4,4′-Bipyridine–2-hydroxy­propane-1,2,3-tricarboxylic acid (3/2)

Soleimannejad, J.; Aghabozorg, H.; Najafi, S.; Nasibipour, M.; Attar Gharamaleki, J.

doi:10.1107/S1600536809004607

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Pages o532-o533

doi:10.1107/S1600536809004607

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4,4′-Bipyridine–2-hydroxypropane-1,2,3-tricarboxylic acid (3/2)

Janet Soleimannejad,^a ^* Hossein Aghabozorg,^b Shokoh Najafi,^a Mina Nasibipour ^a and Jafar Attar Gharamaleki ^b

^aDepartment of Chemistry, Faculty of Science, Ilam University, Ilam, Iran, and ^bFaculty of Chemistry, Tarbiat Moallem University, 49 Mofateh Avenue, 15614 Tehran, Iran
^*Correspondence e-mail: janet_soleimannejad@yahoo.com

(Received 19 January 2009; accepted 9 February 2009; online 18 February 2009)

The combination of 2-hydroxypropane-1,2,3-tricarboxylic acid (H₃hypta, also called citric acid) and 4,4′-bipyridine (4,4′-bipy) in a 1:1.5 molar ratio leads to the formation of the title molecular cocrystal, 1.5C₁₀H₈N₂·C₆H₈O₇. The asymmetric unit contains one and a half 4,4′-bipy units, with one lying across a centre of inversion, and one H₃hypta molecule. The significant differences in the C—O bond distances support the existence of the un-ionized acid molecule and confirm the formation of a cocrystal. There are π–π and C—H⋯π stacking interactions between the aromatic rings of 4,4′-bipy [with interplanar distances of 3.7739 (8) and 3.7970 (8) Å] and between CH groups of H₃hypta [with an H⋯π distance of 2.63 Å]. In the crystal structure, intermolecular O—H⋯N hydrogen bonds occur and an O—H⋯O hydrogen bond occurs within the citric acid moiety.

Related literature

For related literature on cocrystals and hydrogen bonding, see: Aakeroy & Seddon (1993 ); Aghabozorg et al. (2006 ); Aghabozorg, Heidari et al. (2008 ); Aghabozorg, Manteghi & Sheshmani (2008 ); Baures (1999 ); Biradha et al. (1993 ); Desiraju (1989 ); Desiraju & Steiner (1999 ); Houk et al. (1999 ).

Experimental

Crystal data

1.5C₁₀H₈N₂·C₆H₈O₇
M_r = 426.40
Monoclinic, P 2₁ /n
a = 7.0371 (2) Å
b = 33.5054 (10) Å
c = 8.4715 (2) Å
β = 90.302 (2)°
V = 1997.39 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 150 K
0.31 × 0.26 × 0.22 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.896, T_max = 0.977
63749 measured reflections
6045 independent reflections
4986 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.116
S = 1.05
6045 reflections
284 parameters
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯N3ⁱ	0.84	1.80	2.6275 (14)	168
O3—H3A⋯N1ⁱⁱ	0.84	1.75	2.5880 (14)	173
O6—H6A⋯N2ⁱⁱⁱ	0.84	1.82	2.6443 (14)	168
O7—H7A⋯O4	0.84	2.22	2.6538 (13)	112
C2—H2A⋯Cg^iv	0.99	2.63	3.5579 (13)	160
Symmetry codes: (i) x+1, y, z; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) x, y, z-1; (iv) x-1, y, z. Cg is the centroid of the N3,C17–C21 ring.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809004607/su2092sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809004607/su2092Isup2.hkl

checkCIF report

Comment top

The creation of new functional materials through the control of intermolecular bonding is a key aim of crystal engineering (Desiraju, 1989). The synthesis of crystalline supramolecular structures mediated by hydrogen bonds is of considerable importance. Among all the non-bonded interactions, hydrogen bonding has proved to be the most useful and reliable, because of its strength and directional properties (Aakeroy & Seddon, 1993; Aghabozorg, Heidari et al., 2008).

In the case of cocrystals, these are generally formed by dissolution and recrystallization from a suitable solvent, although sublimation and growth from the melt are also used. Co-crystallization is a deliberate attempt at bringing together different molecular species in one crystalline lattice without making or breaking covalent bonds (Aghabozorg et al., 2006). Cocrystals are used to reveal specific recognition motifs, such as those proposed for rational drug design (Baures, 1999; Houk et al., 1999) and crystal engineering applications.

