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The structures of three isomeric compounds, C7H4ClNO4·C8H6N2, of phthalazine with chloro- and nitro-substituted benzoic acid, namely, 3-chloro-2-nitro­benzoic acid–phthalazine (1/1), (I), 4-chloro-2-nitro­benzoic acid–phthalazine (1/1), (II), and 4-chloro-3-nitro­benzoic acid–phthalazine (1/1), (III), have been determined at 190 K. In the asymmetric unit of each compound, there are two crystallographically independent chloro­nitro­benzoic acid–phthalazine units, in each of which the two components are held together by a short hydrogen bond between an N atom of the base and a carboxyl O atom. In one hydrogen-bonded unit of (I) and in two units of (II), a weak C—H...O inter­action is also observed between the two components. The N...O distances are 2.5715 (15) and 2.5397 (17) Å for (I), 2.5655 (13) and 2.6081 (13) Å for (II), and 2.613 (2) and 2.589 (2) Å for (III). In both hydrogen-bonded units of (I) and (II), the H atoms are each disordered over two positions with (N site):(O site) occupancies of 0.35 (3):0.65 (3) and 0.31 (3):0.69 (3) for (I), and 0.32 (3):0.68 (3) and 0.30 (3):0.70 (3) for (II). The H atoms in the hydrogen-bonded units of (III) are located at the O-atom sites.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111044829/fg3232sup1.cif
Contains datablocks global, I, II, III

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111044829/fg3232Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111044829/fg3232IIsup3.hkl
Contains datablock II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111044829/fg3232IIIsup4.hkl
Contains datablock III

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Portable Document Format (PDF) file https://doi.org/10.1107/S0108270111044829/fg3232sup5.pdf
Supplementary material

CCDC references: 855977; 855978; 855979

Comment top

The hydrogen bonds formed between organic acids and organic bases vary from an O—H···N to an O···H—N type with increasing pKa or proton affinities (PA) of the bases, and at an appropriate ΔpKa [pKa(base) - pKa(acid)] the critical (inversion) point at 50% proton transfer occurs, in the region of which a short strong hydrogen bond with a broad single minimum potential-energy curve for the H atom or a double-minimum potential is expected (Jerzykiewicz et al., 1998; Kalenik et al., 1989; Steiner et al., 2001; Schmidtmann & Wilson, 2008; Gilli & Gilli, 2009). For the pyridine derivative–chloro- and nitro-substituted benzoic acid systems, we have shown that the three isomeric compounds, namely, quinoline–3-chloro-2-nitrobenzoic acid (1/1), (IV), quinoline–4-chloro-2-nitrobenzoic acid (1/1), (V), and quinoline–5-chloro-2-nitrobenzoic acid (1/1), (VI), are in a critical region and have a short double-well N···H···O hydrogen bond between the pyridine N atom and the carboxyl group (Gotoh & Ishida, 2009). The (N site):(O site) occupancies of the H atom are 0.39 (3):0.61 (3), 0.47 (3):0.53 (3) and 0.65 (3):0.35 (3) for (IV), (V) and (VI), respectively. The ΔpKa values are 3.08, 2.93 and 3.04, respectively, for (IV), (V) and (VI).

In this communication, we report the three isomeric compounds, phthalazine–3-chloro-2-nitrobenzoic acid (1/1), (I), phthalazine–4-chloro-2-nitrobenzoic acid (1/1), (II), and phthalazine–4-chloro-3-nitrobenzoic acid (1/1), (III), in order to extend our studies of the critical region and hydrogen bonding in the pyridine derivative–chloro- and nitro-substituted benzoic acid systems (Gotoh & Ishida, 2007, 2009). Phthalazine is a weaker base (pKa 3.47) than quinoline (pKa 4.90), and the ΔpKa values are 1.65, 1.50 and 0.12, respectively, for (I), (II) and (III).

The molecular structures of the three compounds, (I), (II) and (III), are shown in Figs. 1, 2 and 3, respectively. The asymmetric unit of each compound consists of two crystallographically independent chloronitrobenzoic acid–phthalazine units, where the two components are held together by a short hydrogen bond between one N atom of the base and the carboxyl group of the acid (Tables 1–3). The N···O distances are 2.5715 (15) and 2.5397 (17) Å for (I), 2.5655 (13) and 2.6081 (13) Å for (II), and 2.613 (2) and 2.589 (2) Å for (III). In the hydrogen bonds of (I) and (II), the H atoms were found to be disordered from difference Fourier maps (see supplementary figure), each of which shows two distinct peaks. The site occupancies refined to 0.35 (3):0.65 (3) (N2 site:O1 site) and 0.31 (3):0.69 (3) (N5 site:O5 site) for (I), and 0.32 (3):0.68 (3) (N2 site:O1 site) and 0.30 (3):0.70 (3) (N5 site:O5 site) for (II). On the other hand, in (III) no disordered H atom was observed, although one of the O···N distances [2.589 (2) Å] is shorter than the O5···N5 distance [2.6081 (3) Å] in (I); the H atoms in the hydrogen bonds are located at an O site (Table 3). In addition, a weak C—H···O interaction is observed in one hydrogen-bonded unit of (I) (C15—H15···O2; Table 2) and in each unit of (II) (C15—H15···O2 and C30—H30···O6; Table 3).

In the hydrogen-bonded units of (I) and (II), the benzene (C1–C6 or C16–C21) ring, the carboxyl (O1/C7/O2 or O5/C22/O6) plane and the phthalazine (N2/N3/C8–C15 or N5/N6/C23–C30) ring system are slightly twisted relative to each other. The dihedral angles between the C1–C6 and O1/C7/O2 planes, the C16–C21 and O5/C22/O6 planes, the O1/C7/O2 and N2/N3/C8–C15 planes, the O5/C22/O6 and N5/N6/C23–C30 planes, the C1–C6 and N2/N3/C8–C15 planes, and the C16–C21 and N5/N6/C23–C30 planes are 11.41 (14), 2.93 (15), 2.99 (14), 11.93 (15), 8.59 (5) and 9.02 (5)°, respectively, in (I), and 2.75 (17), 18.76 (17), 14.24 (16), 22.03 (16), 16.84 (5) and 9.56 (5)°, respectively, in (II). By contrast, in (III) these three planes are approximately coplanar with each other; the corresponding dihedral angles are 2.2 (2), 2.1 (3), 1.3 (2), 1.5 (3), 1.03 (8) and 0.66 (8)°. The planarity in both units of (III) may lead to a packing scheme accompanied by ππ stacking interactions in the crystal structure, as mentioned below.

The packing diagrams of the three compounds are given in Figs. 4–9. In (I), the two crystallographically independent hydrogen-bonded units are alternately arranged via C—H···O and C—H···N hydrogen bonds (C5—H5···O6, C8—H8···O5i, C20—H20···O4iii, C21—H21···N3iii and C28—H28···O2; details and symmetry codes in Table 1), forming a tape structure along the [110] direction (Fig. 4). These tapes are further linked via C—H···O and C—H···Cl hydrogen bonds (C12—H12···O3ii and C23—H23···Cl2ii; details and symmetry code in Table 1) into a sheet expanding parallel to the (110) plane (Fig. 5). Between these sheets, which are related to each other by an inversion centre, a C—H···O interaction (C23—H23···O3iv; see Table 1 for symmetry code) and ππ stacking interactions between the C1–C6 and N2/N3/C8/C9/C14/C15 rings, and the C16–C21 and C24–C29 rings, are observed. The centroid-to-centroid distances are in the range 3.5926 (9)–3.8215 (10) Å and the detailed geometries are given in Table 4.

In (II), there are fewer observable intermolecular hydrogen bonds than in (I), which may reflect the less dense crystal than (I). The two independent hydrogen-bonded units are alternately linked in a head-to-tail manner via C—H···O hydrogen bonds (C10—H10···O7i and C25—H25···O3; details and symmetry codes in Table 2), forming a tape structure along the a axis (Fig. 6). These tapes, related to each other by an inversion centre, are further linked by a weak C—H···O interaction (C15—H15···O8ii; details and symmetry code in Table 2) and a ππ stacking interaction between the N2/N3/C8/C9/C14/C15 and C9–C14 rings (Table 5), forming a double-tape structure (Fig. 7). Between the double-tapes other ππ stacking interactions are also observed (Table 4). The centroid-to-centroid distances are in the range 3.6109 (7)–3.8139 (7) Å.

In (III), the two hydrogen-bonded units are linked by C—H···O hydrogen bonds (C13—H13···O6, C20—H20···O2, C26—H26···O4ii and C27—H27···O7iii; details and symmetry codes in Table 3), forming a molecular sheet parallel to the (101) plane (Fig. 8). The arrangement of the two components in the sheet is similar to that in (I), but there are fewer hydrogen bonds than (I). On the other hand, between the sheets, related to each other by an inversion centre, relatively short ππ interactions between the acid rings and the phthalazine ring systems are observed, with centroid-to-centroid distances of 3.5985 (12)–3.7248 (12) Å (Table 4), and each hydrogen-bonded unit is stacked in a column in an antiparallel manner along the a axis (Fig. 9), resulting in the most dense crystal of the three compounds.

We have thus shown the existence of short double-well N···H···O hydrogen bonds in the structures of (I) and (II). Therefore, the critical region of chloronitrobenzoic acid–phthalazine systems may be expected around ΔpKa = 1.6, which is much smaller than ΔpKa = 2.93–3.08 found in quinoline–chloronitrobenzoic acid systems.

Related literature top

For related literature, see: Gilli & Gilli (2009); Gotoh & Ishida (2007, 2009); Jerzykiewicz et al. (1998); Kalenik et al. (1989); Schmidtmann & Wilson (2008); Steiner et al. (2001).

Experimental top

Crystals of all three compounds were obtained by slow evaporation from acetonitrile solutions of phthalazine with the corresponding chloro- and nitro-substituted benzoic acid in a 1:1 molar ratio at room temperature [acetonitrile solution (50 ml) of phthalazine (0.200 g) and 3-chloro-2-nitrobenzoic acid (0.310 g) for (I), acetonitrile solution (30 ml) of phthalazine (0.161 g) and 4-chloro-2-nitrobenzoic acid (0.249 g) for (II), and acetonitrile solution (90 ml) of phthalazine (0.096 g) and 4-chloro-3-nitrobenzoic acid (0.149 g) for (III)].

Refinement top

For all three compounds, all H atoms were found in difference Fourier maps. H atoms in(I) and (II) which are involved in N···H···O hydrogen bonds were found to be disordered over two positions in difference Fourier maps. Since the site-occupancy factors and isotropic displacement parameters were strongly correlated, the positional parameters and occupancy factors were refined, with Uiso(H) = 1.5Ueq(N or O). The positional parameters were refined with bond restraints of O—H = 0.84 (2) Å and N—H = 0.88 (2) Å. Atoms H1 and H5A in (III) were refined isotropically. The refined distances are given in Tables 1–3. The remaining H atoms of all compounds were positioned geometrically (C—H = 0.95 Å) and treated as riding, with Uiso(H) = 1.2Ueq(C).

