In the title compound, C
7H
4ClNO
4·C
4H
4N
2, the two components are connected by an O—H
N hydrogen bond. C—H
O hydrogen bonds connect the C
7H
4ClNO
4·C
4H
4N
2 units to afford a macrocycle with graph-set descriptor
R44(16); this ring is located on an inversion center.
Supporting information
CCDC reference: 198949
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.003 Å
- R factor = 0.046
- wR factor = 0.087
- Data-to-parameter ratio = 13.5
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
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.
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.
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.
Crystal data top
C7H4ClNO4·C4H4N2 | F(000) = 576.0 |
Mr = 281.65 | Dx = 1.546 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 25 reflections |
a = 3.7659 (4) Å | θ = 11.4–12.4° |
b = 27.486 (6) Å | µ = 0.33 mm−1 |
c = 11.7723 (15) Å | T = 298 K |
β = 96.677 (10)° | Prismatic, pale brown |
V = 1210.3 (3) Å3 | 0.35 × 0.30 × 0.25 mm |
Z = 4 | |
Data collection top
Rigaku AFC-5R diffractometer | 1582 reflections with I > 2σ(I) |
Radiation source: Rigaku rotating anode | Rint = 0.022 |
Graphite monochromator | θmax = 27.5°, θmin = 1.7° |
ω–2θ scans | h = −1→4 |
Absorption correction: ψ scan (North et al., 1968) | k = 0→35 |
Tmin = 0.873, Tmax = 0.921 | l = −15→15 |
4090 measured reflections | 3 standard reflections every 97 reflections |
2767 independent reflections | intensity decay: 1.1% |
Refinement top
Refinement on F2 | 0 constraints |
Least-squares matrix: full | All H-atom parameters refined |
R[F2 > 2σ(F2)] = 0.046 | Weighting 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 = 1.19 | Δρmax = 0.41 e Å−3 |
2767 reflections | Δρmin = −0.42 e Å−3 |
205 parameters | Extinction correction: Zachariasen (1967), equ(3) Acta Cryst.(1968) A24, p213. |
0 restraints | Extinction coefficient: 9.3 (16)×10-7 |
Crystal data top
C7H4ClNO4·C4H4N2 | V = 1210.3 (3) Å3 |
Mr = 281.65 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 3.7659 (4) Å | µ = 0.33 mm−1 |
b = 27.486 (6) Å | T = 298 K |
c = 11.7723 (15) Å | 0.35 × 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 = 0.921 | 3 standard reflections every 97 reflections |
4090 measured reflections | intensity decay: 1.1% |
2767 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.087 | All H-atom parameters refined |
S = 1.19 | Δρmax = 0.41 e Å−3 |
2767 reflections | Δρmin = −0.42 e Å−3 |
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 | x | y | z | Uiso*/Ueq | |
