2-Amino-4-nitro­phenol–1-(2,4,6-trihy­droxy­phen­yl)ethanone (1/1)

Kocabıyık, C.; Paşaoğlu, H.; Basılı, T.; Ağar, E.

doi:10.1107/S1600536812017497

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 5| May 2012| Pages o1527-o1528

doi:10.1107/S1600536812017497

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2-Amino-4-nitrophenol–1-(2,4,6-trihydroxyphenyl)ethanone (1/1)

Can Kocabıyık,^a ^* Hümeyra Paşaoğlu,^a Taşkın Basılı ^b and Erbil Ağar ^b

^aOndokuz Mayıs University, Faculty of Arts and Sciences, Department of Physics, 55139 Kurupelit Samsun, Turkey, and ^bOndokuz Mayıs University, Faculty of Arts and Sciences, Department of Chemistry, 55139 Kurupelit Samsun, Turkey
^*Correspondence e-mail: cankocabiyik@hotmail.com

(Received 5 April 2012; accepted 19 April 2012; online 25 April 2012)

In the title compound, C₆H₆N₂O₃·C₈H₈O₄, the 2-amino-4-nitrophenol (ANP) and 1-(2,4,6-trihydroxyphenyl)ethanone (THA) molecules are both nearly planar, with r.m.s. deviations of 0.0630 and 0.0313 Å, respectively. The angle between the least-squares planes of THA and ANP is 48.99 (2)°. In THA, an intramolecular O—H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, N—H⋯O, O—H⋯O and O—H⋯N hydrogen bonds lead to the formation of a three-dimensional network. There are also intermolecular π–π interactions between the benzene rings of ANP–ANP and of THA–THA molecules, with centroid–centroid distances of 3.5313 (14) and 3.8440 (16) Å, respectively. Weak C—O⋯π and N—O⋯π interactions also occur.

Related literature

For the use of nitroaromatics as intermediates in explosives, dyestuffs, pesticides and organic synthesis, see: Yan et al. (2006 ). For the occurrence of nitroaromatics in industrial wastes and as direct pollutants in the environment, see: Yan et al. (2006); Soojhawon et al. (2005 ). For graph-set motifs, see: Bernstein et al. (1995 ). For related structures, see: Tanak et al. (2009 , 2010 ); Ali et al. (2008 ); Bi et al. (2009 ); Garden et al. (2004 ); Serdiuk et al. (2011 ).

Experimental

Crystal data

C₆H₆N₂O₃·C₈H₈O₄
M_r = 322.27
Monoclinic, P 2/c
a = 7.7255 (6) Å
b = 13.2184 (11) Å
c = 15.8335 (12) Å
β = 118.148 (5)°
V = 1425.67 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 296 K
0.80 × 0.35 × 0.09 mm

Data collection

Stoe IPDS 2 diffractometer
Absorption correction: integration (X-RED; Stoe & Cie, 2002 ) T_min = 0.942, T_max = 0.992
15333 measured reflections
2961 independent reflections
1841 reflections with I > 2σ(I)
R_int = 0.065

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.098
S = 0.97
2961 reflections
252 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C7–C12 and C1–C6 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O6ⁱ	0.93 (3)	2.28 (3)	3.067 (2)	141.5 (19)
N2—H2B⋯O6ⁱⁱ	0.93 (3)	2.36 (3)	3.241 (3)	157 (2)
O3—H3A⋯N1ⁱⁱⁱ	0.84 (3)	2.59 (3)	3.358 (3)	153 (3)
O3—H3A⋯O1ⁱⁱⁱ	0.84 (3)	2.39 (3)	2.953 (3)	125 (3)
O3—H3A⋯O2ⁱⁱⁱ	0.84 (3)	2.13 (3)	2.975 (3)	178 (3)
O4—H4⋯N2	0.86 (3)	1.94 (3)	2.784 (2)	166 (2)
O5—H5A⋯O7ⁱ	0.88 (3)	1.87 (3)	2.748 (2)	175 (3)
O6—H6⋯O7	0.92 (3)	1.64 (3)	2.478 (2)	150 (2)
N1—O2⋯Cg2^iv	1.22 (1)	3.82 (1)	3.599 (3)	70 (1)
C13—O7⋯Cg1^v	1.25 (1)	3.52 (1)	3.722 (3)	89 (1)
Symmetry codes: (i) $[x, -y, z+{\script{1\over 2}}]$ ; (ii) -x+1, -y, -z+1; (iii) $[x-1, -y+1, z-{\script{1\over 2}}]$ ; (iv) $[-x, y, -z+{\script{1\over 2}}]$ ; (v) -x+2, -y, -z+1.