Computing details top

For all compounds, 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, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and WinGX (Farrugia, 1999); software used to prepare material for publication: CrystalStructure (Rigaku/MSC, 2004) and PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The O—H···N hydrogen bonds are indicated by dashed lines.
[Figure 2] Fig. 2. The asymmetric unit of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The N—H···O hydrogen bonds are indicated by dashed lines.
[Figure 3] Fig. 3. The asymmetric unit of (III), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. The O—H···N hydrogen bonds are indicated by dashed lines.
[Figure 4] Fig. 4. A packing diagram for (I), showing the hydrogen-bonded tape running along the [110] direction. H atoms not involved in the O···H···N, C—H···O and C—H···N hydrogen bonds (dashed lines) have been omitted. [Symmetry codes: (i) x - 1, y + 1, z; (iii) x + 1, y - 1, z.]
[Figure 5] Fig. 5. A packing diagram for (I), showing the hydrogen-bonded sheet structure parallel to the (110) plane. H atoms not involved in the O···H···N, C—H···O, C—H···N and C—H···Cl hydrogen bonds (dashed lines) have been omitted. [Symmetry codes: (i) x - 1, y + 1, z; (ii) x, y, z - 1; (iii) x + 1, y - 1, z.]
[Figure 6] Fig. 6. A packing diagram for (II), showing the hydrogen-bonded tape running along the a axis. Dashed lines indicate N···H···O and C—H···O hydrogen bonds. H atoms not involved in the hydrogen bonds have been omitted. [Symmetry codes: (i) x + 1, y, z; (iii) x - 1, y, z.]
[Figure 7] Fig. 7. A packing diagram for (II), showing the double-tape structure. N···H···O and C—H···O hydrogen bonds are indicated by dashed lines. H atoms not involved in the hydrogen bonds have been omitted. [Symmetry codes: (i) x + 1, y, z; (ii) -x, -y + 1, -z + 1; (iv) -x + 1, -y + 1, -z + 1.]
[Figure 8] Fig. 8. A packing diagram for (III), showing the hydrogen-bonded sheet structure parallel to the (101) plane. O—H···N and C—H···O hydrogen bonds are indicated by dashed lines. H atoms not involved in the hydrogen bonds have been omitted. [Symmetry codes: (ii) x - 1, y + 1, z + 1; (iii) x, y + 1, z.]
[Figure 9] Fig. 9. A packing diagram for (III), showing the ππ stacking structures of the two independent hydrogen-bonded units. Dashed lines indicate O—H···N hydrogen bonds and H atoms not involved in the hydrogen bonds have been omitted. [Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (iv) -x + 1, -y + 1, -z; (v) -x + 2, -y + 1, -z; (vi) -x, -y + 1, -z + 1.]
(I) 3-chloro-2-nitrobenzoic acid–phthalazine (1/1) top
Crystal data top
C7H3.67ClNO4·C8H6.33N2Z = 4
Mr = 331.71F(000) = 680.00
Triclinic, P1Dx = 1.542 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71075 Å
a = 9.7764 (15) ÅCell parameters from 18876 reflections
b = 12.0384 (14) Åθ = 3.0–30.2°
c = 12.8889 (15) ŵ = 0.29 mm1
α = 81.491 (3)°T = 190 K
β = 72.328 (5)°Block, colourless
γ = 88.390 (5)°0.40 × 0.28 × 0.18 mm
V = 1429.2 (3) Å3
Data collection top
Rigaku R-AXIS RAPID II
diffractometer
6364 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm-1Rint = 0.035
ω scansθmax = 30.0°
Absorption correction: numerical
(NUMABS; Higashi, 1999)
h = 1313
Tmin = 0.874, Tmax = 0.949k = 1616
31515 measured reflectionsl = 1718
8271 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112H atoms treated by a mixture of independent and constrained refinement
S = 1.10 w = 1/[σ2(Fo2) + (0.0642P)2 + 0.0877P]
where P = (Fo2 + 2Fc2)/3
8271 reflections(Δ/σ)max = 0.001
429 parametersΔρmax = 0.30 e Å3
4 restraintsΔρmin = 0.41 e Å3
Crystal data top
C7H3.67ClNO4·C8H6.33N2γ = 88.390 (5)°
Mr = 331.71V = 1429.2 (3) Å3
Triclinic, P1Z = 4
a = 9.7764 (15) ÅMo Kα radiation
b = 12.0384 (14) ŵ = 0.29 mm1
c = 12.8889 (15) ÅT = 190 K
α = 81.491 (3)°0.40 × 0.28 × 0.18 mm
β = 72.328 (5)°
Data collection top
Rigaku R-AXIS RAPID II
diffractometer
8271 independent reflections
Absorption correction: numerical
(NUMABS; Higashi, 1999)
6364 reflections with I > 2σ(I)
Tmin = 0.874, Tmax = 0.949Rint = 0.035
31515 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0374 restraints
wR(F2) = 0.112H atoms treated by a mixture of independent and constrained refinement
S = 1.10Δρmax = 0.30 e Å3
8271 reflectionsΔρmin = 0.41 e Å3
429 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
xyzUiso*/UeqOcc. (<1)
Cl10.54704 (3)0.82797 (3)0.97698 (2)0.04315 (9)
Cl21.06363 (3)0.32598 (3)0.99901 (2)0.04380 (9)
O10.38359 (10)0.91589 (7)0.60952 (7)0.03756 (19)
H10.346 (3)0.939 (2)0.5577 (18)0.056*0.65 (3)
O20.47212 (11)0.77883 (8)0.51170 (8)0.0479 (2)
O30.27519 (9)0.87264 (8)0.85370 (7)0.0419 (2)
O40.43919 (10)1.00169 (7)0.80694 (8)0.0427 (2)
O50.98421 (13)0.31165 (10)0.53057 (8)0.0608 (3)
H5A0.928 (3)0.337 (3)0.495 (3)0.091*0.69 (3)
O60.84798 (11)0.40838 (9)0.65469 (9)0.0554 (3)
O70.77750 (10)0.35976 (9)0.90326 (9)0.0538 (3)
O80.92297 (11)0.50129 (7)0.83597 (9)0.0493 (2)
N10.39857 (10)0.90591 (8)0.81376 (7)0.0307 (2)
N20.25921 (11)0.96842 (8)0.45998 (8)0.0336 (2)
H20.295 (5)0.947 (4)0.515 (3)0.050*0.35 (3)
N30.17253 (11)1.05913 (8)0.47405 (8)0.0350 (2)
N40.89335 (11)0.40241 (8)0.85017 (8)0.0340 (2)
N50.83498 (12)0.38076 (9)0.40414 (8)0.0380 (2)
H5B0.886 (5)0.363 (5)0.450 (4)0.057*0.31 (3)
N60.86168 (12)0.32058 (9)0.31839 (9)0.0408 (2)
C10.53417 (11)0.78574 (9)0.67521 (9)0.0291 (2)
C20.50836 (11)0.82266 (9)0.77708 (9)0.0280 (2)
C30.58214 (12)0.77997 (9)0.85109 (9)0.0312 (2)
C40.68321 (13)0.69848 (10)0.82410 (11)0.0371 (3)
H40.73340.66810.87410.045*
C50.71093 (13)0.66125 (10)0.72273 (11)0.0393 (3)
H50.78120.60570.70320.047*
C60.63705 (12)0.70439 (9)0.64974 (10)0.0352 (2)
H60.65740.67760.58100.042*
C70.45901 (12)0.82764 (9)0.59034 (9)0.0324 (2)
C80.10711 (12)1.09080 (9)0.39997 (9)0.0330 (2)
H80.04601.15360.41030.040*
C90.12024 (11)1.03859 (9)0.30516 (9)0.0289 (2)
C100.04878 (13)1.07522 (10)0.22679 (10)0.0372 (3)
H100.01511.13640.23660.045*
C110.07215 (14)1.02161 (11)0.13590 (10)0.0401 (3)
H110.02431.04620.08270.048*
C120.16524 (14)0.93168 (10)0.12117 (9)0.0384 (3)
H120.18160.89640.05740.046*
C130.23381 (13)0.89338 (10)0.19804 (9)0.0350 (2)
H130.29570.83100.18800.042*
C140.21175 (12)0.94705 (9)0.29152 (9)0.0291 (2)
C150.27834 (13)0.91545 (9)0.37540 (9)0.0337 (2)
H150.33980.85260.36950.040*
C161.03212 (11)0.29781 (8)0.69955 (9)0.0276 (2)
C171.00879 (11)0.32664 (8)0.80473 (9)0.0272 (2)
C181.09072 (12)0.28327 (9)0.87156 (9)0.0300 (2)
C191.19546 (12)0.20639 (10)0.83629 (10)0.0350 (2)
H191.25120.17520.88190.042*
C201.21802 (13)0.17540 (10)0.73274 (10)0.0360 (2)
H201.28930.12190.70800.043*
C211.13844 (12)0.22119 (9)0.66496 (9)0.0318 (2)
H211.15700.19980.59400.038*
C220.94465 (12)0.34541 (9)0.62580 (9)0.0326 (2)
C230.79757 (13)0.35112 (10)0.24345 (10)0.0373 (3)
H230.81760.30990.18320.045*
C240.70101 (12)0.44042 (10)0.24518 (9)0.0317 (2)
C250.63438 (14)0.47098 (12)0.16209 (11)0.0434 (3)
H250.65760.43400.09890.052*
C260.53647 (16)0.55426 (13)0.17443 (14)0.0556 (4)
