5-Bromo-3-(indan-1-yl­oxy)pyridin-2-amine

Cho-Schultz, S.; Kath, J.C.; Moore, C.; Rheingold, A.L.; Yanovsky, A.

doi:10.1107/S1600536811005332

organic compounds

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Volume 67| Part 3| March 2011| Page o650

doi:10.1107/S1600536811005332

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5-Bromo-3-(indan-1-yloxy)pyridin-2-amine

Sujin Cho-Schultz,^a John C. Kath,^a Curtis Moore,^b Arnold L. Rheingold ^b and Alex Yanovsky ^a ^*

^aPfizer Global Research and Development, La Jolla Labs, 10770 Science Center Drive, San Diego, CA 92121, USA, and ^bDepartment of Chemistry and Biochemistry, University of California, San Diego, 9500 Gilman Drive, La Jolla, CA 92093, USA
^*Correspondence e-mail: alex.yanovsky@pfizer.com

(Received 29 January 2011; accepted 13 February 2011; online 19 February 2011)

The title compound, C₁₄H₁₃BrN₂O, was obtained by reaction of indan-1-yl methanesulfonate with 2-amino-5-bromopyridin-3-ol in the presence of caesium carbonate. The indane ring system is approximately planar [all but one of the C atoms are coplanar within 0.03 Å, the latter atom being displaced by 0.206 (2) Å from the mean plane through the remaining atoms] and forms a dihedral angle of 58.41 (4)° with the pyridine ring. In the crystal, centrosymmetrically related molecules are linked into dimers by N—H⋯N hydrogen bonds.

Related literature

For related structures with an indane group linked to a pyridine derivative through a C—O—C bridge, see: Dinçer et al. (2004 ); Lifshits et al. (2008 ).

Experimental

Crystal data

C₁₄H₁₃BrN₂O
M_r = 305.17
Monoclinic, P 2₁ /n
a = 11.3944 (18) Å
b = 9.4515 (15) Å
c = 12.438 (2) Å
β = 110.678 (2)°
V = 1253.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 3.27 mm⁻¹
T = 100 K
0.21 × 0.16 × 0.08 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.547, T_max = 0.780
23669 measured reflections
2942 independent reflections
2595 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.054
S = 1.03
2942 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2NA⋯N1ⁱ	0.88	2.10	2.975 (2)	178
Symmetry code: (i) -x+2, -y+1, -z+2.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811005332/rz2555sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811005332/rz2555Isup2.hkl

checkCIF report

Comment top

The present study confirmed the expected structure of the title compound, the product of reaction between indan-1-yl methanesulfonate and 2-amino-5-bromopyridin-3-ol in the presence of caesium carbonate (Fig. 1).

All C atoms of the indane fragment with the exception of C7 are coplanar within 0.03 Å; the latter atom is displaced by 0.206 (2) Å from the mean plane based on all the remaining atoms of the bicyclic system. The O1 atom deviates from this plane by 1.008 (2) Å in the same direction as the C7 atom. The central C2—O1—C6 bridge is in fact coplanar with the pyridine ring so that the N1/C1/C2/C3/C3/C4/C5/O1/C6 fragment is planar within 0.01 Å and its plane forms the dihedral angle of 57.6 (3)° with the above mentioned indane plane. It is noteworthy, that general conformations of a few other structurally studied molecules featuring indane group linked to pyridine derivatives through the C—O—C bridge (Dinçer et al., 2004; Lifshits et al., 2008) bear close resemblance to that of the molecule of the title compound.

The N2—H2NA···N1ⁱ bonds [symmetry code (i): 2 - x, 1 - y, 2 - z] (Table 1) link molecules in the crystal of the title compounds into centrosymmetric dimers (Fig. 2). One more intermolecular contact N2—H2NB···Br1ⁱⁱ [symmetry code (ii): x - 1/2, 1.5 - y, z - 1/2] may also play certain role in the stability of the packing, although corresponding interaction seems to be too weak to be qualified as one more independent H-bond.

Related literature top

For related structures with an indane group linked to a pyridine derivative through a C—O—C bridge, see: Dinçer et al. (2004); Lifshits et al. (2008).

