research communications
Synthesis and crystal structures of 3,6-dihydroxypicolinic acid and its labile intermediate dipotassium 3-hydroxy-6-(sulfonatooxy)pyridine-2-carboxylate monohydrate
aDepartment of Chemistry & Biochemistry, The Ohio State University, 484 W. 12th Avenue, Columbus, Ohio, 43210, USA, and bDepartment of Chemistry, University of Kentucky, 505 Rose Street, Lexington, Kentucky, 40506, USA
*Correspondence e-mail: behrman.1@osu.edu
A simplified two-step synthesis of 3,6-dihydroxypicolinic acid (3-hydroxy-6-oxo-1,6-dihydropyridine-2-carboxylic acid), C6H5NO4 (II), an intermediate in the metabolism of picolinic acid, is described. The of II, along with that of a labile intermediate, dipotassium 3-hydroxy-6-(sulfonatooxy)pyridine-2-carboxylate monohydrate, 2K+·C6H3NO7S2−·H2O (I), is also described. Compound I comprises a pyridine ring with carboxylate, hydroxyl (connected by an intramolecular O—H⋯O hydrogen bond), and sulfate groups at the 2-, 3-, and 6-positions, respectively, along with two potassium cations for charge balance and one water molecule of crystallization. These components are connected into a three-dimensional network by O—H⋯O hydrogen bonds arising from the water molecule, C—H⋯O interactions and π–π stacking of pyridine rings. In II, the ring nitrogen atom is protonated, with charge balance provided by the carboxylate group (i.e., a zwitterion). The intramolecular O—H⋯O hydrogen bond observed in I is preserved in II. Crystals of II have unusual space-group symmetry of type Abm2 in which extended planar networks of O—H⋯O and N—H⋯O hydrogen-bonded molecules form sheets lying parallel to the ac plane, constrained to b = 0.25 (and 0.75). The structure was refined as a 50:50 A minor disorder component was modeled by reflection of the major component across a mirror plane perpendicular to c.
1. Chemical context
3,6-Dihydroxypicolinic acid (3-hydroxy-6-pyridone-2-carboxylic acid), C6H5NO4, is an intermediate in the metabolism of picolinic acid by several microorganisms (Shukla & Kaul, 1973; Shukla et al., 1977; Qiu et al., 2019). It was isolated from culture media and partially characterized by Shukla & Kaul (1973; Shukla et al., 1977) whose work is misrepresented by Qiu et al. (2019) by stating that their work was only theoretical. It was synthesized by a six-step procedure from 3-hydroxypicolinic acid and characterized by and NMR data (Qiu et al., 2019, with C. Shen).
We report here a two-step synthesis also starting with 3-hydroxypicolinic acid by an Elbs oxidation (Behrman, 1988; 2021) and crystal structures of both the intermediate sulfate ester (I) and of 3,6-dihydroxypicolinic acid (II). We considered two routes, as shown in Fig. 1. Both give the desired product but we chose the pathway from 3-hydroxypicolinic acid because in the first step, the dipotassium salt of the 6-sulfate ester precipitates from the mixture in an almost pure state.
This sulfate ester is extraordinarily sensitive to acid-catalyzed hydrolysis; acidification at room temperature (RT) gives complete hydrolysis in a few minutes. The isomeric 6-oxo-picolinic acid-3-sulfate is much more stable although subject to ); it is not completely hydrolyzed after 22 h, RT, pH 2. Nantka-Namirski & Rykowski (1972a,b) used boiling 20% sulfuric acid for four hours to effect the hydrolyses of the 5-sulfate of two dihydroxynicotinic acids. For the rapid hydrolysis of pyridyl-4-sulfate see Jerfy & Roy (1970) and Goren & Kochansky (1973) for the effects of impurities. A reasonable representation of the mechanism of the hydrolysis for the 4-sulfate is shown in Fig. 2a. The 2-sulfate should behave similarly (Fig. 2b). Jerfy & Roy (1970) also showed that sulfation of 2-pyridone gives the sulfamate, so that it has not yet been possible to prepare the pyridyl-2-sulfate for comparative purposes. However, a route to 5-hydroxypyridine-2-sulfate together with the isomeric 4- and 6-sulfate is known (Behrman & Pitt, 1958). Examination of these mixed by shows that all three are rapidly hydrolyzed under acid catalysis, as predicted by the model. The reaction between potassium peroxydisulfate and 3-hydroxypicolinic acid was carried out as usual in KOH solution except that if there is excess peroxy-disulfate, the sulfate ester and the peroxide precipitate from the reaction mixture together: to avoid this the persulfate was used as the limiting reagent. The ester was crystallized from water and 3,6-dihydroxypicolinic acid obtained by hydrolysis.
(Benkovic, 19662. Structural commentary
The I (Fig. 3) contains a single pyridine ring with a carboxylate group at the 2-position, a hydroxyl group at the 3-position, and a sulfate group attached to the 6-position. Charge balance is provided by a pair of K+ cations. There is also a single water molecule of crystallization present. The carboxylate C—O distances are 1.2510 (16) and 1.2758 (16) Å for C7—O3 and C7—O4, respectively. The longer of these is part of an S(6) intramolecular hydrogen-bonded ring with the hydroxyl group. In the sulfate group, the oxygen atom bound at the 6-position [C6—O2 = 1.3968 (14) Å] is longer [S1—O2 = 1.6343 (9) Å] than the other three S=O bonds [range 1.4361 (9) to 1.4486 (9) Å], as would be expected for this bonding arrangement.
inIn II (Fig. 4), the nitrogen atom of the ring is protonated. Charge balance is provided by the deprotonated 2-carboxylate group [C7—O3 = 1.262 (3), C7—O4 = 1.259 (3) Å], leading to a zwitterionic molecule. The intramolecular S(6) hydrogen-bonded ring from I is preserved in II. The 6-position of the ring is occupied by a second hydroxyl group. As discussed in more detail in section 6 (Refinement), there is a small minor disorder component [refined occupancy 4.7 (3)%] and probable inversion twinning.
3. Supramolecular features
In the packing of I, strong Ow—H⋯O (w = water) hydrogen bonds exist in which the water molecule acts as a linker between c-glide-related anions. The water oxygen is also coordinated to the K+ cations, both of which are seven coordinate. Around K1, coordination distances range from 2.7376 (9)–2.9102 (10) Å (for K⋯O) and 2.7869 (11) Å (K1⋯N). For K2, coordination distances range from 2.6769 (9) to 2.9525 (10) Å (all K⋯O). The coordination geometry about each K+ cation is very roughly pentagonal bipyramidal, with K1 much more distorted than K2. As each K+ cation is coordinated to the water molecule, the KO6N and KO7 polyhedra augment the extended chains that propagate parallel to c (Fig. 5, Table 1). In addition, there are weaker C—H⋯O contacts: pairs of C5—H5⋯O6ii interactions form R22(12) inversion-related dimers and C4—H4⋯O5i contacts link molecules via c-glide symmetry (symmetry codes as per Table 1). This in turn joins c-glide-related pyridine rings into an extended π–π stack along the c-axis direction. Adjacent rings within the stacks are almost parallel; the dihedral angle being 0.38 (4)° with a centroid–centroid distance of 3.698 (1) Å. These columns of hydrogen-bonded and π-stacked molecules are interlinked by the aforementioned chains of K+ cations and water molecules into a three-dimensional network (Fig. 5).
