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3,3 Di­methyl 7 phenyl 2 oxa 1,4 di­thia 5,6,8,9 tetra­aza 3H cyclo­penta­[f]­azulene 1,1 dioxide

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organic papers

o1826

Li Tian and Lun-Zu Liu C14H12N4O3S2 DOI: 10.1107/S1600536804021385 Acta Cryst.(2004). E60, o1826±o1827 Acta Crystallographica Section E

Structure Reports Online

ISSN 1600-5368

3,3-Dimethyl-7-phenyl-2-oxa-1,4-dithia-5,6,8,9-tetraaza-3

H

-cyclopenta[

f

]azulene 1,1-dioxide

Li Tiana* and Lun-Zu Liub

aCollege of Chemistry and Life Sciences, Tianjin

Normal University, Tianjin 300074, People's Republic of China, andbState Key Laboratory

and Institute of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, People's Republic of China

Correspondence e-mail: lilytianli@hotmail.com

Key indicators Single-crystal X-ray study T= 293 K

Mean(C±C) = 0.006 AÊ Rfactor = 0.056 wRfactor = 0.132

Data-to-parameter ratio = 12.9

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved

The title compound, C14H12N4O3S2, has normal bond lengths and angles. The molecule includes a benzene ring, a 1,2,4-triazole ring, a sultone ring and a seven-membered sulfur-containing ring. The crystal packing is mainly stabilized by van der Waals interactions.

Comment

The Vilsmeier reagent, HCONR1R2/POCl3(R1=R2= Me), is used extensively in the synthesis of aldehyde derivatives and formamidines (Meth-Cohn, 1991). Recently, we found that the Vilsmeier reaction applied to acetyl phosphonate leads stereospeci®cally to (Z)--phosphonyl-- chlorovinylaldehyde (Qian, 2000). We applied this synthesis to-carbonyl sultone (Ingate, 1997). Chloroformylation of-carbonyl sultone with the Vilsmeier reagent (DMF/POCl3) afforded the cyclic -chlorovinylaldehyde (4-chloro-5,5-dimethyl-3-formyl-1,2-oxa-thiolene 2,2-dioxide), (I). Compound (I) is a useful inter-mediate for the synthesis of heterocyclic compounds. The reaction of (I) with 5-phenyl-4-amino-3-mercapto-(4H )-1,2,4-triazole gave the title compound, (II), with a seven-membered ring which is commonly considered unstable because of the high strain in the ring. We report here the crystal structure of (II).

The molecular structure of (II) is shown in Fig. 1. All bond lengths and angles are normal (Table 1) and clearly show that the bonding sequence of the N3/N4/C11/C10/C9/S1/C8 ring is N3ÐN4 C11ÐC10 C9ÐS1ÐC8. The crystal packing (Fig. 2) is mainly stabilized by van der Waals interactions.

Experimental

To a solution of (I) in dichloromethane (5 ml) was added dropwise a solution of 5-phenyl-4-amino-3-mercapto-(4H)-1,2,4-triazole (0.19 g) in water (3 ml) at 283 K, and then K2CO3(0.14 g) in water

(2 ml) was added dropwise. The reaction mixture was kept at room temperature for 2±3 h. The aqueous layer was extracted with di-chloromethane. The combined organic layers were washed with saturated brine, dried, ®ltered and concentrated. The residue was separated by silica gel to afford the title compound, which was puri®ed by recrystallization from ethyl acetate±petroleum ether.

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Crystal data

C14H12N4O3S2 Mr= 348.40

Monoclinic,P21=n a= 7.290 (2) AÊ b= 22.131 (7) AÊ c= 9.513 (3) AÊ = 90.115 (5) V= 1534.8 (8) AÊ3 Z= 4

Dx= 1.508 Mg mÿ3

MoKradiation Cell parameters from 796

re¯ections = 3.5±24.2

= 0.37 mmÿ1 T= 293 (2) K Prism, pale yellow 0.200.160.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer

'and!scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin= 0.925,Tmax= 0.957

7903 measured re¯ections

2712 independent re¯ections 1876 re¯ections withI> 2(I) Rint= 0.045

max= 25.0 h=ÿ8!4 k=ÿ26!26 l=ÿ11!10

Re®nement

Re®nement onF2 R[F2> 2(F2)] = 0.056 wR(F2) = 0.132 S= 1.07 2712 re¯ections 210 parameters

H-atom parameters constrained

w= 1/[2(F

o2) + (0.0553P)2

+ 0.8529P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.30 e AÊÿ3

min=ÿ0.26 e AÊÿ3

Table 1

Selected geometric parameters (AÊ,).

