1-Chloro-4-hydroxy­anthraquinone

In the title crystal structure, C₁₄H₇ClO₃, the mol­ecules are linked by weak inter­molecular hydrogen bonds to form a one-dimensional chain.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.061
• wR factor = 0.200
• Data-to-parameter ratio = 16.9

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT333_ALERT_2_B Large Average Benzene C-C Dist.  C1     -C14           1.49 Ang.

Alert level C
PLAT048_ALERT_1_C MoietyFormula Not Given ........................          ?
PLAT152_ALERT_1_C Supplied and Calc Volume s.u. Inconsistent .....          ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O1     -   C2      ..       6.41 su
PLAT480_ALERT_4_C Long H...A H-Bond Reported H1     ..  CL1     ..       3.16 Ang.

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   4 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion

---

S1. Comment

1-Hydroxyanthraquinone in its deprotonated form should function as a bidentate chelate to metal ions. However, there is little interest in this class of ligands, and only a small number of metal complexes of 1-hydroxyanthraquinone and its derivatives have been reported to date (Ali et al., 2005). A recent study has documented the structure of 1,4-dihydroxyanthraquinone (Zain & Ng, 2005). The title compound, (I), has a Cl substituent in the 4-position of 1-hydroxyanthraquinone (Fig. 1), and it exists in a nearly planar conformation.

The hydroxy group forms an intramolecular hydrogen bond. Adjacent molecules are linked by weak interactions (Table 1) into a chain motif (Fig. 2). Other chloroanthraquinones that have been reported are limited to 1-chloroanthraquinone (Klimasenko & Gol'der, 1969; Meng et al., 1999) and 1,5-dichloroanthraquinone (Bailey, 1958; Nakata & Takaki, 1984; Wang, 1979) only.

S2. Experimental

Crystals of 1-chloro-4-hydroxyanthraquinone were obtained by recrystallizing the commerically available compound from pyridine.

S3. Refinement

The two aromatic rings were refined as rigid hexagons of 1.39 Å in order to raise the reflections-to-parameters ratio, as the crystal was not a strongly diffracting specimen. The H atoms were placed in calculated positions (C—H = 0.93 Å and O—H = 0.82 Å), and they were included in the refinement in the riding-model approximation, with U_iso(H) = 1.2U_eq(C,O). The hydroxy group was rotated to fit the electron density.

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. A plot of the molecule of (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
	Fig. 2. A plot showing the weak interactions that link adjacent molecules of (I) into a chain.

1-Chloro-4-hydroxyanthraquinone

Crystal data

C14H7ClO3	F(000) = 528
Mr = 258.65	Dx = 1.581 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1782 reflections
a = 7.4180 (7) Å	θ = 2.4–26.1°
b = 10.2724 (9) Å	µ = 0.35 mm^−1
c = 14.262 (1) Å	T = 295 K
β = 90.588 (2)°	Block, red
V = 1086.7 (2) Å^3	0.42 × 0.34 × 0.16 mm
Z = 4

Data collection

Bruker SMART area-detector diffractometer	1306 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.030
Graphite monochromator	θmax = 27.1°, θmin = 2.4°
ϕ and ω scans	h = −9→9
6405 measured reflections	k = −13→12
2366 independent reflections	l = −12→18