The asymmetric unit of the title cocrystal is shown in Fig. 1, and geometrical parameters are availabe in the archived CIF. The asymmetric unit contains one and a half 4,4'-bipy units and one H₃hypta molecule. One 4,4'-bipy unit is located on a center of inversion. The C—O distances support the existence of the unionized acid molecules, indicating cocrystal formation; the C1—O1 [1.3203 (15) Å], C5—O6 [1.3197 (15) Å] and C6—O3 [1.3045 (15) Å] bond lengths are significantly longer than the C1—O2 [1.2070 (16) Å], C5—O5 [1.2084 (15) Å] and C6—O4 [1.2131 (15) Å] bond lengths.

The dihedral angle involving the aromatic rings, N1/C7–C9/C15/C16 (Cg1) and N2/C10–C14 (Cg2), of a 4,4'-bipy is 18.67°, which shows these units are not in the same plane, and also indicates the flexibility of the central C—C bond.

As shown in Fig. 2, there are π–π stacking interactions between two aromatic rings, Cg1 and Cg2, of the 4,4'-bipy units, with distances of 3.7739 (8) Å [1/2 + x, 1/2 - y, -1/2 + z] and 3.7970 (8) Å [-1/2 + x, 1/2 - y, -1/2 + z]. It can be seen in Fig. 3, that there are also C—H···π stacking interactions between CH groups of 2-hydroxypropane-1,2,3-tricarboxylic acid and the aromatic rings of 4,4'-bipyridine, with an H···π distance of 2.63 Å for C2—O2A···Cg3 [-1 + x, y, z; where Cg3 is the centroid of ring N3/C17–C21].

A remarkable feature in the crystal structure of the title compound is the presence of a large number of O—H···O, O—H···N and C—H···O hydrogen bonds (Table 1). There is an intramolecular O7—H7A···O4 hydrogen bond between the hydroxyl group and the carboxylate carbonyl group of the H₃hypta unit, with distance D···A of 2.6538 (13) Å. Two 4,4'-bipy and H₃hypta fragments are linked together by O—H···N and C—H···O hydrogen bonds and form chains (Fig. 4). C—H···O hydrogen bonding is widely accepted (Desiraju & Steiner, 1999; Biradha et al., 1993), and weak hydrogen bonding can be exploited in supramolecular chemistry and crystal structure design (Aghabozorg, Manteghi & Sheshmani, 2008). The crystal packing of the title compound is illustrated in Fig. 5.

Related literature top

For related literature on cocrystals and hydrogen bonding, see: Aakeroy & Seddon (1993); Aghabozorg et al. (2006); Aghabozorg, Heidari et al. (2008); Aghabozorg, Manteghi & Sheshmani (2008); Baures (1999); Biradha et al. (1993); Desiraju (1989); Desiraju & Steiner (1999); Houk et al. (1999).

Experimental top

An aqueous solution (50 ml) of 4,4'-bipyridine (100 mg, 6 mmol) and 84 mg (4 mmol) of 2-hydroxypropane-1,2,3-tricarboxylicacid, [H₃hypta, also called citric acid] were refluxed for two hours. Yellow crystals of the title compound were obtained from the solution after a few weeks at room temperature.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, showing the displacement ellipsoids drawn at the 50% probability level. [The suffix a denotes atoms generated by the symmetry operator (-x, -y, -z + 1).
	Fig. 2. A view of the π–π stacking interaction between two Cg1 and Cg2 aromatic rings of the 4,4'-bipyridine units, with distances of 3.7739 (8) Å; 1/2 + x, 1/2 - y, -1/2 + z and 3.7970 (8) Å; -1/2 + x, 1/2 - y, -1/2 + z [Cg1 and Cg2 are centroids for the aromatic rings N1/C7–C9/C15/C16 and N2/C10–C14, respectively].
	Fig. 3. A view of the C—H···π stacking interactions between CH groups of 2-hydroxypropane-1,2,3-tricarboxylic acid with the aromatic rings of 4,4'-bipyridine: H···π distance of 2.634 Å for C2—O2A···Cg3 (-1 + x, y, z) [Cg3 is the centroid of ring N3/C17–C21].
	Fig. 4. Two 4,4'-bipy and H₃hypta fragments are linked together by O—H···N and C—H···O hydrogen bonds.
	Fig. 5. Crystal packing of the title compound viewed down the c axis (hydrogen bonds are shown as dashed lines).

