−0.0029 (3)	−0.0012 (3)
C8	0.0124 (4)	0.0105 (3)	0.0092 (3)	0.0006 (3)	0.0005 (3)	−0.0004 (3)
C9	0.0128 (4)	0.0100 (3)	0.0132 (4)	−0.0004 (3)	0.0006 (3)	0.0002 (3)
C10	0.0252 (5)	0.0099 (4)	0.0127 (4)	−0.0022 (3)	0.0047 (4)	0.0019 (3)
C11	0.0193 (4)	0.0094 (3)	0.0144 (4)	−0.0018 (3)	0.0053 (3)	0.0004 (3)
C12	0.0218 (5)	0.0158 (4)	0.0195 (4)	−0.0004 (4)	0.0029 (4)	−0.0013 (4)
C13	0.0238 (5)	0.0228 (5)	0.0239 (5)	−0.0051 (4)	0.0040 (4)	−0.0084 (4)
C14	0.0280 (6)	0.0147 (4)	0.0302 (6)	−0.0059 (4)	0.0126 (5)	−0.0070 (4)
C15	0.0289 (6)	0.0111 (4)	0.0259 (5)	0.0028 (4)	0.0118 (4)	0.0016 (4)
C16	0.0223 (5)	0.0137 (4)	0.0175 (4)	0.0019 (4)	0.0059 (4)	0.0024 (3)
C17	0.0180 (4)	0.0108 (4)	0.0115 (4)	0.0009 (3)	0.0024 (3)	−0.0022 (3)
C18	0.0231 (5)	0.0096 (4)	0.0132 (4)	−0.0026 (3)	0.0042 (3)	−0.0027 (3)
C19	0.0155 (4)	0.0097 (3)	0.0113 (3)	0.0005 (3)	0.0013 (3)	−0.0017 (3)
C20	0.0140 (4)	0.0146 (4)	0.0178 (4)	0.0018 (3)	−0.0006 (3)	−0.0039 (3)
C21	0.0219 (5)	0.0186 (4)	0.0158 (4)	0.0056 (4)	−0.0070 (4)	−0.0041 (4)
C22	0.0287 (6)	0.0165 (4)	0.0118 (4)	0.0045 (4)	0.0010 (4)	0.0008 (3)
C23	0.0199 (5)	0.0169 (4)	0.0163 (4)	−0.0009 (4)	0.0045 (4)	0.0015 (3)
C24	0.0163 (4)	0.0150 (4)	0.0138 (4)	−0.0025 (3)	0.0005 (3)	−0.0005 (3)

Geometric parameters (Å, º) top

O1—C2	1.3369 (12)	C7—H7A	0.9800
O1—C1	1.4488 (13)	C7—H7B	0.9800
O2—C2	1.2037 (12)	C7—H7C	0.9800
O3—C9	1.3546 (12)	C10—C11	1.5061 (14)
O3—C10	1.4462 (12)	C10—H10A	0.9900
O4—C9	1.2321 (12)	C10—H10B	0.9900
O5—C17	1.2147 (12)	C11—C16	1.3958 (15)
O6—C17	1.3377 (12)	C11—C12	1.3966 (16)
O6—C18	1.4626 (12)	C12—C13	1.3943 (16)
N1—C8	1.3326 (12)	C12—H12	0.9500
N1—C3	1.4550 (12)	C13—C14	1.3923 (19)
N1—H1N	0.849 (16)	C13—H13	0.9500
N2—C8	1.3225 (12)	C14—C15	1.386 (2)
N2—C9	1.3628 (12)	C14—H14	0.9500
N3—C17	1.3756 (12)	C15—C16	1.3954 (15)
N3—C8	1.3864 (12)	C15—H15	0.9500
N3—H3N	0.873 (16)	C16—H16	0.9500
C1—H1A	0.9800	C18—C19	1.5011 (14)
C1—H1B	0.9800	C18—H18A	0.9900
C1—H1C	0.9800	C18—H18B	0.9900
C2—C3	1.5230 (13)	C19—C20	1.3944 (14)
C3—C4	1.5397 (14)	C19—C24	1.3947 (15)
C3—H3	1.0000	C20—C21	1.3944 (16)
C4—C5	1.5366 (14)	C20—H20	0.9500
C4—H4A	0.9900	C21—C22	1.3895 (18)
C4—H4B	0.9900	C21—H21	0.9500
C5—C7	1.5286 (15)	C22—C23	1.3920 (17)
C5—C6	1.5355 (17)	C22—H22	0.9500
C5—H5	1.0000	C23—C24	1.3910 (15)
C6—H6A	0.9800	C23—H23	0.9500
C6—H6B	0.9800	C24—H24	0.9500
C6—H6C	0.9800

