Synthesis and crystal structures of two purpurin derivatives: 1,4-dihy­droxy-2-propoxyanthra­quinone and 2-but­oxy-1,4-di­hydroxy­anthra­quinone

Bosch, E.; McClain, E.N.

doi:10.1107/S2056989017014724

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ISSN: 2056-9890

Volume 73| Part 11| November 2017| Pages 1687-1691

https://doi.org/10.1107/S2056989017014724

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Synthesis and crystal structures of two purpurin derivatives: 1,4-dihydroxy-2-propoxyanthraquinone and 2-butoxy-1,4-dihydroxyanthraquinone

Eric Bosch ^a ^* and Emily N. McClain ^a

^aDepartment of Chemistry, Missouri State University, Springfield, MO 65897, USA
^*Correspondence e-mail: ericbosch@missouristate.edu

Edited by S. Parkin, University of Kentucky, USA (Received 11 August 2017; accepted 11 October 2017; online 20 October 2017)

The title compounds were obtained by deprotonation of 1,2,4-trihydroxyanthraquinone (purpurin) using sodium hydride followed by reaction with either 1-bromopropane or 1-bromobutane. 1,4-Dihydroxy-2-propoxyanthraquinone crystallizes as a 1:1 solvate from acetonitrile, C₁₇H₁₄O₅·CH₃CN. The anthraquinone core of the molecule is essentially planar and both hydroxy groups participate in intramolecular O—H⋯O (carbonyl) hydrogen bonds. The propyl chain is angled slightly above the plane of the anthraquinone moiety with a maximum deviation of 0.247 (2) Å above the plane for the terminal carbon atom. In contrast, 2-butoxy-1,4-dihydroxyanthraquinone, C₁₈H₁₆O₅, crystallizes from nitromethane with two independent molecules in the asymmetric unit. The anthraquinone core of each independent molecule is essentially planar and both hydroxy groups on both molecules participate in intramolecular O—H⋯O(carbonyl) hydrogen bonds. The butyl chain in one molecule is also angled slightly above the plane of the anthraquinone moiety, with a maximum deviation of 0.833 (5) Å above the plane for the terminal carbon atom. In contrast, the butyl group on the second molecule is twisted out of the plane of the anthraquinone core with a torsion angle of 65.1 (3)°, resulting in a maximum deviation of 1.631 (5) Å above the plane for the terminal carbon atom.

Keywords: crystal structure; purpurin; anthraquinone; hydrogen bonding.

CCDC references: 1579381; 1579380

1. Chemical context

Purpurin, 1,2,4-trihydroxy anthraquinone, is a major component of the dye extracted from madder root (Schweppe & Winter, 1997 ). The extract from madder root has been used to dye wool and other fabrics since antiquity. Purpurin is commercially available and we here report two derivatives, 1,4-dihydroxy-2-propoxy anthraquinone and 2-butoxy-1,4-dihydroxy anthraquinone, prepared by selective deprotonation of purpurin followed by alkylation with the either 1-bromopropane or 1-bromobutane.

2. Structural commentary

The asymmetric unit of 1,4-dihydroxy-2-propoxy anthraquinone (1), crystallized from acetonitrile solvent, contains a single anthraquinone molecule and one acetonitrile solvate molecule as shown in Fig. 1. The two intramolecular hydrogen bonds (Table 1) are typical for the 1,4-dihydroxy anthraquinones and 1-hydroxyanthraquinones. These hydrogen bonds are maintained in chloroform solution, as shown by the chemical shift of 13.47 and 13.56 ppm for the two hydroxyl protons. The anthraquinone moiety is planar, with an average root mean square (r.m.s.) deviation of atoms C1 to C14 of 0.021 Å, in which the maximum deviation from the plane defined by atoms C1 to C14 is 0.044 (1) Å for C9. The propyl chain is angled slightly above the plane of the anthraquinone moiety, with deviations of 0.043 (2), 0.143 (2) and 0.247 (2) Å for atoms C15, C16 and C17, respectively, from the plane defined by atoms C1–C14. The acetonitrile is angled towards H10 with a N1⋯C10 distance of 3.401 (2) Å. The final difference map shows several peaks of 0.2 to 0.7 e Å⁻³ in the anthraquinone plane that suggest the presence of minor whole-molecule disorder in which the anthraquinone is translated in the plane and/or flipped over.

Table 1
Hydrogen-bond geometry (Å, °) for (1)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O5	0.88 (1)	1.75 (1)	2.5537 (13)	152 (2)
O3—H3O⋯O4	0.87 (1)	1.75 (1)	2.5578 (13)	153 (2)
C10—H10⋯N1	0.95	2.73	3.4009 (19)	128
C15—H15A⋯O3ⁱ	0.99	2.57	3.2179 (16)	123
C11—H11⋯O5ⁱⁱ	0.95	2.47	3.2446 (17)	138
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+2, -y+2, -z+1.

Figure 1
Molecular structure of (1) with the included acetonitrile. Displacement ellipsoids of non-H atoms are drawn at the 50% probability level and H atoms are shown as circles of arbitrary size.

In contrast, the asymmetric unit of 2-butoxy-1,4-dihydroxy anthraquinone (2) crystallized from nitromethane solvent, contains two unique anthraquinone molecules as shown in Fig. 2. Both molecules feature two intramolecular hydrogen bonds (Table 2) similar to those observed in (1). These hydrogen bonds are also maintained in chloroform solution, as shown by the chemical shift of 13.46 and 13.55 ppm for the two hydroxyl protons. The anthraquinone moieties in both molecules are planar. The r.m.s deviation of atoms C1 to C14 is 0.006 Å, with a maximum deviation from the plane defined by atoms C1 to C14 of 0.011 (2) Å for C13. The r.m.s. deviation from the plane defined by atoms C19 to C32 is 0.025 Å, with a maximum deviation of 0.048 (2) Å for C31. The butyl chain attached to O2 is twisted out of the C1–C14 anthraquinone plane with a O2—C15—C16—C17 torsion angle of −65.1 (3)°. The butyl chain has an anti-conformation, the C15—C16—C17—C18 torsion angle being −173.1 (2)°. The deviations of the butyl carbon atoms from the anthraquinone plane defined by atoms C1 to C14 are 0.101 (4), 0.194 (4), 1.467 (4) and 1.631 (5) Å for atoms C15, C16, C17 and C18, respectively. The butyl chain in the second unique molecule, attached to O7, is tilted slightly out of the plane of the anthraquinone with a C20—O7—C33—C34 torsion angle of −167.3 (2)°. This butyl chain also adopts an anti-conformation, the C33—C34—C35—C36 torsion angle being −175.2 (3)°. The resultant deviations of the butyl carbon atoms from the plane defined by atoms C19–C32 are 0.077 (4), 0.428 (4), 0.356 (4) and 0.833 (5) Å for atoms C33, C34, C35 and C36, respectively. There is a close intermolecular contact between phenyl hydrogen atom H3 and carbonyl oxygen atom O10, with a C3⋯O10 distance of 3.494 (3) Å (labelled X in Fig. 2). A second close intermolecular contact, between phenyl hydrogen atom H29 and hydroxyl oxygen atom O3 gives a C29⋯O3 distance of 3.231 (4) Å (labelled Y in Fig. 2).

Table 2
Hydrogen-bond geometry (Å, °) for (2)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O5	0.85 (2)	1.78 (2)	2.564 (3)	153 (3)
O3—H3O⋯O4	0.87 (2)	1.74 (2)	2.536 (3)	151 (3)
O6—H6O⋯O10	0.86 (2)	1.72 (2)	2.542 (3)	158 (3)
O8—H8O⋯O9	0.87 (2)	1.73 (2)	2.554 (3)	155 (3)
C3—H3⋯O10	0.95	2.55	3.494 (3)	173
C29—H29⋯O3	0.95	2.41	3.231 (4)	144
C15—H15B⋯O6ⁱ	0.99	2.52	3.485 (3)	164
C21—H21⋯O8ⁱⁱ	0.95	2.55	3.502 (3)	180
C33—H33A⋯O9ⁱⁱⁱ	0.99	2.56	3.547 (4)	172
Symmetry codes: (i) x-1, y, z; (ii) -x+3, -y+1, -z+1; (iii) -x+2, -y+1, -z+1.

Figure 2
Asymmetric unit of (2) showing the close intermolecular C—H⋯O contacts X and Y (see text). Displacement ellipsoids of non-H atoms are drawn at the 50% probability level and H atoms are shown as circles of arbitrary size.

3. Supramolecular features

In the crystal, molecules of (1) form planes that incorporate the acetonitrile molecule, as shown in Fig. 3. The acetonitrile molecule is almost coplanar with the anthraquinone moiety, with deviations of 0.401 (2), 0.536 (2) and 0.722 (2) Å for atoms N1, C18, and C19, respectively, from the plane defined by atoms C1–C14. There is a close C—H⋯O interaction (Table 1) between a phenyl hydrogen atom and an adjacent carbonyl oxygen atom of an inversion-related molecule of (1). The C11⋯O5#2 distance is 3.245 (2) Å [symmetry code: (#2) 2 − x, 2 − y, 1 − z] and the interaction is labelled x in Fig. 3. The methylene hydrogen H15A is close to the carbonyl oxygen O3 of a second inversion-related molecule of (1). The C15⋯O3#1 distance is 3.218 (2) Å [symmetry code: (#1) 1 − x, −y, 1 − z], and the interaction is labelled y in Fig. 3. The anthraquinone units of (1) alternately π-stack in pairs as shown in Fig. 4. Each π-stacked pair (A and B in Fig. 4) has significant overlap of the anthraquinone moiety with Cg1⋯Cg3#3, Cg2⋯Cg2#3 [symmetry code: (#3) 1 − x, 1 − y, 1 − z; Cg1, Cg2 and Cg3 are the centroids of the six-membered rings C1–C5/C14, C5–C7/C12–C14 and C7–C12, respectively] distances of 3.607 (1) and 3.569 (1) Å, respectively, with slippages of 1.304 and 1.331 Å, respectively. The pairs of π-stacked molecules of (1) are offset π-stacked and the alkyl chain has a C—H⋯π interaction with one end of the anthraquinone unit, as shown in Fig. 4 (molecules labelled A and C). The C16⋯Cg3#4 distance is 3.587 (2) Å [symmetry code: (#4) 2 − x, 1 − y, 1 − z].

Figure 3
Structure of (1) viewed along the [101] direction, with close C—H⋯O contacts labelled x and y (see text).

Figure 4
Repetitive π-stacking of (1). Displacement ellipsoids of non-H atoms are drawn at the 50% probability level [symmetry codes: (#1) − x, −y, 1 − z; (#2) 2 − x, 2 − y, 2 − z; (#3) 1 − x, 1 − y, 1 − z; (#4) 2 − x, 1 − y, 1 − z].

The two unique anthraquinone molecules in the asymmetric unit of (2) offset π-stack in individual columns. There are three close C—H⋯O contacts (Table 2) between these offset π-stacked columns. The C⋯O distances are 3.485 (3), 3.502 (3) and 3.548 (4) Å for C15⋯O6#1, C21⋯O8#2, and C33⋯O9#3. respectively [symmetry codes: (#1) x − 1, y, z; (#2) 3 − x, 1 − y, 1 − z; (#3) 2 − x, 1 − y, 1 − z]. The interactions within each of the two unique sets of π-stacked molecules are shown in Fig. 5. For the anthraquinone unit defined by C1–C14 (Fig. 5a), the centroid-to-centroid distances Cg2⋯Cg1#1 and Cg3⋯Cg2#1 are 3.521 (2) and 3.517 (2) Å, with slippages of 0.960 and 0.948 Å, respectively, where Cg1, Cg2 and Cg3 are the centroids of the six-membered rings C1–C5/C14, C5–C7/C12–C14 and C7–C12, respectively. The methylene hydrogen atom H15A#1 is positioned above centroid Cg1 with a C15⋯Cg1 distance of 3.690 (3) Å. For the anthraquinone unit defined by C19–C32 (Fig. 5b), the centroid-to-centroid distances Cg5⋯Cg4#4 and Cg6⋯Cg5#4 [symmetry code: (#4) 1 + x, y, z; Cg4, Cg5 and Cg6 are the centroids of the C19–C23/C32, C23—C25/C30-C32 and C25–C30 rings, respectively] are 3.520 (1) and 4.009 (1) Å with slippages of 0.960 and 2.145 Å, respectively.

Figure 5
π-Stacking of the two unique molecules of (2) showing the C—H⋯π and π–π interactions as grey dashed lines. Part (a) shows the C1–C14 anthraquinone unit and (b) the C19–C32 anthraquinone unit. Displacement ellipsoids drawn at the 50% probability level [symmetry codes: (#1) x − 1, y z; (#2) 3 − x, 1 − y, 1 − z; (#3) 2 − x, 1 − y, 1 − z; (#4) 1 + x, y, z].

4. Database survey

A search of the Cambridge Crystallographic Database (Version 5.38, Nov. 2016; Groom et al., 2016 ) using Conquest (Bruno et al., 2002 ) for the anthraquinone ring system with oxygen atoms at positions 1, 2 and 4 without restriction on substitution of the other aromatic position, revealed 15 structures. Database entries not including atomic coordinates were excluded. The structure of the parent compound, 1,2,4-trihydroxy anthraquinone monohydrate has been reported (refcode QEGNEV; Yatsenko et al., 2000 ). In addition, structures have been determined for several organic derivatives that were isolated from natural sources. For example, the derivative most closely related to the structures reported here, 1,4-dihydroxy-2-methoxy-7-methylanthracene-9,10-dione, has been isolated from two different fungi and the structure reported [refcodes GEPCOU (She et al., 2006 ) and GEPCOU01 (Muangsin et al., 2008 )]. Complexes of purpurin with rhenium (refcodes CEVNIB, CEVNOH and AVABEF; Sathiyendiran, et al., 2006 , 2011 ), copper [refcode ZOMSEB; Das, et al., 2014 ), tin (refcodes MOQTAO and MOQTES; de Sousa et al., 2009 ), calcium and aluminum (refcode LAYBAO; Bergerhoff & Wunderlich, 1993 ) have been reported. In each of the reported structures, those compounds with a free hydroxyl group flanking the anthraquinone carbonyl also exhibit the intramolecular hydrogen bond reported for (1) and (2).

5. Synthesis and crystallization

Synthesis of 1,4-dihydroxy-2-propoxy anthraquinone (1). In a flask under an atmosphere of argon, a dark red–orange solution of purpurin (0.26 g) in dimethylformamide (10 mL) and tetrahydrofuran (20 mL) was cooled in an ice–salt bath. Sodium hydride (0.081 g, 1 eq.) was added and the resultant violet solution was stirred in the ice bath for 20 minutes. Excess 1-bromopropane (1 mL) was added, a water condenser attached, and the flask was removed from the cooling bath and heated to 353 K for 24 h. The flask was cooled to room temperature and the solvents evaporated. The crude product was purified by column chromatography with silica gel (0.65–0.40 mm) and mixtures of hexane and ethyl acetate of increasing polarity. The eluant was monitored by TLC with a 5:1 mixture of hexane and ethyl acetate. The solvent was evaporated and the product obtained as a red–orange solid (0.15 g). ¹H NMR: (400MHz, CDCl₃) δ 13.56 (s, 1H), 13.47 (s, 1H), 8.33 (dd, J = 2.0, 7.0 Hz, 2H), 7.84–7.77 (m, 2H), 6.67 (s, 1H), 4.09 (t, J = 8.0 Hz, 2H), 1.97 (s, J = 7.0 Hz, 2H), 1.11 (t, J = 7.4 Hz, 3H). ¹³C NMR: 189.87, 186.98, 163.64, 159.97, 153.30, 137.17, 136.78, 136.41, 135.95, 129.63, 129.47, 115.07, 110.03, 108.64, 73.84, 24.68, 13.02. Compound (1) crystallized from acetonitrile as large dark-red blocks that included an acetonitrile molecule as a 1:1 solvate. When these blocks were cut to small individual pieces or ground with a mortar and pestle they appeared orange. The crystals lost luster after removal from the mother liquor, presumably due to loss of the acetonitrile.

