research communications
Crystal structures of 3-chloro-2-nitrobenzoic acid with quinoline derivatives: 3-chloro-2-nitrobenzoic acid–5-nitroquinoline (1/1), 3-chloro-2-nitrobenzoic acid–6-nitroquinoline (1/1) and 8-hydroxyquinolinium 3-chloro-2-nitrobenzoate
aDepartment of Chemistry, Faculty of Science, Okayama University, Okayama 700-8530, Japan
*Correspondence e-mail: ishidah@cc.okayama-u.ac.jp
The structures of three compounds of 3-chloro-2-nitrobenzoic acid with 5-nitroquinoline, (I), 6-nitroquinoline, (II), and 8-hydroxyquinoline, (III), have been determined at 190 K. In each of the two isomeric compounds, (I) and (II), C7H4ClNO4·C9H6N2O2, the acid and base molecules are held together by O—H⋯N and C—H⋯O hydrogen bonds. In compound (III), C9H8NO+·C7H3ClNO4−, an acid–base interaction involving H-atom transfer occurs and the H atom is located at the N site of the base molecule. In the crystal of (I), the hydrogen-bonded acid–base units are linked by C—H⋯O hydrogen bonds, forming a tape structure along the b-axis direction. Adjacent tapes, which are related by a twofold rotation axis, are linked by a third C—H⋯O hydrogen bond, forming wide ribbons parallel to the (03) plane. These ribbons are stacked via π–π interactions between the quinoline ring systems [centroid–centroid distances = 3.4935 (5)–3.7721 (6) Å], forming layers parallel to the ab plane. In the crystal of (II), the hydrogen-bonded acid–base units are also linked into a tape structure along the b-axis direction via C—H⋯O hydrogen bonds. Inversion-related tapes are linked by further C—H⋯O hydrogen bonds to form wide ribbons parallel to the (08) plane. The ribbons are linked by weak π–π interactions [centroid–centroid distances = 3.8016 (8)–3.9247 (9) Å], forming a three-dimensional structure. In the crystal of (III), the cations and the anions are alternately linked via N—H⋯O and O—H⋯O hydrogen bonds, forming a 21 helix running along the b-axis direction. The cations and the anions are further stacked alternately in columns along the a-axis direction via π–π interactions [centroid–centroid distances = 3.8016 (8)–3.9247 (9) Å], and the molecular chains are linked into layers parallel to the ab plane through these interactions.
1. Chemical context
The hydrogen bonds formed between organic acids and organic bases vary from an O—H⋯N type to an O−⋯H—N+ type depending on the pKa values of the acids and bases as well as intermolecular interactions in the crystals, and at an appropriate ΔpKa [pKa(base) − pKa(acid)] value, a short strong hydrogen bond with a broad single minimum curve for the H atom or a double-minimum potential is observed (Schmidtmann & Wilson, 2008; Gilli & Gilli, 2009). For the system of quinoline–chloro- and nitro-substituted benzoic acids, we have shown that three compounds of quinoline with 3-chloro-2-nitrobenzoic acid, 4-chloro-2-nitrobenzoic acid and 5-chloro-2-nitrobenzoic acid, the ΔpKa values of which are 3.08, 2.93 and 3.04, respectively, have a short double-well O⋯H⋯N hydrogen bond between the carboxy O atom and the aromatic N atom (Gotoh & Ishida, 2009). Similar O⋯H⋯N hydrogen bonds have been also observed in compounds of phthalazine with 3-chloro-2-nitrobenzoic acid and 4-chloro-2-nitrobenzoic acid with ΔpKa values of 1.65 and 1.50, respectively (Gotoh & Ishida, 2011), and of isoquinoline with 3-chloro-2-nitrobenzoic acid with ΔpKa = 3.58 (Gotoh & Ishida, 2015).
We report here the crystal structures of the title compounds in order to extend our studies of short hydrogen bonding in pyridine derivative–chloro- and nitro-substituted benzoic acid systems. The ΔpKa values are 0.98 and 1.42 and 3.02 for 3-chloro-2-nitrobenzoic acid–5-nitroquinoline (1/1), (I), 3-chloro-2-nitrobenzoic acid–6-nitroquinoline (1/1), (II), and 8-hydroxyquinolium 3-chloro-2-nitrobenzoate, (III), respectively.
2. Structural commentary
The molecular structure of (I) is shown in Fig. 1. The acid and base molecules are held together by an O—H⋯N hydrogen bond between the carboxy group and the N atom of the base. In addition, a weak C—H⋯O interaction is formed between the acid and base molecules (Table 1). In the hydrogen-bonded acid–base unit, the quinoline ring system (N2/C8–C16), the carboxy group (O1/C7/O2) and the benzene ring (C1–C6) are almost coplanar with each other; the carboxy group makes dihedral angles of 9.95 (12) and 9.45 (12)°, respectively, with the quinoline ring system and the benzene ring, and the dihedral angle between the quinoline ring system and the benzene ring is 2.59 (4)°. On the other hand, the benzene ring and the nitro group (O3/N1/O4) in the acid molecule is almost perpendicular, with a dihedral angle of 86.14 (13)°. The quinoline ring system and the attached nitro group (O5/N3/O6) are somewhat twisted with a dihedral angle of 31.67 (11)°.
The molecular structure of (II) is shown in Fig. 2. Similar to (I), the acid and base molecules are held together by an O—H⋯N hydrogen bond and an additional C—H⋯O interaction (Table 2). In the acid–base unit, the quinoline ring system, the carboxy group and the benzene ring of the acid are slightly twisted to each other; the carboxy group makes dihedral angles of 12.08 (13) and 2.40 (13)°, respectively, with the quinoline ring system and the benzene ring, and the dihedral angle between the quinoline ring system and the benzene ring is 10.99 (4)°. In the acid molecule, the benzene ring and the nitro group (O3/N1/O4) are almost perpendicular with a dihedral angle of 88.54 (13)°. On the other hand, in the base molecule the quinoline ring system and the nitro group (O5/N3/O6) are almost coplanar with a dihedral angle of 5.58 (12)°.
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The molecular structure of (III) is shown in Fig. 3. An acid–base interaction involving H-atom transfer occurs and the acid and base molecules are linked by an N+—H⋯O− hydrogen bond (Table 3). In the hydrogen-bonded unit, the quinoline ring system makes dihedral angles of 34.96 (13) and 30.80 (14)°, respectively, with the carboxylate group and the benzene ring of the acid. In the acid molecule, the benzene ring makes dihedral angles of 4.71 (13) and 86.12 (11)°, respectively, with the carboxylate and nitro groups.
3. Supramolecular features
In the crystal of (I), the hydrogen-bonded acid–base units are linked by C—H⋯O hydrogen bonds (C5—H5⋯O2i and C14—H14⋯O5i; symmetry codes as in Table 1), forming a tape structure along the b-axis direction. Adjacent tapes, which are related by a twofold rotation axis, are linked by a third C—H⋯O hydrogen bond (C13—H13⋯O6ii), forming wide ribbons parallel to the (03) plane (Fig. 4). These ribbons are stacked via π–π interactions between the quinoline ring systems, forming layers parallel to the ab plane (Fig. 5). The centroid–centroid distances are 3.4935 (5), 3.6761 (6) and 3.7721 (6) Å, respectively, for Cg4⋯Cg4iii, Cg2⋯Cg2iii and Cg2⋯Cg3iii, where Cg2, Cg3 and Cg4 are the centroids of the N2/C8–C11/C16, C11–C16 and N2/C8–C16 rings, respectively, of the base molecule [symmetry code: (iii) −x + 1, y, −z + 2].
