1,5-Dichloro-4,8-dinitro­anthraquinone

Armaghan, M.; Amini, M.M.; Ng, S.W.

doi:10.1107/S1600536810029156

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o2130

https://doi.org/10.1107/S1600536810029156

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1,5-Dichloro-4,8-dinitroanthraquinone

Mahsa Armaghan,^a Mostafa M. Amini ^a and Seik Weng Ng ^b ^*

^aDepartment of Chemistry, General Campus, Shahid Beheshti University, Tehran 1983963113, Iran, and ^bDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 10 July 2010; accepted 22 July 2010; online 31 July 2010)

The ring skeleton of the title compound, C₁₄H₄Cl₂N₂O₆, is close to planar (r.m.s. deviation of the carbon atoms 0.091 Å); the nitro goups are twisted with respect to the mean plane of the ring system by 70.8 (1) and 86.7 (2)°. The crystal studied was found to be a merohedral twin, with a domain ratio of 0.61 (8):0.39 (8).

Related literature

For dehydrosulfurization by using anthraquinone-based catalysts, see: Nagai et al. (1993 ). For a related structure, see: Armaghan et al. (2010 ).

Experimental

Crystal data

C₁₄H₄Cl₂N₂O₆
M_r = 367.09
Monoclinic, P 2₁
a = 5.9596 (6) Å
b = 11.3897 (11) Å
c = 9.8667 (9) Å
β = 93.519 (1)°
V = 668.47 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.53 mm⁻¹
T = 100 K
0.12 × 0.12 × 0.12 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS, Sheldrick, 1996 ) T_min = 0.940, T_max = 0.940
6510 measured reflections
3028 independent reflections
2779 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.095
S = 1.04
3028 reflections
218 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.34 e Å⁻³
Absolute structure: Flack (Flack, 1983 ), 1402 Friedel pairs
Flack parameter: 0.39 (8)

Data collection: APEX2 (Bruker, 2009 ); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810029156/kp2270sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810029156/kp2270Isup2.hkl

checkCIF report

Comment top

The title compound (Scheme I, Fig. 1) belongs to a class of catalysts used for dehydrosulfurisation (Nagai et al., 1993). We have embarked on a study of dehydrosulfurisation, and have recently reported the crysal structure of 1,8-dihydroxy-2,4,5,7-tetranitro-9,10-anthraquinone (Armaghan et al., 2010). These compounds are synthesised by the reaction of fuming nitric acid on the substituted anthraquinone.

Related literature top

For dehydrosulfurization by using similar catalysts, see: Nagai et al. (1993). For a related structure, see: Armaghan et al. (2010).

Experimental top

Fuming nitric acid (10 ml) was added dropwise to a solution of 1,5-dichloroanthraquinone (277 mg, 1 mmol) in concentrated sulfuric acid (5 ml). The mixture was kept at 333 K. After two hours, the mixture was poured into ice (100 g). The organic compound was collected and dried. Crystals suitable for X-ray analysis were obtained by recrystallisation from toluene; m.p. > 540 K.

Structure description top

For dehydrosulfurization by using similar catalysts, see: Nagai et al. (1993). For a related structure, see: Armaghan et al. (2010).

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Displacement ellipsoid plot (Barbour, 2001) of I at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.

1,5-Dichloro-4,8-dinitroanthraquinone top

Crystal data top

C₁₄H₄Cl₂N₂O₆	F(000) = 368
M_r = 367.09	D_x = 1.824 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2429 reflections
a = 5.9596 (6) Å	θ = 2.7–28.3°
b = 11.3897 (11) Å	µ = 0.53 mm⁻¹
c = 9.8667 (9) Å	T = 100 K
β = 93.519 (1)°	Cube, yellow
V = 668.47 (11) Å³	0.12 × 0.12 × 0.12 mm
Z = 2

Data collection top

Bruker SMART APEX diffractometer	3028 independent reflections
Radiation source: fine-focus sealed tube	2779 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.026
ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS, Sheldrick, 1996)	h = −7→7
T_min = 0.940, T_max = 0.940	k = −14→14
6510 measured reflections	l = −12→12

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.095	w = 1/[σ²(F_o²) + (0.0477P)² + 0.339P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
3028 reflections	Δρ_max = 0.54 e Å⁻³
218 parameters	Δρ_min = −0.34 e Å⁻³
1 restraint	Absolute structure: Flack (Flack, 1983) parameter from 1402 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.39 (8)

Crystal data top

C₁₄H₄Cl₂N₂O₆	V = 668.47 (11) Å³
M_r = 367.09	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 5.9596 (6) Å	µ = 0.53 mm⁻¹
b = 11.3897 (11) Å	T = 100 K
c = 9.8667 (9) Å	0.12 × 0.12 × 0.12 mm
β = 93.519 (1)°