Experimental top

To a solution of 2-amino-5-bromopyridin-3-ol (1.640 g, 8.48 mmol) in 42 ml of DMF was added 2,3-dihydro-1H-inden-1-yl methanesulfonate (0.9 g, 4.24 mmol) and caesium carbonate (1.380 g, 4.24 mmol) and heated to 60°C overnight. The reaction mixture was quenched with water and the aqueous layer was extracted with EtOAc (3 x 20 ml). The organic layers were combined, dried over MgSO₄, filtered and concentrated. The product was purified by flash chromatography (silica gel, 10–50% EtOAc/heptane) to give 525 mg (46%) 5-bromo-3-(2,3-dihydro-1H-inden-1-yloxy)pyridin-2-amine as a white solid.

The colorless crystals were grown by slow cooling of the solution of the title compound in boiling dichloroetane.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound, showing 50% probability displacement ellipsoids. H atoms are drawn as circles of arbitrary small radius.
	Fig. 2. Packing diagram of the title compound viewed down the b axis. H-bonds are shown as dashed lines.

5-Bromo-3-(indan-1-yloxy)pyridin-2-amine top

Crystal data top

C₁₄H₁₃BrN₂O	F(000) = 616
M_r = 305.17	D_x = 1.617 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9797 reflections
a = 11.3944 (18) Å	θ = 2.8–27.7°
b = 9.4515 (15) Å	µ = 3.27 mm⁻¹
c = 12.438 (2) Å	T = 100 K
β = 110.678 (2)°	Block, colorless
V = 1253.2 (3) Å³	0.21 × 0.16 × 0.08 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	2942 independent reflections
Radiation source: fine-focus sealed tube	2595 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −15→14
T_min = 0.547, T_max = 0.780	k = −12→12
23669 measured reflections	l = −16→15

Refinement top

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.054	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0191P)² + 0.7815P] where P = (F_o² + 2F_c²)/3
2942 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₄H₁₃BrN₂O	V = 1253.2 (3) Å³
M_r = 305.17	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 11.3944 (18) Å	µ = 3.27 mm⁻¹
b = 9.4515 (15) Å	T = 100 K
c = 12.438 (2) Å	0.21 × 0.16 × 0.08 mm
β = 110.678 (2)°

Data collection top

Bruker APEXII CCD diffractometer	2942 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2595 reflections with I > 2σ(I)
T_min = 0.547, T_max = 0.780	R_int = 0.046
23669 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.054	H-atom parameters constrained
S = 1.03	Δρ_max = 0.38 e Å⁻³
2942 reflections	Δρ_min = −0.30 e Å⁻³
163 parameters

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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) top