In the crystal of (II), the hydrogen-bonded acid–base units are also linked into a tape structure along the b-axis direction via C—H⋯O hydrogen bonds (C8—H8⋯O6i and C14—H14⋯O4iii; symmetry codes as in Table 2). Inversion-related tapes are linked by a further C—H⋯O hydrogen bond (C12—H12⋯O5ii; Table 2), forming wide ribbons parallel to the (08) plane (Fig. 6). The acid and base molecules are further stacked in a column along [11] in an ⋯A⋯A⋯B⋯B⋯A⋯A⋯B⋯B⋯ manner (A: acid and B: base) via weak π–π interactions (Fig. 7), so forming a three-dimensional structure. The centroid–centroid distances are 3.8016 (8), 3.8666 (8), 3.9247 (9) and 3.8225 (8) Å, respectively, for Cg1⋯Cg1iv, Cg1⋯Cg3v, Cg2⋯Cg2vi and Cg2⋯Cg4vi, where Cg1, Cg2, Cg3 and Cg4 are, respectively, the centroids of the C1–C6 ring of the acid molecule, and the N2/C8–C11/C16, C11–C16 and N2/C8–C16 rings of the base molecule [symmetry codes: (iv) −x, −y + 2, −z; (v) x − 1, y + 1, z; (vi) −x + 1, −y + 1, −z + 1]. A pair of short O⋯N contacts [O6⋯N3vii = 2.8453 (13) Å; symmetry code: (vii) −x + 1, −y, −x + 1] between the nitro groups of the base molecule are alsso observed.
In the crystal of compound (III), the cations and the anions are alternately linked via N—H⋯O and O—H⋯O hydrogen bonds (N2—H2⋯O1 and O5—H5O⋯O2i; symmetry code as in Table 3), forming a 21 helical chain running along the b-axis direction (Fig. 8). In the chain, a C—H⋯O (C4—H4⋯O3ii; Table 3) interaction formed between the anions and a π–π interaction between the C1–C6 ring and the C11–C16 ring are observed [Cg1⋯Cg3i = 3.5570 (6) Å]; Cg1 and Cg3 are, respectively, the centroids of the C1–C6 ring of the anion and the C11–C16 ring of the cation. In addition to the π–π interaction (Cg1⋯Cg3i), other π–π interactions are observed; the centroid–centroid distances are 3.5469 (6), 3.8550 (6) and 3.5133 (6) Å, respectively, for Cg1⋯Cg2iii, Cg1⋯Cg3iii and Cg1⋯Cg4iii, where Cg2 and Cg4 are the centroids of the N2/C8–C11/C16 and N2/C8–C16 rings of the cation, respectively [symmetry code: (iii) −x + , y + , −z + ]. The cations and the anions are stacked alternately in columns along the a-axis direction via the π–π interactions (Fig. 9), and the molecular chains are linked into layers parallel to the ab plane through these interactions. A short Cl⋯O contact [Cl1⋯O3iv = 3.0669 (10) Å; symmetry code: (iv) −x + 2, −y + 1, −z + 1] is observed between the layers.
4. Database survey
A search of the Cambridge Structural Database (Version 5.40, last update May 2019; Groom et al., 2016) for organic co-crystals of 3-chloro-2-nitrobonzoic acid with base molecules gave six hits (five compounds), namely, 4-benzpylpyridine (1/1) (refcode UHAQUP; Sugiyama et al., 2002), quinolone (1/1) (AJIWOG; Gotoh & Ishida, 2009), phthalazine (1/1) (CALJUW; Gotoh & Ishida, 2011), isoquinoline (1/1) (NOVLAN; Gotoh & Ishida, 2015) and 4,4′-bipyridine (2/1) (XICGUO and XICGUO01; Rawat et al., 2018). The structure of 3-chloro-2-nitrobonzoic acid itself (XICHAV) was also reported by Rawat et al. (2018). There is no structure for a salt of 3-chloro-2-nitrobonzoic acid with an organic base molecule. In the acid molecules of the above compounds, the dihedral angles between the benzene ring and the nitro group, and between the benzene ring and the carboxy group are in the ranges 79.1 (3)–89.9 (3)° and 1.4 (3)–14.2 (3)°, respectively, which agree with those in the three title compounds. The ΔpKa values for UHAQUP, AJIWOG, CALJUW, NOVLAN and XICGUO are 1.32, 3.08, 1.65, 3.58 and 3.27, respectively, and these compounds show short O⋯N distances in the O—H⋯N hydrogen bonds of 2.600 (3), 2.561 (1), 2.540 (2)–2.571 (2), 2.573 (1) and 2.613 (3) Å, respectively. Furthermore, in the short hydrogen bonds of AJIWOG, CALJUW and NOVLAN, the H atom is disordered over two positions. On the other hand, the compounds (I), (II) and (III) with ΔpKa values of 0.98, 1.42 and 3.02, respectively, show longer O⋯N distances of 2.673 (1), 2.631 (1) and 2.636 (1) Å, which suggests that the ΔpKa value is not an effective measure of hydrogen-bond strength in the 3-chloro-2-nitrobenzoic acid–organic base system.
A search for organic co-crystals/salts of 5-nitroquinoline showed six structures. Limiting the search to benzoic acid derivatives gave two hits, namely, 3-aminobenzoic acid–5-nitroquinoline (1/1) (PANYIM; Lynch et al., 1997) and 4-animobenzoic acid–5-nitroquinoline (1/2) (PANZEJ; Lynch et al., 1997). No structure was found in the CSD for organic co-crystals/salts of 6-nitroquinoline. A search for organic co-crystals/salts of 8-hydroxyquinoline gave 17 hits. Of these compounds, one related compound is 8-hydroxyquinolinium 2-chloro-4-nitrobenzoate (WOPDEM; Babu & Chandrasekaran, 2014; ΔpKa = 2.80), in which the O⋯N distance of the N—H⋯O hydrogen bond is 2.644 (3) Å.
5. Synthesis and crystallization
Crystals of all three compounds, (I)–(III), were obtained by slow evaporation from acetonitrile solutions of 3-chloro-2-nitrobenzoic acid with quinoline derivatives in a 1:1 molar ratio at room temperature [100 ml acetonitrile solution of 3-chloro-2-nitrobenzoic acid (0.39 g) and 5-nitroquinoline (0.34 g) for (I), 150 ml acetonitrile solution of 3-chloro-2-nitrobenzoic acid (0.45 g) and 6-nitroquinoline (0.39 g) for (II), and 120 ml acetonitrile solution of 3-chloro-2-nitrobenzoic acid (0.55 g) and 8-hydroxyqunoline (0.40 mg) for (III)] .
6. Refinement
Crystal data, data collection and structure . All H atoms in compounds (I)–(III) were found in difference-Fourier maps. O- and N-bound H atoms in (I)–(III) were refined freely [refined distances: O1—H1 = 0.88 (2) Å in (I), N1—H1 = 0.87 (3) Å in (II), and N2—H2 = 0.880 (16) and O5—H5O = 0.872 (19) Å in (III),]. Other H atoms were positioned geometrically (C—H = 0.95 Å) and treated as riding, with Uiso(H) = 1.2Ueq(C).