Data collection top

Bruker SMART APEX diffractometer	3028 independent reflections
Absorption correction: multi-scan (SADABS, Sheldrick, 1996)	2779 reflections with I > 2σ(I)
T_min = 0.940, T_max = 0.940	R_int = 0.026
6510 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.095	Δρ_max = 0.54 e Å⁻³
S = 1.04	Δρ_min = −0.34 e Å⁻³
3028 reflections	Absolute structure: Flack (Flack, 1983) parameter from 1402 Friedel pairs
218 parameters	Absolute structure parameter: 0.39 (8)
1 restraint

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

	x	y	z	U_iso*/U_eq
Cl1	0.62144 (12)	0.00005 (6)	0.17540 (8)	0.02356 (19)
Cl2	0.36066 (13)	0.69418 (6)	0.31405 (8)	0.0250 (2)
O1	0.0933 (4)	0.3072 (2)	0.6211 (2)	0.0271 (5)
O2	−0.1258 (4)	0.3417 (2)	0.4440 (2)	0.0277 (5)
O3	0.2920 (4)	0.4726 (2)	0.4346 (2)	0.0339 (6)
O4	1.1628 (4)	0.3759 (2)	0.0667 (2)	0.0280 (5)
O5	0.9158 (4)	0.3677 (3)	−0.1002 (2)	0.0404 (7)
O6	0.8065 (5)	0.2199 (2)	0.1277 (3)	0.0548 (9)
N1	0.0447 (4)	0.3022 (2)	0.4997 (3)	0.0147 (5)
N2	0.9756 (4)	0.3942 (2)	0.0136 (3)	0.0163 (5)
C1	0.4613 (5)	0.0953 (3)	0.2635 (3)	0.0142 (6)
C2	0.2957 (5)	0.0447 (3)	0.3375 (3)	0.0198 (6)
H2	0.2742	−0.0379	0.3350	0.024*
C3	0.1616 (5)	0.1141 (3)	0.4149 (3)	0.0162 (7)
H3	0.0494	0.0799	0.4668	0.019*
C4	0.1953 (5)	0.2341 (3)	0.4148 (3)	0.0136 (6)
C5	0.3553 (5)	0.2890 (3)	0.3409 (3)	0.0126 (6)
C6	0.3801 (5)	0.4179 (3)	0.3468 (3)	0.0181 (6)
C7	0.5285 (4)	0.4765 (3)	0.2507 (3)	0.0150 (6)
C8	0.5362 (5)	0.5992 (3)	0.2339 (3)	0.0153 (6)
C9	0.6860 (5)	0.6510 (3)	0.1494 (3)	0.0170 (6)
H9	0.6890	0.7340	0.1399	0.020*
C10	0.8297 (5)	0.5827 (3)	0.0795 (3)	0.0183 (7)
H10	0.9342	0.6178	0.0229	0.022*
C11	0.8195 (5)	0.4621 (3)	0.0930 (3)	0.0132 (6)
C12	0.6693 (5)	0.4075 (3)	0.1766 (3)	0.0132 (6)
C13	0.6668 (5)	0.2752 (3)	0.1839 (3)	0.0224 (7)
C14	0.4913 (4)	0.2177 (3)	0.2625 (3)	0.0121 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0243 (3)	0.0116 (4)	0.0366 (4)	0.0019 (3)	0.0164 (3)	−0.0016 (3)
Cl2	0.0267 (4)	0.0132 (4)	0.0370 (4)	0.0049 (3)	0.0168 (3)	0.0022 (3)
O1	0.0307 (11)	0.0364 (13)	0.0147 (9)	0.0029 (10)	0.0041 (8)	−0.0053 (9)
O2	0.0209 (10)	0.0342 (13)	0.0276 (11)	0.0143 (10)	−0.0015 (9)	−0.0066 (10)
O3	0.0459 (13)	0.0198 (12)	0.0393 (13)	−0.0033 (10)	0.0285 (11)	−0.0054 (10)
O4	0.0191 (11)	0.0362 (14)	0.0284 (11)	0.0091 (9)	−0.0015 (9)	−0.0033 (10)
O5	0.0300 (12)	0.070 (2)	0.0210 (11)	0.0167 (12)	0.0000 (9)	−0.0185 (12)
O6	0.0656 (17)	0.0125 (12)	0.094 (2)	−0.0058 (12)	0.0693 (17)	−0.0087 (12)
N1	0.0140 (11)	0.0161 (13)	0.0147 (11)	−0.0012 (9)	0.0070 (9)	0.0004 (10)
N2	0.0167 (12)	0.0142 (13)	0.0188 (12)	−0.0046 (10)	0.0064 (10)	0.0013 (10)
C1	0.0172 (13)	0.0089 (14)	0.0168 (14)	−0.0012 (11)	0.0039 (11)	0.0026 (11)
C2	0.0225 (15)	0.0122 (15)	0.0252 (15)	−0.0012 (12)	0.0051 (12)	0.0029 (12)
C3	0.0133 (14)	0.0175 (18)	0.0183 (14)	−0.0027 (12)	0.0048 (11)	0.0054 (12)
C4	0.0109 (12)	0.0172 (16)	0.0133 (13)	0.0020 (11)	0.0036 (10)	−0.0002 (11)
C5	0.0140 (13)	0.0131 (15)	0.0106 (12)	−0.0012 (10)	0.0009 (10)	−0.0013 (10)
C6	0.0212 (14)	0.0118 (14)	0.0226 (14)	−0.0022 (11)	0.0104 (12)	−0.0021 (11)
C7	0.0144 (12)	0.0151 (17)	0.0154 (13)	−0.0035 (11)	0.0018 (10)	0.0006 (10)
C8	0.0108 (13)	0.0167 (16)	0.0186 (14)	0.0029 (11)	0.0025 (11)	−0.0036 (12)
C9	0.0208 (13)	0.0108 (14)	0.0198 (13)	−0.0027 (11)	0.0046 (11)	0.0010 (11)
C10	0.0232 (16)	0.0157 (17)	0.0166 (14)	−0.0026 (13)	0.0053 (12)	0.0008 (12)
C11	0.0136 (12)	0.0127 (15)	0.0137 (12)	−0.0025 (11)	0.0045 (10)	−0.0013 (10)
C12	0.0131 (12)	0.0129 (16)	0.0138 (13)	−0.0017 (12)	0.0013 (10)	0.0002 (10)
C13	0.0279 (15)	0.0142 (15)	0.0271 (16)	−0.0009 (12)	0.0170 (13)	−0.0024 (12)
C14	0.0109 (12)	0.0115 (16)	0.0142 (12)	0.0004 (10)	0.0039 (10)	0.0002 (10)