	x	y	z	U_iso*/U_eq
Br1	1.235622 (16)	1.080477 (17)	1.070416 (15)	0.02063 (6)
O1	0.95752 (11)	0.77404 (12)	0.71352 (10)	0.0192 (3)
N1	1.06647 (13)	0.68706 (14)	1.01301 (12)	0.0179 (3)
N2	0.95112 (15)	0.56292 (15)	0.84811 (13)	0.0227 (3)
H2NA	0.9477	0.4894	0.8903	0.027*
H2NB	0.9150	0.5591	0.7729	0.027*
C1	1.01219 (16)	0.68247 (17)	0.89913 (14)	0.0163 (3)
C2	1.01793 (15)	0.79884 (17)	0.82822 (14)	0.0165 (3)
C3	1.08206 (16)	0.91835 (17)	0.87805 (15)	0.0171 (3)
H3	1.0868	0.9979	0.8331	0.020*
C4	1.14048 (16)	0.91900 (16)	0.99797 (15)	0.0161 (3)
C5	1.13089 (16)	0.80499 (17)	1.06228 (15)	0.0180 (3)
H5	1.1704	0.8086	1.1435	0.022*
C6	0.95743 (16)	0.88611 (17)	0.63483 (14)	0.0168 (3)
H6	1.0431	0.9283	0.6559	0.020*
C7	0.85977 (17)	1.00246 (18)	0.62819 (15)	0.0209 (4)
H7A	0.8003	0.9696	0.6647	0.025*
H7B	0.9019	1.0892	0.6681	0.025*
C8	0.78992 (16)	1.03247 (17)	0.49914 (15)	0.0184 (3)
H8A	0.6983	1.0385	0.4815	0.022*
H8B	0.8193	1.1220	0.4759	0.022*
C9	0.82218 (16)	0.90756 (16)	0.43914 (15)	0.0164 (3)
C10	0.91601 (15)	0.82524 (17)	0.51553 (14)	0.0163 (3)
C11	0.96492 (16)	0.70772 (17)	0.47841 (15)	0.0200 (4)
H11	1.0284	0.6517	0.5316	0.024*
C12	0.91930 (17)	0.67388 (18)	0.36230 (16)	0.0225 (4)
H12	0.9523	0.5947	0.3353	0.027*
C13	0.82497 (17)	0.75614 (19)	0.28514 (15)	0.0224 (4)
H13	0.7942	0.7322	0.2059	0.027*
C14	0.77560 (17)	0.87233 (18)	0.32274 (15)	0.0204 (4)
H14	0.7109	0.9272	0.2699	0.025*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02147 (10)	0.01833 (9)	0.01970 (10)	−0.00397 (7)	0.00432 (7)	−0.00082 (6)
O1	0.0247 (7)	0.0182 (6)	0.0125 (6)	−0.0039 (5)	0.0038 (5)	0.0033 (4)
N1	0.0195 (7)	0.0179 (7)	0.0156 (7)	−0.0011 (6)	0.0055 (6)	0.0024 (5)
N2	0.0298 (9)	0.0198 (7)	0.0140 (7)	−0.0074 (6)	0.0021 (6)	0.0035 (6)
C1	0.0150 (8)	0.0174 (7)	0.0168 (8)	0.0007 (6)	0.0058 (7)	0.0029 (6)
C2	0.0149 (8)	0.0209 (8)	0.0137 (8)	0.0019 (6)	0.0052 (6)	0.0030 (6)
C3	0.0178 (8)	0.0168 (8)	0.0172 (9)	0.0013 (6)	0.0070 (7)	0.0039 (6)
C4	0.0141 (8)	0.0155 (7)	0.0184 (8)	−0.0002 (6)	0.0053 (7)	−0.0013 (6)
C5	0.0187 (9)	0.0201 (8)	0.0145 (8)	0.0009 (7)	0.0049 (7)	0.0003 (6)
C6	0.0195 (9)	0.0169 (7)	0.0140 (8)	−0.0022 (6)	0.0057 (7)	0.0033 (6)
C7	0.0257 (10)	0.0202 (8)	0.0161 (9)	0.0025 (7)	0.0067 (7)	0.0009 (7)
C8	0.0184 (9)	0.0171 (8)	0.0180 (9)	0.0002 (6)	0.0045 (7)	0.0020 (6)
C9	0.0170 (8)	0.0158 (7)	0.0166 (8)	−0.0037 (6)	0.0062 (7)	0.0018 (6)
C10	0.0159 (8)	0.0177 (8)	0.0158 (8)	−0.0032 (6)	0.0061 (7)	0.0012 (6)
C11	0.0179 (9)	0.0193 (8)	0.0225 (9)	−0.0002 (7)	0.0067 (7)	0.0013 (7)
C12	0.0233 (9)	0.0200 (8)	0.0262 (10)	−0.0048 (7)	0.0113 (8)	−0.0068 (7)
C13	0.0256 (10)	0.0258 (9)	0.0154 (9)	−0.0086 (7)	0.0066 (7)	−0.0050 (7)
C14	0.0213 (9)	0.0199 (8)	0.0169 (9)	−0.0040 (7)	0.0028 (7)	0.0029 (7)

