Crystal structure of 4-bromo-N-(2-bromo-3-nitro-benz-yl)-2-nitro-naphthalen-1-amine.

In the title compound, C17H11Br2N3O4, the dihedral angle between the planes of the naphthalene system and the benzene ring is 52.86 (8)°. The nitro substituent and the attached naphthalene system are almost coplanar [dihedral angle = 5.6 (4)°], probably as a consequence of an intra-molecular N-H⋯O hydrogen bond with the amine group. The nitro substituent attached to the benzene ring is disordered over two sets of sites with occupancies of 0.694 (3) and 0.306 (3). The major component deviates significantly from the ring plane [dihedral angle = 53.6 (2)°]. In the crystal, the mol-ecules are linked into a three-dimensional array by extensive π-π inter-actions involving both the naphthalene and benzene rings [range of centroid-centroid distances = 3.5295 (16)-3.9629 (18) Å] and C-H⋯O inter-actions involving the methyl-ene H atoms and the phenyl-attached nitro group.

Related literature

For the role of secondary inter­actions in stabilizing organoselenium compounds, see; Singh et al. (2010 ▶, 2012 ▶); Mugesh & Singh (2000 ▶). For the isolation of novel photoluminescent seleno­spiro­cyclic compounds via inter­molecular C—C bond formation, see: Singh et al. (2011 ▶).

Experimental

Crystal data

C17H11Br2N3O4

M = 481.11

Triclinic,

a = 8.3675 (4) Å

b = 8.5812 (5) Å

c = 12.2691 (5) Å

α = 76.973 (4)°

β = 81.053 (4)°

γ = 76.302 (5)°

V = 829.00 (8) Å3

Z = 2

Mo Kα radiation

μ = 4.92 mm−1

T = 123 K

0.44 × 0.32 × 0.12 mm

Data collection

Agilent Xcalibur (Ruby, Gemini) diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012 ▶) T min = 0.345, T max = 1.000

12164 measured reflections

6700 independent reflections

4118 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.129

S = 1.02

6700 reflections

246 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.04 e Å−3

Δρmin = −0.77 e Å−3

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S160053681401719X/tk5325sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681401719X/tk5325Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S160053681401719X/tk5325Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S160053681401719X/tk5325fig1.tif

The reaction scheme.

Click here for additional data file.

17 11 2 3 4 . DOI: 10.1107/S160053681401719X/tk5325fig2.tif

The mol­ecular structure of C17H11Br2N3O4 showing the numbering scheme and 30% probability displacement ellipsoids and the intra­molecular N—H⋯O n class="Chemical">hydrogen bond (shown as a dashed bond).

Click here for additional data file.

17 11 2 3 4 c . DOI: 10.1107/S160053681401719X/tk5325fig3.tif

The mol­ecular packing for C17H11Br2N3O4 viewed along the c axis showing the linking of the mol­ecules into a three-dimensional array by π–π inter­actions as well as a network of C—H⋯O inter­actions (shown as dashed bonds).

CCDC reference: 1015963

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

C17H11Br2N3O4	Z = 2
Mr = 481.11	F(000) = 472
Triclinic, P1	Dx = 1.927 Mg m−3
a = 8.3675 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.5812 (5) Å	Cell parameters from 3926 reflections
c = 12.2691 (5) Å	θ = 5.0–34.9°
α = 76.973 (4)°	µ = 4.92 mm−1
β = 81.053 (4)°	T = 123 K
γ = 76.302 (5)°	Plate, orange
V = 829.00 (8) Å3	0.44 × 0.32 × 0.12 mm