The most remarkable feature of the packing in II are extended di-periodic hydrogen-bonded networks lying parallel to the ac plane (Fig. 6, Table 2) that are constrained to b = 0.25 (and 0.75) as a consequence of the unusual space-group symmetry of type Abm2. Strong O2—H2O⋯O3i and N1—H1N⋯O4i hydrogen bonds link pairs of 21 screw-related molecules into R22(8) motifs that extend to form ribbons parallel to c. Weaker C4—H4⋯O2iii and C5—H5⋯O1ii (symmetry codes as per Table 2) interactions join 21 screw-related ribbons to form the aforementioned networks. Contacts between these planar networks are limited to weak van der Waals interactions.
4. Database survey
A search of the Cambridge Structure Database (CSD v5.42, Nov. 2020; Groom et al., 2016) on a fragment composed of 3-picolinic acid with `any non-H' at the 6-position gave only seven hits. None of these have much in common with I or II, but the most similar were AGUMEV (ammonium 2,4,6-tricarboxypyridine-3-olate monohydrate; Li et al., 2010) and MAFTEU (6-chloro-3-trifluoromethoxy pyridine-2-carboxylic acid; Manteau et al., 2010) in that their main components consist of a single pyridine ring with a carboxylic acid group adjacent to the ring nitrogen and an oxygen (O− in AGUMEV; O—CF3 in MAFTEU) at the 3-position.
Space group Abm2 is not common, with only 62 entries listed in v5.42 of the CSD. Excluding polymers, entries flagged with known errors, and those without deposited coordinates left only 47 hits, i.e. <0.005% of known structures. Of these, only 29 have R1 ≤ 5% and none form planar networks in a manner similar to II. By any measure, the of II is unusual.
5. Synthesis and crystallization
3-Hydroxypyridine-2-carboxylic acid-6-sulfate dipotassium salt monohydrate (I): Potassium hydroxide (85%, 1 g, 15 mmol) was dissolved in 10 ml of water and cooled. 3-Hydroxypicolinic acid (0.82 g, 6 mmol) followed by potassium peroxydisulfate (0.9 g, 3.3 mmol) were added. The reaction mixture was stirred at RT for 24 h. The precipitate was filtered and dried by washing with acetone, yielding 0.46–0.49 g (∼44%) of the dipotassium salt of 3-hydroxypyridine-2-carboxylic acid-6-sulfate monohydrate (I). Compound I migrates on paper at pH 7.5 with Rp = 2 as a fluorescent spot. Rp is the migration distance relative to picric acid at Rp = 1 (the starting material has Rp = 1.1). Crystals of I grow from aqueous solution when treated as follows: 0.16 g were suspended in 2.0 ml of water, dissolved by heating carefully to about 313 K, and then cooled slowly to RT. Further cooling to 278 K overnight gave 0.12 g of needles. Analysis (%) calculated for C6H5NO8K2S: C, 2l.88; H, 1.53; N, 4.25. Found: C, 21.97; H, 1.44; N, 4.25. IR(Nujol): 3485, 3310, 3096, 1701, 1684, 1624, 1574, 1250, 1059, 957, 860, 833, 768, 716, 638 cm−1. NMR(D2O, 600 MHz) δ 7.27 (d, J = 8.82 Hz), 7.45 (d, J = 8.82 Hz). UV (in water): λmax, (nm), ɛ (l mol−1 cm−1): 307, 1120; 230, 1200; 205, 4180. Heating behavior: I begins to discolor at about 448 K and then gets darker without melting up to 523 K.
3,6-Dihydroxypicolinic acid (II): The crude sulfate (I, 150 mg), was suspended in 2 ml of water and then heated to about 313 K to dissolve it. HCl was then added to about pH 2. A heavy precipitate formed immediately. After cooling, the colorless solid was filtered and washed with cold water to yield 50–60 mg of the product (yield 67–80%), Rp = 1. The proton NMR spectrum of II agreed with that reported by Qiu et al. (2019) except that our spectrum was taken in D2O, 600 MHz, δ 6.69 (d, J = 9.65 Hz) and 7.45 (d, J = 9.65 Hz). These are shifted because of the solvent difference from Qiu et al. (2019), but the couplings are the same, as is the difference between the two resonances (δ 0.76). 50 mg of II was crystallized from 11 ml of hot water under argon to form 35 mg of crystals. Analytical results show that the precipitate is very nearly as clean as the crystals. Analysis (%): calculated for C6H5NO4: C, 46.46; H, 3.25; N, 9.03. Found (crystals), C, 46.22; H, 3.20; N, 9.07. (precipitate), C, 45.65; H, 3.16; N, 9.10. IR: Nujol, 3120, 1614, 1540, 1360, 1269, 1100, 845, 810, 760, 621 cm−1. Later, larger crystals were obtained using 88% formic acid as solvent. Upon heating, II carbonizes above 473 K without melting. UV (in water): λmax, (nm), ɛ (l mol−1 cm−1) at pH 7: 346, 5970; 243, 4350; 221.5, 9450. Shukla & Kaul (1973) reported the pH-dependence of the spectrum. [See also Qiu et al. (2019), but on p. S2, line 3, read `240' for `360'.]
6. Data collection, structure solution and refinement
The crystals were mounted using polyisobutene oil on the tip of fine glass fibers, which were fastened in copper mounting pins with electrical solder. Crystals of I were placed directly into the cold gas stream of a liquid-N2 based cryostat, while crystals of II were handled using methods developed for macromolecular cryocrystallography (Parkin & Hope, 1998b). Diffraction data were collected with the crystals at 90 K. Crystal data, data collection and details are summarized in Table 3. In II, a small minor disorder component was apparent in a difference map. It was modeled by reflection of the major component across a mirror plane perpendicular to its c axis, with coordinates related by the mirror plane and constrained by mapping its coordinates to the major component via SHELXL FVAR parameters. A test for using the [x = 0.5 (3); Flack & Bernardinelli, 1999] was indeterminate. The Hooft (Hooft et al., 2008) and Parsons (Parsons et al., 2013) parameters [y = 0.63 (7); z = 0.62 (10), respectively], however, each gave a much stronger suggestion of Since the itself has a twofold parallel to its c axis, this results in a mirror operation (i.e. a twofold rotation combined with inversion). Thus, the and disorder in II may effectively be treated by the same operation, not unlike that in uric acid dihydrate (Parkin & Hope, 1998a; Parkin, 2000). To ensure satisfactory of disorder, constraints (SHELXL command EADP) were used to equalize displacement parameters of superimposed groups. Full occupancy (and major component for II) hydrogen atoms were found in difference-Fourier maps. Carbon-bound hydrogen atoms were included using riding models with constrained distances set to 0.95 Å (Csp2H). In I, the water H atoms were refined but subject to distance and angle–distance restraints, while the hydroxyl H atom was refined freely. In II, for O—H and N—H groups, riding models that allowed the bond distance to refine were used. Uiso(H) parameters were set to values of either 1.2Ueq or 1.5Ueq (OH only) of the attached atom. The structures were validated using PLATON and checkCIF (Spek, 2020).
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Supporting information
https://doi.org/10.1107/S2056989021004904/hb7975sup1.cif
contains datablocks I, II, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989021004904/hb7975Isup2.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989021004904/hb7975IIsup3.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989021004904/hb7975Isup4.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989021004904/hb7975IIsup5.cml
For both structures, data collection: APEX3 (Bruker, 2016); cell
APEX3 (Bruker, 2016); data reduction: APEX3 (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELX (Sheldrick, 2008) and CIFFIX (Parkin, 2013).2K+·C6H3NO7S2−·H2O | F(000) = 664 |
Mr = 329.37 | Dx = 2.000 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 13.3366 (4) Å | Cell parameters from 9459 reflections |
b = 11.5467 (3) Å | θ = 3.1–27.5° |
c = 7.3078 (2) Å | µ = 1.09 mm−1 |
β = 103.553 (1)° | T = 90 K |
V = 1094.02 (5) Å3 | Block, colourless |
Z = 4 | 0.18 × 0.16 × 0.13 mm |
Bruker D8 Venture dual source diffractometer | 2505 independent reflections |
Radiation source: microsource | 2423 reflections with I > 2σ(I) |
Detector resolution: 7.41 pixels mm-1 | Rint = 0.036 |
φ and ω scans | θmax = 27.5°, θmin = 1.6° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −17→17 |
Tmin = 0.793, Tmax = 0.862 | k = −14→14 |
22347 measured reflections | l = −9→9 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.020 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.056 | w = 1/[σ2(Fo2) + (0.0254P)2 + 0.7213P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max = 0.001 |
2505 reflections | Δρmax = 0.40 e Å−3 |
174 parameters | Δρmin = −0.44 e Å−3 |
3 restraints | Extinction correction: SHELXL2018/3 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0116 (12) |
Experimental. The crystal was mounted using polyisobutene oil on the tip of a fine glass fibre, which was fastened in a copper mounting pin with electrical solder. It was placed directly into the cold gas stream of a liquid-nitrogen based cryostat (Hope, 1994; Parkin & Hope, 1998). Diffraction data were collected with the crystal at 90K, which is standard practice in this laboratory for the majority of flash-cooled crystals. |
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. |
Refinement. Refinement progress was checked using Platon (Spek, 2020) and by an R-tensor (Parkin, 2000). The final model was further checked with the IUCr utility checkCIF. |
x | y | z | Uiso*/Ueq | ||
K1 | −0.11303 (2) | 0.44196 (2) | 0.29817 (4) | 0.01068 (9) | |
K2 | 0.65851 (2) | 0.37254 (2) | 0.80722 (4) | 0.01048 (9) | |
S1 | 0.39446 (2) | 0.56402 (3) | 0.68497 (4) | 0.00841 (9) | |
O1 | 0.18689 (8) | 0.05598 (7) | 0.56350 (13) | 0.01168 (19) | |
H1O | 0.1278 (15) | 0.0662 (15) | 0.584 (3) | 0.018* | |
O2 | 0.32641 (7) | 0.49448 (8) | 0.50302 (12) | 0.00997 (18) | |
O3 | 0.01000 (7) | 0.34563 (8) | 0.61547 (13) | 0.01185 (19) | |
O4 | 0.02411 (7) | 0.15242 (8) | 0.61413 (13) | 0.01227 (19) | |
O5 | 0.32663 (7) | 0.58023 (8) | 0.81136 (13) | 0.01295 (19) | |
O6 | 0.41500 (7) | 0.66929 (8) | 0.59303 (13) | 0.01295 (19) | |
O7 | 0.48251 (7) | 0.49241 (8) | 0.76027 (14) | 0.0149 (2) | |
N1 | 0.20276 (8) | 0.37108 (9) | 0.55903 (14) | 0.0088 (2) | |
C2 | 0.16613 (9) | 0.26318 (11) | 0.57169 (17) | 0.0088 (2) | |
C3 | 0.22393 (10) | 0.16468 (11) | 0.55284 (17) | 0.0093 (2) | |
C4 | 0.32289 (10) | 0.17884 (11) | 0.52150 (17) | 0.0105 (2) | |
H4 | 0.363874 | 0.113328 | 0.509029 | 0.013* | |
C5 | 0.35984 (9) | 0.28931 (11) | 0.50905 (17) | 0.0104 (2) | |
H5 | 0.426568 | 0.302283 | 0.487955 | 0.013* | |
C6 | 0.29543 (10) | 0.38126 (10) | 0.52862 (17) | 0.0089 (2) | |
C7 | 0.05895 (9) | 0.25453 (11) | 0.60404 (17) | 0.0096 (2) | |
O1W | 0.85262 (7) | 0.30218 (9) | 0.79832 (14) | 0.0151 (2) | |
H1W | 0.8909 (13) | 0.3167 (17) | 0.726 (2) | 0.023* | |
H2W | 0.8914 (13) | 0.3145 (17) | 0.903 (2) | 0.023* |
U11 | U22 | U33 | U12 | U13 | U23 | |
K1 | 0.00957 (14) | 0.00968 (14) | 0.01288 (14) | 0.00117 (9) | 0.00285 (10) | −0.00086 (9) |
K2 | 0.00967 (14) | 0.01126 (14) | 0.01074 (14) | 0.00044 (9) | 0.00281 (10) | 0.00146 (9) |
S1 | 0.00738 (15) | 0.00825 (15) | 0.00966 (15) | −0.00042 (10) | 0.00215 (11) | −0.00085 (10) |
O1 | 0.0117 (5) | 0.0075 (4) | 0.0169 (5) | −0.0005 (3) | 0.0054 (4) | 0.0000 (3) |
O2 | 0.0121 (4) | 0.0089 (4) | 0.0087 (4) | −0.0027 (3) | 0.0019 (3) | −0.0002 (3) |
O3 | 0.0096 (4) | 0.0123 (4) | 0.0142 (4) | 0.0010 (3) | 0.0038 (3) | 0.0002 (3) |
O4 | 0.0109 (4) | 0.0112 (4) | 0.0154 (4) | −0.0017 (3) | 0.0044 (3) | 0.0009 (3) |
O5 | 0.0123 (4) | 0.0164 (5) | 0.0111 (4) | −0.0004 (4) | 0.0048 (3) | −0.0019 (4) |
O6 | 0.0147 (5) | 0.0093 (4) | 0.0160 (4) | −0.0028 (3) | 0.0059 (4) | −0.0002 (3) |
O7 | 0.0108 (4) | 0.0139 (4) | 0.0180 (5) | 0.0033 (3) | −0.0005 (4) | −0.0017 (4) |
N1 | 0.0096 (5) | 0.0093 (5) | 0.0072 (5) | −0.0002 (4) | 0.0015 (4) | −0.0006 (4) |
C2 | 0.0086 (5) | 0.0101 (6) | 0.0076 (5) | −0.0008 (4) | 0.0018 (4) | 0.0005 (4) |
C3 | 0.0112 (6) | 0.0082 (6) | 0.0078 (5) | −0.0010 (4) | 0.0008 (4) | 0.0000 (4) |
C4 | 0.0104 (6) | 0.0109 (6) | 0.0101 (6) | 0.0021 (4) | 0.0023 (4) | −0.0014 (4) |
C5 | 0.0087 (5) | 0.0132 (6) | 0.0096 (5) | −0.0002 (5) | 0.0026 (4) | −0.0014 (4) |
C6 | 0.0108 (6) | 0.0082 (5) | 0.0070 (5) | −0.0021 (4) | 0.0010 (4) | −0.0001 (4) |
C7 | 0.0091 (6) | 0.0129 (6) | 0.0065 (5) | −0.0007 (4) | 0.0011 (4) | 0.0002 (4) |
O1W | 0.0113 (5) | 0.0165 (5) | 0.0181 (5) | 0.0005 (4) | 0.0044 (4) | 0.0003 (4) |
K1—O4i | 2.7376 (9) | K2—K2x | 4.6216 (3) |
K1—O3 | 2.7428 (10) | S1—O7 | 1.4361 (9) |
K1—O5ii | 2.7843 (10) | S1—O6 | 1.4457 (9) |
K1—N1ii | 2.7869 (11) | S1—O5 | 1.4486 (9) |
K1—O3ii | 2.8099 (10) | S1—O2 | 1.6343 (9) |
K1—O1Wiii | 2.856 (1) | O1—C3 | 1.3577 (15) |
K1—O1iv | 2.9102 (10) | O1—H1O | 0.843 (19) |
K1—S1ii | 3.7848 (4) | O2—C6 | 1.3968 (14) |
K1—K1ii | 3.9268 (5) | O3—C7 | 1.2510 (16) |
K1—K2v | 4.2041 (4) | O4—C7 | 1.2758 (16) |
K1—K2iii | 4.7508 (4) | N1—C6 | 1.3112 (16) |
K2—O7 | 2.6769 (9) | N1—C2 | 1.3492 (16) |
K2—O6vi | 2.7084 (10) | C2—C3 | 1.3988 (17) |
K2—O1W | 2.7286 (10) | C2—C7 | 1.5057 (17) |
K2—O2vii | 2.7842 (9) | C3—C4 | 1.4010 (17) |
K2—O5viii | 2.8012 (9) | C4—C5 | 1.3781 (18) |
K2—O6vii | 2.8993 (10) | C4—H4 | 0.9500 |
K2—O1ix | 2.9525 (10) | C5—C6 | 1.3940 (17) |
K2—S1vii | 3.5751 (4) | C5—H5 | 0.9500 |
K2—S1vi | 3.6348 (4) | O1W—H1W | 0.832 (15) |
K2—K2i | 4.6216 (3) | O1W—H2W | 0.831 (15) |
O4i—K1—O3 | 85.28 (3) | O5viii—K2—K1xi | 41.02 (2) |
O4i—K1—O5ii | 125.34 (3) | O6vii—K2—K1xi | 154.00 (2) |
O3—K1—O5ii | 125.08 (3) | O1ix—K2—K1xi | 43.784 (19) |
O4i—K1—N1ii | 152.53 (3) | S1vii—K2—K1xi | 138.793 (10) |
O3—K1—N1ii | 102.82 (3) | S1vi—K2—K1xi | 106.147 (8) |
O5ii—K1—N1ii | 71.26 (3) | O7—K2—K2i | 112.19 (2) |
O4i—K1—O3ii | 96.31 (3) | O6vi—K2—K2i | 75.48 (2) |
O3—K1—O3ii | 90.00 (3) | O1W—K2—K2i | 67.86 (2) |
O5ii—K1—O3ii | 123.94 (3) | O2vii—K2—K2i | 71.370 (18) |
N1ii—K1—O3ii | 58.00 (3) | O5viii—K2—K2i | 153.22 (2) |
O4i—K1—O1Wiii | 74.51 (3) | O6vii—K2—K2i | 33.178 (19) |
O3—K1—O1Wiii | 70.34 (3) | O1ix—K2—K2i | 124.254 (19) |
O5ii—K1—O1Wiii | 75.87 (3) | S1vii—K2—K2i | 50.703 (5) |
N1ii—K1—O1Wiii | 132.96 (3) | S1vi—K2—K2i | 56.517 (8) |
O3ii—K1—O1Wiii | 158.67 (3) | K1xi—K2—K2i | 131.084 (6) |
O4i—K1—O1iv | 81.77 (3) | O7—K2—K2x | 104.80 (2) |
O3—K1—O1iv | 163.61 (3) | O6vi—K2—K2x | 35.86 (2) |
O5ii—K1—O1iv | 71.02 (3) | O1W—K2—K2x | 90.71 (2) |
N1ii—K1—O1iv | 84.60 (3) | O2vii—K2—K2x | 174.19 (2) |
O3ii—K1—O1iv | 81.53 (3) | O5viii—K2—K2x | 49.13 (2) |
O1Wiii—K1—O1iv | 115.26 (3) | O6vii—K2—K2x | 129.27 (2) |
O4i—K1—S1ii | 142.24 (2) | O1ix—K2—K2x | 108.403 (19) |
O3—K1—S1ii | 111.50 (2) | S1vii—K2—K2x | 152.157 (10) |
O5ii—K1—S1ii | 18.571 (19) | S1vi—K2—K2x | 49.568 (8) |
N1ii—K1—S1ii | 59.06 (2) | K1xi—K2—K2x | 64.932 (5) |
O3ii—K1—S1ii | 116.43 (2) | K2i—K2—K2x | 104.485 (11) |
O1Wiii—K1—S1ii | 79.72 (2) | O7—S1—O6 | 115.80 (6) |
O1iv—K1—S1ii | 84.87 (2) | O7—S1—O5 | 114.01 (6) |
O4i—K1—K1ii | 91.22 (2) | O6—S1—O5 | 113.72 (6) |
O3—K1—K1ii | 45.69 (2) | O7—S1—O2 | 106.09 (5) |
O5ii—K1—K1ii | 143.23 (2) | O6—S1—O2 | 99.47 (5) |
N1ii—K1—K1ii | 77.04 (2) | O5—S1—O2 | 105.75 (5) |
O3ii—K1—K1ii | 44.305 (19) | O7—S1—K2vii | 117.03 (4) |
O1Wiii—K1—K1ii | 115.57 (2) | O6—S1—K2vii | 51.28 (4) |
O1iv—K1—K1ii | 124.38 (2) | O5—S1—K2vii | 127.54 (4) |
S1ii—K1—K1ii | 125.061 (11) | O2—S1—K2vii | 48.78 (3) |
O4i—K1—K2v | 86.50 (2) | O7—S1—K2ix | 134.65 (4) |
O3—K1—K2v | 144.54 (2) | O6—S1—K2ix | 40.71 (4) |
O5ii—K1—K2v | 41.328 (19) | O5—S1—K2ix | 73.18 (4) |
N1ii—K1—K2v | 100.27 (2) | O2—S1—K2ix | 114.92 (3) |
O3ii—K1—K2v | 125.21 (2) | K2vii—S1—K2ix | 79.729 (8) |
O1Wiii—K1—K2v | 74.21 (2) | O7—S1—K1ii | 134.83 (4) |
O1iv—K1—K2v | 44.587 (19) | O6—S1—K1ii | 109.13 (4) |
S1ii—K1—K2v | 59.892 (7) | O5—S1—K1ii | 37.75 (4) |
K1ii—K1—K2v | 168.952 (12) | O2—S1—K1ii | 69.61 (3) |
O4i—K1—K2iii | 101.95 (2) | K2vii—S1—K1ii | 94.176 (9) |
O3—K1—K2iii | 86.38 (2) | K2ix—S1—K1ii | 79.600 (8) |
O5ii—K1—K2iii | 46.95 (2) | C3—O1—K1xii | 114.60 (7) |
N1ii—K1—K2iii | 104.70 (2) | C3—O1—K2vi | 116.45 (7) |
O3ii—K1—K2iii | 161.00 (2) | K1xii—O1—K2vi | 91.63 (3) |
O1Wiii—K1—K2iii | 30.91 (2) | C3—O1—H1O | 104.4 (12) |
O1iv—K1—K2iii | 106.07 (2) | K1xii—O1—H1O | 95.2 (12) |
S1ii—K1—K2iii | 48.809 (6) | K2vi—O1—H1O | 131.0 (12) |
K1ii—K1—K2iii | 129.234 (11) | C6—O2—S1 | 118.44 (7) |
K2v—K1—K2iii | 61.786 (6) | C6—O2—K2vii | 134.86 (7) |
O7—K2—O6vi | 96.93 (3) | S1—O2—K2vii | 105.02 (4) |
O7—K2—O1W | 163.59 (3) | C7—O3—K1 | 120.18 (8) |
O6vi—K2—O1W | 98.84 (3) | C7—O3—K1ii | 120.90 (8) |
O7—K2—O2vii | 80.73 (3) | K1—O3—K1ii | 90.00 (3) |
O6vi—K2—O2vii | 142.83 (3) | C7—O4—K1x | 133.68 (8) |
O1W—K2—O2vii | 83.96 (3) | S1—O5—K1ii | 123.68 (5) |
O7—K2—O5viii | 83.24 (3) | S1—O5—K2viii | 138.63 (5) |
O6vi—K2—O5viii | 81.17 (3) | K1ii—O5—K2viii | 97.65 (3) |
O1W—K2—O5viii | 103.61 (3) | S1—O6—K2ix | 118.92 (5) |
O2vii—K2—O5viii | 134.52 (3) | S1—O6—K2vii | 105.82 (5) |
O7—K2—O6vii | 82.98 (3) | K2ix—O6—K2vii | 110.96 (3) |
O6vi—K2—O6vii | 93.96 (2) | S1—O7—K2 | 163.84 (6) |
O1W—K2—O6vii | 91.42 (3) | C6—N1—C2 | 117.72 (11) |
O2vii—K2—O6vii | 48.87 (3) | C6—N1—K1ii | 119.90 (8) |
O5viii—K2—O6vii | 164.72 (3) | C2—N1—K1ii | 119.70 (8) |
O7—K2—O1ix | 101.29 (3) | N1—C2—C3 | 121.82 (11) |
O6vi—K2—O1ix | 143.63 (3) | N1—C2—C7 | 116.38 (11) |
O1W—K2—O1ix | 68.03 (3) | C3—C2—C7 | 121.79 (11) |
O2vii—K2—O1ix | 71.74 (3) | O1—C3—C2 | 121.99 (11) |
O5viii—K2—O1ix | 70.16 (3) | O1—C3—C4 | 119.11 (11) |
O6vii—K2—O1ix | 119.21 (3) | C2—C3—C4 | 118.90 (11) |
O7—K2—S1vii | 78.73 (2) | C5—C4—C3 | 118.94 (11) |
O6vi—K2—S1vii | 116.72 (2) | C5—C4—H4 | 120.5 |
O1W—K2—S1vii | 90.11 (2) | C3—C4—H4 | 120.5 |
O2vii—K2—S1vii | 26.201 (18) | C4—C5—C6 | 117.37 (11) |
O5viii—K2—S1vii | 155.84 (2) | C4—C5—H5 | 121.3 |
O6vii—K2—S1vii | 22.895 (18) | C6—C5—H5 | 121.3 |
O1ix—K2—S1vii | 97.67 (2) | N1—C6—C5 | 125.24 (11) |
O7—K2—S1vi | 109.94 (2) | N1—C6—O2 | 115.26 (11) |
O6vi—K2—S1vi | 20.38 (2) | C5—C6—O2 | 119.36 (11) |
O1W—K2—S1vi | 84.12 (2) | O3—C7—O4 | 124.78 (11) |
O2vii—K2—S1vi | 127.21 (2) | O3—C7—C2 | 118.96 (11) |
O5viii—K2—S1vi | 98.27 (2) | O4—C7—C2 | 116.25 (11) |
O6vii—K2—S1vi | 80.302 (19) | K2—O1W—K1xiii | 116.56 (4) |
O1ix—K2—S1vi | 145.27 (2) | K2—O1W—H1W | 132.9 (13) |
S1vii—K2—S1vi | 102.902 (10) | K1xiii—O1W—H1W | 94.4 (14) |
O7—K2—K1xi | 116.69 (2) | K2—O1W—H2W | 108.4 (13) |
O6vi—K2—K1xi | 99.86 (2) | K1xiii—O1W—H2W | 96.0 (14) |
O1W—K2—K1xi | 64.86 (2) | H1W—O1W—H2W | 102.0 (15) |
O2vii—K2—K1xi | 114.43 (2) | ||
O7—S1—O2—C6 | 55.28 (10) | K1ii—S1—O7—K2 | 142.06 (18) |
O6—S1—O2—C6 | 175.77 (9) | C6—N1—C2—C3 | −0.18 (17) |
O5—S1—O2—C6 | −66.14 (10) | K1ii—N1—C2—C3 | −161.62 (9) |
K2vii—S1—O2—C6 | 167.38 (11) | C6—N1—C2—C7 | −179.2 (1) |
K2ix—S1—O2—C6 | −144.57 (8) | K1ii—N1—C2—C7 | 19.36 (14) |
K1ii—S1—O2—C6 | −77.22 (8) | K1xii—O1—C3—C2 | 101.95 (11) |
O7—S1—O2—K2vii | −112.10 (5) | K2vi—O1—C3—C2 | −152.82 (9) |
O6—S1—O2—K2vii | 8.39 (5) | K1xii—O1—C3—C4 | −77.87 (12) |
O5—S1—O2—K2vii | 126.48 (5) | K2vi—O1—C3—C4 | 27.36 (14) |
K2ix—S1—O2—K2vii | 48.05 (4) | N1—C2—C3—O1 | −179.28 (11) |
K1ii—S1—O2—K2vii | 115.40 (3) | C7—C2—C3—O1 | −0.31 (18) |
O7—S1—O5—K1ii | −133.28 (6) | N1—C2—C3—C4 | 0.54 (18) |
O6—S1—O5—K1ii | 90.99 (7) | C7—C2—C3—C4 | 179.51 (11) |
O2—S1—O5—K1ii | −17.12 (7) | O1—C3—C4—C5 | 179.41 (11) |
K2vii—S1—O5—K1ii | 32.58 (8) | C2—C3—C4—C5 | −0.41 (18) |
K2ix—S1—O5—K1ii | 94.73 (5) | C3—C4—C5—C6 | −0.03 (18) |
O7—S1—O5—K2viii | 43.85 (10) | C2—N1—C6—C5 | −0.32 (18) |
O6—S1—O5—K2viii | −91.88 (9) | K1ii—N1—C6—C5 | 161.09 (9) |
O2—S1—O5—K2viii | 160.01 (7) | C2—N1—C6—O2 | 175.49 (10) |
K2vii—S1—O5—K2viii | −150.29 (5) | K1ii—N1—C6—O2 | −23.10 (13) |
K2ix—S1—O5—K2viii | −88.14 (7) | C4—C5—C6—N1 | 0.42 (19) |
K1ii—S1—O5—K2viii | 177.13 (12) | C4—C5—C6—O2 | −175.23 (11) |
O7—S1—O6—K2ix | −129.41 (6) | S1—O2—C6—N1 | 94.96 (11) |
O5—S1—O6—K2ix | 5.50 (8) | K2vii—O2—C6—N1 | −102.36 (12) |
O2—S1—O6—K2ix | 117.46 (5) | S1—O2—C6—C5 | −88.96 (12) |
K2vii—S1—O6—K2ix | 125.55 (7) | K2vii—O2—C6—C5 | 73.72 (14) |
K1ii—S1—O6—K2ix | 45.88 (6) | K1—O3—C7—O4 | −88.64 (13) |
O7—S1—O6—K2vii | 105.04 (6) | K1ii—O3—C7—O4 | 160.99 (9) |
O5—S1—O6—K2vii | −120.05 (5) | K1—O3—C7—C2 | 89.91 (11) |
