Diethyl 4-(4,5-dihydro­furan-2-yl)-3,5-di­methyl-1-phenyl-1,4-dihydro­pyrazine-2,6-dicarboxyl­ate

He, J.-Y.; Tan, Z.-L.; Yan, H.

doi:10.1107/S1600536809013749

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1129

doi:10.1107/S1600536809013749

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Diethyl 4-(4,5-dihydrofuran-2-yl)-3,5-dimethyl-1-phenyl-1,4-dihydropyrazine-2,6-dicarboxylate

Jing-Yu He,^a Zhi-Lin Tan ^a and Hong Yan ^a ^*

^aCollege of Life Science and Bioengineering, Beijing University of Technology, Beijing 100124, People's Republic of China
^*Correspondence e-mail: hongyan@bjut.edu.cn

(Received 25 March 2009; accepted 13 April 2009; online 25 April 2009)

In the title compound, C₂₂H₂₆N₂O₅, the central 1,4-dihydropyrazine ring adopts a boat conformation, while the benzene ring and the two disordered components of the furan ring are inclined at angles of 77.9 (5) and 61.9 (7)°. Three of the C atoms of the furan ring are disordered over two positions with occupancies of 0.655 (18) and 0.345 (18). In the crystal structure, weak intermolecular C—H⋯O hydrogen bonds link the molecules into chains propagating in [010].

Related literature

For the biological properties of 1,4-dihydropyrazines, see: Goto et al. (1968 ); Teranishi & Goto (1990 ). For their biomedical applications, see: Brook et al. (1992 ); Sit et al. (2002 ). For the synthesis of 1,4-dihydropyrazines, see: Wolfbeis (1977 ); Chorvat & Rorig (1988 ); Rodrigues et al. (2004 ).

Experimental

Crystal data

C₂₂H₂₆N₂O₅
M_r = 398.45
Triclinic, $[P \overline 1]$
a = 10.069 (2) Å
b = 10.242 (2) Å
c = 12.519 (3) Å
α = 72.37 (3)°
β = 77.59 (3)°
γ = 63.76 (3)°
V = 1098.8 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.50 × 0.40 × 0.25 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.958, T_max = 0.979
7345 measured reflections
3768 independent reflections
1555 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.059
wR(F²) = 0.182
S = 0.84
3768 reflections
291 parameters
52 restraints
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12C⋯O5ⁱ	0.96	2.67	3.618 (5)	169
Symmetry code: (i) x, y-1, z.

Data collection: RAPID-AUTO (Rigaku, 2000 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2000 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809013749/hb2937sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809013749/hb2937Isup2.hkl

checkCIF report

Comment top

The application of 1,4-dihydropyrazines in the field of biological agents and medicines has been widely investigated (Brook, et al., 1992, Sit, et al., 2002.), because 1,4-dihydropyrazine unit was found to be a component of the flavin coenzymes and several marine luciferins (Goto et al., 1968; Teranishi & Goto, 1990). Although the synthesis of 1,4-dihydropyrazines has been studied for many years (Wolfbeis 1977; Chorvat & Rorig 1988; Rodrigues et al. 2004), their photochemical properties have not been paid much attention in the literature to date.

The photochemical stability of 2,6-diethoxycarbonyl-3,5-dimethyl-1-phenyl-1,4-dihydro- pyrazine (II) was investigated in a variety of conventional solvents such as benzene, THF, acetone, ethyl acetate, ethyl nitrile, n-hexane, ether, methanol and dichloromethane. In THF, the title compound (I), was obtained in a yield of ca 5% after irradiation for 8 h with a high-pressure Hg lamp. A similar transformation also occurred by irradiation with sunlight, ultraviolet, or other lower powered light sources. The present X-ray crystal structure analysis was undertaken, to study the stereochemistry and crystal packing of (I).

In (I) (Fig. 1), the 1,4-dihydropyrazine ring (N1/C3/C2/N2/C6/C7) adopts a boat conformation: atoms C2, C3, C6 and C7 are coplanar, with atoms N1 and N2 deviating from this plane by 0.517 (4) and 0.362 (5) Å, respectively. The dihedral angle between the phenyl ring and C2/C3/C6/C7 plane is 70.46 (18)°. with those between the phenyl ring and the two disorder components of the furan ring are 77.9 (5)° and 61.9 (7)° respectively. In the crystal structure, weak intermolecular C—H···O hydrogen bonds (Table 1) link the molecules into chains propagated along b axis.