Cl | −0.25098 (17) | 0.29459 (2) | 0.46430 (5) | 0.05835 (19) | |
O1 | 0.4005 (5) | 0.50518 (6) | 0.67740 (14) | 0.0646 (6) | |
O2 | 0.5046 (5) | 0.46031 (6) | 0.83497 (14) | 0.0698 (6) | |
O3 | −0.0819 (6) | 0.29424 (6) | 0.81027 (17) | 0.0832 (7) | |
O4 | 0.1625 (6) | 0.25680 (6) | 0.67908 (17) | 0.0827 (7) | |
N1 | 0.0455 (5) | 0.29297 (7) | 0.71987 (18) | 0.0540 (6) | |
N2 | 0.7041 (5) | 0.57500 (7) | 0.80698 (16) | 0.0523 (6) | |
N3 | 0.6793 (5) | 0.61845 (7) | 0.75648 (15) | 0.0519 (6) | |
C1 | 0.2263 (5) | 0.42307 (7) | 0.66602 (17) | 0.0385 (6) | |
C2 | 0.2018 (6) | 0.37880 (8) | 0.71908 (19) | 0.0416 (7) | |
C3 | 0.0610 (6) | 0.33935 (7) | 0.65770 (17) | 0.0393 (6) | |
C4 | −0.0656 (6) | 0.34315 (7) | 0.54292 (17) | 0.0403 (6) | |
C5 | −0.0482 (6) | 0.38788 (8) | 0.49044 (19) | 0.0465 (7) | |
C6 | 0.1004 (6) | 0.42720 (8) | 0.55086 (19) | 0.0459 (7) | |
C7 | 0.3917 (6) | 0.46473 (8) | 0.7353 (2) | 0.0463 (7) | |
C8 | 0.8260 (7) | 0.65586 (9) | 0.8137 (2) | 0.0551 (8) | |
C9 | 0.9976 (7) | 0.65282 (10) | 0.9240 (2) | 0.0585 (9) | |
C10 | 1.0198 (7) | 0.60872 (11) | 0.9734 (2) | 0.0613 (9) | |
C11 | 0.8669 (7) | 0.57023 (10) | 0.9108 (2) | 0.0604 (9) | |
H1 | 0.276 (5) | 0.3751 (7) | 0.7983 (17) | 0.045 (6)* | |
H2 | −0.138 (6) | 0.3908 (7) | 0.4140 (17) | 0.056 (7)* | |
H3 | 0.113 (5) | 0.4575 (7) | 0.5148 (16) | 0.044 (6)* | |
H4 | 0.515 (8) | 0.5267 (10) | 0.725 (2) | 0.112 (10)* | |
H5 | 0.795 (7) | 0.6845 (9) | 0.7792 (19) | 0.068 (8)* | |
H6 | 1.093 (7) | 0.6814 (9) | 0.956 (2) | 0.085 (8)* | |
H7 | 1.137 (6) | 0.6035 (8) | 1.044 (2) | 0.071 (8)* | |
H8 | 0.872 (6) | 0.5381 (8) | 0.940 (2) | 0.078 (8)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl | 0.0641 (4) | 0.0504 (3) | 0.0581 (4) | −0.0069 (3) | −0.0033 (3) | −0.0174 (3) |
O1 | 0.0938 (14) | 0.0388 (10) | 0.0573 (11) | −0.0144 (9) | −0.0083 (10) | −0.0011 (8) |
O2 | 0.0994 (14) | 0.0522 (10) | 0.0510 (11) | −0.0139 (10) | −0.0197 (10) | −0.0034 (8) |
O3 | 0.1208 (17) | 0.0687 (12) | 0.0627 (12) | −0.0028 (12) | 0.0214 (12) | 0.0187 (11) |
O4 | 0.1148 (17) | 0.0382 (10) | 0.0941 (15) | 0.0121 (11) | 0.0077 (12) | 0.0014 (10) |
N1 | 0.0635 (14) | 0.0400 (11) | 0.0554 (13) | −0.0024 (11) | −0.0060 (11) | 0.0046 (11) |
N2 | 0.0626 (14) | 0.0400 (11) | 0.0538 (13) | −0.0041 (10) | 0.0047 (10) | −0.0041 (10) |
N3 | 0.0597 (14) | 0.0492 (12) | 0.0453 (11) | −0.0021 (10) | −0.0011 (10) | −0.0017 (10) |
C1 | 0.0385 (13) | 0.0343 (11) | 0.0417 (12) | 0.0025 (10) | 0.0005 (10) | −0.0037 (9) |