O2—S1—O6—K2vii | −8.09 (5) | K1ii—O3—C7—C2 | −20.46 (14) |
K2ix—S1—O6—K2vii | −125.55 (7) | K1x—O4—C7—O3 | −30.63 (18) |
K1ii—S1—O6—K2vii | −79.67 (4) | K1x—O4—C7—C2 | 150.78 (8) |
O6—S1—O7—K2 | −44.2 (2) | N1—C2—C7—O3 | 0.67 (17) |
O5—S1—O7—K2 | −179.00 (19) | C3—C2—C7—O3 | −178.36 (11) |
O2—S1—O7—K2 | 65.0 (2) | N1—C2—C7—O4 | 179.34 (10) |
K2vii—S1—O7—K2 | 13.6 (2) | C3—C2—C7—O4 | 0.31 (17) |
K2ix—S1—O7—K2 | −89.3 (2) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x, −y+1, −z+1; (iii) x−1, −y+1/2, z−1/2; (iv) −x, y+1/2, −z+1/2; (v) x−1, y, z−1; (vi) −x+1, y−1/2, −z+3/2; (vii) −x+1, −y+1, −z+1; (viii) −x+1, −y+1, −z+2; (ix) −x+1, y+1/2, −z+3/2; (x) x, −y+1/2, z+1/2; (xi) x+1, y, z+1; (xii) −x, y−1/2, −z+1/2; (xiii) x+1, −y+1/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1O···O4 | 0.843 (19) | 1.760 (19) | 2.5429 (13) | 153.6 (17) |
C4—H4···O5i | 0.95 | 2.64 | 3.3682 (16) | 133 |
C5—H5···O6vii | 0.95 | 2.35 | 3.2943 (15) | 175 |
O1W—H1W···O3xiv | 0.83 (2) | 1.97 (2) | 2.7852 (13) | 165 (2) |
O1W—H2W···O4xiii | 0.83 (2) | 2.09 (2) | 2.8910 (14) | 161 (2) |
Symmetry codes: (i) x, −y+1/2, z−1/2; (vii) −x+1, −y+1, −z+1; (xiii) x+1, −y+1/2, z+1/2; (xiv) x+1, y, z. |
C6H5NO4 | Dx = 1.693 Mg m−3 |
Mr = 155.11 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, Abm2 | Cell parameters from 3820 reflections |
a = 10.2045 (6) Å | θ = 4.3–78.5° |
b = 6.1282 (4) Å | µ = 1.27 mm−1 |
c = 9.7293 (6) Å | T = 90 K |
V = 608.42 (7) Å3 | Plate, colourless |
Z = 4 | 0.14 × 0.10 × 0.02 mm |
F(000) = 320 |
Bruker D8 Venture dual source diffractometer | 700 independent reflections |
Radiation source: microsource | 690 reflections with I > 2σ(I) |
Detector resolution: 7.41 pixels mm-1 | Rint = 0.025 |
φ and ω scans | θmax = 77.8°, θmin = 4.3° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −11→12 |
Tmin = 0.799, Tmax = 0.971 | k = −7→7 |
4025 measured reflections | l = −11→12 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.024 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.068 | w = 1/[σ2(Fo2) + (0.050P)2 + 0.0512P] where P = (Fo2 + 2Fc2)/3 |
S = 1.11 | (Δ/σ)max = 0.024 |
700 reflections | Δρmax = 0.20 e Å−3 |
74 parameters | Δρmin = −0.25 e Å−3 |
4 restraints | Absolute structure: Refined as a perfect inversion twin |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.5 |
Experimental. The crystal was mounted using polyisobutene oil on the tip of a fine glass fibre, which was fastened in a copper mounting pin with electrical solder. It was placed directly into the cold gas stream of a liquid-nitrogen based cryostat (Hope, 1994; Parkin & Hope, 1998). Diffraction data were collected with the crystal at 90K, which is standard practice in this laboratory for the majority of flash-cooled crystals. |
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. |
Refinement. Refined as a two-component perfect inversion twin. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
N1 | 0.3327 (2) | 0.250000 | 0.44103 (19) | 0.0146 (4) | 0.953 (3) |
H1N | 0.421 (3) | 0.25000 (2) | 0.3976 (15) | 0.017* | 0.953 (3) |
C2 | 0.3260 (2) | 0.250000 | 0.5827 (2) | 0.0131 (5) | 0.953 (3) |
C3 | 0.2033 (3) | 0.250000 | 0.6458 (3) | 0.0148 (5) | 0.953 (3) |
O1 | 0.19022 (19) | 0.250000 | 0.7831 (2) | 0.0188 (4) | 0.953 (3) |
H1O | 0.269 (4) | 0.25000 (2) | 0.8219 (19) | 0.028* | 0.953 (3) |
C4 | 0.0919 (3) | 0.250000 | 0.5626 (3) | 0.0194 (6) | 0.953 (3) |
H4 | 0.007769 | 0.250000 | 0.604343 | 0.023* | 0.953 (3) |
C5 | 0.1011 (2) | 0.250000 | 0.4226 (3) | 0.0191 (5) | 0.953 (3) |
H5 | 0.024166 | 0.250000 | 0.367711 | 0.023* | 0.953 (3) |
C6 | 0.2280 (2) | 0.250000 | 0.3592 (3) | 0.0154 (5) | 0.953 (3) |
O2 | 0.2369 (2) | 0.250000 | 0.22580 (18) | 0.0186 (4) | 0.953 (3) |
H2O | 0.326 (3) | 0.25000 (2) | 0.200 (1) | 0.028* | 0.953 (3) |
C7 | 0.4488 (2) | 0.250000 | 0.6616 (2) | 0.0158 (5) | 0.953 (3) |
O3 | 0.55590 (18) | 0.250000 | 0.59684 (19) | 0.0182 (4) | 0.953 (3) |
O4 | 0.43850 (17) | 0.250000 | 0.7906 (2) | 0.0224 (5) | 0.953 (3) |
N1' | 0.3327 (2) | 0.250000 | 0.55897 (19) | 0.0131 (5) | 0.047 (3) |
H1'N | 0.421 (3) | 0.25000 (2) | 0.6024 (16) | 0.016* | 0.047 (3) |
C2' | 0.3260 (2) | 0.250000 | 0.4173 (2) | 0.0146 (4) | 0.047 (3) |
C3' | 0.2033 (3) | 0.250000 | 0.3542 (3) | 0.0154 (5) | 0.047 (3) |
O1' | 0.19022 (19) | 0.250000 | 0.2169 (2) | 0.0186 (4) | 0.047 (3) |
H1'O | 0.269 (4) | 0.25000 (2) | 0.178 (2) | 0.028* | 0.047 (3) |
C4' | 0.0919 (3) | 0.250000 | 0.4374 (3) | 0.0191 (5) | 0.047 (3) |
