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In the title compound, C7H4ClNO4·C4H4N2, the two components are connected by an O—H...N hydrogen bond. C—H...O hydrogen bonds connect the C7H4ClNO4·C4H4N2 units to afford a macrocycle with graph-set descriptor R44(16); this ring is located on an inversion center.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802015933/ob6171sup1.cif
Contains datablocks General, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802015933/ob6171Isup2.hkl
Contains datablock I

CCDC reference: 198949

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.046
  • wR factor = 0.087
  • Data-to-parameter ratio = 13.5

checkCIF results

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ADDSYM reports no extra symmetry








Comment top

The title compound, (I), 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 et al., 2001a,b,c,d,e). In the crystal, molecules of pyridazine and 4-chloro-3-nitrobenzoic acid are held together by a short O—H···N hydrogen bond (Table 2), forming a C7H4ClNO4·C4H4N2 unit (Fig. 1). All atoms of the unit except the O atoms of the nitro group are located almost on a plane; the dihedral angle between the carboxyl group and the benzene ring is 1.1 (3)°, and 8.53 (11)° between the planes of the pyridazine and benzene rings. The nitro group is twisted out of the benzene ring plane, with a dihedral angle of 50.27 (13)°. C—H···O hydrogen bonds (Table 2) between the pyridazine ring and the carboxyl group connect the C7H4ClNO4·C4H4N2 units, resulting in a centrosymmetric macro ring with graph-set descriptor R44(16) (Bernstein et al., 1995), which is stacked along the a axis (Fig. 2). A short contact [Cl···O3ii, 3.206 (2) Å; symmetry code: (ii) −1/2 + x, 1/2 − y, −1/2 + z] is observed between the rings.

Experimental top

Crystals of (I) were obtained by slow evaporation from a benzene solution of pyridazine with 4-chloro-3-nitrobenzoic acid with molar ratio of 1:1.

Refinement top

H atoms were found in difference Fourier maps and refined isotropically. Refined distances: C—H = 0.89 (3) − 0.95 (2) and O—H = 0.89 (3) Å.

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1990); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1997-1999); program(s) used to solve structure: SIR92 (Altomare, et al. 1993); program(s) used to refine structure: TEXSAN for Windows; software used to prepare material for publication: TEXSAN for Windows.

Figures top
[Figure 1] Fig. 1. ORTEP-3 (Farrugia, 1997) drawing of (I) with the atom-labeling. Displacement ellipsoids of non-H atoms are drawn at the 50% probability level. An O—H···N hydrogen bond is indicated by a dashed line.
[Figure 2] Fig. 2. Packing diagram showing the macro ring formed via O—H···N and C—H···O hydrogen bonds indicated by dashed and dotted lines, respectively [symmetry code: (i) 2 − x, 1 − y, 2 − z].
(I) top
Crystal data top
C7H4ClNO4·C4H4N2F(000) = 576.0
Mr = 281.65Dx = 1.546 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 25 reflections
a = 3.7659 (4) Åθ = 11.4–12.4°
b = 27.486 (6) ŵ = 0.33 mm1
c = 11.7723 (15) ÅT = 298 K
β = 96.677 (10)°Prismatic, pale brown
V = 1210.3 (3) Å30.35 × 0.30 × 0.25 mm
Z = 4
Data collection top
Rigaku AFC-5R
diffractometer
1582 reflections with I > 2σ(I)
Radiation source: Rigaku rotating anodeRint = 0.022
Graphite monochromatorθmax = 27.5°, θmin = 1.7°
ω–2θ scansh = 14
Absorption correction: ψ scan
(North et al., 1968)
k = 035
Tmin = 0.873, Tmax = 0.921l = 1515
4090 measured reflections3 standard reflections every 97 reflections
2767 independent reflections intensity decay: 1.1%
Refinement top
Refinement on F20 constraints
Least-squares matrix: fullAll H-atom parameters refined
R[F2 > 2σ(F2)] = 0.046Weighting scheme based on measured s.u.'s w = 1/[σ2(Fo) + 0.00013|Fo|2]
wR(F2) = 0.087(Δ/σ)max = 0.01
S = 1.19Δρmax = 0.41 e Å3
2767 reflectionsΔρmin = 0.42 e Å3
205 parametersExtinction correction: Zachariasen (1967), equ(3) Acta Cryst.(1968) A24, p213.
0 restraintsExtinction coefficient: 9.3 (16)×10-7
Crystal data top
C7H4ClNO4·C4H4N2V = 1210.3 (3) Å3
Mr = 281.65Z = 4
Monoclinic, P21/nMo Kα radiation
a = 3.7659 (4) ŵ = 0.33 mm1
b = 27.486 (6) ÅT = 298 K
c = 11.7723 (15) Å0.35 × 0.30 × 0.25 mm
β = 96.677 (10)°
Data collection top
Rigaku AFC-5R
diffractometer
1582 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.022
Tmin = 0.873, Tmax = 0.9213 standard reflections every 97 reflections
4090 measured reflections intensity decay: 1.1%
2767 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0460 restraints
wR(F2) = 0.087All H-atom parameters refined
S = 1.19Δρmax = 0.41 e Å3
2767 reflectionsΔρmin = 0.42 e Å3
205 parameters
Special details top

Experimental. The scan width was (1.68 + 0.30tanθ)° with an ω scan speed of 6° per minute (up to 3 scans to achieve I/σ(I) > 10). Stationary background counts were recorded at each end of the scan, and the scan time:background time ratio was 2:1.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl0.25098 (17)0.29459 (2)0.46430 (5)0.05835 (19)
O10.4005 (5)0.50518 (6)0.67740 (14)0.0646 (6)
O20.5046 (5)0.46031 (6)0.83497 (14)0.0698 (6)
O30.0819 (6)0.29424 (6)0.81027 (17)0.0832 (7)
O40.1625 (6)0.25680 (6)0.67908 (17)0.0827 (7)
N10.0455 (5)0.29297 (7)0.71987 (18)0.0540 (6)
N20.7041 (5)0.57500 (7)0.80698 (16)0.0523 (6)
N30.6793 (5)0.61845 (7)0.75648 (15)0.0519 (6)
C10.2263 (5)0.42307 (7)0.66602 (17)0.0385 (6)
C20.2018 (6)0.37880 (8)0.71908 (19)0.0416 (7)
C30.0610 (6)0.33935 (7)0.65770 (17)0.0393 (6)
C40.0656 (6)0.34315 (7)0.54292 (17)0.0403 (6)
C50.0482 (6)0.38788 (8)0.49044 (19)0.0465 (7)
C60.1004 (6)0.42720 (8)0.55086 (19)0.0459 (7)
C70.3917 (6)0.46473 (8)0.7353 (2)0.0463 (7)
C80.8260 (7)0.65586 (9)0.8137 (2)0.0551 (8)
C90.9976 (7)0.65282 (10)0.9240 (2)0.0585 (9)
C101.0198 (7)0.60872 (11)0.9734 (2)0.0613 (9)
C110.8669 (7)0.57023 (10)0.9108 (2)0.0604 (9)
H10.276 (5)0.3751 (7)0.7983 (17)0.045 (6)*
H20.138 (6)0.3908 (7)0.4140 (17)0.056 (7)*
H30.113 (5)0.4575 (7)0.5148 (16)0.044 (6)*
H40.515 (8)0.5267 (10)0.725 (2)0.112 (10)*
H50.795 (7)0.6845 (9)0.7792 (19)0.068 (8)*
H61.093 (7)0.6814 (9)0.956 (2)0.085 (8)*
H71.137 (6)0.6035 (8)1.044 (2)0.071 (8)*
H80.872 (6)0.5381 (8)0.940 (2)0.078 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl0.0641 (4)0.0504 (3)0.0581 (4)0.0069 (3)0.0033 (3)0.0174 (3)
O10.0938 (14)0.0388 (10)0.0573 (11)0.0144 (9)0.0083 (10)0.0011 (8)
O20.0994 (14)0.0522 (10)0.0510 (11)0.0139 (10)0.0197 (10)0.0034 (8)
O30.1208 (17)0.0687 (12)0.0627 (12)0.0028 (12)0.0214 (12)0.0187 (11)
O40.1148 (17)0.0382 (10)0.0941 (15)0.0121 (11)0.0077 (12)0.0014 (10)
N10.0635 (14)0.0400 (11)0.0554 (13)0.0024 (11)0.0060 (11)0.0046 (11)
N20.0626 (14)0.0400 (11)0.0538 (13)0.0041 (10)0.0047 (10)0.0041 (10)
N30.0597 (14)0.0492 (12)0.0453 (11)0.0021 (10)0.0011 (10)0.0017 (10)
C10.0385 (13)0.0343 (11)0.0417 (12)0.0025 (10)0.0005 (10)0.0037 (9)
C20.0434 (14)0.0408 (13)0.0387 (13)0.0030 (10)0.0024 (11)0.0012 (10)
C30.0414 (13)0.0323 (11)0.0436 (13)0.0019 (10)0.0021 (10)0.0016 (9)
C40.0403 (13)0.0386 (12)0.0414 (12)0.0004 (10)0.0026 (10)0.0102 (10)
C50.0548 (16)0.0505 (14)0.0326 (12)0.0010 (12)0.0012 (11)0.0038 (11)
C60.0562 (15)0.0357 (12)0.0450 (14)0.0025 (11)0.0029 (11)0.0036 (11)
C70.0463 (14)0.0388 (13)0.0525 (15)0.0011 (11)0.0005 (11)0.0044 (11)
C80.0630 (17)0.0443 (15)0.0578 (16)0.0030 (13)0.0058 (13)0.0006 (13)
C90.0573 (17)0.0589 (17)0.0587 (17)0.0106 (14)0.0040 (13)0.0175 (14)
C100.0536 (17)0.084 (2)0.0432 (15)0.0019 (15)0.0064 (13)0.0023 (15)
C110.0692 (19)0.0518 (16)0.0589 (17)0.0027 (14)0.0029 (14)0.0111 (14)
Geometric parameters (Å, º) top
Cl—C41.725 (2)C2—H10.95 (2)
O1—C71.307 (3)C3—C41.383 (3)
O1—H40.89 (3)C4—C51.381 (3)
O2—C71.206 (3)C5—C61.377 (3)
O3—N11.218 (3)C5—H20.93 (2)
O4—N11.209 (3)C6—H30.94 (2)
N1—C31.474 (3)C8—C91.385 (4)
N2—N31.333 (3)C8—H50.89 (3)
N2—C111.309 (3)C9—C101.343 (4)
N3—C81.315 (3)C9—H60.93 (3)
C1—C21.376 (3)C10—C111.377 (4)
C1—C61.388 (3)C10—H70.91 (3)
C1—C71.499 (3)C11—H80.95 (2)
C2—C31.375 (3)
Cl···O3i3.206 (2)O3···C9iv3.431 (4)
O1···N22.629 (3)O4···C8v3.335 (3)
O1···N33.382 (3)O4···C8vi3.373 (4)
O2···N23.266 (3)O4···C9vi3.412 (3)
O2···C10ii3.310 (3)O4···N1vii3.450 (3)
O2···C113.392 (3)N2···C73.324 (3)
O3···O4iii3.243 (3)N3···C5viii3.369 (3)
O3···N1iii3.335 (3)
C7—O1—H4106 (2)C6—C5—H2120.9 (14)
O3—N1—O4124.7 (2)C1—C6—C5120.8 (2)
O3—N1—C3116.8 (2)C1—C6—H3119.0 (13)
O4—N1—C3118.5 (2)C5—C6—H3120.1 (13)
N3—N2—C11120.5 (2)O1—C7—O2124.4 (2)
N2—N3—C8118.0 (2)O1—C7—C1113.6 (2)
C2—C1—C6118.9 (2)O2—C7—C1122.0 (2)
C2—C1—C7118.3 (2)N3—C8—C9123.8 (3)
C6—C1—C7122.8 (2)N3—C8—H5115.8 (17)
C1—C2—C3120.1 (2)C9—C8—H5120.3 (17)
C1—C2—H1120.9 (13)C8—C9—C10117.3 (3)
C3—C2—H1119.0 (13)C8—C9—H6116.6 (18)
N1—C3—C2117.1 (2)C10—C9—H6126.0 (18)
N1—C3—C4121.4 (2)C9—C10—C11117.4 (3)
C2—C3—C4121.5 (2)C9—C10—H7122.6 (17)
Cl—C4—C3122.54 (18)C11—C10—H7119.9 (17)
Cl—C4—C5119.08 (18)N2—C11—C10123.0 (3)
C3—C4—C5118.4 (2)N2—C11—H8114.9 (16)
C4—C5—C6120.4 (2)C10—C11—H8122.1 (16)
C4—C5—H2118.7 (14)
Cl—C4—C3—N10.2 (3)N2—C11—C10—C90.0 (5)
Cl—C4—C3—C2178.80 (19)N3—N2—C11—C100.0 (4)
Cl—C4—C5—C6179.6 (2)N3—C8—C9—C101.5 (5)
O1—C7—C1—C2179.6 (2)C1—C2—C3—C41.4 (4)
O1—C7—C1—C61.0 (3)C1—C6—C5—C41.8 (4)
O2—C7—C1—C20.5 (4)C2—C1—C6—C50.3 (4)
O2—C7—C1—C6178.9 (3)C2—C3—C4—C50.1 (4)
O3—N1—C3—C249.0 (3)C3—C2—C1—C61.3 (4)
O3—N1—C3—C4130.1 (3)C3—C2—C1—C7178.2 (2)
O4—N1—C3—C2130.1 (3)C3—C4—C5—C61.7 (4)
O4—N1—C3—C450.8 (3)C5—C6—C1—C7179.7 (2)
N1—C3—C2—C1179.5 (2)C8—N3—N2—C110.7 (4)
N1—C3—C4—C5178.9 (2)C8—C9—C10—C110.7 (4)
N2—N3—C8—C91.4 (4)
Symmetry codes: (i) x1/2, y+1/2, z1/2; (ii) x+2, y+1, z+2; (iii) x1, y, z; (iv) x+1, y+1, z+2; (v) x+1/2, y1/2, z+3/2; (vi) x+3/2, y1/2, z+3/2; (vii) x+1, y, z; (viii) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H4···N20.89 (3)1.74 (3)2.629 (3)172 (3)
C10—H7···O2ii0.91 (2)2.55 (2)3.310 (3)142 (2)
Symmetry code: (ii) x+2, y+1, z+2.

Experimental details

Crystal data
Chemical formulaC7H4ClNO4·C4H4N2
Mr281.65
Crystal system, space groupMonoclinic, P21/n
Temperature (K)298
a, b, c (Å)3.7659 (4), 27.486 (6), 11.7723 (15)
β (°) 96.677 (10)
V3)1210.3 (3)
Z4
Radiation typeMo Kα
µ (mm1)0.33
Crystal size (mm)0.35 × 0.30 × 0.25
Data collection
DiffractometerRigaku AFC-5R
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.873, 0.921
No. of measured, independent and
observed [I > 2σ(I)] reflections
4090, 2767, 1582
Rint0.022
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.046, 0.087, 1.19
No. of reflections2767
No. of parameters205
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.41, 0.42

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1990), MSC/AFC Diffractometer Control Software, TEXSAN for Windows (Molecular Structure Corporation, 1997-1999), SIR92 (Altomare, et al. 1993), TEXSAN for Windows.

Selected bond lengths (Å) top
Cl—C41.725 (2)N1—C31.474 (3)
O1—C71.307 (3)N2—N31.333 (3)
O2—C71.206 (3)N2—C111.309 (3)
O3—N11.218 (3)N3—C81.315 (3)
O4—N11.209 (3)C1—C71.499 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H4···N20.89 (3)1.74 (3)2.629 (3)172 (3)
C10—H7···O2i0.91 (2)2.55 (2)3.310 (3)142.4 (18)
Symmetry code: (i) x+2, y+1, z+2.
 

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