details are summarized in Table 4
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Supporting information
https://doi.org/10.1107/S2056989019012799/lh5922sup1.cif
contains datablocks global, I, II, III. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019012799/lh5922Isup2.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989019012799/lh5922IIsup3.hkl
Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S2056989019012799/lh5922IIIsup4.hkl
For all structures, data collection: RAPID-AUTO (Rigaku, 2006); cell
RAPID-AUTO (Rigaku, 2006); data reduction: RAPID-AUTO (Rigaku, 2006); program(s) used to solve structure: SHELXT2018/2 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and Mercury (Macrae et al., 2006); software used to prepare material for publication: CrystalStructure (Rigaku, 2018) and PLATON (Spek, 2015).C7H4ClNO4·C9H6N2O2 | F(000) = 1536.00 |
Mr = 375.72 | Dx = 1.594 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71075 Å |
a = 20.5876 (4) Å | Cell parameters from 25710 reflections |
b = 7.6889 (3) Å | θ = 3.1–30.1° |
c = 20.4312 (4) Å | µ = 0.29 mm−1 |
β = 104.5338 (7)° | T = 190 K |
V = 3130.70 (16) Å3 | Block, colorless |
Z = 8 | 0.45 × 0.40 × 0.30 mm |
Rigaku R-AXIS RAPIDII diffractometer | 4077 reflections with I > 2σ(I) |
Detector resolution: 10.000 pixels mm-1 | Rint = 0.022 |
ω scans | θmax = 30.0°, θmin = 3.1° |
Absorption correction: numerical (NUMABS; Higashi, 1999) | h = −26→28 |
Tmin = 0.837, Tmax = 0.918 | k = −10→10 |
30107 measured reflections | l = −28→28 |
4549 independent reflections |
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)] = 0.037 | Hydrogen site location: mixed |
wR(F2) = 0.104 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0636P)2 + 1.2587P] where P = (Fo2 + 2Fc2)/3 |
4549 reflections | (Δ/σ)max = 0.001 |
239 parameters | Δρmax = 0.30 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.03434 (2) | 0.24994 (4) | 0.50043 (2) | 0.03753 (9) | |
O1 | 0.34832 (4) | 0.34621 (10) | 0.61778 (4) | 0.03292 (17) | |
O2 | 0.27238 (4) | 0.55880 (10) | 0.60848 (5) | 0.03766 (19) | |
O3 | 0.14558 (5) | 0.57618 (11) | 0.50150 (4) | 0.0412 (2) | |
O4 | 0.12329 (5) | 0.55420 (11) | 0.59855 (5) | 0.0414 (2) | |
O5 | 0.64633 (4) | 0.97971 (11) | 0.75715 (4) | 0.03764 (19) | |
O6 | 0.72372 (4) | 0.82403 (14) | 0.73078 (5) | 0.0472 (2) | |
N1 | 0.14396 (4) | 0.49673 (11) | 0.55218 (5) | 0.02666 (17) | |
N2 | 0.43699 (4) | 0.60692 (11) | 0.64264 (4) | 0.02613 (17) | |
N3 | 0.66566 (4) | 0.84775 (12) | 0.73417 (4) | 0.02984 (18) | |
C1 | 0.23369 (5) | 0.26976 (12) | 0.58259 (5) | 0.02307 (18) | |
C2 | 0.16614 (4) | 0.31430 (12) | 0.55708 (5) | 0.02215 (17) | |
C3 | 0.11699 (5) | 0.18860 (13) | 0.53478 (5) | 0.02620 (19) | |
C4 | 0.13470 (5) | 0.01433 (14) | 0.53907 (6) | 0.0320 (2) | |
H4 | 0.101547 | −0.072633 | 0.523966 | 0.038* | |
C5 | 0.20130 (6) | −0.03225 (14) | 0.56561 (6) | 0.0344 (2) | |
H5 | 0.213441 | −0.151718 | 0.569282 | 0.041* | |
C6 | 0.25043 (5) | 0.09415 (13) | 0.58689 (6) | 0.0296 (2) | |
H6 | 0.295828 | 0.060186 | 0.604524 | 0.035* | |
C7 | 0.28632 (5) | 0.40747 (12) | 0.60433 (5) | 0.02479 (18) | |
C8 | 0.41075 (5) | 0.76300 (13) | 0.63187 (5) | 0.0281 (2) | |
H8 | 0.363528 | 0.772862 | 0.614770 | 0.034* | |
C9 | 0.44900 (5) | 0.91633 (13) | 0.64438 (5) | 0.0290 (2) | |
H9 | 0.427911 | 1.026448 | 0.634382 | 0.035* | |
C10 | 0.51692 (5) | 0.90588 (12) | 0.67109 (5) | 0.02615 (19) | |
H10 | 0.543243 | 1.008630 | 0.680454 | 0.031* | |
C11 | 0.54753 (5) | 0.74008 (11) | 0.68461 (5) | 0.02182 (17) | |
C12 | 0.61745 (5) | 0.70585 (13) | 0.71097 (5) | 0.02475 (18) | |
C13 | 0.64371 (5) | 0.54231 (14) | 0.71854 (6) | 0.0311 (2) | |
H13 | 0.690681 | 0.525741 | 0.735325 | 0.037* | |
C14 | 0.60078 (6) | 0.39830 (14) | 0.70133 (6) | 0.0356 (2) | |
H14 | 0.618748 | 0.283873 | 0.706670 | 0.043* | |
C15 | 0.53282 (6) | 0.42258 (13) | 0.67677 (6) | 0.0313 (2) | |
H15 | 0.504064 | 0.324562 | 0.665699 | 0.038* | |
C16 | 0.50536 (5) | 0.59203 (12) | 0.66783 (5) | 0.02310 (18) | |
H1 | 0.3780 (11) | 0.430 (3) | 0.6264 (10) | 0.073 (6)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.02113 (13) | 0.03817 (16) | 0.04799 (17) | −0.00501 (9) | −0.00126 (11) | −0.00276 (10) |
O1 | 0.0197 (3) | 0.0265 (4) | 0.0495 (5) | −0.0024 (3) | 0.0029 (3) | −0.0014 (3) |
O2 | 0.0245 (4) | 0.0230 (3) | 0.0615 (5) | −0.0035 (3) | 0.0033 (3) | −0.0040 (3) |
O3 | 0.0537 (5) | 0.0289 (4) | 0.0359 (4) | 0.0016 (3) | 0.0018 (4) | 0.0084 (3) |
O4 | 0.0421 (5) | 0.0322 (4) | 0.0559 (5) | 0.0007 (3) | 0.0237 (4) | −0.0094 (4) |
O5 | 0.0346 (4) | 0.0320 (4) | 0.0431 (4) | −0.0071 (3) | 0.0037 (3) | −0.0078 (3) |
O6 | 0.0214 (4) | 0.0566 (6) | 0.0631 (6) | −0.0097 (4) | 0.0097 (4) | −0.0088 (5) |