S1ÐC8 1.723 (4)

S1ÐC9 1.748 (3)

N3ÐC8 1.380 (4)

N3ÐN4 1.389 (4)

N4ÐC11 1.275 (4)

C9ÐC10 1.338 (4)

C10ÐC11 1.448 (5)

C8ÐS1ÐC9 98.58 (17)

O2ÐS2ÐO3 117.38 (18)

C7ÐN3ÐC8 105.7 (3)

C7ÐN3ÐN4 121.8 (3)

C8ÐN3ÐN4 132.1 (3)

C11ÐN4ÐN3 118.2 (3)

N2ÐC8ÐS1 122.6 (3)

N3ÐC8ÐS1 127.6 (3)

C10ÐC9ÐC12 116.2 (3)

C10ÐC9ÐS1 123.9 (3)

C12ÐC9ÐS1 119.8 (2)

C9ÐC10ÐC11 131.2 (3)

C9ÐC10ÐS2 108.2 (3)

C11ÐC10ÐS2 120.2 (2)

N4ÐC11ÐC10 131.5 (3)

N4ÐC11ÐH11 114.2

C10ÐC11ÐH11 114.2

All H atoms were placed in calculated positions, with CÐH = 0.93 or 0.96 AÊ, and included in the ®nal cycles of re®nement using a riding model, withUiso(H) = 1.2Ueq(C).

Data collection:SMART(Bruker, 1998); cell re®nement:SMART;

structure:SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:

SHELXTL (Bruker, 1999); software used to prepare material for publication:SHELXTL.

Financial support from the PhD Programs Foundation of the Ministry of Education of China is gratefully acknowl-edged.

References

Bruker (1998).SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Bruker (1999). SAINT and SHELXTL. Bruker AXS Inc., Madison,

Wisconsin, USA.

Ingate, S. T. (1997).Tetrahedron,53, 17795±17804.

Meth-Cohn, O. (1991).Comprehensive Organic Synthesis, Vol. 2, pp. 777±779, edited by B. M. Trost. Oxford: Pergamon.

Qian, D. Q. (2000).Phosphorus Sulfur Silicon,158, 179±184. Sheldrick, G. M. (1996).SADABS.University of GoÈttingen, Germany. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of

GoÈttingen, Germany.

Figure 2

The molecular packing of (II), viewed along thebaxis.

Figure 1

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supporting information

sup-1 Acta Cryst. (2004). E60, o1826–o1827

supporting information

Acta Cryst. (2004). E60, o1826–o1827 [https://doi.org/10.1107/S1600536804021385]

3,3-Dimethyl-7-phenyl-2-oxa-1,4-dithia-5,6,8,9-tetraaza-3

H

-cyclo-penta[

f

]azulene 1,1-dioxide

Li Tian and Lun-Zu Liu

3,3-Dimethyl-7-phenyl-2-oxa-1,4-dithia-5,6,8,9-tetraaza-3H-cyclopenta[f]azulene 1,1-dioxide

Crystal data

C14H12N4O3S2

Mr = 348.40

Monoclinic, P21/n

Hall symbol: -P2yn

a = 7.290 (2) Å

b = 22.131 (7) Å

c = 9.513 (3) Å

β = 90.115 (5)°

V = 1534.8 (8) Å3

Z = 4

F(000) = 720

Dx = 1.508 Mg m−3

Mo radiation, λ = 0.71073 Å Cell parameters from 796 reflections

θ = 3.5–24.2°

µ = 0.37 mm−1

T = 293 K

Prism, pale yellow 0.20 × 0.16 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin = 0.925, Tmax = 0.957

7903 measured reflections 2712 independent reflections 1876 reflections with I > 2σ(I)

Rint = 0.045

θmax = 25.0°, θmin = 2.3°

h = −8→4

k = −26→26

l = −11→10

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 > 2σ(F2)] = 0.056

wR(F2) = 0.132

S = 1.07 2712 reflections 210 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2(F

o2) + (0.0553P)2 + 0.8529P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max < 0.001

Δρmax = 0.30 e Å−3

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Special details

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)

x y z Uiso*/Ueq

S1 0.37246 (12) 0.13412 (5) 0.84897 (12) 0.0584 (3) S2 −0.11265 (11) 0.03342 (4) 0.77879 (10) 0.0465 (3) O1 0.0421 (3) 0.00759 (13) 0.6831 (3) 0.0691 (9) O2 −0.1673 (4) −0.01071 (14) 0.8766 (3) 0.0778 (9) O3 −0.2506 (3) 0.05917 (12) 0.6928 (3) 0.0575 (7) N1 0.3932 (5) 0.15187 (15) 1.2500 (4) 0.0618 (9) N2 0.4666 (4) 0.13827 (14) 1.1194 (4) 0.0599 (9) N3 0.1726 (4) 0.15522 (12) 1.0937 (3) 0.0432 (7) N4 −0.0017 (4) 0.16818 (14) 1.0425 (3) 0.0503 (8) C1 −0.0922 (6) 0.16415 (19) 1.3475 (5) 0.0643 (12)

H1 −0.1438 0.1454 1.2693 0.077*

C2 −0.1998 (8) 0.1772 (2) 1.4617 (5) 0.0802 (14)

H2 −0.3237 0.1673 1.4605 0.096*

C3 −0.1254 (9) 0.2050 (2) 1.5778 (5) 0.0842 (16)

H3 −0.1986 0.2134 1.6554 0.101*

C4 0.0587 (9) 0.2204 (2) 1.5792 (6) 0.0842 (16)

H4 0.1093 0.2394 1.6574 0.101*

C5 0.1673 (7) 0.20757 (17) 1.4639 (5) 0.0682 (13)

H5 0.2906 0.2184 1.4644 0.082*

C6 0.0936 (6) 0.17862 (16) 1.3476 (4) 0.0553 (11) C7 0.2171 (5) 0.16271 (16) 1.2328 (4) 0.0503 (10) C8 0.3344 (5) 0.14045 (15) 1.0271 (4) 0.0469 (9) C9 0.1942 (4) 0.08426 (16) 0.8081 (4) 0.0426 (9) C10 0.0224 (4) 0.09044 (16) 0.8551 (4) 0.0411 (8) C11 −0.0623 (4) 0.13714 (17) 0.9395 (4) 0.0482 (9)

H11 −0.1825 0.1461 0.9141 0.058*

C12 0.2271 (4) 0.03324 (16) 0.7080 (4) 0.0438 (9) C13 0.3421 (5) −0.01596 (17) 0.7731 (5) 0.0558 (11)

H13A 0.2841 −0.0301 0.8574 0.084*

H13B 0.4615 −0.0003 0.7954 0.084*

H13C 0.3540 −0.0488 0.7079 0.084*

C14 0.2981 (6) 0.0540 (2) 0.5671 (4) 0.0653 (12)

