2-(Dimethyl­amino)­anthraquinone

Fei, Z.; Cai, Q.; Li, L.

doi:10.1107/S1600536810044636

organic compounds

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ISSN: 2056-9890

Volume 66| Part 12| December 2010| Page o3091

https://doi.org/10.1107/S1600536810044636

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2-(Dimethylamino)anthraquinone

Zhuan Fei,^a Qun Cai ^a and Lin Li ^a ^*

^aKey Laboratory of Pesticide and Chemical Biology of the Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, People's Republic of China
^*Correspondence e-mail: feizhuan123@163.com

(Received 13 October 2010; accepted 1 November 2010; online 6 November 2010)

The molecule of the title compound, C₁₆H₁₃NO₂, is almost planar, with a maximum deviation of 0.013 (2) Å from the best plane; the dihedral angle between the two aromatic rings is 1.06 (1)°. In the crystal, molecules are linked through weak intramolecular C—H⋯O interactions, forming chains running parallel to [10 $[\overline{1}]$ ].

Related literature

For the preparation, see: Havlik et al. (2008 ). For a related structure, see: Janczak (1995 ).

Experimental

Crystal data

C₁₆H₁₃NO₂
M_r = 251.27
Monoclinic, P 2₁ /n
a = 4.8614 (6) Å
b = 19.945 (2) Å
c = 12.8624 (15) Å
β = 95.979 (2)°
V = 1240.3 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.23 × 0.20 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
14833 measured reflections
3050 independent reflections
2267 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.161
S = 1.03
3050 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯O1ⁱ	0.93	2.50	3.272 (2)	140
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1999 ); 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 I, global. DOI: https://doi.org/10.1107/S1600536810044636/ng5045sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810044636/ng5045Isup2.hkl

checkCIF report

Comment top

The aminoanthraquinone derivatives are important compounds as dyes and intermediates. We report here the crystal structure of the title compound.

The molecular is almost planar, with a maximum deviation of 0.013 (2)Å from the best plane. The dihedral angle between the two benzene rings is 1.06 (1)° (Fig 1). The bond distances and bond angles are in good agreement with those in a closely related crystal structure (Janczak et al., 1995). In the crystal structure, the crystal packing is stabilized by a weak intramolecular C(9)—H(9)···O(1) (x + 1/2, -y + 1/2, z - 1/2) hydrogen bond [C(9)···O(1) 3.275 (2) Å1,Table 1].

Related literature top

For the preparation, see: Havlik et al. (2008). For a related structure, see: Janczak (1995).

Experimental top

The title compound was synthesized according to the reported literature (Havlik et al., 2008). Crystals of (I) suitablefor X-ray diffraction were grown by slow evaporation of a chloroform-methanol(1:1) solution of the title compound under 293 K.

Structure description top

The aminoanthraquinone derivatives are important compounds as dyes and intermediates. We report here the crystal structure of the title compound.

For the preparation, see: Havlik et al. (2008). For a related structure, see: Janczak (1995).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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. A view of (I), showing the atom-labelling scheme, with displacement ellipsoids drawn at the 30% probability level. H atoms omitted for clarity.

2-(Dimethylamino)anthraquinone top

Crystal data top

C₁₆H₁₃NO₂	F(000) = 528
M_r = 251.27	D_x = 1.346 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4567 reflections
a = 4.8614 (6) Å	θ = 2.6–28.1°
b = 19.945 (2) Å	µ = 0.09 mm⁻¹
c = 12.8624 (15) Å	T = 298 K
β = 95.979 (2)°	Block, red
V = 1240.3 (3) Å³	0.23 × 0.20 × 0.12 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2267 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.022
Graphite monochromator	θ_max = 28.3°, θ_min = 2.6°
phi and ω scans	h = −6→6
14833 measured reflections	k = −26→26
3050 independent reflections	l = −17→17