N1 | 0.0211 (4) | 0.0221 (4) | 0.0344 (4) | −0.0018 (3) | 0.0025 (3) | −0.0014 (3) |
N2 | 0.0195 (4) | 0.0268 (4) | 0.0299 (4) | −0.0039 (3) | 0.0020 (3) | 0.0007 (3) |
N3 | 0.0221 (4) | 0.0337 (4) | 0.0314 (4) | −0.0067 (3) | 0.0022 (3) | −0.0007 (3) |
C1 | 0.0209 (4) | 0.0210 (4) | 0.0265 (4) | −0.0031 (3) | 0.0044 (3) | −0.0008 (3) |
C2 | 0.0215 (4) | 0.0196 (4) | 0.0248 (4) | −0.0018 (3) | 0.0047 (3) | −0.0002 (3) |
C3 | 0.0216 (4) | 0.0260 (4) | 0.0294 (4) | −0.0046 (3) | 0.0036 (3) | −0.0019 (3) |
C4 | 0.0300 (5) | 0.0237 (5) | 0.0405 (5) | −0.0075 (4) | 0.0057 (4) | −0.0040 (4) |
C5 | 0.0341 (5) | 0.0196 (4) | 0.0477 (6) | −0.0026 (4) | 0.0068 (5) | −0.0018 (4) |
C6 | 0.0259 (4) | 0.0221 (4) | 0.0391 (5) | 0.0000 (3) | 0.0050 (4) | −0.0001 (4) |
C7 | 0.0200 (4) | 0.0239 (4) | 0.0290 (4) | −0.0032 (3) | 0.0035 (3) | 0.0002 (3) |
C8 | 0.0197 (4) | 0.0304 (5) | 0.0321 (5) | −0.0014 (3) | 0.0025 (4) | 0.0042 (4) |
C9 | 0.0245 (4) | 0.0241 (4) | 0.0369 (5) | 0.0014 (3) | 0.0053 (4) | 0.0051 (4) |
C10 | 0.0230 (4) | 0.0216 (4) | 0.0332 (5) | −0.0019 (3) | 0.0059 (4) | 0.0017 (3) |
C11 | 0.0186 (4) | 0.0219 (4) | 0.0243 (4) | −0.0020 (3) | 0.0042 (3) | −0.0004 (3) |
C12 | 0.0187 (4) | 0.0275 (4) | 0.0267 (4) | −0.0030 (3) | 0.0032 (3) | −0.0015 (3) |
C13 | 0.0223 (4) | 0.0319 (5) | 0.0368 (5) | 0.0049 (4) | 0.0032 (4) | 0.0004 (4) |
C14 | 0.0325 (5) | 0.0246 (5) | 0.0470 (6) | 0.0061 (4) | 0.0047 (5) | −0.0010 (4) |
C15 | 0.0287 (5) | 0.0218 (4) | 0.0409 (5) | −0.0016 (3) | 0.0038 (4) | −0.0022 (4) |
C16 | 0.0203 (4) | 0.0220 (4) | 0.0259 (4) | −0.0027 (3) | 0.0037 (3) | −0.0007 (3) |
Cl1—C3 | 1.7352 (10) | C5—C6 | 1.3913 (14) |
O1—C7 | 1.3231 (12) | C5—H5 | 0.9500 |
O1—H1 | 0.88 (2) | C6—H6 | 0.9500 |
O2—C7 | 1.2065 (13) | C8—C9 | 1.4051 (14) |
O3—N1 | 1.2099 (12) | C8—H8 | 0.9500 |
O4—N1 | 1.2150 (12) | C9—C10 | 1.3699 (13) |
O5—N3 | 1.2256 (13) | C9—H9 | 0.9500 |
O6—N3 | 1.2282 (12) | C10—C11 | 1.4182 (13) |
N1—C2 | 1.4708 (12) | C10—H10 | 0.9500 |
N2—C8 | 1.3118 (13) | C11—C16 | 1.4205 (12) |
N2—C16 | 1.3768 (12) | C11—C12 | 1.4290 (13) |
N3—C12 | 1.4711 (13) | C12—C13 | 1.3621 (14) |
C1—C6 | 1.3909 (13) | C13—C14 | 1.4053 (16) |
C1—C2 | 1.3997 (13) | C13—H13 | 0.9500 |
C1—C7 | 1.5002 (13) | C14—C15 | 1.3755 (16) |
C2—C3 | 1.3909 (12) | C14—H14 | 0.9500 |
C3—C4 | 1.3857 (14) | C15—C16 | 1.4138 (13) |
C4—C5 | 1.3889 (16) | C15—H15 | 0.9500 |
C4—H4 | 0.9500 | ||
C7—O1—H1 | 111.7 (14) | O1—C7—C1 | 113.43 (8) |
O3—N1—O4 | 125.03 (10) | N2—C8—C9 | 123.28 (9) |
O3—N1—C2 | 117.71 (9) | N2—C8—H8 | 118.4 |
O4—N1—C2 | 117.21 (9) | C9—C8—H8 | 118.4 |
C8—N2—C16 | 118.56 (8) | C10—C9—C8 | 119.51 (9) |
O5—N3—O6 | 123.97 (9) | C10—C9—H9 | 120.2 |
O5—N3—C12 | 118.67 (8) | C8—C9—H9 | 120.2 |
O6—N3—C12 | 117.33 (9) | C9—C10—C11 | 119.32 (9) |
C6—C1—C2 | 117.92 (8) | C9—C10—H10 | 120.3 |
C6—C1—C7 | 121.16 (9) | C11—C10—H10 | 120.3 |
C2—C1—C7 | 120.92 (8) | C10—C11—C16 | 117.28 (8) |
C3—C2—C1 | 121.68 (9) | C10—C11—C12 | 126.54 (8) |
C3—C2—N1 | 116.90 (8) | C16—C11—C12 | 116.12 (8) |
C1—C2—N1 | 121.41 (8) | C13—C12—C11 | 123.12 (9) |
C4—C3—C2 | 119.53 (9) | C13—C12—N3 | 115.57 (9) |
C4—C3—Cl1 | 120.28 (7) | C11—C12—N3 | 121.28 (9) |
C2—C3—Cl1 | 120.18 (8) | C12—C13—C14 | 119.48 (9) |
C3—C4—C5 | 119.50 (9) | C12—C13—H13 | 120.3 |
C3—C4—H4 | 120.3 | C14—C13—H13 | 120.3 |
C5—C4—H4 | 120.3 | C15—C14—C13 | 120.17 (10) |
C4—C5—C6 | 120.72 (10) | C15—C14—H14 | 119.9 |
C4—C5—H5 | 119.6 | C13—C14—H14 | 119.9 |
C6—C5—H5 | 119.6 | C14—C15—C16 | 120.63 (9) |
C1—C6—C5 | 120.61 (10) | C14—C15—H15 | 119.7 |
C1—C6—H6 | 119.7 | C16—C15—H15 | 119.7 |
C5—C6—H6 | 119.7 | N2—C16—C15 | 117.59 (8) |
O2—C7—O1 | 124.25 (9) | N2—C16—C11 | 121.96 (8) |
O2—C7—C1 | 122.32 (9) | C15—C16—C11 | 120.46 (9) |
C6—C1—C2—C3 | −1.77 (14) | C8—C9—C10—C11 | 1.01 (15) |
C7—C1—C2—C3 | 178.02 (9) | C9—C10—C11—C16 | 1.49 (14) |
C6—C1—C2—N1 | 178.69 (9) | C9—C10—C11—C12 | 178.64 (9) |
C7—C1—C2—N1 | −1.53 (14) | C10—C11—C12—C13 | −175.60 (10) |
O3—N1—C2—C3 | −92.47 (11) | C16—C11—C12—C13 | 1.57 (14) |
O4—N1—C2—C3 | 85.14 (11) | C10—C11—C12—N3 | 6.67 (15) |
O3—N1—C2—C1 | 87.09 (12) | C16—C11—C12—N3 | −176.16 (8) |
O4—N1—C2—C1 | −95.29 (11) | O5—N3—C12—C13 | −148.03 (10) |
C1—C2—C3—C4 | 1.39 (15) | O6—N3—C12—C13 | 30.14 (14) |
N1—C2—C3—C4 | −179.05 (9) | O5—N3—C12—C11 | 29.86 (14) |
C1—C2—C3—Cl1 | −177.45 (7) | O6—N3—C12—C11 | −151.97 (10) |
N1—C2—C3—Cl1 | 2.11 (12) | C11—C12—C13—C14 | −1.45 (16) |
C2—C3—C4—C5 | 0.03 (16) | N3—C12—C13—C14 | 176.40 (10) |
Cl1—C3—C4—C5 | 178.87 (9) | C12—C13—C14—C15 | 0.27 (18) |
C3—C4—C5—C6 | −1.02 (18) | C13—C14—C15—C16 | 0.68 (18) |
C2—C1—C6—C5 | 0.76 (16) | C8—N2—C16—C15 | −177.79 (10) |
C7—C1—C6—C5 | −179.03 (10) | C8—N2—C16—C11 | 2.30 (14) |
C4—C5—C6—C1 | 0.62 (18) | C14—C15—C16—N2 | 179.60 (10) |