C2—O1—C1	116.17 (8)	O4—C9—N2	130.27 (9)
C9—O3—C10	115.54 (8)	O3—C9—N2	108.40 (8)
C17—O6—C18	114.50 (8)	O3—C10—C11	107.12 (8)
C8—N1—C3	122.83 (8)	O3—C10—H10A	110.3
C8—N1—H1N	118.5 (11)	C11—C10—H10A	110.3
C3—N1—H1N	118.6 (11)	O3—C10—H10B	110.3
C8—N2—C9	120.56 (8)	C11—C10—H10B	110.3
C17—N3—C8	126.62 (8)	H10A—C10—H10B	108.5
C17—N3—H3N	121.8 (10)	C16—C11—C12	119.34 (10)
C8—N3—H3N	111.1 (10)	C16—C11—C10	120.13 (10)
O1—C1—H1A	109.5	C12—C11—C10	120.53 (10)
O1—C1—H1B	109.5	C13—C12—C11	120.18 (11)
H1A—C1—H1B	109.5	C13—C12—H12	119.9
O1—C1—H1C	109.5	C11—C12—H12	119.9
H1A—C1—H1C	109.5	C14—C13—C12	120.09 (12)
H1B—C1—H1C	109.5	C14—C13—H13	120.0
O2—C2—O1	124.94 (9)	C12—C13—H13	120.0
O2—C2—C3	125.25 (9)	C15—C14—C13	119.99 (11)
O1—C2—C3	109.80 (8)	C15—C14—H14	120.0
N1—C3—C2	108.37 (8)	C13—C14—H14	120.0
N1—C3—C4	111.68 (8)	C14—C15—C16	120.10 (11)
C2—C3—C4	110.18 (8)	C14—C15—H15	120.0
N1—C3—H3	108.9	C16—C15—H15	120.0
C2—C3—H3	108.9	C15—C16—C11	120.30 (11)
C4—C3—H3	108.9	C15—C16—H16	119.9
C5—C4—C3	114.87 (8)	C11—C16—H16	119.9
C5—C4—H4A	108.5	O5—C17—O6	124.96 (9)
C3—C4—H4A	108.5	O5—C17—N3	125.94 (9)
C5—C4—H4B	108.5	O6—C17—N3	109.10 (8)
C3—C4—H4B	108.5	O6—C18—C19	107.47 (8)
H4A—C4—H4B	107.5	O6—C18—H18A	110.2
C7—C5—C6	110.55 (9)	C19—C18—H18A	110.2
C7—C5—C4	112.21 (8)	O6—C18—H18B	110.2
C6—C5—C4	109.24 (9)	C19—C18—H18B	110.2
C7—C5—H5	108.2	H18A—C18—H18B	108.5
C6—C5—H5	108.2	C20—C19—C24	119.53 (9)
C4—C5—H5	108.2	C20—C19—C18	120.56 (9)
C5—C6—H6A	109.5	C24—C19—C18	119.88 (9)
C5—C6—H6B	109.5	C19—C20—C21	120.08 (10)
H6A—C6—H6B	109.5	C19—C20—H20	120.0
C5—C6—H6C	109.5	C21—C20—H20	120.0
H6A—C6—H6C	109.5	C22—C21—C20	120.35 (10)
H6B—C6—H6C	109.5	C22—C21—H21	119.8
C5—C7—H7A	109.5	C20—C21—H21	119.8
C5—C7—H7B	109.5	C21—C22—C23	119.50 (10)
H7A—C7—H7B	109.5	C21—C22—H22	120.2
C5—C7—H7C	109.5	C23—C22—H22	120.2
H7A—C7—H7C	109.5	C24—C23—C22	120.42 (11)
H7B—C7—H7C	109.5	C24—C23—H23	119.8
N2—C8—N1	119.24 (8)	C22—C23—H23	119.8
N2—C8—N3	122.53 (8)	C23—C24—C19	120.10 (10)
N1—C8—N3	118.24 (8)	C23—C24—H24	119.9
O4—C9—O3	121.32 (9)	C19—C24—H24	119.9

C1—O1—C2—O2	−1.94 (16)	O3—C10—C11—C12	54.29 (13)
C1—O1—C2—C3	177.18 (9)	C16—C11—C12—C13	0.00 (16)
C8—N1—C3—C2	−132.15 (10)	C10—C11—C12—C13	−179.77 (10)
C8—N1—C3—C4	106.31 (11)	C11—C12—C13—C14	−0.20 (18)
O2—C2—C3—N1	−5.64 (14)	C12—C13—C14—C15	0.08 (18)
O1—C2—C3—N1	175.24 (8)	C13—C14—C15—C16	0.24 (18)
O2—C2—C3—C4	116.82 (11)	C14—C15—C16—C11	−0.45 (17)
O1—C2—C3—C4	−62.30 (11)	C12—C11—C16—C15	0.33 (16)
N1—C3—C4—C5	−64.38 (11)	C10—C11—C16—C15	−179.91 (10)
C2—C3—C4—C5	175.13 (8)	C18—O6—C17—O5	2.47 (16)
C3—C4—C5—C7	−65.68 (11)	C18—O6—C17—N3	−177.91 (9)
C3—C4—C5—C6	171.35 (9)	C8—N3—C17—O5	−3.52 (19)
C9—N2—C8—N1	−178.87 (9)	C8—N3—C17—O6	176.87 (10)
C9—N2—C8—N3	1.53 (15)	C17—O6—C18—C19	177.95 (9)
C3—N1—C8—N2	1.03 (15)	O6—C18—C19—C20	−120.63 (10)
C3—N1—C8—N3	−179.35 (9)	O6—C18—C19—C24	61.55 (12)
C17—N3—C8—N2	−176.29 (10)	C24—C19—C20—C21	0.56 (15)
C17—N3—C8—N1	4.11 (16)	C18—C19—C20—C21	−177.26 (9)
C10—O3—C9—O4	2.71 (15)	C19—C20—C21—C22	−1.28 (16)
C10—O3—C9—N2	−176.60 (9)	C20—C21—C22—C23	0.85 (16)
C8—N2—C9—O4	−0.78 (18)	C21—C22—C23—C24	0.28 (16)
C8—N2—C9—O3	178.44 (9)	C22—C23—C24—C19	−0.99 (16)
C9—O3—C10—C11	−174.34 (9)	C20—C19—C24—C23	0.56 (15)
O3—C10—C11—C16	−125.47 (10)	C18—C19—C24—C23	178.40 (9)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O5	0.849 (16)	2.051 (16)	2.7047 (11)	133.3 (14)
N3—H3N···O4	0.873 (16)	1.898 (16)	2.6306 (11)	140.4 (14)

Experimental details

Crystal data
Chemical formula	C₂₄H₂₉N₃O₆
M_r	455.50
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	90
a, b, c (Å)	7.7203 (5), 14.2043 (10), 21.280 (2)
V (Å³)	2333.6 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.28 × 0.15

Data collection
Diffractometer	Nonius KappaCCD (with an Oxford Cryosystems Cryostream cooler)
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	43001, 10411, 9219
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.829

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.101, 1.02
No. of reflections	10411
No. of parameters	307
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.28
Absolute structure	Flack (1983), 4545 Friedel pairs
Absolute structure parameter	0.2 (5)

Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).