H260.49020.57540.11960.067*
C270.50337 (15)0.60902 (12)0.26717 (15)0.0548 (4)
H270.43300.66580.27480.066*
C280.56916 (14)0.58351 (10)0.34749 (12)0.0443 (3)
H280.54700.62320.40890.053*
C290.67014 (12)0.49723 (9)0.33681 (9)0.0313 (2)
C300.74498 (13)0.46245 (10)0.41426 (9)0.0351 (2)
H300.72840.50070.47620.042*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.04729 (18)0.05455 (19)0.03517 (15)0.01104 (13)0.02333 (13)0.00920 (13)
Cl20.04574 (17)0.0612 (2)0.03053 (14)0.00811 (14)0.01602 (12)0.01759 (13)
O10.0486 (5)0.0402 (4)0.0311 (4)0.0143 (4)0.0214 (4)0.0106 (3)
O20.0621 (6)0.0534 (5)0.0367 (5)0.0188 (4)0.0224 (4)0.0208 (4)
O30.0285 (4)0.0608 (5)0.0376 (4)0.0079 (4)0.0085 (3)0.0155 (4)
O40.0473 (5)0.0351 (4)0.0553 (5)0.0133 (4)0.0269 (4)0.0153 (4)
O50.0775 (8)0.0806 (7)0.0384 (5)0.0474 (6)0.0345 (5)0.0252 (5)
O60.0566 (6)0.0710 (6)0.0566 (6)0.0370 (5)0.0357 (5)0.0332 (5)
O70.0332 (5)0.0610 (6)0.0615 (6)0.0090 (4)0.0010 (4)0.0215 (5)
O80.0595 (6)0.0325 (4)0.0678 (6)0.0136 (4)0.0317 (5)0.0202 (4)
N10.0304 (5)0.0389 (5)0.0274 (4)0.0105 (4)0.0146 (4)0.0092 (4)
N20.0390 (5)0.0359 (5)0.0291 (5)0.0032 (4)0.0152 (4)0.0057 (4)
N30.0406 (5)0.0352 (5)0.0325 (5)0.0013 (4)0.0131 (4)0.0107 (4)
N40.0352 (5)0.0357 (5)0.0365 (5)0.0099 (4)0.0148 (4)0.0158 (4)
N50.0424 (6)0.0437 (5)0.0323 (5)0.0071 (4)0.0179 (4)0.0062 (4)
N60.0411 (6)0.0417 (5)0.0408 (5)0.0101 (4)0.0126 (4)0.0110 (5)
C10.0280 (5)0.0293 (5)0.0293 (5)0.0027 (4)0.0079 (4)0.0036 (4)
C20.0246 (5)0.0285 (5)0.0305 (5)0.0048 (4)0.0087 (4)0.0034 (4)
C30.0299 (5)0.0330 (5)0.0328 (5)0.0033 (4)0.0137 (4)0.0025 (4)
C40.0333 (6)0.0335 (5)0.0464 (7)0.0065 (4)0.0177 (5)0.0006 (5)
C50.0323 (6)0.0325 (5)0.0513 (7)0.0092 (4)0.0112 (5)0.0055 (5)
C60.0344 (6)0.0319 (5)0.0365 (6)0.0063 (4)0.0054 (5)0.0085 (5)
C70.0345 (6)0.0364 (5)0.0262 (5)0.0031 (4)0.0089 (4)0.0054 (4)
C80.0354 (6)0.0307 (5)0.0348 (5)0.0029 (4)0.0114 (4)0.0095 (4)
C90.0308 (5)0.0282 (5)0.0284 (5)0.0004 (4)0.0098 (4)0.0046 (4)
C100.0398 (6)0.0365 (6)0.0397 (6)0.0059 (5)0.0194 (5)0.0049 (5)
C110.0478 (7)0.0449 (6)0.0338 (6)0.0001 (5)0.0226 (5)0.0031 (5)
C120.0469 (7)0.0434 (6)0.0273 (5)0.0037 (5)0.0126 (5)0.0095 (5)
C130.0404 (6)0.0345 (5)0.0313 (5)0.0046 (5)0.0102 (5)0.0104 (5)
C140.0324 (5)0.0292 (5)0.0269 (5)0.0005 (4)0.0107 (4)0.0043 (4)
C150.0383 (6)0.0339 (5)0.0313 (5)0.0056 (4)0.0143 (5)0.0050 (4)
C160.0283 (5)0.0278 (5)0.0296 (5)0.0043 (4)0.0120 (4)0.0067 (4)
C170.0261 (5)0.0266 (5)0.0305 (5)0.0035 (4)0.0091 (4)0.0086 (4)
C180.0304 (5)0.0353 (5)0.0267 (5)0.0012 (4)0.0107 (4)0.0075 (4)
C190.0337 (6)0.0401 (6)0.0352 (6)0.0081 (5)0.0168 (5)0.0056 (5)
C200.0346 (6)0.0392 (6)0.0375 (6)0.0133 (5)0.0142 (5)0.0110 (5)
C210.0330 (5)0.0352 (5)0.0297 (5)0.0085 (4)0.0113 (4)0.0107 (4)
C220.0341 (5)0.0328 (5)0.0351 (5)0.0065 (4)0.0158 (4)0.0083 (4)
C230.0381 (6)0.0418 (6)0.0324 (6)0.0021 (5)0.0071 (5)0.0141 (5)
C240.0295 (5)0.0379 (6)0.0278 (5)0.0049 (4)0.0090 (4)0.0036 (4)
C250.0439 (7)0.0546 (7)0.0351 (6)0.0105 (6)0.0195 (5)0.0011 (5)
C260.0477 (8)0.0587 (8)0.0648 (9)0.0097 (6)0.0353 (7)0.0178 (7)
C270.0415 (7)0.0413 (7)0.0795 (11)0.0065 (6)0.0228 (7)0.0064 (7)
C280.0407 (7)0.0354 (6)0.0544 (8)0.0067 (5)0.0110 (6)0.0077 (6)
C290.0300 (5)0.0307 (5)0.0328 (5)0.0008 (4)0.0092 (4)0.0041 (4)
C300.0417 (6)0.0373 (6)0.0287 (5)0.0021 (5)0.0121 (5)0.0097 (5)
Geometric parameters (Å, º) top
Cl1—C31.7357 (12)C9—C101.4078 (15)
Cl2—C181.7353 (11)C10—C111.3763 (17)
O1—C71.2870 (14)C10—H100.9500
O1—H10.860 (17)C11—C121.3917 (18)
O2—C71.2175 (14)C11—H110.9500
O3—N11.2122 (13)C12—C131.3764 (16)
O4—N11.2122 (13)C12—H120.9500
O5—C221.2930 (15)C13—C141.4073 (15)
O5—H5A0.844 (18)C13—H130.9500
O6—C221.1985 (14)C14—C151.4244 (15)
O7—N41.2136 (14)C15—H150.9500
O8—N41.2071 (13)C16—C211.3843 (14)
N1—C21.4669 (13)C16—C171.3990 (14)
N2—C151.3058 (15)C16—C221.5060 (14)
N2—N31.3626 (13)C17—C181.3850 (14)
N2—H20.879 (19)C18—C191.3785 (15)
N3—C81.3097 (15)C19—C201.3904 (16)
N4—C171.4655 (13)C19—H190.9500
N5—C301.2953 (15)C20—C211.3850 (15)
N5—N61.3659 (14)C20—H200.9500
N5—H5B0.88 (2)C21—H210.9500
N6—C231.3078 (16)C23—C241.4088 (17)
C1—C61.3849 (14)C23—H230.9500
C1—C21.3966 (15)C24—C291.4016 (16)
C1—C71.5148 (15)C24—C251.4143 (16)
C2—C31.3950 (14)C25—C261.359 (2)
C3—C41.3775 (15)C25—H250.9500
C4—C51.3903 (18)C26—C271.398 (2)
C4—H40.9500C26—H260.9500
C5—C61.3869 (17)C27—C281.371 (2)
C5—H50.9500C27—H270.9500
C6—H60.9500C28—C291.4052 (16)
C8—C91.4256 (15)C28—H280.9500
C8—H80.9500C29—C301.4176 (16)
C9—C141.3972 (15)C30—H300.9500
C7—O1—H1111.4 (18)C12—C13—H13120.2
C22—O5—H5A109 (2)C14—C13—H13120.2
O4—N1—O3124.98 (10)C9—C14—C13119.51 (10)
O4—N1—C2117.37 (9)C9—C14—C15116.06 (10)
O3—N1—C2117.55 (9)C13—C14—C15124.43 (10)
C15—N2—N3121.67 (9)N2—C15—C14123.36 (10)
C15—N2—H2124 (3)N2—C15—H15118.3
N3—N2—H2114 (3)C14—C15—H15118.3
C8—N3—N2117.45 (9)C21—C16—C17117.52 (9)
O8—N4—O7125.41 (10)C21—C16—C22120.14 (9)
O8—N4—C17117.40 (10)C17—C16—C22122.33 (9)
O7—N4—C17117.10 (9)C18—C17—C16121.91 (9)
C30—N5—N6121.72 (10)C18—C17—N4116.96 (9)
C30—N5—H5B122 (4)C16—C17—N4121.11 (9)
N6—N5—H5B116 (4)C19—C18—C17119.85 (10)
C23—N6—N5117.69 (10)C19—C18—Cl2119.68 (8)
C6—C1—C2117.28 (10)C17—C18—Cl2120.47 (8)
C6—C1—C7117.42 (10)C18—C19—C20118.82 (10)
C2—C1—C7125.30 (9)C18—C19—H19120.6
C3—C2—C1121.99 (9)C20—C19—H19120.6
C3—C2—N1116.23 (9)C21—C20—C19121.16 (10)
C1—C2—N1121.75 (9)C21—C20—H20119.4
C4—C3—C2119.59 (10)C19—C20—H20119.4
C4—C3—Cl1119.78 (9)C16—C21—C20120.70 (10)
C2—C3—Cl1120.64 (8)C16—C21—H21119.6
C3—C4—C5119.20 (11)C20—C21—H21119.6
C3—C4—H4120.4O6—C22—O5124.42 (11)
C5—C4—H4120.4O6—C22—C16121.99 (10)
C6—C5—C4120.71 (10)O5—C22—C16113.59 (9)
C6—C5—H5119.6N6—C23—C24125.00 (11)
C4—C5—H5119.6N6—C23—H23117.5
C1—C6—C5121.23 (11)C24—C23—H23117.5
C1—C6—H6119.4C29—C24—C23116.11 (10)
C5—C6—H6119.4C29—C24—C25120.69 (11)
O2—C7—O1124.95 (10)C23—C24—C25123.18 (11)
O2—C7—C1120.47 (10)C26—C25—C24118.71 (13)
O1—C7—C1114.58 (9)C26—C25—H25120.6
N3—C8—C9125.25 (10)C24—C25—H25120.6
N3—C8—H8117.4C25—C26—C27120.48 (13)
C9—C8—H8117.4C25—C26—H26119.8
C14—C9—C10120.03 (10)C27—C26—H26119.8
C14—C9—C8116.20 (9)C28—C27—C26122.16 (13)
C10—C9—C8123.77 (10)C28—C27—H27118.9
C11—C10—C9119.46 (11)C26—C27—H27118.9
C11—C10—H10120.3C27—C28—C29118.35 (13)
C9—C10—H10120.3C27—C28—H28120.8
C10—C11—C12120.59 (11)C29—C28—H28120.8
C10—C11—H11119.7C24—C29—C28119.57 (11)
C12—C11—H11119.7C24—C29—C30116.55 (10)
C13—C12—C11120.71 (11)C28—C29—C30123.88 (11)
C13—C12—H12119.6N5—C30—C29122.82 (10)
C11—C12—H12119.6N5—C30—H30118.6
C12—C13—C14119.68 (11)C29—C30—H30118.6
C15—N2—N3—C80.84 (16)C13—C14—C15—N2178.10 (11)
C30—N5—N6—C232.81 (18)C21—C16—C17—C181.75 (16)
C6—C1—C2—C30.13 (16)C22—C16—C17—C18179.36 (10)
C7—C1—C2—C3179.99 (10)C21—C16—C17—N4176.69 (10)
C6—C1—C2—N1178.05 (10)C22—C16—C17—N42.21 (16)
C7—C1—C2—N12.09 (17)O8—N4—C17—C1889.08 (13)
O4—N1—C2—C379.90 (12)O7—N4—C17—C1887.66 (13)
O3—N1—C2—C396.42 (12)O8—N4—C17—C1692.41 (13)
O4—N1—C2—C1102.07 (12)O7—N4—C17—C1690.85 (14)
O3—N1—C2—C181.61 (13)C16—C17—C18—C192.29 (17)
C1—C2—C3—C40.35 (17)N4—C17—C18—C19176.21 (10)
N1—C2—C3—C4177.68 (10)C16—C17—C18—Cl2177.11 (8)
C1—C2—C3—Cl1179.99 (8)N4—C17—C18—Cl24.40 (14)
N1—C2—C3—Cl11.96 (14)C17—C18—C19—C201.04 (18)
C2—C3—C4—C50.75 (17)Cl2—C18—C19—C20178.36 (9)
Cl1—C3—C4—C5179.61 (9)C18—C19—C20—C210.67 (19)
C3—C4—C5—C60.68 (18)C17—C16—C21—C200.01 (17)
C2—C1—C6—C50.20 (17)C22—C16—C21—C20178.93 (11)
C7—C1—C6—C5179.92 (10)C19—C20—C21—C161.19 (19)
C4—C5—C6—C10.19 (18)C21—C16—C22—O6176.94 (12)
C6—C1—C7—O211.53 (17)C17—C16—C22—O61.93 (18)
C2—C1—C7—O2168.61 (11)C21—C16—C22—O53.00 (16)
C6—C1—C7—O1168.51 (10)C17—C16—C22—O5178.14 (11)
C2—C1—C7—O111.35 (16)N5—N6—C23—C241.07 (19)
N2—N3—C8—C90.59 (17)N6—C23—C24—C291.96 (18)
N3—C8—C9—C140.54 (17)N6—C23—C24—C25179.73 (12)
N3—C8—C9—C10179.68 (11)C29—C24—C25—C261.99 (18)
C14—C9—C10—C111.31 (17)C23—C24—C25—C26176.25 (12)
C8—C9—C10—C11177.80 (11)C24—C25—C26—C270.5 (2)
C9—C10—C11—C120.16 (19)C25—C26—C27—C281.4 (2)
C10—C11—C12—C131.12 (19)C26—C27—C28—C291.8 (2)
C11—C12—C13—C141.23 (18)C23—C24—C29—C28176.72 (11)
C10—C9—C14—C131.19 (16)C25—C24—C29—C281.64 (17)
C8—C9—C14—C13177.98 (10)C23—C24—C29—C303.20 (15)
C10—C9—C14—C15179.48 (10)C25—C24—C29—C30178.44 (10)
C8—C9—C14—C151.35 (15)C27—C28—C29—C240.23 (18)
C12—C13—C14—C90.08 (17)C27—C28—C29—C30179.69 (12)
C12—C13—C14—C15179.20 (11)N6—N5—C30—C291.41 (19)
N3—N2—C15—C140.06 (18)C24—C29—C30—N51.72 (17)
C9—C14—C15—N21.19 (17)C28—C29—C30—N5178.20 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N20.86 (3)1.71 (3)2.5715 (15)173 (3)
O5—H5A···N50.84 (3)1.71 (3)2.5397 (17)170 (4)
N2—H2···O10.89 (4)1.69 (4)2.5715 (15)172 (4)
N5—H5B···O50.88 (5)1.66 (5)2.5397 (17)172 (6)
C5—H5···O60.952.563.4174 (17)150
C8—H8···O5i0.952.583.3560 (17)140
C12—H12···O3ii0.952.563.4609 (15)158
C15—H15···O20.952.593.2204 (17)124
C20—H20···O4iii0.952.523.2207 (17)131
C21—H21···N3iii0.952.433.2952 (16)152
C23—H23···Cl2ii0.952.813.4707 (14)128
C23—H23···O3iv0.952.563.3131 (16)136
C28—H28···O20.952.423.3222 (17)158
Symmetry codes: (i) x1, y+1, z; (ii) x, y, z1; (iii) x+1, y1, z; (iv) x+1, y+1, z+1.
(II) 4-chloro-2-nitrobenzoic acid–phthalazine (1/1) top
Crystal data top
C7H3.69ClNO4·C8H6.31N2F(000) = 1360.00
Mr = 331.71Dx = 1.535 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71075 Å
Hall symbol: -P 2ybcCell parameters from 42486 reflections
a = 12.2261 (5) Åθ = 3.1–29.9°
b = 16.9779 (7) ŵ = 0.29 mm1
c = 14.4537 (6) ÅT = 190 K
β = 106.8955 (13)°Block, colourless
V = 2870.7 (2) Å30.35 × 0.35 × 0.30 mm
Z = 8
Data collection top
Rigaku R-AXIS RAPID II
diffractometer
6797 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm-1Rint = 0.030
ω scansθmax = 30.0°
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
h = 1717
Tmin = 0.790, Tmax = 0.916k = 2323
60079 measured reflectionsl = 2020
8318 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0667P)2 + 0.6974P]
where P = (Fo2 + 2Fc2)/3
8318 reflections(Δ/σ)max = 0.002
429 parametersΔρmax = 0.71 e Å3
4 restraintsΔρmin = 0.41 e Å3
Crystal data top
C7H3.69ClNO4·C8H6.31N2V = 2870.7 (2) Å3
Mr = 331.71Z = 8
Monoclinic, P21/cMo Kα radiation
a = 12.2261 (5) ŵ = 0.29 mm1
b = 16.9779 (7) ÅT = 190 K
c = 14.4537 (6) Å0.35 × 0.35 × 0.30 mm
β = 106.8955 (13)°
Data collection top
Rigaku R-AXIS RAPID II
diffractometer
8318 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)
6797 reflections with I > 2σ(I)
Tmin = 0.790, Tmax = 0.916Rint = 0.030
60079 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0424 restraints
wR(F2) = 0.123H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.71 e Å3
8318 reflectionsΔρmin = 0.41 e Å3
429 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
xyzUiso*/UeqOcc. (<1)
Cl10.55901 (4)1.18856 (2)0.62196 (4)0.05865 (14)
Cl20.05353 (4)0.066117 (18)0.64095 (3)0.04574 (11)
O10.59811 (8)0.80083 (5)0.69175 (8)0.0376 (2)
H10.585 (3)0.7517 (11)0.686 (2)0.056*0.68 (3)
O20.40830 (9)0.80837 (6)0.63575 (11)0.0538 (3)
O30.26069 (10)0.93500 (8)0.65252 (10)0.0584 (3)
O40.25733 (12)0.93652 (10)0.50401 (9)0.0726 (5)
O50.10102 (8)0.45715 (5)0.67381 (8)0.0373 (2)
H5A0.086 (3)0.5065 (11)0.662 (2)0.056*0.70 (3)
O60.08500 (9)0.45017 (6)0.59582 (11)0.0615 (4)
O70.20781 (10)0.34531 (9)0.68478 (9)0.0617 (4)
O80.26342 (8)0.30349 (7)0.53870 (8)0.0462 (3)
N10.30491 (9)0.94554 (6)0.58779 (9)0.0324 (2)
N20.56386 (9)0.65231 (6)0.66595 (8)0.0283 (2)
H20.581 (5)0.7017 (15)0.681 (4)0.042*0.32 (3)
N30.65839 (9)0.60476 (6)0.67948 (8)0.0297 (2)
N40.19120 (9)0.31371 (6)0.61492 (8)0.0298 (2)
N50.06751 (10)0.60825 (6)0.64760 (9)0.0320 (2)
H5B0.085 (5)0.5573 (14)0.653 (5)0.048*0.30 (3)
N60.15748 (9)0.65793 (6)0.65039 (9)0.0341 (2)
C10.51646 (9)0.92627 (6)0.65260 (8)0.0230 (2)
C20.42328 (10)0.97588 (7)0.61631 (8)0.0248 (2)
C30.43361 (11)1.05618 (7)0.60624 (9)0.0307 (3)
H30.36821.08840.58100.037*
C40.54271 (12)1.08825 (7)0.63415 (10)0.0322 (3)
C50.63826 (11)1.04195 (7)0.67217 (9)0.0303 (2)
H50.71231.06490.69200.036*
C60.62447 (10)0.96126 (7)0.68098 (9)0.0258 (2)
H60.69000.92920.70690.031*
C70.50191 (10)0.83864 (7)0.65949 (9)0.0267 (2)
C80.64130 (10)0.52950 (7)0.66122 (9)0.0265 (2)
H80.70650.49660.67070.032*
C90.53156 (9)0.49356 (6)0.62818 (8)0.0218 (2)
C100.51489 (10)0.41204 (7)0.61081 (9)0.0273 (2)
H100.57840.37740.62190.033*
C110.40532 (11)0.38357 (7)0.57769 (9)0.0301 (2)
H110.39340.32870.56650.036*
C120.31042 (11)0.43415 (7)0.56005 (9)0.0299 (2)
H120.23550.41300.53610.036*
C130.32442 (10)0.51367 (7)0.57697 (9)0.0272 (2)
H130.26000.54760.56530.033*
C140.43612 (9)0.54386 (6)0.61201 (8)0.0222 (2)
C150.45979 (10)0.62467 (7)0.63407 (9)0.0262 (2)
H150.39750.66010.62530.031*
C160.01848 (10)0.33121 (6)0.64156 (8)0.0238 (2)
C170.07593 (10)0.28156 (7)0.62597 (8)0.0244 (2)
C180.06837 (11)0.20045 (7)0.62387 (9)0.0285 (2)
H180.13460.16830.61180.034*
C190.03963 (11)0.16757 (7)0.64005 (9)0.0295 (2)
C200.13647 (11)0.21412 (7)0.65704 (9)0.0297 (2)
H200.20970.19060.66830.036*
C210.12533 (10)0.29557 (7)0.65749 (9)0.0272 (2)
H210.19160.32760.66880.033*
C220.00558 (10)0.41941 (7)0.63517 (9)0.0293 (2)
C230.13553 (10)0.73295 (7)0.63441 (10)0.0301 (2)
H230.19760.76690.63550.036*
C240.02458 (9)0.76726 (6)0.61544 (8)0.0235 (2)
C250.00269 (11)0.84859 (7)0.60091 (10)0.0293 (2)
H250.06320.88410.60210.035*
C260.10699 (11)0.87592 (7)0.58500 (10)0.0318 (3)
H260.12200.93070.57540.038*
C270.19758 (11)0.82383 (8)0.58274 (9)0.0304 (2)
H270.27290.84390.57130.036*
C280.17816 (10)0.74457 (7)0.59685 (9)0.0281 (2)
H280.23940.70970.59560.034*
C290.06596 (9)0.71544 (7)0.61326 (8)0.0235 (2)
C300.03699 (11)0.63489 (7)0.63011 (9)0.0284 (2)
H300.09630.59840.62870.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0642 (3)0.02301 (17)0.0863 (3)0.00631 (16)0.0179 (2)0.01464 (17)
Cl20.0610 (2)0.01785 (14)0.0515 (2)0.00608 (13)0.00546 (17)0.00207 (12)
O10.0260 (4)0.0196 (4)0.0629 (7)0.0009 (3)0.0062 (4)0.0011 (4)
O20.0274 (5)0.0239 (5)0.1024 (10)0.0036 (4)0.0066 (6)0.0012 (5)
O30.0417 (6)0.0732 (8)0.0690 (8)0.0217 (6)0.0300 (6)0.0239 (7)
O40.0535 (7)0.1081 (12)0.0420 (7)0.0334 (8)0.0085 (6)0.0052 (7)
O50.0254 (4)0.0196 (4)0.0618 (6)0.0004 (3)0.0044 (4)0.0018 (4)
O60.0372 (6)0.0224 (5)0.0987 (10)0.0037 (4)0.0216 (6)0.0015 (5)
O70.0464 (6)0.0907 (10)0.0448 (6)0.0345 (7)0.0084 (5)0.0099 (6)
O80.0271 (5)0.0572 (7)0.0449 (6)0.0003 (4)0.0043 (4)0.0013 (5)
N10.0240 (5)0.0273 (5)0.0420 (6)0.0002 (4)0.0034 (4)0.0000 (4)
N20.0311 (5)0.0180 (4)0.0336 (5)0.0001 (4)0.0058 (4)0.0001 (4)
N30.0250 (5)0.0236 (5)0.0383 (6)0.0017 (4)0.0058 (4)0.0014 (4)
N40.0243 (5)0.0293 (5)0.0339 (5)0.0024 (4)0.0053 (4)0.0043 (4)
N50.0337 (5)0.0198 (5)0.0405 (6)0.0013 (4)0.0076 (5)0.0003 (4)
N60.0282 (5)0.0251 (5)0.0480 (7)0.0025 (4)0.0095 (5)0.0005 (4)
C10.0239 (5)0.0201 (5)0.0251 (5)0.0005 (4)0.0073 (4)0.0016 (4)
C20.0232 (5)0.0239 (5)0.0266 (5)0.0007 (4)0.0063 (4)0.0004 (4)
C30.0332 (6)0.0238 (5)0.0335 (6)0.0041 (5)0.0073 (5)0.0053 (4)
C40.0406 (7)0.0210 (5)0.0359 (6)0.0042 (5)0.0123 (5)0.0036 (5)
C50.0302 (6)0.0256 (6)0.0352 (6)0.0080 (5)0.0098 (5)0.0009 (5)
C60.0237 (5)0.0231 (5)0.0301 (5)0.0012 (4)0.0071 (4)0.0019 (4)
C70.0249 (5)0.0207 (5)0.0340 (6)0.0006 (4)0.0076 (4)0.0031 (4)
C80.0218 (5)0.0232 (5)0.0334 (6)0.0011 (4)0.0060 (4)0.0025 (4)
C90.0224 (5)0.0185 (5)0.0242 (5)0.0008 (4)0.0064 (4)0.0010 (4)
C100.0280 (6)0.0187 (5)0.0349 (6)0.0035 (4)0.0084 (5)0.0001 (4)
C110.0336 (6)0.0204 (5)0.0349 (6)0.0034 (4)0.0077 (5)0.0030 (4)
C120.0254 (5)0.0302 (6)0.0319 (6)0.0051 (5)0.0047 (5)0.0024 (5)
C130.0221 (5)0.0279 (5)0.0298 (6)0.0027 (4)0.0047 (4)0.0012 (4)
C140.0235 (5)0.0199 (5)0.0227 (5)0.0028 (4)0.0057 (4)0.0004 (4)
C150.0281 (5)0.0192 (5)0.0297 (5)0.0034 (4)0.0059 (4)0.0002 (4)
C160.0241 (5)0.0187 (5)0.0259 (5)0.0015 (4)0.0031 (4)0.0002 (4)
C170.0229 (5)0.0232 (5)0.0247 (5)0.0026 (4)0.0031 (4)0.0000 (4)
C180.0310 (6)0.0216 (5)0.0293 (6)0.0037 (4)0.0029 (5)0.0009 (4)
C190.0398 (6)0.0181 (5)0.0277 (6)0.0042 (5)0.0050 (5)0.0008 (4)
C200.0293 (6)0.0253 (5)0.0322 (6)0.0085 (5)0.0051 (5)0.0000 (4)
C210.0238 (5)0.0233 (5)0.0323 (6)0.0022 (4)0.0047 (4)0.0006 (4)
C220.0268 (6)0.0198 (5)0.0369 (6)0.0019 (4)0.0022 (5)0.0005 (4)
C230.0239 (5)0.0255 (6)0.0411 (7)0.0005 (4)0.0095 (5)0.0004 (5)
C240.0229 (5)0.0201 (5)0.0264 (5)0.0010 (4)0.0057 (4)0.0005 (4)
C250.0294 (6)0.0195 (5)0.0380 (6)0.0023 (4)0.0082 (5)0.0012 (4)
C260.0353 (6)0.0219 (5)0.0372 (6)0.0046 (5)0.0088 (5)0.0020 (5)
C270.0262 (5)0.0319 (6)0.0330 (6)0.0067 (5)0.0086 (5)0.0024 (5)
C280.0240 (5)0.0295 (6)0.0309 (6)0.0023 (4)0.0080 (4)0.0003 (4)
C290.0242 (5)0.0214 (5)0.0242 (5)0.0019 (4)0.0060 (4)0.0006 (4)
C300.0313 (6)0.0198 (5)0.0326 (6)0.0036 (4)0.0070 (5)0.0000 (4)
Geometric parameters (Å, º) top
Cl1—C41.7296 (13)C9—C101.4108 (15)
Cl2—C191.7304 (12)C10—C111.3728 (17)
O1—C71.3015 (15)C10—H100.9500
O1—H10.849 (18)C11—C121.4060 (18)
O2—C71.2097 (15)C11—H110.9500
O3—N11.2222 (17)C12—C131.3737 (17)
O4—N11.1911 (16)C12—H120.9500
O5—C221.3059 (15)C13—C141.4079 (16)
O5—H5A0.865 (18)C13—H130.9500
O6—C221.2068 (15)C14—C151.4191 (15)
O7—N41.2115 (16)C15—H150.9500
O8—N41.2074 (14)C16—C171.3937 (16)
N1—C21.4774 (15)C16—C211.3967 (15)
N2—C151.3079 (16)C16—C221.5057 (15)
N2—N31.3763 (14)C17—C181.3812 (16)
N2—H20.87 (2)C18—C191.3894 (18)
N3—C81.3092 (15)C18—H180.9500
N4—C171.4761 (15)C19—C201.3848 (18)
N5—C301.3089 (16)C20—C211.3897 (16)
N5—N61.3773 (15)C20—H200.9500
N5—H5B0.89 (2)C21—H210.9500
N6—C231.3084 (16)C23—C241.4276 (16)
C1—C21.3911 (16)C23—H230.9500
C1—C61.3965 (15)C24—C291.4072 (15)
C1—C71.5051 (15)C24—C251.4105 (16)
C2—C31.3808 (16)C25—C261.3738 (18)
C3—C41.3877 (18)C25—H250.9500
C3—H30.9500C26—C271.4103 (18)
C4—C51.3826 (19)C26—H260.9500
C5—C61.3905 (16)C27—C281.3714 (17)
C5—H50.9500C27—H270.9500
C6—H60.9500C28—C291.4119 (16)
C8—C91.4242 (15)C28—H280.9500
C8—H80.9500C29—C301.4159 (15)
C9—C141.4096 (15)C30—H300.9500
C7—O1—H1109 (2)C12—C13—H13120.7
C22—O5—H5A106 (2)C14—C13—H13120.7
O4—N1—O3124.43 (13)C13—C14—C9120.57 (10)
O4—N1—C2118.55 (12)C13—C14—C15123.09 (10)
O3—N1—C2116.92 (11)C9—C14—C15116.33 (10)
C15—N2—N3122.03 (10)N2—C15—C14122.68 (10)
C15—N2—H2124 (4)N2—C15—H15118.7
N3—N2—H2114 (4)C14—C15—H15118.7
C8—N3—N2117.75 (10)C17—C16—C21117.11 (10)
O8—N4—O7124.67 (12)C17—C16—C22121.63 (10)
O8—N4—C17117.88 (11)C21—C16—C22121.15 (10)
O7—N4—C17117.36 (11)C18—C17—C16123.30 (11)
C30—N5—N6121.37 (10)C18—C17—N4115.73 (10)
C30—N5—H5B123 (4)C16—C17—N4120.91 (10)
N6—N5—H5B115 (4)C17—C18—C19117.60 (11)
C23—N6—N5118.02 (10)C17—C18—H18121.2
C2—C1—C6117.01 (10)C19—C18—H18121.2
C2—C1—C7121.59 (10)C20—C19—C18121.48 (11)
C6—C1—C7121.39 (10)C20—C19—Cl2119.33 (10)
C3—C2—C1123.20 (11)C18—C19—Cl2119.19 (10)
C3—C2—N1115.28 (10)C19—C20—C21119.27 (11)
C1—C2—N1121.51 (10)C19—C20—H20120.4
C2—C3—C4117.81 (11)C21—C20—H20120.4
C2—C3—H3121.1C20—C21—C16121.23 (11)
C4—C3—H3121.1C20—C21—H21119.4
C5—C4—C3121.48 (11)C16—C21—H21119.4
C5—C4—Cl1119.43 (10)O6—C22—O5124.94 (11)
C3—C4—Cl1119.09 (10)O6—C22—C16121.65 (11)
C4—C5—C6119.06 (11)O5—C22—C16113.39 (10)
C4—C5—H5120.5N6—C23—C24124.46 (11)
C6—C5—H5120.5N6—C23—H23117.8
C5—C6—C1121.44 (11)C24—C23—H23117.8
C5—C6—H6119.3C29—C24—C25119.65 (10)
C1—C6—H6119.3C29—C24—C23116.52 (10)
O2—C7—O1125.03 (11)C25—C24—C23123.82 (11)
O2—C7—C1121.43 (11)C26—C25—C24119.30 (11)
O1—C7—C1113.54 (10)C26—C25—H25120.4
N3—C8—C9124.43 (11)C24—C25—H25120.4
N3—C8—H8117.8C25—C26—C27120.92 (11)
C9—C8—H8117.8C25—C26—H26119.5
C14—C9—C10119.68 (10)C27—C26—H26119.5
C14—C9—C8116.73 (10)C28—C27—C26120.73 (11)
C10—C9—C8123.60 (10)C28—C27—H27119.6
C11—C10—C9118.90 (11)C26—C27—H27119.6
C11—C10—H10120.5C27—C28—C29119.11 (11)
C9—C10—H10120.5C27—C28—H28120.4
C10—C11—C12121.22 (11)C29—C28—H28120.4
C10—C11—H11119.4C24—C29—C28120.28 (10)
C12—C11—H11119.4C24—C29—C30116.37 (10)
C13—C12—C11120.96 (11)C28—C29—C30123.33 (11)
C13—C12—H12119.5N5—C30—C29123.25 (11)
C11—C12—H12119.5N5—C30—H30118.4
C12—C13—C14118.66 (11)C29—C30—H30118.4
C15—N2—N3—C81.41 (18)C9—C14—C15—N21.27 (17)
C30—N5—N6—C230.41 (19)C21—C16—C17—C181.25 (18)
C6—C1—C2—C30.98 (17)C22—C16—C17—C18174.87 (11)
C7—C1—C2—C3178.01 (12)C21—C16—C17—N4175.93 (10)
C6—C1—C2—N1177.55 (11)C22—C16—C17—N47.94 (17)
C7—C1—C2—N13.45 (17)O8—N4—C17—C1865.48 (15)
O4—N1—C2—C379.00 (17)O7—N4—C17—C18111.16 (14)
O3—N1—C2—C397.57 (15)O8—N4—C17—C16117.13 (13)
O4—N1—C2—C1102.36 (16)O7—N4—C17—C1666.22 (17)
O3—N1—C2—C181.07 (16)C16—C17—C18—C191.25 (18)
C1—C2—C3—C40.15 (19)N4—C17—C18—C19176.07 (10)
N1—C2—C3—C4178.47 (11)C17—C18—C19—C200.43 (18)
C2—C3—C4—C50.93 (19)C17—C18—C19—Cl2178.47 (9)
C2—C3—C4—Cl1179.65 (10)C18—C19—C20—C210.31 (19)
C3—C4—C5—C61.1 (2)Cl2—C19—C20—C21179.21 (10)
Cl1—C4—C5—C6179.47 (10)C19—C20—C21—C160.29 (19)
C4—C5—C6—C10.22 (19)C17—C16—C21—C200.45 (18)
C2—C1—C6—C50.79 (17)C22—C16—C21—C20175.70 (11)
C7—C1—C6—C5178.21 (11)C17—C16—C22—O617.0 (2)
C2—C1—C7—O21.73 (19)C21—C16—C22—O6158.95 (15)
C6—C1—C7—O2179.31 (13)C17—C16—C22—O5164.43 (12)
C2—C1—C7—O1177.63 (11)C21—C16—C22—O519.60 (17)
C6—C1—C7—O11.32 (17)N5—N6—C23—C240.9 (2)
N2—N3—C8—C90.11 (18)N6—C23—C24—C290.65 (19)
N3—C8—C9—C141.81 (18)N6—C23—C24—C25178.23 (13)
N3—C8—C9—C10178.63 (12)C29—C24—C25—C260.12 (18)
C14—C9—C10—C110.46 (17)C23—C24—C25—C26178.72 (12)
C8—C9—C10—C11179.09 (11)C24—C25—C26—C270.2 (2)
C9—C10—C11—C120.66 (19)C25—C26—C27—C280.3 (2)
C10—C11—C12—C131.1 (2)C26—C27—C28—C290.34 (19)
C11—C12—C13—C140.32 (19)C25—C24—C29—C280.15 (17)
C12—C13—C14—C90.80 (17)C23—C24—C29—C28178.77 (11)
C12—C13—C14—C15178.39 (12)C25—C24—C29—C30178.94 (11)
C10—C9—C14—C131.20 (17)C23—C24—C29—C300.02 (16)
C8—C9—C14—C13178.38 (11)C27—C28—C29—C240.26 (17)
C10—C9—C14—C15178.04 (11)C27—C28—C29—C30178.96 (12)
C8—C9—C14—C152.38 (15)N6—N5—C30—C290.2 (2)
N3—N2—C15—C140.70 (18)C24—C29—C30—N50.44 (18)
C13—C14—C15—N2179.50 (11)C28—C29—C30—N5178.31 (12)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N20.85 (2)1.72 (2)2.5655 (13)175 (3)
O5—H5A···N50.86 (2)1.75 (2)2.6081 (13)174 (2)
N2—H2···O10.88 (3)1.70 (3)2.5655 (13)171 (6)
N5—H5B···O50.89 (3)1.73 (3)2.6081 (13)170 (6)
C10—H10···O7i0.952.563.4371 (18)153
C15—H15···O20.952.523.1832 (16)127
C15—H15···O8ii0.952.543.1627 (17)124
C25—H25···O30.952.473.3602 (19)157
C30—H30···O60.952.573.2026 (16)124
Symmetry codes: (i) x+1, y, z; (ii) x, y+1, z+1.
(III) 4-chloro-3-nitrobenzoic acid–phthalazine (1/1) top
Crystal data top
C7H4ClNO4·C8H6N2Z = 4
Mr = 331.71F(000) = 680.00
Triclinic, P1Dx = 1.571 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71075 Å
a = 6.9197 (5) ÅCell parameters from 15895 reflections
b = 14.4263 (12) Åθ = 3.0–30.1°
c = 14.4750 (9) ŵ = 0.30 mm1
α = 81.704 (2)°T = 190 K
β = 79.0781 (18)°Needle, colourless
γ = 85.647 (2)°0.40 × 0.18 × 0.06 mm
V = 1402.20 (17) Å3
Data collection top
Rigaku R-AXIS RAPID II
diffractometer
4765 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm-1Rint = 0.056
ω scansθmax = 30.0°
Absorption correction: numerical
(NUMABS; Higashi, 1999)
h = 99
Tmin = 0.929, Tmax = 0.982k = 2020
22476 measured reflectionsl = 2020
7849 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.057Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.154H atoms treated by a mixture of independent and constrained refinement
S = 0.99 w = 1/[σ2(Fo2) + (0.081P)2]
where P = (Fo2 + 2Fc2)/3
7849 reflections(Δ/σ)max < 0.001
423 parametersΔρmax = 0.53 e Å3
0 restraintsΔρmin = 0.48 e Å3
Crystal data top
C7H4ClNO4·C8H6N2γ = 85.647 (2)°
Mr = 331.71V = 1402.20 (17) Å3
Triclinic, P1Z = 4
a = 6.9197 (5) ÅMo Kα radiation
b = 14.4263 (12) ŵ = 0.30 mm1
c = 14.4750 (9) ÅT = 190 K
α = 81.704 (2)°0.40 × 0.18 × 0.06 mm
β = 79.0781 (18)°
Data collection top
Rigaku R-AXIS RAPID II
diffractometer
7849 independent reflections
Absorption correction: numerical
(NUMABS; Higashi, 1999)
4765 reflections with I > 2σ(I)
Tmin = 0.929, Tmax = 0.982Rint = 0.056
22476 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0570 restraints
wR(F2) = 0.154H atoms treated by a mixture of independent and constrained refinement
S = 0.99Δρmax = 0.53 e Å3
7849 reflectionsΔρmin = 0.48 e Å3
423 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
xyzUiso*/Ueq
Cl10.90846 (8)0.11798 (4)0.29615 (4)0.03773 (15)
Cl20.44568 (8)0.11350 (4)0.20068 (4)0.04165 (16)
O10.7875 (2)0.49754 (10)0.07530 (10)0.0390 (4)
O20.7307 (2)0.39169 (11)0.05393 (10)0.0394 (4)
O30.6714 (3)0.06281 (12)0.00799 (13)0.0578 (5)
O40.9263 (3)0.01878 (12)0.10527 (13)0.0575 (5)
O50.2416 (3)0.41899 (11)0.51448 (11)0.0415 (4)
O60.2946 (2)0.52181 (10)0.38222 (11)0.0400 (4)
O70.3389 (3)0.09591 (11)0.50899 (11)0.0538 (5)
O80.2970 (3)0.03085 (11)0.39038 (12)0.0477 (4)
N10.8053 (3)0.07913 (12)0.07481 (13)0.0348 (4)
N20.7277 (3)0.62891 (12)0.03523 (12)0.0327 (4)
N30.7535 (3)0.71534 (13)0.01737 (12)0.0343 (4)
N40.3245 (2)0.09936 (12)0.42563 (12)0.0314 (4)
N50.1963 (2)0.56614 (12)0.60132 (12)0.0315 (4)
N60.1509 (3)0.54527 (12)0.69854 (12)0.0338 (4)
C10.8083 (3)0.33866 (14)0.09750 (13)0.0259 (4)
C20.7880 (3)0.24528 (14)0.05996 (14)0.0268 (4)
H20.74960.22840.00660.032*
C30.8238 (3)0.17658 (14)0.11969 (14)0.0274 (4)
C40.8761 (3)0.20009 (14)0.21815 (14)0.0276 (4)
C50.8941 (3)0.29344 (14)0.25478 (14)0.0290 (4)
H50.92850.31060.32150.035*
C60.8623 (3)0.36230 (14)0.19538 (13)0.0275 (4)
H60.87750.42620.22150.033*
C70.7714 (3)0.41187 (14)0.03132 (14)0.0286 (4)
C80.7271 (3)0.78899 (15)0.02742 (14)0.0313 (4)
H80.74430.84870.00980.038*
C90.6748 (3)0.78670 (14)0.12736 (13)0.0258 (4)
C100.6488 (3)0.86741 (15)0.17393 (15)0.0318 (4)
H100.66480.92800.13850.038*
C110.6000 (3)0.85712 (16)0.27094 (15)0.0352 (5)
H110.58210.91110.30280.042*
C120.5762 (3)0.76823 (17)0.32376 (15)0.0350 (5)
H120.54290.76290.39100.042*
C130.6002 (3)0.68848 (15)0.28024 (14)0.0321 (4)
H130.58340.62850.31680.039*
C140.6501 (3)0.69723 (14)0.18042 (14)0.0262 (4)
C150.6794 (3)0.62040 (14)0.12769 (14)0.0298 (4)
H150.66320.55910.16150.036*
C160.3195 (3)0.35862 (14)0.36924 (14)0.0266 (4)
C170.3045 (3)0.26855 (14)0.41692 (14)0.0263 (4)
H170.26880.25930.48420.032*
C180.3409 (3)0.19156 (13)0.36776 (13)0.0256 (4)
C190.3927 (3)0.20401 (14)0.26844 (14)0.0280 (4)
C200.4088 (3)0.29465 (15)0.22163 (14)0.0308 (4)
H200.44590.30430.15450.037*
C210.3719 (3)0.37094 (14)0.27075 (14)0.0297 (4)
H210.38240.43250.23710.036*
C220.2831 (3)0.44220 (14)0.42219 (14)0.0293 (4)
C230.1152 (3)0.61542 (14)0.74862 (14)0.0303 (4)
H230.08070.60090.81560.036*
C240.1242 (3)0.71131 (14)0.71005 (14)0.0262 (4)
C250.0860 (3)0.78511 (15)0.76636 (15)0.0332 (5)
H250.05110.77200.83350.040*
C260.0999 (3)0.87563 (15)0.72323 (17)0.0375 (5)
H260.07410.92560.76070.045*
C270.1519 (3)0.89573 (15)0.62415 (17)0.0380 (5)
H270.16190.95920.59560.046*
C280.1886 (3)0.82524 (15)0.56790 (15)0.0335 (5)
H280.22290.83960.50090.040*
C290.1746 (3)0.73151 (13)0.61081 (14)0.0258 (4)
C300.2083 (3)0.65275 (15)0.56057 (14)0.0308 (4)
H300.24150.66370.49330.037*
H10.755 (5)0.544 (3)0.028 (3)0.108 (12)*
H5A0.216 (5)0.479 (3)0.545 (3)0.125 (14)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0435 (3)0.0352 (3)0.0387 (3)0.0052 (2)0.0098 (2)0.0196 (2)
Cl20.0505 (3)0.0405 (3)0.0370 (3)0.0057 (2)0.0070 (3)0.0206 (2)
O10.0614 (10)0.0236 (8)0.0303 (8)0.0008 (7)0.0011 (7)0.0088 (6)
O20.0559 (10)0.0366 (9)0.0247 (7)0.0062 (7)0.0003 (7)0.0087 (6)
O30.0684 (12)0.0377 (10)0.0560 (11)0.0067 (9)0.0107 (10)0.0043 (8)
O40.0800 (13)0.0303 (9)0.0560 (11)0.0088 (9)0.0001 (10)0.0080 (8)
O50.0687 (11)0.0239 (8)0.0320 (8)0.0000 (7)0.0068 (8)0.0089 (6)
O60.0574 (10)0.0220 (8)0.0408 (9)0.0028 (7)0.0092 (8)0.0038 (6)
O70.0978 (14)0.0318 (9)0.0320 (8)0.0124 (9)0.0116 (9)0.0003 (7)
O80.0722 (11)0.0238 (8)0.0512 (10)0.0038 (8)0.0163 (9)0.0109 (7)
N10.0418 (10)0.0266 (9)0.0352 (9)0.0017 (8)0.0050 (9)0.0046 (7)
N20.0372 (9)0.0279 (9)0.0344 (9)0.0011 (7)0.0065 (8)0.0105 (7)
N30.0433 (10)0.0331 (10)0.0278 (9)0.0006 (8)0.0079 (8)0.0075 (7)
N40.0357 (9)0.0267 (9)0.0318 (9)0.0006 (7)0.0040 (8)0.0071 (7)
N50.0376 (9)0.0277 (9)0.0309 (9)0.0001 (7)0.0064 (8)0.0096 (7)
N60.0419 (10)0.0265 (9)0.0333 (9)0.0016 (7)0.0070 (8)0.0041 (7)
C10.0242 (9)0.0270 (10)0.0271 (9)0.0009 (7)0.0030 (8)0.0082 (8)
C20.0269 (9)0.0292 (10)0.0242 (9)0.0007 (8)0.0033 (8)0.0054 (8)
C30.0258 (9)0.0248 (10)0.0321 (10)0.0013 (7)0.0050 (8)0.0060 (8)
C40.0251 (9)0.0305 (11)0.0293 (10)0.0033 (8)0.0055 (8)0.0124 (8)
C50.0292 (10)0.0334 (11)0.0252 (9)0.0020 (8)0.0049 (8)0.0086 (8)
C60.0282 (10)0.0267 (10)0.0270 (9)0.0005 (8)0.0033 (8)0.0045 (8)
C70.0269 (10)0.0311 (11)0.0286 (10)0.0013 (8)0.0034 (8)0.0091 (8)
C80.0378 (11)0.0279 (11)0.0283 (10)0.0001 (8)0.0067 (9)0.0041 (8)
C90.0253 (9)0.0266 (10)0.0273 (9)0.0010 (7)0.0072 (8)0.0072 (8)
C100.0321 (10)0.0278 (11)0.0367 (11)0.0006 (8)0.0059 (9)0.0095 (9)
C110.0327 (11)0.0371 (12)0.0393 (12)0.0038 (9)0.0070 (10)0.0185 (10)
C120.0290 (10)0.0509 (14)0.0265 (10)0.0023 (9)0.0044 (9)0.0123 (9)
C130.0294 (10)0.0358 (12)0.0296 (10)0.0003 (8)0.0038 (9)0.0021 (9)
C140.0225 (9)0.0285 (10)0.0288 (10)0.0010 (7)0.0059 (8)0.0070 (8)
C150.0321 (10)0.0246 (10)0.0339 (10)0.0007 (8)0.0078 (9)0.0062 (8)
C160.0248 (9)0.0259 (10)0.0305 (10)0.0003 (7)0.0066 (8)0.0068 (8)
C170.0273 (9)0.0270 (10)0.0260 (9)0.0016 (7)0.0048 (8)0.0075 (8)
C180.0271 (9)0.0235 (10)0.0270 (9)0.0005 (7)0.0071 (8)0.0044 (7)
C190.0272 (9)0.0309 (11)0.0283 (10)0.0017 (8)0.0075 (8)0.0107 (8)
C200.0294 (10)0.0389 (12)0.0239 (9)0.0004 (8)0.0037 (8)0.0059 (8)
C210.0313 (10)0.0269 (10)0.0298 (10)0.0017 (8)0.0047 (9)0.0016 (8)
C220.0299 (10)0.0264 (11)0.0329 (10)0.0014 (8)0.0063 (9)0.0072 (8)
C230.0338 (10)0.0304 (11)0.0268 (10)0.0017 (8)0.0053 (9)0.0042 (8)
C240.0222 (9)0.0278 (10)0.0287 (10)0.0005 (7)0.0036 (8)0.0052 (8)
C250.0341 (11)0.0340 (12)0.0324 (11)0.0018 (9)0.0041 (9)0.0120 (9)
C260.0341 (11)0.0282 (11)0.0506 (13)0.0013 (8)0.0031 (10)0.0148 (10)
C270.0343 (11)0.0237 (11)0.0517 (13)0.0006 (8)0.0005 (10)0.0012 (9)
C280.0345 (11)0.0294 (11)0.0328 (11)0.0002 (8)0.0002 (9)0.0000 (9)
C290.0221 (9)0.0249 (10)0.0292 (10)0.0001 (7)0.0010 (8)0.0050 (8)
C300.0319 (10)0.0323 (11)0.0277 (10)0.0013 (8)0.0018 (9)0.0071 (8)
Geometric parameters (Å, º) top
Cl1—C41.7257 (18)C10—C111.370 (3)
Cl2—C191.7210 (19)C10—H100.9500
O1—C71.309 (3)C11—C121.399 (3)
O1—H11.01 (4)C11—H110.9500
O2—C71.210 (2)C12—C131.374 (3)
O3—N11.215 (2)C12—H120.9500
O4—N11.230 (2)C13—C141.410 (3)
O5—C221.311 (2)C13—H130.9500
O5—H5A1.02 (4)C14—C151.415 (3)
O6—C221.210 (2)C15—H150.9500
O7—N41.223 (2)C16—C171.382 (3)
O8—N41.218 (2)C16—C211.391 (3)
N1—C31.465 (3)C16—C221.501 (3)
N2—C151.307 (3)C17—C181.386 (2)
N2—N31.369 (3)C17—H170.9500
N3—C81.307 (2)C18—C191.403 (3)
N4—C181.466 (3)C19—C201.385 (3)
N5—C301.304 (3)C20—C211.377 (3)
N5—N61.376 (2)C20—H200.9500
N6—C231.310 (2)C21—H210.9500
C1—C21.385 (3)C23—C241.416 (3)
C1—C61.394 (3)C23—H230.9500
C1—C71.502 (2)C24—C291.405 (3)
C2—C31.386 (2)C24—C251.412 (3)
C2—H20.9500C25—C261.366 (3)
C3—C41.400 (3)C25—H250.9500
C4—C51.380 (3)C26—C271.404 (3)
C5—C61.384 (2)C26—H260.9500
C5—H50.9500C27—C281.372 (3)
C6—H60.9500C27—H270.9500
C8—C91.419 (3)C28—C291.407 (3)
C8—H80.9500C28—H280.9500
C9—C141.408 (3)C29—C301.417 (3)
C9—C101.411 (3)C30—H300.9500
C7—O1—H1110 (2)C9—C14—C13119.81 (18)
C22—O5—H5A108 (2)C9—C14—C15116.13 (18)
O3—N1—O4123.56 (19)C13—C14—C15124.06 (19)
O3—N1—C3117.54 (17)N2—C15—C14123.76 (19)
O4—N1—C3118.89 (18)N2—C15—H15118.1
C15—N2—N3120.85 (16)C14—C15—H15118.1
C8—N3—N2118.15 (17)C17—C16—C21118.89 (17)
O8—N4—O7123.10 (19)C17—C16—C22120.99 (18)
O8—N4—C18120.11 (17)C21—C16—C22120.11 (18)
O7—N4—C18116.79 (16)C16—C17—C18120.75 (18)
C30—N5—N6121.11 (16)C16—C17—H17119.6
C23—N6—N5117.75 (17)C18—C17—H17119.6
C2—C1—C6119.32 (17)C17—C18—C19120.35 (18)
C2—C1—C7118.94 (17)C17—C18—N4116.12 (17)
C6—C1—C7121.74 (18)C19—C18—N4123.53 (17)
C1—C2—C3119.83 (18)C20—C19—C18118.28 (17)
C1—C2—H2120.1C20—C19—Cl2117.52 (15)
C3—C2—H2120.1C18—C19—Cl2124.16 (16)
C2—C3—C4121.03 (18)C21—C20—C19121.16 (18)
C2—C3—N1116.85 (17)C21—C20—H20119.4
C4—C3—N1122.12 (17)C19—C20—H20119.4
C5—C4—C3118.60 (17)C20—C21—C16120.56 (19)
C5—C4—Cl1118.46 (15)C20—C21—H21119.7
C3—C4—Cl1122.88 (16)C16—C21—H21119.7
C4—C5—C6120.69 (18)O6—C22—O5124.83 (18)
C4—C5—H5119.7O6—C22—C16122.36 (18)
C6—C5—H5119.7O5—C22—C16112.80 (18)
C5—C6—C1120.52 (19)N6—C23—C24124.70 (19)
C5—C6—H6119.7N6—C23—H23117.7
C1—C6—H6119.7C24—C23—H23117.7
O2—C7—O1124.59 (18)C29—C24—C25119.96 (19)
O2—C7—C1122.13 (19)C29—C24—C23116.91 (17)
O1—C7—C1113.28 (17)C25—C24—C23123.13 (19)
N3—C8—C9125.0 (2)C26—C25—C24119.2 (2)
N3—C8—H8117.5C26—C25—H25120.4
C9—C8—H8117.5C24—C25—H25120.4
C14—C9—C10120.10 (18)C25—C26—C27120.79 (19)
C14—C9—C8116.09 (17)C25—C26—H26119.6
C10—C9—C8123.81 (19)C27—C26—H26119.6
C11—C10—C9119.0 (2)C28—C27—C26121.1 (2)
C11—C10—H10120.5C28—C27—H27119.5
C9—C10—H10120.5C26—C27—H27119.5
C10—C11—C12120.94 (19)C27—C28—C29119.1 (2)
C10—C11—H11119.5C27—C28—H28120.4
C12—C11—H11119.5C29—C28—H28120.4
C13—C12—C11121.27 (19)C24—C29—C28119.86 (17)
C13—C12—H12119.4C24—C29—C30115.69 (18)
C11—C12—H12119.4C28—C29—C30124.45 (19)
C12—C13—C14118.9 (2)N5—C30—C29123.81 (19)
C12—C13—H13120.6N5—C30—H30118.1
C14—C13—H13120.6C29—C30—H30118.1
C15—N2—N3—C80.5 (3)C13—C14—C15—N2179.26 (18)
C30—N5—N6—C231.7 (3)C21—C16—C17—C180.0 (3)
C6—C1—C2—C30.8 (3)C22—C16—C17—C18179.10 (17)
C7—C1—C2—C3179.15 (17)C16—C17—C18—C190.3 (3)
C1—C2—C3—C41.5 (3)C16—C17—C18—N4178.84 (16)
C1—C2—C3—N1178.21 (16)O8—N4—C18—C17158.68 (18)
O3—N1—C3—C239.3 (3)O7—N4—C18—C1721.1 (3)
O4—N1—C3—C2139.6 (2)O8—N4—C18—C1922.2 (3)
O3—N1—C3—C4141.0 (2)O7—N4—C18—C19158.08 (19)
O4—N1—C3—C440.1 (3)C17—C18—C19—C200.9 (3)
C2—C3—C4—C50.9 (3)N4—C18—C19—C20178.24 (17)
N1—C3—C4—C5178.81 (17)C17—C18—C19—Cl2178.65 (15)
C2—C3—C4—Cl1176.15 (15)N4—C18—C19—Cl20.5 (3)
N1—C3—C4—Cl14.2 (3)C18—C19—C20—C211.1 (3)
C3—C4—C5—C60.4 (3)Cl2—C19—C20—C21178.99 (15)
Cl1—C4—C5—C6177.59 (15)C19—C20—C21—C160.7 (3)
C4—C5—C6—C11.1 (3)C17—C16—C21—C200.1 (3)
C2—C1—C6—C50.5 (3)C22—C16—C21—C20178.93 (17)
C7—C1—C6—C5179.56 (17)C17—C16—C22—O6179.76 (19)
C2—C1—C7—O22.4 (3)C21—C16—C22—O61.2 (3)
C6—C1—C7—O2177.53 (18)C17—C16—C22—O51.2 (3)
C2—C1—C7—O1177.47 (17)C21—C16—C22—O5177.84 (17)
C6—C1—C7—O12.6 (3)N5—N6—C23—C241.5 (3)
N2—N3—C8—C90.5 (3)N6—C23—C24—C290.2 (3)
N3—C8—C9—C140.1 (3)N6—C23—C24—C25179.51 (19)
N3—C8—C9—C10179.46 (19)C29—C24—C25—C260.4 (3)
C14—C9—C10—C110.2 (3)C23—C24—C25—C26179.38 (18)
C8—C9—C10—C11179.36 (18)C24—C25—C26—C270.2 (3)
C9—C10—C11—C120.1 (3)C25—C26—C27—C280.6 (3)
C10—C11—C12—C130.2 (3)C26—C27—C28—C290.4 (3)
C11—C12—C13—C140.1 (3)C25—C24—C29—C280.5 (3)
C10—C9—C14—C130.3 (3)C23—C24—C29—C28179.22 (17)
C8—C9—C14—C13179.29 (16)C25—C24—C29—C30179.44 (17)
C10—C9—C14—C15179.90 (17)C23—C24—C29—C300.8 (3)
C8—C9—C14—C150.3 (3)C27—C28—C29—C240.2 (3)
C12—C13—C14—C90.1 (3)C27—C28—C29—C30179.82 (19)
C12—C13—C14—C15179.70 (18)N6—N5—C30—C290.7 (3)
N3—N2—C15—C140.1 (3)C24—C29—C30—N50.6 (3)
C9—C14—C15—N20.3 (3)C28—C29—C30—N5179.45 (18)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N21.01 (4)1.61 (4)2.613 (2)171 (4)
O5—H5A···N51.02 (4)1.58 (4)2.589 (2)172 (3)
C13—H13···O60.952.573.316 (3)136
C20—H20···O20.952.523.203 (3)129
C23—H23···O2i0.952.513.220 (2)132
C26—H26···O4ii0.952.533.441 (3)160
C27—H27···O7iii0.952.463.340 (3)155
Symmetry codes: (i) x+1, y+1, z+1; (ii) x1, y+1, z+1; (iii) x, y+1, z.

Experimental details

(I)(II)(III)
Crystal data
Chemical formulaC7H3.67ClNO4·C8H6.33N2C7H3.69ClNO4·C8H6.31N2C7H4ClNO4·C8H6N2
Mr331.71331.71331.71
Crystal system, space groupTriclinic, P1Monoclinic, P21/cTriclinic, P1
Temperature (K)190190190
a, b, c (Å)9.7764 (15), 12.0384 (14), 12.8889 (15)12.2261 (5), 16.9779 (7), 14.4537 (6)6.9197 (5), 14.4263 (12), 14.4750 (9)
α, β, γ (°)81.491 (3), 72.328 (5), 88.390 (5)90, 106.8955 (13), 9081.704 (2), 79.0781 (18), 85.647 (2)
V3)1429.2 (3)2870.7 (2)1402.20 (17)
Z484
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.290.290.30
Crystal size (mm)0.40 × 0.28 × 0.180.35 × 0.35 × 0.300.40 × 0.18 × 0.06
Data collection
DiffractometerRigaku R-AXIS RAPID II
diffractometer
Rigaku R-AXIS RAPID II
diffractometer
Rigaku R-AXIS RAPID II
diffractometer
Absorption correctionNumerical
(NUMABS; Higashi, 1999)
Multi-scan
(ABSCOR; Higashi, 1995)
Numerical
(NUMABS; Higashi, 1999)
Tmin, Tmax0.874, 0.9490.790, 0.9160.929, 0.982
No. of measured, independent and
observed [I > 2σ(I)] reflections
31515, 8271, 6364 60079, 8318, 6797 22476, 7849, 4765
Rint0.0350.0300.056
(sin θ/λ)max1)0.7030.7030.704
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.112, 1.10 0.042, 0.123, 1.07 0.057, 0.154, 0.99
No. of reflections827183187849
No. of parameters429429423
No. of restraints440
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.30, 0.410.71, 0.410.53, 0.48

Computer programs: PROCESS-AUTO (Rigaku/MSC, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and WinGX (Farrugia, 1999), CrystalStructure (Rigaku/MSC, 2004) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N20.86 (3)1.71 (3)2.5715 (15)173 (3)
O5—H5A···N50.84 (3)1.71 (3)2.5397 (17)170 (4)
N2—H2···O10.89 (4)1.69 (4)2.5715 (15)172 (4)
N5—H5B···O50.88 (5)1.66 (5)2.5397 (17)172 (6)
C5—H5···O60.952.563.4174 (17)150
C8—H8···O5i0.952.583.3560 (17)140
C12—H12···O3ii0.952.563.4609 (15)158
C15—H15···O20.952.593.2204 (17)124
C20—H20···O4iii0.952.523.2207 (17)131
C21—H21···N3iii0.952.433.2952 (16)152
C23—H23···Cl2ii0.952.813.4707 (14)128
C23—H23···O3iv0.952.563.3131 (16)136
C28—H28···O20.952.423.3222 (17)158
Symmetry codes: (i) x1, y+1, z; (ii) x, y, z1; (iii) x+1, y1, z; (iv) x+1, y+1, z+1.
Hydrogen-bond geometry (Å, º) for (II) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N20.849 (19)1.719 (19)2.5655 (13)175 (3)
O5—H5A···N50.864 (19)1.747 (19)2.6081 (13)174 (2)
N2—H2···O10.88 (3)1.70 (3)2.5655 (13)171 (6)
N5—H5B···O50.89 (3)1.73 (3)2.6081 (13)170 (6)
C10—H10···O7i0.952.563.4371 (18)153
C15—H15···O20.952.523.1832 (16)127
C15—H15···O8ii0.952.543.1627 (17)124
C25—H25···O30.952.473.3602 (19)157
C30—H30···O60.952.573.2026 (16)124
Symmetry codes: (i) x+1, y, z; (ii) x, y+1, z+1.
Hydrogen-bond geometry (Å, º) for (III) top
D—H···AD—HH···AD···AD—H···A
O1—H1···N21.01 (4)1.61 (4)2.613 (2)171 (4)
O5—H5A···N51.02 (4)1.58 (4)2.589 (2)172 (3)
C13—H13···O60.952.573.316 (3)136
C20—H20···O20.952.523.203 (3)129
C23—H23···O2i0.952.513.220 (2)132
C26—H26···O4ii0.952.533.441 (3)160
C27—H27···O7iii0.952.463.340 (3)155
Symmetry codes: (i) x+1, y+1, z+1; (ii) x1, y+1, z+1; (iii) x, y+1, z.
Geometries of ππ stacking interactions for compounds (I)–(III) top
CgI···CgJ, α, CgI-Perp and CgJ-Perp are, respectively, the centroid-to-centroid distance between rings I and J (Å), the inter-ring dihedral angle (°), the perpendicular distance of CgI from ring J (Å) and the perpendicular distance of CgJ from ring I (Å). Cg1, Cg2, Cg3, Cg4, Cg5 and Cg6 are the centroids of the C1–C6, C16–C21, N2/N3/C8/C9/C14/C15, C9–C14, N5/N6/C23/C24/C29/C30 and C24–C29 rings, respectively.
CgI···CgJαCgI-PerpCgJ-Perp
(I)
Cg1···Cg3i3.5926 (9)9.40 (6)3.3707 (5)3.4833 (5)
Cg2···Cg6ii3.8215 (9)7.77 (6)3.4644 (5)3.5953 (6)
(II)
Cg1···Cg3iii3.6109 (7)4.35 (6)3.4477 (5)3.4910 (5)
Cg1···Cg4iii3.7346 (7)3.20 (6)3.4567 (5)3.4135 (5)
Cg2···Cg5iv3.8139 (7)7.07 (6)3.4937 (5)3.4622 (5)
Cg2···Cg6iv3.7051 (7)6.55 (6)3.4873 (5)3.5827 (5)
Cg3···Cg4v3.6714 (7)1.58 (6)3.4791 (5)3.4485 (5)
(III)
Cg1···Cg3vi3.7248 (12)0.78 (10)3.5065 (4)3.5066 (4)
Cg1···Cg3vii3.5985 (12)0.78 (10)3.44488 (4)3.4722 (4)
Cg1···Cg4vi3.6921 (13)1.29 (10)3.4319 (4)3.4669 (4)
Cg1···Cg4vii3.6698 (13)1.29 (10)3.4485 (4)3.4336 (4)
Cg2···Cg6viii3.6536 (12)0.89 (10)3.3383 (4)3.3225 (5)
Cg2···Cg6v3.7211 (12)0.89 (10)3.4475 (5)3.4475 (5)
Cg2···Cg7viii3.6812 (13)0.60 (10)3.4475 (5)3.4475 (5)
Cg2···Cg7v3.6555 (13)0.60 (10)3.4475 (5)3.4475 (5)
Symmetry codes: (i) -x + 1, -y + 2, -z + 1; (ii) -x + 2, -y + 1, -z + 1; (iii) -x + 1, y + 1/2, -z + 3/2; (iv) -x, y - 1/2, -z + 3/2; (v) -x + 1, -y + 1, -z + 1; (vi) -x + 1, -y + 1, -z + 1; (vii) -x + 2, -y + 1, -z; (viii) -x, -y + 1, -z + 1.
 

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