6-Bromo-N-(6-bromo-pyridin-2-yl)-N-[4-(2,3-di-hydro-thieno[3,4-b][1,4]dioxin-5-yl)phen-yl]pyridin-2-amine.

In the title mol-ecule, C22H15Br2N3O2S, the central benzene ring forms dihedral angles of 12.39 (17), 56.66 (17) and 74.71 (19)°, respectively, with the mean planes of the thio-phene and two pyridine rings. The dioxane ring is in a half-chair conformation. An intra-molecular C-H⋯O hydrogen forms an S(6) ring. The amine N atom is sp (2)-hybridized.

Related literature

For related structures, see: Chen et al. (2011 ▶); Sotzing & Reynolds (1996 ▶); de Betterncourt-Dias et al. (2011 ▶). For applications of simliar compounds, see: Chahma et al. (2007 ▶); Roncali et al. (2005 ▶). For the synthesis of the starting material 4-(2,3-di­hydro­thieno[3,4-b][1,4]dioxin-5-yl)aniline, see: Trippé-Allard & Lacroix (2013 ▶). For the calculation of the functionality of the <span class="Chemical">aminen> group in terms of hybridization, see: Allen et al. (1995 ▶). For <span class="Chemical">hydrogen-bond graph-set motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

<span class="Chemical">C22H15Br2N3O2Sn>

M = 545.25

Triclinic,

a = 4.483 (4) Å

b = 12.151 (9) Å

c = 18.958 (13) Å

α = 75.807 (18)°

β = 87.67 (3)°

γ = 89.62 (2)°

V = 1000.3 (13) Å3

Z = 2

Mo Kα radiation

μ = 4.18 mm−1

T = 100 K

0.22 × 0.03 × 0.03 mm

Data collection

Rigaku Saturn724+ diffractometer

Absorption correction: multi-scan (ABSCOR; Higashi, 2001 ▶) T min = 0.563, T max = 1.000

13439 measured reflections

3521 independent reflections

2732 reflections with I > 2σ(I)

R int = 0.079

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.128

S = 1.00

3521 reflections

271 parameters

H-atom parameters constrained

Δρmax = 1.06 e Å−3

Δρmin = −0.83 e Å−3

Data collection: CrystalClear (Rigaku, 2008 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) within WinGX (Farrugia, 2012 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and POV-RAY (Cason, 2004 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814013191/lh5709sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814013191/lh5709Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814013191/lh5709Isup3.cml

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

C22H15Br2N3O2S	Z = 2
Mr = 545.25	F(000) = 540
Triclinic, P1	Dx = 1.810 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71075 Å
a = 4.483 (4) Å	Cell parameters from 3281 reflections
b = 12.151 (9) Å	θ = 1.7–27.7°
c = 18.958 (13) Å	µ = 4.18 mm−1
α = 75.807 (18)°	T = 100 K
β = 87.67 (3)°	Prism, colorless
γ = 89.62 (2)°	0.22 × 0.03 × 0.03 mm
V = 1000.3 (13) Å3

Rigaku Saturn724+ diffractometer	3521 independent reflections
Radiation source: fine-focus sealed tube	2732 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.079
Detector resolution: 28.5714 pixels mm-1	θmax = 25.0°, θmin = 1.7°
dtprofit.ref scans	h = −5→5
Absorption correction: multi-scan (ABSCOR; Higashi, 2001)	k = −14→14
Tmin = 0.563, Tmax = 1.000	l = −22→22
13439 measured reflections

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0638P)2] where P = (Fo2 + 2Fc2)/3
3521 reflections	(Δ/σ)max = 0.001
271 parameters	Δρmax = 1.06 e Å−3
0 restraints	Δρmin = −0.83 e Å−3

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.

