4,4′-Bipyrid­yl–2-chloro-4-nitro­benzoic acid (1/2)

Gotoh, K.; Ishida, H.

doi:10.1107/S1600536807052865

4,4′-Bipyridyl–2-chloro-4-nitrobenzoic acid (1/2)

In the crystal structure of the title 1:2 cocrystal, C₁₀H₈N₂·2C₇H₄ClNO₄, the two components are held together by short O—H

N hydrogen bonds. The pyridine rings of the bipyridyl molecule are twisted by 27.90 (5)° with respect to each other. The 1:2 units are connected by C—H

O hydrogen bonds, forming a centrosymmetric supramolecular ring.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807052865/tk2205sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807052865/tk2205Isup2.hkl Contains datablock I

checkCIF report

Key indicators

Single-crystal X-ray study
T = 173 K
Mean (C-C) = 0.002 Å
R factor = 0.034
wR factor = 0.091
Data-to-parameter ratio = 15.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.12 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.82 Ratio
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O3     -   N1      ..       5.17 su
PLAT355_ALERT_3_C Long    O-H Bond (0.82A)   O6     -   H6O    ...       1.05 Ang.
PLAT430_ALERT_2_C Short Inter D...A Contact  O1     ..  N1      ..       2.88 Ang.
PLAT430_ALERT_2_C Short Inter D...A Contact  O5     ..  N2      ..       2.90 Ang.

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

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

The title compound was investigated as part of a study on D—H···A hydrogen bonding (D = N, O or C; A = N, O or Cl) in chloro- and nitro-substituted benzoic acid–amine systems (Ishida & Fukunaga, 2004; Ishida et al., 2004).

The asymmetric unit comprises one 4,4'-bipyridyl and two 2-chloro-4-nitorobenzoic acid molecules (Fig. 1), which are held together by short O—H···N hydrogen bonds (Table 1) to form a 1:2 unit. The pyridine rings of the bipyridyl molecule are twisted by 27.90 (5)° to each other. The pyridine N3/C15—C18 ring makes a dihedral angle of 16.82 (5)° with the benzene C1—C6 ring of the adjacent benzoic acid, while the N4/C20—C24 ring forms an angle of 64.52 (5)° with the C8—C13 ring. The benzene C1—C6 ring makes dihedral angles of 31.17 (3) and 9.85 (3)° with the carboxyl C7/O1/O2 plane and the nitro N1/O3/O4 plane, respectively, and the benzene C8—C13 ring forms angles of 39.25 (3) and 15.99 (3)° with the C14/O5/O6 and N2/O7/O8 planes, respectively.

The two 1:2 units related by an inversion center are connected by C—H···O hydrgoen bonds (Table 1) to form a supramolecular ring (Fig. 2). The rings are further connected by C—H···O hydrogen bonds, leading to a three-dimensional hydrogen-bonded network.

Related literature top

For related compounds, see: Ishida & Fukunaga (2004); Ishida et al. (2004).

Experimental top

Single crystals of the title compound were obtained by slow evaporation from an acetonitrile solution of 4,4'-bipyridyl (20 mg) and 2-chloro-4-nitrobenzoic acid (51 mg).

Structure description top

For related compounds, see: Ishida & Fukunaga (2004); Ishida et al. (2004).

Computing details top

Data collection: PROCESS-AUTO (Rigaku/MSC, 2004); cell refinement: PROCESS-AUTO (Rigaku/MSC, 2004); data reduction: CrystalStructure (Rigaku/MSC, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004) and PLATON (Spek, 2003).

Figures top

	Fig. 1. The molecular structure of the title compound, with the atom labeling. Displacement ellipsoids for non-H atoms are drawn at 50% probability level. The dashed lines indicate hydrogen bonds.
	Fig. 2. A partial packing diagram of the title compound, viewed approximately down the b axis. The dashed lines indicate hydrogen bonds. symmetry operation are given in Table 1.

4,4'-Bipyridyl–2-chloro-4-nitrobenzoic acid (1/2) top

Crystal data top

C₁₀H₈N₂·2C₇H₄ClNO₄	F(000) = 1144.00
M_r = 559.32	D_x = 1.577 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2yn	Cell parameters from 3516 reflections
a = 12.0875 (11) Å	θ = 6.1–29.9°
b = 8.0695 (9) Å	µ = 0.34 mm⁻¹
c = 24.610 (2) Å	T = 173 K
β = 101.143 (2)°	Block, colorless
V = 2355.2 (4) Å³	0.48 × 0.45 × 0.38 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID-II diffractometer	4838 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm^-1	R_int = 0.023
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −15→15
T_min = 0.780, T_max = 0.880	k = −10→10
19103 measured reflections	l = −30→31
5379 independent 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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0521P)² + 0.6629P] where P = (F_o² + 2F_c²)/3
5379 reflections	(Δ/σ)_max = 0.002
351 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

C₁₀H₈N₂·2C₇H₄ClNO₄	V = 2355.2 (4) Å³
M_r = 559.32	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.0875 (11) Å	µ = 0.34 mm⁻¹
b = 8.0695 (9) Å	T = 173 K
c = 24.610 (2) Å	0.48 × 0.45 × 0.38 mm
β = 101.143 (2)°

Data collection top

Rigaku R-AXIS RAPID-II diffractometer	5379 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	4838 reflections with I > 2σ(I)
T_min = 0.780, T_max = 0.880	R_int = 0.023
19103 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.091	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.24 e Å⁻³
5379 reflections	Δρ_min = −0.44 e Å⁻³
351 parameters

Special details top

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
Cl1	0.43587 (3)	0.07017 (5)	0.694192 (13)	0.03123 (10)
Cl2	0.77647 (3)	0.41014 (4)	0.053835 (13)	0.03098 (9)
O1	0.64197 (9)	0.44155 (12)	0.63346 (4)	0.0305 (2)
O2	0.56764 (9)	0.19023 (13)	0.61217 (4)	0.0325 (2)
O3	0.63818 (8)	0.07543 (12)	0.89943 (4)	0.0294 (2)
O4	0.76390 (8)	0.27037 (13)	0.91028 (4)	0.0323 (2)
O5	0.51496 (8)	0.60528 (13)	0.12896 (4)	0.0293 (2)
O6	0.70335 (8)	0.59355 (14)	0.14746 (4)	0.0316 (2)
O7	0.65421 (9)	0.68033 (15)	−0.14127 (4)	0.0372 (2)
O8	0.49099 (9)	0.79252 (13)	−0.14216 (4)	0.0357 (2)
N1	0.69168 (9)	0.18509 (13)	0.88134 (4)	0.0239 (2)
N2	0.57867 (9)	0.72654 (14)	−0.11814 (4)	0.0267 (2)
N3	0.57221 (9)	0.28775 (14)	0.51053 (4)	0.0264 (2)
N4	0.67380 (9)	0.53108 (15)	0.24725 (4)	0.0275 (2)
C1	0.62647 (10)	0.26355 (15)	0.70768 (5)	0.0219 (2)
C2	0.55600 (10)	0.16182 (15)	0.73223 (5)	0.0205 (2)
C3	0.57687 (10)	0.13632 (15)	0.78929 (5)	0.0214 (2)
H3	0.5292	0.0669	0.8059	0.026*
C4	0.66862 (10)	0.21453 (15)	0.82118 (5)	0.0214 (2)
C5	0.73956 (11)	0.31852 (17)	0.79904 (5)	0.0279 (3)
H5	0.8012	0.3726	0.8220	0.033*
C6	0.71721 (11)	0.34070 (18)	0.74214 (5)	0.0286 (3)
H6	0.7652	0.4107	0.7260	0.034*
C7	0.61162 (10)	0.30665 (16)	0.64683 (5)	0.0240 (2)
C8	0.60901 (10)	0.63901 (15)	0.05405 (5)	0.0212 (2)
C9	0.68021 (10)	0.55902 (15)	0.02378 (5)	0.0210 (2)
C10	0.67249 (10)	0.58905 (15)	−0.03255 (5)	0.0226 (2)
H10	0.7211	0.5347	−0.0529	0.027*
C11	0.59194 (10)	0.70030 (15)	−0.05791 (5)	0.0223 (2)
C12	0.51996 (11)	0.78311 (17)	−0.02985 (5)	0.0269 (3)
H12	0.4657	0.8595	−0.0484	0.032*
C13	0.52944 (11)	0.75120 (17)	0.02624 (5)	0.0265 (3)
H13	0.4808	0.8068	0.0463	0.032*
C14	0.60568 (10)	0.60941 (15)	0.11444 (5)	0.0224 (2)
C15	0.64224 (12)	0.41360 (17)	0.50570 (5)	0.0283 (3)
H15	0.6778	0.4700	0.5383	0.034*
C16	0.66500 (11)	0.46500 (17)	0.45522 (5)	0.0264 (3)
H16	0.7151	0.5548	0.4537	0.032*
C17	0.61383 (10)	0.38400 (16)	0.40671 (5)	0.0222 (2)
C18	0.54069 (11)	0.25415 (17)	0.41208 (5)	0.0270 (3)
H18	0.5037	0.1956	0.3802	0.032*
C19	0.52215 (11)	0.21083 (18)	0.46407 (5)	0.0280 (3)
H19	0.4716	0.1225	0.4669	0.034*
C20	0.57619 (11)	0.46059 (17)	0.25273 (5)	0.0270 (3)
H20	0.5199	0.4440	0.2205	0.032*
C21	0.55386 (11)	0.41087 (16)	0.30343 (5)	0.0254 (3)
H21	0.4837	0.3607	0.3055	0.031*
C22	0.63533 (11)	0.43498 (15)	0.35154 (5)	0.0225 (2)
C23	0.73605 (11)	0.50991 (19)	0.34539 (5)	0.0295 (3)
H23	0.7935	0.5299	0.3769	0.035*
C24	0.75228 (12)	0.55521 (19)	0.29311 (6)	0.0318 (3)
H24	0.8217	0.6053	0.2897	0.038*
H2O	0.568 (2)	0.230 (3)	0.5766 (11)	0.081 (8)*
H6O	0.692 (2)	0.573 (4)	0.1880 (13)	0.103 (10)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.02687 (16)	0.0445 (2)	0.02162 (15)	−0.01317 (13)	0.00296 (12)	−0.00208 (13)
Cl2	0.03437 (18)	0.03004 (17)	0.02701 (17)	0.01092 (12)	0.00216 (13)	0.00226 (12)
O1	0.0397 (5)	0.0305 (5)	0.0223 (4)	−0.0026 (4)	0.0084 (4)	0.0046 (4)
O2	0.0406 (5)	0.0384 (5)	0.0186 (4)	−0.0114 (4)	0.0056 (4)	0.0007 (4)
O3	0.0352 (5)	0.0320 (5)	0.0223 (4)	0.0032 (4)	0.0092 (4)	0.0053 (4)
O4	0.0369 (5)	0.0349 (5)	0.0218 (4)	0.0021 (4)	−0.0021 (4)	−0.0056 (4)
O5	0.0260 (5)	0.0390 (5)	0.0243 (4)	0.0020 (4)	0.0081 (4)	0.0045 (4)
O6	0.0253 (5)	0.0506 (6)	0.0184 (4)	−0.0021 (4)	0.0033 (4)	0.0038 (4)
O7	0.0367 (5)	0.0524 (6)	0.0250 (5)	−0.0062 (5)	0.0124 (4)	0.0023 (5)
O8	0.0395 (6)	0.0390 (6)	0.0246 (5)	0.0009 (4)	−0.0036 (4)	0.0064 (4)
N1	0.0272 (5)	0.0262 (5)	0.0178 (5)	0.0066 (4)	0.0033 (4)	−0.0009 (4)
N2	0.0309 (6)	0.0288 (5)	0.0198 (5)	−0.0073 (4)	0.0034 (4)	0.0021 (4)
N3	0.0274 (5)	0.0335 (6)	0.0180 (5)	0.0016 (4)	0.0034 (4)	0.0029 (4)
N4	0.0290 (5)	0.0355 (6)	0.0185 (5)	0.0016 (5)	0.0060 (4)	0.0015 (4)
C1	0.0217 (5)	0.0252 (6)	0.0190 (5)	0.0006 (4)	0.0046 (4)	0.0021 (5)
C2	0.0194 (5)	0.0227 (6)	0.0192 (5)	−0.0002 (4)	0.0033 (4)	−0.0012 (4)
C3	0.0232 (5)	0.0233 (6)	0.0189 (5)	0.0001 (4)	0.0068 (4)	0.0005 (5)
C4	0.0244 (6)	0.0237 (6)	0.0163 (5)	0.0040 (4)	0.0041 (4)	0.0001 (4)
C5	0.0259 (6)	0.0320 (7)	0.0238 (6)	−0.0057 (5)	−0.0001 (5)	0.0009 (5)
C6	0.0271 (6)	0.0338 (7)	0.0248 (6)	−0.0081 (5)	0.0045 (5)	0.0049 (5)
C7	0.0216 (6)	0.0313 (6)	0.0195 (6)	0.0008 (5)	0.0051 (4)	0.0024 (5)
C8	0.0225 (5)	0.0221 (5)	0.0193 (5)	−0.0028 (4)	0.0042 (4)	0.0014 (5)
C9	0.0216 (5)	0.0193 (5)	0.0212 (6)	−0.0011 (4)	0.0018 (4)	0.0011 (4)
C10	0.0239 (6)	0.0232 (6)	0.0211 (6)	−0.0021 (4)	0.0053 (4)	−0.0025 (5)
C11	0.0244 (6)	0.0242 (6)	0.0177 (5)	−0.0050 (5)	0.0026 (4)	0.0019 (4)
C12	0.0264 (6)	0.0287 (6)	0.0255 (6)	0.0037 (5)	0.0046 (5)	0.0061 (5)
C13	0.0270 (6)	0.0295 (6)	0.0243 (6)	0.0050 (5)	0.0086 (5)	0.0027 (5)
C14	0.0266 (6)	0.0207 (5)	0.0202 (6)	−0.0011 (4)	0.0056 (5)	0.0001 (4)
C15	0.0329 (7)	0.0326 (7)	0.0185 (6)	0.0003 (5)	0.0027 (5)	−0.0017 (5)
C16	0.0307 (6)	0.0264 (6)	0.0216 (6)	−0.0026 (5)	0.0040 (5)	−0.0007 (5)
C17	0.0232 (6)	0.0257 (6)	0.0173 (5)	0.0049 (5)	0.0028 (4)	0.0015 (5)
C18	0.0300 (6)	0.0307 (6)	0.0187 (5)	−0.0020 (5)	0.0006 (5)	0.0007 (5)
C19	0.0281 (6)	0.0329 (7)	0.0222 (6)	−0.0028 (5)	0.0028 (5)	0.0040 (5)
C20	0.0290 (6)	0.0330 (7)	0.0180 (6)	0.0011 (5)	0.0019 (5)	−0.0005 (5)
C21	0.0256 (6)	0.0301 (6)	0.0202 (6)	−0.0003 (5)	0.0033 (5)	0.0010 (5)
C22	0.0261 (6)	0.0238 (6)	0.0174 (6)	0.0037 (5)	0.0038 (5)	0.0003 (4)
C23	0.0265 (6)	0.0409 (8)	0.0196 (6)	−0.0025 (5)	0.0009 (5)	0.0008 (5)
C24	0.0274 (6)	0.0445 (8)	0.0236 (6)	−0.0040 (6)	0.0053 (5)	0.0016 (6)

Geometric parameters (Å, º) top

Cl1—C2	1.7338 (12)	C8—C13	1.3994 (17)
Cl2—C9	1.7354 (12)	C8—C9	1.4001 (17)
O1—C7	1.2142 (16)	C8—C14	1.5136 (16)
O2—C7	1.3105 (16)	C9—C10	1.3926 (17)
O2—H2O	0.93 (3)	C10—C11	1.3814 (17)
O3—N1	1.2292 (15)	C10—H10	0.9500
O4—N1	1.2257 (15)	C11—C12	1.3830 (18)
O5—C14	1.2176 (15)	C12—C13	1.3869 (17)
O6—C14	1.3037 (16)	C12—H12	0.9500
O6—H6O	1.05 (3)	C13—H13	0.9500
O7—N2	1.2239 (15)	C15—C16	1.3868 (18)
O8—N2	1.2304 (15)	C15—H15	0.9500
N1—C4	1.4720 (15)	C16—C17	1.3963 (17)
N2—C11	1.4749 (15)	C16—H16	0.9500
N3—C19	1.3382 (17)	C17—C18	1.3936 (18)
N3—C15	1.3420 (18)	C17—C22	1.4889 (17)
N4—C20	1.3399 (18)	C18—C19	1.3859 (18)
N4—C24	1.3408 (17)	C18—H18	0.9500
C1—C6	1.3965 (18)	C19—H19	0.9500
C1—C2	1.4012 (17)	C20—C21	1.3858 (18)
C1—C7	1.5140 (16)	C20—H20	0.9500
C2—C3	1.3934 (16)	C21—C22	1.3996 (17)
C3—C4	1.3812 (17)	C21—H21	0.9500
C3—H3	0.9500	C22—C23	1.3935 (18)
C4—C5	1.3845 (18)	C23—C24	1.3874 (19)
C5—C6	1.3854 (18)	C23—H23	0.9500
C5—H5	0.9500	C24—H24	0.9500
C6—H6	0.9500

C7—O2—H2O	106.9 (16)	C10—C11—N2	118.53 (11)
C14—O6—H6O	109.7 (16)	C12—C11—N2	118.40 (11)
O4—N1—O3	124.00 (10)	C11—C12—C13	117.92 (12)
O4—N1—C4	117.97 (11)	C11—C12—H12	121.0
O3—N1—C4	118.02 (10)	C13—C12—H12	121.0
O7—N2—O8	123.99 (11)	C12—C13—C8	121.58 (12)
O7—N2—C11	118.53 (11)	C12—C13—H13	119.2
O8—N2—C11	117.47 (11)	C8—C13—H13	119.2
C19—N3—C15	117.66 (11)	O5—C14—O6	124.96 (11)
C20—N4—C24	118.06 (11)	O5—C14—C8	119.25 (11)
C6—C1—C2	118.10 (11)	O6—C14—C8	115.77 (10)
C6—C1—C7	115.31 (11)	N3—C15—C16	122.91 (12)
C2—C1—C7	126.53 (11)	N3—C15—H15	118.5
C3—C2—C1	120.95 (11)	C16—C15—H15	118.5
C3—C2—Cl1	116.79 (9)	C15—C16—C17	119.61 (12)
C1—C2—Cl1	122.19 (9)	C15—C16—H16	120.2
C4—C3—C2	118.31 (11)	C17—C16—H16	120.2
C4—C3—H3	120.8	C18—C17—C16	117.08 (11)
C2—C3—H3	120.8	C18—C17—C22	121.33 (11)
C3—C4—C5	122.94 (11)	C16—C17—C22	121.59 (12)
C3—C4—N1	118.22 (11)	C19—C18—C17	119.73 (12)
C5—C4—N1	118.84 (11)	C19—C18—H18	120.1
C4—C5—C6	117.48 (11)	C17—C18—H18	120.1
C4—C5—H5	121.3	N3—C19—C18	123.00 (13)
C6—C5—H5	121.3	N3—C19—H19	118.5
C5—C6—C1	122.21 (12)	C18—C19—H19	118.5
C5—C6—H6	118.9	N4—C20—C21	122.82 (12)
C1—C6—H6	118.9	N4—C20—H20	118.6
O1—C7—O2	124.90 (11)	C21—C20—H20	118.6
O1—C7—C1	119.31 (11)	C20—C21—C22	119.59 (12)
O2—C7—C1	115.77 (11)	C20—C21—H21	120.2
C13—C8—C9	118.23 (11)	C22—C21—H21	120.2
C13—C8—C14	115.87 (11)	C23—C22—C21	117.07 (11)
C9—C8—C14	125.83 (11)	C23—C22—C17	121.94 (11)
C10—C9—C8	121.31 (11)	C21—C22—C17	120.99 (12)
C10—C9—Cl2	117.08 (9)	C24—C23—C22	119.88 (12)
C8—C9—Cl2	121.52 (9)	C24—C23—H23	120.1
C11—C10—C9	117.94 (11)	C22—C23—H23	120.1
C11—C10—H10	121.0	N4—C24—C23	122.58 (13)
C9—C10—H10	121.0	N4—C24—H24	118.7
C10—C11—C12	123.02 (11)	C23—C24—H24	118.7

C6—C1—C2—C3	−0.97 (18)	O7—N2—C11—C12	166.12 (12)
C7—C1—C2—C3	−177.76 (12)	O8—N2—C11—C12	−14.64 (17)
C6—C1—C2—Cl1	175.86 (10)	C10—C11—C12—C13	−0.40 (19)
C7—C1—C2—Cl1	−0.92 (18)	N2—C11—C12—C13	176.83 (11)
C1—C2—C3—C4	0.29 (18)	C11—C12—C13—C8	0.0 (2)
Cl1—C2—C3—C4	−176.71 (9)	C9—C8—C13—C12	0.28 (19)
C2—C3—C4—C5	0.90 (19)	C14—C8—C13—C12	−176.81 (12)
C2—C3—C4—N1	−178.94 (10)	C13—C8—C14—O5	37.27 (17)
O4—N1—C4—C3	−170.86 (11)	C9—C8—C14—O5	−139.58 (13)
O3—N1—C4—C3	9.85 (16)	C13—C8—C14—O6	−141.32 (12)
O4—N1—C4—C5	9.29 (17)	C9—C8—C14—O6	41.84 (17)
O3—N1—C4—C5	−169.99 (11)	C19—N3—C15—C16	−0.6 (2)
C3—C4—C5—C6	−1.3 (2)	N3—C15—C16—C17	0.0 (2)
N1—C4—C5—C6	178.52 (12)	C15—C16—C17—C18	0.44 (19)
C4—C5—C6—C1	0.6 (2)	C15—C16—C17—C22	179.80 (12)
C2—C1—C6—C5	0.5 (2)	C16—C17—C18—C19	−0.22 (19)
C7—C1—C6—C5	177.68 (13)	C22—C17—C18—C19	−179.57 (12)
C6—C1—C7—O1	−29.31 (17)	C15—N3—C19—C18	0.8 (2)
C2—C1—C7—O1	147.56 (13)	C17—C18—C19—N3	−0.4 (2)
C6—C1—C7—O2	149.46 (12)	C24—N4—C20—C21	−0.6 (2)
C2—C1—C7—O2	−33.68 (18)	N4—C20—C21—C22	0.4 (2)
C13—C8—C9—C10	−0.20 (18)	C20—C21—C22—C23	0.27 (19)
C14—C8—C9—C10	176.58 (11)	C20—C21—C22—C17	179.61 (12)
C13—C8—C9—Cl2	−176.64 (10)	C18—C17—C22—C23	−152.85 (13)
C14—C8—C9—Cl2	0.14 (17)	C16—C17—C22—C23	27.82 (19)
C8—C9—C10—C11	−0.17 (18)	C18—C17—C22—C21	27.84 (18)
Cl2—C9—C10—C11	176.42 (9)	C16—C17—C22—C21	−151.49 (13)
C9—C10—C11—C12	0.48 (19)	C21—C22—C23—C24	−0.7 (2)
C9—C10—C11—N2	−176.75 (10)	C17—C22—C23—C24	179.96 (13)
O7—N2—C11—C10	−16.52 (17)	C20—N4—C24—C23	0.1 (2)
O8—N2—C11—C10	162.71 (11)	C22—C23—C24—N4	0.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2O···N3	0.93 (3)	1.70 (3)	2.6330 (14)	176 (2)
O6—H6O···N4	1.05 (3)	1.55 (3)	2.5984 (14)	177 (3)
C10—H10···O4ⁱ	0.95	2.41	3.2271 (16)	144
C13—H13···O3ⁱⁱ	0.95	2.34	3.2926 (17)	175
C15—H15···O3ⁱⁱⁱ	0.95	2.59	3.4360 (17)	149
C24—H24···O8^iv	0.95	2.52	3.2552 (19)	134

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

Experimental details

Crystal data
Chemical formula	C₁₀H₈N₂·2C₇H₄ClNO₄
M_r	559.32
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	12.0875 (11), 8.0695 (9), 24.610 (2)
β (°)	101.143 (2)
V (Å³)	2355.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.48 × 0.45 × 0.38

Data collection
Diffractometer	Rigaku R-AXIS RAPID-II
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.780, 0.880
No. of measured, independent and observed [I > 2σ(I)] reflections	19103, 5379, 4838
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.091, 1.08
No. of reflections	5379
No. of parameters	351
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.44

Computer programs: PROCESS-AUTO (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), CrystalStructure (Rigaku/MSC, 2004) and PLATON (Spek, 2003).