Synthesis of 4-butoxy-1,2-dihydroxyanthraquinone (2). The same procedure was used with 1 mL of 1-bromobutane. The compound was isolated as a dark red–purple solid. ¹H NMR: (400MHz, CDCl₃) δ 13.55 (s, 1H), 13.46 (s,1H), 8.33 (dd, J = 2.0, 7.0 Hz, 2H), 7.84–7.76 (m, 2H), 6.66 (s, 1H), 4.13 (t, J = 6.6 Hz, 2H), 1.92 (m, 2H), 1.56 (m, 2H), 1.02 (t, J = 7.4 Hz, 3H). ¹³C NMR: 187.40, 184.50, 161.22, 157.56, 150.87, 134.72, 134.33, 133.96, 133.51, 107.57, 106.18, 69.73, 30.85, 19.37, 13.98. Compound (2) was recrystallized from nitromethane as dark red–black blocks. When these blocks were cut to small individual pieces or ground with a mortar and pestle they appeared orange–red.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. Hydrogen atoms potentially involved in hydrogen-bonding interactions were located by difference methods and initially restrained in the refinement with O—H = 0.84 (2) Å and with U_iso(H) = 1.2U_eq(O). Other H atoms were included in the refinement at calculated positions, C—H = 0.95 Å for aromatic, C—H = 0.99 Å for methylene and C—H = 0.98 Å for methyl hydrogens with U_iso(H) = 1.2U_eq(C) for aromatic and methylene H atoms and 1.5U_eq(C) for methyl H atoms.

Table 3
Experimental details

	(1)	(2)
Crystal data
Chemical formula	C₁₇H₁₄O₅·C₂H₃N	C₁₈H₁₆O₅
M_r	339.33	312.31
Crystal system, space group	Triclinic, P $[\overline{1}]$	Monoclinic, P2₁/n
Temperature (K)	100	100
a, b, c (Å)	8.2160 (11), 9.8605 (13), 10.7410 (14)	4.7730 (9), 44.272 (8), 13.807 (3)
α, β, γ (°)	95.999 (2), 90.181 (2), 113.774 (2)	90, 95.164 (2), 90
V (Å³)	790.99 (18)	2905.8 (9)
Z	2	8
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.10	0.10
Crystal size (mm)	0.45 × 0.18 × 0.09	0.48 × 0.10 × 0.03

Data collection
Diffractometer	Bruker APEXII CCD	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )	Multi-scan (SADABS; Bruker, 2014)
T_min, T_max	0.869, 1.000	0.854, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	10216, 3548, 2718	36901, 6456, 3747
R_int	0.022	0.104
(sin θ/λ)_max (Å⁻¹)	0.644	0.643

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.153, 1.06	0.063, 0.166, 1.04
No. of reflections	3548	6456
No. of parameters	234	429
No. of restraints	2	4
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.71, −0.27	0.26, −0.27
Computer programs: SMART and SAINT (Bruker, 2014), SHELXT2014 (Sheldrick, 2015a ), SHELXL2017 (Sheldrick, 2015b ) and X-SEED (Barbour, 2001 ).

Supporting information

CCDC references: 1579381; 1579380

Crystal structure: contains datablocks 1, 2, global. DOI: https://doi.org/10.1107/S2056989017014724/pk2605sup1.cif

Structure factors: contains datablock 1. DOI: https://doi.org/10.1107/S2056989017014724/pk26051sup2.hkl

Structure factors: contains datablock 2. DOI: https://doi.org/10.1107/S2056989017014724/pk26052sup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989017014724/pk26051sup4.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2056989017014724/pk26051sup5.cml

checkCIF report

Computing details top

For both structures, data collection: SMART (Bruker, 2014); cell refinement: SMART (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2017 (Sheldrick, 2015b); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: X-SEED (Barbour, 2001).

1,4-Dihydroxy-2-propoxyanthraquinone acetonitrile monosolvate (1) top

Crystal data top

C₁₇H₁₄O₅·C₂H₃N	Z = 2
M_r = 339.33	F(000) = 356
Triclinic, P1	D_x = 1.425 Mg m⁻³
a = 8.2160 (11) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.8605 (13) Å	Cell parameters from 3016 reflections
c = 10.7410 (14) Å	θ = 2.7–27.2°
α = 95.999 (2)°	µ = 0.10 mm⁻¹
β = 90.181 (2)°	T = 100 K
γ = 113.774 (2)°	Cut irregular block, orange
V = 790.99 (18) Å³	0.45 × 0.18 × 0.09 mm

Data collection top

Bruker APEXII CCD diffractometer	3548 independent reflections
Radiation source: fine-focus sealed tube	2718 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
Detector resolution: 8.3660 pixels mm^-1	θ_max = 27.3°, θ_min = 1.9°
phi and ω scans	h = −10→10
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −12→12
T_min = 0.869, T_max = 1.000	l = −13→13
10216 measured reflections

Refinement top

Refinement on F²	2 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.052	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.153	w = 1/[σ²(F_o²) + (0.0962P)² + 0.0684P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
3548 reflections	Δρ_max = 0.71 e Å⁻³
234 parameters	Δρ_min = −0.27 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.

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

	x	y	z	U_iso*/U_eq
O1	0.93351 (13)	0.54640 (11)	0.31245 (9)	0.0224 (2)
H1O	0.943 (2)	0.6376 (15)	0.3329 (15)	0.027*
N1	0.69308 (19)	1.25060 (16)	0.93564 (13)	0.0376 (4)
C1	0.83016 (17)	0.46925 (15)	0.39909 (12)	0.0179 (3)
O2	0.85708 (12)	0.26110 (10)	0.29025 (9)	0.0216 (2)
C2	0.78580 (17)	0.31187 (15)	0.38774 (12)	0.0186 (3)
O3	0.50110 (13)	0.19718 (10)	0.64607 (9)	0.0231 (3)
H3O	0.471 (2)	0.2555 (17)	0.6993 (14)	0.028*
C3	0.67840 (17)	0.22550 (15)	0.47188 (12)	0.0190 (3)
H3	0.650425	0.121543	0.464073	0.023*
O4	0.48044 (13)	0.42907 (11)	0.76272 (9)	0.0236 (2)
C4	0.60915 (17)	0.28978 (15)	0.56995 (12)	0.0184 (3)
O5	0.90743 (13)	0.77360 (10)	0.43289 (9)	0.0237 (3)
C5	0.65148 (17)	0.44303 (14)	0.58446 (12)	0.0168 (3)
C6	0.58069 (17)	0.50732 (15)	0.68671 (12)	0.0186 (3)
C7	0.63155 (17)	0.67078 (15)	0.70039 (12)	0.0182 (3)
C8	0.57026 (18)	0.73660 (16)	0.80017 (12)	0.0215 (3)
H8	0.496307	0.676508	0.858499	0.026*
C9	0.61668 (18)	0.88946 (16)	0.81480 (13)	0.0230 (3)
H9	0.577257	0.934122	0.884204	0.028*
C10	0.72114 (18)	0.97713 (15)	0.72752 (13)	0.0232 (3)
H10	0.750414	1.081320	0.736488	0.028*
C11	0.78274 (18)	0.91324 (15)	0.62752 (13)	0.0211 (3)
H11	0.854261	0.973685	0.568420	0.025*
C12	0.73939 (17)	0.75953 (14)	0.61376 (12)	0.0175 (3)
C13	0.80994 (17)	0.69324 (15)	0.50858 (12)	0.0185 (3)
C14	0.76399 (17)	0.53320 (14)	0.49710 (12)	0.0171 (3)
C15	0.80376 (18)	0.10079 (14)	0.26995 (12)	0.0197 (3)
H15A	0.672284	0.048972	0.262662	0.024*
H15B	0.847744	0.066928	0.341400	0.024*
C16	0.88231 (18)	0.06548 (15)	0.15066 (12)	0.0216 (3)
H16A	1.013724	0.117694	0.158502	0.026*
H16B	0.839009	0.100713	0.079785	0.026*
C17	0.8285 (2)	−0.10258 (15)	0.12525 (13)	0.0259 (3)
H17A	0.864454	−0.138135	0.198037	0.039*
H17B	0.887518	−0.124293	0.051405	0.039*
H17C	0.699127	−0.153202	0.110002	0.039*
C18	0.7439 (2)	1.37684 (18)	0.95263 (14)	0.0300 (3)
C19	0.8085 (2)	1.53842 (19)	0.97699 (19)	0.0451 (5)
H19A	0.707605	1.567300	0.974361	0.068*
H19B	0.891236	1.584642	0.913041	0.068*
H19C	0.870055	1.572114	1.059963	0.068*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0257 (5)	0.0171 (5)	0.0230 (5)	0.0076 (4)	0.0075 (4)	0.0008 (4)
N1	0.0451 (8)	0.0342 (8)	0.0356 (8)	0.0199 (7)	0.0016 (6)	−0.0023 (6)
C1	0.0159 (6)	0.0174 (6)	0.0186 (6)	0.0052 (5)	0.0005 (5)	0.0013 (5)
O2	0.0243 (5)	0.0157 (5)	0.0244 (5)	0.0086 (4)	0.0078 (4)	−0.0012 (4)
C2	0.0173 (6)	0.0200 (7)	0.0190 (6)	0.0092 (5)	0.0005 (5)	−0.0026 (5)
O3	0.0278 (5)	0.0164 (5)	0.0249 (5)	0.0086 (4)	0.0091 (4)	0.0029 (4)
C3	0.0188 (6)	0.0151 (6)	0.0230 (7)	0.0071 (5)	0.0002 (5)	0.0003 (5)
O4	0.0263 (5)	0.0202 (5)	0.0239 (5)	0.0092 (4)	0.0069 (4)	0.0018 (4)
C4	0.0176 (6)	0.0184 (6)	0.0194 (6)	0.0076 (5)	0.0011 (5)	0.0021 (5)
O5	0.0271 (5)	0.0170 (5)	0.0247 (5)	0.0066 (4)	0.0067 (4)	0.0018 (4)
C5	0.0165 (6)	0.0167 (6)	0.0170 (6)	0.0071 (5)	−0.0007 (5)	0.0000 (5)
C6	0.0178 (6)	0.0193 (7)	0.0193 (6)	0.0086 (5)	0.0004 (5)	0.0007 (5)
C7	0.0168 (6)	0.0182 (7)	0.0195 (6)	0.0078 (5)	−0.0019 (5)	−0.0012 (5)
C8	0.0225 (7)	0.0233 (7)	0.0192 (6)	0.0106 (6)	0.0007 (5)	−0.0004 (5)
C9	0.0228 (7)	0.0245 (7)	0.0230 (7)	0.0131 (6)	−0.0025 (5)	−0.0056 (5)
C10	0.0235 (7)	0.0183 (7)	0.0282 (7)	0.0107 (6)	−0.0037 (6)	−0.0042 (5)
C11	0.0207 (7)	0.0189 (6)	0.0236 (7)	0.0084 (5)	−0.0014 (5)	0.0008 (5)
C12	0.0167 (6)	0.0173 (7)	0.0180 (6)	0.0073 (5)	−0.0029 (5)	−0.0018 (5)
C13	0.0175 (6)	0.0170 (7)	0.0201 (6)	0.0065 (5)	−0.0009 (5)	0.0006 (5)
C14	0.0161 (6)	0.0156 (7)	0.0185 (6)	0.0061 (5)	−0.0015 (5)	−0.0012 (5)
C15	0.0206 (7)	0.0139 (6)	0.0233 (7)	0.0065 (5)	0.0030 (5)	−0.0017 (5)
C16	0.0223 (7)	0.0212 (7)	0.0208 (7)	0.0089 (5)	0.0021 (5)	−0.0006 (5)
C17	0.0319 (8)	0.0222 (7)	0.0228 (7)	0.0113 (6)	0.0068 (6)	−0.0028 (5)
C18	0.0311 (8)	0.0349 (9)	0.0271 (7)	0.0178 (7)	−0.0004 (6)	−0.0015 (6)
C19	0.0445 (10)	0.0300 (9)	0.0596 (11)	0.0163 (8)	−0.0157 (9)	−0.0045 (8)

Geometric parameters (Å, º) top

O1—C1	1.3410 (15)	C9—C10	1.392 (2)
O1—H1O	0.875 (13)	C9—H9	0.9500
N1—C18	1.136 (2)	C10—C11	1.3877 (19)
C1—C14	1.3938 (19)	C10—H10	0.9500
C1—C2	1.4353 (19)	C11—C12	1.4013 (18)
O2—C2	1.3493 (16)	C11—H11	0.9500
O2—C15	1.4516 (15)	C12—C13	1.4814 (19)
C2—C3	1.3714 (19)	C13—C14	1.4584 (19)
O3—C4	1.3407 (15)	C15—C16	1.5075 (18)
O3—H3O	0.874 (14)	C15—H15A	0.9900
C3—C4	1.4106 (18)	C15—H15B	0.9900
C3—H3	0.9500	C16—C17	1.5265 (18)
O4—C6	1.2505 (16)	C16—H16A	0.9900
C4—C5	1.3983 (18)	C16—H16B	0.9900
O5—C13	1.2480 (16)	C17—H17A	0.9800
C5—C14	1.4292 (19)	C17—H17B	0.9800
C5—C6	1.4498 (18)	C17—H17C	0.9800
C6—C7	1.4836 (18)	C18—C19	1.456 (2)
C7—C8	1.3947 (18)	C19—H19A	0.9800
C7—C12	1.4025 (18)	C19—H19B	0.9800
C8—C9	1.3887 (19)	C19—H19C	0.9800
C8—H8	0.9500

C1—O1—H1O	104.0 (11)	C12—C11—H11	120.0
O1—C1—C14	123.72 (12)	C11—C12—C7	119.64 (12)
O1—C1—C2	117.06 (11)	C11—C12—C13	119.48 (12)
C14—C1—C2	119.22 (12)	C7—C12—C13	120.88 (12)
C2—O2—C15	116.12 (10)	O5—C13—C14	121.35 (12)
O2—C2—C3	125.11 (12)	O5—C13—C12	120.31 (12)
O2—C2—C1	114.62 (12)	C14—C13—C12	118.33 (12)
C3—C2—C1	120.27 (12)	C1—C14—C5	120.48 (12)
C4—O3—H3O	104.0 (11)	C1—C14—C13	119.04 (12)
C2—C3—C4	120.53 (12)	C5—C14—C13	120.47 (12)
C2—C3—H3	119.7	O2—C15—C16	107.99 (10)
C4—C3—H3	119.7	O2—C15—H15A	110.1
O3—C4—C5	122.48 (11)	C16—C15—H15A	110.1
O3—C4—C3	116.90 (12)	O2—C15—H15B	110.1
C5—C4—C3	120.61 (12)	C16—C15—H15B	110.1
C4—C5—C14	118.88 (12)	H15A—C15—H15B	108.4
C4—C5—C6	119.80 (12)	C15—C16—C17	109.75 (11)
C14—C5—C6	121.32 (12)	C15—C16—H16A	109.7
O4—C6—C5	121.78 (12)	C17—C16—H16A	109.7
O4—C6—C7	120.05 (11)	C15—C16—H16B	109.7
C5—C6—C7	118.17 (12)	C17—C16—H16B	109.7
C8—C7—C12	119.70 (12)	H16A—C16—H16B	108.2
C8—C7—C6	119.52 (12)	C16—C17—H17A	109.5
C12—C7—C6	120.79 (12)	C16—C17—H17B	109.5
C9—C8—C7	120.41 (13)	H17A—C17—H17B	109.5
C9—C8—H8	119.8	C16—C17—H17C	109.5
C7—C8—H8	119.8	H17A—C17—H17C	109.5
C8—C9—C10	119.86 (12)	H17B—C17—H17C	109.5
C8—C9—H9	120.1	N1—C18—C19	178.89 (17)
C10—C9—H9	120.1	C18—C19—H19A	109.5
C11—C10—C9	120.40 (12)	C18—C19—H19B	109.5
C11—C10—H10	119.8	H19A—C19—H19B	109.5
C9—C10—H10	119.8	C18—C19—H19C	109.5
C10—C11—C12	119.97 (13)	H19A—C19—H19C	109.5
C10—C11—H11	120.0	H19B—C19—H19C	109.5

C15—O2—C2—C3	4.50 (19)	C9—C10—C11—C12	0.2 (2)
C15—O2—C2—C1	−175.30 (10)	C10—C11—C12—C7	0.9 (2)
O1—C1—C2—O2	0.80 (18)	C10—C11—C12—C13	−178.36 (11)
C14—C1—C2—O2	−179.69 (11)	C8—C7—C12—C11	−0.8 (2)
O1—C1—C2—C3	−179.01 (11)	C6—C7—C12—C11	178.81 (11)
C14—C1—C2—C3	0.5 (2)	C8—C7—C12—C13	178.54 (11)
O2—C2—C3—C4	−179.31 (12)	C6—C7—C12—C13	−1.9 (2)
C1—C2—C3—C4	0.5 (2)	C11—C12—C13—O5	0.1 (2)
C2—C3—C4—O3	178.11 (11)	C7—C12—C13—O5	−179.19 (11)
C2—C3—C4—C5	−1.2 (2)	C11—C12—C13—C14	179.48 (11)
O3—C4—C5—C14	−178.34 (11)	C7—C12—C13—C14	0.19 (19)
C3—C4—C5—C14	0.9 (2)	O1—C1—C14—C5	178.71 (11)
O3—C4—C5—C6	1.4 (2)	C2—C1—C14—C5	−0.8 (2)
C3—C4—C5—C6	−179.28 (11)	O1—C1—C14—C13	−0.8 (2)
C4—C5—C6—O4	−0.6 (2)	C2—C1—C14—C13	179.77 (11)
C14—C5—C6—O4	179.13 (11)	C4—C5—C14—C1	0.1 (2)
C4—C5—C6—C7	178.82 (11)	C6—C5—C14—C1	−179.73 (11)
C14—C5—C6—C7	−1.4 (2)	C4—C5—C14—C13	179.51 (11)
O4—C6—C7—C8	1.5 (2)	C6—C5—C14—C13	−0.3 (2)
C5—C6—C7—C8	−177.94 (11)	O5—C13—C14—C1	−0.3 (2)
O4—C6—C7—C12	−178.03 (11)	C12—C13—C14—C1	−179.62 (11)
C5—C6—C7—C12	2.49 (19)	O5—C13—C14—C5	−179.72 (11)
C12—C7—C8—C9	−0.6 (2)	C12—C13—C14—C5	0.91 (19)
C6—C7—C8—C9	179.85 (11)	C2—O2—C15—C16	174.51 (10)
C7—C8—C9—C10	1.7 (2)	O2—C15—C16—C17	−179.69 (10)
C8—C9—C10—C11	−1.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O5	0.88 (1)	1.75 (1)	2.5537 (13)	152 (2)
O3—H3O···O4	0.87 (1)	1.75 (1)	2.5578 (13)	153 (2)
C10—H10···N1	0.95	2.73	3.4009 (19)	128
C15—H15A···O3ⁱ	0.99	2.57	3.2179 (16)	123
C11—H11···O5ⁱⁱ	0.95	2.47	3.2446 (17)	138

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

2-Butoxy-1,4-dihydroxyanthraquinone (2) top

Crystal data top

C₁₈H₁₆O₅	F(000) = 1312
M_r = 312.31	D_x = 1.428 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 4.7730 (9) Å	Cell parameters from 2921 reflections
b = 44.272 (8) Å	θ = 2.4–23.8°
c = 13.807 (3) Å	µ = 0.10 mm⁻¹
β = 95.164 (2)°	T = 100 K
V = 2905.8 (9) Å³	Cut irregular block, orange-red
Z = 8	0.48 × 0.10 × 0.03 mm

Data collection top

Bruker APEXII CCD diffractometer	6456 independent reflections
Radiation source: fine-focus sealed tube	3747 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.104
Detector resolution: 8.3660 pixels mm^-1	θ_max = 27.2°, θ_min = 1.6°
phi and ω scans	h = −6→6
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −56→56
T_min = 0.854, T_max = 1.000	l = −17→17
36901 measured reflections

Refinement top

Refinement on F²	4 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.063	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.166	w = 1/[σ²(F_o²) + (0.047P)² + 2.0816P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max = 0.001
6456 reflections	Δρ_max = 0.26 e Å⁻³
429 parameters	Δρ_min = −0.27 e Å⁻³

Special details top

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

	x	y	z	U_iso*/U_eq
O1	−0.3186 (4)	0.27290 (4)	0.38526 (14)	0.0341 (5)
H1O	−0.448 (5)	0.2616 (6)	0.359 (2)	0.041*
C1	−0.3234 (6)	0.29688 (6)	0.32535 (19)	0.0272 (6)
O2	0.0428 (4)	0.31529 (4)	0.43337 (13)	0.0312 (5)
C2	−0.1245 (6)	0.32043 (6)	0.3504 (2)	0.0275 (6)
O3	−0.2823 (4)	0.37359 (4)	0.15477 (15)	0.0350 (5)
H3O	−0.399 (6)	0.3708 (7)	0.1034 (17)	0.042*
C3	−0.1160 (6)	0.34561 (6)	0.2928 (2)	0.0287 (6)
H3	0.017152	0.361103	0.309821	0.034*
O4	−0.6827 (4)	0.35220 (4)	0.04208 (14)	0.0367 (5)
C4	−0.3032 (6)	0.34858 (6)	0.2089 (2)	0.0286 (6)
O5	−0.7188 (4)	0.25237 (4)	0.26716 (15)	0.0375 (5)
C5	−0.5023 (5)	0.32611 (6)	0.18344 (19)	0.0254 (6)
O6	0.7609 (4)	0.39771 (4)	0.48700 (15)	0.0355 (5)
H6O	0.636 (6)	0.3937 (7)	0.4395 (17)	0.043*
C6	−0.6920 (6)	0.32954 (6)	0.0958 (2)	0.0293 (6)
O7	1.1866 (4)	0.42067 (4)	0.59154 (14)	0.0367 (5)
C7	−0.9003 (5)	0.30521 (6)	0.07061 (19)	0.0266 (6)
O8	1.2269 (4)	0.50371 (4)	0.37289 (15)	0.0341 (5)
H8O	1.123 (6)	0.5094 (7)	0.3208 (16)	0.041*
C8	−1.0870 (6)	0.30801 (6)	−0.0124 (2)	0.0328 (7)
H8	−1.081236	0.325412	−0.052455	0.039*
O9	0.8632 (4)	0.50517 (4)	0.22553 (14)	0.0359 (5)
C9	−1.2818 (6)	0.28529 (7)	−0.0366 (2)	0.0349 (7)
H9	−1.410599	0.287331	−0.092840	0.042*
O10	0.4078 (4)	0.40025 (4)	0.33801 (14)	0.0346 (5)
C10	−1.2893 (6)	0.25958 (6)	0.0210 (2)	0.0340 (7)
H10	−1.419875	0.243897	0.003368	0.041*
C11	−1.1065 (6)	0.25689 (6)	0.1040 (2)	0.0321 (7)
H11	−1.114821	0.239564	0.144244	0.038*
C12	−0.9090 (6)	0.27958 (6)	0.12909 (19)	0.0274 (6)
C13	−0.7114 (6)	0.27581 (6)	0.2171 (2)	0.0286 (6)
C14	−0.5100 (5)	0.29996 (6)	0.2427 (2)	0.0264 (6)
C15	0.2386 (6)	0.33909 (6)	0.4653 (2)	0.0313 (6)
H15B	0.136313	0.358244	0.473426	0.038*
H15A	0.375876	0.342303	0.416602	0.038*
C16	0.3885 (6)	0.32930 (6)	0.5611 (2)	0.0339 (7)
H16A	0.538850	0.344065	0.580570	0.041*
H16B	0.479215	0.309504	0.552161	0.041*
C17	0.1962 (7)	0.32659 (7)	0.6425 (2)	0.0402 (7)
H17A	0.060155	0.310046	0.626768	0.048*
H17B	0.088094	0.345572	0.646233	0.048*
C18	0.3532 (8)	0.32039 (7)	0.7413 (2)	0.0488 (9)
H18A	0.475930	0.302797	0.736548	0.073*
H18B	0.217716	0.316330	0.788912	0.073*
H18C	0.467288	0.338036	0.761934	0.073*
C19	0.8649 (6)	0.42371 (6)	0.4540 (2)	0.0296 (6)
C20	1.0975 (6)	0.43683 (6)	0.5119 (2)	0.0301 (6)
C21	1.2100 (6)	0.46359 (6)	0.4840 (2)	0.0302 (6)
H21	1.362242	0.472501	0.522992	0.036*
C22	1.1009 (6)	0.47784 (6)	0.3981 (2)	0.0300 (6)
C23	0.8739 (6)	0.46552 (6)	0.3399 (2)	0.0278 (6)
C24	0.7634 (6)	0.48070 (6)	0.2524 (2)	0.0293 (6)
C25	0.5272 (6)	0.46627 (6)	0.1918 (2)	0.0300 (6)
C26	0.4175 (6)	0.48005 (7)	0.1061 (2)	0.0365 (7)
H26	0.489850	0.498971	0.087551	0.044*
C27	0.2030 (7)	0.46627 (7)	0.0475 (2)	0.0413 (8)
H27	0.132225	0.475545	−0.011761	0.050*
C28	0.0917 (6)	0.43906 (7)	0.0752 (2)	0.0394 (7)
H28	−0.057104	0.429841	0.035422	0.047*
C29	0.1970 (6)	0.42527 (6)	0.1608 (2)	0.0354 (7)
H29	0.120415	0.406580	0.179632	0.042*
C30	0.4146 (6)	0.43869 (6)	0.2195 (2)	0.0305 (6)
C31	0.5203 (6)	0.42406 (6)	0.3111 (2)	0.0296 (6)
C32	0.7571 (6)	0.43774 (6)	0.3698 (2)	0.0290 (6)
C33	1.4201 (6)	0.43232 (6)	0.6555 (2)	0.0354 (7)
H33A	1.359002	0.449853	0.692861	0.042*
H33B	1.575349	0.438816	0.617335	0.042*
C34	1.5157 (7)	0.40682 (7)	0.7235 (2)	0.0392 (7)
H34A	1.589349	0.390176	0.685154	0.047*
H34B	1.351732	0.398995	0.754780	0.047*
C35	1.7415 (7)	0.41641 (7)	0.8018 (2)	0.0449 (8)
H35A	1.663659	0.431719	0.844235	0.054*
H35B	1.900044	0.425732	0.771114	0.054*
C36	1.8488 (8)	0.38931 (8)	0.8632 (2)	0.0525 (9)
H36A	1.695632	0.381183	0.898166	0.079*
H36B	2.003713	0.395739	0.910094	0.079*
H36C	1.915812	0.373660	0.820721	0.079*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0317 (11)	0.0275 (11)	0.0412 (12)	−0.0051 (9)	−0.0072 (9)	0.0049 (9)
C1	0.0237 (14)	0.0243 (14)	0.0334 (15)	0.0016 (11)	0.0025 (12)	0.0025 (12)
O2	0.0262 (10)	0.0271 (10)	0.0389 (11)	−0.0023 (8)	−0.0038 (9)	−0.0001 (8)
C2	0.0236 (14)	0.0239 (14)	0.0350 (15)	0.0027 (11)	0.0020 (12)	−0.0028 (11)
O3	0.0343 (12)	0.0276 (11)	0.0423 (12)	−0.0038 (9)	−0.0007 (9)	0.0058 (9)
C3	0.0229 (14)	0.0232 (14)	0.0400 (16)	−0.0018 (11)	0.0033 (12)	−0.0031 (12)
O4	0.0353 (12)	0.0298 (11)	0.0446 (12)	0.0010 (9)	0.0009 (9)	0.0078 (9)
C4	0.0251 (15)	0.0226 (14)	0.0387 (16)	0.0024 (11)	0.0057 (12)	0.0020 (12)
O5	0.0347 (12)	0.0297 (11)	0.0464 (12)	−0.0070 (9)	−0.0060 (9)	0.0081 (9)
C5	0.0211 (14)	0.0233 (13)	0.0325 (15)	0.0019 (11)	0.0059 (11)	−0.0008 (11)
O6	0.0331 (12)	0.0261 (10)	0.0468 (13)	−0.0057 (9)	0.0015 (9)	0.0027 (9)
C6	0.0236 (14)	0.0279 (15)	0.0364 (16)	0.0066 (11)	0.0024 (12)	0.0021 (12)
O7	0.0321 (11)	0.0302 (11)	0.0467 (12)	−0.0039 (9)	−0.0022 (9)	0.0032 (9)
C7	0.0224 (14)	0.0272 (14)	0.0306 (15)	0.0048 (11)	0.0048 (12)	−0.0013 (11)
O8	0.0304 (11)	0.0261 (10)	0.0456 (12)	−0.0053 (9)	0.0028 (9)	0.0013 (9)
C8	0.0322 (16)	0.0337 (16)	0.0324 (16)	0.0068 (13)	0.0024 (13)	0.0022 (12)
O9	0.0342 (12)	0.0263 (11)	0.0474 (12)	−0.0037 (9)	0.0047 (9)	0.0027 (9)
C9	0.0273 (16)	0.0401 (17)	0.0360 (17)	0.0071 (13)	−0.0035 (13)	−0.0072 (13)
O10	0.0291 (11)	0.0263 (11)	0.0487 (12)	−0.0046 (8)	0.0049 (9)	−0.0003 (9)
C10	0.0279 (16)	0.0323 (16)	0.0411 (17)	−0.0001 (12)	−0.0006 (13)	−0.0099 (13)
C11	0.0292 (16)	0.0276 (15)	0.0394 (16)	−0.0003 (12)	0.0030 (13)	−0.0039 (12)
C12	0.0235 (14)	0.0266 (14)	0.0323 (15)	0.0036 (11)	0.0029 (12)	−0.0039 (12)
C13	0.0239 (14)	0.0282 (15)	0.0335 (15)	0.0013 (12)	0.0008 (12)	−0.0015 (12)
C14	0.0207 (13)	0.0232 (14)	0.0355 (15)	0.0006 (11)	0.0033 (11)	−0.0004 (11)
C15	0.0266 (15)	0.0225 (14)	0.0443 (17)	−0.0034 (11)	0.0009 (13)	−0.0019 (12)
C16	0.0295 (16)	0.0277 (15)	0.0427 (17)	−0.0001 (12)	−0.0065 (13)	−0.0047 (13)
C17	0.0374 (18)	0.0405 (18)	0.0415 (18)	0.0057 (14)	−0.0024 (14)	−0.0005 (14)
C18	0.061 (2)	0.0373 (19)	0.0463 (19)	0.0090 (16)	−0.0058 (17)	−0.0034 (15)
C19	0.0277 (15)	0.0196 (13)	0.0425 (17)	−0.0021 (11)	0.0083 (13)	−0.0014 (12)
C20	0.0263 (15)	0.0263 (14)	0.0382 (16)	0.0031 (12)	0.0058 (13)	−0.0011 (12)
C21	0.0243 (15)	0.0255 (14)	0.0412 (17)	−0.0009 (11)	0.0058 (13)	−0.0041 (12)
C22	0.0265 (15)	0.0216 (14)	0.0432 (17)	−0.0018 (11)	0.0107 (13)	−0.0056 (12)
C23	0.0235 (14)	0.0217 (14)	0.0386 (16)	0.0013 (11)	0.0058 (12)	−0.0025 (12)
C24	0.0236 (14)	0.0238 (14)	0.0413 (16)	0.0001 (11)	0.0069 (12)	−0.0037 (12)
C25	0.0247 (15)	0.0257 (14)	0.0404 (16)	0.0012 (11)	0.0064 (12)	−0.0027 (12)
C26	0.0330 (17)	0.0319 (16)	0.0445 (18)	−0.0002 (13)	0.0029 (14)	0.0034 (13)
C27	0.0371 (18)	0.0395 (18)	0.0462 (19)	0.0042 (14)	−0.0024 (15)	0.0013 (14)
C28	0.0311 (17)	0.0384 (17)	0.0475 (19)	0.0008 (13)	−0.0022 (14)	−0.0066 (14)
C29	0.0277 (16)	0.0303 (16)	0.0483 (18)	−0.0006 (12)	0.0049 (14)	−0.0055 (13)
C30	0.0240 (15)	0.0278 (15)	0.0401 (17)	0.0020 (11)	0.0055 (13)	−0.0051 (12)
C31	0.0250 (15)	0.0234 (14)	0.0416 (17)	0.0023 (11)	0.0095 (13)	−0.0047 (12)
C32	0.0227 (14)	0.0242 (14)	0.0405 (16)	0.0004 (11)	0.0059 (12)	−0.0039 (12)
C33	0.0313 (16)	0.0294 (15)	0.0446 (18)	−0.0043 (13)	−0.0009 (13)	−0.0040 (13)
C34	0.0383 (18)	0.0347 (17)	0.0440 (18)	0.0003 (14)	−0.0001 (14)	0.0010 (14)
C35	0.046 (2)	0.0380 (18)	0.0495 (19)	0.0035 (15)	−0.0053 (16)	−0.0038 (15)
C36	0.056 (2)	0.047 (2)	0.052 (2)	0.0065 (17)	−0.0088 (17)	−0.0009 (16)

Geometric parameters (Å, º) top

O1—C1	1.345 (3)	C16—H16A	0.9900
O1—H1O	0.848 (18)	C16—H16B	0.9900
C1—C14	1.390 (4)	C17—C18	1.520 (4)
C1—C2	1.431 (4)	C17—H17A	0.9900
O2—C2	1.356 (3)	C17—H17B	0.9900
O2—C15	1.450 (3)	C18—H18A	0.9800
C2—C3	1.372 (4)	C18—H18B	0.9800
O3—C4	1.344 (3)	C18—H18C	0.9800
O3—H3O	0.870 (17)	C19—C32	1.377 (4)
C3—C4	1.404 (4)	C19—C20	1.432 (4)
C3—H3	0.9500	C20—C21	1.370 (4)
O4—C6	1.251 (3)	C21—C22	1.402 (4)
C4—C5	1.399 (4)	C21—H21	0.9500
O5—C13	1.249 (3)	C22—C23	1.400 (4)
C5—C14	1.420 (4)	C23—C32	1.426 (4)
C5—C6	1.453 (4)	C23—C24	1.441 (4)
O6—C19	1.349 (3)	C24—C25	1.486 (4)
O6—H6O	0.863 (18)	C25—C26	1.392 (4)
C6—C7	1.485 (4)	C25—C30	1.401 (4)
O7—C20	1.348 (3)	C26—C27	1.388 (4)
O7—C33	1.453 (3)	C26—H26	0.9500
C7—C8	1.393 (4)	C27—C28	1.384 (4)
C7—C12	1.396 (4)	C27—H27	0.9500
O8—C22	1.354 (3)	C28—C29	1.384 (4)
O8—H8O	0.874 (17)	C28—H28	0.9500
C8—C9	1.390 (4)	C29—C30	1.392 (4)
C8—H8	0.9500	C29—H29	0.9500
O9—C24	1.253 (3)	C30—C31	1.469 (4)
C9—C10	1.391 (4)	C31—C32	1.462 (4)
C9—H9	0.9500	C33—C34	1.512 (4)
O10—C31	1.254 (3)	C33—H33A	0.9900
C10—C11	1.381 (4)	C33—H33B	0.9900
C10—H10	0.9500	C34—C35	1.517 (4)
C11—C12	1.399 (4)	C34—H34A	0.9900
C11—H11	0.9500	C34—H34B	0.9900
C12—C13	1.479 (4)	C35—C36	1.531 (4)
C13—C14	1.460 (4)	C35—H35A	0.9900
C15—C16	1.510 (4)	C35—H35B	0.9900
C15—H15B	0.9900	C36—H36A	0.9800
C15—H15A	0.9900	C36—H36B	0.9800
C16—C17	1.518 (4)	C36—H36C	0.9800

C1—O1—H1O	103 (2)	C17—C18—H18C	109.5
O1—C1—C14	123.8 (2)	H18A—C18—H18C	109.5
O1—C1—C2	116.9 (2)	H18B—C18—H18C	109.5
C14—C1—C2	119.3 (2)	O6—C19—C32	123.3 (2)
C2—O2—C15	116.7 (2)	O6—C19—C20	116.6 (2)
O2—C2—C3	125.4 (2)	C32—C19—C20	120.1 (2)
O2—C2—C1	114.2 (2)	O7—C20—C21	125.8 (3)
C3—C2—C1	120.4 (2)	O7—C20—C19	114.4 (2)
C4—O3—H3O	105 (2)	C21—C20—C19	119.9 (3)
C2—C3—C4	120.3 (2)	C20—C21—C22	120.1 (3)
C2—C3—H3	119.9	C20—C21—H21	120.0
C4—C3—H3	119.9	C22—C21—H21	120.0
O3—C4—C5	121.9 (2)	O8—C22—C23	121.4 (3)
O3—C4—C3	117.5 (2)	O8—C22—C21	117.3 (2)
C5—C4—C3	120.5 (2)	C23—C22—C21	121.3 (2)
C4—C5—C14	119.2 (2)	C22—C23—C32	118.2 (2)
C4—C5—C6	119.6 (2)	C22—C23—C24	120.4 (2)
C14—C5—C6	121.2 (2)	C32—C23—C24	121.4 (2)
C19—O6—H6O	100 (2)	O9—C24—C23	122.1 (3)
O4—C6—C5	121.7 (2)	O9—C24—C25	119.7 (3)
O4—C6—C7	120.1 (2)	C23—C24—C25	118.2 (2)
C5—C6—C7	118.2 (2)	C26—C25—C30	119.3 (3)
C20—O7—C33	118.4 (2)	C26—C25—C24	119.9 (3)
C8—C7—C12	119.9 (3)	C30—C25—C24	120.8 (3)
C8—C7—C6	119.6 (2)	C27—C26—C25	120.3 (3)
C12—C7—C6	120.6 (2)	C27—C26—H26	119.8
C22—O8—H8O	103 (2)	C25—C26—H26	119.8
C9—C8—C7	119.9 (3)	C28—C27—C26	120.2 (3)
C9—C8—H8	120.1	C28—C27—H27	119.9
C7—C8—H8	120.1	C26—C27—H27	119.9
C8—C9—C10	120.4 (3)	C27—C28—C29	120.1 (3)
C8—C9—H9	119.8	C27—C28—H28	120.0
C10—C9—H9	119.8	C29—C28—H28	120.0
C11—C10—C9	119.9 (3)	C28—C29—C30	120.2 (3)
C11—C10—H10	120.1	C28—C29—H29	119.9
C9—C10—H10	120.1	C30—C29—H29	119.9
C10—C11—C12	120.3 (3)	C29—C30—C25	119.9 (3)
C10—C11—H11	119.9	C29—C30—C31	119.5 (3)
C12—C11—H11	119.9	C25—C30—C31	120.6 (3)
C7—C12—C11	119.7 (2)	O10—C31—C32	121.0 (3)
C7—C12—C13	121.1 (2)	O10—C31—C30	120.2 (2)
C11—C12—C13	119.2 (2)	C32—C31—C30	118.9 (2)
O5—C13—C14	121.7 (2)	C19—C32—C23	120.5 (2)
O5—C13—C12	120.0 (2)	C19—C32—C31	119.5 (2)
C14—C13—C12	118.2 (2)	C23—C32—C31	120.0 (2)
C1—C14—C5	120.3 (2)	O7—C33—C34	106.5 (2)
C1—C14—C13	119.1 (2)	O7—C33—H33A	110.4
C5—C14—C13	120.6 (2)	C34—C33—H33A	110.4
O2—C15—C16	107.4 (2)	O7—C33—H33B	110.4
O2—C15—H15B	110.2	C34—C33—H33B	110.4
C16—C15—H15B	110.2	H33A—C33—H33B	108.6
O2—C15—H15A	110.2	C33—C34—C35	112.9 (2)
C16—C15—H15A	110.2	C33—C34—H34A	109.0
H15B—C15—H15A	108.5	C35—C34—H34A	109.0
C15—C16—C17	113.7 (2)	C33—C34—H34B	109.0
C15—C16—H16A	108.8	C35—C34—H34B	109.0
C17—C16—H16A	108.8	H34A—C34—H34B	107.8
C15—C16—H16B	108.8	C34—C35—C36	110.9 (3)
C17—C16—H16B	108.8	C34—C35—H35A	109.5
H16A—C16—H16B	107.7	C36—C35—H35A	109.5
C16—C17—C18	113.3 (3)	C34—C35—H35B	109.5
C16—C17—H17A	108.9	C36—C35—H35B	109.5
C18—C17—H17A	108.9	H35A—C35—H35B	108.1
C16—C17—H17B	108.9	C35—C36—H36A	109.5
C18—C17—H17B	108.9	C35—C36—H36B	109.5
H17A—C17—H17B	107.7	H36A—C36—H36B	109.5
C17—C18—H18A	109.5	C35—C36—H36C	109.5
C17—C18—H18B	109.5	H36A—C36—H36C	109.5
H18A—C18—H18B	109.5	H36B—C36—H36C	109.5