H14A 0.3056 0.0200 0.5045 0.098*

H14B 0.4178 0.0714 0.5787 0.098*

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supporting information

sup-3 Acta Cryst. (2004). E60, o1826–o1827

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23

S1 0.0343 (5) 0.0639 (7) 0.0769 (8) −0.0129 (4) 0.0021 (5) −0.0134 (6) S2 0.0303 (5) 0.0560 (6) 0.0530 (6) −0.0057 (4) −0.0065 (4) −0.0052 (5) O1 0.0287 (14) 0.080 (2) 0.098 (2) −0.0042 (13) −0.0023 (14) −0.0430 (17) O2 0.079 (2) 0.074 (2) 0.081 (2) −0.0303 (16) −0.0154 (16) 0.0162 (17) O3 0.0360 (13) 0.0785 (19) 0.0581 (17) 0.0051 (12) −0.0132 (12) −0.0084 (14) N1 0.063 (2) 0.055 (2) 0.068 (3) −0.0005 (17) −0.0295 (19) 0.0011 (18) N2 0.0456 (19) 0.0464 (19) 0.087 (3) −0.0011 (15) −0.0270 (18) −0.0013 (18) N3 0.0404 (16) 0.0385 (16) 0.0505 (19) −0.0003 (13) −0.0170 (14) −0.0038 (14) N4 0.0372 (17) 0.058 (2) 0.055 (2) 0.0089 (14) −0.0124 (14) −0.0096 (16) C1 0.085 (3) 0.059 (3) 0.048 (3) −0.016 (2) −0.010 (2) −0.002 (2) C2 0.102 (4) 0.068 (3) 0.070 (4) −0.008 (3) 0.008 (3) −0.003 (3) C3 0.135 (5) 0.060 (3) 0.057 (3) 0.021 (3) 0.003 (3) 0.001 (2) C4 0.134 (5) 0.054 (3) 0.065 (4) 0.025 (3) −0.043 (3) −0.014 (2) C5 0.092 (3) 0.045 (2) 0.067 (3) 0.011 (2) −0.031 (3) −0.013 (2) C6 0.080 (3) 0.034 (2) 0.051 (3) −0.0005 (19) −0.019 (2) 0.0012 (18) C7 0.057 (2) 0.036 (2) 0.057 (3) −0.0032 (17) −0.023 (2) −0.0006 (18) C8 0.0372 (19) 0.0358 (19) 0.068 (3) −0.0008 (15) −0.0139 (18) −0.0090 (18) C9 0.0322 (18) 0.044 (2) 0.052 (2) −0.0029 (15) −0.0068 (15) 0.0005 (17) C10 0.0278 (17) 0.050 (2) 0.046 (2) −0.0003 (15) −0.0096 (14) −0.0042 (17) C11 0.0306 (18) 0.065 (2) 0.049 (2) 0.0044 (17) −0.0092 (16) −0.008 (2) C12 0.0244 (17) 0.048 (2) 0.059 (2) −0.0035 (15) −0.0039 (15) −0.0087 (18) C13 0.040 (2) 0.052 (2) 0.075 (3) 0.0047 (17) −0.0019 (19) 0.006 (2) C14 0.064 (3) 0.076 (3) 0.056 (3) 0.013 (2) 0.000 (2) −0.001 (2)

Geometric parameters (Å, º)

S1—C8 1.723 (4) C3—C4 1.385 (7)

S1—C9 1.748 (3) C3—H3 0.9300

S2—O2 1.407 (3) C4—C5 1.383 (7)

S2—O3 1.415 (3) C4—H4 0.9300

S2—O1 1.559 (3) C5—C6 1.386 (6)

S2—C10 1.757 (3) C5—H5 0.9300

O1—C12 1.482 (4) C6—C7 1.460 (6)

N1—C7 1.316 (5) C9—C10 1.338 (4)

N1—N2 1.386 (5) C9—C12 1.497 (5)

N2—C8 1.303 (5) C10—C11 1.448 (5)

N3—C7 1.372 (5) C11—H11 0.9300

N3—C8 1.380 (4) C12—C13 1.507 (5)

N3—N4 1.389 (4) C12—C14 1.509 (5)

N4—C11 1.275 (4) C13—H13A 0.9600

C1—C2 1.372 (6) C13—H13B 0.9600

C1—C6 1.392 (6) C13—H13C 0.9600

C1—H1 0.9300 C14—H14A 0.9600

C2—C3 1.375 (7) C14—H14B 0.9600

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C8—S1—C9 98.58 (17) N1—C7—C6 123.7 (4)

O2—S2—O3 117.38 (18) N3—C7—C6 127.3 (3)

O2—S2—O1 109.7 (2) N2—C8—N3 109.3 (4)

O3—S2—O1 108.92 (17) N2—C8—S1 122.6 (3)

O2—S2—C10 112.63 (18) N3—C8—S1 127.6 (3)

O3—S2—C10 110.28 (17) C10—C9—C12 116.2 (3)

O1—S2—C10 95.67 (15) C10—C9—S1 123.9 (3)

C12—O1—S2 115.2 (2) C12—C9—S1 119.8 (2)

C7—N1—N2 107.9 (3) C9—C10—C11 131.2 (3)

C8—N2—N1 108.0 (3) C9—C10—S2 108.2 (3)

C7—N3—C8 105.7 (3) C11—C10—S2 120.2 (2)

C7—N3—N4 121.8 (3) N4—C11—C10 131.5 (3)

C8—N3—N4 132.1 (3) N4—C11—H11 114.2

C11—N4—N3 118.2 (3) C10—C11—H11 114.2

C2—C1—C6 120.6 (4) O1—C12—C9 104.1 (2)

C2—C1—H1 119.7 O1—C12—C13 107.1 (3)

C6—C1—H1 119.7 C9—C12—C13 111.9 (3)

C1—C2—C3 120.4 (5) O1—C12—C14 106.8 (3)

C1—C2—H2 119.8 C9—C12—C14 113.1 (3)

C3—C2—H2 119.8 C13—C12—C14 113.1 (3)

C2—C3—C4 119.9 (5) C12—C13—H13A 109.5

C2—C3—H3 120.1 C12—C13—H13B 109.5

C4—C3—H3 120.1 H13A—C13—H13B 109.5

C5—C4—C3 119.9 (5) C12—C13—H13C 109.5

C5—C4—H4 120.1 H13A—C13—H13C 109.5

C3—C4—H4 120.1 H13B—C13—H13C 109.5

C4—C5—C6 120.4 (5) C12—C14—H14A 109.5

C4—C5—H5 119.8 C12—C14—H14B 109.5

C6—C5—H5 119.8 H14A—C14—H14B 109.5

C5—C6—C1 118.9 (4) C12—C14—H14C 109.5

C5—C6—C7 118.0 (4) H14A—C14—H14C 109.5

C1—C6—C7 123.0 (4) H14B—C14—H14C 109.5

N1—C7—N3 109.1 (4)

O2—S2—O1—C12 −108.9 (3) C7—N3—C8—S1 −171.8 (3)

O3—S2—O1—C12 121.4 (3) N4—N3—C8—S1 0.9 (5)

C10—S2—O1—C12 7.6 (3) C9—S1—C8—N2 135.6 (3)

C7—N1—N2—C8 −0.7 (4) C9—S1—C8—N3 −52.6 (3)

C7—N3—N4—C11 −148.4 (4) C8—S1—C9—C10 45.8 (3)

C8—N3—N4—C11 39.8 (5) C8—S1—C9—C12 −138.2 (3)

C6—C1—C2—C3 0.1 (7) C12—C9—C10—C11 −172.8 (4)

C1—C2—C3—C4 0.7 (7) S1—C9—C10—C11 3.3 (6)

C2—C3—C4—C5 −0.3 (7) C12—C9—C10—S2 0.0 (4)

C3—C4—C5—C6 −0.9 (7) S1—C9—C10—S2 176.1 (2)

C4—C5—C6—C1 1.6 (6) O2—S2—C10—C9 109.7 (3)

C4—C5—C6—C7 −176.1 (4) O3—S2—C10—C9 −117.0 (3)

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supporting information

sup-5 Acta Cryst. (2004). E60, o1826–o1827

C2—C1—C6—C7 176.3 (4) O2—S2—C10—C11 −76.5 (3)

N2—N1—C7—N3 1.3 (4) O3—S2—C10—C11 56.8 (3)

N2—N1—C7—C6 179.9 (3) O1—S2—C10—C11 169.4 (3)

C8—N3—C7—N1 −1.3 (4) N3—N4—C11—C10 −4.0 (6)

N4—N3—C7—N1 −175.0 (3) C9—C10—C11—N4 −37.2 (7)

C8—N3—C7—C6 −179.9 (3) S2—C10—C11—N4 150.7 (4)

N4—N3—C7—C6 6.4 (5) S2—O1—C12—C9 −8.2 (4)

C5—C6—C7—N1 27.5 (6) S2—O1—C12—C13 110.4 (3)

C1—C6—C7—N1 −150.1 (4) S2—O1—C12—C14 −128.1 (3)

C5—C6—C7—N3 −154.1 (4) C10—C9—C12—O1 4.8 (4)

C1—C6—C7—N3 28.3 (6) S1—C9—C12—O1 −171.5 (2)

N1—N2—C8—N3 −0.1 (4) C10—C9—C12—C13 −110.6 (3)

N1—N2—C8—S1 173.0 (3) S1—C9—C12—C13 73.1 (4)

C7—N3—C8—N2 0.9 (4) C10—C9—C12—C14 120.3 (4)

References

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