C6—C1—C7—O2 | −171.24 (11) | C14—C15—C16—C11 | −0.50 (16) |
C2—C1—C7—O2 | 8.99 (15) | C10—C11—C16—N2 | −3.23 (14) |
C6—C1—C7—O1 | 9.12 (14) | C12—C11—C16—N2 | 179.32 (8) |
C2—C1—C7—O1 | −170.66 (9) | C10—C11—C16—C15 | 176.87 (9) |
C16—N2—C8—C9 | 0.41 (16) | C12—C11—C16—C15 | −0.58 (14) |
N2—C8—C9—C10 | −2.09 (17) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N2 | 0.88 (2) | 1.80 (2) | 2.6727 (12) | 178 (2) |
C8—H8···O2 | 0.95 | 2.48 | 3.1820 (13) | 131 |
C5—H5···O2i | 0.95 | 2.57 | 3.4860 (14) | 163 |
C14—H14···O5i | 0.95 | 2.56 | 3.4644 (14) | 159 |
C13—H13···O6ii | 0.95 | 2.32 | 3.1495 (14) | 146 |
Symmetry codes: (i) x, y−1, z; (ii) −x+3/2, y−1/2, −z+3/2. |
C7H4ClNO4·C9H6N2O2 | Z = 2 |
Mr = 375.72 | F(000) = 384.00 |
Triclinic, P1 | Dx = 1.571 Mg m−3 |
a = 7.7282 (10) Å | Mo Kα radiation, λ = 0.71075 Å |
b = 10.2839 (14) Å | Cell parameters from 14524 reflections |
c = 11.2828 (16) Å | θ = 3.1–30.1° |
α = 71.990 (4)° | µ = 0.28 mm−1 |
β = 79.724 (4)° | T = 190 K |
γ = 69.051 (3)° | Block, colorless |
V = 794.08 (19) Å3 | 0.38 × 0.35 × 0.30 mm |
Rigaku R-AXIS RAPIDII diffractometer | 4029 reflections with I > 2σ(I) |
Detector resolution: 10.000 pixels mm-1 | Rint = 0.026 |
ω scans | θmax = 30.0°, θmin = 3.1° |
Absorption correction: numerical (NUMABS; Higashi, 1999) | h = −10→10 |
Tmin = 0.887, Tmax = 0.919 | k = −14→14 |
16549 measured reflections | l = −15→15 |
4622 independent reflections |
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)] = 0.039 | Hydrogen site location: mixed |
wR(F2) = 0.113 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.072P)2 + 0.0976P] where P = (Fo2 + 2Fc2)/3 |
4622 reflections | (Δ/σ)max = 0.001 |
239 parameters | Δρmax = 0.50 e Å−3 |
0 restraints | Δρmin = −0.33 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Cl1 | −0.21217 (4) | 1.44247 (3) | −0.00166 (3) | 0.04778 (11) | |
O1 | 0.17321 (12) | 0.77718 (8) | 0.24868 (9) | 0.03883 (19) | |
O2 | 0.30609 (12) | 0.94833 (9) | 0.20949 (10) | 0.0464 (2) | |
O3 | 0.23107 (11) | 1.23134 (10) | 0.01395 (9) | 0.0439 (2) | |
O4 | 0.12561 (13) | 1.25965 (10) | 0.19770 (10) | 0.0477 (2) | |
O5 | 0.83957 (13) | −0.07571 (9) | 0.45563 (10) | 0.0469 (2) | |
O6 | 0.58065 (12) | −0.04120 (8) | 0.38490 (8) | 0.03651 (18) | |
N1 | 0.12435 (12) | 1.22061 (9) | 0.10689 (9) | 0.03234 (19) | |
N2 | 0.50541 (13) | 0.60187 (9) | 0.31357 (9) | 0.03239 (19) | |
N3 | 0.69185 (13) | 0.00332 (9) | 0.41169 (8) | 0.03128 (18) | |
C1 | −0.00331 (13) | 1.01631 (10) | 0.15345 (9) | 0.02609 (18) | |
C2 | −0.02570 (12) | 1.16317 (10) | 0.10624 (9) | 0.02667 (18) | |
C3 | −0.18851 (13) | 1.26120 (10) | 0.05510 (10) | 0.0299 (2) | |
C4 | −0.33392 (14) | 1.21363 (12) | 0.04976 (10) | 0.0325 (2) | |
H4 | −0.445873 | 1.280397 | 0.015146 | 0.039* | |
C5 | −0.31344 (14) | 1.06810 (12) | 0.09541 (10) | 0.0318 (2) | |
H5 | −0.411793 | 1.034696 | 0.091986 | 0.038* | |
C6 | −0.14952 (13) | 0.97031 (11) | 0.14634 (9) | 0.02906 (19) | |
H6 | −0.137031 | 0.870569 | 0.176756 | 0.035* | |
C7 | 0.17485 (14) | 0.91108 (10) | 0.20737 (10) | 0.0302 (2) | |
C8 | 0.62786 (17) | 0.65774 (11) | 0.32741 (12) | 0.0382 (2) | |
H8 | 0.593373 | 0.759863 | 0.309365 | 0.046* | |
C9 | 0.80676 (17) | 0.57424 (13) | 0.36745 (13) | 0.0413 (3) | |
H9 | 0.890518 | 0.619663 | 0.374699 | 0.050* | |
C10 | 0.85796 (16) | 0.42727 (12) | 0.39567 (12) | 0.0367 (2) | |
H10 | 0.977047 | 0.368770 | 0.424193 | 0.044* | |
C11 | 0.73037 (14) | 0.36326 (10) | 0.38169 (9) | 0.02805 (19) | |
C12 | 0.77423 (14) | 0.21193 (10) | 0.40730 (10) | 0.02926 (19) | |
H12 | 0.890452 | 0.148054 | 0.437393 | 0.035* | |
C13 | 0.64508 (14) | 0.16024 (10) | 0.38761 (9) | 0.02718 (19) | |
C14 | 0.47039 (14) | 0.24888 (11) | 0.34310 (10) | 0.0302 (2) | |
H14 | 0.385636 | 0.207883 | 0.329622 | 0.036* | |
C15 | 0.42557 (14) | 0.39522 (11) | 0.31976 (10) | 0.0310 (2) | |
H15 | 0.307926 | 0.457014 | 0.290674 | 0.037* | |
C16 | 0.55426 (13) | 0.45484 (10) | 0.33887 (9) | 0.02686 (18) | |
H1 | 0.285 (3) | 0.723 (3) | 0.270 (2) | 0.089 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.03623 (16) | 0.02349 (14) | 0.0773 (2) | −0.00733 (10) | −0.02054 (14) | 0.00154 (12) |
O1 | 0.0321 (4) | 0.0222 (3) | 0.0574 (5) | −0.0076 (3) | −0.0081 (3) | −0.0028 (3) |
O2 | 0.0339 (4) | 0.0274 (4) | 0.0765 (6) | −0.0091 (3) | −0.0234 (4) | −0.0020 (4) |
O3 | 0.0315 (4) | 0.0410 (4) | 0.0603 (5) | −0.0196 (3) | −0.0013 (4) | −0.0068 (4) |
O4 | 0.0429 (5) | 0.0451 (5) | 0.0664 (6) | −0.0136 (4) | −0.0170 (4) | −0.0240 (4) |
O5 | 0.0430 (4) | 0.0235 (4) | 0.0679 (6) | −0.0034 (3) | −0.0177 (4) | −0.0047 (4) |
O6 | 0.0471 (4) | 0.0304 (4) | 0.0395 (4) | −0.0196 (3) | −0.0002 (3) | −0.0132 (3) |
N1 | 0.0246 (4) | 0.0221 (4) | 0.0508 (5) | −0.0070 (3) | −0.0109 (4) | −0.0065 (3) |
N2 | 0.0329 (4) | 0.0204 (4) | 0.0417 (5) | −0.0051 (3) | −0.0079 (3) | −0.0066 (3) |
N3 | 0.0368 (4) | 0.0225 (4) | 0.0340 (4) | −0.0100 (3) | −0.0023 (3) | −0.0066 (3) |
C1 | 0.0231 (4) | 0.0236 (4) | 0.0311 (4) | −0.0078 (3) | −0.0029 (3) | −0.0060 (3) |
C2 | 0.0217 (4) | 0.0244 (4) | 0.0349 (4) | −0.0085 (3) | −0.0041 (3) | −0.0071 (3) |
C3 | 0.0250 (4) | 0.0238 (4) | 0.0389 (5) | −0.0071 (3) | −0.0065 (4) | −0.0042 (4) |
C4 | 0.0220 (4) | 0.0342 (5) | 0.0401 (5) | −0.0080 (4) | −0.0063 (4) | −0.0075 (4) |
C5 | 0.0255 (4) | 0.0365 (5) | 0.0374 (5) | −0.0152 (4) | −0.0011 (4) | −0.0099 (4) |
C6 | 0.0273 (4) | 0.0282 (4) | 0.0335 (4) | −0.0132 (4) | 0.0008 (3) | −0.0075 (4) |
C7 | 0.0287 (4) | 0.0229 (4) | 0.0370 (5) | −0.0068 (3) | −0.0050 (4) | −0.0054 (3) |
C8 | 0.0433 (6) | 0.0228 (4) | 0.0506 (6) | −0.0102 (4) | −0.0097 (5) | −0.0097 (4) |
C9 | 0.0420 (6) | 0.0310 (5) | 0.0588 (7) | −0.0157 (4) | −0.0144 (5) | −0.0122 (5) |
C10 | 0.0328 (5) | 0.0294 (5) | 0.0518 (6) | −0.0100 (4) | −0.0144 (4) | −0.0099 (4) |
C11 | 0.0282 (4) | 0.0229 (4) | 0.0343 (5) | −0.0078 (3) | −0.0074 (3) | −0.0071 (3) |
C12 | 0.0269 (4) | 0.0218 (4) | 0.0373 (5) | −0.0048 (3) | −0.0091 (4) | −0.0054 (3) |
C13 | 0.0303 (4) | 0.0204 (4) | 0.0307 (4) | −0.0082 (3) | −0.0044 (3) | −0.0055 (3) |
C14 | 0.0298 (4) | 0.0270 (4) | 0.0359 (5) | −0.0115 (4) | −0.0083 (4) | −0.0055 (4) |
C15 | 0.0270 (4) | 0.0258 (4) | 0.0385 (5) | −0.0068 (3) | −0.0103 (4) | −0.0041 (4) |
C16 | 0.0275 (4) | 0.0210 (4) | 0.0309 (4) | −0.0064 (3) | −0.0054 (3) | −0.0053 (3) |
Cl1—C3 | 1.7257 (10) | C5—C6 | 1.3921 (14) |
O1—C7 | 1.3142 (12) | C5—H5 | 0.9500 |
O1—H1 | 0.87 (3) | C6—H6 | 0.9500 |
O2—C7 | 1.2117 (13) | C8—C9 | 1.4096 (16) |
O3—N1 | 1.2153 (13) | C8—H8 | 0.9500 |
O4—N1 | 1.2132 (13) | C9—C10 | 1.3646 (15) |
O5—N3 | 1.2243 (12) | C9—H9 | 0.9500 |
O6—N3 | 1.2244 (12) | C10—C11 | 1.4193 (14) |
N1—C2 | 1.4796 (12) | C10—H10 | 0.9500 |
N2—C8 | 1.3218 (14) | C11—C12 | 1.4142 (13) |
N2—C16 | 1.3688 (12) | C11—C16 | 1.4175 (13) |
N3—C13 | 1.4682 (12) | C12—C13 | 1.3637 (14) |
C1—C2 | 1.3940 (13) | C12—H12 | 0.9500 |
C1—C6 | 1.3947 (13) | C13—C14 | 1.4088 (13) |
C1—C7 | 1.5044 (13) | C14—C15 | 1.3671 (14) |
C2—C3 | 1.3873 (13) | C14—H14 | 0.9500 |
C3—C4 | 1.3934 (13) | C15—C16 | 1.4163 (14) |
C4—C5 | 1.3832 (15) | C15—H15 | 0.9500 |
C4—H4 | 0.9500 | ||
C7—O1—H1 | 107.0 (16) | O1—C7—C1 | 113.28 (9) |
O4—N1—O3 | 125.19 (9) | N2—C8—C9 | 123.66 (10) |
O4—N1—C2 | 117.34 (9) | N2—C8—H8 | 118.2 |
O3—N1—C2 | 117.37 (9) | C9—C8—H8 | 118.2 |
C8—N2—C16 | 118.54 (9) | C10—C9—C8 | 119.08 (10) |
O5—N3—O6 | 123.52 (9) | C10—C9—H9 | 120.5 |
O5—N3—C13 | 118.83 (9) | C8—C9—H9 | 120.5 |
O6—N3—C13 | 117.64 (9) | C9—C10—C11 | 118.90 (10) |
C2—C1—C6 | 117.80 (9) | C9—C10—H10 | 120.5 |
C2—C1—C7 | 120.79 (8) | C11—C10—H10 | 120.5 |
C6—C1—C7 | 121.39 (8) | C12—C11—C16 | 119.20 (9) |
C3—C2—C1 | 121.41 (9) | C12—C11—C10 | 122.22 (9) |
C3—C2—N1 | 117.24 (8) | C16—C11—C10 | 118.57 (9) |
C1—C2—N1 | 121.35 (8) | C13—C12—C11 | 118.16 (9) |
C2—C3—C4 | 120.06 (9) | C13—C12—H12 | 120.9 |
C2—C3—Cl1 | 120.21 (7) | C11—C12—H12 | 120.9 |
C4—C3—Cl1 | 119.73 (8) | C12—C13—C14 | 123.80 (9) |
C5—C4—C3 | 119.26 (9) | C12—C13—N3 | 118.24 (9) |
C5—C4—H4 | 120.4 | C14—C13—N3 | 117.95 (8) |
C3—C4—H4 | 120.4 | C15—C14—C13 | 118.50 (9) |
C4—C5—C6 | 120.36 (9) | C15—C14—H14 | 120.8 |
C4—C5—H5 | 119.8 | C13—C14—H14 | 120.8 |
C6—C5—H5 | 119.8 | C14—C15—C16 | 120.10 (9) |
C5—C6—C1 | 121.10 (9) | C14—C15—H15 | 120.0 |
C5—C6—H6 | 119.4 | C16—C15—H15 | 119.9 |
C1—C6—H6 | 119.4 | N2—C16—C15 | 118.54 (9) |
O2—C7—O1 | 124.46 (9) | N2—C16—C11 | 121.22 (9) |
O2—C7—C1 | 122.25 (9) | C15—C16—C11 | 120.23 (9) |
C6—C1—C2—C3 | 0.76 (15) | N2—C8—C9—C10 | −1.0 (2) |
C7—C1—C2—C3 | 179.34 (9) | C8—C9—C10—C11 | 1.07 (19) |
C6—C1—C2—N1 | −178.31 (9) | C9—C10—C11—C12 | 179.07 (11) |
C7—C1—C2—N1 | 0.27 (15) | C9—C10—C11—C16 | −0.01 (17) |
O4—N1—C2—C3 | 90.22 (12) | C16—C11—C12—C13 | 1.04 (15) |
O3—N1—C2—C3 | −86.34 (12) | C10—C11—C12—C13 | −178.04 (10) |
O4—N1—C2—C1 | −90.67 (12) | C11—C12—C13—C14 | 0.05 (16) |
O3—N1—C2—C1 | 92.76 (12) | C11—C12—C13—N3 | 178.77 (9) |
C1—C2—C3—C4 | −0.19 (16) | O5—N3—C13—C12 | 4.41 (15) |
N1—C2—C3—C4 | 178.92 (9) | O6—N3—C13—C12 | −174.69 (9) |
C1—C2—C3—Cl1 | 179.61 (8) | O5—N3—C13—C14 | −176.79 (10) |
N1—C2—C3—Cl1 | −1.28 (14) | O6—N3—C13—C14 | 4.11 (14) |
C2—C3—C4—C5 | −0.26 (16) | C12—C13—C14—C15 | −0.97 (16) |
Cl1—C3—C4—C5 | 179.94 (8) | N3—C13—C14—C15 | −179.70 (9) |
C3—C4—C5—C6 | 0.12 (16) | C13—C14—C15—C16 | 0.76 (15) |
C4—C5—C6—C1 | 0.48 (15) | C8—N2—C16—C15 | −177.77 (10) |
C2—C1—C6—C5 | −0.90 (14) | C8—N2—C16—C11 | 1.38 (15) |
C7—C1—C6—C5 | −179.48 (9) | C14—C15—C16—N2 | 179.46 (9) |
C2—C1—C7—O2 | −1.69 (16) | C14—C15—C16—C11 | 0.30 (15) |
