Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807041335/gk2090sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807041335/gk2090Isup2.hkl |
CCDC reference: 660356
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.002 Å
- R factor = 0.041
- wR factor = 0.132
- Data-to-parameter ratio = 17.3
checkCIF/PLATON results
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Alert level G PLAT199_ALERT_1_G Check the Reported _cell_measurement_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 1 ALERT level G = General alerts; check 1 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 0 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
7-Azathieno[2,3-c]cinnoline was prepared by intramolecular diazo coupling of the diazonium ion intermediate, made by NOBF4 diazotization (Holt & Fiksdahl, 2006) of the 3-amino-4-(thiophen-3-yl)pyridine precursor. Single crystals were grown by crystallization from ethyl acetate (Stockmann & Fiksdahl, 2007).
All H atoms were found from a difference map and were refined with isotropic displacement parameters.
The crystal structure of the title compound 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 et al., 1972). A view of the title molecule with the atomic numbering scheme is presented in Fig. 1. The bond lengths are within the normal range of such bonds and also in accordance with the regio-isomer 7-azathieno[3,2-c]cinnoline (Hansen et al., 2007) and other benzo[c]cinnoline derivatives (Hökelek et al., 1990, 1991a,b). The mean N═N distance for seven similar structures is 1.293 (10) Å, ranging from 1.283 (4) to 1.306 (2) Å. The C6—C7 bonds are always significantly shorter than the C7—C8 bonds. Mean C6—C7 bond is 1.364 (10) Å while the mean C7—C8 bond is 1.409 (10) Å. Also the angles show the same systematic differences. The mean C8—C9—C3 angle and the mean C4—C8—C9 angle are 117.8(2.) and 116.1(1.9)°, respectively, while the mean N2—C4—C8 angle is 122.3(2.0)° (see van der Meer, 1972 and references cited therein). The C—H groups of the thiophene ring are involved in intermolecular C—H···N interactions.
For related literature, see: Barton et al. (1985); Hansen et al. (2007); Holt & Fiksdahl (2006); Hökelek et al. (1990, 1991a,b); Stockmann & Fiksdahl (2007); van der Meer et al. (1972).
Data collection: CAD-4-PC Software (Enraf–Nonius, 1992); cell refinement: CELDIM in CAD-4-PC Software (Enraf–Nonius, 1992); data reduction: XCAD (McArdle & Higgins, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEX (McArdle, 1995) and ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: OSCAIL (McArdle, 1993).
Fig. 1. A view of the title molecule with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. |
C9H5N3S | Z = 2 |
Mr = 187.22 | F(000) = 192 |
Triclinic, P1 | Dx = 1.514 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71069 Å |
a = 6.8340 (18) Å | Cell parameters from 25 reflections |
b = 7.656 (2) Å | θ = 12–18° |
c = 8.847 (2) Å | µ = 0.34 mm−1 |
α = 104.172 (3)° | T = 293 K |