4,4'-Bipyridine–2-hydroxypropane-1,2,3-tricarboxylic acid (3/2) top

Crystal data top

1.5C₁₀H₈N₂·C₆H₈O₇	F(000) = 892
M_r = 426.40	D_x = 1.418 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 20381 reflections
a = 7.0371 (2) Å	θ = 2.7–29.6°
b = 33.5054 (10) Å	µ = 0.11 mm⁻¹
c = 8.4715 (2) Å	T = 150 K
β = 90.302 (2)°	Block, yellow
V = 1997.39 (9) Å³	0.31 × 0.26 × 0.22 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	6045 independent reflections
Radiation source: fine-focus sealed tube	4986 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ϕ and ω scans	θ_max = 30.5°, θ_min = 1.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→10
T_min = 0.896, T_max = 0.977	k = −47→47
63749 measured reflections	l = −12→12

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.116	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.046P)² + 1.026P] where P = (F_o² + 2F_c²)/3
6045 reflections	(Δ/σ)_max < 0.001
284 parameters	Δρ_max = 0.40 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Crystal data top

1.5C₁₀H₈N₂·C₆H₈O₇	V = 1997.39 (9) Å³
M_r = 426.40	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.0371 (2) Å	µ = 0.11 mm⁻¹
b = 33.5054 (10) Å	T = 150 K
c = 8.4715 (2) Å	0.31 × 0.26 × 0.22 mm
β = 90.302 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	6045 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	4986 reflections with I > 2σ(I)
T_min = 0.896, T_max = 0.977	R_int = 0.033
63749 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.116	H-atom parameters constrained
S = 1.05	Δρ_max = 0.40 e Å⁻³
6045 reflections	Δρ_min = −0.24 e Å⁻³
284 parameters

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.