Geometric parameters (Å, º) top

Cl1—C1	1.716 (3)	C3—H3	0.9500
Cl2—C8	1.730 (3)	C4—C5	1.385 (4)
O1—N1	1.216 (3)	C5—C14	1.411 (4)
O2—N1	1.211 (3)	C5—C6	1.476 (5)
O3—C6	1.213 (4)	C6—C7	1.493 (4)
O4—N2	1.221 (3)	C7—C12	1.390 (4)
O5—N2	1.197 (3)	C7—C8	1.408 (5)
O6—C13	1.205 (4)	C8—C9	1.390 (4)
N1—C4	1.483 (4)	C9—C10	1.373 (5)
N2—C11	1.472 (4)	C9—H9	0.9500
C1—C2	1.388 (4)	C10—C11	1.382 (5)
C1—C14	1.405 (5)	C10—H10	0.9500
C2—C3	1.386 (5)	C11—C12	1.399 (4)
C2—H2	0.9500	C12—C13	1.509 (5)
C3—C4	1.382 (4)	C13—C14	1.492 (4)

O2—N1—O1	124.9 (3)	C12—C7—C8	118.3 (3)
O2—N1—C4	117.3 (2)	C12—C7—C6	118.8 (3)
O1—N1—C4	117.7 (2)	C8—C7—C6	122.9 (3)
O5—N2—O4	124.8 (3)	C9—C8—C7	121.2 (3)
O5—N2—C11	118.1 (3)	C9—C8—Cl2	115.9 (3)
O4—N2—C11	116.9 (2)	C7—C8—Cl2	122.8 (3)
C2—C1—C14	120.7 (3)	C10—C9—C8	120.3 (3)
C2—C1—Cl1	116.0 (3)	C10—C9—H9	119.9
C14—C1—Cl1	123.3 (2)	C8—C9—H9	119.9
C3—C2—C1	120.4 (3)	C9—C10—C11	118.8 (3)
C3—C2—H2	119.8	C9—C10—H10	120.6
C1—C2—H2	119.8	C11—C10—H10	120.6
C4—C3—C2	118.3 (3)	C10—C11—C12	122.1 (3)
C4—C3—H3	120.8	C10—C11—N2	116.0 (3)
C2—C3—H3	120.8	C12—C11—N2	121.9 (3)
C3—C4—C5	123.4 (3)	C7—C12—C11	119.2 (3)
C3—C4—N1	115.1 (3)	C7—C12—C13	122.1 (3)
C5—C4—N1	121.5 (3)	C11—C12—C13	118.7 (3)
C4—C5—C14	117.8 (3)	O6—C13—C14	122.4 (3)
C4—C5—C6	119.8 (3)	O6—C13—C12	119.4 (3)
C14—C5—C6	122.3 (3)	C14—C13—C12	118.2 (3)
O3—C6—C5	119.6 (3)	C1—C14—C5	119.3 (3)
O3—C6—C7	121.5 (3)	C1—C14—C13	122.2 (3)
C5—C6—C7	118.7 (3)	C5—C14—C13	118.5 (3)

C14—C1—C2—C3	−2.0 (4)	C9—C10—C11—N2	179.0 (2)
Cl1—C1—C2—C3	178.3 (2)	O5—N2—C11—C10	−87.6 (4)
C1—C2—C3—C4	0.9 (4)	O4—N2—C11—C10	87.7 (4)
C2—C3—C4—C5	0.3 (5)	O5—N2—C11—C12	92.1 (4)
C2—C3—C4—N1	179.8 (2)	O4—N2—C11—C12	−92.5 (3)
O2—N1—C4—C3	−94.0 (3)	C8—C7—C12—C11	2.7 (4)
O1—N1—C4—C3	81.0 (3)	C6—C7—C12—C11	−175.8 (3)
O2—N1—C4—C5	85.4 (3)	C8—C7—C12—C13	−177.7 (3)
O1—N1—C4—C5	−99.5 (3)	C6—C7—C12—C13	3.8 (4)
C3—C4—C5—C14	−0.4 (4)	C10—C11—C12—C7	−1.3 (4)
N1—C4—C5—C14	−179.8 (2)	N2—C11—C12—C7	179.0 (2)
C3—C4—C5—C6	−179.9 (3)	C10—C11—C12—C13	179.1 (3)
N1—C4—C5—C6	0.7 (4)	N2—C11—C12—C13	−0.6 (4)
C4—C5—C6—O3	13.8 (5)	C7—C12—C13—O6	−173.0 (3)
C14—C5—C6—O3	−165.6 (3)	C11—C12—C13—O6	6.6 (5)
C4—C5—C6—C7	−170.8 (2)	C7—C12—C13—C14	6.2 (5)
C14—C5—C6—C7	9.7 (4)	C11—C12—C13—C14	−174.2 (2)
O3—C6—C7—C12	163.6 (3)	C2—C1—C14—C5	1.9 (4)
C5—C6—C7—C12	−11.6 (4)	Cl1—C1—C14—C5	−178.4 (2)
O3—C6—C7—C8	−14.9 (5)	C2—C1—C14—C13	−179.7 (3)
C5—C6—C7—C8	169.9 (3)	Cl1—C1—C14—C13	0.0 (4)
C12—C7—C8—C9	−2.3 (4)	C4—C5—C14—C1	−0.7 (4)
C6—C7—C8—C9	176.2 (3)	C6—C5—C14—C1	178.8 (3)
C12—C7—C8—Cl2	176.9 (2)	C4—C5—C14—C13	−179.1 (3)
C6—C7—C8—Cl2	−4.6 (4)	C6—C5—C14—C13	0.4 (4)
C7—C8—C9—C10	0.3 (4)	O6—C13—C14—C1	−7.4 (5)
Cl2—C8—C9—C10	−178.9 (2)	C12—C13—C14—C1	173.4 (3)
C8—C9—C10—C11	1.2 (4)	O6—C13—C14—C5	171.0 (3)
C9—C10—C11—C12	−0.7 (5)	C12—C13—C14—C5	−8.2 (4)

Experimental details

Crystal data
Chemical formula	C₁₄H₄Cl₂N₂O₆
M_r	367.09
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	100
a, b, c (Å)	5.9596 (6), 11.3897 (11), 9.8667 (9)
β (°)	93.519 (1)
V (Å³)	668.47 (11)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.53
Crystal size (mm)	0.12 × 0.12 × 0.12

Data collection
Diffractometer	Bruker SMART APEX diffractometer
Absorption correction	Multi-scan (SADABS, Sheldrick, 1996)
T_min, T_max	0.940, 0.940
No. of measured, independent and observed [I > 2σ(I)] reflections	6510, 3028, 2779
R_int	0.026
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.095, 1.04
No. of reflections	3028
No. of parameters	218
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.34
Absolute structure	Flack (Flack, 1983) parameter from 1402 Friedel pairs
Absolute structure parameter	0.39 (8)

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Acknowledgements

We thank Shahid Beheshti University and the University of Malaya for supporting this study.

References

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