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.161	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0842P)² + 0.2178P] where P = (F_o² + 2F_c²)/3
3050 reflections	(Δ/σ)_max < 0.001
174 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₆H₁₃NO₂	V = 1240.3 (3) Å³
M_r = 251.27	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 4.8614 (6) Å	µ = 0.09 mm⁻¹
b = 19.945 (2) Å	T = 298 K
c = 12.8624 (15) Å	0.23 × 0.20 × 0.12 mm
β = 95.979 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2267 reflections with I > 2σ(I)
14833 measured reflections	R_int = 0.022
3050 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	0 restraints
wR(F²) = 0.161	H-atom parameters constrained
S = 1.03	Δρ_max = 0.30 e Å⁻³
3050 reflections	Δρ_min = −0.17 e Å⁻³
174 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
C1	0.6324 (3)	−0.00602 (7)	0.25988 (10)	0.0429 (3)
C2	0.6624 (3)	0.00659 (8)	0.36860 (11)	0.0478 (3)
H2	0.5603	−0.0184	0.4120	0.057*
C3	0.8390 (3)	0.05496 (8)	0.41090 (10)	0.0478 (4)
H3	0.8533	0.0623	0.4827	0.057*
C4	0.9988 (3)	0.09367 (7)	0.34945 (10)	0.0426 (3)
C5	1.1903 (3)	0.14348 (8)	0.39853 (11)	0.0505 (4)
C6	1.3534 (3)	0.18380 (7)	0.32916 (12)	0.0473 (3)
C7	1.5374 (4)	0.23222 (9)	0.37330 (14)	0.0618 (4)
H7	1.5556	0.2395	0.4451	0.074*
C8	1.6923 (4)	0.26926 (9)	0.30989 (17)	0.0708 (5)
H8	1.8159	0.3012	0.3395	0.085*
C9	1.6661 (4)	0.25959 (9)	0.20389 (17)	0.0677 (5)
H9	1.7712	0.2850	0.1621	0.081*
C10	1.4840 (3)	0.21210 (8)	0.15899 (14)	0.0580 (4)
H10	1.4665	0.2057	0.0870	0.070*
C11	1.3265 (3)	0.17382 (7)	0.22145 (11)	0.0461 (3)
C12	1.1329 (3)	0.12237 (8)	0.17157 (11)	0.0471 (3)
C13	0.9685 (3)	0.08246 (7)	0.24153 (10)	0.0407 (3)
C14	0.7881 (3)	0.03404 (7)	0.19746 (10)	0.0438 (3)
H14	0.7694	0.0279	0.1254	0.053*
C15	0.3016 (4)	−0.09571 (9)	0.28401 (14)	0.0622 (4)
H15A	0.4210	−0.1127	0.3422	0.093*
H15B	0.2182	−0.1325	0.2443	0.093*
H15C	0.1597	−0.0685	0.3092	0.093*
C16	0.3996 (4)	−0.06205 (9)	0.10626 (13)	0.0647 (5)
H16A	0.3266	−0.0204	0.0778	0.097*
H16B	0.2655	−0.0970	0.0911	0.097*
H16C	0.5656	−0.0730	0.0755	0.097*
N1	0.4616 (3)	−0.05562 (7)	0.21809 (10)	0.0534 (3)
O1	1.2204 (3)	0.15165 (7)	0.49310 (9)	0.0779 (4)
O2	1.1100 (3)	0.11368 (7)	0.07767 (8)	0.0725 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0394 (7)	0.0500 (7)	0.0395 (7)	0.0056 (6)	0.0045 (5)	0.0006 (6)
C2	0.0503 (8)	0.0574 (8)	0.0372 (7)	−0.0002 (6)	0.0118 (6)	0.0048 (6)
C3	0.0533 (8)	0.0607 (9)	0.0300 (6)	0.0038 (6)	0.0072 (5)	−0.0004 (6)
C4	0.0428 (7)	0.0500 (8)	0.0348 (7)	0.0063 (6)	0.0031 (5)	0.0003 (5)
C5	0.0528 (8)	0.0572 (8)	0.0405 (7)	0.0033 (7)	0.0007 (6)	−0.0029 (6)
C6	0.0428 (7)	0.0468 (7)	0.0511 (8)	0.0049 (6)	−0.0008 (6)	0.0015 (6)
C7	0.0619 (10)	0.0573 (9)	0.0636 (10)	−0.0020 (8)	−0.0054 (8)	−0.0038 (8)
C8	0.0616 (11)	0.0525 (9)	0.0953 (15)	−0.0101 (8)	−0.0066 (9)	0.0051 (9)
C9	0.0583 (10)	0.0566 (10)	0.0880 (14)	−0.0053 (8)	0.0064 (9)	0.0207 (9)
C10	0.0536 (9)	0.0602 (9)	0.0604 (10)	0.0034 (7)	0.0073 (7)	0.0147 (7)
C11	0.0403 (7)	0.0492 (8)	0.0486 (8)	0.0069 (6)	0.0037 (6)	0.0068 (6)
C12	0.0456 (8)	0.0590 (8)	0.0371 (7)	0.0037 (6)	0.0060 (6)	0.0040 (6)
C13	0.0389 (7)	0.0486 (7)	0.0347 (6)	0.0064 (5)	0.0043 (5)	0.0024 (5)
C14	0.0456 (7)	0.0558 (8)	0.0301 (6)	0.0039 (6)	0.0043 (5)	0.0002 (6)
C15	0.0617 (10)	0.0640 (10)	0.0616 (10)	−0.0096 (8)	0.0105 (8)	0.0028 (8)
C16	0.0747 (11)	0.0685 (10)	0.0499 (9)	−0.0116 (9)	0.0008 (8)	−0.0073 (8)
N1	0.0556 (7)	0.0605 (8)	0.0445 (7)	−0.0093 (6)	0.0065 (5)	−0.0016 (6)
O1	0.0973 (10)	0.0948 (10)	0.0405 (6)	−0.0258 (8)	0.0023 (6)	−0.0124 (6)
O2	0.0806 (8)	0.1016 (10)	0.0368 (6)	−0.0258 (7)	0.0128 (5)	−0.0003 (6)

