Crystal structure of 12-benzyl­sulfanyl-2,9-di­bromo-6H-dibenzo[b,g][1,8]naphthyridin-11-one

Sebastian Resch; Thomas Quell; Dieter Schollmeyer; Siegfried R Waldvogel

doi:10.1107/S2056989015014541

. 2015 Aug 22;71(Pt 9):o675–o676. doi: 10.1107/S2056989015014541

Crystal structure of 12-benzylsulfanyl-2,9-dibromo-6H-dibenzo[b,g][1,8]naphthyridin-11-one

Sebastian Resch ^a, Thomas Quell ^a, Dieter Schollmeyer ^a, Siegfried R Waldvogel ^a,^*

PMCID: PMC4555377 PMID: 26396899

Abstract

The heterotetracene skeleton of the title molecule, C₂₃H₁₄Br₂N₂OS, is defined by linear annulation of four six-membered rings, including two N heteroatoms. This moiety is nearly planar (r.m.s. deviation = 0.055 Å), with a slight twist of 4.1 (2)° between the two halves of the aromatic system. The dihedral angle between the least-squares plane of the skeleton and the benzyl group is 24.5 (3)°; the C—S—C angle involving the benzylsulfanyl group is 99.2 (4)°. In the crystal, molecules are π-stacked in an antiparallel fashion along [110], with a distance between the aromatic planes of 3.47 (2) Å. Intermolecular N—H⋯O hydrogen bonds form chains extending parallel to [001] and bridge the antiparallel interdigitated stacks of molecules.

Keywords: crystal structure; 1,8-naphthyridine; heterotetracene

Related literature

The title compound was prepared as part of a study towards sulfur-containing 1,8-naphthyridine derivatives (Resch et al., 2015 ▸) in which the structure of a dibenzo[b,g][1,2]dithiolo[3,4,5-d,e][1,8]naphthyridine derivative is reported. For the structure of tetracene, see: Holmes et al. (1999 ▸).

Experimental

Crystal data

C₂₃H₁₄Br₂N₂OS
M _r = 526.24
Monoclinic,
a = 15.4915 (10) Å
b = 9.3953 (4) Å
c = 13.6501 (9) Å
β = 101.251 (5)°
V = 1948.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 4.29 mm⁻¹
T = 193 K
0.27 × 0.12 × 0.04 mm

Data collection

Stoe IPDS 2T diffractometer
Absorption correction: integration X-RED (Stoe & Cie, 1995 ▸) T _min = 0.363, T _max = 0.811
10437 measured reflections
4807 independent reflections
2850 reflections with I > 2σ(I)
R _int = 0.058

Refinement

R[F ² > 2σ(F ²)] = 0.068
wR(F ²) = 0.222
S = 1.05
4807 reflections
262 parameters
H-atom parameters constrained
Δρ_max = 2.29 e Å⁻³
Δρ_min = −1.21 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 1995 ▸); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 1995 ▸); program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: PLATON (Spek, 2009 ▸); software used to prepare material for publication: publCIF (Westrip, 2010 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015014541/wm5191sup1.cif

e-71-0o675-sup1.cif^{(379.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015014541/wm5191Isup2.hkl

e-71-0o675-Isup2.hkl^{(382.8KB, hkl)}

Click here for additional data file.^{(7.1KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015014541/wm5191Isup3.cml

Click here for additional data file.^{(1.3MB, tif)}

. DOI: 10.1107/S2056989015014541/wm5191fig1.tif

The molecular structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level.

Click here for additional data file.^{(1.5MB, tif)}

. DOI: 10.1107/S2056989015014541/wm5191fig2.tif

The crystal structure of the title compound in a view along [010]. N—H⋯O hydrogen bonds are shown as dashed lines.

CCDC reference: 1416554

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
N5H5O1ⁱ	0.88	2.28	3.001(7)	140

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was generously supported by the Federal Ministry of Education and Research (BMBF, HE-Lion, 03X4612B) and the German Research Foundation (DFG) in the frame of the research unit FOR1616.

supplementary crystallographic information

S1. Synthesis and crystallization

In argon atmosphere, 50 mg (2.0 mmol, 3 eq) NaH and 340 mg (2.7 mmol, 4 eq) benzyl thiol were given to 40 ml of anhydrous dioxane and stirred at room temperature for 30 min. 300 mg (0.68 mmol, 1 eq) of 6H-12-chloro-2,9-dibromodibenzo[b,g]-1,8-naphthyridin-11-one were added and the mixture stirred at room temperature for additional 5 h. After completion of the reaction, the solvent was removed under reduced pressure and the residue purified by column chromatography on silica gel using a mixture of dichloromethane and acetic acid (97:3). The solvent was removed under reduced pressure and the residue alkalized using 1M ammonium hydroxide solution. Yield: 276 mg (0.52 mmol, 77%) of an orange solid with mp. = > 513 K (decomposition). Suitable single crystals were obtained by slowly diluting a saturated solution of the title compound in dichloromethane/methanol (5:1) by cyclohexane (diffusion method).

S2. Refinement

Hydrogen atoms attached to carbon atoms were placed at calculated positions with C—H = 0.95 Å (aromatic) or 0.99 Å (methylene C atom). The H atom bonded to the N atom was placed at calculated positions with N—H = 0.88 Å. All H atoms were refined in the riding-model approximation with isotropic displacement parameters (set at 1.2–1.5U_eq of the parent atom).