Agilent Xcalibur (Ruby, Gemini) diffractometer	4118 reflections with I > 2σ(I)
Detector resolution: 10.5081 pixels mm-1	Rint = 0.033
ω scans	θmax = 35.0°, θmin = 5.0°
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2012)	h = −13→13
Tmin = 0.345, Tmax = 1.000	k = −12→13
12164 measured reflections	l = −19→19
6700 independent 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)] = 0.053	Hydrogen site location: mixed
wR(F2) = 0.129	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0498P)2 + 0.3384P] where P = (Fo2 + 2Fc2)/3
6700 reflections	(Δ/σ)max = 0.001
246 parameters	Δρmax = 1.04 e Å−3
1 restraint	Δρmin = −0.77 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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Br1	0.52119 (4)	0.68126 (4)	0.76444 (2)	0.03410 (10)
Br2	0.98711 (4)	0.82225 (4)	0.23405 (3)	0.03346 (10)
O1	0.9351 (3)	0.3484 (3)	0.5032 (2)	0.0374 (6)
O2	0.8810 (3)	0.4048 (3)	0.3315 (2)	0.0346 (5)
O3A	1.3573 (4)	0.6322 (4)	0.0114 (3)	0.0334 (7)	0.694 (3)
O4A	1.2701 (4)	0.8769 (5)	0.0461 (4)	0.0480 (10)	0.694 (3)
O3B	1.3147 (8)	0.8513 (9)	−0.0408 (7)	0.0334 (7)	0.306 (3)
O4B	1.3038 (10)	0.6768 (10)	0.1138 (8)	0.0480 (10)	0.306 (3)
N1	0.6518 (3)	0.6613 (3)	0.2639 (2)	0.0230 (5)
H1N	0.724 (4)	0.577 (4)	0.254 (3)	0.027 (9)*
N2	0.8518 (3)	0.4286 (3)	0.4272 (2)	0.0240 (5)
N3	1.2471 (3)	0.7536 (3)	0.0266 (2)	0.0276 (6)
C1	0.6183 (3)	0.6659 (3)	0.3756 (2)	0.0171 (5)
C2	0.7114 (3)	0.5555 (3)	0.4567 (2)	0.0196 (5)
C3	0.6804 (3)	0.5624 (3)	0.5728 (2)	0.0211 (5)
H3A	0.7467	0.4854	0.6252	0.025*
C4	0.5575 (3)	0.6778 (4)	0.6087 (2)	0.0216 (5)
C5	0.4516 (3)	0.7931 (3)	0.5332 (2)	0.0183 (5)
C6	0.3170 (3)	0.9116 (4)	0.5696 (3)	0.0264 (6)
H6A	0.2998	0.9217	0.6463	0.032*
C7	0.2119 (3)	1.0113 (4)	0.4962 (3)	0.0292 (7)
H7A	0.1240	1.0917	0.5220	0.035*
C8	0.2318 (3)	0.9967 (4)	0.3842 (3)	0.0267 (6)
H8A	0.1552	1.0642	0.3346	0.032*
C9	0.3622 (3)	0.8845 (3)	0.3448 (2)	0.0216 (5)
H9A	0.3741	0.8749	0.2682	0.026*
C10	0.4788 (3)	0.7832 (3)	0.4170 (2)	0.0171 (5)
C12	0.6425 (3)	0.8012 (4)	0.1692 (2)	0.0224 (6)
H12A	0.6430	0.9014	0.1961	0.027*
H12B	0.5383	0.8185	0.1351	0.027*
C13	0.7896 (3)	0.7678 (3)	0.0821 (2)	0.0196 (5)
C14	0.9489 (3)	0.7762 (3)	0.0981 (2)	0.0197 (5)
C15	1.0768 (3)	0.7462 (4)	0.0142 (2)	0.0220 (6)
C16	1.0535 (3)	0.7066 (4)	−0.0846 (2)	0.0265 (6)
H16A	1.1437	0.6861	−0.1406	0.032*
C17	0.8958 (4)	0.6977 (4)	−0.1002 (2)	0.0286 (6)
H17A	0.8765	0.6709	−0.1674	0.034*
C18	0.7659 (3)	0.7280 (4)	−0.0171 (2)	0.0251 (6)
H18A	0.6581	0.7213	−0.0284	0.030*