C6—C1—C7—O2 | 176.84 (11) | C12—C11—C16—N2 | 179.64 (9) |
C2—C1—C7—O1 | 179.50 (9) | C10—C11—C16—N2 | −1.25 (15) |
C6—C1—C7—O1 | −1.96 (14) | C12—C11—C16—C15 | −1.22 (15) |
C16—N2—C8—C9 | −0.26 (18) | C10—C11—C16—C15 | 177.89 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···N2 | 0.87 (3) | 1.76 (3) | 2.6310 (14) | 176 (3) |
C8—H8···O2 | 0.95 | 2.53 | 3.2082 (16) | 128 |
C8—H8···O6i | 0.95 | 2.41 | 3.2387 (15) | 145 |
C14—H14···O4ii | 0.95 | 2.52 | 3.3226 (16) | 142 |
C12—H12···O5iii | 0.95 | 2.37 | 3.2526 (16) | 155 |
Symmetry codes: (i) x, y+1, z; (ii) x, y−1, z; (iii) −x+2, −y, −z+1. |
C7H3ClNO4·C9H8NO | F(000) = 712.00 |
Mr = 346.73 | Dx = 1.561 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71075 Å |
a = 7.3409 (5) Å | Cell parameters from 25520 reflections |
b = 7.4689 (4) Å | θ = 3.0–30.0° |
c = 27.0427 (14) Å | µ = 0.29 mm−1 |
β = 95.7158 (19)° | T = 190 K |
V = 1475.33 (15) Å3 | Block, pale yellow |
Z = 4 | 0.45 × 0.30 × 0.26 mm |
Rigaku R-AXIS RAPIDII diffractometer | 3937 reflections with I > 2σ(I) |
Detector resolution: 10.000 pixels mm-1 | Rint = 0.019 |
ω scans | θmax = 30.0°, θmin = 3.0° |
Absorption correction: numerical (NUMABS; Higashi, 1999) | h = −10→10 |
Tmin = 0.844, Tmax = 0.927 | k = −10→10 |
29560 measured reflections | l = −37→37 |
4311 independent reflections |
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)] = 0.033 | Hydrogen site location: mixed |
wR(F2) = 0.092 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0517P)2 + 0.422P] where P = (Fo2 + 2Fc2)/3 |
4311 reflections | (Δ/σ)max = 0.001 |
225 parameters | Δρmax = 0.39 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.86076 (4) | 0.71237 (3) | 0.49827 (2) | 0.03111 (8) | |
O1 | 0.49893 (14) | 0.57049 (11) | 0.27915 (3) | 0.0388 (2) | |
O2 | 0.50879 (12) | 0.37292 (10) | 0.34157 (3) | 0.03253 (18) | |
O3 | 0.81650 (12) | 0.34758 (10) | 0.42238 (3) | 0.03453 (19) | |
O4 | 0.56116 (14) | 0.41075 (12) | 0.45203 (3) | 0.0406 (2) | |
O5 | 0.25608 (11) | 0.64218 (10) | 0.18109 (3) | 0.03011 (17) | |
N1 | 0.68835 (12) | 0.44696 (11) | 0.42827 (3) | 0.02456 (17) | |
N2 | 0.41002 (11) | 0.32651 (12) | 0.21056 (3) | 0.02279 (16) | |
C1 | 0.63355 (12) | 0.66248 (12) | 0.35750 (3) | 0.02025 (17) | |
C2 | 0.69708 (12) | 0.62802 (12) | 0.40684 (3) | 0.01940 (16) | |
C3 | 0.77981 (12) | 0.76019 (13) | 0.43755 (3) | 0.02089 (17) | |
C4 | 0.80144 (13) | 0.93180 (13) | 0.41926 (4) | 0.02407 (18) | |
H4 | 0.857461 | 1.022784 | 0.440109 | 0.029* | |
C5 | 0.74011 (14) | 0.96853 (13) | 0.37014 (4) | 0.02617 (19) | |
H5 | 0.754706 | 1.085267 | 0.357150 | 0.031* | |
C6 | 0.65741 (13) | 0.83530 (13) | 0.33982 (4) | 0.02399 (18) | |
H6 | 0.616164 | 0.862693 | 0.306263 | 0.029* | |
C7 | 0.53938 (13) | 0.52246 (13) | 0.32319 (4) | 0.02389 (18) | |
C8 | 0.47845 (15) | 0.17222 (14) | 0.22785 (4) | 0.0276 (2) | |
H8 | 0.530731 | 0.164820 | 0.261364 | 0.033* | |
C9 | 0.47520 (16) | 0.02008 (14) | 0.19773 (4) | 0.0314 (2) | |
H9 | 0.520396 | −0.091226 | 0.210789 | 0.038* | |
C10 | 0.40556 (15) | 0.03461 (14) | 0.14900 (4) | 0.0292 (2) | |
H10 | 0.404556 | −0.067323 | 0.127964 | 0.035* | |
C11 | 0.33516 (13) | 0.19899 (13) | 0.12955 (4) | 0.02402 (19) | |
C12 | 0.26151 (15) | 0.22187 (16) | 0.07953 (4) | 0.0303 (2) | |
H12 | 0.260234 | 0.124767 | 0.056813 | 0.036* | |
C13 | 0.19225 (15) | 0.38479 (17) | 0.06420 (4) | 0.0317 (2) | |
H13 | 0.145274 | 0.400180 | 0.030447 | 0.038* | |
C14 | 0.18881 (14) | 0.53056 (16) | 0.09724 (4) | 0.0287 (2) | |
H14 | 0.138468 | 0.641773 | 0.085598 | 0.034* | |
C15 | 0.25798 (13) | 0.51294 (13) | 0.14634 (4) | 0.02325 (18) | |
C16 | 0.33572 (12) | 0.34640 (13) | 0.16246 (3) | 0.02087 (17) | |
H2 | 0.421 (2) | 0.417 (2) | 0.2315 (6) | 0.044 (4)* | |
H5O | 0.173 (3) | 0.722 (2) | 0.1717 (7) | 0.049 (5)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.04386 (16) | 0.02719 (13) | 0.02051 (12) | −0.00200 (9) | −0.00565 (9) | −0.00222 (8) |
O1 | 0.0621 (6) | 0.0278 (4) | 0.0233 (4) | −0.0053 (4) | −0.0116 (3) | −0.0018 (3) |
O2 | 0.0403 (4) | 0.0219 (3) | 0.0328 (4) | −0.0084 (3) | −0.0092 (3) | 0.0002 (3) |
O3 | 0.0389 (4) | 0.0186 (3) | 0.0436 (5) | 0.0042 (3) | −0.0082 (3) | 0.0010 (3) |
O4 | 0.0546 (5) | 0.0327 (4) | 0.0368 (4) | −0.0104 (4) | 0.0154 (4) | 0.0047 (3) |
O5 | 0.0389 (4) | 0.0219 (3) | 0.0282 (4) | 0.0071 (3) | −0.0033 (3) | −0.0022 (3) |
N1 | 0.0342 (4) | 0.0172 (3) | 0.0211 (4) | −0.0033 (3) | −0.0036 (3) | 0.0004 (3) |
N2 | 0.0267 (4) | 0.0202 (4) | 0.0214 (4) | 0.0002 (3) | 0.0019 (3) | −0.0013 (3) |
C1 | 0.0217 (4) | 0.0178 (4) | 0.0206 (4) | 0.0009 (3) | −0.0011 (3) | −0.0016 (3) |
C2 | 0.0219 (4) | 0.0152 (4) | 0.0208 (4) | 0.0006 (3) | 0.0008 (3) | 0.0002 (3) |
C3 | 0.0228 (4) | 0.0187 (4) | 0.0206 (4) | 0.0012 (3) | −0.0007 (3) | −0.0023 (3) |
C4 | 0.0256 (4) | 0.0165 (4) | 0.0292 (5) | −0.0006 (3) | −0.0022 (3) | −0.0030 (3) |
C5 | 0.0300 (5) | 0.0161 (4) | 0.0315 (5) | 0.0002 (3) | −0.0013 (4) | 0.0023 (3) |
C6 | 0.0277 (4) | 0.0194 (4) | 0.0240 (4) | 0.0016 (3) | −0.0016 (3) | 0.0025 (3) |
C7 | 0.0263 (4) | 0.0205 (4) | 0.0236 (4) | 0.0007 (3) | −0.0040 (3) | −0.0032 (3) |
C8 | 0.0318 (5) | 0.0250 (5) | 0.0259 (4) | 0.0026 (4) | 0.0025 (4) | 0.0029 (4) |
C9 | 0.0361 (5) | 0.0219 (5) | 0.0368 (5) | 0.0044 (4) | 0.0066 (4) | 0.0014 (4) |
C10 | 0.0321 (5) | 0.0219 (4) | 0.0348 (5) | −0.0013 (4) | 0.0090 (4) | −0.0065 (4) |
C11 | 0.0228 (4) | 0.0249 (4) | 0.0249 (4) | −0.0035 (3) | 0.0053 (3) | −0.0040 (3) |
C12 | 0.0300 (5) | 0.0367 (6) | 0.0246 (5) | −0.0062 (4) | 0.0042 (4) | −0.0083 (4) |
C13 | 0.0289 (5) | 0.0450 (6) | 0.0207 (4) | −0.0029 (4) | 0.0002 (3) | −0.0003 (4) |
C14 | 0.0272 (4) | 0.0335 (5) | 0.0251 (5) | 0.0015 (4) | 0.0012 (4) | 0.0054 (4) |
C15 | 0.0232 (4) | 0.0229 (4) | 0.0237 (4) | −0.0004 (3) | 0.0024 (3) | 0.0006 (3) |
C16 | 0.0202 (4) | 0.0212 (4) | 0.0214 (4) | −0.0019 (3) | 0.0030 (3) | −0.0010 (3) |
Cl1—C3 | 1.7268 (10) | C5—C6 | 1.3898 (14) |
O1—C7 | 1.2511 (12) | C5—H5 | 0.9500 |
O2—C7 | 1.2519 (13) | C6—H6 | 0.9500 |
O3—N1 | 1.2211 (12) | C8—C9 | 1.3969 (15) |
O4—N1 | 1.2154 (12) | C8—H8 | 0.9500 |
O5—C15 | 1.3483 (12) | C9—C10 | 1.3695 (16) |
O5—H5O | 0.872 (19) | C9—H9 | 0.9500 |
N1—C2 | 1.4751 (12) | C10—C11 | 1.4132 (15) |
N2—C8 | 1.3236 (13) | C10—H10 | 0.9500 |
N2—C16 | 1.3676 (12) | C11—C16 | 1.4154 (13) |
N2—H2 | 0.880 (16) | C11—C12 | 1.4161 (14) |
C1—C2 | 1.3930 (12) | C12—C13 | 1.3671 (17) |
C1—C6 | 1.3935 (13) | C12—H12 | 0.9500 |
C1—C7 | 1.5180 (13) | C13—C14 | 1.4103 (16) |
C2—C3 | 1.3902 (12) | C13—H13 | 0.9500 |
C3—C4 | 1.3887 (13) | C14—C15 | 1.3798 (14) |
C4—C5 | 1.3870 (14) | C14—H14 | 0.9500 |
C4—H4 | 0.9500 | C15—C16 | 1.4189 (13) |
C15—O5—H5O | 109.9 (12) | N2—C8—C9 | 121.23 (10) |
O4—N1—O3 | 125.17 (9) | N2—C8—H8 | 119.4 |
O4—N1—C2 | 118.51 (9) | C9—C8—H8 | 119.4 |
O3—N1—C2 | 116.22 (9) | C10—C9—C8 | 118.66 (10) |
C8—N2—C16 | 122.14 (9) | C10—C9—H9 | 120.7 |
C8—N2—H2 | 115.9 (11) | C8—C9—H9 | 120.7 |
C16—N2—H2 | 121.9 (11) | C9—C10—C11 | 120.97 (9) |
C2—C1—C6 | 117.27 (8) | C9—C10—H10 | 119.5 |
C2—C1—C7 | 123.14 (8) | C11—C10—H10 | 119.5 |
C6—C1—C7 | 119.58 (8) | C10—C11—C16 | 117.63 (9) |
C3—C2—C1 | 121.72 (8) | C10—C11—C12 | 123.44 (9) |
C3—C2—N1 | 116.73 (8) | C16—C11—C12 | 118.92 (9) |
C1—C2—N1 | 121.48 (8) | C13—C12—C11 | 119.49 (10) |
C4—C3—C2 | 120.08 (9) | C13—C12—H12 | 120.3 |
C4—C3—Cl1 | 119.26 (7) | C11—C12—H12 | 120.3 |
C2—C3—Cl1 | 120.64 (7) | C12—C13—C14 | 121.63 (10) |
C5—C4—C3 | 119.08 (9) | C12—C13—H13 | 119.2 |
C5—C4—H4 | 120.5 | C14—C13—H13 | 119.2 |
C3—C4—H4 | 120.5 | C15—C14—C13 | 120.53 (10) |
C4—C5—C6 | 120.29 (9) | C15—C14—H14 | 119.7 |
C4—C5—H5 | 119.9 | C13—C14—H14 | 119.7 |
C6—C5—H5 | 119.9 | O5—C15—C14 | 125.04 (9) |
C5—C6—C1 | 121.56 (9) | O5—C15—C16 | 116.43 (8) |
C5—C6—H6 | 119.2 | C14—C15—C16 | 118.52 (9) |
C1—C6—H6 | 119.2 | N2—C16—C11 | 119.30 (9) |
O1—C7—O2 | 126.78 (9) | N2—C16—C15 | 119.84 (8) |
O1—C7—C1 | 115.77 (9) | C11—C16—C15 | 120.85 (9) |
O2—C7—C1 | 117.44 (8) | ||
C6—C1—C2—C3 | 0.47 (14) | C16—N2—C8—C9 | −1.11 (16) |
C7—C1—C2—C3 | −178.81 (9) | N2—C8—C9—C10 | 2.40 (16) |
C6—C1—C2—N1 | −176.32 (8) | C8—C9—C10—C11 | −1.12 (16) |
C7—C1—C2—N1 | 4.41 (14) | C9—C10—C11—C16 | −1.33 (15) |
O4—N1—C2—C3 | 85.64 (11) | C9—C10—C11—C12 | −179.99 (10) |
O3—N1—C2—C3 | −91.03 (11) | C10—C11—C12—C13 | 178.41 (10) |
O4—N1—C2—C1 | −97.42 (11) | C16—C11—C12—C13 | −0.23 (14) |
O3—N1—C2—C1 | 85.91 (11) | C11—C12—C13—C14 | −1.28 (16) |
C1—C2—C3—C4 | −0.17 (14) | C12—C13—C14—C15 | 0.76 (16) |
N1—C2—C3—C4 | 176.76 (8) | C13—C14—C15—O5 | −177.90 (10) |
C1—C2—C3—Cl1 | −178.87 (7) | C13—C14—C15—C16 | 1.27 (15) |
N1—C2—C3—Cl1 | −1.94 (12) | C8—N2—C16—C11 | −1.46 (14) |
C2—C3—C4—C5 | −0.23 (14) | C8—N2—C16—C15 | 177.62 (9) |
Cl1—C3—C4—C5 | 178.49 (8) | C10—C11—C16—N2 | 2.62 (13) |
C3—C4—C5—C6 | 0.32 (15) | C12—C11—C16—N2 | −178.66 (9) |
C4—C5—C6—C1 | −0.01 (15) | C10—C11—C16—C15 | −176.45 (9) |
C2—C1—C6—C5 | −0.38 (14) | C12—C11—C16—C15 | 2.27 (14) |
C7—C1—C6—C5 | 178.92 (9) | O5—C15—C16—N2 | −2.60 (13) |
C2—C1—C7—O1 | −176.23 (9) | C14—C15—C16—N2 | 178.16 (9) |
C6—C1—C7—O1 | 4.51 (14) | O5—C15—C16—C11 | 176.47 (8) |
C2—C1—C7—O2 | 4.37 (14) | C14—C15—C16—C11 | −2.77 (14) |
C6—C1—C7—O2 | −174.89 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1 | 0.880 (16) | 1.776 (16) | 2.6355 (12) | 164.7 (14) |
O5—H5O···O2i | 0.872 (19) | 1.756 (19) | 2.6247 (12) | 173.2 (19) |
C4—H4···O3ii | 0.95 | 2.49 | 3.1082 (12) | 123 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x, y+1, z. |
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