1,4-Bis(4-methyl-2-nitro­phen­oxy)butane

Zhang, H.; Wang, H.; Yu, J.

doi:10.1107/S2414314617017345

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 12| December 2017| x171734

https://doi.org/10.1107/S2414314617017345

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1,4-Bis(4-methyl-2-nitrophenoxy)butane

Huihui Zhang,^a,^b Haiyan Wang ^a,^b and Jianhua Yu ^a,^b ^*

^aDepartment of Chemistry, Anhui University, Hefei 230601, People's Republic of China, and ^bKey Laboratory of Functional Inorganic Materials Chemistry, Hefei 230601, People's Republic of China
^*Correspondence e-mail: iu_jh@163.com

Edited by K. Fejfarova, Institute of Biotechnology CAS, Czech Republic (Received 10 August 2017; accepted 4 December 2017; online 12 December 2017)

The asymmetric unit of the title compound, C₁₈H₂₀N₂O₆, contains one-half molecule, the mid-point of the central C—C bond being located on a crystallographic inversion centre. In the crystal, weak C—H⋯O interactions generate a layered structure. The O atoms of the nitro group are disordered over two sets of sites with a refined occupancy ratio of 0.700 (8):0.300 (8).

Keywords: crystal structure; layered structure; C—H⋯O interactions.

CCDC reference: 1535126

Structure description

The title compound (Fig. 1) crystallizes with the molecule being situated on a crystallographic inversion centre located at the midpoint of the C7—C7A bond. The two parallel phenyl rings are linked by an ethereal chain, forming a non-coplanar structure similar to that described by Elizondo et al. (2009 ).

Figure 1
The molecular structure of the title molecule, with displacement ellipsoids drawn at the 50% probability level.

In the crystal, the molecules are linked into chains by the C7—H7A⋯O3 interactions (Table 1, Fig. 2). The chains are connected into layers by C9—H9A⋯O2 interactions (Table 1, Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯O3ⁱ	0.97	2.69	3.637 (3)	166
C9—H9A⋯O2ⁱⁱ	0.96	2.71	3.516 (4)	143
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) x-1, y, z.

Figure 2
The chains generated by C7—H7A⋯O3 interactions (green dashed lines). H atoms not involved in these interactions have been omitted.

Figure 3
A view along the c axis of the crystal packing of the title compound. The C9—H9A⋯O interactions are represented by purple dashed lines.

Synthesis and crystallization

To a solution of 4-methyl-2-nitrophenol (5.00 g, 32.7 mmol) in acetonitrile (100 ml) were added potassium carbonate (6.78 g, 50.0 mmol) and 1,4-dibromobutane (3.30 g, 15.3 mmol). After the reaction mixture had been refluxed for 6 h, all the volatile components were evaporated and the residue was partitioned between dichloromethane and water. The organic phase was washed with water, then dried in calcium chloride, and concentrated in vacuo to give an off-white solid. White single crystals were obtained in a yield of 62% using acetonitrile crude extraction.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The O atoms of the nitro group are disordered over two sets of sites (O2/O2′ and O3/O3′) with a refined occupancy ratio of 0.700 (8):0.300 (8).

Table 2
Experimental details

Crystal data
Chemical formula	C₁₈H₂₀N₂O₆
M_r	360.36
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	4.7936 (7), 12.9828 (19), 14.632 (2)
β (°)	92.986 (2)
V (Å³)	909.4 (2)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.2 × 0.2 × 0.2

Data collection
Diffractometer	Bruker SMART CCD area detector
Absorption correction	Multi-scan (SADABS; Bruker, 2004 )
T_min, T_max	0.950, 0.966
No. of measured, independent and observed [I > 2σ(I)] reflections	6305, 1603, 1348
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.124, 1.08
No. of reflections	1603
No. of parameters	137
No. of restraints	16
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.18
Computer programs: SMART and SAINT (Bruker, 2004), SHELXS97 and SHELXTL (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ) and DIAMOND (Brandenburg, 2007 ).

Structural data

CCDC reference: 1535126

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617017345/ff4019sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617017345/ff4019Isup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617017345/ff4019Isup4.cml

checkCIF report

Computing details top

Data collection: SMARTSAINT (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008) and DIAMOND (Brandenburg, 2007); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

1,4-Bis(4-methyl-2-nitrophenoxy)butane top

Crystal data top

C₁₈H₂₀N₂O₆	F(000) = 380
M_r = 360.36	D_x = 1.316 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 4.7936 (7) Å	Cell parameters from 3390 reflections
b = 12.9828 (19) Å	θ = 2.9–25.0°
c = 14.632 (2) Å	µ = 0.10 mm⁻¹
β = 92.986 (2)°	T = 296 K
V = 909.4 (2) Å³	Block, white
Z = 2	0.2 × 0.2 × 0.2 mm

Data collection top

Bruker SMART CCD area detector diffractometer	1348 reflections with I > 2σ(I)
none scans	R_int = 0.022
Absorption correction: multi-scan (SADABS; Bruker, 2004)	θ_max = 25.0°, θ_min = 2.1°
T_min = 0.950, T_max = 0.966	h = −5→5
6305 measured reflections	k = −14→15
1603 independent reflections	l = −17→17

Refinement top

Refinement on F²	16 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.124	w = 1/[σ²(F_o²) + (0.0608P)² + 0.1678P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
1603 reflections	Δρ_max = 0.21 e Å⁻³
137 parameters	Δρ_min = −0.18 e Å⁻³

Special details top

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

Refinement. All hydrogen atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.93 Å and U_ISO(H) = 1.2 U_eq.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
C1	0.5424 (3)	0.69514 (12)	0.46590 (10)	0.0557 (4)
C2	0.7120 (4)	0.62215 (12)	0.42827 (11)	0.0625 (4)
H2	0.8114	0.5764	0.4665	0.075*
C3	0.7361 (3)	0.61619 (12)	0.33476 (11)	0.0597 (4)
C4	0.5797 (4)	0.68498 (13)	0.28134 (11)	0.0619 (4)
H4	0.5918	0.6826	0.2181	0.074*
C5	0.4057 (3)	0.75731 (12)	0.31813 (11)	0.0579 (4)
H5	0.3029	0.8018	0.2796	0.069*
C6	0.3835 (3)	0.76397 (11)	0.41205 (10)	0.0506 (4)
C7	−0.0937 (3)	0.97110 (12)	0.46540 (12)	0.0615 (4)
H7A	−0.2184	0.9270	0.4978	0.074*
H7B	−0.2074	1.0203	0.4303	0.074*
C9	0.9223 (4)	0.53703 (15)	0.29328 (15)	0.0833 (6)
H9A	1.0814	0.5243	0.3343	0.125*
H9B	0.9840	0.5623	0.2361	0.125*
H9C	0.8200	0.4742	0.2831	0.125*
C10	0.0657 (3)	0.90647 (13)	0.40078 (11)	0.0609 (4)
H10A	−0.0619	0.8727	0.3567	0.073*
H10B	0.1926	0.9491	0.3678	0.073*
O1	0.2189 (2)	0.83138 (8)	0.45505 (7)	0.0604 (3)
N1	0.5373 (4)	0.69963 (13)	0.56589 (11)	0.0819 (5)
O2	0.5488 (9)	0.6235 (2)	0.6110 (2)	0.1177 (11)	0.7
O3	0.5494 (5)	0.78584 (16)	0.60470 (12)	0.0886 (6)	0.7
O2'	0.739 (2)	0.6707 (9)	0.6058 (5)	0.177 (4)	0.3
O3'	0.2837 (15)	0.6876 (6)	0.5918 (4)	0.141 (3)	0.3

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0667 (9)	0.0528 (8)	0.0476 (8)	0.0036 (7)	0.0022 (7)	0.0013 (6)
C2	0.0664 (10)	0.0537 (9)	0.0664 (10)	0.0092 (7)	−0.0050 (8)	0.0002 (7)
C3	0.0558 (9)	0.0574 (9)	0.0663 (10)	−0.0025 (7)	0.0067 (7)	−0.0111 (7)
C4	0.0663 (10)	0.0688 (10)	0.0511 (8)	−0.0019 (8)	0.0071 (7)	−0.0071 (7)
C5	0.0615 (9)	0.0610 (9)	0.0508 (8)	0.0028 (7)	−0.0002 (7)	0.0034 (7)
C6	0.0515 (8)	0.0478 (8)	0.0526 (8)	0.0000 (6)	0.0044 (6)	−0.0007 (6)
C7	0.0490 (8)	0.0572 (9)	0.0777 (11)	0.0043 (7)	−0.0025 (7)	−0.0042 (8)
C9	0.0799 (12)	0.0762 (12)	0.0949 (14)	0.0115 (10)	0.0164 (10)	−0.0192 (11)
C10	0.0570 (9)	0.0601 (9)	0.0646 (9)	0.0081 (7)	−0.0067 (7)	0.0000 (7)
O1	0.0699 (7)	0.0556 (6)	0.0562 (6)	0.0144 (5)	0.0083 (5)	0.0020 (5)
N1	0.1193 (14)	0.0729 (8)	0.0541 (9)	0.0261 (9)	0.0099 (9)	0.0099 (6)
O2	0.194 (3)	0.0827 (15)	0.0775 (16)	0.0153 (18)	0.0220 (19)	0.0265 (12)
O3	0.1283 (17)	0.0881 (11)	0.0489 (10)	0.0176 (12)	−0.0013 (10)	−0.0082 (8)
O2'	0.244 (10)	0.218 (10)	0.062 (4)	0.064 (8)	−0.063 (6)	0.014 (5)
O3'	0.176 (6)	0.186 (7)	0.064 (3)	0.028 (6)	0.041 (4)	0.030 (4)

Geometric parameters (Å, º) top

C1—C2	1.382 (2)	C7—C7ⁱ	1.516 (3)
C1—C6	1.392 (2)	C7—H7A	0.9700
C1—N1	1.466 (2)	C7—H7B	0.9700
C2—C3	1.381 (2)	C9—H9A	0.9600
C2—H2	0.9300	C9—H9B	0.9600
C3—C4	1.382 (2)	C9—H9C	0.9600
C3—C9	1.509 (2)	C10—O1	1.4353 (18)
C4—C5	1.383 (2)	C10—H10A	0.9700
C4—H4	0.9300	C10—H10B	0.9700
C5—C6	1.387 (2)	N1—O2'	1.164 (7)
C5—H5	0.9300	N1—O2	1.188 (3)
C6—O1	1.3550 (18)	N1—O3	1.255 (2)
C7—C10	1.502 (2)	N1—O3'	1.301 (6)

C2—C1—C6	122.06 (14)	C7ⁱ—C7—H7B	108.9
C2—C1—N1	117.77 (14)	H7A—C7—H7B	107.8
C6—C1—N1	120.16 (14)	C3—C9—H9A	109.5
C3—C2—C1	120.97 (15)	C3—C9—H9B	109.5
C3—C2—H2	119.5	H9A—C9—H9B	109.5
C1—C2—H2	119.5	C3—C9—H9C	109.5
C2—C3—C4	116.94 (14)	H9A—C9—H9C	109.5
C2—C3—C9	121.21 (17)	H9B—C9—H9C	109.5
C4—C3—C9	121.84 (16)	O1—C10—C7	107.07 (13)
C3—C4—C5	122.61 (15)	O1—C10—H10A	110.3
C3—C4—H4	118.7	C7—C10—H10A	110.3
C5—C4—H4	118.7	O1—C10—H10B	110.3
C4—C5—C6	120.46 (15)	C7—C10—H10B	110.3
C4—C5—H5	119.8	H10A—C10—H10B	108.6
C6—C5—H5	119.8	C6—O1—C10	118.39 (12)
O1—C6—C5	125.24 (14)	O2—N1—O3	119.4 (2)
O1—C6—C1	117.81 (13)	O2'—N1—O3'	125.3 (6)
C5—C6—C1	116.94 (14)	O2'—N1—C1	115.6 (5)
C10—C7—C7ⁱ	113.19 (16)	O2—N1—C1	121.2 (2)
C10—C7—H7A	108.9	O3—N1—C1	118.97 (16)
C7ⁱ—C7—H7A	108.9	O3'—N1—C1	110.5 (3)
C10—C7—H7B	108.9

C6—C1—C2—C3	1.6 (3)	C7ⁱ—C7—C10—O1	61.7 (2)
N1—C1—C2—C3	−177.34 (16)	C5—C6—O1—C10	−3.8 (2)
C1—C2—C3—C4	−1.1 (2)	C1—C6—O1—C10	176.66 (13)
C1—C2—C3—C9	179.65 (16)	C7—C10—O1—C6	−179.22 (12)
C2—C3—C4—C5	0.1 (2)	C2—C1—N1—O2'	26.8 (7)
C9—C3—C4—C5	179.30 (16)	C6—C1—N1—O2'	−152.2 (7)
C3—C4—C5—C6	0.5 (3)	C2—C1—N1—O2	−37.3 (4)
C4—C5—C6—O1	−179.66 (14)	C6—C1—N1—O2	143.8 (3)
C4—C5—C6—C1	−0.1 (2)	C2—C1—N1—O3	135.5 (2)
C2—C1—C6—O1	178.64 (14)	C6—C1—N1—O3	−43.5 (3)
N1—C1—C6—O1	−2.4 (2)	C2—C1—N1—O3'	−122.8 (4)
C2—C1—C6—C5	−0.9 (2)	C6—C1—N1—O3'	58.2 (4)
N1—C1—C6—C5	177.98 (16)

Symmetry code: (i) −x, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7A···O3ⁱⁱ	0.97	2.69	3.637 (3)	166
C9—H9A···O2ⁱⁱⁱ	0.96	2.71	3.516 (4)	143

Symmetry codes: (ii) −x+2, −y+1, −z+1; (iii) x−1, y, z.

Funding information

This work was supported by the Graduate Students Innovative Program of Anhui University (J18515024, J18515019, 201310357155).

References

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