C2 | 0.0434 (14) | 0.0408 (13) | 0.0387 (13) | 0.0030 (10) | −0.0024 (11) | −0.0012 (10) |
C3 | 0.0414 (13) | 0.0323 (11) | 0.0436 (13) | 0.0019 (10) | 0.0021 (10) | 0.0016 (9) |
C4 | 0.0403 (13) | 0.0386 (12) | 0.0414 (12) | 0.0004 (10) | 0.0026 (10) | −0.0102 (10) |
C5 | 0.0548 (16) | 0.0505 (14) | 0.0326 (12) | 0.0010 (12) | −0.0012 (11) | −0.0038 (11) |
C6 | 0.0562 (15) | 0.0357 (12) | 0.0450 (14) | 0.0025 (11) | 0.0029 (11) | 0.0036 (11) |
C7 | 0.0463 (14) | 0.0388 (13) | 0.0525 (15) | 0.0011 (11) | 0.0005 (11) | −0.0044 (11) |
C8 | 0.0630 (17) | 0.0443 (15) | 0.0578 (16) | −0.0030 (13) | 0.0058 (13) | 0.0006 (13) |
C9 | 0.0573 (17) | 0.0589 (17) | 0.0587 (17) | −0.0106 (14) | 0.0040 (13) | −0.0175 (14) |
C10 | 0.0536 (17) | 0.084 (2) | 0.0432 (15) | 0.0019 (15) | −0.0064 (13) | −0.0023 (15) |
C11 | 0.0692 (19) | 0.0518 (16) | 0.0589 (17) | 0.0027 (14) | 0.0029 (14) | 0.0111 (14) |
Geometric parameters (Å, º) top
Cl—C4 | 1.725 (2) | C2—H1 | 0.95 (2) |
O1—C7 | 1.307 (3) | C3—C4 | 1.383 (3) |
O1—H4 | 0.89 (3) | C4—C5 | 1.381 (3) |
O2—C7 | 1.206 (3) | C5—C6 | 1.377 (3) |
O3—N1 | 1.218 (3) | C5—H2 | 0.93 (2) |
O4—N1 | 1.209 (3) | C6—H3 | 0.94 (2) |
N1—C3 | 1.474 (3) | C8—C9 | 1.385 (4) |
N2—N3 | 1.333 (3) | C8—H5 | 0.89 (3) |
N2—C11 | 1.309 (3) | C9—C10 | 1.343 (4) |
N3—C8 | 1.315 (3) | C9—H6 | 0.93 (3) |
C1—C2 | 1.376 (3) | C10—C11 | 1.377 (4) |
C1—C6 | 1.388 (3) | C10—H7 | 0.91 (3) |
C1—C7 | 1.499 (3) | C11—H8 | 0.95 (2) |
C2—C3 | 1.375 (3) | | |
| | | |
Cl···O3i | 3.206 (2) | O3···C9iv | 3.431 (4) |
O1···N2 | 2.629 (3) | O4···C8v | 3.335 (3) |
O1···N3 | 3.382 (3) | O4···C8vi | 3.373 (4) |
O2···N2 | 3.266 (3) | O4···C9vi | 3.412 (3) |
O2···C10ii | 3.310 (3) | O4···N1vii | 3.450 (3) |
O2···C11 | 3.392 (3) | N2···C7 | 3.324 (3) |
O3···O4iii | 3.243 (3) | N3···C5viii | 3.369 (3) |
O3···N1iii | 3.335 (3) | | |
| | | |
C7—O1—H4 | 106 (2) | C6—C5—H2 | 120.9 (14) |
O3—N1—O4 | 124.7 (2) | C1—C6—C5 | 120.8 (2) |
O3—N1—C3 | 116.8 (2) | C1—C6—H3 | 119.0 (13) |
O4—N1—C3 | 118.5 (2) | C5—C6—H3 | 120.1 (13) |
N3—N2—C11 | 120.5 (2) | O1—C7—O2 | 124.4 (2) |
N2—N3—C8 | 118.0 (2) | O1—C7—C1 | 113.6 (2) |
C2—C1—C6 | 118.9 (2) | O2—C7—C1 | 122.0 (2) |
C2—C1—C7 | 118.3 (2) | N3—C8—C9 | 123.8 (3) |
C6—C1—C7 | 122.8 (2) | N3—C8—H5 | 115.8 (17) |
C1—C2—C3 | 120.1 (2) | C9—C8—H5 | 120.3 (17) |
C1—C2—H1 | 120.9 (13) | C8—C9—C10 | 117.3 (3) |
C3—C2—H1 | 119.0 (13) | C8—C9—H6 | 116.6 (18) |
N1—C3—C2 | 117.1 (2) | C10—C9—H6 | 126.0 (18) |
N1—C3—C4 | 121.4 (2) | C9—C10—C11 | 117.4 (3) |
C2—C3—C4 | 121.5 (2) | C9—C10—H7 | 122.6 (17) |