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.061	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.200	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.113P)^2 + 0.225P] where P = (Fo^2 + 2Fc^2)/3
2366 reflections	(Δ/σ)max = 0.001
140 parameters	Δρmax = 0.54 e Å^−3
0 restraints	Δρmin = −0.40 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.5779 (2)	0.5695 (1)	0.76656 (6)	0.0782 (4)
O1	0.7012 (4)	0.8646 (2)	0.4227 (1)	0.0644 (7)
O2	0.8141 (4)	0.6547 (2)	0.3449 (1)	0.0677 (7)
O3	0.6708 (4)	0.3650 (2)	0.6467 (2)	0.0767 (8)
C1	0.7085 (3)	0.6512 (2)	0.5004 (1)	0.042 (1)
C2	0.6761 (3)	0.7844 (2)	0.4992 (1)	0.052 (1)
C3	0.6135 (3)	0.8464 (2)	0.5792 (1)	0.060 (1)
C4	0.5831 (3)	0.7751 (2)	0.6603 (1)	0.057 (1)
C5	0.6155 (3)	0.6418 (1)	0.6615 (1)	0.047 (1)
C6	0.6782 (3)	0.5799 (1)	0.5816 (1)	0.039 (1)
C7	0.7078 (4)	0.4344 (3)	0.5812 (2)	0.045 (1)
C8	0.7855 (3)	0.3750 (2)	0.4953 (1)	0.042 (1)
C9	0.8214 (3)	0.2422 (2)	0.4951 (1)	0.057 (1)
C10	0.8910 (3)	0.1836 (2)	0.4154 (2)	0.066 (1)
C11	0.9246 (3)	0.2577 (2)	0.3360 (1)	0.064 (1)
C12	0.8886 (3)	0.3905 (2)	0.3362 (1)	0.053 (1)
C13	0.8191 (3)	0.4492 (2)	0.4158 (1)	0.042 (1)
C14	0.7819 (4)	0.5899 (3)	0.4156 (2)	0.044 (1)
H1	0.7470	0.8228	0.3801	0.097*
H3	0.5918	0.9356	0.5783	0.072*
H4	0.5412	0.8166	0.7138	0.068*
H9	0.7989	0.1927	0.5483	0.068*
H10	0.9150	0.0947	0.4153	0.079*
H11	0.9711	0.2184	0.2827	0.076*
H12	0.9111	0.4400	0.2830	0.064*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.1166 (9)	0.0770 (7)	0.0414 (5)	−0.0033 (6)	0.0245 (5)	−0.0007 (4)
O1	0.095 (2)	0.049 (1)	0.049 (1)	0.007 (1)	0.020 (1)	0.014 (1)
O2	0.088 (2)	0.076 (2)	0.040 (1)	0.000 (1)	0.021 (1)	0.007 (1)
O3	0.119 (2)	0.060 (2)	0.051 (1)	0.002 (2)	0.034 (1)	0.008 (1)
C1	0.037 (2)	0.052 (2)	0.036 (1)	0.001 (1)	0.003 (1)	0.001 (1)
C2	0.052 (2)	0.057 (2)	0.047 (2)	0.004 (2)	0.003 (1)	0.002 (2)
C3	0.060 (2)	0.053 (2)	0.067 (2)	0.008 (2)	0.005 (2)	−0.006 (2)
C4	0.054 (2)	0.070 (2)	0.046 (2)	0.006 (2)	0.008 (2)	−0.017 (2)
C5	0.042 (2)	0.062 (2)	0.036 (2)	−0.003 (2)	0.006 (1)	−0.005 (1)
C6	0.030 (1)	0.055 (2)	0.032 (1)	−0.002 (1)	0.001 (1)	−0.005 (1)
C7	0.043 (2)	0.056 (2)	0.036 (2)	−0.002 (1)	0.006 (1)	0.002 (1)
C8	0.036 (2)	0.051 (2)	0.039 (2)	−0.004 (1)	0.003 (1)	−0.008 (1)
C9	0.061 (2)	0.058 (2)	0.052 (2)	−0.001 (2)	0.003 (2)	−0.006 (2)
C10	0.060 (2)	0.065 (2)	0.072 (2)	0.0016 (2)	0.005 (2)	−0.022 (2)
C11	0.052 (2)	0.083 (3)	0.056 (2)	0.000 (2)	0.006 (2)	−0.032 (2)
C12	0.047 (2)	0.075 (2)	0.038 (2)	−0.006 (2)	0.008 (1)	−0.011 (2)
C13	0.033 (2)	0.058 (2)	0.036 (2)	−0.004 (1)	0.002 (1)	−0.008 (1)
C14	0.038 (2)	0.062 (2)	0.033 (2)	−0.005 (1)	0.005 (1)	0.004 (1)

Geometric parameters (Å, º)

Cl1—C5	1.698 (2)	C8—C13	1.3900
O1—C2	1.381 (2)	C9—C10	1.3900
O2—C14	1.234 (3)	C10—C11	1.3900
O3—C7	1.209 (3)	C11—C12	1.3900
C1—C2	1.3900	C12—C13	1.3900
C1—C6	1.3900	C13—C14	1.472 (3)
C1—C14	1.473 (3)	O1—H1	0.82
C2—C3	1.3900	C3—H3	0.93
C3—C4	1.3900	C4—H4	0.93
C4—C5	1.3900	C9—H9	0.93
C5—C6	1.3900	C10—H10	0.93
C6—C7	1.510 (3)	C11—H11	0.93
C7—C8	1.490 (3)	C12—H12	0.93
C8—C9	1.3900
C2—C1—C6	120.0	C10—C11—C12	120.0
C2—C1—C14	118.4 (2)	C11—C12—C13	120.0
C6—C1—C14	121.5 (2)	C12—C13—C8	120.0
O1—C2—C1	124.9 (2)	C12—C13—C14	119.7 (2)
O1—C2—C3	115.1 (2)	C8—C13—C14	120.3 (2)
C1—C2—C3	120.0	O2—C14—C13	119.6 (2)
C4—C3—C2	120.0	O2—C14—C1	121.1 (3)
C5—C4—C3	120.0	C13—C14—C1	119.3 (2)
C6—C5—C4	120.0	C2—O1—H1	109.5
C6—C5—Cl1	125.6 (1)	C4—C3—H3	120.0
C4—C5—Cl1	114.3 (1)	C2—C3—H3	120.0
C5—C6—C1	120.0	C5—C4—H4	120.0
C5—C6—C7	120.4 (2)	C3—C4—H4	120.0
C1—C6—C7	119.6 (2)	C8—C9—H9	120.0
O3—C7—C8	119.1 (3)	C10—C9—H9	120.0
O3—C7—C6	123.1 (3)	C11—C10—H10	120.0
C8—C7—C6	117.7 (2)	C9—C10—H10	120.0
C9—C8—C13	120.0	C10—C11—H11	120.0
C9—C8—C7	118.6 (2)	C12—C11—H11	120.0
C13—C8—C7	121.4 (2)	C11—C12—H12	120.0
C8—C9—C10	120.0	C13—C12—H12	120.0
C11—C10—C9	120.0
C6—C1—C2—O1	−179.9 (2)	C6—C7—C8—C9	177.13 (18)
C14—C1—C2—O1	2.6 (2)	O3—C7—C8—C13	175.7 (2)
C14—C1—C2—C3	−177.5 (2)	C6—C7—C8—C13	−4.0 (3)
O1—C2—C3—C4	179.9 (2)	C7—C8—C9—C10	178.9 (2)
C3—C4—C5—Cl1	178.3 (2)	C11—C12—C13—C14	179.8 (2)
Cl1—C5—C6—C1	−178.1 (2)	C7—C8—C13—C12	−178.9 (2)
C4—C5—C6—C7	−178.0 (2)	C9—C8—C13—C14	−179.8 (2)
Cl1—C5—C6—C7	3.9 (2)	C7—C8—C13—C14	1.3 (3)
C14—C1—C6—C5	177.5 (2)	C12—C13—C14—O2	−0.5 (3)
C2—C1—C6—C7	178.0 (2)	C8—C13—C14—O2	179.3 (2)
C14—C1—C6—C7	−4.6 (2)	C12—C13—C14—C1	−179.9 (2)
C5—C6—C7—O3	3.9 (4)	C8—C13—C14—C1	−0.1 (3)
C1—C6—C7—O3	−174.0 (3)	C2—C1—C14—O2	0.0 (3)
C5—C6—C7—C8	−176.5 (2)	C6—C1—C14—O2	−177.5 (2)
C1—C6—C7—C8	5.6 (3)	C2—C1—C14—C13	179.3 (2)
O3—C7—C8—C9	−3.2 (4)	C6—C1—C14—C13	1.8 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2	0.82	1.87	2.569 (3)	143
O1—H1···Cl1^i	0.82	3.16	3.655 (2)	122
C4—H4···O2^ii	0.93	2.55	3.397 (3)	152

Symmetry codes: (i) x+1/2, −y+3/2, z−1/2; (ii) x−1/2, −y+3/2, z+1/2.