Crystal structures of two hydrogen-bonded compounds of chloranilic acid–ethyl­eneurea (1/1) and chloranilic acid–hydantoin (1/2)

Gotoh, K.; Ishida, H.

doi:10.1107/S205698901801561X

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ISSN: 2056-9890

Volume 74| Part 12| December 2018| Pages 1727-1730

https://doi.org/10.1107/S205698901801561X

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Crystal structures of two hydrogen-bonded compounds of chloranilic acid–ethyleneurea (1/1) and chloranilic acid–hydantoin (1/2)

Kazuma Gotoh ^a and Hiroyuki Ishida ^a ^*

^aDepartment of Chemistry, Faculty of Science, Okayama University, Okayama 700-8530, Japan
^*Correspondence e-mail: ishidah@cc.okayama-u.ac.jp

Edited by A. J. Lough, University of Toronto, Canada (Received 29 October 2018; accepted 4 November 2018; online 9 November 2018)

The structures of the hydrogen-bonded 1:1 co-crystal of chloranilic acid (systematic name: 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone) with ethyleneurea (systematic name: imidazolidin-2-one), C₆H₂Cl₂O₄·C₃H₆N₂O, (I), and the 1:2 co-crystal of chloranilic acid with hydantoin (systematic name: imidazolidine-2,4-dione), C₆H₂Cl₂O₄·2C₃H₄N₂O₂, (II), have been determined at 180 K. In the crystals of both compounds, the base molecules are in the lactam form and no acid–base interaction involving H-atom transfer is observed. The asymmetric unit of (I) consists of two independent half-molecules of chloranilic acid, with each of the acid molecules lying about an inversion centre, and one ethyleneurea molecule. The asymmetric unit of (II) consists of one half-molecule of chloranilic acid, which lies about an inversion centre, and one hydantoin molecule. In the crystal of (I), the acid and base molecules are linked via O—H⋯O and N—H⋯O hydrogen bonds, forming an undulating sheet structure parallel to the ab plane. In (II), the base molecules form an inversion dimer via a pair of N—H⋯O hydrogen bonds, and the base dimers are further linked through another N—H⋯O hydrogen bond into a layer structure parallel to ( $[\overline{1}]$ 01). The acid molecule and the base molecule are linked via an O—H⋯O hydrogen bond.

Keywords: crystal structure; chloranilic acid; ethyleneurea; imidazolidin-2-one; hydantoin; imidazolidine-2,4-dione; hydrogen bond.

CCDC references: 1876998; 1876997

1. Chemical context

Chloranilic acid, a dibasic acid with hydrogen-bond donor as well as acceptor groups, appears particularly attractive as a template for generating tightly bound self-assemblies with various organic bases, and also as a model compound for investigating hydrogen-transfer motions in O—H⋯N and N—H⋯O hydrogen-bonded systems (Zaman et al., 2004 ; Seliger et al., 2009 ; Asaji et al. 2010 ; Molčanov & Kojić-Prodić, 2010 ). In the present study, we have prepared two hydrogen-bonded compounds of chloranilic acid–ethyleneurea (1/1) and chloranilic acid–hydantoin (1/2) in order to extend our study on D—H⋯A hydrogen bonding (D = N, O, or C; A = N, O or Cl) in chloranilic acid–organic base systems (Gotoh & Ishida, 2017a ,b , and references therein).

2. Structural commentary

In compound (I), the base molecule is in the lactam form and no acid–base interaction involving H-atom transfer is observed (Fig. 1). In the asymmetric unit, there is one ethyleneurea molecule and two crystallographically independent half-molecules of chloranilic acid, with each of the acid molecules lying about an inversion centre. The O atom of ethyleneurea participates in two O—H⋯O hydrogen bonds as an acceptor for two O—H groups of chloranilic acid (O2—H2⋯O5 and O4—H4⋯O5; Table 1). The base ring (C7/N1/C8/C9/N2) is essentially planar and makes dihedral angles of 88.75 (6) and 3.27 (6)°, respectively, with the acid C1–C3/C1ⁱⁱⁱ–C3ⁱⁱⁱ and C4–C6/C4ⁱⁱ–C6ⁱⁱ rings [symmetry codes: (ii) −x, −y + 1, −z + 1; (iii) −x + 1, −y, −z + 1].

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O5	0.81 (2)	1.82 (2)	2.6090 (11)	164 (2)
O4—H4⋯O5	0.86 (2)	1.88 (2)	2.6635 (12)	151.0 (19)
N1—H1N⋯O1ⁱ	0.85 (2)	2.06 (2)	2.9003 (15)	168 (2)
N2—H2N⋯O3ⁱⁱ	0.85 (2)	2.06 (2)	2.8654 (15)	158.6 (17)
Symmetry codes: (i) -x+2, -y, -z+1; (ii) -x, -y+1, -z+1.

Figure 1
The molecular structure of compound (I)

, showing the atom-numbering scheme. Displacement ellipsoids of non-H atoms are drawn at the 50% probability level and H atoms are drawn as small spheres of arbitrary radii. O—H⋯O and N—H⋯O hydrogen bonds are shown by dashed lines. [Symmetry codes: (ii) −x, −y + 1, −z + 1; (iii) −x + 1, −y, −z + 1.]

In compound (II), the base molecule is also in the lactam form and no acid–base interaction involving H-atom transfer is observed (Fig. 2). The chloranilic acid molecule is located on an inversion centre and the asymmetric unit consists of one hydantoin molecule and a half-molecule of chloranilic acid. The acid and base molecules are linked via an O—H⋯O hydrogen bond (O2—H2⋯O3; Table 2), forming a centrosymmetric 1:2 aggregate of the acid and the base. The 1:2 unit is approximately planar with a dihedral angle of 5.42 (5)° between the acid and base rings.

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O3	0.86 (2)	1.97 (2)	2.7917 (15)	160 (2)
N1—H1N⋯O3ⁱ	0.91 (2)	2.00 (2)	2.8927 (13)	165 (2)
N2—H2N⋯O4ⁱⁱ	0.91 (2)	1.85 (2)	2.7560 (14)	176 (2)
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
The molecular structure of compound (II)

, showing the atom-numbering scheme. Displacement ellipsoids of non-H atoms are drawn at the 50% probability level and H atoms are drawn as small spheres of arbitrary radii. O—H⋯O hydrogen bonds are shown by dashed lines. [Symmetry code: (iii) −x + $[{1\over 2}]$ , −y + $[{5\over 2}]$ , −z + 1.]

3. Supramolecular features

In the crystal of compound (I), the acid and base molecules are alternately arranged through O—H⋯O and N—H⋯O hydrogen bonds (O4—H4⋯O5, N1—H1N⋯O1ⁱ, N2—H2H⋯O3ⁱⁱ; symmetry codes as in Table 1), forming an undulating tape structure along [3 $[\overline{1}]$ 0]. The tapes are stacked along the a axis via another O—H⋯O hydrogen bond (O2—H2—O5; Table 1) into a sheet structure parallel to the ab plane (Fig. 3).

Figure 3
A partial packing diagram of compound (I)

, showing the undulating sheet structure formed by O—H⋯O and N—H⋯O hydrogen bonds (light-blue dotted lines). [Symmetry code: (ii) −x, −y + 1, −z + 1.]

In the crystal of (II), two adjacent base molecules, which are related by an inversion centre, form a dimer via a pair of N—H⋯O hydrogen bonds (N1—H1N⋯O3ⁱ; symmetry code as in Table 2), and the base dimer and the acid molecule are alternately linked through an O—H⋯O hydrogen bond (O2—H2⋯O3; Table 2), forming a flat tape structure along the a-axis direction (Fig. 4). The base dimers are assembled via another N—H⋯O hydrogen bond (N2—H2N⋯O4ⁱⁱ; symmetry code as in Table 2), forming a layer parallel to ( $[\overline{1}]$ 01) as shown in Fig. 5. The O—H⋯O hydrogen bond (O2—H2⋯O3; Table 2) formed between the acid and base molecules links the layers.

Figure 4
A partial packing diagram of compound (II)

viewed approximately along the b axis, showing a hydrogen-bonded tape structure formed by acid molecules and pairs of base molecules. O—H⋯O and N—H⋯O hydrogen bonds are shown by light-blue dotted lines. [Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (iii) −x + $[{1\over 2}]$ , −y + $[{5\over 2}]$ , −z + 1.]

Figure 5
A partial packing diagram of compound (II)

, showing hydrogen-bonding scheme in the layer formed by base molecules. N—H⋯O hydrogen bonds between the base molecules are shown by light-blue dotted lines, while O—H⋯O hydrogen bonds between the base and acid molecules are shown by red dotted lines. [Symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) −x + $[{1\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (iv) −x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ .]

4. Database survey

A search of the Cambridge Structural Database (Version 5.39, last update August 2018; Groom et al., 2016 ) for organic crystals of chloranilic acid with lactam-form base molecules gave ten hits. In the seven crystals of these compounds, O—H⋯O hydrogen bonds between the O—H group of chloranilic acid and the carbonyl group of base are observed [refcodes ACOJIO (Gotoh & Ishida, 2017a), AJAGIB (Luo & Palmore, 2002 ), HUFZUE (Jasinski et al., 2010 ), ODIHIU, SADTIC, SADTOI and SADTUO (Gotoh & Ishida, 2011 )]. In particular, the compounds of chloranilic acid with 2-pyridone (ACOJIO), gabapentin-lactum (HUFZUE), pyrrolidin-2-one (ODIHIU) and piperidin-2-one (SADTUO) show short O—H⋯O hydrogen bonds (O⋯O shorter than 2.5 Å). In the O—H⋯O hydrogen bond [O⋯O = 2.4484 (10) Å] of chloranilic acid–piperidin-2-one (1/2) (SADTUO), the H atom is disordered over two positions.

5. Synthesis and crystallization

Single crystals of compound (I) were obtained by slow evaporation from an acetonitrile solution (150 ml) of chloranilic acid (330 mg) with ethyleneurea (140 mg) at room temperature. Crystals of compound (II) were obtained by slow evaporation from an acetonitrile solution (250 ml) of chloranilic acid (350 mg) with hydantoin (340 mg) at room temperature.

6. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3. All H atoms in compounds (I) and (II) were found in difference Fourier maps. The O- and N-bound H atoms were freely refined. C-bound H atoms were positioned geometrically (C—H = 0.99 Å) and were treated as riding with U_iso(H) = 1.2U_eq(C).

Table 3
Experimental details

	(I)	(II)
Crystal data
Chemical formula	C₆H₂Cl₂O₄·C₃H₆N₂O	C₆H₂Cl₂O₄·2C₃H₄N₂O₂
M_r	295.08	409.14
Crystal system, space group	Monoclinic, P2₁/c	Monoclinic, C2/c
Temperature (K)	180	180
a, b, c (Å)	5.0180 (4), 14.6142 (10), 15.8882 (11)	19.5690 (8), 5.18661 (10), 16.6103 (3)
β (°)	105.563 (3)	117.965 (3)
V (Å³)	1122.43 (15)	1489.03 (8)
Z	4	4
Radiation type	Mo Kα	Mo Kα
μ (mm⁻¹)	0.59	0.49
Crystal size (mm)	0.45 × 0.29 × 0.23	0.49 × 0.33 × 0.24

Data collection
Diffractometer	Rigaku R-AXIS RAPIDII	Rigaku R-AXIS RAPIDII
Absorption correction	Numerical (NUMABS; Higashi, 1999 )	Numerical (NUMABS; Higashi, 1999)
T_min, T_max	0.716, 0.873	0.808, 0.888
No. of measured, independent and observed [I > 2σ(I)] reflections	21546, 3266, 3040	14622, 2181, 2029
R_int	0.057	0.072
(sin θ/λ)_max (Å⁻¹)	0.704	0.704

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.033, 0.092, 1.07	0.036, 0.100, 1.08
No. of reflections	3266	2181
No. of parameters	179	130
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)	0.54, −0.31	0.44, −0.40
Computer programs: RAPID-AUTO (Rigaku, 2006 ), SIR92 (Altomare et al., 1993 ), SHELXT2018 (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2006 ), CrystalStructure (Rigaku, 2018 ) and PLATON (Spek, 2015 ).

Supporting information

CCDC references: 1876998; 1876997

Crystal structure: contains datablocks General, I, II. DOI: https://doi.org/10.1107/S205698901801561X/lh5884sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S205698901801561X/lh5884Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S205698901801561X/lh5884IIsup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S205698901801561X/lh5884Isup4.cml

Supporting information file. DOI: https://doi.org/10.1107/S205698901801561X/lh5884IIsup5.cml

checkCIF report

Computing details top

For both structures, data collection: RAPID-AUTO (Rigaku, 2006); cell refinement: RAPID-AUTO (Rigaku, 2006); data reduction: RAPID-AUTO (Rigaku, 2006). Program(s) used to solve structure: SIR92 (Altomare et al., 1993) for (I); SHELXT2018 (Sheldrick, 2015a) for (II). For both structures, program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: CrystalStructure (Rigaku, 2018) and PLATON (Spek, 2015).

2,5-Dichloro-3,6-dihydroxy-1,4-benzoquinone–imidazolidin-2-one (1/1) (I) top

Crystal data top

C₆H₂Cl₂O₄·C₃H₆N₂O	F(000) = 600.00
M_r = 295.08	D_x = 1.746 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71075 Å
a = 5.0180 (4) Å	Cell parameters from 19204 reflections
b = 14.6142 (10) Å	θ = 3.0–30.1°
c = 15.8882 (11) Å	µ = 0.59 mm⁻¹
β = 105.563 (3)°	T = 180 K
V = 1122.43 (15) Å³	Block, brown
Z = 4	0.45 × 0.29 × 0.23 mm

Data collection top

Rigaku R-AXIS RAPIDII diffractometer	3040 reflections with I > 2σ(I)
Detector resolution: 10.000 pixels mm^-1	R_int = 0.057
ω scans	θ_max = 30.0°, θ_min = 3.0°
Absorption correction: numerical (NUMABS; Higashi, 1999)	h = −7→7
T_min = 0.716, T_max = 0.873	k = −20→19
21546 measured reflections	l = −21→22
3266 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.033	Hydrogen site location: mixed
wR(F²) = 0.092	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0573P)² + 0.2007P] where P = (F_o² + 2F_c²)/3
3266 reflections	(Δ/σ)_max = 0.001
179 parameters	Δρ_max = 0.54 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³
Primary atom site location: structure-invariant direct methods

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
Cl1	1.06653 (5)	0.00389 (2)	0.64704 (2)	0.02517 (9)
Cl2	0.28647 (6)	0.43040 (2)	0.69108 (2)	0.03101 (9)
O1	0.64834 (18)	−0.14266 (6)	0.60507 (6)	0.03198 (19)
O2	0.83758 (17)	0.15225 (5)	0.51887 (5)	0.02612 (17)
O3	−0.17821 (19)	0.55990 (6)	0.63245 (6)	0.03138 (19)
O4	0.43441 (18)	0.37722 (6)	0.52805 (6)	0.03039 (19)
O5	0.70481 (17)	0.29928 (5)	0.42370 (5)	0.02644 (17)
N1	0.8521 (2)	0.24152 (9)	0.30842 (7)	0.0372 (3)
N2	0.4933 (2)	0.33134 (8)	0.27881 (7)	0.0323 (2)
C1	0.5873 (2)	−0.07583 (7)	0.55745 (7)	0.02118 (19)
C2	0.7619 (2)	0.00483 (7)	0.56565 (7)	0.02058 (19)
C3	0.6846 (2)	0.07805 (7)	0.51226 (6)	0.02064 (19)
C4	−0.0902 (2)	0.53136 (7)	0.57314 (7)	0.0233 (2)
C5	0.1390 (2)	0.46653 (7)	0.58624 (7)	0.0238 (2)
C6	0.2263 (2)	0.43578 (7)	0.51801 (7)	0.0236 (2)
C7	0.6858 (2)	0.29121 (7)	0.34329 (7)	0.0224 (2)
C8	0.7865 (2)	0.24974 (8)	0.21442 (8)	0.0275 (2)
H8A	0.737465	0.189643	0.185683	0.033*
H8B	0.943169	0.276222	0.195803	0.033*
C9	0.5369 (3)	0.31466 (9)	0.19376 (8)	0.0325 (2)
H9A	0.578932	0.372186	0.166986	0.039*
H9B	0.372898	0.285493	0.153938	0.039*
H1N	0.989 (4)	0.2121 (14)	0.3405 (14)	0.059 (6)*
H2N	0.381 (4)	0.3687 (13)	0.2915 (12)	0.041 (5)*
H2	0.766 (4)	0.1933 (16)	0.4861 (14)	0.056 (6)*
H4	0.476 (4)	0.3613 (13)	0.4811 (13)	0.045 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02251 (14)	0.02897 (15)	0.02081 (14)	−0.00049 (8)	0.00027 (10)	0.00183 (8)
Cl2	0.03685 (16)	0.03457 (16)	0.02165 (15)	0.00812 (10)	0.00789 (11)	0.00275 (9)
O1	0.0284 (4)	0.0277 (4)	0.0345 (4)	−0.0009 (3)	−0.0007 (3)	0.0114 (3)
O2	0.0273 (4)	0.0226 (4)	0.0252 (4)	−0.0031 (3)	0.0014 (3)	0.0039 (3)
O3	0.0355 (4)	0.0356 (4)	0.0262 (4)	0.0082 (3)	0.0138 (3)	−0.0009 (3)
O4	0.0333 (4)	0.0350 (4)	0.0243 (4)	0.0124 (3)	0.0100 (3)	0.0016 (3)
O5	0.0319 (4)	0.0244 (4)	0.0230 (4)	0.0017 (3)	0.0071 (3)	0.0006 (3)
N1	0.0378 (6)	0.0468 (6)	0.0272 (5)	0.0224 (5)	0.0093 (4)	0.0057 (4)
N2	0.0336 (5)	0.0411 (5)	0.0240 (5)	0.0163 (4)	0.0106 (4)	0.0045 (4)
C1	0.0207 (4)	0.0220 (4)	0.0204 (4)	0.0018 (3)	0.0047 (3)	0.0012 (3)
C2	0.0192 (4)	0.0236 (5)	0.0178 (4)	0.0012 (3)	0.0029 (3)	0.0002 (3)
C3	0.0215 (4)	0.0221 (4)	0.0181 (4)	0.0003 (3)	0.0049 (3)	−0.0006 (3)
C4	0.0253 (5)	0.0233 (5)	0.0225 (5)	−0.0001 (4)	0.0083 (4)	−0.0004 (4)
C5	0.0260 (5)	0.0245 (5)	0.0213 (5)	0.0019 (4)	0.0070 (4)	0.0010 (4)
C6	0.0244 (5)	0.0231 (5)	0.0240 (5)	0.0016 (3)	0.0077 (4)	0.0002 (3)
C7	0.0239 (4)	0.0191 (4)	0.0246 (5)	−0.0005 (3)	0.0070 (4)	0.0021 (3)
C8	0.0254 (5)	0.0315 (5)	0.0275 (5)	0.0034 (4)	0.0100 (4)	−0.0007 (4)
C9	0.0346 (6)	0.0416 (6)	0.0240 (5)	0.0125 (5)	0.0127 (4)	0.0075 (4)

Geometric parameters (Å, º) top

Cl1—C2	1.7169 (10)	N2—C9	1.4464 (15)
Cl2—C5	1.7145 (11)	N2—H2N	0.849 (19)
O1—C1	1.2230 (13)	C1—C2	1.4537 (14)
O2—C3	1.3165 (12)	C1—C3ⁱ	1.5092 (14)
O2—H2	0.81 (2)	C2—C3	1.3560 (14)
O3—C4	1.2168 (13)	C4—C5	1.4612 (14)
O4—C6	1.3264 (12)	C4—C6ⁱⁱ	1.5045 (15)
O4—H4	0.86 (2)	C5—C6	1.3504 (15)
O5—C7	1.2609 (13)	C8—C9	1.5348 (15)
N1—C7	1.3338 (14)	C8—H8A	0.9900
N1—C8	1.4455 (15)	C8—H8B	0.9900
N1—H1N	0.85 (2)	C9—H9A	0.9900
N2—C7	1.3397 (14)	C9—H9B	0.9900

C3—O2—H2	114.1 (14)	C6—C5—Cl2	121.94 (8)
C6—O4—H4	115.8 (13)	C4—C5—Cl2	117.13 (8)
C7—N1—C8	112.92 (10)	O4—C6—C5	122.18 (10)
C7—N1—H1N	121.2 (15)	O4—C6—C4ⁱⁱ	117.46 (9)
C8—N1—H1N	125.7 (15)	C5—C6—C4ⁱⁱ	120.35 (9)
C7—N2—C9	112.46 (10)	O5—C7—N1	125.87 (10)
C7—N2—H2N	119.3 (12)	O5—C7—N2	125.24 (10)
C9—N2—H2N	127.5 (12)	N1—C7—N2	108.88 (10)
O1—C1—C2	123.17 (9)	N1—C8—C9	102.65 (9)
O1—C1—C3ⁱ	117.64 (9)	N1—C8—H8A	111.2
C2—C1—C3ⁱ	119.19 (8)	C9—C8—H8A	111.2
C3—C2—C1	121.28 (9)	N1—C8—H8B	111.2
C3—C2—Cl1	121.68 (8)	C9—C8—H8B	111.2
C1—C2—Cl1	117.03 (7)	H8A—C8—H8B	109.2
O2—C3—C2	122.48 (9)	N2—C9—C8	102.92 (9)
O2—C3—C1ⁱ	117.99 (9)	N2—C9—H9A	111.2
C2—C3—C1ⁱ	119.53 (9)	C8—C9—H9A	111.2
O3—C4—C5	123.19 (10)	N2—C9—H9B	111.2
O3—C4—C6ⁱⁱ	118.08 (10)	C8—C9—H9B	111.2
C5—C4—C6ⁱⁱ	118.73 (9)	H9A—C9—H9B	109.1
C6—C5—C4	120.92 (9)

O1—C1—C2—C3	−179.04 (11)	C4—C5—C6—O4	179.73 (10)
C3ⁱ—C1—C2—C3	0.34 (16)	Cl2—C5—C6—O4	−1.31 (16)
O1—C1—C2—Cl1	−0.19 (14)	C4—C5—C6—C4ⁱⁱ	0.61 (17)
C3ⁱ—C1—C2—Cl1	179.19 (7)	Cl2—C5—C6—C4ⁱⁱ	179.57 (8)
C1—C2—C3—O2	179.32 (9)	C8—N1—C7—O5	−176.92 (10)
Cl1—C2—C3—O2	0.52 (15)	C8—N1—C7—N2	3.23 (15)
C1—C2—C3—C1ⁱ	−0.34 (16)	C9—N2—C7—O5	175.71 (11)
Cl1—C2—C3—C1ⁱ	−179.14 (7)	C9—N2—C7—N1	−4.43 (15)
O3—C4—C5—C6	178.94 (11)	C7—N1—C8—C9	−0.84 (14)
C6ⁱⁱ—C4—C5—C6	−0.60 (17)	C7—N2—C9—C8	3.73 (14)
O3—C4—C5—Cl2	−0.07 (15)	N1—C8—C9—N2	−1.64 (13)
C6ⁱⁱ—C4—C5—Cl2	−179.61 (8)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O5	0.81 (2)	1.82 (2)	2.6090 (11)	164 (2)
O4—H4···O5	0.86 (2)	1.88 (2)	2.6635 (12)	151.0 (19)
N1—H1N···O1ⁱⁱⁱ	0.85 (2)	2.06 (2)	2.9003 (15)	168 (2)
N2—H2N···O3ⁱⁱ	0.85 (2)	2.06 (2)	2.8654 (15)	158.6 (17)

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

2,5-Dichloro-3,6-dihydroxy-1,4-benzoquinone–imidazolidine-2,4-dione (1/2) (II) top

Crystal data top

C₆H₂Cl₂O₄·2C₃H₄N₂O₂	F(000) = 832.00
M_r = 409.14	D_x = 1.825 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71075 Å
a = 19.5690 (8) Å	Cell parameters from 13670 reflections
b = 5.18661 (10) Å	θ = 3.3–30.2°
c = 16.6103 (3) Å	µ = 0.49 mm⁻¹
β = 117.965 (3)°	T = 180 K
V = 1489.03 (8) Å³	Block, brown
Z = 4	0.49 × 0.33 × 0.24 mm

Data collection top

Rigaku R-AXIS RAPIDII diffractometer	2029 reflections with I > 2σ(I)
Detector resolution: 10.000 pixels mm^-1	R_int = 0.072
ω scans	θ_max = 30.0°, θ_min = 4.1°
Absorption correction: numerical (NUMABS; Higashi, 1999)	h = −27→27
T_min = 0.808, T_max = 0.888	k = −7→7
14622 measured reflections	l = −22→23
2181 independent reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.036	Hydrogen site location: mixed
wR(F²) = 0.100	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0633P)² + 0.4572P] where P = (F_o² + 2F_c²)/3
2181 reflections	(Δ/σ)_max < 0.001
130 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.40 e Å⁻³
Primary atom site location: structure-invariant direct methods

Special details top

Refinement. Refinement was performed using all reflections. The weighted R-factor (wR) and goodness of fit (S) are based on F². R-factor (gt) are based on F. The threshold expression of F² > 2.0 sigma(F²) is used only for calculating R-factor (gt).

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

	x	y	z	U_iso*/U_eq
Cl1	0.09683 (2)	1.02553 (6)	0.33978 (2)	0.02980 (12)
O1	0.11596 (5)	1.47273 (17)	0.45960 (6)	0.0313 (2)
O2	0.25729 (5)	0.82514 (16)	0.40485 (6)	0.02794 (19)
O3	0.39430 (5)	0.57413 (17)	0.43836 (6)	0.02824 (19)
O4	0.31705 (4)	−0.10296 (18)	0.23989 (6)	0.0296 (2)
N1	0.46359 (5)	0.26895 (19)	0.40528 (6)	0.0269 (2)
N2	0.33612 (5)	0.25929 (18)	0.32811 (6)	0.02336 (19)
C1	0.17655 (6)	1.3650 (2)	0.47556 (7)	0.0229 (2)
C2	0.18138 (6)	1.1410 (2)	0.42588 (7)	0.0228 (2)
C3	0.25018 (6)	1.0302 (2)	0.44779 (7)	0.0223 (2)
C4	0.39913 (6)	0.3869 (2)	0.39566 (7)	0.0226 (2)
C5	0.35871 (6)	0.0519 (2)	0.29613 (7)	0.0229 (2)
C6	0.44610 (6)	0.0494 (2)	0.34539 (8)	0.0255 (2)
H6A	0.466307	−0.112237	0.380266	0.031*
H6B	0.467588	0.070964	0.302420	0.031*
H1N	0.5127 (12)	0.308 (4)	0.4484 (15)	0.054 (5)*
H2	0.3043 (12)	0.772 (4)	0.4269 (14)	0.049 (5)*
H2N	0.2861 (11)	0.313 (4)	0.3055 (13)	0.045 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02000 (16)	0.03480 (18)	0.02881 (17)	−0.00423 (8)	0.00662 (12)	−0.00241 (9)
O1	0.0206 (4)	0.0327 (4)	0.0358 (4)	0.0052 (3)	0.0091 (3)	−0.0012 (3)
O2	0.0237 (4)	0.0269 (4)	0.0314 (4)	0.0015 (3)	0.0114 (3)	−0.0036 (3)
O3	0.0219 (4)	0.0300 (4)	0.0288 (4)	0.0015 (3)	0.0085 (3)	−0.0058 (3)
O4	0.0198 (4)	0.0324 (4)	0.0321 (4)	−0.0038 (3)	0.0085 (3)	−0.0086 (3)
N1	0.0160 (4)	0.0312 (5)	0.0288 (4)	−0.0018 (3)	0.0067 (3)	−0.0071 (4)
N2	0.0158 (4)	0.0268 (4)	0.0239 (4)	0.0003 (3)	0.0063 (3)	−0.0025 (3)
C1	0.0191 (4)	0.0254 (5)	0.0226 (4)	0.0009 (3)	0.0084 (4)	0.0032 (4)
C2	0.0177 (4)	0.0257 (5)	0.0220 (4)	−0.0009 (3)	0.0069 (3)	0.0020 (4)
C3	0.0205 (4)	0.0232 (5)	0.0226 (4)	0.0002 (3)	0.0094 (4)	0.0021 (3)
C4	0.0180 (4)	0.0256 (5)	0.0221 (4)	−0.0010 (3)	0.0076 (3)	0.0003 (4)
C5	0.0173 (4)	0.0262 (5)	0.0239 (5)	−0.0002 (3)	0.0086 (4)	−0.0002 (4)
C6	0.0162 (4)	0.0276 (5)	0.0295 (5)	−0.0008 (3)	0.0079 (4)	−0.0049 (4)

Geometric parameters (Å, º) top

Cl1—C2	1.7094 (10)	N2—C5	1.3620 (14)
O1—C1	1.2222 (12)	N2—C4	1.3857 (13)
O2—C3	1.3237 (13)	N2—H2N	0.912 (18)
O2—H2	0.86 (2)	C1—C2	1.4536 (15)
O3—C4	1.2318 (14)	C1—C3ⁱ	1.5035 (14)
O4—C5	1.2117 (13)	C2—C3	1.3475 (14)
N1—C4	1.3425 (13)	C5—C6	1.5106 (14)
N1—C6	1.4436 (14)	C6—H6A	0.9900
N1—H1N	0.91 (2)	C6—H6B	0.9900

C3—O2—H2	112.8 (14)	O2—C3—C1ⁱ	116.58 (9)
C4—N1—C6	111.82 (8)	C2—C3—C1ⁱ	120.65 (9)
C4—N1—H1N	125.3 (13)	O3—C4—N1	127.75 (10)
C6—N1—H1N	122.5 (13)	O3—C4—N2	124.29 (9)
C5—N2—C4	111.40 (8)	N1—C4—N2	107.95 (9)
C5—N2—H2N	124.3 (12)	O4—C5—N2	126.87 (10)
C4—N2—H2N	124.2 (12)	O4—C5—C6	126.41 (10)
O1—C1—C2	123.86 (10)	N2—C5—C6	106.71 (9)
O1—C1—C3ⁱ	117.46 (10)	N1—C6—C5	102.06 (8)
C2—C1—C3ⁱ	118.67 (8)	N1—C6—H6A	111.4
C3—C2—C1	120.68 (9)	C5—C6—H6A	111.4
C3—C2—Cl1	121.94 (8)	N1—C6—H6B	111.4
C1—C2—Cl1	117.37 (7)	C5—C6—H6B	111.4
O2—C3—C2	122.77 (10)	H6A—C6—H6B	109.2

O1—C1—C2—C3	−179.33 (10)	C6—N1—C4—N2	−1.64 (12)
C3ⁱ—C1—C2—C3	−0.32 (16)	C5—N2—C4—O3	−176.84 (11)
O1—C1—C2—Cl1	0.48 (15)	C5—N2—C4—N1	2.61 (12)
C3ⁱ—C1—C2—Cl1	179.49 (7)	C4—N2—C5—O4	176.75 (11)
C1—C2—C3—O2	179.56 (9)	C4—N2—C5—C6	−2.45 (12)
Cl1—C2—C3—O2	−0.24 (15)	C4—N1—C6—C5	0.19 (12)
C1—C2—C3—C1ⁱ	0.32 (16)	O4—C5—C6—N1	−177.85 (11)
Cl1—C2—C3—C1ⁱ	−179.48 (7)	N2—C5—C6—N1	1.35 (11)
C6—N1—C4—O3	177.78 (11)

Symmetry code: (i) −x+1/2, −y+5/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O3	0.86 (2)	1.97 (2)	2.7917 (15)	160 (2)
N1—H1N···O3ⁱⁱ	0.91 (2)	2.00 (2)	2.8927 (13)	165 (2)
N2—H2N···O4ⁱⁱⁱ	0.91 (2)	1.85 (2)	2.7560 (14)	176 (2)

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

References

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Volume 74| Part 12| December 2018| Pages 1727-1730

https://doi.org/10.1107/S205698901801561X

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

Crystal structures of two hydrogen-bonded compounds of chloranilic acid–ethyl­eneurea (1/1) and chloranilic acid–hydantoin (1/2)

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Database survey

5. Synthesis and crystallization

6. Refinement

Supporting information

References

research communications

Crystal structures of two hydrogen-bonded compounds of chloranilic acid–ethyleneurea (1/1) and chloranilic acid–hydantoin (1/2)

3. Supramolecular features