Cl—C4—C3 | 122.54 (18) | C11—C10—H7 | 119.9 (17) |
Cl—C4—C5 | 119.08 (18) | N2—C11—C10 | 123.0 (3) |
C3—C4—C5 | 118.4 (2) | N2—C11—H8 | 114.9 (16) |
C4—C5—C6 | 120.4 (2) | C10—C11—H8 | 122.1 (16) |
C4—C5—H2 | 118.7 (14) | | |
| | | |
Cl—C4—C3—N1 | 0.2 (3) | N2—C11—C10—C9 | 0.0 (5) |
Cl—C4—C3—C2 | −178.80 (19) | N3—N2—C11—C10 | 0.0 (4) |
Cl—C4—C5—C6 | −179.6 (2) | N3—C8—C9—C10 | 1.5 (5) |
O1—C7—C1—C2 | −179.6 (2) | C1—C2—C3—C4 | −1.4 (4) |
O1—C7—C1—C6 | 1.0 (3) | C1—C6—C5—C4 | −1.8 (4) |
O2—C7—C1—C2 | 0.5 (4) | C2—C1—C6—C5 | 0.3 (4) |
O2—C7—C1—C6 | −178.9 (3) | C2—C3—C4—C5 | −0.1 (4) |
O3—N1—C3—C2 | 49.0 (3) | C3—C2—C1—C6 | 1.3 (4) |
O3—N1—C3—C4 | −130.1 (3) | C3—C2—C1—C7 | −178.2 (2) |
O4—N1—C3—C2 | −130.1 (3) | C3—C4—C5—C6 | 1.7 (4) |
O4—N1—C3—C4 | 50.8 (3) | C5—C6—C1—C7 | 179.7 (2) |
N1—C3—C2—C1 | 179.5 (2) | C8—N3—N2—C11 | 0.7 (4) |
N1—C3—C4—C5 | 178.9 (2) | C8—C9—C10—C11 | −0.7 (4) |
N2—N3—C8—C9 | −1.4 (4) | | |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x+2, −y+1, −z+2; (iii) x−1, y, z; (iv) −x+1, −y+1, −z+2; (v) −x+1/2, y−1/2, −z+3/2; (vi) −x+3/2, y−1/2, −z+3/2; (vii) x+1, y, z; (viii) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H4···N2 | 0.89 (3) | 1.74 (3) | 2.629 (3) | 172 (3) |
C10—H7···O2ii | 0.91 (2) | 2.55 (2) | 3.310 (3) | 142 (2) |
Symmetry code: (ii) −x+2, −y+1, −z+2. |
Experimental details
Crystal data |
Chemical formula | C7H4ClNO4·C4H4N2 |
Mr | 281.65 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 3.7659 (4), 27.486 (6), 11.7723 (15) |
β (°) | 96.677 (10) |
V (Å3) | 1210.3 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.33 |
Crystal size (mm) | 0.35 × 0.30 × 0.25 |
|
Data collection |
Diffractometer | Rigaku AFC-5R diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.873, 0.921 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4090, 2767, 1582 |
Rint | 0.022 |
(sin θ/λ)max (Å−1) | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.087, 1.19 |
No. of reflections | 2767 |
No. of parameters | 205 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.41, −0.42 |
Selected bond lengths (Å) topCl—C4 | 1.725 (2) | N1—C3 | 1.474 (3) |
O1—C7 | 1.307 (3) | N2—N3 | 1.333 (3) |
O2—C7 | 1.206 (3) | N2—C11 | 1.309 (3) |
O3—N1 | 1.218 (3) | N3—C8 | 1.315 (3) |
O4—N1 | 1.209 (3) | C1—C7 | 1.499 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H4···N2 | 0.89 (3) | 1.74 (3) | 2.629 (3) | 172 (3) |
C10—H7···O2i | 0.91 (2) | 2.55 (2) | 3.310 (3) | 142.4 (18) |
Symmetry code: (i) −x+2, −y+1, −z+2. |
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.