	U11	U22	U33	U12	U13	U23
Br1	0.03423 (17)	0.0569 (2)	0.01698 (15)	−0.01906 (15)	0.00074 (12)	−0.01145 (14)
Br2	0.03155 (17)	0.0494 (2)	0.02682 (17)	−0.01218 (14)	−0.00825 (13)	−0.01525 (14)
O1	0.0319 (11)	0.0295 (13)	0.0449 (15)	0.0057 (9)	−0.0109 (11)	−0.0035 (11)
O2	0.0336 (12)	0.0256 (12)	0.0354 (13)	0.0041 (9)	0.0090 (10)	−0.0068 (10)
O3A	0.0187 (13)	0.0379 (18)	0.0399 (18)	−0.0008 (12)	−0.0021 (12)	−0.0062 (14)
O4A	0.0293 (16)	0.042 (2)	0.077 (3)	−0.0142 (15)	−0.0194 (17)	−0.0033 (19)
O3B	0.0187 (13)	0.0379 (18)	0.0399 (18)	−0.0008 (12)	−0.0021 (12)	−0.0062 (14)
O4B	0.0293 (16)	0.042 (2)	0.077 (3)	−0.0142 (15)	−0.0194 (17)	−0.0033 (19)
N1	0.0283 (12)	0.0210 (13)	0.0178 (11)	−0.0034 (10)	0.0014 (9)	−0.0045 (9)
N2	0.0187 (10)	0.0158 (12)	0.0353 (14)	−0.0023 (9)	−0.0050 (10)	−0.0002 (10)
N3	0.0184 (11)	0.0345 (16)	0.0282 (13)	−0.0085 (11)	−0.0050 (10)	0.0023 (11)
C1	0.0144 (10)	0.0196 (13)	0.0179 (12)	−0.0063 (9)	0.0009 (9)	−0.0039 (10)
C2	0.0168 (11)	0.0173 (13)	0.0237 (13)	−0.0033 (10)	−0.0009 (10)	−0.0032 (10)
C3	0.0202 (12)	0.0237 (14)	0.0189 (13)	−0.0079 (10)	−0.0044 (10)	0.0020 (10)
C4	0.0213 (12)	0.0310 (15)	0.0162 (12)	−0.0127 (11)	−0.0005 (10)	−0.0056 (11)
C5	0.0145 (10)	0.0204 (13)	0.0220 (13)	−0.0078 (9)	0.0028 (9)	−0.0075 (10)
C6	0.0230 (13)	0.0292 (16)	0.0311 (16)	−0.0082 (11)	0.0046 (12)	−0.0163 (12)
C7	0.0185 (12)	0.0239 (16)	0.046 (2)	−0.0037 (11)	0.0035 (12)	−0.0147 (14)
C8	0.0173 (12)	0.0191 (14)	0.0401 (18)	−0.0009 (10)	−0.0033 (12)	−0.0016 (12)
C9	0.0164 (11)	0.0251 (15)	0.0229 (13)	−0.0046 (10)	−0.0052 (10)	−0.0018 (11)
C10	0.0148 (10)	0.0152 (12)	0.0206 (13)	−0.0032 (9)	−0.0023 (9)	−0.0021 (9)
C12	0.0187 (11)	0.0292 (15)	0.0179 (13)	−0.0031 (10)	−0.0026 (10)	−0.0033 (11)
C13	0.0185 (11)	0.0246 (14)	0.0149 (12)	−0.0050 (10)	−0.0023 (9)	−0.0010 (10)
C14	0.0221 (12)	0.0208 (14)	0.0167 (12)	−0.0060 (10)	−0.0062 (10)	−0.0002 (10)
C15	0.0141 (11)	0.0264 (15)	0.0244 (14)	−0.0056 (10)	−0.0039 (10)	−0.0003 (11)
C16	0.0183 (12)	0.0381 (18)	0.0205 (14)	−0.0055 (12)	0.0021 (10)	−0.0036 (12)
C17	0.0287 (14)	0.0424 (19)	0.0159 (13)	−0.0087 (13)	−0.0025 (11)	−0.0066 (12)
C18	0.0205 (12)	0.0385 (18)	0.0185 (14)	−0.0105 (12)	−0.0042 (10)	−0.0039 (12)

Br1—C4	1.893 (3)	C6—C7	1.364 (5)
Br2—C14	1.887 (3)	C6—H6A	0.9500
O1—N2	1.231 (3)	C7—C8	1.388 (5)
O2—N2	1.214 (3)	C7—H7A	0.9500
O3A—N3	1.245 (4)	C8—C9	1.378 (4)
O4A—N3	1.199 (4)	C8—H8A	0.9500
O3B—N3	1.214 (7)	C9—C10	1.419 (4)
O4B—N3	1.224 (9)	C9—H9A	0.9500
N1—C1	1.363 (3)	C12—C13	1.517 (4)
N1—C12	1.467 (4)	C12—H12A	0.9900
N1—H1N	0.85 (3)	C12—H12B	0.9900
N2—C2	1.461 (3)	C13—C18	1.390 (4)
N3—C15	1.474 (3)	C13—C14	1.398 (4)
C1—C2	1.400 (4)	C14—C15	1.386 (4)
C1—C10	1.457 (4)	C15—C16	1.383 (4)
C2—C3	1.420 (4)	C16—C17	1.385 (4)
C3—C4	1.344 (4)	C16—H16A	0.9500
C3—H3A	0.9500	C17—C18	1.388 (4)
C4—C5	1.432 (4)	C17—H17A	0.9500
C5—C6	1.417 (4)	C18—H18A	0.9500
C5—C10	1.426 (4)
C1—N1—C12	127.2 (2)	C9—C8—C7	120.2 (3)
C1—N1—H1N	111 (2)	C9—C8—H8A	119.9
C12—N1—H1N	116 (2)	C7—C8—H8A	119.9
O2—N2—O1	122.8 (3)	C8—C9—C10	121.0 (3)
O2—N2—C2	120.1 (2)	C8—C9—H9A	119.5
O1—N2—C2	117.1 (3)	C10—C9—H9A	119.5
O3B—N3—O4B	122.8 (5)	C9—C10—C5	118.2 (2)
O4A—N3—O3A	125.1 (3)	C9—C10—C1	121.3 (2)
O4A—N3—C15	118.2 (3)	C5—C10—C1	120.5 (2)
O3B—N3—C15	119.2 (4)	N1—C12—C13	109.3 (2)
O4B—N3—C15	117.1 (4)	N1—C12—H12A	109.8
O3A—N3—C15	116.7 (3)	C13—C12—H12A	109.8
N1—C1—C2	122.2 (2)	N1—C12—H12B	109.8
N1—C1—C10	121.2 (2)	C13—C12—H12B	109.8
C2—C1—C10	116.6 (2)	H12A—C12—H12B	108.3
C1—C2—C3	122.5 (2)	C18—C13—C14	118.7 (2)
C1—C2—N2	122.3 (3)	C18—C13—C12	119.2 (2)
C3—C2—N2	115.1 (3)	C14—C13—C12	122.1 (3)
C4—C3—C2	120.1 (3)	C15—C14—C13	118.8 (3)
C4—C3—H3A	120.0	C15—C14—Br2	121.3 (2)
C2—C3—H3A	120.0	C13—C14—Br2	119.9 (2)
C3—C4—C5	121.8 (3)	C16—C15—C14	122.6 (2)
C3—C4—Br1	118.3 (2)	C16—C15—N3	116.3 (2)
C5—C4—Br1	119.9 (2)	C14—C15—N3	121.1 (3)
C6—C5—C10	118.8 (3)	C15—C16—C17	118.5 (3)
C6—C5—C4	122.8 (3)	C15—C16—H16A	120.7
C10—C5—C4	118.4 (2)	C17—C16—H16A	120.7
C7—C6—C5	121.0 (3)	C16—C17—C18	119.7 (3)
C7—C6—H6A	119.5	C16—C17—H17A	120.2
C5—C6—H6A	119.5	C18—C17—H17A	120.2
C6—C7—C8	120.8 (3)	C17—C18—C13	121.7 (3)
C6—C7—H7A	119.6	C17—C18—H18A	119.2
C8—C7—H7A	119.6	C13—C18—H18A	119.2
C12—N1—C1—C2	−141.9 (3)	N1—C1—C10—C9	7.0 (4)
C12—N1—C1—C10	40.5 (4)	C2—C1—C10—C9	−170.8 (2)
N1—C1—C2—C3	178.1 (2)	N1—C1—C10—C5	−176.1 (2)
C10—C1—C2—C3	−4.1 (4)	C2—C1—C10—C5	6.2 (3)
N1—C1—C2—N2	0.6 (4)	C1—N1—C12—C13	138.6 (3)
C10—C1—C2—N2	178.3 (2)	N1—C12—C13—C18	105.6 (3)
O2—N2—C2—C1	−7.7 (4)	N1—C12—C13—C14	−74.5 (3)
O1—N2—C2—C1	173.1 (2)	C18—C13—C14—C15	0.6 (4)
O2—N2—C2—C3	174.6 (2)	C12—C13—C14—C15	−179.2 (3)
O1—N2—C2—C3	−4.6 (3)	C18—C13—C14—Br2	−177.7 (2)
C1—C2—C3—C4	0.2 (4)	C12—C13—C14—Br2	2.4 (4)
N2—C2—C3—C4	177.9 (2)	C13—C14—C15—C16	−0.6 (4)
C2—C3—C4—C5	1.9 (4)	Br2—C14—C15—C16	177.7 (2)
C2—C3—C4—Br1	179.86 (19)	C13—C14—C15—N3	179.9 (3)
C3—C4—C5—C6	177.4 (3)	Br2—C14—C15—N3	−1.7 (4)
Br1—C4—C5—C6	−0.6 (3)	O4A—N3—C15—C16	125.2 (4)
C3—C4—C5—C10	0.2 (4)	O3B—N3—C15—C16	60.9 (6)
Br1—C4—C5—C10	−177.74 (18)	O4B—N3—C15—C16	−129.3 (6)
C10—C5—C6—C7	2.0 (4)	O3A—N3—C15—C16	−52.1 (4)
C4—C5—C6—C7	−175.2 (3)	O4A—N3—C15—C14	−55.3 (4)
C5—C6—C7—C8	1.5 (4)	O3B—N3—C15—C14	−119.6 (6)
C6—C7—C8—C9	−2.3 (4)	O4B—N3—C15—C14	50.2 (6)
C7—C8—C9—C10	−0.5 (4)	O3A—N3—C15—C14	127.4 (3)
C8—C9—C10—C5	3.9 (4)	C14—C15—C16—C17	0.4 (5)
C8—C9—C10—C1	−179.1 (2)	N3—C15—C16—C17	179.8 (3)
C6—C5—C10—C9	−4.6 (4)	C15—C16—C17—C18	−0.1 (5)
C4—C5—C10—C9	172.7 (2)	C16—C17—C18—C13	0.2 (5)
C6—C5—C10—C1	178.4 (2)	C14—C13—C18—C17	−0.4 (4)
C4—C5—C10—C1	−4.3 (4)	C12—C13—C18—C17	179.4 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O2	0.84 (3)	1.91 (3)	2.624 (3)	141 (3)
C12—H12A···O3Bi	0.99	2.57	3.117 (8)	115
C12—H12B···O4Aii	0.99	2.54	3.532 (4)	177
C12—H12B···O4Bii	0.99	2.61	3.462 (8)	144

Ring 1	Ring 2	Distance	Perpedicular distance	Slippage	Symmetry
Cg1	Cg1	3.5295 (16)	3.3867 (11)	0.94	1-x,1-y,1-z
Cg2	Cg2	3.8868 (15)	3.3859 (12)	1.91	1-x,-y,1-z
Cg3	Cg3	3.9629 (18)	3.5873 (12)	1.68	-x,1-y,2-z

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O2	0.84 (3)	1.91 (3)	2.624 (3)	141 (3)
C12—H12B⋯O4A i	0.99	2.54	3.532 (4)	177
C12—H12B⋯O4B i	0.99	2.61	3.462 (8)	144

Symmetry code: (i) .