Geometric parameters (Å, º) top

C1—N1	1.3651 (19)	C9—C10	1.381 (3)
C1—C14	1.4079 (19)	C9—H9	0.9300
C1—C2	1.4133 (19)	C10—C11	1.394 (2)
C2—C3	1.366 (2)	C10—H10	0.9300
C2—H2	0.9300	C11—C12	1.491 (2)
C3—C4	1.3970 (19)	C12—O2	1.2138 (17)
C3—H3	0.9300	C12—C13	1.4939 (19)
C4—C13	1.3987 (18)	C13—C14	1.385 (2)
C4—C5	1.459 (2)	C14—H14	0.9300
C5—O1	1.2208 (17)	C15—N1	1.449 (2)
C5—C6	1.490 (2)	C15—H15A	0.9600
C6—C11	1.392 (2)	C15—H15B	0.9600
C6—C7	1.396 (2)	C15—H15C	0.9600
C7—C8	1.380 (3)	C16—N1	1.444 (2)
C7—H7	0.9300	C16—H16A	0.9600
C8—C9	1.370 (3)	C16—H16B	0.9600
C8—H8	0.9300	C16—H16C	0.9600

N1—C1—C14	121.85 (12)	C11—C10—H10	120.0
N1—C1—C2	120.95 (13)	C6—C11—C10	119.66 (14)
C14—C1—C2	117.20 (13)	C6—C11—C12	121.08 (13)
C3—C2—C1	121.02 (13)	C10—C11—C12	119.26 (14)
C3—C2—H2	119.5	O2—C12—C11	120.97 (13)
C1—C2—H2	119.5	O2—C12—C13	121.60 (14)
C2—C3—C4	121.89 (12)	C11—C12—C13	117.43 (12)
C2—C3—H3	119.1	C14—C13—C4	120.94 (12)
C4—C3—H3	119.1	C14—C13—C12	118.73 (12)
C3—C4—C13	117.77 (13)	C4—C13—C12	120.33 (13)
C3—C4—C5	119.92 (12)	C13—C14—C1	121.15 (12)
C13—C4—C5	122.31 (13)	C13—C14—H14	119.4
O1—C5—C4	121.78 (14)	C1—C14—H14	119.4
O1—C5—C6	120.58 (14)	N1—C15—H15A	109.5
C4—C5—C6	117.64 (12)	N1—C15—H15B	109.5
C11—C6—C7	119.56 (14)	H15A—C15—H15B	109.5
C11—C6—C5	121.20 (13)	N1—C15—H15C	109.5
C7—C6—C5	119.23 (14)	H15A—C15—H15C	109.5
C8—C7—C6	119.71 (17)	H15B—C15—H15C	109.5
C8—C7—H7	120.1	N1—C16—H16A	109.5
C6—C7—H7	120.1	N1—C16—H16B	109.5
C9—C8—C7	120.86 (17)	H16A—C16—H16B	109.5
C9—C8—H8	119.6	N1—C16—H16C	109.5
C7—C8—H8	119.6	H16A—C16—H16C	109.5
C8—C9—C10	120.12 (16)	H16B—C16—H16C	109.5
C8—C9—H9	119.9	C1—N1—C16	120.78 (13)
C10—C9—H9	119.9	C1—N1—C15	120.72 (12)
C9—C10—C11	120.08 (17)	C16—N1—C15	117.68 (13)
C9—C10—H10	120.0