	x	y	z	Uiso*/Ueq
C1	0.4149 (12)	0.8677 (5)	0.3436 (3)	0.0254 (13)
H1	0.4019	0.9100	0.2958	0.030*
C2	0.5672 (11)	0.7710 (5)	0.3635 (3)	0.0223 (12)
C3	0.7454 (12)	0.6007 (5)	0.3458 (3)	0.0244 (13)
H3A	0.8736	0.5675	0.3141	0.029*
H3B	0.5491	0.5663	0.3489	0.029*
C4	0.8723 (12)	0.5774 (5)	0.4210 (3)	0.0238 (12)
H4A	0.8982	0.4962	0.4395	0.029*
H4B	1.0666	0.6133	0.4177	0.029*
C5	0.5503 (10)	0.7210 (5)	0.4403 (3)	0.0188 (11)
C6	0.3812 (11)	0.7836 (5)	0.4784 (3)	0.0214 (12)
C7	0.3032 (11)	0.7649 (4)	0.5558 (3)	0.0181 (11)
C8	0.0814 (12)	0.8290 (5)	0.5805 (3)	0.0238 (12)
H8	−0.0179	0.8841	0.5467	0.029*
C9	0.0052 (12)	0.8131 (5)	0.6533 (3)	0.0235 (12)
H9	−0.1470	0.8560	0.6680	0.028*
C10	0.1546 (11)	0.7335 (5)	0.7049 (3)	0.0216 (12)
C11	0.3738 (11)	0.6680 (5)	0.6820 (3)	0.0215 (12)
H11	0.4733	0.6138	0.7163	0.026*
C12	0.4468 (11)	0.6822 (5)	0.6089 (3)	0.0208 (12)
H12	0.5927	0.6366	0.5945	0.025*
C13	0.0144 (11)	0.8117 (5)	0.8102 (3)	0.0201 (12)
C14	0.1319 (11)	0.9198 (5)	0.7798 (3)	0.0248 (13)
H14	0.2632	0.9325	0.7393	0.030*
C15	0.0499 (12)	1.0077 (5)	0.8109 (3)	0.0264 (13)
H15	0.1216	1.0809	0.7910	0.032*
C16	−0.1433 (12)	0.9848 (5)	0.8729 (3)	0.0257 (13)
H16	−0.2045	1.0416	0.8954	0.031*
C17	−0.2361 (11)	0.8761 (5)	0.8984 (3)	0.0235 (12)
C18	0.0708 (11)	0.6057 (5)	0.8273 (3)	0.0204 (12)
C19	0.2220 (12)	0.5796 (5)	0.8916 (3)	0.0230 (12)
H19	0.3344	0.6341	0.9057	0.028*
C20	0.2000 (11)	0.4706 (5)	0.9338 (3)	0.0239 (12)
H20	0.2952	0.4508	0.9778	0.029*
C21	0.0373 (11)	0.3899 (5)	0.9114 (3)	0.0221 (12)
H21	0.0175	0.3157	0.9394	0.027*
C22	−0.0947 (11)	0.4255 (5)	0.8448 (3)	0.0214 (12)
N1	−0.1728 (9)	0.7893 (4)	0.8702 (2)	0.0208 (10)
N2	0.0834 (10)	0.7185 (4)	0.7811 (2)	0.0223 (10)
N3	−0.0829 (9)	0.5300 (4)	0.8032 (2)	0.0208 (10)
O1	0.7239 (8)	0.7215 (3)	0.31571 (18)	0.0250 (9)
O2	0.6761 (8)	0.6202 (3)	0.47078 (18)	0.0228 (9)
S1	0.2461 (3)	0.90420 (13)	0.41770 (7)	0.0266 (3)
Br1	−0.49638 (12)	0.83856 (5)	0.98380 (3)	0.02763 (19)
Br2	−0.31232 (12)	0.31910 (5)	0.80909 (3)	0.02536 (18)

	U11	U22	U33	U12	U13	U23
C1	0.042 (3)	0.024 (3)	0.009 (3)	0.000 (3)	0.005 (2)	−0.002 (2)
C2	0.028 (3)	0.026 (3)	0.017 (3)	−0.004 (2)	0.004 (2)	−0.014 (2)
C3	0.033 (3)	0.025 (3)	0.019 (3)	0.002 (2)	0.001 (2)	−0.014 (3)
C4	0.028 (3)	0.025 (3)	0.022 (3)	0.002 (2)	0.001 (2)	−0.012 (2)
C5	0.018 (3)	0.026 (3)	0.015 (3)	0.000 (2)	0.0007 (19)	−0.009 (2)
C6	0.026 (3)	0.023 (3)	0.018 (3)	0.002 (2)	−0.002 (2)	−0.010 (2)
C7	0.025 (3)	0.019 (3)	0.011 (2)	0.001 (2)	0.001 (2)	−0.006 (2)
C8	0.029 (3)	0.024 (3)	0.019 (3)	0.007 (2)	−0.003 (2)	−0.006 (2)
C9	0.032 (3)	0.021 (3)	0.018 (3)	0.004 (2)	0.009 (2)	−0.009 (2)
C10	0.026 (3)	0.024 (3)	0.018 (3)	−0.003 (2)	0.001 (2)	−0.011 (2)
C11	0.029 (3)	0.022 (3)	0.015 (3)	0.000 (2)	−0.001 (2)	−0.006 (2)
C12	0.025 (3)	0.020 (3)	0.018 (3)	0.004 (2)	0.003 (2)	−0.007 (2)
C13	0.028 (3)	0.019 (3)	0.014 (3)	0.001 (2)	0.001 (2)	−0.008 (2)
C14	0.029 (3)	0.027 (3)	0.020 (3)	−0.001 (2)	0.005 (2)	−0.010 (3)
C15	0.033 (3)	0.024 (3)	0.022 (3)	−0.005 (2)	0.002 (2)	−0.006 (2)
C16	0.038 (3)	0.023 (3)	0.021 (3)	0.001 (3)	0.004 (2)	−0.015 (3)
C17	0.025 (3)	0.033 (4)	0.017 (3)	0.006 (2)	−0.003 (2)	−0.016 (3)
C18	0.022 (3)	0.025 (3)	0.018 (3)	0.005 (2)	0.001 (2)	−0.013 (2)
C19	0.024 (3)	0.033 (3)	0.016 (3)	0.003 (2)	−0.001 (2)	−0.014 (3)
C20	0.028 (3)	0.027 (3)	0.018 (3)	0.003 (2)	−0.001 (2)	−0.008 (3)
C21	0.025 (3)	0.022 (3)	0.018 (3)	0.002 (2)	0.001 (2)	−0.003 (2)
C22	0.029 (3)	0.023 (3)	0.015 (3)	−0.001 (2)	0.008 (2)	−0.011 (2)
N1	0.027 (2)	0.021 (3)	0.016 (2)	0.0047 (19)	−0.0002 (18)	−0.009 (2)
N2	0.032 (2)	0.021 (3)	0.017 (2)	−0.001 (2)	0.0055 (18)	−0.011 (2)
N3	0.029 (2)	0.022 (3)	0.013 (2)	0.000 (2)	0.0068 (18)	−0.009 (2)
O1	0.035 (2)	0.030 (2)	0.0138 (18)	−0.0010 (17)	0.0057 (15)	−0.0128 (17)
O2	0.031 (2)	0.027 (2)	0.0130 (18)	0.0098 (17)	0.0015 (15)	−0.0090 (17)
S1	0.0396 (8)	0.0243 (8)	0.0158 (7)	0.0065 (6)	0.0026 (6)	−0.0057 (6)
Br1	0.0357 (3)	0.0294 (4)	0.0196 (3)	0.0038 (3)	0.0076 (2)	−0.0111 (3)
Br2	0.0329 (3)	0.0260 (4)	0.0200 (3)	−0.0033 (2)	0.0029 (2)	−0.0115 (2)

C1—C2	1.335 (7)	C11—H11	0.9300
C1—S1	1.719 (5)	C12—H12	0.9300
C1—H1	0.9300	C13—N1	1.360 (6)
C2—O1	1.374 (6)	C13—C14	1.396 (8)
C2—C5	1.433 (7)	C13—N2	1.403 (7)
C3—O1	1.442 (6)	C14—C15	1.382 (8)
C3—C4	1.517 (7)	C14—H14	0.9300
C3—H3A	0.9700	C15—C16	1.403 (7)
C3—H3B	0.9700	C15—H15	0.9300
C4—O2	1.450 (6)	C16—C17	1.353 (8)
C4—H4A	0.9700	C16—H16	0.9300
C4—H4B	0.9700	C17—N1	1.318 (7)
C5—O2	1.351 (6)	C17—Br1	1.919 (5)
C5—C6	1.376 (7)	C18—N3	1.330 (7)
C6—C7	1.457 (7)	C18—C19	1.386 (7)
C6—S1	1.748 (5)	C18—N2	1.435 (7)
C7—C8	1.394 (7)	C19—C20	1.371 (8)
C7—C12	1.409 (7)	C19—H19	0.9300
C8—C9	1.375 (7)	C20—C21	1.384 (8)
C8—H8	0.9300	C20—H20	0.9300
C9—C10	1.386 (7)	C21—C22	1.386 (7)
C9—H9	0.9300	C21—H21	0.9300
C10—C11	1.382 (7)	C22—N3	1.319 (7)
C10—N2	1.433 (6)	C22—Br2	1.893 (6)
C11—C12	1.380 (7)
C2—C1—S1	111.4 (4)	C11—C12—H12	119.6
C2—C1—H1	124.3	C7—C12—H12	119.6
S1—C1—H1	124.3	N1—C13—C14	122.3 (5)
C1—C2—O1	124.1 (5)	N1—C13—N2	115.4 (5)
C1—C2—C5	113.8 (5)	C14—C13—N2	122.3 (5)
O1—C2—C5	122.1 (5)	C15—C14—C13	118.9 (5)
O1—C3—C4	109.9 (4)	C15—C14—H14	120.6
O1—C3—H3A	109.7	C13—C14—H14	120.6
C4—C3—H3A	109.7	C14—C15—C16	118.9 (6)
O1—C3—H3B	109.7	C14—C15—H15	120.5
C4—C3—H3B	109.7	C16—C15—H15	120.5
H3A—C3—H3B	108.2	C17—C16—C15	116.7 (5)
O2—C4—C3	111.0 (4)	C17—C16—H16	121.6
O2—C4—H4A	109.4	C15—C16—H16	121.6
C3—C4—H4A	109.4	N1—C17—C16	127.3 (5)
O2—C4—H4B	109.4	N1—C17—Br1	113.8 (4)
C3—C4—H4B	109.4	C16—C17—Br1	118.9 (4)
H4A—C4—H4B	108.0	N3—C18—C19	123.6 (5)
O2—C5—C6	124.2 (5)	N3—C18—N2	116.0 (4)
O2—C5—C2	122.8 (4)	C19—C18—N2	120.3 (5)
C6—C5—C2	112.9 (5)	C20—C19—C18	117.6 (5)
C5—C6—C7	131.5 (5)	C20—C19—H19	121.2
C5—C6—S1	109.3 (4)	C18—C19—H19	121.2
C7—C6—S1	119.2 (4)	C19—C20—C21	120.5 (5)
C8—C7—C12	117.1 (5)	C19—C20—H20	119.8
C8—C7—C6	120.9 (4)	C21—C20—H20	119.8
C12—C7—C6	122.0 (4)	C20—C21—C22	116.3 (5)
C9—C8—C7	121.9 (5)	C20—C21—H21	121.8
C9—C8—H8	119.0	C22—C21—H21	121.8
C7—C8—H8	119.0	N3—C22—C21	125.0 (5)
C8—C9—C10	120.2 (5)	N3—C22—Br2	116.1 (4)
C8—C9—H9	119.9	C21—C22—Br2	118.9 (4)
C10—C9—H9	119.9	C17—N1—C13	115.8 (5)
C11—C10—C9	119.1 (5)	C13—N2—C10	121.0 (4)
C11—C10—N2	120.1 (5)	C13—N2—C18	119.9 (4)
C9—C10—N2	120.8 (5)	C10—N2—C18	119.0 (4)
C12—C11—C10	120.8 (5)	C22—N3—C18	116.9 (4)
C12—C11—H11	119.6	C2—O1—C3	110.1 (4)
C10—C11—H11	119.6	C5—O2—C4	113.7 (4)
C11—C12—C7	120.9 (5)	C1—S1—C6	92.6 (3)
S1—C1—C2—O1	179.9 (4)	C18—C19—C20—C21	1.4 (8)
S1—C1—C2—C5	0.8 (6)	C19—C20—C21—C22	0.8 (7)
O1—C3—C4—O2	62.8 (6)	C20—C21—C22—N3	−2.0 (8)
C1—C2—C5—O2	176.4 (5)	C20—C21—C22—Br2	178.4 (4)
O1—C2—C5—O2	−2.7 (8)	C16—C17—N1—C13	2.2 (8)
C1—C2—C5—C6	−0.5 (7)	Br1—C17—N1—C13	−179.1 (3)
O1—C2—C5—C6	−179.6 (5)	C14—C13—N1—C17	−0.3 (7)
O2—C5—C6—C7	2.6 (9)	N2—C13—N1—C17	179.3 (4)
C2—C5—C6—C7	179.5 (5)	N1—C13—N2—C10	151.1 (5)
O2—C5—C6—S1	−176.9 (4)	C14—C13—N2—C10	−29.4 (7)
C2—C5—C6—S1	−0.1 (6)	N1—C13—N2—C18	−26.2 (7)
C5—C6—C7—C8	−167.6 (6)	C14—C13—N2—C18	153.3 (5)
S1—C6—C7—C8	11.9 (7)	C11—C10—N2—C13	142.0 (5)
C5—C6—C7—C12	12.5 (9)	C9—C10—N2—C13	−38.1 (7)
S1—C6—C7—C12	−168.0 (4)	C11—C10—N2—C18	−40.6 (7)
C12—C7—C8—C9	0.2 (8)	C9—C10—N2—C18	139.2 (5)
C6—C7—C8—C9	−179.7 (5)	N3—C18—N2—C13	130.1 (5)
C7—C8—C9—C10	1.5 (9)	C19—C18—N2—C13	−52.2 (7)
C8—C9—C10—C11	−2.0 (9)	N3—C18—N2—C10	−47.3 (6)
C8—C9—C10—N2	178.1 (5)	C19—C18—N2—C10	130.4 (5)
C9—C10—C11—C12	0.8 (9)	C21—C22—N3—C18	0.8 (7)
N2—C10—C11—C12	−179.4 (5)	Br2—C22—N3—C18	−179.6 (3)
C10—C11—C12—C7	1.0 (9)	C19—C18—N3—C22	1.7 (7)
C8—C7—C12—C11	−1.5 (8)	N2—C18—N3—C22	179.4 (4)
C6—C7—C12—C11	178.4 (5)	C1—C2—O1—C3	−153.8 (5)
N1—C13—C14—C15	−1.5 (8)	C5—C2—O1—C3	25.2 (7)
N2—C13—C14—C15	179.0 (5)	C4—C3—O1—C2	−53.4 (5)
C13—C14—C15—C16	1.4 (8)	C6—C5—O2—C4	−173.1 (5)
C14—C15—C16—C17	0.2 (8)	C2—C5—O2—C4	10.3 (7)
C15—C16—C17—N1	−2.3 (9)	C3—C4—O2—C5	−39.1 (6)
C15—C16—C17—Br1	179.2 (4)	C2—C1—S1—C6	−0.7 (5)
N3—C18—C19—C20	−2.8 (8)	C5—C6—S1—C1	0.4 (4)
N2—C18—C19—C20	179.6 (4)	C7—C6—S1—C1	−179.2 (5)

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O2	0.93	2.42	3.036 (7)	124

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯O2	0.93	2.42	3.036 (7)	124