β = 101.376 (4)° | Prism, colourless |
γ = 107.042 (5)° | 0.40 × 0.30 × 0.20 mm |
V = 410.63 (18) Å3 |
Enraf–Nonius CAD-4 diffractometer | 1805 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.008 |
Graphite monochromator | θmax = 29.9°, θmin = 2.5° |
ω/2θ scans | h = 0→9 |
Absorption correction: ψ scan [ABSCALC in OSCAIL (McArdle & Daly, 1999; North et al., 1968)] | k = −10→10 |
Tmin = 0.882, Tmax = 0.935 | l = −12→12 |
2646 measured reflections | 3 standard reflections every 120 min |
2387 independent reflections | intensity decay: 1% |
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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.132 | All H-atom parameters refined |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0802P)2 + 0.041P] where P = (Fo2 + 2Fc2)/3 |
2387 reflections | (Δ/σ)max = 0.016 |
138 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.28 e Å−3 |
C9H5N3S | γ = 107.042 (5)° |
Mr = 187.22 | V = 410.63 (18) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.8340 (18) Å | Mo Kα radiation |
b = 7.656 (2) Å | µ = 0.34 mm−1 |
c = 8.847 (2) Å | T = 293 K |
α = 104.172 (3)° | 0.40 × 0.30 × 0.20 mm |
β = 101.376 (4)° |
Enraf–Nonius CAD-4 diffractometer | 1805 reflections with I > 2σ(I) |
Absorption correction: ψ scan [ABSCALC in OSCAIL (McArdle & Daly, 1999; North et al., 1968)] | Rint = 0.008 |
Tmin = 0.882, Tmax = 0.935 | 3 standard reflections every 120 min |
2646 measured reflections | intensity decay: 1% |
2387 independent reflections |
R[F2 > 2σ(F2)] = 0.041 | 0 restraints |
wR(F2) = 0.132 | All H-atom parameters refined |
S = 1.09 | Δρmax = 0.37 e Å−3 |
2387 reflections | Δρmin = −0.28 e Å−3 |
138 parameters |
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. Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane) - 0.8879 (0.0025) x + 6.8684 (0.0030) y - 5.7312 (0.0029) z = 1.8667 (0.0014) * 0.0357 (0.0008) S1 * -0.0053 (0.0012) N1 * -0.0173 (0.0012) N2 * 0.0186 (0.0014) N3 * 0.0049 (0.0013) C1 * -0.0149 (0.0013) C2 * 0.0030 (0.0013) C3 * -0.0112 (0.0013) C4 * 0.0111 (0.0015) C5 * 0.0122 (0.0014) C6 * -0.0038 (0.0013) C7 * -0.0169 (0.0012) C8 * -0.0161 (0.0012) C9 Rms deviation of fitted atoms = 0.0156 |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.31663 (8) | 0.41015 (6) | 0.11053 (5) | 0.05756 (17) | |
N2 | 0.78580 (19) | 0.7761 (2) | 0.48565 (19) | 0.0527 (3) | |
N1 | 0.6832 (2) | 0.6459 (2) | 0.34347 (19) | 0.0516 (3) | |
N3 | 0.7020 (3) | 1.0644 (2) | 0.83784 (19) | 0.0640 (4) | |
H2 | 0.009 (3) | 0.557 (3) | 0.340 (3) | 0.064 (6)* | |
H5 | 0.937 (4) | 1.042 (3) | 0.766 (3) | 0.071 (6)* | |
H6 | 0.419 (4) | 1.059 (4) | 0.871 (3) | 0.083 (7)* | |
H7 | 0.203 (4) | 0.833 (4) | 0.648 (3) | 0.084 (7)* | |
H1 | −0.045 (3) | 0.332 (3) | 0.077 (2) | 0.057 (5)* | |
C1 | 0.0860 (3) | 0.4135 (2) | 0.1556 (2) | 0.0521 (4) | |
C2 | 0.1168 (2) | 0.5381 (2) | 0.30372 (18) | 0.0440 (3) | |
C3 | 0.4669 (2) | 0.5808 (2) | 0.29745 (17) | 0.0400 (3) | |
C4 | 0.6725 (2) | 0.8437 (2) | 0.58315 (18) | 0.0421 (3) | |
C5 | 0.7900 (3) | 0.9894 (3) | 0.7357 (2) | 0.0584 (4) | |
C6 | 0.4846 (3) | 1.0005 (3) | 0.7961 (2) | 0.0576 (4) | |
C7 | 0.3532 (3) | 0.8628 (2) | 0.65419 (18) | 0.0449 (3) | |
C8 | 0.44728 (19) | 0.77948 (18) | 0.54209 (15) | 0.0349 (3) | |
C9 | 0.33770 (19) | 0.63693 (18) | 0.38810 (15) | 0.0342 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0703 (3) | 0.0558 (3) | 0.0418 (2) | 0.0245 (2) | 0.01587 (18) | 0.00583 (17) |
N2 | 0.0308 (6) | 0.0565 (8) | 0.0718 (9) | 0.0165 (5) | 0.0131 (6) | 0.0227 (7) |
N1 | 0.0395 (6) | 0.0590 (8) | 0.0648 (8) | 0.0245 (6) | 0.0224 (6) | 0.0205 (7) |
N3 | 0.0738 (10) | 0.0452 (7) | 0.0484 (8) | 0.0114 (7) | −0.0071 (7) | 0.0048 (6) |
C1 | 0.0461 (8) | 0.0480 (8) | 0.0460 (8) | 0.0091 (6) | −0.0026 (6) | 0.0096 (6) |
C2 | 0.0311 (6) | 0.0470 (7) | 0.0487 (8) | 0.0118 (5) | 0.0057 (5) | 0.0139 (6) |
C3 | 0.0390 (6) | 0.0418 (7) | 0.0426 (7) | 0.0178 (5) | 0.0136 (5) | 0.0139 (5) |
C4 | 0.0314 (6) | 0.0393 (7) | 0.0492 (7) | 0.0090 (5) | 0.0024 (5) | 0.0151 (6) |
C5 | 0.0450 (8) | 0.0463 (8) | 0.0611 (10) | 0.0050 (7) | −0.0090 (7) | 0.0116 (7) |
C6 | 0.0773 (12) | 0.0485 (8) | 0.0421 (8) | 0.0242 (8) | 0.0131 (8) | 0.0076 (6) |
C7 | 0.0481 (8) | 0.0444 (7) | 0.0426 (7) | 0.0177 (6) | 0.0157 (6) | 0.0115 (6) |
C8 | 0.0315 (6) | 0.0347 (6) | 0.0373 (6) | 0.0115 (5) | 0.0077 (5) | 0.0119 (5) |
C9 | 0.0291 (5) | 0.0368 (6) | 0.0367 (6) | 0.0126 (5) | 0.0083 (4) | 0.0121 (5) |
S1—C1 | 1.7058 (19) | C2—H2 | 0.89 (2) |
S1—C3 | 1.7267 (17) | C3—C9 | 1.3929 (18) |
N2—N1 | 1.302 (2) | C4—C8 | 1.4114 (18) |
N2—C4 | 1.375 (2) | C4—C5 | 1.421 (2) |
N1—C3 | 1.3534 (19) | C5—H5 | 0.92 (2) |
N3—C5 | 1.293 (3) | C6—C7 | 1.359 (2) |
N3—C6 | 1.361 (3) | C6—H6 | 0.97 (2) |
C1—C2 | 1.354 (2) | C7—C8 | 1.4089 (19) |
C1—H1 | 0.95 (2) | C7—H7 | 0.97 (3) |
C2—C9 | 1.4205 (18) | C8—C9 | 1.4136 (18) |
C1—S1—C3 | 90.68 (7) | N3—C5—C4 | 123.69 (16) |
N1—N2—C4 | 119.47 (12) | N3—C5—H5 | 115.1 (15) |
N2—N1—C3 | 118.30 (13) | C4—C5—H5 | 121.2 (15) |
C5—N3—C6 | 117.91 (15) | C7—C6—N3 | 124.48 (17) |
C2—C1—S1 | 114.11 (12) | C7—C6—H6 | 117.7 (15) |
C2—C1—H1 | 127.8 (12) | N3—C6—H6 | 117.8 (15) |
S1—C1—H1 | 118.1 (12) | C6—C7—C8 | 118.13 (16) |
C1—C2—C9 | 111.69 (14) | C6—C7—H7 | 112.6 (15) |
C1—C2—H2 | 122.8 (14) | C8—C7—H7 | 129.3 (15) |
C9—C2—H2 | 125.4 (14) | C7—C8—C4 | 118.27 (13) |
N1—C3—C9 | 126.65 (14) | C7—C8—C9 | 126.32 (12) |
N1—C3—S1 | 121.77 (11) | C4—C8—C9 | 115.40 (12) |
C9—C3—S1 | 111.58 (11) | C3—C9—C8 | 115.56 (12) |
N2—C4—C8 | 124.60 (13) | C3—C9—C2 | 111.93 (13) |
N2—C4—C5 | 117.89 (14) | C8—C9—C2 | 132.50 (12) |
C8—C4—C5 | 117.51 (15) | ||
C4—N2—N1—C3 | −0.5 (2) | C6—C7—C8—C9 | −179.09 (14) |
C3—S1—C1—C2 | 0.64 (13) | N2—C4—C8—C7 | −179.74 (13) |
S1—C1—C2—C9 | −0.48 (18) | C5—C4—C8—C7 | −0.2 (2) |
N2—N1—C3—C9 | −0.8 (2) | N2—C4—C8—C9 | −0.6 (2) |
N2—N1—C3—S1 | 179.35 (11) | C5—C4—C8—C9 | 178.96 (13) |
C1—S1—C3—N1 | 179.21 (14) | N1—C3—C9—C8 | 1.4 (2) |
C1—S1—C3—C9 | −0.63 (11) | S1—C3—C9—C8 | −178.80 (9) |
N1—N2—C4—C8 | 1.2 (2) | N1—C3—C9—C2 | −179.35 (14) |
N1—N2—C4—C5 | −178.37 (15) | S1—C3—C9—C2 | 0.49 (15) |
C6—N3—C5—C4 | −0.4 (3) | C7—C8—C9—C3 | 178.46 (13) |
N2—C4—C5—N3 | −179.99 (16) | C4—C8—C9—C3 | −0.58 (18) |
C8—C4—C5—N3 | 0.4 (3) | C7—C8—C9—C2 | −0.6 (2) |
C5—N3—C6—C7 | 0.1 (3) | C4—C8—C9—C2 | −179.69 (14) |
N3—C6—C7—C8 | 0.1 (3) | C1—C2—C9—C3 | −0.02 (18) |
C6—C7—C8—C4 | −0.1 (2) | C1—C2—C9—C8 | 179.12 (14) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···N3i | 0.943 (19) | 2.441 (18) | 3.352 (3) | 159.1 (18) |
C2—H2···N1ii | 0.89 (2) | 2.52 (2) | 3.360 (2) | 158 (2) |
Symmetry codes: (i) x−1, y−1, z−1; (ii) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C9H5N3S |
Mr | 187.22 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 6.8340 (18), 7.656 (2), 8.847 (2) |
α, β, γ (°) | 104.172 (3), 101.376 (4), 107.042 (5) |
V (Å3) | 410.63 (18) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.34 |
Crystal size (mm) | 0.40 × 0.30 × 0.20 |
Data collection | |
Diffractometer | Enraf–Nonius CAD-4 |
Absorption correction | ψ scan [ABSCALC in OSCAIL (McArdle & Daly, 1999; North et al., 1968)] |
Tmin, Tmax | 0.882, 0.935 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2646, 2387, 1805 |
Rint | 0.008 |
(sin θ/λ)max (Å−1) | 0.702 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.132, 1.09 |
No. of reflections | 2387 |
No. of parameters | 138 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.37, −0.28 |
Computer programs: CELDIM in CAD-4-PC Software (Enraf–Nonius, 1992), XCAD (McArdle & Higgins, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEX (McArdle, 1995) and ORTEPIII (Burnett & Johnson, 1996), OSCAIL (McArdle, 1993).
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···N3i | 0.943 (19) | 2.441 (18) | 3.352 (3) | 159.1 (18) |
C2—H2···N1ii | 0.89 (2) | 2.52 (2) | 3.360 (2) | 158 (2) |
Symmetry codes: (i) x−1, y−1, z−1; (ii) x−1, y, z. |
The crystal structure of the title compound 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 et al., 1972). A view of the title molecule with the atomic numbering scheme is presented in Fig. 1. The bond lengths are within the normal range of such bonds and also in accordance with the regio-isomer 7-azathieno[3,2-c]cinnoline (Hansen et al., 2007) and other benzo[c]cinnoline derivatives (Hökelek et al., 1990, 1991a,b). The mean N═N distance for seven similar structures is 1.293 (10) Å, ranging from 1.283 (4) to 1.306 (2) Å. The C6—C7 bonds are always significantly shorter than the C7—C8 bonds. Mean C6—C7 bond is 1.364 (10) Å while the mean C7—C8 bond is 1.409 (10) Å. Also the angles show the same systematic differences. The mean C8—C9—C3 angle and the mean C4—C8—C9 angle are 117.8(2.) and 116.1(1.9)°, respectively, while the mean N2—C4—C8 angle is 122.3(2.0)° (see van der Meer, 1972 and references cited therein). The C—H groups of the thiophene ring are involved in intermolecular C—H···N interactions.