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The title compound, also known as pyrido[4,3-e]thieno[3,2-c]­pyridazine, C9H5N3S, was crystallized from ethyl acetate. The molecule is planar and the N=N bond is 1.304 (3) Å compared with 1.306 (2) Å for the regio-isomer 7-aza­thieno[2,3-c]cinnoline and also in good agreement with similar compounds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807029947/sg2180sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807029947/sg2180Isup2.hkl
Contains datablock I

CCDC reference: 655015

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.043
  • wR factor = 0.109
  • Data-to-parameter ratio = 13.8

checkCIF/PLATON results

No syntax errors found



Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 26.36 From the CIF: _reflns_number_total 1623 Count of symmetry unique reflns 948 Completeness (_total/calc) 171.20% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 675 Fraction of Friedel pairs measured 0.712 Are heavy atom types Z>Si present yes PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 0 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The crystal structure of the title compound (I) was solved as part of a study of new tris-heterocyclic compounds with potential biological activity (Stockmann & Fiksdahl, 2007). Thieno[c]cinnolines (Barton et al., 1985) have been described in the literature and the crystal structure of benzo[c]cinnoline (9,10-diazaphenanthrene) has been solved (Van der Meer,1972). A view of molecule (I) with the atomic numbering is presented in Fig 1. The bond lengths are within the normal range of such bonds (Allen et al., 1987) and also in accordance with the regio-isomer thieno[2,3-c]-7-azacinnoline (Hansen et al., 2007) and other benzo[c]cinnoline derivatives (Hökelek et al., 1990, 1991a,1991b).

Related literature top

For related literature, see: Allen et al. (1987); Barton et al. (1985); Hökelek et al. (1990, 1991a, 1991b); Hansen et al. (2007); Holt & Fiksdahl (2006); Stockmann & Fiksdahl (2007); Van der Meer (1972).

Experimental top

Thieno[3,2-c]-7-azacinnoline (I) was prepared by intramolecular diazo coupling of the diazonium ion intermediate, made by NOBF4 diazotization (Holt & Fiksdahl, 2006) of the 3-amino-4-(thiophen-2-yl)pyridine precursor. Single crystals were grown by crystallization from ethyl acetate (Stockmann & Fiksdahl, 2007).

Refinement top

The H atoms were placed in idealized locations C—H = 0.93 Å and refined as riding with Uiso(H) = 1.2Ueq(C).

Structure description top

The crystal structure of the title compound (I) was solved as part of a study of new tris-heterocyclic compounds with potential biological activity (Stockmann & Fiksdahl, 2007). Thieno[c]cinnolines (Barton et al., 1985) have been described in the literature and the crystal structure of benzo[c]cinnoline (9,10-diazaphenanthrene) has been solved (Van der Meer,1972). A view of molecule (I) with the atomic numbering is presented in Fig 1. The bond lengths are within the normal range of such bonds (Allen et al., 1987) and also in accordance with the regio-isomer thieno[2,3-c]-7-azacinnoline (Hansen et al., 2007) and other benzo[c]cinnoline derivatives (Hökelek et al., 1990, 1991a,1991b).

For related literature, see: Allen et al. (1987); Barton et al. (1985); Hökelek et al. (1990, 1991a, 1991b); Hansen et al. (2007); Holt & Fiksdahl (2006); Stockmann & Fiksdahl (2007); Van der Meer (1972).

Computing details top

Data collection: CrystalClear (Rigaku/MSC, 2005); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: CrystalStructure.

Figures top
[Figure 1] Fig. 1. A view of I with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
pyrido[4,3-e]thieno[3,2-c]pyridazine top
Crystal data top
C9H5N3SF(000) = 384.00
Mr = 187.22Dx = 1.545 Mg m3
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71070 Å
Hall symbol: P 2c -2nCell parameters from 2489 reflections
a = 13.0233 (13) Åθ = 2.6–26.3°
b = 15.969 (3) ŵ = 0.35 mm1
c = 3.869 (1) ÅT = 293 K
V = 804.6 (3) Å3Needle, colorless
Z = 40.43 × 0.06 × 0.05 mm
Data collection top
Rigaku Saturn
diffractometer
1368 reflections with F2 > 2σ(F2)
Detector resolution: 7.31 pixels mm-1Rint = 0.043
ω scansθmax = 26.4°
Absorption correction: multi-scan
(Jacobson, 1998)
h = 1616
Tmin = 0.970, Tmax = 0.990k = 1919
5659 measured reflectionsl = 44
1623 independent reflections
Refinement top
Refinement on F2 w = 1/[σ2(Fo2) + (0.0638P)2 + 0.0832P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.043(Δ/σ)max = 0.001
wR(F2) = 0.110Δρmax = 0.24 e Å3
S = 0.99Δρmin = 0.20 e Å3
1623 reflectionsAbsolute structure: Flack (1983), 678 Friedel pairs
118 parametersAbsolute structure parameter: 0.15 (13)
H-atom parameters constrained
Crystal data top
C9H5N3SV = 804.6 (3) Å3
Mr = 187.22Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 13.0233 (13) ŵ = 0.35 mm1
b = 15.969 (3) ÅT = 293 K
c = 3.869 (1) Å0.43 × 0.06 × 0.05 mm
Data collection top
Rigaku Saturn
diffractometer
1623 independent reflections
Absorption correction: multi-scan
(Jacobson, 1998)
1368 reflections with F2 > 2σ(F2)
Tmin = 0.970, Tmax = 0.990Rint = 0.043
5659 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.043H-atom parameters constrained
wR(F2) = 0.110Δρmax = 0.24 e Å3
S = 0.99Δρmin = 0.20 e Å3
1623 reflectionsAbsolute structure: Flack (1983), 678 Friedel pairs
118 parametersAbsolute structure parameter: 0.15 (13)
Special details top

Refinement. Refinement using reflections with F2 > 2.0 σ(F2). The weighted R-factor(wR), goodness of fit (S) and R-factor (gt) are based on F, with F set to zero for negative F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.48118 (5)0.39555 (5)0.2592 (2)0.0501 (2)
N30.11539 (19)0.53593 (13)0.2017 (8)0.0518 (6)
N20.18936 (17)0.31858 (12)0.2581 (8)0.0480 (5)
N10.26250 (19)0.26614 (14)0.1794 (8)0.0522 (7)
C40.1992 (2)0.40207 (16)0.1722 (7)0.0385 (6)
C80.28477 (19)0.43726 (16)0.0052 (6)0.0358 (6)
C30.3492 (2)0.29597 (17)0.0150 (7)0.0433 (6)
C50.1168 (2)0.45587 (17)0.2577 (9)0.0464 (6)
H50.05940.43210.36190.056*
C70.2824 (2)0.52393 (17)0.0661 (8)0.0426 (6)
H70.33660.54980.18050.051*
C90.3634 (2)0.37936 (17)0.0712 (7)0.0378 (6)
C60.1989 (2)0.56885 (18)0.0363 (8)0.0489 (7)
H60.19860.62600.00950.059*
C20.4355 (2)0.2449 (2)0.0781 (10)0.0562 (8)
H20.43920.18740.04090.067*
C10.5099 (2)0.2903 (2)0.2255 (12)0.0573 (8)
H10.57140.26740.30250.069*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0385 (3)0.0645 (4)0.0472 (4)0.0017 (3)0.0040 (4)0.0007 (4)
N30.0461 (13)0.0451 (13)0.0643 (17)0.0070 (10)0.0060 (14)0.0018 (15)
N20.0452 (12)0.0423 (12)0.0564 (14)0.0076 (9)0.0008 (15)0.0024 (13)
N10.0520 (14)0.0407 (11)0.064 (2)0.0023 (11)0.0039 (13)0.0056 (13)
C40.0340 (13)0.0422 (14)0.0393 (18)0.0011 (10)0.0040 (11)0.0002 (11)
C80.0337 (14)0.0381 (14)0.0357 (14)0.0019 (10)0.0063 (11)0.0010 (11)
C30.0437 (15)0.0386 (14)0.0475 (17)0.0030 (12)0.0063 (13)0.0001 (13)
C50.0337 (14)0.0525 (15)0.0530 (17)0.0002 (11)0.0003 (17)0.0012 (18)
C70.0398 (15)0.0418 (15)0.0462 (16)0.0066 (11)0.0057 (13)0.0083 (13)
C90.0330 (14)0.0474 (15)0.0331 (15)0.0006 (10)0.0037 (12)0.0020 (12)
C60.0514 (17)0.0364 (15)0.059 (2)0.0013 (13)0.0106 (15)0.0005 (13)
C20.062 (2)0.0455 (16)0.0614 (18)0.0187 (15)0.0095 (17)0.0075 (16)
C10.0488 (17)0.069 (2)0.054 (2)0.0200 (14)0.0006 (17)0.012 (2)
Geometric parameters (Å, º) top
S1—C91.718 (2)C8—C91.411 (3)
S1—C11.726 (3)C3—C91.385 (3)
N3—C51.297 (3)C3—C21.434 (4)
N3—C61.366 (4)C7—C61.362 (4)
N2—N11.304 (3)C2—C11.339 (4)
N2—C41.380 (3)C5—H50.930
N1—C31.381 (3)C7—H70.930
C4—C81.406 (3)C6—H60.930
C4—C51.414 (3)C2—H20.930
C8—C71.412 (3)C1—H10.930
C9—S1—C190.87 (14)S1—C9—C3111.4 (2)
C5—N3—C6116.5 (2)C8—C9—C3118.9 (2)
N1—N2—C4119.8 (2)N3—C6—C7124.7 (2)
N2—N1—C3118.9 (2)C3—C2—C1111.4 (2)
N2—C4—C8124.8 (2)S1—C1—C2113.8 (2)
N2—C4—C5117.4 (2)N3—C5—H5117.6
C8—C4—C5117.8 (2)C4—C5—H5117.6
C4—C8—C7117.7 (2)C8—C7—H7120.7
C4—C8—C9114.2 (2)H7—C7—C6120.8
C7—C8—C9128.1 (2)N3—C6—H6117.7
N1—C3—C9123.4 (2)C7—C6—H6117.7
N1—C3—C2124.0 (2)C3—C2—H2124.3
C9—C3—C2112.5 (2)H2—C2—C1124.3
N3—C5—C4124.8 (2)S1—C1—H1123.1
C8—C7—C6118.5 (2)C2—C1—H1123.1
S1—C9—C8129.7 (2)
C9—S1—C1—C20.5 (3)C5—C4—C8—C9179.94 (19)
C1—S1—C9—C8179.8 (2)C4—C8—C7—C61.4 (4)
C1—S1—C9—C30.6 (2)C4—C8—C9—S1177.9 (2)
C5—N3—C6—C71.1 (5)C4—C8—C9—C31.2 (3)
C6—N3—C5—C42.5 (5)C7—C8—C9—S12.3 (4)
N1—N2—C4—C80.9 (4)C7—C8—C9—C3178.5 (2)
N1—N2—C4—C5178.8 (3)C9—C8—C7—C6178.9 (2)
C4—N2—N1—C30.9 (4)N1—C3—C9—S1177.9 (2)
N2—N1—C3—C90.2 (4)N1—C3—C9—C81.4 (4)
N2—N1—C3—C2178.7 (3)N1—C3—C2—C1178.2 (3)
N2—C4—C8—C7179.6 (2)C9—C3—C2—C10.4 (4)
N2—C4—C8—C90.2 (3)C2—C3—C9—S10.7 (3)
N2—C4—C5—N3178.3 (3)C2—C3—C9—C8180.0 (2)
C8—C4—C5—N31.9 (4)C8—C7—C6—N30.8 (4)
C5—C4—C8—C70.2 (3)C3—C2—C1—S10.1 (3)

Experimental details

Crystal data
Chemical formulaC9H5N3S
Mr187.22
Crystal system, space groupOrthorhombic, Pna21
Temperature (K)293
a, b, c (Å)13.0233 (13), 15.969 (3), 3.869 (1)
V3)804.6 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.35
Crystal size (mm)0.43 × 0.06 × 0.05
Data collection
DiffractometerRigaku Saturn
Absorption correctionMulti-scan
(Jacobson, 1998)
Tmin, Tmax0.970, 0.990
No. of measured, independent and
observed [F2 > 2σ(F2)] reflections
5659, 1623, 1368
Rint0.043
(sin θ/λ)max1)0.625
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.043, 0.110, 0.99
No. of reflections1623
No. of parameters118
No. of restraints?
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.24, 0.20
Absolute structureFlack (1983), 678 Friedel pairs
Absolute structure parameter0.15 (13)

Computer programs: CrystalClear (Rigaku/MSC, 2005), CrystalClear, CrystalStructure (Rigaku/MSC, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), CrystalStructure.

 

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