C15—O2—C2—C3	2.6 (4)	C33—O7—C20—C21	0.9 (4)
C15—O2—C2—C1	−176.8 (2)	C33—O7—C20—C19	−179.4 (2)
O1—C1—C2—O2	−0.6 (3)	O6—C19—C20—O7	1.7 (4)
C14—C1—C2—O2	178.7 (2)	C32—C19—C20—O7	−178.9 (2)
O1—C1—C2—C3	179.9 (2)	O6—C19—C20—C21	−178.5 (2)
C14—C1—C2—C3	−0.7 (4)	C32—C19—C20—C21	0.8 (4)
O2—C2—C3—C4	−179.2 (2)	O7—C20—C21—C22	178.6 (3)
C1—C2—C3—C4	0.2 (4)	C19—C20—C21—C22	−1.1 (4)
C2—C3—C4—O3	−179.2 (2)	C20—C21—C22—O8	−177.9 (2)
C2—C3—C4—C5	0.6 (4)	C20—C21—C22—C23	1.0 (4)
O3—C4—C5—C14	178.8 (2)	O8—C22—C23—C32	178.2 (2)
C3—C4—C5—C14	−1.0 (4)	C21—C22—C23—C32	−0.7 (4)
O3—C4—C5—C6	0.4 (4)	O8—C22—C23—C24	−1.7 (4)
C3—C4—C5—C6	−179.4 (2)	C21—C22—C23—C24	179.4 (3)
C4—C5—C6—O4	−0.1 (4)	C22—C23—C24—O9	−0.4 (4)
C14—C5—C6—O4	−178.5 (3)	C32—C23—C24—O9	179.7 (3)
C4—C5—C6—C7	179.8 (2)	C22—C23—C24—C25	178.4 (3)
C14—C5—C6—C7	1.4 (4)	C32—C23—C24—C25	−1.5 (4)
O4—C6—C7—C8	−0.8 (4)	O9—C24—C25—C26	−0.3 (4)
C5—C6—C7—C8	179.3 (2)	C23—C24—C25—C26	−179.1 (3)
O4—C6—C7—C12	178.8 (3)	O9—C24—C25—C30	179.0 (3)
C5—C6—C7—C12	−1.0 (4)	C23—C24—C25—C30	0.2 (4)
C12—C7—C8—C9	0.1 (4)	C30—C25—C26—C27	−1.4 (4)
C6—C7—C8—C9	179.8 (3)	C24—C25—C26—C27	178.0 (3)
C7—C8—C9—C10	−0.8 (4)	C25—C26—C27—C28	1.6 (5)
C8—C9—C10—C11	1.5 (4)	C26—C27—C28—C29	−0.9 (5)
C9—C10—C11—C12	−1.6 (4)	C27—C28—C29—C30	0.1 (4)
C8—C7—C12—C11	−0.2 (4)	C28—C29—C30—C25	0.1 (4)
C6—C7—C12—C11	−179.9 (2)	C28—C29—C30—C31	178.8 (3)
C8—C7—C12—C13	179.3 (2)	C26—C25—C30—C29	0.6 (4)
C6—C7—C12—C13	−0.3 (4)	C24—C25—C30—C29	−178.8 (3)
C10—C11—C12—C7	1.0 (4)	C26—C25—C30—C31	−178.2 (3)
C10—C11—C12—C13	−178.6 (2)	C24—C25—C30—C31	2.5 (4)
C7—C12—C13—O5	−178.4 (3)	C29—C30—C31—O10	−2.8 (4)
C11—C12—C13—O5	1.2 (4)	C25—C30—C31—O10	176.0 (2)
C7—C12—C13—C14	1.3 (4)	C29—C30—C31—C32	177.3 (3)
C11—C12—C13—C14	−179.1 (2)	C25—C30—C31—C32	−3.9 (4)
O1—C1—C14—C5	179.7 (2)	O6—C19—C32—C23	178.8 (2)
C2—C1—C14—C5	0.4 (4)	C20—C19—C32—C23	−0.5 (4)
O1—C1—C14—C13	−1.0 (4)	O6—C19—C32—C31	−0.9 (4)
C2—C1—C14—C13	179.6 (2)	C20—C19—C32—C31	179.8 (2)
C4—C5—C14—C1	0.5 (4)	C22—C23—C32—C19	0.5 (4)
C6—C5—C14—C1	178.9 (2)	C24—C23—C32—C19	−179.6 (3)
C4—C5—C14—C13	−178.8 (2)	C22—C23—C32—C31	−179.9 (2)
C6—C5—C14—C13	−0.4 (4)	C24—C23—C32—C31	0.0 (4)
O5—C13—C14—C1	−0.6 (4)	O10—C31—C32—C19	2.4 (4)
C12—C13—C14—C1	179.7 (2)	C30—C31—C32—C19	−177.7 (2)
O5—C13—C14—C5	178.7 (3)	O10—C31—C32—C23	−177.2 (2)
C12—C13—C14—C5	−1.0 (4)	C30—C31—C32—C23	2.7 (4)
C2—O2—C15—C16	176.7 (2)	C20—O7—C33—C34	−167.3 (2)
O2—C15—C16—C17	−65.1 (3)	O7—C33—C34—C35	−174.3 (3)
C15—C16—C17—C18	−173.1 (2)	C33—C34—C35—C36	−175.2 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O5	0.85 (2)	1.78 (2)	2.564 (3)	153 (3)
O3—H3O···O4	0.87 (2)	1.74 (2)	2.536 (3)	151 (3)
O6—H6O···O10	0.86 (2)	1.72 (2)	2.542 (3)	158 (3)
O8—H8O···O9	0.87 (2)	1.73 (2)	2.554 (3)	155 (3)
C3—H3···O10	0.95	2.55	3.494 (3)	173
C29—H29···O3	0.95	2.41	3.231 (4)	144
C15—H15B···O6ⁱ	0.99	2.52	3.485 (3)	164
C21—H21···O8ⁱⁱ	0.95	2.55	3.502 (3)	180
C33—H33A···O9ⁱⁱⁱ	0.99	2.56	3.547 (4)	172

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

Acknowledgements

We thank the Missouri State University Provost Incentive Fund that funded the purchase of the X-ray diffractometer.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS
Bergerhoff, G. & Wunderlich, C. H. (1993). Z. Kristallogr. 207, 189–192. CAS
Bruker (2014). SMART, SAINT, and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002). Acta Cryst. B58, 389–397. Web of Science CSD CrossRef CAS IUCr Journals
Das, P., Jain, C. K., Dey, S. K., Saha, R., Chowdhury, A. D., Roychoudhury, S., Kumar, S., Majumder, H. K. & Das, S. (2014). RSC Adv. 4, 59344–59357. CSD CrossRef CAS
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CSD CrossRef IUCr Journals
Muangsin, N., Wisetsakdakorn, W., Chaichit, N., Sihanonth, P., Petsom, A. & Sangvanich, P. (2008). Dyes Pigments, 77, 653–656. CSD CrossRef CAS
Sathiyendiran, M., Liao, R. T., Thanasekaran, P., Luo, T. T., Venkataramanan, N. S., Lee, G. H., Peng, S. M. & Lu, K. L. (2006). Inorg. Chem. 45, 10052–10054. CSD CrossRef PubMed CAS
Sathiyendiran, M., Tsai, C. C., Thanasekaran, P., Luo, T. T., Yang, C. I., Lee, G. H., Peng, S. M. & Lu, K. L. (2011). Chem. Eur. J. 17, 3343–3346. CSD CrossRef CAS PubMed
Schweppe, H. & Winter, J. (1997). Artists Pigments, 3, edited by E. W. Fitzhugh, pp. 109–142. New York: Oxford University Press.
She, Z.-G., Huang, H.-R., Lin, Y.-C., Vrijmoed, L. L. P. & Jones, E. B. G. (2006). Acta Cryst. E62, o3737–o3738. CSD CrossRef IUCr Journals
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals
Sousa, A. T. de, Bessler, K. E., Lemos, S. S., Ellena, J. & Gatto, C. C. (2009). Z. Anorg. Allg. Chem. 635, 106–111.
Yatsenko, A. V., Chernyshev, V. V., Popov, S. I., Sonneveld, E. J. & Schenk, H. (2000). Dyes Pigments, 45, 169–176. CSD CrossRef CAS

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Volume 73| Part 11| November 2017| Pages 1687-1691

https://doi.org/10.1107/S2056989017014724

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Synthesis and crystal structures of two purpurin derivatives: 1,4-dihy­dr­oxy-2-propoxyanthra­quinone and 2-but­­oxy-1,4-di­hy­droxy­anthra­quinone

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

Acknowledgements

References

research communications

Synthesis and crystal structures of two purpurin derivatives: 1,4-dihydroxy-2-propoxyanthraquinone and 2-butoxy-1,4-dihydroxyanthraquinone

3. Supramolecular features