Geometric parameters (Å, º) top

Br1—C4	1.9044 (16)	C7—C8	1.545 (2)
O1—C2	1.368 (2)	C7—H7A	0.9900
O1—C6	1.4419 (19)	C7—H7B	0.9900
N1—C1	1.331 (2)	C8—C9	1.510 (2)
N1—C5	1.356 (2)	C8—H8A	0.9900
N2—C1	1.361 (2)	C8—H8B	0.9900
N2—H2NA	0.8800	C9—C10	1.391 (2)
N2—H2NB	0.8800	C9—C14	1.395 (2)
C1—C2	1.426 (2)	C10—C11	1.393 (2)
C2—C3	1.369 (2)	C11—C12	1.388 (3)
C3—C4	1.402 (2)	C11—H11	0.9500
C3—H3	0.9500	C12—C13	1.397 (3)
C4—C5	1.369 (2)	C12—H12	0.9500
C5—H5	0.9500	C13—C14	1.388 (3)
C6—C10	1.504 (2)	C13—H13	0.9500
C6—C7	1.546 (2)	C14—H14	0.9500
C6—H6	1.0000

C2—O1—C6	117.49 (13)	C6—C7—H7A	110.4
C1—N1—C5	118.79 (14)	C8—C7—H7B	110.4
C1—N2—H2NA	120.0	C6—C7—H7B	110.4
C1—N2—H2NB	120.0	H7A—C7—H7B	108.6
H2NA—N2—H2NB	120.0	C9—C8—C7	104.11 (13)
N1—C1—N2	119.49 (15)	C9—C8—H8A	110.9
N1—C1—C2	121.84 (15)	C7—C8—H8A	110.9
N2—C1—C2	118.66 (15)	C9—C8—H8B	110.9
O1—C2—C3	127.25 (15)	C7—C8—H8B	110.9
O1—C2—C1	113.39 (14)	H8A—C8—H8B	109.0
C3—C2—C1	119.35 (15)	C10—C9—C14	119.63 (16)
C2—C3—C4	117.53 (15)	C10—C9—C8	111.25 (15)
C2—C3—H3	121.2	C14—C9—C8	129.04 (16)
C4—C3—H3	121.2	C9—C10—C11	121.40 (16)
C5—C4—C3	120.80 (15)	C9—C10—C6	110.97 (14)
C5—C4—Br1	120.25 (13)	C11—C10—C6	127.55 (15)
C3—C4—Br1	118.94 (12)	C12—C11—C10	118.81 (16)
N1—C5—C4	121.67 (16)	C12—C11—H11	120.6
N1—C5—H5	119.2	C10—C11—H11	120.6
C4—C5—H5	119.2	C11—C12—C13	120.06 (16)
O1—C6—C10	108.27 (13)	C11—C12—H12	120.0
O1—C6—C7	112.76 (14)	C13—C12—H12	120.0
C10—C6—C7	104.49 (14)	C14—C13—C12	120.92 (16)
O1—C6—H6	110.4	C14—C13—H13	119.5
C10—C6—H6	110.4	C12—C13—H13	119.5
C7—C6—H6	110.4	C13—C14—C9	119.18 (16)
C8—C7—C6	106.45 (14)	C13—C14—H14	120.4
C8—C7—H7A	110.4	C9—C14—H14	120.4

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2NA···N1ⁱ	0.88	2.10	2.975 (2)	178

Symmetry code: (i) −x+2, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₃BrN₂O
M_r	305.17
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	100
a, b, c (Å)	11.3944 (18), 9.4515 (15), 12.438 (2)
β (°)	110.678 (2)
V (Å³)	1253.2 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.27
Crystal size (mm)	0.21 × 0.16 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.547, 0.780
No. of measured, independent and observed [I > 2σ(I)] reflections	23669, 2942, 2595
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.054, 1.03
No. of reflections	2942
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.30

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2NA···N1ⁱ	0.88	2.10	2.975 (2)	178

Symmetry code: (i) −x+2, −y+1, −z+2.

References

Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dinçer, M., Özdemir, N., Akdemir, N., Özdil, M., Agˇar, E. & Büyükgüngör, O. (2004). Acta Cryst. E60, o896–o898. Web of Science CSD CrossRef IUCr Journals Google Scholar
Lifshits, O., Alberico, D., Zakharian, I. & Chartte, A. B. (2008). J. Org. Chem. 73, 6838–6840. Web of Science PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o650

doi:10.1107/S1600536811005332

Open

access