H4' | 0.007769 | 0.250000 | 0.395657 | 0.023* | 0.047 (3) |
C5' | 0.1011 (2) | 0.250000 | 0.5774 (3) | 0.0194 (6) | 0.047 (3) |
H5' | 0.024166 | 0.250000 | 0.632289 | 0.023* | 0.047 (3) |
C6' | 0.2280 (2) | 0.250000 | 0.6408 (3) | 0.0148 (5) | 0.047 (3) |
O2' | 0.2369 (2) | 0.250000 | 0.77420 (18) | 0.0188 (4) | 0.047 (3) |
H2'O | 0.326 (4) | 0.25000 (2) | 0.8001 (11) | 0.028* | 0.047 (3) |
C7' | 0.4488 (2) | 0.250000 | 0.3384 (2) | 0.0158 (5) | 0.047 (3) |
O3' | 0.55590 (18) | 0.250000 | 0.40316 (19) | 0.0182 (4) | 0.047 (3) |
O4' | 0.43850 (17) | 0.250000 | 0.2094 (2) | 0.0224 (5) | 0.047 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0142 (9) | 0.0190 (8) | 0.0105 (11) | 0.000 | 0.0000 (9) | 0.000 |
C2 | 0.0127 (12) | 0.0155 (9) | 0.0112 (10) | 0.000 | −0.0016 (9) | 0.000 |
C3 | 0.0151 (10) | 0.0180 (11) | 0.0113 (11) | 0.000 | 0.0040 (8) | 0.000 |
O1 | 0.0167 (9) | 0.0274 (9) | 0.0123 (8) | 0.000 | 0.0041 (7) | 0.000 |
C4 | 0.0159 (12) | 0.0222 (10) | 0.0202 (13) | 0.000 | 0.0025 (10) | 0.000 |
C5 | 0.0150 (11) | 0.0259 (10) | 0.0166 (10) | 0.000 | −0.0017 (9) | 0.000 |
C6 | 0.0150 (12) | 0.017 (1) | 0.0141 (12) | 0.000 | −0.0031 (9) | 0.000 |
O2 | 0.0163 (9) | 0.0295 (8) | 0.0101 (8) | 0.000 | 0.0003 (6) | 0.000 |
C7 | 0.0167 (10) | 0.0196 (12) | 0.0112 (14) | 0.000 | −0.0002 (9) | 0.000 |
O3 | 0.0141 (8) | 0.0268 (7) | 0.0137 (8) | 0.000 | −0.0008 (6) | 0.000 |
O4 | 0.0148 (12) | 0.0368 (11) | 0.0157 (9) | 0.000 | −0.0014 (7) | 0.000 |
N1' | 0.0127 (12) | 0.0155 (9) | 0.0112 (10) | 0.000 | −0.0016 (9) | 0.000 |
C2' | 0.0142 (9) | 0.0190 (8) | 0.0105 (11) | 0.000 | 0.0000 (9) | 0.000 |
C3' | 0.0150 (12) | 0.017 (1) | 0.0141 (12) | 0.000 | −0.0031 (9) | 0.000 |
O1' | 0.0163 (9) | 0.0295 (8) | 0.0101 (8) | 0.000 | 0.0003 (6) | 0.000 |
C4' | 0.0150 (11) | 0.0259 (10) | 0.0166 (10) | 0.000 | −0.0017 (9) | 0.000 |
C5' | 0.0159 (12) | 0.0222 (10) | 0.0202 (13) | 0.000 | 0.0025 (10) | 0.000 |
C6' | 0.0151 (10) | 0.0180 (11) | 0.0113 (11) | 0.000 | 0.0040 (8) | 0.000 |
O2' | 0.0167 (9) | 0.0274 (9) | 0.0123 (8) | 0.000 | 0.0041 (7) | 0.000 |
C7' | 0.0167 (10) | 0.0196 (12) | 0.0112 (14) | 0.000 | −0.0002 (9) | 0.000 |
O3' | 0.0141 (8) | 0.0268 (7) | 0.0137 (8) | 0.000 | −0.0008 (6) | 0.000 |
O4' | 0.0148 (12) | 0.0368 (11) | 0.0157 (9) | 0.000 | −0.0014 (7) | 0.000 |
N1—C6 | 1.333 (3) | N1'—C6' | 1.333 (3) |
N1—C2 | 1.381 (3) | N1'—C2' | 1.381 (3) |
N1—H1N | 0.99 (3) | N1'—H1'N | 0.99 (4) |
C2—C3 | 1.394 (3) | C2'—C3' | 1.394 (3) |
C2—C7 | 1.470 (3) | C2'—C7' | 1.470 (3) |
C3—O1 | 1.342 (3) | C3'—O1' | 1.342 (3) |
C3—C4 | 1.395 (4) | C3'—C4' | 1.395 (4) |
O1—H1O | 0.89 (4) | O1'—H1'O | 0.89 (4) |
C4—C5 | 1.365 (3) | C4'—C5' | 1.365 (3) |
C4—H4 | 0.9500 | C4'—H4' | 0.9500 |
C5—C6 | 1.434 (3) | C5'—C6' | 1.434 (3) |
C5—H5 | 0.9500 | C5'—H5' | 0.9500 |
C6—O2 | 1.301 (3) | C6'—O2' | 1.301 (3) |
O2—H2O | 0.94 (4) | O2'—H2'O | 0.94 (4) |
C7—O4 | 1.259 (3) | C7'—O4' | 1.259 (3) |
C7—O3 | 1.262 (3) | C7'—O3' | 1.262 (3) |
C6—N1—C2 | 123.81 (19) | C6'—N1'—C2' | 123.81 (19) |
C6—N1—H1N | 118.1 | C6'—N1'—H1'N | 118.1 |
C2—N1—H1N | 118.1 | C2'—N1'—H1'N | 118.1 |
N1—C2—C3 | 119.0 (2) | N1'—C2'—C3' | 119.0 (2) |
N1—C2—C7 | 118.6 (2) | N1'—C2'—C7' | 118.6 (2) |
C3—C2—C7 | 122.41 (19) | C3'—C2'—C7' | 122.41 (19) |
O1—C3—C2 | 121.8 (2) | O1'—C3'—C2' | 121.8 (2) |
O1—C3—C4 | 119.8 (2) | O1'—C3'—C4' | 119.8 (2) |
C2—C3—C4 | 118.4 (2) | C2'—C3'—C4' | 118.4 (2) |
C3—O1—H1O | 109.5 | C3'—O1'—H1'O | 109.5 |
C5—C4—C3 | 121.5 (2) | C5'—C4'—C3' | 121.5 (2) |
C5—C4—H4 | 119.2 | C5'—C4'—H4' | 119.2 |
C3—C4—H4 | 119.2 | C3'—C4'—H4' | 119.2 |
C4—C5—C6 | 119.5 (2) | C4'—C5'—C6' | 119.5 (2) |
C4—C5—H5 | 120.3 | C4'—C5'—H5' | 120.3 |
C6—C5—H5 | 120.3 | C6'—C5'—H5' | 120.3 |
O2—C6—N1 | 122.7 (2) | O2'—C6'—N1' | 122.7 (2) |
O2—C6—C5 | 119.5 (2) | O2'—C6'—C5' | 119.5 (2) |
N1—C6—C5 | 117.8 (2) | N1'—C6'—C5' | 117.8 (2) |
C6—O2—H2O | 109.5 | C6'—O2'—H2'O | 109.5 |
O4—C7—O3 | 124.8 (2) | O4'—C7'—O3' | 124.8 (2) |
O4—C7—C2 | 116.7 (2) | O4'—C7'—C2' | 116.7 (2) |
O3—C7—C2 | 118.53 (19) | O3'—C7'—C2' | 118.53 (19) |
C6—N1—C2—C3 | 0.000 (1) | C6'—N1'—C2'—C3' | 0.000 (1) |
C6—N1—C2—C7 | 180.000 (1) | C6'—N1'—C2'—C7' | 180.000 (1) |
N1—C2—C3—O1 | 180.000 (1) | N1'—C2'—C3'—O1' | 180.000 (1) |
C7—C2—C3—O1 | 0.000 (1) | C7'—C2'—C3'—O1' | 0.000 (1) |
N1—C2—C3—C4 | 0.000 (1) | N1'—C2'—C3'—C4' | 0.000 (1) |
C7—C2—C3—C4 | 180.000 (1) | C7'—C2'—C3'—C4' | 180.000 (1) |
O1—C3—C4—C5 | 180.000 (1) | O1'—C3'—C4'—C5' | 180.000 (1) |
C2—C3—C4—C5 | 0.000 (1) | C2'—C3'—C4'—C5' | 0.000 (1) |
C3—C4—C5—C6 | 0.000 (1) | C3'—C4'—C5'—C6' | 0.000 (1) |
C2—N1—C6—O2 | 180.000 (1) | C2'—N1'—C6'—O2' | 180.000 (1) |
C2—N1—C6—C5 | 0.000 (1) | C2'—N1'—C6'—C5' | 0.000 (1) |
C4—C5—C6—O2 | 180.000 (1) | C4'—C5'—C6'—O2' | 180.000 (1) |
C4—C5—C6—N1 | 0.000 (1) | C4'—C5'—C6'—N1' | 0.000 (1) |
N1—C2—C7—O4 | 180.000 (1) | N1'—C2'—C7'—O4' | 180.000 (1) |
C3—C2—C7—O4 | 0.000 (1) | C3'—C2'—C7'—O4' | 0.000 (1) |
N1—C2—C7—O3 | 0.000 (1) | N1'—C2'—C7'—O3' | 0.000 (1) |
C3—C2—C7—O3 | 180.000 (1) | C3'—C2'—C7'—O3' | 180.000 (1) |
The D···A distance for C4—H4···O2iii is rather long, but within the bounds noted by Desiraju & Steiner (1999). |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O4i | 0.99 | 1.77 | 2.755 (3) | 169 |
O1—H1O···O4 | 0.89 | 1.76 | 2.535 (3) | 145 |
C5—H5···O1ii | 0.95 | 2.34 | 3.269 (3) | 166 |
C4—H4···O2iii | 0.95 | 2.76 | 3.712 (4) | 180 |
O2—H2O···O3i | 0.94 | 1.57 | 2.459 (3) | 156 |
O2—H2O···O4i | 0.94 | 2.56 | 3.372 (3) | 144 |
Symmetry codes: (i) −x+1, −y+1/2, z−1/2; (ii) −x, −y+1/2, z−1/2; (iii) −x, −y+1/2, z+1/2. |
Acknowledgements
Analytical data were provided by Robertson Microlit Laboratories. The D8 Venture diffractometer was funded by the NSF (MRI CHE1625732), and by the University of Kentucky.
Funding information
Funding for this research was provided by: The OSU Emeritus Academy.
References
Behrman, E. J. (1988). Org. React. 35, 421–511. CAS Google Scholar
Behrman, E. J. (2021). Mini-Rev. Org. Chem. 18, 621–625. Google Scholar
Behrman, E. J. & Pitt, B. M. (1958). J. Am. Chem. Soc. 80, 3717–3718. CrossRef CAS Web of Science Google Scholar
Benkovic, S. J. (1966). J. Am. Chem. Soc. 88, 5511–5515. CrossRef CAS Web of Science Google Scholar
Bruker (2016). APEX3 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Desiraju, G. R. & Steiner, T. (1999). The Weak Hydrogen Bond in Structural Chemistry and Biology, p49. Oxford University Press. Google Scholar
Flack, H. D. & Bernardinelli, G. (1999). Acta Cryst. A55, 908–915. Web of Science CrossRef CAS IUCr Journals Google Scholar
Goren, M. B. & Kochansky, M. E. (1973). J. Org. Chem. 38, 3510–3513. CrossRef CAS PubMed Web of Science Google Scholar
Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171–179. Web of Science CrossRef IUCr Journals Google Scholar
Hooft, R. W. W., Straver, L. H. & Spek, A. L. (2008). J. Appl. Cryst. 41, 96–103. Web of Science CrossRef CAS IUCr Journals Google Scholar
Jerfy, A. & Roy, A. B. (1970). Aust. J. Chem. 23, 847–852. CrossRef CAS Web of Science Google Scholar
Krause, L., Herbst-Irmer, R., Sheldrick, G. M. & Stalke, D. (2015). J. Appl. Cryst. 48, 3–10. Web of Science CSD CrossRef ICSD CAS IUCr Journals Google Scholar
Li, C.-J., Lin, Z., Yun, L., Xie, Y.-L., Leng, J.-D., Ou, Y.-C. & Tong, M.-L. (2010). CrystEngComm, 12, 425–433. Web of Science CSD CrossRef CAS Google Scholar
Manteau, B., Genix, P., Brelot, L., Vors, J.-P., Pazenok, S., Giornal, F., Leuenberger, C. & Leroux, F. R. (2010). Eur. J. Org. Chem. pp. 6043–6066. Web of Science CSD CrossRef Google Scholar
Nantka-Namirski, P. & Rykowski, A. (1972a). Acta Pol. Pharm. 29, 129–134 [Eng. Trans.]. Google Scholar
Nantka-Namirski, P. & Rykowski, A. (1972b). Acta Pol. Pharm. 29, 233–238. [Eng. Trans.]. Google Scholar
Parkin, S. (2000). Acta Cryst. A56, 157–162. Web of Science CrossRef CAS IUCr Journals Google Scholar
Parkin, S. (2013). CIFFIX. https://xray.uky.edu/Resources/scripts/ciffix Google Scholar
Parkin, S. & Hope, H. (1998a). Acta Cryst. B54, 339–344. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Parkin, S. & Hope, H. (1998b). J. Appl. Cryst. 31, 945–953. Web of Science CrossRef CAS IUCr Journals Google Scholar
Parsons, S., Flack, H. D. & Wagner, T. (2013). Acta Cryst. B69, 249–259. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Qiu, J., Zhang, Y., Yao, S., Ren, H., Qian, M., Hong, Q., Lu, Z. & He, J. (2019). J. Bact. 201, e00665–18. Web of Science CAS PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Shukla, O. P. & Kaul, S. M. (1973). Indian J. Biochem. Biophys. 10, 176–178. CAS PubMed Web of Science Google Scholar
Shukla, O. P., Kaul, S. M. & Khanna, M. (1977). Indian J. Biochem. Biophys. 14, 292–295. CAS PubMed Web of Science Google Scholar
Spek, A. L. (2020). Acta Cryst. E76, 1–11. Web of Science CrossRef IUCr Journals Google Scholar
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