N1—C1—C2—C3	178.16 (13)	C9—C10—C11—C6	0.1 (2)
C14—C1—C2—C3	−1.1 (2)	C9—C10—C11—C12	−179.45 (14)
C1—C2—C3—C4	−0.5 (2)	C6—C11—C12—O2	−179.89 (14)
C2—C3—C4—C13	1.3 (2)	C10—C11—C12—O2	−0.4 (2)
C2—C3—C4—C5	−178.30 (14)	C6—C11—C12—C13	0.4 (2)
C3—C4—C5—O1	1.6 (2)	C10—C11—C12—C13	179.92 (13)
C13—C4—C5—O1	−178.05 (14)	C3—C4—C13—C14	−0.7 (2)
C3—C4—C5—C6	−179.42 (12)	C5—C4—C13—C14	178.97 (13)
C13—C4—C5—C6	1.0 (2)	C3—C4—C13—C12	179.82 (12)
O1—C5—C6—C11	178.32 (15)	C5—C4—C13—C12	−0.5 (2)
C4—C5—C6—C11	−0.7 (2)	O2—C12—C13—C14	0.6 (2)
O1—C5—C6—C7	−1.4 (2)	C11—C12—C13—C14	−179.66 (12)
C4—C5—C6—C7	179.60 (13)	O2—C12—C13—C4	−179.87 (14)
C11—C6—C7—C8	−0.5 (2)	C11—C12—C13—C4	−0.14 (19)
C5—C6—C7—C8	179.16 (15)	C4—C13—C14—C1	−0.9 (2)
C6—C7—C8—C9	0.6 (3)	C12—C13—C14—C1	178.63 (12)
C7—C8—C9—C10	−0.3 (3)	N1—C1—C14—C13	−177.49 (13)
C8—C9—C10—C11	−0.1 (3)	C2—C1—C14—C13	1.7 (2)
C7—C6—C11—C10	0.2 (2)	C14—C1—N1—C16	−10.0 (2)
C5—C6—C11—C10	−179.49 (13)	C2—C1—N1—C16	170.79 (14)
C7—C6—C11—C12	179.74 (13)	C14—C1—N1—C15	−179.41 (14)
C5—C6—C11—C12	0.0 (2)	C2—C1—N1—C15	1.4 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9···O1ⁱ	0.93	2.50	3.272 (2)	140

Symmetry code: (i) x+1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₃NO₂
M_r	251.27
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	4.8614 (6), 19.945 (2), 12.8624 (15)
β (°)	95.979 (2)
V (Å³)	1240.3 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.23 × 0.20 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	14833, 3050, 2267
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.667

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.161, 1.03
No. of reflections	3050
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.17

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1999), 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
C9—H9···O1ⁱ	0.93	2.50	3.272 (2)	140.1

Symmetry code: (i) x+1/2, −y+1/2, z−1/2.

Acknowledgements

The author are grateful to Central China Normal University for financial support and thank Dr Xiang-Gao Meng for the data collection.

References

Bruker (1997). SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (1999). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Havlik, M., Kral, V., Kaplanek, R. & Dolensky, B. (2008). Org. Lett. 10, 4767–4769. Web of Science CrossRef PubMed CAS Google Scholar
Janczak, J. (1995). Acta Cryst. C51, 1381–1382. CSD CrossRef CAS Web of Science IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar