2,3,4-Triacet­oxy-1-[5-(1,2,3,4-tetra­acetoxy­butyl)pyrazin-2-yl]butyl acetate

Gainsford, G.J.; Benjes, P.A.

doi:10.1107/S1600536807062344

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o50

https://doi.org/10.1107/S1600536807062344

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2,3,4-Triacetoxy-1-[5-(1,2,3,4-tetraacetoxybutyl)pyrazin-2-yl]butyl acetate

Graeme J. Gainsford ^a ^* and Paul A. Benjes ^a

^aIndustrial Research Limited, PO Box 31-310, Lower Hutt, New Zealand
^*Correspondence e-mail: g.gainsford@irl.cri.nz

(Received 14 November 2007; accepted 22 November 2007; online 6 December 2007)

The title compound, C₂₈H₃₆N₂O₁₆, was obtained unintentionally in an attempt to synthesize 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-D-mannopyranose. The crystal packing utilizes methyl–acetoxy C—H⋯O and methyl–pyrazine C—H⋯N hydrogen bonding.

Related literature

For general background, see: Vasella et al. (1991 ); Alper et al. (1996 ). For related literature, see: Bovin et al. (1981 ); Paulsen & Stenzel (1978 ); Paulsen et al. (1985 ); Pavliak & Kovac (1991 ). For related structures, see: Klein et al. (1999 ); Myers et al. (2000 ), found in a search of the Cambridge Structural Database (Version 5.28; Allen; 2002 ).

Experimental

Crystal data

C₂₈H₃₆N₂O₁₆
M_r = 656.59
Triclinic, P 1
a = 5.6931 (8) Å
b = 9.9132 (15) Å
c = 15.5048 (11) Å
α = 81.344 (2)°
β = 80.635 (2)°
γ = 73.986 (2)°
V = 824.71 (18) Å³
Z = 1
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 159 (2) K
0.72 × 0.24 × 0.11 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
7120 measured reflections
3304 independent reflections
2954 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.103
S = 1.11
3304 reflections
424 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯N1ⁱ	0.95	2.61	3.338 (5)	134
C6—H6⋯N4ⁱⁱ	0.95	2.60	3.331 (5)	134
C7—H7B⋯O2ⁱⁱ	0.98	2.57	3.400 (5)	142
C19—H19A⋯O12ⁱⁱⁱ	0.98	2.58	3.443 (5)	147
C19—H19B⋯O10ⁱⁱ	0.98	2.58	3.407 (5)	142
C19—H19C⋯O2ⁱⁱⁱ	0.98	2.53	3.472 (6)	161
C26—H26B⋯O14ⁱ	0.98	2.60	3.471 (6)	148
Symmetry codes: (i) x+1, y, z; (ii) x-1, y, z; (iii) x, y-1, z.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2003 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807062344/sj2446sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807062344/sj2446Isup2.hkl

checkCIF report

Comment top

We were attempting to establish suitable process routes towards 2-azido-2-deoxy-D-manno- and -D-glucopyranoses utilizing diazo-transfer chemistry as described in the literature (Vasella et al., 1991; Alper et al., 1996). These monosaccharides have been described in the literature as existing in the gum state (Paulsen & Stenzel, 1978; Paulsen et al., 1985). In order to obtain crystalline materials, the acetate derivatives of these sugars were targeted. Both anomers of 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-D-glucopyranose have been reported as crystalline (Paulsen & Stenzel, 1978; Paulsen et al., 1985, Pavliak & Kovac, 1991; Bovin et al., 1981) as has 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α-D-mannopyranose (Paulsen et al., 1985; Bovin et al., 1981). Although 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α- and –β-D-mannopyranoses were produced, about one third of the product mixture was the title compound which preferentially crystallized from ethyl acetate/hexanes.

There is only one other pyrazine derivative reported (Allen, 2002) in the CSD (JOQQAH: 2,3-bis(1-Phenyliminoethyl)pyrazine, Klein et al., 1999), and one related piperazine (XERGAC, Myers et al., 2000). Crystal packing is provided through (methyl)C—H···O (acetoxy) and C—H···N (pyrazine) hydrogen bonding (Table 1).

Related literature top

For general background, see: Vasella et al. (1991); Alper et al. (1996). For related literature, see: Bovin et al. (1981); Paulsen & Stenzel (1978); Paulsen et al. (1985); Pavliak & Kovac (1991). For related structures, see: Klein et al. (1999); Myers et al. (2000); sourced from Allen (2002).

Experimental top

Aqueous mannosamine hydrochloride was treated with stoichiometric potassium carbonate and subsequently with a solution of excess triflic azide (trifluromethanesulfonyl azide) in dichloromethane, in the presence of a catalytic amount (1 mol%) of copper(II) sulfate. Methanol was utilized as required to ensure homogeneity of the reaction mixture. Once all the starting material had been consumed, the mixture was concentrated to a syrup and then subjected to per-acetylation by dissolution in pyridine and treatment with excess acetic anhydride in the presence of catalytic 4-(N,N-dimethylamino)pyridine. The mixture was concentrated to a brown syrup, dissolved in ethyl acetate and passed through a plug of silica gel. Concentration again afforded a brown syrup which appeared to contain a mixture of compounds, two of which were identified (by NMR comparison with authentic samples) as being the desired 1,3,4,6-tetra-O-acetyl-2-azido-2-deoxy-α- and –β-D-mannopyranoses. Approximately one third of the product mixture was the title compound which preferentially crystallized during an attempted crystallization from ethyl acetate/hexanes. Suitable crystals were grown from ethyl acetate solution by addition of small amounts of hexanes until turbity was observed, heated to a clear solution; crystals obtained on cooling were washed with hexanes.

Structure description top

For general background, see: Vasella et al. (1991); Alper et al. (1996). For related literature, see: Bovin et al. (1981); Paulsen & Stenzel (1978); Paulsen et al. (1985); Pavliak & Kovac (1991). For related structures, see: Klein et al. (1999); Myers et al. (2000); sourced from Allen (2002).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003).

Figures top

Fig. 1. The structure of (I) with 30% probabilility ellipsoids (ORTEP-3; Farrugia, 1997).

2,3,4-Triacetoxy-1-[5-(1,2,3,4-tetraacetoxybutyl)pyrazin-2-yl]butyl acetate top

Crystal data top

C₂₈H₃₆N₂O₁₆	Z = 1
M_r = 656.59	F(000) = 346
Triclinic, P1	D_x = 1.322 Mg m⁻³
Hall symbol: P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.6931 (8) Å	Cell parameters from 5104 reflections
b = 9.9132 (15) Å	θ = 4.4–26.4°
c = 15.5048 (11) Å	µ = 0.11 mm⁻¹
α = 81.344 (2)°	T = 159 K
β = 80.635 (2)°	Needle, colorless
γ = 73.986 (2)°	0.72 × 0.24 × 0.11 mm
V = 824.71 (18) Å³

Data collection top

Siemens SMART CCD area-detector diffractometer	2954 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.029
Graphite monochromator	θ_max = 26.4°, θ_min = 2.2°
Detector resolution: 8.192 pixels mm^-1	h = −3→7
φ and ω scans	k = −12→12
7120 measured reflections	l = −19→19
3304 independent 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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0468P)² + 0.2195P] where P = (F_o² + 2F_c²)/3
3304 reflections	(Δ/σ)_max = 0.009
424 parameters	Δρ_max = 0.18 e Å⁻³
3 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₂₈H₃₆N₂O₁₆	γ = 73.986 (2)°
M_r = 656.59	V = 824.71 (18) Å³
Triclinic, P1	Z = 1
a = 5.6931 (8) Å	Mo Kα radiation
b = 9.9132 (15) Å	µ = 0.11 mm⁻¹
c = 15.5048 (11) Å	T = 159 K
α = 81.344 (2)°	0.72 × 0.24 × 0.11 mm
β = 80.635 (2)°

Data collection top

Siemens SMART CCD area-detector diffractometer	2954 reflections with I > 2σ(I)
7120 measured reflections	R_int = 0.029
3304 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	3 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.11	Δρ_max = 0.18 e Å⁻³
3304 reflections	Δρ_min = −0.19 e Å⁻³
424 parameters

Special details top

Experimental. Crystal decay was monitored by repeating the initial 10 frames at the end of the data collection and analyzing duplicate reflections. The standard 0.8 mm diameter collimator was used.

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	0.1773 (4)	0.7258 (2)	0.61777 (15)	0.0260 (5)
O2	0.3590 (5)	0.9030 (3)	0.5790 (3)	0.0582 (10)
O3	0.2283 (4)	0.4418 (2)	0.70327 (15)	0.0253 (5)
O4	0.5514 (5)	0.2533 (3)	0.6832 (2)	0.0477 (8)
O5	0.4938 (4)	0.4054 (3)	0.88213 (16)	0.0324 (6)
O6	0.3058 (6)	0.2322 (4)	0.9229 (3)	0.0688 (11)
O7	0.4371 (4)	0.6945 (2)	0.79743 (16)	0.0275 (5)
O8	0.1083 (5)	0.8765 (3)	0.8170 (3)	0.0589 (10)
O9	0.6049 (4)	0.2219 (2)	0.33102 (15)	0.0260 (5)
O10	0.9351 (5)	0.0465 (3)	0.3595 (2)	0.0520 (8)
O11	0.4486 (4)	0.5073 (2)	0.24872 (15)	0.0256 (5)
O12	0.5623 (5)	0.7043 (3)	0.2567 (2)	0.0472 (8)
O13	0.8382 (4)	0.5509 (3)	0.06940 (16)	0.0310 (6)
O14	0.5172 (6)	0.7186 (4)	0.0242 (3)	0.0676 (11)
O15	0.9951 (4)	0.2621 (2)	0.15420 (16)	0.0280 (5)
O16	0.8672 (5)	0.0803 (3)	0.1278 (3)	0.0581 (9)
N1	0.3344 (5)	0.5037 (3)	0.51401 (19)	0.0284 (7)
N4	0.8257 (5)	0.4504 (3)	0.43623 (19)	0.0264 (6)
C1	0.4152 (5)	0.6276 (4)	0.6262 (2)	0.0230 (7)
H1	0.5363	0.6814	0.6313	0.028*
C2	0.5011 (5)	0.5497 (3)	0.5451 (2)	0.0229 (7)
C3	0.7430 (6)	0.5242 (4)	0.5062 (2)	0.0256 (7)
H3	0.8550	0.5599	0.5296	0.031*
C4	0.1747 (7)	0.8635 (4)	0.5934 (2)	0.0313 (8)
C5	0.6607 (5)	0.4030 (3)	0.4065 (2)	0.0221 (7)
C6	0.4154 (6)	0.4294 (4)	0.4455 (2)	0.0292 (8)
H6	0.3034	0.3932	0.4225	0.035*
C7	−0.0781 (7)	0.9536 (4)	0.5866 (3)	0.0410 (9)
H7A	−0.1403	1.0011	0.6399	0.061*
H7B	−0.1858	0.8948	0.5801	0.061*
H7C	−0.0757	1.0244	0.5353	0.061*
C8	0.3913 (6)	0.5271 (4)	0.7099 (2)	0.0241 (7)
H8	0.5576	0.4642	0.7197	0.029*
C9	0.3341 (6)	0.3066 (4)	0.6861 (2)	0.0315 (8)
C10	0.1456 (7)	0.2369 (4)	0.6714 (3)	0.0432 (10)
H10A	0.2276	0.1491	0.6453	0.065*
H10B	0.0356	0.3002	0.6315	0.065*
H10C	0.0494	0.2155	0.7278	0.065*
C11	0.2789 (6)	0.6045 (4)	0.7911 (2)	0.0256 (7)
H11	0.1108	0.6652	0.7816	0.031*
C12	0.2596 (6)	0.5074 (4)	0.8747 (2)	0.0317 (8)
H12A	0.2132	0.5627	0.9258	0.038*
H12B	0.1305	0.4581	0.8743	0.038*
C13	0.4913 (7)	0.2697 (4)	0.9063 (2)	0.0343 (9)
C14	0.7445 (8)	0.1760 (4)	0.9068 (3)	0.0423 (10)
H14A	0.7598	0.1207	0.9645	0.064*
H14B	0.8637	0.2335	0.8948	0.064*
H14C	0.7771	0.1120	0.8613	0.064*
C15	0.3246 (6)	0.8303 (4)	0.8119 (2)	0.0294 (8)
C16	0.5035 (8)	0.9104 (5)	0.8197 (3)	0.0423 (10)
H16A	0.4744	0.9978	0.7794	0.063*
H16B	0.6715	0.8529	0.8048	0.063*
H16C	0.4828	0.9336	0.8802	0.063*
C17	0.7464 (5)	0.3247 (4)	0.3258 (2)	0.0241 (7)
H17	0.9255	0.2753	0.3242	0.029*
C18	0.7229 (6)	0.0834 (4)	0.3507 (2)	0.0280 (8)
C19	0.5532 (7)	−0.0086 (4)	0.3588 (3)	0.0428 (10)
H19A	0.6211	−0.0818	0.3189	0.064*
H19B	0.3923	0.0483	0.3433	0.064*
H19C	0.5341	−0.0531	0.4194	0.064*
C20	0.7033 (5)	0.4248 (3)	0.2418 (2)	0.0226 (7)
H20	0.8146	0.4894	0.2331	0.027*
C21	0.4017 (6)	0.6466 (4)	0.2599 (2)	0.0293 (8)
C22	0.1323 (7)	0.7117 (5)	0.2744 (3)	0.0479 (11)
H22A	0.1015	0.8148	0.2673	0.072*
H22B	0.0661	0.6801	0.3341	0.072*
H22C	0.0516	0.6832	0.2316	0.072*
C23	0.7427 (6)	0.3479 (4)	0.1605 (2)	0.0258 (7)
H23	0.6290	0.2847	0.1694	0.024 (9)*
C24	0.7002 (7)	0.4464 (4)	0.0770 (2)	0.0313 (8)
H24A	0.7533	0.3918	0.0256	0.038*
H24B	0.5225	0.4938	0.0779	0.038*
C25	0.7234 (7)	0.6849 (4)	0.0426 (3)	0.0349 (9)
C26	0.8816 (7)	0.7823 (4)	0.0403 (3)	0.0421 (10)
H26A	0.8792	0.8427	−0.0159	0.063*
H26B	1.0509	0.7273	0.0466	0.063*
H26C	0.8191	0.8412	0.0887	0.063*
C27	1.0321 (7)	0.1277 (4)	0.1357 (2)	0.0303 (8)
C28	1.2961 (7)	0.0510 (4)	0.1289 (3)	0.0407 (9)
H28A	1.3411	0.0139	0.1879	0.061*
H28B	1.3961	0.1157	0.1010	0.061*
H28C	1.3260	−0.0274	0.0934	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0195 (10)	0.0230 (13)	0.0343 (13)	−0.0038 (9)	−0.0021 (9)	−0.0040 (10)
O2	0.0329 (15)	0.0335 (18)	0.105 (3)	−0.0122 (13)	−0.0085 (16)	0.0092 (17)
O3	0.0231 (11)	0.0209 (12)	0.0316 (13)	−0.0063 (9)	0.0003 (9)	−0.0051 (10)
O4	0.0324 (15)	0.0315 (16)	0.082 (2)	0.0007 (11)	−0.0141 (14)	−0.0234 (15)
O5	0.0338 (13)	0.0276 (14)	0.0350 (14)	−0.0075 (10)	−0.0045 (10)	−0.0021 (11)
O6	0.052 (2)	0.0374 (19)	0.120 (3)	−0.0234 (16)	−0.018 (2)	0.011 (2)
O7	0.0260 (11)	0.0253 (13)	0.0326 (13)	−0.0041 (9)	−0.0035 (9)	−0.0125 (10)
O8	0.0356 (17)	0.0365 (19)	0.107 (3)	−0.0002 (13)	−0.0094 (16)	−0.0326 (19)
O9	0.0229 (11)	0.0236 (13)	0.0331 (13)	−0.0074 (9)	−0.0047 (9)	−0.0044 (10)
O10	0.0324 (15)	0.0292 (16)	0.092 (3)	−0.0027 (12)	−0.0165 (14)	0.0010 (15)
O11	0.0227 (11)	0.0229 (13)	0.0325 (13)	−0.0041 (9)	−0.0061 (9)	−0.0072 (10)
O12	0.0345 (14)	0.0271 (16)	0.083 (2)	−0.0088 (12)	0.0005 (14)	−0.0237 (15)
O13	0.0344 (13)	0.0266 (14)	0.0307 (14)	−0.0070 (10)	−0.0032 (10)	−0.0022 (11)
O14	0.0464 (19)	0.042 (2)	0.113 (3)	−0.0079 (15)	−0.0280 (19)	0.010 (2)
O15	0.0255 (12)	0.0275 (13)	0.0314 (13)	−0.0073 (10)	0.0021 (9)	−0.0099 (10)
O16	0.0386 (16)	0.0363 (18)	0.107 (3)	−0.0088 (13)	−0.0085 (16)	−0.0329 (18)
N1	0.0184 (12)	0.0431 (19)	0.0266 (16)	−0.0106 (12)	0.0003 (10)	−0.0113 (13)
N4	0.0177 (13)	0.0339 (17)	0.0290 (16)	−0.0072 (11)	−0.0011 (10)	−0.0091 (13)
C1	0.0154 (14)	0.0269 (19)	0.0286 (18)	−0.0065 (13)	−0.0047 (12)	−0.0048 (14)
C2	0.0208 (14)	0.0259 (18)	0.0225 (17)	−0.0064 (13)	−0.0039 (12)	−0.0025 (13)
C3	0.0201 (15)	0.032 (2)	0.0293 (19)	−0.0111 (13)	−0.0030 (12)	−0.0107 (15)
C4	0.0320 (19)	0.029 (2)	0.033 (2)	−0.0072 (16)	−0.0045 (15)	−0.0047 (16)
C5	0.0214 (14)	0.0225 (17)	0.0213 (17)	−0.0043 (12)	−0.0038 (12)	−0.0002 (13)
C6	0.0208 (15)	0.041 (2)	0.0310 (19)	−0.0124 (14)	−0.0043 (13)	−0.0110 (16)
C7	0.038 (2)	0.028 (2)	0.054 (3)	−0.0022 (16)	−0.0120 (18)	−0.0019 (18)
C8	0.0171 (15)	0.0230 (18)	0.0318 (19)	−0.0045 (12)	0.0002 (13)	−0.0069 (14)
C9	0.0294 (19)	0.029 (2)	0.037 (2)	−0.0074 (15)	−0.0025 (14)	−0.0082 (16)
C10	0.039 (2)	0.036 (2)	0.061 (3)	−0.0159 (18)	−0.0094 (19)	−0.009 (2)
C11	0.0259 (17)	0.0274 (19)	0.0243 (18)	−0.0076 (14)	−0.0018 (13)	−0.0058 (15)
C12	0.0341 (18)	0.0256 (19)	0.0307 (19)	−0.0012 (14)	0.0010 (14)	−0.0066 (15)
C13	0.048 (2)	0.030 (2)	0.028 (2)	−0.0131 (18)	−0.0111 (16)	−0.0019 (16)
C14	0.049 (2)	0.028 (2)	0.049 (3)	−0.0037 (18)	−0.0100 (18)	−0.0066 (18)
C15	0.037 (2)	0.0250 (19)	0.0250 (18)	−0.0030 (15)	−0.0057 (14)	−0.0056 (15)
C16	0.053 (3)	0.035 (2)	0.045 (2)	−0.0152 (19)	−0.0136 (19)	−0.0074 (19)
C17	0.0166 (14)	0.0259 (18)	0.0307 (19)	−0.0053 (12)	−0.0017 (12)	−0.0079 (14)
C18	0.0314 (19)	0.0227 (19)	0.0274 (19)	−0.0044 (15)	0.0017 (14)	−0.0053 (15)
C19	0.045 (2)	0.033 (2)	0.053 (3)	−0.0170 (19)	−0.0065 (19)	−0.0024 (19)
C20	0.0193 (15)	0.0227 (17)	0.0263 (17)	−0.0037 (12)	−0.0025 (12)	−0.0077 (14)
C21	0.0292 (18)	0.024 (2)	0.035 (2)	−0.0031 (15)	−0.0041 (14)	−0.0101 (16)
C22	0.031 (2)	0.039 (3)	0.068 (3)	−0.0009 (17)	−0.0030 (19)	−0.007 (2)
C23	0.0244 (16)	0.0253 (18)	0.0297 (19)	−0.0089 (14)	−0.0020 (13)	−0.0062 (14)
C24	0.0402 (19)	0.031 (2)	0.0278 (19)	−0.0125 (15)	−0.0089 (15)	−0.0066 (15)
C25	0.035 (2)	0.030 (2)	0.034 (2)	−0.0011 (16)	0.0007 (15)	−0.0039 (17)
C26	0.047 (2)	0.029 (2)	0.048 (2)	−0.0081 (18)	−0.0035 (18)	−0.0008 (18)
C27	0.0361 (19)	0.030 (2)	0.0258 (19)	−0.0101 (16)	−0.0002 (14)	−0.0068 (15)
C28	0.036 (2)	0.033 (2)	0.050 (3)	−0.0026 (16)	0.0024 (17)	−0.0120 (19)

Geometric parameters (Å, º) top

O1—C4	1.358 (4)	C8—H8	1.0000
O1—C1	1.446 (3)	C9—C10	1.489 (5)
O2—C4	1.195 (5)	C10—H10A	0.9800
O3—C9	1.357 (4)	C10—H10B	0.9800
O3—C8	1.441 (4)	C10—H10C	0.9800
O4—C9	1.200 (4)	C11—C12	1.503 (5)
O5—C13	1.345 (5)	C11—H11	1.0000
O5—C12	1.443 (4)	C12—H12A	0.9900
O6—C13	1.191 (5)	C12—H12B	0.9900
O7—C15	1.356 (4)	C13—C14	1.484 (6)
O7—C11	1.454 (4)	C14—H14A	0.9800
O8—C15	1.183 (4)	C14—H14B	0.9800
O9—C18	1.364 (4)	C14—H14C	0.9800
O9—C17	1.449 (4)	C15—C16	1.483 (5)
O10—C18	1.186 (4)	C16—H16A	0.9800
O11—C21	1.365 (4)	C16—H16B	0.9800
O11—C20	1.451 (4)	C16—H16C	0.9800
O12—C21	1.196 (4)	C17—C20	1.524 (5)
O13—C25	1.344 (5)	C17—H17	1.0000
O13—C24	1.445 (4)	C18—C19	1.481 (5)
O14—C25	1.197 (5)	C19—H19A	0.9800
O15—C27	1.358 (5)	C19—H19B	0.9800
O15—C23	1.450 (4)	C19—H19C	0.9800
O16—C27	1.189 (4)	C20—C23	1.524 (4)
N1—C6	1.331 (4)	C20—H20	1.0000
N1—C2	1.339 (4)	C21—C22	1.485 (5)
N4—C5	1.329 (4)	C22—H22A	0.9800
N4—C3	1.348 (4)	C22—H22B	0.9800
C1—C2	1.517 (5)	C22—H22C	0.9800
C1—C8	1.524 (5)	C23—C24	1.510 (5)
C1—H1	1.0000	C23—H23	1.0000
C2—C3	1.381 (4)	C24—H24A	0.9900
C3—H3	0.9500	C24—H24B	0.9900
C4—C7	1.481 (5)	C25—C26	1.485 (6)
C5—C6	1.398 (4)	C26—H26A	0.9800
C5—C17	1.514 (5)	C26—H26B	0.9800
C6—H6	0.9500	C26—H26C	0.9800
C7—H7A	0.9800	C27—C28	1.480 (5)
C7—H7B	0.9800	C28—H28A	0.9800
C7—H7C	0.9800	C28—H28B	0.9800
C8—C11	1.529 (4)	C28—H28C	0.9800

C4—O1—C1	116.8 (3)	H14A—C14—H14C	109.5
C9—O3—C8	117.1 (3)	H14B—C14—H14C	109.5
C13—O5—C12	117.4 (3)	O8—C15—O7	122.5 (3)
C15—O7—C11	117.0 (3)	O8—C15—C16	125.3 (4)
C18—O9—C17	117.2 (2)	O7—C15—C16	112.1 (3)
C21—O11—C20	117.7 (2)	C15—C16—H16A	109.5
C25—O13—C24	117.1 (3)	C15—C16—H16B	109.5
C27—O15—C23	116.3 (3)	H16A—C16—H16B	109.5
C6—N1—C2	116.6 (3)	C15—C16—H16C	109.5
C5—N4—C3	116.1 (3)	H16A—C16—H16C	109.5
O1—C1—C2	109.5 (2)	H16B—C16—H16C	109.5
O1—C1—C8	108.3 (2)	O9—C17—C5	108.2 (3)
C2—C1—C8	112.0 (3)	O9—C17—C20	108.2 (3)
O1—C1—H1	109.0	C5—C17—C20	111.3 (3)
C2—C1—H1	109.0	O9—C17—H17	109.7
C8—C1—H1	109.0	C5—C17—H17	109.7
N1—C2—C3	121.4 (3)	C20—C17—H17	109.7
N1—C2—C1	117.3 (3)	O10—C18—O9	122.1 (3)
C3—C2—C1	121.3 (3)	O10—C18—C19	126.5 (4)
N4—C3—C2	122.3 (3)	O9—C18—C19	111.4 (3)
N4—C3—H3	118.9	C18—C19—H19A	109.5
C2—C3—H3	118.9	C18—C19—H19B	109.5
O2—C4—O1	122.2 (3)	H19A—C19—H19B	109.5
O2—C4—C7	125.9 (4)	C18—C19—H19C	109.5
O1—C4—C7	111.9 (3)	H19A—C19—H19C	109.5
N4—C5—C6	121.6 (3)	H19B—C19—H19C	109.5
N4—C5—C17	117.1 (3)	O11—C20—C17	109.4 (2)
C6—C5—C17	121.2 (3)	O11—C20—C23	105.6 (2)
N1—C6—C5	121.9 (3)	C17—C20—C23	113.0 (3)
N1—C6—H6	119.0	O11—C20—H20	109.6
C5—C6—H6	119.0	C17—C20—H20	109.6
C4—C7—H7A	109.5	C23—C20—H20	109.6
C4—C7—H7B	109.5	O12—C21—O11	122.5 (3)
H7A—C7—H7B	109.5	O12—C21—C22	126.8 (4)
C4—C7—H7C	109.5	O11—C21—C22	110.8 (3)
H7A—C7—H7C	109.5	C21—C22—H22A	109.5
H7B—C7—H7C	109.5	C21—C22—H22B	109.5
O3—C8—C1	110.7 (3)	H22A—C22—H22B	109.5
O3—C8—C11	105.3 (2)	C21—C22—H22C	109.5
C1—C8—C11	112.7 (3)	H22A—C22—H22C	109.5
O3—C8—H8	109.3	H22B—C22—H22C	109.5
C1—C8—H8	109.3	O15—C23—C24	110.2 (3)
C11—C8—H8	109.3	O15—C23—C20	106.1 (2)
O4—C9—O3	123.2 (3)	C24—C23—C20	113.3 (3)
O4—C9—C10	125.9 (4)	O15—C23—H23	109.0
O3—C9—C10	110.9 (3)	C24—C23—H23	109.0
C9—C10—H10A	109.5	C20—C23—H23	109.0
C9—C10—H10B	109.5	O13—C24—C23	109.7 (3)
H10A—C10—H10B	109.5	O13—C24—H24A	109.7
C9—C10—H10C	109.5	C23—C24—H24A	109.7
H10A—C10—H10C	109.5	O13—C24—H24B	109.7
H10B—C10—H10C	109.5	C23—C24—H24B	109.7
O7—C11—C12	110.0 (3)	H24A—C24—H24B	108.2
O7—C11—C8	106.2 (2)	O14—C25—O13	122.8 (4)
C12—C11—C8	113.6 (3)	O14—C25—C26	125.5 (4)
O7—C11—H11	109.0	O13—C25—C26	111.7 (3)
C12—C11—H11	109.0	C25—C26—H26A	109.5
C8—C11—H11	109.0	C25—C26—H26B	109.5
O5—C12—C11	109.3 (3)	H26A—C26—H26B	109.5
O5—C12—H12A	109.8	C25—C26—H26C	109.5
C11—C12—H12A	109.8	H26A—C26—H26C	109.5
O5—C12—H12B	109.8	H26B—C26—H26C	109.5
C11—C12—H12B	109.8	O16—C27—O15	122.4 (3)
H12A—C12—H12B	108.3	O16—C27—C28	125.9 (4)
O6—C13—O5	122.8 (4)	O15—C27—C28	111.7 (3)
O6—C13—C14	125.6 (4)	C27—C28—H28A	109.5
O5—C13—C14	111.6 (3)	C27—C28—H28B	109.5
C13—C14—H14A	109.5	H28A—C28—H28B	109.5
C13—C14—H14B	109.5	C27—C28—H28C	109.5
H14A—C14—H14B	109.5	H28A—C28—H28C	109.5
C13—C14—H14C	109.5	H28B—C28—H28C	109.5

C4—O1—C1—C2	−101.0 (3)	C8—C11—C12—O5	49.8 (4)
C4—O1—C1—C8	136.6 (3)	C12—O5—C13—O6	−1.4 (6)
C6—N1—C2—C3	1.7 (5)	C12—O5—C13—C14	177.0 (3)
C6—N1—C2—C1	−176.7 (3)	C11—O7—C15—O8	−1.9 (5)
O1—C1—C2—N1	−43.2 (4)	C11—O7—C15—C16	178.3 (3)
C8—C1—C2—N1	77.0 (4)	C18—O9—C17—C5	−106.6 (3)
O1—C1—C2—C3	138.3 (3)	C18—O9—C17—C20	132.6 (3)
C8—C1—C2—C3	−101.5 (3)	N4—C5—C17—O9	149.7 (3)
C5—N4—C3—C2	−0.1 (5)	C6—C5—C17—O9	−33.0 (4)
N1—C2—C3—N4	−1.0 (5)	N4—C5—C17—C20	−91.5 (3)
C1—C2—C3—N4	177.3 (3)	C6—C5—C17—C20	85.8 (4)
C1—O1—C4—O2	0.4 (5)	C17—O9—C18—O10	−3.2 (5)
C1—O1—C4—C7	179.7 (3)	C17—O9—C18—C19	176.8 (3)
C3—N4—C5—C6	0.4 (5)	C21—O11—C20—C17	107.7 (3)
C3—N4—C5—C17	177.7 (3)	C21—O11—C20—C23	−130.4 (3)
C2—N1—C6—C5	−1.4 (5)	O9—C17—C20—O11	66.6 (3)
N4—C5—C6—N1	0.3 (5)	C5—C17—C20—O11	−52.2 (3)
C17—C5—C6—N1	−176.8 (3)	O9—C17—C20—C23	−50.7 (3)
C9—O3—C8—C1	102.4 (3)	C5—C17—C20—C23	−169.5 (2)
C9—O3—C8—C11	−135.4 (3)	C20—O11—C21—O12	6.4 (5)
O1—C1—C8—O3	64.7 (3)	C20—O11—C21—C22	−174.5 (3)
C2—C1—C8—O3	−56.2 (3)	C27—O15—C23—C24	−101.2 (3)
O1—C1—C8—C11	−53.0 (3)	C27—O15—C23—C20	135.7 (3)
C2—C1—C8—C11	−173.9 (2)	O11—C20—C23—O15	−178.5 (3)
C8—O3—C9—O4	6.0 (5)	C17—C20—C23—O15	−59.0 (3)
C8—O3—C9—C10	−173.8 (3)	O11—C20—C23—C24	60.5 (3)
C15—O7—C11—C12	−103.5 (3)	C17—C20—C23—C24	180.0 (3)
C15—O7—C11—C8	133.2 (3)	C25—O13—C24—C23	−137.3 (3)
O3—C8—C11—O7	−178.4 (3)	O15—C23—C24—O13	−68.2 (3)
C1—C8—C11—O7	−57.5 (3)	C20—C23—C24—O13	50.5 (4)
O3—C8—C11—C12	60.6 (3)	C24—O13—C25—O14	−1.0 (6)
C1—C8—C11—C12	−178.5 (3)	C24—O13—C25—C26	178.2 (3)
C13—O5—C12—C11	−134.8 (3)	C23—O15—C27—O16	−2.4 (5)
O7—C11—C12—O5	−69.1 (3)	C23—O15—C27—C28	178.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N1ⁱ	0.95	2.61	3.338 (5)	134
C6—H6···N4ⁱⁱ	0.95	2.60	3.331 (5)	134
C7—H7B···O2ⁱⁱ	0.98	2.57	3.400 (5)	142
C19—H19A···O12ⁱⁱⁱ	0.98	2.58	3.443 (5)	147
C19—H19B···O10ⁱⁱ	0.98	2.58	3.407 (5)	142
C19—H19C···O2ⁱⁱⁱ	0.98	2.53	3.472 (6)	161
C26—H26B···O14ⁱ	0.98	2.60	3.471 (6)	148

Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₂₈H₃₆N₂O₁₆
M_r	656.59
Crystal system, space group	Triclinic, P1
Temperature (K)	159
a, b, c (Å)	5.6931 (8), 9.9132 (15), 15.5048 (11)
α, β, γ (°)	81.344 (2), 80.635 (2), 73.986 (2)
V (Å³)	824.71 (18)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.72 × 0.24 × 0.11

Data collection
Diffractometer	Siemens SMART CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7120, 3304, 2954
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.103, 1.11
No. of reflections	3304
No. of parameters	424
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.19

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 1997) and PLATON (Spek, 2003).

Selected geometric parameters (Å, º) top

N1—C6	1.331 (4)	C4—C7	1.481 (5)
N4—C3	1.348 (4)	C5—C17	1.514 (5)

O1—C1—C8—O3	64.7 (3)	N4—C5—C17—O9	149.7 (3)
C1—C8—C11—C12	−178.5 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N1ⁱ	0.95	2.61	3.338 (5)	134
C6—H6···N4ⁱⁱ	0.95	2.60	3.331 (5)	134
C7—H7B···O2ⁱⁱ	0.98	2.57	3.400 (5)	142
C19—H19A···O12ⁱⁱⁱ	0.98	2.58	3.443 (5)	147
C19—H19B···O10ⁱⁱ	0.98	2.58	3.407 (5)	142
C19—H19C···O2ⁱⁱⁱ	0.98	2.53	3.472 (6)	161
C26—H26B···O14ⁱ	0.98	2.60	3.471 (6)	148

Symmetry codes: (i) x+1, y, z; (ii) x−1, y, z; (iii) x, y−1, z.

Acknowledgements

We thank Professor Ward T. Robinson and Dr J. Wikaira of the University of Canterbury for their assistance.

References

Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

2,3,4-Triacet­­oxy-1-[5-(1,2,3,4-tetra­acet­oxy­butyl)pyrazin-2-yl]butyl acetate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

2,3,4-Triacetoxy-1-[5-(1,2,3,4-tetraacetoxybutyl)pyrazin-2-yl]butyl acetate