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812017497/kj2199sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812017497/kj2199Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812017497/kj2199Isup3.cml

checkCIF report

Comment top

Nitroaromatics are widely used either as materials or as intermediates in explosives, dyestuffs, pesticides and organic synthesis (Yan et al., 2006). Nitroaromatics occur as industrial wastes and direct pollutants in the environment, and are relatively soluble in water and detectable in rivers, ponds and soil (Yan et al., 2006; Soojhawon et al., 2005).

The title compound (Fig. 1) crystallizes in the monoclinic space group P2/c with Z = 4 in the unit cell. The asymmetric unit in the crystal structure therefore contains only one formula unit. The bond lengths and angles of the ANP and THA moieties have normal values. The C4—N1 [1.448 (3) Å] and C13—C14 [1.486 (3) Å] bond distances are comparable to those observed in related structures (Ali et al., 2008; Tanak et al., 2009; Tanak et al., 2010; Bi et al., 2009; Garden et al., 2004; Serdiuk et al. 2011). The ANP and THA molecules are almost planar with the maximum deviations, -0.0694 (18) Å for atom O1 in the ANP and -0.152 (2) Å for atom C14 in the THA molecules. The dihedral angle between these rings is 48.99 (2)°.

The crystal packing of the title compound is stabilized by non-covalent hydrogen bond, π-π and X—Y···π-ring interactions. It can be seen from Fig. 2 that neighbouring ANP moieties are linked by O3—H3A···O1ⁱⁱⁱ and O3—H3A···O2ⁱⁱⁱ (iii: x - 1, -y + 1, z - 1/2) hydrogen bonds to form C(8) chains in direction [201], producing R¹₂(4) rings (Bernstein et al., 1995). In addition, THA moieties are mutually connected to each other by O5—H5A···O7ⁱ hydrogen bonds (i: x, -y, z + 1/2), forming a C(8) chain running in direction [001] (Fig. 3). These two chains are further connected by N2—H2A···O6ⁱ, N2—H2B···O6ⁱⁱ (ii: -x + 1, -y, -z + 1) and O4—H4···N2 hydrogen bonds between ANP and THA moieties. The arrangement of ANP and THA gives rise to R²₂(8) and R³₄(12) rings. The N2 (in ANP) and O6 (in THA) atoms act as both donor and acceptor. Finally, the intra-molecular O6—H6···O7 hydrogen bond of THA generates an S(6) ring motif (Fig. 4).

In the extended structure of the compound, there are weak π-π and X—Y···π-ring interactions. The intermolecular π-π contact occurs between the two symmetry-related ANP (ring A) rings of neighboring molecules. Ring A is oriented in such a way that the distance between the ring centroids is 3.8440 (16) Å. The other π-π interaction is between THA (ring B) rings, with a distance of 3.5313 (14) Å between the ring centroids. Rings A and B are also involved in intermolecular N—O···π and C—O···π interactions through N atom of ANP and C atom of THA. With regard to the N—O···π contact, for two neighboring B rings,the distance between atom O2 and the center of ring B (CgB) is 3.822 (2) Å and the N1—O2···CgB angle is 70.29 (15)°. In addition, there are also C—O···π interactions between C13—O7 and A rings, which can be characterized by the O7···CgA distance of 3.521 (3) Å and the C13—O7···CgA angle of 89.33 (15)°.

Related literature top

For the use of nitroaromatics as intermediates in explosives, dyestuffs, pesticides and organic synthesis, see: Yan et al. (2006). For the occurrence of nitroaromatics in industrial wastes and as direct pollutants in the environment, see: Yan et al. (2006); Soojhawon et al. (2005). For graph-set motifs, see: Bernstein et al. (1995). For related structures, see: Tanak et al. (2009, 2010); Ali et al. (2008); Bi et al. (2009); Garden et al. (2004); Serdiuk et al. (2011).

Experimental top

1-(2,4,6-trihydroxyphenyl)ethanone-2-amino-4-nitrophenol (1/1) was prepared by refluxing a mixture of a solution containing 2,4,6-trihydroxyacetephenone (18,6 mg, 0,1 mmol) in ethanol (25 ml) and a solution containing 2-amino-4-nitrophenol (15,4 mg, 0,1 mmol) in ethanol (20 ml). The reaction mixture was stirred for 4 h under reflux. Single crystals of the title compound for X-ray analysis were obtained by slow evaporation of an ethanol solution (Yield 74%; m.p 442.-446 K).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the atom-numbering scheme and 50% probability displacement ellipsoids.
	Fig. 2. H-bonds (dotted lines) form R¹₂(4) rings and C(8) chains running in the [201] direction.
	Fig. 3. The C(8) chain structure running along the [001] direction formed by H-bonds (dotted lines) between 2,4,6-trihydroxyacetephenone molecules.
	Fig. 4. H-bonds (dotted lines) form R³₄(12) and S(6)-rings.

2-Amino-4-nitrophenol–1-(2,4,6-trihydroxyphenyl)ethanone (1/1) top

Crystal data top

C₆H₆N₂O₃·C₈H₈O₄	F(000) = 672
M_r = 322.27	D_x = 1.501 Mg m⁻³
Monoclinic, P2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yc	Cell parameters from 12619 reflections
a = 7.7255 (6) Å	θ = 2.1–27.3°
b = 13.2184 (11) Å	µ = 0.12 mm⁻¹
c = 15.8335 (12) Å	T = 296 K
β = 118.148 (5)°	Prism, yellow
V = 1425.67 (19) Å³	0.80 × 0.35 × 0.09 mm
Z = 4

Data collection top

Stoe IPDS 2 diffractometer	2961 independent reflections
Radiation source: fine-focus sealed tube	1841 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.065
Detector resolution: 6.67 pixels mm^-1	θ_max = 26.5°, θ_min = 2.1°
rotation method scans	h = −9→9
Absorption correction: integration (X-RED; Stoe & Cie, 2002)	k = −16→16
T_min = 0.942, T_max = 0.992	l = −19→19
15333 measured reflections

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ²(F_o²) + (0.0466P)²] where P = (F_o² + 2F_c²)/3
2961 reflections	(Δ/σ)_max < 0.001
252 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

C₆H₆N₂O₃·C₈H₈O₄	V = 1425.67 (19) Å³
M_r = 322.27	Z = 4
Monoclinic, P2/c	Mo Kα radiation
a = 7.7255 (6) Å	µ = 0.12 mm⁻¹
b = 13.2184 (11) Å	T = 296 K
c = 15.8335 (12) Å	0.80 × 0.35 × 0.09 mm
β = 118.148 (5)°

Data collection top

Stoe IPDS 2 diffractometer	2961 independent reflections
Absorption correction: integration (X-RED; Stoe & Cie, 2002)	1841 reflections with I > 2σ(I)
T_min = 0.942, T_max = 0.992	R_int = 0.065
15333 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.098	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	Δρ_max = 0.15 e Å⁻³
2961 reflections	Δρ_min = −0.24 e Å⁻³
252 parameters

Special details top

Experimental. IR (KBr, cm^-1): 3523 ν(OH)_THA, 3383 ν(NH₂)_asym, 3353 ν(NH₂)_sym+ν(OH)_THA, 3298 ν(OH)_THA, 3090–3000 ν(CH), 2850–2700 ν(CH₃), 1628 ν(C=O)+δ(OH)_THA+ν(ring)_THA, 1614 ν(NH₂)+ν(ring)_ANP, 1571 δ(NH₂), 1524 ν(NO₂)_asym, 1496–1476 δ(CH)+δ(OH)_ANP, 1364–1339 δ(CH₃)+δ(OH)_THA, 1311–1251 ν(NO₂)+ν(CO)_ANP, 1203–1167–1147 ν(ring)+δ(OH). UV/Visible (nm): 226 (2,212 Å; ε= 19230 L mol^-1cm^-1) and 288 (1,815 Å; ε= 15780 L mol^-1cm^-1) π→π^* transitions of benzene ring (E bands), 380 nm (0,345 Å; ε= 3000 L mol^-1cm^-1) π→π^* transition of aniline (E₂ band).

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	0.5977 (3)	0.40750 (14)	0.66694 (13)	0.0394 (5)
C2	0.6191 (4)	0.51128 (15)	0.67342 (16)	0.0498 (6)
C3	0.7703 (4)	0.55477 (16)	0.75249 (17)	0.0520 (6)
C4	0.8964 (3)	0.49206 (15)	0.82522 (14)	0.0456 (5)
C5	0.8776 (3)	0.38806 (15)	0.82066 (14)	0.0411 (5)
C6	0.7271 (3)	0.34480 (13)	0.74077 (13)	0.0361 (4)
C7	0.7798 (3)	0.00373 (15)	0.64563 (14)	0.0411 (5)
C8	0.7390 (3)	−0.09742 (14)	0.62254 (14)	0.0423 (5)
C9	0.7120 (3)	−0.13396 (15)	0.53533 (15)	0.0461 (5)
C10	0.7236 (3)	−0.06837 (14)	0.47110 (13)	0.0409 (5)
C11	0.7631 (3)	0.03665 (14)	0.49051 (13)	0.0380 (5)
C12	0.7933 (3)	0.06963 (14)	0.58187 (14)	0.0395 (5)
C13	0.7601 (3)	0.10280 (15)	0.41713 (15)	0.0466 (5)
C14	0.7792 (5)	0.21463 (17)	0.42704 (19)	0.0779 (9)
H14A	0.7731	0.2432	0.3700	0.117*
H14B	0.9027	0.2316	0.4810	0.117*
H14C	0.6742	0.2414	0.4365	0.117*
N1	1.0593 (3)	0.53726 (17)	0.90766 (15)	0.0622 (6)
N2	0.7059 (3)	0.23928 (13)	0.72998 (14)	0.0473 (5)
O1	1.0834 (3)	0.62880 (15)	0.91011 (15)	0.0944 (7)
O2	1.1715 (3)	0.48199 (16)	0.97227 (13)	0.0774 (6)
O3	0.4543 (3)	0.35925 (12)	0.59151 (11)	0.0571 (5)
O4	0.8398 (3)	0.16790 (11)	0.60576 (12)	0.0587 (5)
O5	0.7222 (3)	−0.16375 (12)	0.68295 (12)	0.0640 (5)
O6	0.6904 (3)	−0.10661 (12)	0.38519 (11)	0.0579 (5)
O7	0.7370 (3)	0.06669 (11)	0.33974 (10)	0.0605 (5)
H2	0.532 (3)	0.5607 (15)	0.6211 (15)	0.053 (6)*
H2A	0.764 (3)	0.2079 (17)	0.7899 (18)	0.061 (7)*
H2B	0.575 (4)	0.2194 (19)	0.692 (2)	0.078 (9)*
H3	0.790 (3)	0.6232 (17)	0.7574 (15)	0.050 (6)*
H3A	0.375 (5)	0.404 (2)	0.556 (2)	0.100 (11)*
H4	0.812 (4)	0.1827 (18)	0.6505 (19)	0.063 (8)*
H5	0.963 (3)	0.3471 (14)	0.8687 (15)	0.042 (6)*
H5A	0.734 (4)	−0.134 (2)	0.735 (2)	0.093 (10)*
H6	0.702 (4)	−0.0539 (18)	0.3500 (18)	0.067 (8)*
H7	0.802 (3)	0.0289 (14)	0.7084 (14)	0.041 (5)*
H9	0.691 (3)	−0.2043 (18)	0.5206 (16)	0.060 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0367 (12)	0.0479 (11)	0.0311 (10)	−0.0011 (9)	0.0139 (9)	−0.0043 (8)
C2	0.0508 (15)	0.0448 (12)	0.0474 (13)	0.0077 (10)	0.0178 (12)	0.0048 (10)
C3	0.0570 (16)	0.0380 (12)	0.0619 (15)	0.0002 (10)	0.0287 (13)	−0.0089 (10)
C4	0.0387 (13)	0.0540 (12)	0.0407 (11)	−0.0053 (10)	0.0161 (10)	−0.0169 (9)
C5	0.0402 (13)	0.0514 (12)	0.0298 (10)	0.0053 (10)	0.0149 (10)	−0.0007 (9)
C6	0.0402 (12)	0.0384 (10)	0.0328 (10)	0.0000 (8)	0.0199 (9)	−0.0029 (8)
C7	0.0444 (13)	0.0483 (11)	0.0307 (10)	−0.0019 (9)	0.0178 (10)	−0.0075 (8)
C8	0.0452 (14)	0.0439 (11)	0.0382 (11)	0.0033 (9)	0.0199 (10)	0.0011 (8)
C9	0.0573 (15)	0.0368 (11)	0.0455 (12)	−0.0008 (9)	0.0254 (11)	−0.0066 (9)
C10	0.0435 (13)	0.0450 (11)	0.0325 (10)	0.0013 (9)	0.0165 (9)	−0.0100 (8)
C11	0.0346 (12)	0.0460 (11)	0.0335 (10)	−0.0017 (9)	0.0163 (9)	−0.0056 (8)
C12	0.0374 (13)	0.0435 (10)	0.0381 (11)	−0.0055 (9)	0.0183 (9)	−0.0108 (8)
C13	0.0477 (14)	0.0534 (12)	0.0426 (12)	−0.0058 (10)	0.0245 (11)	−0.0056 (9)
C14	0.126 (3)	0.0560 (14)	0.0640 (17)	−0.0166 (15)	0.0552 (18)	0.0019 (12)
N1	0.0463 (14)	0.0798 (15)	0.0543 (13)	−0.0063 (11)	0.0188 (11)	−0.0278 (11)
N2	0.0591 (14)	0.0416 (10)	0.0385 (10)	−0.0016 (9)	0.0208 (10)	0.0011 (8)
O1	0.0808 (15)	0.0721 (12)	0.1081 (17)	−0.0231 (10)	0.0262 (12)	−0.0512 (11)
O2	0.0540 (12)	0.1078 (14)	0.0477 (10)	−0.0066 (11)	0.0053 (9)	−0.0182 (10)
O3	0.0502 (11)	0.0598 (10)	0.0398 (9)	−0.0014 (8)	0.0035 (8)	−0.0051 (7)
O4	0.0895 (14)	0.0454 (8)	0.0572 (10)	−0.0206 (8)	0.0477 (10)	−0.0197 (7)
O5	0.1024 (15)	0.0491 (8)	0.0503 (10)	−0.0017 (8)	0.0441 (10)	0.0014 (7)
O6	0.0865 (13)	0.0525 (9)	0.0414 (8)	−0.0089 (8)	0.0358 (9)	−0.0143 (7)
O7	0.0853 (13)	0.0634 (9)	0.0410 (8)	−0.0037 (8)	0.0366 (9)	−0.0027 (7)

Geometric parameters (Å, º) top

C1—O3	1.346 (2)	C10—O6	1.357 (2)
C1—C2	1.380 (3)	C10—C11	1.424 (3)
C1—C6	1.396 (3)	C11—C12	1.421 (3)
C2—C3	1.372 (3)	C11—C13	1.445 (3)
C2—H2	1.02 (2)	C12—O4	1.353 (2)
C3—C4	1.380 (3)	C13—O7	1.247 (2)
C3—H3	0.91 (2)	C13—C14	1.487 (3)
C4—C5	1.381 (3)	C14—H14A	0.9600
C4—N1	1.447 (3)	C14—H14B	0.9600
C5—C6	1.375 (3)	C14—H14C	0.9600
C5—H5	0.91 (2)	N1—O1	1.222 (3)
C6—N2	1.405 (2)	N1—O2	1.222 (3)
C7—C12	1.374 (3)	N2—H2A	0.93 (3)
C7—C8	1.383 (3)	N2—H2B	0.93 (3)
C7—H7	0.98 (2)	O3—H3A	0.84 (3)
C8—O5	1.348 (2)	O4—H4	0.86 (3)
C8—C9	1.383 (3)	O5—H5A	0.88 (3)
C9—C10	1.371 (3)	O6—H6	0.92 (3)
C9—H9	0.95 (2)

O3—C1—C2	123.81 (19)	O6—C10—C11	119.96 (18)
O3—C1—C6	115.21 (17)	C9—C10—C11	122.61 (18)
C2—C1—C6	120.98 (19)	C12—C11—C10	115.75 (17)
C3—C2—C1	120.3 (2)	C12—C11—C13	124.43 (17)
C3—C2—H2	115.1 (11)	C10—C11—C13	119.73 (17)
C1—C2—H2	124.5 (11)	O4—C12—C7	120.34 (17)
C2—C3—C4	118.2 (2)	O4—C12—C11	118.28 (17)
C2—C3—H3	121.8 (13)	C7—C12—C11	121.37 (17)
C4—C3—H3	120.0 (14)	O7—C13—C11	119.92 (17)
C3—C4—C5	122.63 (19)	O7—C13—C14	116.4 (2)
C3—C4—N1	118.4 (2)	C11—C13—C14	123.62 (19)
C5—C4—N1	118.9 (2)	C13—C14—H14A	109.5
C6—C5—C4	118.97 (19)	C13—C14—H14B	109.5
C6—C5—H5	119.0 (12)	H14A—C14—H14B	109.5
C4—C5—H5	122.0 (12)	C13—C14—H14C	109.5
C5—C6—C1	118.94 (17)	H14A—C14—H14C	109.5
C5—C6—N2	121.59 (19)	H14B—C14—H14C	109.5
C1—C6—N2	119.41 (18)	O1—N1—O2	121.9 (2)
C12—C7—C8	120.37 (18)	O1—N1—C4	119.5 (2)
C12—C7—H7	119.3 (11)	O2—N1—C4	118.7 (2)
C8—C7—H7	120.3 (11)	C6—N2—H2A	110.2 (14)
O5—C8—C9	117.50 (17)	C6—N2—H2B	112.7 (16)
O5—C8—C7	121.84 (18)	H2A—N2—H2B	112 (2)
C9—C8—C7	120.66 (19)	C1—O3—H3A	107 (2)
C10—C9—C8	119.21 (18)	C12—O4—H4	108.3 (16)
C10—C9—H9	119.9 (14)	C8—O5—H5A	112.0 (19)
C8—C9—H9	120.9 (14)	C10—O6—H6	107.3 (15)
O6—C10—C9	117.41 (17)

O3—C1—C2—C3	−179.5 (2)	O6—C10—C11—C12	179.20 (18)
C6—C1—C2—C3	0.9 (4)	C9—C10—C11—C12	1.0 (3)
C1—C2—C3—C4	−1.2 (4)	O6—C10—C11—C13	2.4 (3)
C2—C3—C4—C5	0.9 (3)	C9—C10—C11—C13	−175.8 (2)
C2—C3—C4—N1	178.3 (2)	C8—C7—C12—O4	−177.8 (2)
C3—C4—C5—C6	−0.2 (3)	C8—C7—C12—C11	1.0 (3)
N1—C4—C5—C6	−177.64 (19)	C10—C11—C12—O4	177.22 (19)
C4—C5—C6—C1	−0.2 (3)	C13—C11—C12—O4	−6.2 (3)
C4—C5—C6—N2	177.0 (2)	C10—C11—C12—C7	−1.6 (3)
O3—C1—C6—C5	−179.80 (19)	C13—C11—C12—C7	175.0 (2)
C2—C1—C6—C5	−0.1 (3)	C12—C11—C13—O7	178.3 (2)
O3—C1—C6—N2	3.0 (3)	C10—C11—C13—O7	−5.2 (3)
C2—C1—C6—N2	−177.3 (2)	C12—C11—C13—C14	−2.9 (4)
C12—C7—C8—O5	−179.1 (2)	C10—C11—C13—C14	173.5 (2)
C12—C7—C8—C9	0.3 (3)	C3—C4—N1—O1	−1.4 (3)
O5—C8—C9—C10	178.5 (2)	C5—C4—N1—O1	176.1 (2)
C7—C8—C9—C10	−0.8 (3)	C3—C4—N1—O2	−180.0 (2)
C8—C9—C10—O6	−178.1 (2)	C5—C4—N1—O2	−2.5 (3)
C8—C9—C10—C11	0.2 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C7–C12 and C1–C6 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O6ⁱ	0.93 (3)	2.28 (3)	3.067 (2)	141.5 (19)
N2—H2B···O6ⁱⁱ	0.93 (3)	2.36 (3)	3.241 (3)	157 (2)
O3—H3A···N1ⁱⁱⁱ	0.84 (3)	2.59 (3)	3.358 (3)	153 (3)
O3—H3A···O1ⁱⁱⁱ	0.84 (3)	2.39 (3)	2.953 (3)	125 (3)
O3—H3A···O2ⁱⁱⁱ	0.84 (3)	2.13 (3)	2.975 (3)	178 (3)
O4—H4···N2	0.86 (3)	1.94 (3)	2.784 (2)	166 (2)
O5—H5A···O7ⁱ	0.88 (3)	1.87 (3)	2.748 (2)	175 (3)
O6—H6···O7	0.92 (3)	1.64 (3)	2.478 (2)	150 (2)
N1—O2···Cg2^iv	1.22 (1)	3.82 (1)	3.599 (3)	70 (1)
C13—O7···Cg1^v	1.25 (1)	3.52 (1)	3.722 (3)	89 (1)

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

Experimental details

Crystal data
Chemical formula	C₆H₆N₂O₃·C₈H₈O₄
M_r	322.27
Crystal system, space group	Monoclinic, P2/c
Temperature (K)	296
a, b, c (Å)	7.7255 (6), 13.2184 (11), 15.8335 (12)
β (°)	118.148 (5)
V (Å³)	1425.67 (19)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.80 × 0.35 × 0.09

Data collection
Diffractometer	Stoe IPDS 2 diffractometer
Absorption correction	Integration (X-RED; Stoe & Cie, 2002)
T_min, T_max	0.942, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	15333, 2961, 1841
R_int	0.065
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.098, 0.97
No. of reflections	2961
No. of parameters	252
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.24

Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the C7–C12 and C1–C6 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O6ⁱ	0.93 (3)	2.28 (3)	3.067 (2)	141.5 (19)
N2—H2B···O6ⁱⁱ	0.93 (3)	2.36 (3)	3.241 (3)	157 (2)
O3—H3A···N1ⁱⁱⁱ	0.84 (3)	2.59 (3)	3.358 (3)	153 (3)
O3—H3A···O1ⁱⁱⁱ	0.84 (3)	2.39 (3)	2.953 (3)	125 (3)
O3—H3A···O2ⁱⁱⁱ	0.84 (3)	2.13 (3)	2.975 (3)	178 (3)
O4—H4···N2	0.86 (3)	1.94 (3)	2.784 (2)	166 (2)
O5—H5A···O7ⁱ	0.88 (3)	1.87 (3)	2.748 (2)	175 (3)
O6—H6···O7	0.92 (3)	1.64 (3)	2.478 (2)	150 (2)
N1—O2···Cg2^iv	1.223 (3)	3.822 (2)	3.599 (3)	70.29 (15)
C13—O7···Cg1^v	1.247 (3)	3.521 (3)	3.722 (3)	89.33 (15)

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

Acknowledgements

The authors sincerely thank Professor Dr Orhan Büyükgüngör and Dr Gökhan Kaştaş for their contributions.

References

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Volume 68| Part 5| May 2012| Pages o1527-o1528

doi:10.1107/S1600536812017497

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