Related literature top

For the biological properties of 1,4-dihydropyrazines, see: Goto et al. (1968); Teranishi & Goto (1990). For their biomedical applications, see: Brook et al. (1992); Sit et al. (2002). For the synthesis of 1,4-dihydropyrazines, see: Wolfbeis (1977); Chorvat & Rorig (1988); Rodrigues et al. (2004).

Experimental top

Diethyl 3,5-dimethyl-1-phenyl-1,4-dihydropyrazine-2,6-dicarboxylate, (330 mg, 1 mmol) was dissolved in dry furan (30 ml) and poured into the photolysis unit. The solution was irradiated with a 500 W Hg lamp. The reaction was monitored by TLC. After 8 h, the solvent was removed in vacuo and the crude sample was purified on a silica-gel column using an n-hexane/ethyl acetate (20:1 v/v) as eluant. Colourless blocks of (I) were obtained by slow evaporation of a n-hexane / ethyl acetate solution (3:1 v/v) in a yield of 5.2% (21 mg; m.p. 421–423 K).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2000); cell refinement: RAPID-AUTO (Rigaku, 2000); data reduction: CrystalStructure (Rigaku/MSC, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) showing only the major disorder component of the furan ring. Displacement ellipsoids are drawn at the 30% probability level and H atoms have been omitted for clarity.

Diethyl 4-(4,5-dihydrofuran-2-yl)-3,5-dimethyl-1-phenyl-1,4-dihydropyrazine-2,6-dicarboxylate top

Crystal data top

C₂₂H₂₆N₂O₅	Z = 2
M_r = 398.45	F(000) = 424
Triclinic, P1	D_x = 1.204 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.069 (2) Å	Cell parameters from 7345 reflections
b = 10.242 (2) Å	θ = 2.3–25.0°
c = 12.519 (3) Å	µ = 0.09 mm⁻¹
α = 72.37 (3)°	T = 293 K
β = 77.59 (3)°	Block, colourless
γ = 63.76 (3)°	0.50 × 0.40 × 0.25 mm
V = 1098.8 (4) Å³

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	3768 independent reflections
Radiation source: fine-focus sealed tube	1555 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 10.00 pixels mm^-1	θ_max = 25.0°, θ_min = 2.3°
ω scans	h = −11→10
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −12→12
T_min = 0.958, T_max = 0.979	l = −14→13
7345 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)] = 0.059	H-atom parameters constrained
wR(F²) = 0.182	w = 1/[σ²(F_o²) + (0.102P)²] where P = (F_o² + 2F_c²)/3
S = 0.84	(Δ/σ)_max = 0.005
3768 reflections	Δρ_max = 0.17 e Å⁻³
291 parameters	Δρ_min = −0.13 e Å⁻³
52 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.034 (5)

Crystal data top

C₂₂H₂₆N₂O₅	γ = 63.76 (3)°
M_r = 398.45	V = 1098.8 (4) Å³
Triclinic, P1	Z = 2
a = 10.069 (2) Å	Mo Kα radiation
b = 10.242 (2) Å	µ = 0.09 mm⁻¹
c = 12.519 (3) Å	T = 293 K
α = 72.37 (3)°	0.50 × 0.40 × 0.25 mm
β = 77.59 (3)°

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	3768 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1555 reflections with I > 2σ(I)
T_min = 0.958, T_max = 0.979	R_int = 0.045
7345 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.059	52 restraints
wR(F²) = 0.182	H-atom parameters constrained
S = 0.84	Δρ_max = 0.17 e Å⁻³
3768 reflections	Δρ_min = −0.13 e Å⁻³
291 parameters

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.6304 (3)	0.7169 (3)	0.1028 (2)	0.1226 (10)
O2	0.5222 (2)	0.5632 (3)	0.19260 (19)	0.0867 (7)
O3	0.1854 (3)	0.7014 (4)	0.5774 (2)	0.1395 (12)
O4	0.2987 (3)	0.5488 (3)	0.46179 (19)	0.1043 (9)
N1	0.2832 (3)	0.7643 (3)	0.2761 (2)	0.0696 (7)
N2	0.2680 (3)	1.0189 (3)	0.2870 (4)	0.1035 (11)
C1	0.4963 (4)	1.0117 (4)	0.1529 (3)	0.1177 (15)
H1A	0.4623	1.1095	0.1661	0.177*
H1B	0.5047	1.0198	0.0735	0.177*
H1C	0.5917	0.9491	0.1810	0.177*
C2	0.3879 (4)	0.9443 (4)	0.2120 (3)	0.0866 (11)
C3	0.4005 (3)	0.8073 (4)	0.2125 (3)	0.0699 (9)
C4	0.5280 (4)	0.6958 (4)	0.1640 (3)	0.0765 (9)
C5	0.1917 (4)	0.9956 (5)	0.4888 (4)	0.1324 (17)
H5A	0.1863	1.0960	0.4653	0.199*
H5B	0.2671	0.9352	0.5399	0.199*
H5C	0.0974	0.9967	0.5258	0.199*
C6	0.2298 (4)	0.9315 (5)	0.3880 (4)	0.0951 (12)
C7	0.2464 (3)	0.7984 (4)	0.3838 (3)	0.0760 (9)
C8	0.2383 (4)	0.6822 (5)	0.4836 (4)	0.0944 (11)
C9	0.6449 (4)	0.4402 (4)	0.1523 (3)	0.1075 (13)
H9A	0.6539	0.4641	0.0707	0.129*
H9B	0.7370	0.4254	0.1762	0.129*
C10	0.6198 (5)	0.3060 (5)	0.1958 (4)	0.1389 (18)
H10A	0.7012	0.2253	0.1686	0.208*
H10B	0.5290	0.3207	0.1714	0.208*
H10C	0.6124	0.2818	0.2766	0.208*
C11	0.3014 (6)	0.4218 (5)	0.5561 (4)	0.1469 (19)
H11A	0.3477	0.4207	0.6169	0.176*
H11B	0.2005	0.4318	0.5837	0.176*
C12	0.3823 (5)	0.2857 (6)	0.5208 (4)	0.1332 (16)
H12A	0.3808	0.2031	0.5824	0.200*
H12B	0.4833	0.2739	0.4966	0.200*
H12C	0.3375	0.2880	0.4595	0.200*
C13	0.1673 (3)	0.7858 (3)	0.2185 (3)	0.0658 (8)
C14	0.1859 (3)	0.7952 (4)	0.1046 (3)	0.0800 (10)
H14	0.2763	0.7905	0.0642	0.096*
C15	0.0733 (4)	0.8114 (4)	0.0497 (3)	0.1003 (12)
H15	0.0873	0.8206	−0.0276	0.120*
C16	−0.0604 (4)	0.8142 (4)	0.1082 (4)	0.1045 (12)
H16	−0.1357	0.8220	0.0716	0.125*
C17	−0.0797 (4)	0.8053 (4)	0.2212 (4)	0.0980 (12)
H17	−0.1702	0.8096	0.2612	0.118*
C18	0.0310 (3)	0.7903 (4)	0.2771 (3)	0.0848 (10)
H18	0.0155	0.7831	0.3542	0.102*
O5	0.2634 (3)	1.2572 (3)	0.2789 (2)	0.1113 (9)
C22	0.0984 (5)	1.2576 (5)	0.1768 (4)	0.1378 (18)
H22	0.0796	1.2188	0.1262	0.165*
C19A	0.1706 (10)	1.1824 (7)	0.2786 (9)	0.098 (3)	0.655 (18)
C20A	0.1744 (15)	1.4006 (12)	0.2440 (12)	0.133 (4)	0.655 (18)
H20A	0.2337	1.4551	0.1997	0.160*	0.655 (18)
H20B	0.1250	1.4425	0.3089	0.160*	0.655 (18)
C21A	0.0607 (17)	1.4213 (11)	0.1753 (14)	0.152 (5)	0.655 (18)
H21A	0.0713	1.4796	0.0994	0.182*	0.655 (18)
H21B	−0.0392	1.4690	0.2094	0.182*	0.655 (18)
C19B	0.2390 (19)	1.1784 (12)	0.2077 (18)	0.107 (6)	0.345 (18)
C20B	0.206 (4)	1.427 (3)	0.209 (3)	0.208 (17)	0.345 (18)
H20C	0.1396	1.4977	0.2540	0.250*	0.345 (18)
H20D	0.2851	1.4567	0.1676	0.250*	0.345 (18)
C21B	0.127 (3)	1.400 (2)	0.138 (2)	0.163 (12)	0.345 (18)
H21C	0.1837	1.3997	0.0645	0.196*	0.345 (18)
H21D	0.0321	1.4850	0.1274	0.196*	0.345 (18)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0867 (18)	0.118 (2)	0.146 (2)	−0.0465 (16)	0.0294 (17)	−0.0275 (18)
O2	0.0683 (14)	0.0740 (16)	0.1007 (17)	−0.0191 (12)	0.0113 (12)	−0.0256 (13)
O3	0.131 (2)	0.176 (3)	0.099 (2)	−0.048 (2)	0.0251 (18)	−0.063 (2)
O4	0.119 (2)	0.097 (2)	0.0760 (16)	−0.0355 (16)	0.0076 (14)	−0.0158 (15)
N1	0.0622 (16)	0.0669 (16)	0.0786 (18)	−0.0212 (12)	−0.0053 (14)	−0.0247 (14)
N2	0.081 (2)	0.063 (2)	0.171 (4)	−0.0093 (17)	−0.037 (2)	−0.048 (2)
C1	0.130 (3)	0.105 (3)	0.134 (3)	−0.076 (3)	−0.047 (3)	0.019 (3)
C2	0.091 (3)	0.064 (2)	0.108 (3)	−0.034 (2)	−0.045 (2)	0.005 (2)
C3	0.0558 (19)	0.069 (2)	0.075 (2)	−0.0206 (16)	−0.0101 (16)	−0.0075 (17)
C4	0.064 (2)	0.082 (3)	0.078 (2)	−0.0333 (19)	−0.0047 (18)	−0.008 (2)
C5	0.106 (3)	0.143 (4)	0.177 (4)	−0.029 (3)	−0.001 (3)	−0.118 (4)
C6	0.068 (2)	0.087 (3)	0.127 (4)	−0.017 (2)	−0.011 (2)	−0.044 (3)
C7	0.059 (2)	0.078 (2)	0.092 (3)	−0.0144 (17)	−0.0012 (17)	−0.047 (2)
C8	0.082 (3)	0.100 (3)	0.092 (3)	−0.020 (2)	−0.003 (2)	−0.040 (3)
C9	0.086 (3)	0.092 (3)	0.119 (3)	−0.018 (2)	0.018 (2)	−0.038 (2)
C10	0.133 (4)	0.095 (3)	0.172 (4)	−0.045 (3)	0.042 (3)	−0.051 (3)
C11	0.189 (5)	0.121 (4)	0.089 (3)	−0.057 (4)	0.021 (3)	0.000 (3)
C12	0.153 (4)	0.125 (4)	0.113 (4)	−0.059 (3)	−0.020 (3)	−0.009 (3)
C13	0.060 (2)	0.0530 (18)	0.083 (2)	−0.0165 (14)	−0.0107 (17)	−0.0202 (16)
C14	0.063 (2)	0.088 (2)	0.081 (3)	−0.0254 (17)	−0.0066 (18)	−0.0182 (19)
C15	0.083 (3)	0.124 (3)	0.086 (3)	−0.034 (2)	−0.022 (2)	−0.018 (2)
C16	0.073 (3)	0.118 (3)	0.120 (3)	−0.032 (2)	−0.023 (2)	−0.024 (3)
C17	0.062 (2)	0.111 (3)	0.115 (3)	−0.036 (2)	−0.001 (2)	−0.023 (3)
C18	0.060 (2)	0.101 (3)	0.090 (2)	−0.0280 (18)	−0.0035 (19)	−0.029 (2)
O5	0.1092 (18)	0.0695 (18)	0.166 (3)	−0.0273 (15)	−0.0492 (17)	−0.0316 (17)
C22	0.164 (5)	0.087 (3)	0.166 (4)	−0.034 (3)	−0.097 (4)	−0.006 (3)
C19A	0.088 (5)	0.053 (4)	0.160 (8)	−0.010 (3)	−0.044 (5)	−0.042 (4)
C20A	0.155 (9)	0.044 (5)	0.207 (10)	−0.045 (6)	−0.056 (8)	−0.004 (7)
C21A	0.141 (9)	0.093 (7)	0.218 (12)	−0.029 (6)	−0.094 (9)	−0.008 (7)
C19B	0.082 (10)	0.069 (8)	0.178 (15)	−0.004 (6)	−0.049 (9)	−0.054 (9)
C20B	0.152 (17)	0.117 (19)	0.32 (3)	−0.097 (14)	−0.059 (16)	0.092 (17)
C21B	0.19 (3)	0.073 (12)	0.184 (18)	−0.042 (14)	0.037 (17)	−0.033 (11)

Geometric parameters (Å, º) top

O1—C4	1.207 (3)	C12—H12A	0.9600
O2—C4	1.320 (4)	C12—H12B	0.9600
O2—C9	1.452 (4)	C12—H12C	0.9600
O3—C8	1.216 (4)	C13—C14	1.376 (4)
O4—C8	1.316 (4)	C13—C18	1.398 (4)
O4—C11	1.462 (4)	C14—C15	1.373 (4)
N1—C13	1.404 (4)	C14—H14	0.9300
N1—C7	1.426 (4)	C15—C16	1.380 (5)
N1—C3	1.437 (4)	C15—H15	0.9300
N2—C6	1.399 (5)	C16—C17	1.367 (5)
N2—C2	1.433 (4)	C16—H16	0.9300
N2—C19A	1.504 (7)	C17—C18	1.368 (5)
N2—C19B	1.568 (15)	C17—H17	0.9300
C1—C2	1.492 (5)	C18—H18	0.9300
C1—H1A	0.9600	O5—C20A	1.329 (12)
C1—H1B	0.9600	O5—C19A	1.448 (8)
C1—H1C	0.9600	O5—C19B	1.488 (13)
C2—C3	1.350 (4)	O5—C20B	1.59 (2)
C3—C4	1.453 (4)	C22—C19B	1.357 (12)
C5—C6	1.498 (5)	C22—C19A	1.433 (8)
C5—H5A	0.9600	C22—C21B	1.530 (17)
C5—H5B	0.9600	C22—C21A	1.541 (10)
C5—H5C	0.9600	C22—H22	0.9300
C6—C7	1.314 (5)	C20A—C21A	1.480 (11)
C7—C8	1.458 (5)	C20A—H20A	0.9700
C9—C10	1.430 (5)	C20A—H20B	0.9700
C9—H9A	0.9700	C21A—H21A	0.9700
C9—H9B	0.9700	C21A—H21B	0.9700
C10—H10A	0.9600	C20B—C21B	1.460 (19)
C10—H10B	0.9600	C20B—H20C	0.9700
C10—H10C	0.9600	C20B—H20D	0.9700
C11—C12	1.420 (5)	C21B—H21C	0.9700
C11—H11A	0.9700	C21B—H21D	0.9700
C11—H11B	0.9700

C4—O2—C9	118.7 (3)	C14—C13—C18	118.0 (3)
C8—O4—C11	117.1 (3)	C14—C13—N1	121.6 (3)
C13—N1—C7	118.2 (2)	C18—C13—N1	120.4 (3)
C13—N1—C3	118.2 (3)	C15—C14—C13	121.1 (3)
C7—N1—C3	111.3 (3)	C15—C14—H14	119.5
C6—N2—C2	118.2 (3)	C13—C14—H14	119.5
C6—N2—C19A	110.6 (6)	C14—C15—C16	120.7 (4)
C2—N2—C19A	131.2 (6)	C14—C15—H15	119.7
C6—N2—C19B	148.5 (9)	C16—C15—H15	119.7
C2—N2—C19B	93.3 (8)	C17—C16—C15	118.4 (4)
C19A—N2—C19B	37.9 (5)	C17—C16—H16	120.8
C2—C1—H1A	109.5	C15—C16—H16	120.8
C2—C1—H1B	109.5	C16—C17—C18	121.6 (3)
H1A—C1—H1B	109.5	C16—C17—H17	119.2
C2—C1—H1C	109.5	C18—C17—H17	119.2
H1A—C1—H1C	109.5	C17—C18—C13	120.2 (3)
H1B—C1—H1C	109.5	C17—C18—H18	119.9
C3—C2—N2	114.5 (3)	C13—C18—H18	119.9
C3—C2—C1	125.7 (4)	C20A—O5—C19A	102.0 (6)
N2—C2—C1	119.4 (4)	C20A—O5—C19B	104.9 (6)
C2—C3—N1	116.4 (3)	C19A—O5—C19B	39.8 (6)
C2—C3—C4	125.7 (3)	C20A—O5—C20B	19.4 (15)
N1—C3—C4	117.7 (3)	C19A—O5—C20B	113.8 (11)
O1—C4—O2	121.2 (3)	C19B—O5—C20B	103.7 (12)
O1—C4—C3	125.7 (3)	C19B—C22—C19A	41.9 (7)
O2—C4—C3	113.1 (3)	C19B—C22—C21B	89.5 (15)
C6—C5—H5A	109.5	C19A—C22—C21B	102.7 (12)
C6—C5—H5B	109.5	C19B—C22—C21A	105.4 (7)
H5A—C5—H5B	109.5	C19A—C22—C21A	99.8 (6)
C6—C5—H5C	109.5	C21B—C22—C21A	27.0 (11)
H5A—C5—H5C	109.5	C19B—C22—H22	111.8
H5B—C5—H5C	109.5	C19A—C22—H22	130.1
C7—C6—N2	115.8 (4)	C21B—C22—H22	121.4
C7—C6—C5	128.6 (5)	C21A—C22—H22	130.1
N2—C6—C5	115.3 (4)	C22—C19A—O5	106.0 (6)
C6—C7—N1	117.6 (4)	C22—C19A—N2	114.1 (6)
C6—C7—C8	123.3 (4)	O5—C19A—N2	108.2 (5)
N1—C7—C8	118.9 (3)	O5—C20A—C21A	112.4 (8)
O3—C8—O4	122.4 (4)	O5—C20A—H20A	109.1
O3—C8—C7	125.8 (4)	C21A—C20A—H20A	109.1
O4—C8—C7	111.8 (3)	O5—C20A—H20B	109.1
C10—C9—O2	110.0 (3)	C21A—C20A—H20B	109.1
C10—C9—H9A	109.7	H20A—C20A—H20B	107.9
O2—C9—H9A	109.7	C20A—C21A—C22	101.2 (7)
C10—C9—H9B	109.7	C20A—C21A—H21A	111.5
O2—C9—H9B	109.7	C22—C21A—H21A	111.5
H9A—C9—H9B	108.2	C20A—C21A—H21B	111.5
C9—C10—H10A	109.5	C22—C21A—H21B	111.5
C9—C10—H10B	109.5	H21A—C21A—H21B	109.4
H10A—C10—H10B	109.5	C22—C19B—O5	107.9 (10)
C9—C10—H10C	109.5	C22—C19B—N2	114.6 (12)
H10A—C10—H10C	109.5	O5—C19B—N2	103.0 (11)
H10B—C10—H10C	109.5	C21B—C20B—O5	92.0 (15)
C12—C11—O4	110.0 (4)	C21B—C20B—H20C	113.3
C12—C11—H11A	109.7	O5—C20B—H20C	113.3
O4—C11—H11A	109.7	C21B—C20B—H20D	113.3
C12—C11—H11B	109.7	O5—C20B—H20D	113.3
O4—C11—H11B	109.7	H20C—C20B—H20D	110.6
H11A—C11—H11B	108.2	C20B—C21B—C22	118.7 (18)
C11—C12—H12A	109.5	C20B—C21B—H21C	107.6
C11—C12—H12B	109.5	C22—C21B—H21C	107.6
H12A—C12—H12B	109.5	C20B—C21B—H21D	107.6
C11—C12—H12C	109.5	C22—C21B—H21D	107.6
H12A—C12—H12C	109.5	H21C—C21B—H21D	107.1
H12B—C12—H12C	109.5

C6—N2—C2—C3	33.1 (4)	C14—C13—C18—C17	−0.7 (5)
C19A—N2—C2—C3	−147.6 (4)	N1—C13—C18—C17	−177.4 (3)
C19B—N2—C2—C3	−147.0 (5)	C19B—C22—C19A—O5	61.0 (10)
C6—N2—C2—C1	−139.4 (3)	C21B—C22—C19A—O5	−13.7 (15)
C19A—N2—C2—C1	39.8 (6)	C21A—C22—C19A—O5	−41.1 (12)
C19B—N2—C2—C1	40.5 (5)	C19B—C22—C19A—N2	−58.0 (10)
N2—C2—C3—N1	7.5 (4)	C21B—C22—C19A—N2	−132.6 (11)
C1—C2—C3—N1	179.5 (3)	C21A—C22—C19A—N2	−160.1 (7)
N2—C2—C3—C4	−166.2 (3)	C20A—O5—C19A—C22	42.6 (11)
C1—C2—C3—C4	5.8 (5)	C19B—O5—C19A—C22	−56.4 (9)
C13—N1—C3—C2	96.3 (3)	C20B—O5—C19A—C22	26.4 (16)
C7—N1—C3—C2	−45.5 (4)	C20A—O5—C19A—N2	165.4 (7)
C13—N1—C3—C4	−89.5 (3)	C19B—O5—C19A—N2	66.4 (9)
C7—N1—C3—C4	128.7 (3)	C20B—O5—C19A—N2	149.2 (13)
C9—O2—C4—O1	2.2 (5)	C6—N2—C19A—C22	−126.8 (7)
C9—O2—C4—C3	−178.4 (3)	C2—N2—C19A—C22	53.9 (9)
C2—C3—C4—O1	−11.4 (5)	C19B—N2—C19A—C22	52.9 (9)
N1—C3—C4—O1	175.0 (3)	C6—N2—C19A—O5	115.4 (6)
C2—C3—C4—O2	169.1 (3)	C2—N2—C19A—O5	−63.9 (8)
N1—C3—C4—O2	−4.5 (4)	C19B—N2—C19A—O5	−64.9 (10)
C2—N2—C6—C7	−33.5 (5)	C19A—O5—C20A—C21A	−25.3 (13)
C19A—N2—C6—C7	147.1 (4)	C19B—O5—C20A—C21A	15.6 (16)
C19B—N2—C6—C7	146.8 (9)	C20B—O5—C20A—C21A	104 (4)
C2—N2—C6—C5	140.0 (3)	O5—C20A—C21A—C22	0.7 (14)
C19A—N2—C6—C5	−39.4 (5)	C19B—C22—C21A—C20A	−18.3 (17)
C19B—N2—C6—C5	−39.7 (10)	C19A—C22—C21A—C20A	24.3 (13)
N2—C6—C7—N1	−7.5 (4)	C21B—C22—C21A—C20A	−74 (3)
C5—C6—C7—N1	−180.0 (3)	C19A—C22—C19B—O5	−59.3 (12)
N2—C6—C7—C8	168.5 (3)	C21B—C22—C19B—O5	50.5 (17)
C5—C6—C7—C8	−3.9 (6)	C21A—C22—C19B—O5	28.3 (19)
C13—N1—C7—C6	−95.6 (4)	C19A—C22—C19B—N2	54.7 (13)
C3—N1—C7—C6	46.2 (4)	C21B—C22—C19B—N2	164.5 (13)
C13—N1—C7—C8	88.2 (3)	C21A—C22—C19B—N2	142.4 (9)
C3—N1—C7—C8	−130.0 (3)	C20A—O5—C19B—C22	−28.3 (19)
C11—O4—C8—O3	−0.6 (6)	C19A—O5—C19B—C22	62.6 (12)
C11—O4—C8—C7	178.3 (3)	C20B—O5—C19B—C22	−48 (2)
C6—C7—C8—O3	16.8 (6)	C20A—O5—C19B—N2	−149.9 (8)
N1—C7—C8—O3	−167.2 (3)	C19A—O5—C19B—N2	−58.9 (12)
C6—C7—C8—O4	−162.0 (3)	C20B—O5—C19B—N2	−169.8 (13)
N1—C7—C8—O4	14.0 (4)	C6—N2—C19B—C22	−57.1 (17)
C4—O2—C9—C10	177.9 (3)	C2—N2—C19B—C22	123.1 (12)
C8—O4—C11—C12	−174.4 (4)	C19A—N2—C19B—C22	−57.7 (13)
C7—N1—C13—C14	162.1 (3)	C6—N2—C19B—O5	59.8 (14)
C3—N1—C13—C14	23.0 (4)	C2—N2—C19B—O5	−120.0 (10)
C7—N1—C13—C18	−21.2 (4)	C19A—N2—C19B—O5	59.2 (11)
C3—N1—C13—C18	−160.4 (3)	C20A—O5—C20B—C21B	−81 (4)
C18—C13—C14—C15	1.2 (5)	C19A—O5—C20B—C21B	−25 (2)
N1—C13—C14—C15	177.9 (3)	C19B—O5—C20B—C21B	16 (2)
C13—C14—C15—C16	−1.9 (5)	O5—C20B—C21B—C22	16 (3)
C14—C15—C16—C17	2.1 (6)	C19B—C22—C21B—C20B	−43 (3)
C15—C16—C17—C18	−1.6 (6)	C19A—C22—C21B—C20B	−3 (3)
C16—C17—C18—C13	0.9 (5)	C21A—C22—C21B—C20B	84 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12C···O5ⁱ	0.96	2.67	3.618 (5)	169

Symmetry code: (i) x, y−1, z.

Experimental details

Crystal data
Chemical formula	C₂₂H₂₆N₂O₅
M_r	398.45
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	10.069 (2), 10.242 (2), 12.519 (3)
α, β, γ (°)	72.37 (3), 77.59 (3), 63.76 (3)
V (Å³)	1098.8 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.50 × 0.40 × 0.25

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.958, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	7345, 3768, 1555
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.059, 0.182, 0.84
No. of reflections	3768
No. of parameters	291
No. of restraints	52
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.13

Computer programs: RAPID-AUTO (Rigaku, 2000), CrystalStructure (Rigaku/MSC, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12C···O5ⁱ	0.96	2.67	3.618 (5)	169

Symmetry code: (i) x, y−1, z.

Acknowledgements

The authors thank Professor Jim Simpson of the University of Otago for extensive assistance in refining the single-crystal data and editing the manuscript. This work was supported by the National Natural Sciences Foundation (grant No. 20872009), the Natural Sciences Foundation of Beijing (grant No. 200710005002), and Key Projects in the National Science and Technology Pillar Program during the Eleventh Five-Year Plan Period (grant No. 2008ZX10001-015).

References

Brook, D. J. R., Curtis Haltiwanger, R. & Koch, T. H. (1992). J. Am. Chem. Soc. 114, 6017–6023. CSD CrossRef CAS Web of Science Google Scholar
Chorvat, R. J. & Rorig, K. J. (1988). J. Org. Chem. 53, 5779–5781. CSD CrossRef CAS Web of Science Google Scholar
Goto, T., Inoue, S. & Sugiura, S. (1968). Tetrahedron Lett. 36, 3873–3876. CrossRef CAS PubMed Google Scholar
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2000). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2000). CrystalStructure. Rigaku/MSC, The Woodlands, Texas, USA. Google Scholar
Rodrigues, A., Ferreira, P. M. T. & Monteiro, L. S. (2004). Tetrahedron, 60, 8489–8496. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sit, S. Y., Huang, Y., Antal-Zimanyi, I., Ward, S. & Poindexter, G. S. (2002). Bioorg. Med. Chem. Lett. 12, 337–340. Web of Science CrossRef PubMed CAS Google Scholar
Teranishi, K. & Goto, T. (1990). Bull. Chem. Soc. Jpn, 63, 3132–3140. CrossRef CAS Web of Science Google Scholar
Wolfbeis, O. S. (1977). Synthesis, pp. 136–138. CrossRef Google Scholar

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Volume 65| Part 5| May 2009| Page o1129

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Di­ethyl 4-(4,5-di­hydro­furan-2-yl)-3,5-di­methyl-1-phenyl-1,4-di­hydro­pyrazine-2,6-di­carboxyl­ate

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Experimental

Crystal data

Data collection

Refinement

Supporting information

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References

organic compounds

Diethyl 4-(4,5-dihydrofuran-2-yl)-3,5-dimethyl-1-phenyl-1,4-dihydropyrazine-2,6-dicarboxylate