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 > 2sigma(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
O1	1.22826 (14)	0.02331 (3)	0.66535 (13)	0.0327 (2)
H1A	1.3359	0.0254	0.7078	0.049*
O2	1.27436 (15)	0.08764 (3)	0.60893 (15)	0.0360 (3)
O3	0.85874 (15)	0.12663 (3)	0.72640 (11)	0.0274 (2)
H3A	0.8845	0.1464	0.7838	0.041*
O4	1.00936 (14)	0.16212 (3)	0.54053 (11)	0.0258 (2)
O5	0.59732 (15)	0.15627 (3)	0.37884 (11)	0.0274 (2)
O6	0.52218 (17)	0.10777 (3)	0.20888 (12)	0.0339 (3)
H6A	0.4824	0.1270	0.1541	0.051*
O7	0.99435 (14)	0.10297 (3)	0.33252 (10)	0.02327 (19)
H7A	1.0802	0.1200	0.3467	0.035*
C1	1.17363 (18)	0.05848 (4)	0.61136 (14)	0.0207 (2)
C2	0.97059 (17)	0.05761 (3)	0.55534 (15)	0.0195 (2)
H2A	0.8884	0.0516	0.6468	0.023*
H2B	0.9561	0.0354	0.4789	0.023*
C3	0.89834 (17)	0.09596 (3)	0.47738 (13)	0.0173 (2)
C4	0.68742 (18)	0.08896 (4)	0.43974 (15)	0.0208 (2)
H4A	0.6741	0.0632	0.3832	0.025*
H4B	0.6168	0.0867	0.5401	0.025*
C5	0.59840 (18)	0.12151 (4)	0.34080 (14)	0.0206 (2)
C6	0.92786 (18)	0.13235 (3)	0.58559 (14)	0.0194 (2)
N1	0.42826 (18)	0.31593 (3)	0.42264 (13)	0.0263 (2)
N2	0.42914 (18)	0.16451 (3)	1.00572 (14)	0.0278 (2)
C7	0.4111 (2)	0.32444 (4)	0.57535 (16)	0.0285 (3)
H7	0.3926	0.3515	0.6050	0.034*
C8	0.4188 (2)	0.29590 (4)	0.69282 (15)	0.0262 (3)
H8	0.4064	0.3034	0.8004	0.031*
C9	0.44484 (18)	0.25603 (4)	0.65244 (14)	0.0206 (2)
C10	0.44274 (18)	0.22416 (4)	0.77407 (14)	0.0203 (2)
C11	0.4672 (2)	0.23319 (4)	0.93413 (15)	0.0262 (3)
H11	0.4887	0.2599	0.9670	0.031*
C12	0.4597 (2)	0.20272 (4)	1.04392 (16)	0.0291 (3)
H12	0.4772	0.2093	1.1521	0.035*
C13	0.4046 (2)	0.15593 (4)	0.85302 (16)	0.0275 (3)
H13	0.3824	0.1289	0.8240	0.033*
C14	0.4101 (2)	0.18445 (4)	0.73488 (15)	0.0243 (3)
H14	0.3917	0.1769	0.6278	0.029*
C15	0.4680 (2)	0.24726 (4)	0.49209 (15)	0.0262 (3)
H15	0.4899	0.2206	0.4587	0.031*
C16	0.4587 (2)	0.27789 (4)	0.38298 (15)	0.0282 (3)
H16	0.4747	0.2716	0.2745	0.034*
N3	0.56382 (16)	0.01882 (4)	0.80165 (13)	0.0261 (2)
C17	0.6626 (2)	−0.01444 (4)	0.77585 (17)	0.0292 (3)
H17	0.6137	−0.0332	0.7021	0.035*
C18	0.83276 (19)	−0.02304 (4)	0.85097 (16)	0.0257 (3)
H18	0.8979	−0.0472	0.8286	0.031*
C19	0.90778 (16)	0.00392 (4)	0.95940 (13)	0.0183 (2)
C20	0.8034 (2)	0.03831 (4)	0.98728 (16)	0.0274 (3)
H20	0.8478	0.0575	1.0613	0.033*
C21	0.6342 (2)	0.04450 (4)	0.90668 (17)	0.0295 (3)
H21	0.5649	0.0682	0.9274	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0243 (5)	0.0270 (5)	0.0467 (6)	0.0001 (4)	−0.0148 (4)	0.0088 (4)
O2	0.0232 (5)	0.0249 (5)	0.0597 (7)	−0.0039 (4)	−0.0068 (5)	0.0009 (5)
O3	0.0403 (6)	0.0231 (5)	0.0190 (4)	−0.0043 (4)	0.0041 (4)	−0.0039 (3)
O4	0.0326 (5)	0.0186 (4)	0.0262 (5)	−0.0057 (4)	−0.0031 (4)	0.0012 (3)
O5	0.0372 (6)	0.0198 (4)	0.0250 (5)	0.0051 (4)	−0.0040 (4)	−0.0013 (3)
O6	0.0534 (7)	0.0212 (5)	0.0269 (5)	0.0017 (4)	−0.0190 (5)	0.0016 (4)
O7	0.0287 (5)	0.0223 (4)	0.0189 (4)	−0.0030 (3)	0.0044 (3)	−0.0009 (3)
C1	0.0199 (6)	0.0214 (6)	0.0207 (6)	0.0014 (4)	−0.0018 (4)	−0.0021 (4)
C2	0.0196 (6)	0.0158 (5)	0.0231 (6)	0.0000 (4)	−0.0042 (4)	0.0014 (4)
C3	0.0200 (6)	0.0153 (5)	0.0165 (5)	−0.0001 (4)	−0.0003 (4)	0.0000 (4)
C4	0.0208 (6)	0.0177 (5)	0.0238 (6)	−0.0007 (4)	−0.0053 (4)	0.0034 (4)
C5	0.0218 (6)	0.0200 (5)	0.0200 (6)	0.0016 (4)	−0.0011 (4)	0.0022 (4)
C6	0.0221 (6)	0.0172 (5)	0.0190 (5)	0.0012 (4)	−0.0030 (4)	−0.0008 (4)
N1	0.0366 (6)	0.0232 (5)	0.0193 (5)	0.0002 (4)	0.0017 (4)	0.0028 (4)
N2	0.0362 (6)	0.0247 (5)	0.0225 (5)	0.0027 (5)	−0.0070 (5)	0.0041 (4)
C7	0.0443 (8)	0.0197 (6)	0.0214 (6)	0.0031 (5)	0.0013 (5)	0.0003 (5)
C8	0.0405 (8)	0.0215 (6)	0.0164 (6)	0.0039 (5)	0.0013 (5)	−0.0005 (4)
C9	0.0239 (6)	0.0205 (5)	0.0175 (5)	0.0026 (4)	−0.0006 (4)	0.0008 (4)
C10	0.0216 (6)	0.0214 (6)	0.0178 (5)	0.0036 (4)	−0.0013 (4)	0.0010 (4)
C11	0.0379 (7)	0.0211 (6)	0.0196 (6)	0.0038 (5)	−0.0045 (5)	−0.0003 (4)
C12	0.0430 (8)	0.0255 (6)	0.0188 (6)	0.0047 (6)	−0.0061 (5)	0.0011 (5)
C13	0.0348 (7)	0.0216 (6)	0.0259 (6)	0.0005 (5)	−0.0072 (5)	0.0013 (5)
C14	0.0296 (7)	0.0234 (6)	0.0198 (6)	0.0014 (5)	−0.0037 (5)	−0.0009 (4)
C15	0.0389 (8)	0.0200 (6)	0.0198 (6)	0.0041 (5)	0.0028 (5)	−0.0019 (4)
C16	0.0419 (8)	0.0258 (6)	0.0168 (6)	0.0025 (5)	0.0037 (5)	−0.0005 (5)
N3	0.0197 (5)	0.0314 (6)	0.0272 (6)	0.0009 (4)	−0.0037 (4)	0.0068 (4)
C17	0.0244 (7)	0.0292 (7)	0.0338 (7)	−0.0025 (5)	−0.0087 (5)	−0.0018 (5)
C18	0.0229 (6)	0.0208 (6)	0.0333 (7)	0.0032 (5)	−0.0062 (5)	−0.0041 (5)
C19	0.0176 (5)	0.0203 (5)	0.0169 (5)	0.0015 (4)	−0.0009 (4)	0.0017 (4)
C20	0.0278 (7)	0.0268 (6)	0.0274 (6)	0.0086 (5)	−0.0065 (5)	−0.0057 (5)
C21	0.0277 (7)	0.0300 (7)	0.0306 (7)	0.0114 (5)	−0.0046 (5)	−0.0002 (5)

Geometric parameters (Å, º) top

O1—C1	1.3205 (15)	C8—C9	1.3915 (17)
O1—H1A	0.8400	C8—H8	0.9500
O2—C1	1.2073 (16)	C9—C15	1.4002 (17)
O3—C6	1.3048 (15)	C9—C10	1.4838 (17)
O3—H3A	0.8400	C10—C14	1.3902 (17)
O4—C6	1.2131 (15)	C10—C11	1.3990 (17)
O5—C5	1.2084 (15)	C11—C12	1.3820 (18)
O6—C5	1.3200 (15)	C11—H11	0.9500
O6—H6A	0.8400	C12—H12	0.9500
O7—C3	1.4235 (14)	C13—C14	1.3844 (18)
O7—H7A	0.8400	C13—H13	0.9500
C1—C2	1.5035 (17)	C14—H14	0.9500
C2—C3	1.5306 (16)	C15—C16	1.3825 (18)
C2—H2A	0.9900	C15—H15	0.9500
C2—H2B	0.9900	C16—H16	0.9500
C3—C4	1.5345 (17)	N3—C21	1.3313 (18)
C3—C6	1.5389 (16)	N3—C17	1.3323 (18)
C4—C5	1.5096 (16)	C17—C18	1.3832 (18)
C4—H4A	0.9900	C17—H17	0.9500
C4—H4B	0.9900	C18—C19	1.3906 (17)
N1—C7	1.3309 (17)	C18—H18	0.9500
N1—C16	1.3357 (17)	C19—C20	1.3875 (17)
N2—C13	1.3355 (17)	C19—C19ⁱ	1.489 (2)
N2—C12	1.3379 (18)	C20—C21	1.3851 (18)
C7—C8	1.3810 (18)	C20—H20	0.9500
C7—H7	0.9500	C21—H21	0.9500

C1—O1—H1A	109.5	C8—C9—C10	121.22 (11)
C6—O3—H3A	109.5	C15—C9—C10	121.63 (11)
C5—O6—H6A	109.5	C14—C10—C11	117.23 (11)
C3—O7—H7A	109.5	C14—C10—C9	121.67 (11)
O2—C1—O1	123.93 (12)	C11—C10—C9	121.06 (11)
O2—C1—C2	124.57 (11)	C12—C11—C10	119.19 (12)
O1—C1—C2	111.49 (10)	C12—C11—H11	120.4
C1—C2—C3	115.65 (10)	C10—C11—H11	120.4
C1—C2—H2A	108.4	N2—C12—C11	123.41 (12)
C3—C2—H2A	108.4	N2—C12—H12	118.3
C1—C2—H2B	108.4	C11—C12—H12	118.3
C3—C2—H2B	108.4	N2—C13—C14	123.22 (12)
H2A—C2—H2B	107.4	N2—C13—H13	118.4
O7—C3—C2	110.63 (10)	C14—C13—H13	118.4
O7—C3—C4	108.00 (9)	C13—C14—C10	119.55 (12)
C2—C3—C4	106.27 (9)	C13—C14—H14	120.2
O7—C3—C6	108.65 (9)	C10—C14—H14	120.2
C2—C3—C6	111.39 (9)	C16—C15—C9	119.18 (12)
C4—C3—C6	111.86 (10)	C16—C15—H15	120.4
C5—C4—C3	113.77 (10)	C9—C15—H15	120.4
C5—C4—H4A	108.8	N1—C16—C15	123.18 (12)
C3—C4—H4A	108.8	N1—C16—H16	118.4
C5—C4—H4B	108.8	C15—C16—H16	118.4
C3—C4—H4B	108.8	C21—N3—C17	117.24 (11)
H4A—C4—H4B	107.7	N3—C17—C18	123.37 (13)
O5—C5—O6	123.98 (11)	N3—C17—H17	118.3
O5—C5—C4	123.46 (11)	C18—C17—H17	118.3
O6—C5—C4	112.56 (10)	C17—C18—C19	119.56 (12)
O4—C6—O3	125.98 (11)	C17—C18—H18	120.2
O4—C6—C3	121.77 (11)	C19—C18—H18	120.2
O3—C6—C3	112.24 (10)	C20—C19—C18	116.91 (11)
C7—N1—C16	117.68 (11)	C20—C19—C19ⁱ	121.93 (14)
C13—N2—C12	117.39 (12)	C18—C19—C19ⁱ	121.17 (13)
N1—C7—C8	123.27 (12)	C21—C20—C19	119.66 (12)
N1—C7—H7	118.4	C21—C20—H20	120.2
C8—C7—H7	118.4	C19—C20—H20	120.2
C7—C8—C9	119.50 (12)	N3—C21—C20	123.26 (13)
C7—C8—H8	120.2	N3—C21—H21	118.4
C9—C8—H8	120.2	C20—C21—H21	118.4
C8—C9—C15	117.13 (11)

O2—C1—C2—C3	5.62 (19)	C8—C9—C10—C11	−17.8 (2)
O1—C1—C2—C3	−174.98 (11)	C15—C9—C10—C11	163.88 (13)
C1—C2—C3—O7	66.37 (13)	C14—C10—C11—C12	0.6 (2)
C1—C2—C3—C4	−176.64 (10)	C9—C10—C11—C12	178.46 (13)
C1—C2—C3—C6	−54.58 (14)	C13—N2—C12—C11	−0.1 (2)
O7—C3—C4—C5	−52.92 (13)	C10—C11—C12—N2	−0.3 (2)
C2—C3—C4—C5	−171.64 (10)	C12—N2—C13—C14	0.2 (2)
C6—C3—C4—C5	66.59 (13)	N2—C13—C14—C10	0.1 (2)
C3—C4—C5—O5	−56.85 (17)	C11—C10—C14—C13	−0.5 (2)
C3—C4—C5—O6	123.21 (12)	C9—C10—C14—C13	−178.34 (13)
O7—C3—C6—O4	4.99 (16)	C8—C9—C15—C16	−1.8 (2)
C2—C3—C6—O4	127.10 (12)	C10—C9—C15—C16	176.56 (13)
C4—C3—C6—O4	−114.14 (13)	C7—N1—C16—C15	1.7 (2)
O7—C3—C6—O3	−174.06 (10)	C9—C15—C16—N1	0.0 (2)
C2—C3—C6—O3	−51.95 (14)	C21—N3—C17—C18	−0.6 (2)
C4—C3—C6—O3	66.82 (13)	N3—C17—C18—C19	−0.1 (2)
C16—N1—C7—C8	−1.6 (2)	C17—C18—C19—C20	0.8 (2)
N1—C7—C8—C9	−0.3 (2)	C17—C18—C19—C19ⁱ	−178.91 (15)
C7—C8—C9—C15	2.0 (2)	C18—C19—C20—C21	−0.8 (2)
C7—C8—C9—C10	−176.40 (13)	C19ⁱ—C19—C20—C21	178.91 (15)
C8—C9—C10—C14	159.96 (13)	C17—N3—C21—C20	0.7 (2)
C15—C9—C10—C14	−18.3 (2)	C19—C20—C21—N3	0.1 (2)

Symmetry code: (i) −x+2, −y, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N3ⁱⁱ	0.84	1.80	2.6275 (14)	168
O3—H3A···N1ⁱⁱⁱ	0.84	1.75	2.5880 (14)	173
O6—H6A···N2^iv	0.84	1.82	2.6443 (14)	168
O7—H7A···O4	0.84	2.22	2.6538 (13)	112
C2—H2A···Cg^v	0.99	2.63	3.5579 (13)	160

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

Experimental details

Crystal data
Chemical formula	1.5C₁₀H₈N₂·C₆H₈O₇
M_r	426.40
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	150
a, b, c (Å)	7.0371 (2), 33.5054 (10), 8.4715 (2)
β (°)	90.302 (2)
V (Å³)	1997.39 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.31 × 0.26 × 0.22

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.896, 0.977
No. of measured, independent and observed [I > 2σ(I)] reflections	63749, 6045, 4986
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.715

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.116, 1.05
No. of reflections	6045
No. of parameters	284
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.24

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···N3ⁱ	0.84	1.80	2.6275 (14)	168
O3—H3A···N1ⁱⁱ	0.84	1.75	2.5880 (14)	173
O6—H6A···N2ⁱⁱⁱ	0.84	1.82	2.6443 (14)	168
O7—H7A···O4	0.84	2.22	2.6538 (13)	112
C2—H2A···Cg^iv	0.99	2.63	3.5579 (13)	160

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

Acknowledgements

Financial support from Ilam University is gratefully acknowledged.

References

Aakeroy, C. B. & Seddon, K. R. (1993). Chem. Soc. Rev. 22, 397–407. CrossRef CAS Web of Science Google Scholar
Aghabozorg, H., Ghadermazi, M. & Attar Gharamaleki, J. (2006). Acta Cryst. E62, o3445–o3447. Web of Science CSD CrossRef IUCr Journals Google Scholar
Aghabozorg, H., Heidari, M., Ghadermazi, M. & Attar Gharamaleki, J. (2008). Acta Cryst. E64, o1045–o1046. Web of Science CSD CrossRef IUCr Journals Google Scholar
Aghabozorg, H., Manteghi, F. & Sheshmani, S. (2008). J. Iran. Chem. Soc. 5, 184–227. CrossRef CAS Google Scholar
Baures, P. W. (1999). Org. Lett. 1, 249–252. Web of Science CrossRef PubMed CAS Google Scholar
Biradha, K., Sharma, C. V. K., Panneerselvam, K., Shimoni, L., Carrell, H. L., Zacharias, D. E. & Desiraju, G. R. (1993). Chem. Commun. pp. 1473–1475. CrossRef Google Scholar
Bruker (2005). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Desiraju, G. R. (1989). Crystal Engineering: The Design of Organic Solids. Amsterdam: Elsevier. Google Scholar
Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond In Structural Chemistry and Biology. New York: Oxford University Press. Google Scholar
Houk, K. N., Menzer, S., Newton, S. P., Raymo, F. M., Stoddart, J. F. & Williams, D. J. (1999). J. Am. Chem. Soc. 121, 1479–1487. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar