research communications
Syntheses and crystal structures of four 4-(4-nitrophenyl)piperazinium salts with hydrogen succinate, 4-aminobenzoate, 2-(4-chlorophenyl)acetate and 2,3,4,5,6-pentafluorobenzoate anions
aDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysuru-570 006, India, and bDepartment of Chemistry, University of Kentucky, Lexington, KY, 40506-0055, USA
*Correspondence e-mail: ybb2706@gmail.com, yathirajan@hotmail.com
The syntheses and crystal structures are presented for four organic salts of the 4-(4-nitrophenyl)piperazinium cation, namely, 4-(4-nitrophenyl)piperazinium hydrogen succinate, C10H14N3O2+·C4H5O4− (I), 4-(4-nitrophenyl)piperazinium 4-aminobenzoate monohydrate, C10H14N3O2+·C7H6NO2−·H2O (II), 4-(4-nitrophenyl)piperazinium 2-(4-chlorophenyl)acetate, C10H14N3O2+·C8H6ClO2− (III) and 4-(4-nitrophenyl)piperazinium 2,3,4,5,6-pentafluorobenzoate, C10H14N3O2+·C7F5O2− (IV). The salts form from mixtures of N-(4-nitrophenyl)piperazine and the corresponding acid [succinic acid (I), 4-aminobenzoic acid (II), 2-(4-chlorophenyl)acetic acid (III) and 2,3,4,5,6-pentafluorobenzoic acid (IV)] in mixed solvents of methanol and ethyl acetate. Salts I, III, and IV are anhydrous, whereas II is a monohydrate. In each structure, the overall conformation of the cation is determined by the disposition of the exocyclic N—C bond of the piperazine ring (either axial or equatorial) and twists about the N—C bond between the piperazine ring and its attached 4-nitrophenyl ring. The packing motifs in each structure are quite different, though all are dominated by strong N—H⋯O hydrogen bonds, which are augmented in I and II by O—H⋯O hydrogen bonds, and in III by a π–π stacking interaction between inversion-related 4-nitrophenyl groups.
1. Chemical context
4-Nitrophenylpiperazinium chloride monohydrate has been used as an intermediate in the synthesis of anticancer drugs, transcriptase inhibitors and antifungal reagents (Berkheij et al., 2005; Chaudhary et al., 2006; Kharb et al., 2012; Upadhayaya et al., 2004). It is also an important reagent for potassium channel openers, which show significant biomolecular current-voltage rectification characteristics (Lu, 2007). The design, synthesis and biological profiling of arylpiperazine-based scaffolds for the management of androgen-sensitive prostatic disorders was described by Gupta et al. (2016). 4-Nitrophenylpiperazine was the starting material in the synthesis and biological evaluation of new piperazine-containing hydrazone derivatives (Kaya et al., 2016). A review on the piperazine skeleton in the structural modification of natural products was recently published by Zhang et al. (2021).
As part of our studies in this area, this paper describes the crystal structures of four salts of 4-nitrophenylpiperazine with organic acids, viz, 4-(4-nitrophenyl)piperazinium hydrogen succinate, C10H14N3O2+·C4H5O4− (I), 4-(4-nitrophenyl)piperazinium 4-aminobenzoate monohydrate, C10H14N3O2+·C7H6NO2−·H2O (II), 4-(4-nitrophenyl)piperazinium 2-(4-chlorophenyl)acetate, C10H14N3O2+·C8H6ClO2− (III) and 4-(4-nitrophenyl)piperazinium 2,3,4,5,6-pentafluorobenzoate, C10H14N3O2+·C7F5O2− (IV).
2. Structural commentary
The overall conformations of the 4-nitrophenylpiperazinium cations in I–IV are determined by the N2—C5 bonds, which link the 4-nitrophenyl and piperazinium rings (Figs. 1–4). Within each structure, atom N2 is non-planar, the sums of bond angles being 352.73 (16)° (I), 344.91 (12)° (II), 348.75 (15)° (III), and 348.85 (17)° (IV), so the connection of the exocyclic carbon atom is either equatorial (II, III) or axial (I, IV). The relative twist about these N2—C5 bonds, e.g. quantified by the C2—N2—C5—C6 torsional angles [–168.06 (10)° for I, 149.97 (9)° for II, 167.32 (10)° for III, and −170.03 (10)° for IV] determine the overall cation shape. In each case, the 4-nitro group is essentially coplanar with its attached phenyl ring.
The succinate anion in I has minor twists about its three C—C bonds [torsion angles 165.46 (9), 166.06 (8), and 169.97 (9)° for O4—C11—C12—C13, C11—C12—C13—C14, and C12—C13—C14—O6, respectively], which leads to a dihedral angle of 34.63 (9)° between its carboxylate/carboxylic acid groups. The 4-aminobenzoate anion of II is close to planar, having a dihedral angle between the carboxylate group and its benzene ring of 10.70 (7)°. The amine group at N4 is also slightly non-planar [the sum of angles about N4 is 349 (2)°]. In the 2-(4-chlorophenyl)acetate anion of III, twists about the C11—C12 and C12—C13 bonds place the carboxylate group almost perpendicular [85.02 (9)°] to the benzene ring. Lastly, in the pentafluorobenzoate anion of IV, the carboxylate group is 55.95 (10)° out of coplanarity with the phenyl ring.
Throughout all four structures, individual bond lengths and angles take on normal values except for an elongated O—H bond [1.17 (2) Å] in I, which will be described in more detail in the next section (Supramolecular features).
3. Supramolecular features
Hydrogen bonding plays a significant role in the packing of all four salts (see Tables 1–4). In each structure, the asymmetric units were chosen to give the shortest hydrogen bonds between the cationic NH2 group and the anionic carboxylate groups. In I, II, and IV, these hydrogen bonds to the anion are equatorial relative to the piperazine ring, while that in III is axial. Nevertheless, in each structure, the NH2+ group acts as a hydrogen-bond donor through both its hydrogen atoms. In I, III, and IV this is to a second anion, whereas in II it is to the included water molecule. Throughout the four structures, all conventional N—H⋯O and all but one O—H⋯O (in I, vide infra) hydrogen bonds take on normal distances and angles (Tables 1–4).
|
|
|
The structure of I includes an unusually short O6—H6⋯O4(x, y − 1, z) hydrogen bond [O⋯O = 2.4367 (10) Å], which links adjacent hydrogen-succinate anions into chains that propagate parallel to the b-axis direction (Fig. 5). Difference map density for this hydrogen (H6) appears roughly equidistant from both oxygen atoms (Fig. 6), and refines to give O6—H6 = 1.17 (2) Å (Table 1). For unusually strong hydrogen bonds, the migration of the hydrogen atom towards the midpoint between the donor and acceptor atoms is an expected phenomenon. In such instances, the case for positional of the hydrogen atom, or even placement at the difference map peak coordinates is compelling (Fábry, 2018), and is backed by density-functional theory computational analysis (see e.g. Bhardwaj et al., 2020). A number of weak C—H⋯O interactions also occur.
Structure II also includes N—H⋯O hydrogen bonds from the 4-amino group of its anion to the nitro oxygen atoms of its cation (Table 2). The cation–anion interactions, along with the presence of the water molecule, which acts as an O—H⋯O hydrogen-bond donor to join a pair of translation-related (1 + x, y, z) anions and as an acceptor for an N—H⋯O hydrogen bond, generates a double-layer network lying parallel to (011) (Fig. 7). Of the four structures, II has the most complex hydrogen-bonding interactions.
The primary supramolecular interaction in III joins two pairs of inversion-related ammonium cations and carboxylate anions, forming an R44(12) ring motif (Table 3, Fig. 8). Structure III also includes the only π–π interactions of the four structures, which occurs between inversion-related (−x, 1 − y, −z) nitrophenyl rings, giving an interplanar spacing of 3.3352 (15) Å, though the offset (≃1.92 Å) is large, leading to a centroid–centroid distance of 3.8495 (15) Å (Fig. 8, dashed line).
Supramolecular interactions within IV are the simplest of the four structures: N—H⋯O hydrogen bonds connect cations and anions into continuous chains that extend parallel to its a-axis. These interactions are quantified in Table 4 and shown in Fig. 9.
4. Database survey
A search of the Cambridge Structure Database (CSD v5.43 with updates through September 2022; Groom et al., 2016) for salts that include the 4-(4-nitrophenyl)piperazinium cation returned ten hits. Database entries with refcodes LIJNAU (Lu, 2007) and LIJNAU01 (Rehman et al., 2009) are monohydrates of the chloride salt. The remaining eight structures, CSD entries NEBVOJ, NEBVUP, NEBWAW, NEBWEA, NEBWIE, NEBWOK (Mahesha et al., 2022) and BEFGIG and BEFGOM (Shankara Prasad et al., 2022) are all organic salts with a variety of anions, and all but NEBWOK and BEFGOM are hydrates.
Racemic perhydrotriphenylene forms a polar et al., 1997). The of 4,6-dimethoxypyrimidin-2-amine-1-(4-nitrophenyl)piperazine (LUDMUU), was published by Wang et al. (2014). The synthesis and of a Schiff base, 5-methyl-2-{[4-(4-nitrophenyl)piperazin-1-yl]methyl}phenol (WUWBIC) was published by Ayeni et al. (2019). NMR-based investigations by Wodtke et al. (2018) of acyl-functionalized piperazines concerning their conformational behavior in solution, included crystal structures of 1-(4-fluorobenzoyl)-4-(4-nitrophenyl)piperazine (BIQYIM), 1-(4-bromobenzoyl)-4-(4-nitrophenyl)piperazine (BIRHES), 1-(3-bromobenzoyl)-4-(4-nitrophenyl)piperazine (BIRHIW) and (piperazine-1,4-diyl)bis[(4-fluorophenyl)methanone] (BIRGOB).
with 1-(4-nitrophenyl)piperazine as a guest molecule (NOVWOK; König5. Synthesis, crystallization and spectroscopic details
A solution of commercially available (Sigma-Aldrich) 4-nitrophenylpiperazine (100 mg, 0.483 mol) in methanol (10 ml) was mixed with equimolar solutions of the appropriate acid in methanol (10 ml) and ethyl acetate (10 ml) viz., succinic acid (60 mg, 0.483 mol) for I, 4-aminobenzoic acid (69 mg, 0.483 mol) for II, 2-(4-chlorophenyl)acetic acid (85 mg, 0.483 mol) for III, and 2,3,4,5,6-pentafluorobenzoic acid (102 mg, 0.483 mol) for IV. The resulting solutions were stirred for 30 minutes at 333 K and allowed to stand at room temperature. X-ray quality crystals formed on slow evaporation of solutions in ethanol:acetonitrile (1:1) over the course of a week for all four compounds. The melting points are 398–400 K (I), 473–475 K (II), 431–435 K (III) and 411–415 K (IV).
6. Refinement
Crystal data, data collection, and structure . All hydrogen atoms were found in difference-Fourier maps, but those bound to carbon were subsequently included in the using riding models, with constrained distances set to 0.95 Å (Csp2—H) and 0.99 Å (R2CH2), using Uiso(H) values constrained to 1.2Ueq of the attached carbon atom. All N—H and O—H hydrogen atoms were refined freely (both coordinates and Uiso).
details are given in Table 5
|
Supporting information
https://doi.org/10.1107/S2056989023001093/hb8053sup1.cif
contains datablocks I, II, III, IV, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989023001093/hb8053Isup2.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989023001093/hb8053IIsup3.hkl
Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S2056989023001093/hb8053IIIsup4.hkl
Structure factors: contains datablock IV. DOI: https://doi.org/10.1107/S2056989023001093/hb8053IVsup5.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989023001093/hb8053Isup6.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989023001093/hb8053IIsup7.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989023001093/hb8053IIIsup8.cml
Supporting information file. DOI: https://doi.org/10.1107/S2056989023001093/hb8053IVsup9.cml
For all 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: SHELXL2019/2 (Sheldrick, 2015b); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).C10H14N3O2+·C4H5O4− | F(000) = 1376 |
Mr = 325.32 | Dx = 1.408 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
a = 25.2747 (12) Å | Cell parameters from 9366 reflections |
b = 8.0434 (4) Å | θ = 2.7–27.5° |
c = 15.6617 (5) Å | µ = 0.11 mm−1 |
β = 105.384 (2)° | T = 90 K |
V = 3069.9 (2) Å3 | Cut block, pale yellow |
Z = 8 | 0.30 × 0.22 × 0.18 mm |
Bruker D8 Venture dual source diffractometer | 3518 independent reflections |
Radiation source: microsource | 3130 reflections with I > 2σ(I) |
Detector resolution: 7.41 pixels mm-1 | Rint = 0.036 |
φ and ω scans | θmax = 27.5°, θmin = 2.7° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −32→32 |
Tmin = 0.890, Tmax = 0.971 | k = −10→10 |
25982 measured reflections | l = −20→20 |
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)] = 0.034 | Hydrogen site location: mixed |
wR(F2) = 0.089 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0401P)2 + 2.5912P] where P = (Fo2 + 2Fc2)/3 |
3518 reflections | (Δ/σ)max = 0.001 |
220 parameters | Δρmax = 0.36 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
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 | ||
O1 | 0.14051 (3) | 0.80996 (12) | 0.52439 (6) | 0.0280 (2) | |
O2 | 0.19261 (4) | 0.91415 (12) | 0.64508 (5) | 0.0259 (2) | |
N1 | 0.41855 (4) | 1.00925 (12) | 0.33747 (6) | 0.01449 (19) | |
H1NA | 0.4443 (6) | 0.9234 (19) | 0.3448 (9) | 0.024 (4)* | |
H1NB | 0.4279 (6) | 1.087 (2) | 0.3023 (10) | 0.027 (4)* | |
N2 | 0.32266 (4) | 1.14743 (13) | 0.37425 (6) | 0.0195 (2) | |
N3 | 0.18160 (4) | 0.88788 (12) | 0.56439 (6) | 0.0193 (2) | |
C1 | 0.42042 (4) | 1.07833 (14) | 0.42694 (7) | 0.0162 (2) | |
H1A | 0.457208 | 1.125553 | 0.454157 | 0.019* | |
H1B | 0.413555 | 0.988494 | 0.465866 | 0.019* | |
C2 | 0.37707 (4) | 1.21296 (14) | 0.41778 (7) | 0.0184 (2) | |
H2A | 0.377322 | 1.255726 | 0.477154 | 0.022* | |
H2B | 0.385724 | 1.306506 | 0.382666 | 0.022* | |
C3 | 0.32172 (5) | 1.09046 (16) | 0.28539 (7) | 0.0221 (3) | |
H3A | 0.331073 | 1.184031 | 0.250990 | 0.027* | |
H3B | 0.284357 | 1.051561 | 0.254685 | 0.027* | |
C4 | 0.36260 (4) | 0.94930 (14) | 0.28984 (7) | 0.0185 (2) | |
H4A | 0.352357 | 0.853143 | 0.321552 | 0.022* | |
H4B | 0.362220 | 0.913189 | 0.229253 | 0.022* | |
C5 | 0.28969 (4) | 1.07550 (14) | 0.42138 (7) | 0.0170 (2) | |
C6 | 0.24190 (4) | 0.98517 (15) | 0.37851 (7) | 0.0197 (2) | |
H6 | 0.233839 | 0.966904 | 0.316459 | 0.024* | |
C7 | 0.20687 (4) | 0.92328 (14) | 0.42470 (7) | 0.0187 (2) | |
H7 | 0.175211 | 0.862077 | 0.394892 | 0.022* | |
C8 | 0.21826 (4) | 0.95117 (14) | 0.51539 (7) | 0.0168 (2) | |
C9 | 0.26495 (5) | 1.03778 (15) | 0.55941 (7) | 0.0196 (2) | |
H9 | 0.272248 | 1.056667 | 0.621320 | 0.024* | |
C10 | 0.30066 (4) | 1.09637 (15) | 0.51408 (7) | 0.0191 (2) | |
H10 | 0.333230 | 1.151757 | 0.545403 | 0.023* | |
O3 | 0.49072 (3) | 0.75060 (9) | 0.36438 (6) | 0.01950 (18) | |
O4 | 0.56900 (3) | 0.86516 (9) | 0.35258 (5) | 0.01772 (17) | |
O5 | 0.57855 (3) | 0.25137 (9) | 0.29079 (5) | 0.01729 (17) | |
O6 | 0.53144 (3) | 0.13451 (9) | 0.37722 (5) | 0.01695 (17) | |
H6O | 0.5484 (8) | 0.005 (3) | 0.3625 (13) | 0.065 (6)* | |
C11 | 0.53782 (4) | 0.74028 (12) | 0.35582 (6) | 0.0127 (2) | |
C12 | 0.56315 (4) | 0.57314 (12) | 0.34704 (7) | 0.0145 (2) | |
H12A | 0.601509 | 0.572910 | 0.384282 | 0.017* | |
H12B | 0.564189 | 0.558197 | 0.284757 | 0.017* | |
C13 | 0.53315 (4) | 0.42686 (12) | 0.37343 (7) | 0.0142 (2) | |
H13A | 0.539998 | 0.426052 | 0.438666 | 0.017* | |
H13B | 0.493229 | 0.441729 | 0.347489 | 0.017* | |
C14 | 0.55019 (4) | 0.26118 (12) | 0.34399 (7) | 0.0124 (2) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0196 (4) | 0.0345 (5) | 0.0275 (4) | −0.0090 (4) | 0.0021 (3) | 0.0038 (4) |
O2 | 0.0250 (4) | 0.0339 (5) | 0.0192 (4) | −0.0051 (4) | 0.0063 (3) | 0.0036 (3) |
N1 | 0.0143 (4) | 0.0131 (4) | 0.0171 (4) | 0.0014 (3) | 0.0060 (3) | 0.0020 (3) |
N2 | 0.0142 (4) | 0.0278 (5) | 0.0177 (4) | 0.0021 (4) | 0.0061 (3) | −0.0008 (4) |
N3 | 0.0158 (4) | 0.0198 (5) | 0.0214 (5) | 0.0012 (4) | 0.0031 (4) | 0.0048 (4) |
C1 | 0.0142 (5) | 0.0194 (5) | 0.0148 (5) | −0.0003 (4) | 0.0035 (4) | 0.0003 (4) |
C2 | 0.0181 (5) | 0.0182 (5) | 0.0213 (5) | −0.0007 (4) | 0.0091 (4) | −0.0012 (4) |
C3 | 0.0155 (5) | 0.0371 (7) | 0.0141 (5) | 0.0033 (5) | 0.0043 (4) | 0.0012 (5) |
C4 | 0.0168 (5) | 0.0231 (6) | 0.0167 (5) | −0.0043 (4) | 0.0064 (4) | −0.0038 (4) |
C5 | 0.0142 (5) | 0.0185 (5) | 0.0192 (5) | 0.0056 (4) | 0.0058 (4) | 0.0006 (4) |
C6 | 0.0174 (5) | 0.0240 (6) | 0.0175 (5) | 0.0024 (4) | 0.0044 (4) | −0.0047 (4) |
C7 | 0.0145 (5) | 0.0186 (5) | 0.0216 (5) | 0.0014 (4) | 0.0024 (4) | −0.0030 (4) |
C8 | 0.0145 (5) | 0.0165 (5) | 0.0194 (5) | 0.0031 (4) | 0.0046 (4) | 0.0031 (4) |
C9 | 0.0186 (5) | 0.0236 (6) | 0.0151 (5) | −0.0009 (4) | 0.0020 (4) | 0.0024 (4) |
C10 | 0.0149 (5) | 0.0232 (6) | 0.0176 (5) | −0.0012 (4) | 0.0016 (4) | 0.0007 (4) |
O3 | 0.0158 (4) | 0.0119 (4) | 0.0316 (4) | 0.0021 (3) | 0.0078 (3) | 0.0008 (3) |
O4 | 0.0185 (4) | 0.0093 (4) | 0.0266 (4) | −0.0009 (3) | 0.0080 (3) | −0.0010 (3) |
O5 | 0.0229 (4) | 0.0123 (4) | 0.0193 (4) | −0.0004 (3) | 0.0101 (3) | −0.0018 (3) |
O6 | 0.0197 (4) | 0.0089 (3) | 0.0245 (4) | 0.0002 (3) | 0.0097 (3) | 0.0013 (3) |
C11 | 0.0155 (5) | 0.0099 (5) | 0.0113 (4) | 0.0003 (4) | 0.0010 (4) | −0.0004 (4) |
C12 | 0.0148 (5) | 0.0094 (5) | 0.0192 (5) | 0.0006 (4) | 0.0044 (4) | −0.0010 (4) |
C13 | 0.0163 (5) | 0.0091 (5) | 0.0174 (5) | 0.0013 (4) | 0.0048 (4) | −0.0003 (4) |
C14 | 0.0120 (4) | 0.0102 (5) | 0.0131 (4) | 0.0001 (4) | −0.0001 (4) | 0.0000 (4) |
O1—N3 | 1.2323 (13) | C6—C7 | 1.3763 (16) |
O2—N3 | 1.2380 (13) | C6—H6 | 0.9500 |
N1—C4 | 1.4930 (13) | C7—C8 | 1.3906 (15) |
N1—C1 | 1.4964 (14) | C7—H7 | 0.9500 |
N1—H1NA | 0.934 (15) | C8—C9 | 1.3861 (16) |
N1—H1NB | 0.903 (16) | C9—C10 | 1.3714 (16) |
N2—C5 | 1.3784 (14) | C9—H9 | 0.9500 |
N2—C3 | 1.4594 (14) | C10—H10 | 0.9500 |
N2—C2 | 1.4618 (14) | O3—C11 | 1.2356 (13) |
N3—C8 | 1.4437 (14) | O4—C11 | 1.2860 (13) |
C1—C2 | 1.5199 (15) | O5—C14 | 1.2374 (13) |
C1—H1A | 0.9900 | O6—H6O | 1.17 (2) |
C1—H1B | 0.9900 | O6—C14 | 1.2901 (13) |
C2—H2A | 0.9900 | O6—H6O | 1.17 (2) |
C2—H2B | 0.9900 | C11—C12 | 1.5109 (14) |
C3—C4 | 1.5241 (16) | C12—C13 | 1.5154 (14) |
C3—H3A | 0.9900 | C12—H12A | 0.9900 |
C3—H3B | 0.9900 | C12—H12B | 0.9900 |
C4—H4A | 0.9900 | C13—C14 | 1.5097 (14) |
C4—H4B | 0.9900 | C13—H13A | 0.9900 |
C5—C10 | 1.4139 (15) | C13—H13B | 0.9900 |
C5—C6 | 1.4170 (16) | ||
C4—N1—C1 | 112.23 (8) | C10—C5—C6 | 117.24 (10) |
C4—N1—H1NA | 111.0 (9) | C7—C6—C5 | 121.52 (10) |
C1—N1—H1NA | 108.1 (9) | C7—C6—H6 | 119.2 |
C4—N1—H1NB | 106.6 (9) | C5—C6—H6 | 119.2 |
C1—N1—H1NB | 111.6 (10) | C6—C7—C8 | 119.39 (10) |
H1NA—N1—H1NB | 107.3 (12) | C6—C7—H7 | 120.3 |
C5—N2—C3 | 121.32 (10) | C8—C7—H7 | 120.3 |
C5—N2—C2 | 121.95 (9) | C9—C8—C7 | 120.48 (10) |
C3—N2—C2 | 109.46 (8) | C9—C8—N3 | 119.65 (10) |
O1—N3—O2 | 122.46 (10) | C7—C8—N3 | 119.87 (10) |
O1—N3—C8 | 118.84 (9) | C10—C9—C8 | 120.37 (10) |
O2—N3—C8 | 118.70 (9) | C10—C9—H9 | 119.8 |
N1—C1—C2 | 109.46 (8) | C8—C9—H9 | 119.8 |
N1—C1—H1A | 109.8 | C9—C10—C5 | 120.93 (10) |
C2—C1—H1A | 109.8 | C9—C10—H10 | 119.5 |
N1—C1—H1B | 109.8 | C5—C10—H10 | 119.5 |
C2—C1—H1B | 109.8 | H6O—O6—C14 | 115.4 (10) |
H1A—C1—H1B | 108.2 | H6O—O6—H6O | 0 (3) |
N2—C2—C1 | 110.65 (9) | C14—O6—H6O | 115.4 (10) |
N2—C2—H2A | 109.5 | O3—C11—O4 | 124.74 (9) |
C1—C2—H2A | 109.5 | O3—C11—C12 | 120.89 (9) |
N2—C2—H2B | 109.5 | O4—C11—C12 | 114.37 (9) |
C1—C2—H2B | 109.5 | C11—C12—C13 | 114.29 (8) |
H2A—C2—H2B | 108.1 | C11—C12—H12A | 108.7 |
N2—C3—C4 | 110.55 (9) | C13—C12—H12A | 108.7 |
N2—C3—H3A | 109.5 | C11—C12—H12B | 108.7 |
C4—C3—H3A | 109.5 | C13—C12—H12B | 108.7 |
N2—C3—H3B | 109.5 | H12A—C12—H12B | 107.6 |
C4—C3—H3B | 109.5 | C14—C13—C12 | 113.47 (8) |
H3A—C3—H3B | 108.1 | C14—C13—H13A | 108.9 |
N1—C4—C3 | 108.84 (9) | C12—C13—H13A | 108.9 |
N1—C4—H4A | 109.9 | C14—C13—H13B | 108.9 |
C3—C4—H4A | 109.9 | C12—C13—H13B | 108.9 |
N1—C4—H4B | 109.9 | H13A—C13—H13B | 107.7 |
C3—C4—H4B | 109.9 | O5—C14—O6 | 124.17 (9) |
H4A—C4—H4B | 108.3 | O5—C14—C13 | 121.67 (9) |
N2—C5—C10 | 121.22 (10) | O6—C14—C13 | 114.14 (9) |
N2—C5—C6 | 121.46 (10) | ||
C4—N1—C1—C2 | −54.52 (12) | O1—N3—C8—C9 | −179.41 (10) |
C5—N2—C2—C1 | 89.04 (12) | O2—N3—C8—C9 | 0.67 (16) |
C3—N2—C2—C1 | −61.41 (12) | O1—N3—C8—C7 | −0.13 (15) |
N1—C1—C2—N2 | 57.02 (11) | O2—N3—C8—C7 | 179.94 (10) |
C5—N2—C3—C4 | −88.50 (12) | C7—C8—C9—C10 | −0.33 (17) |
C2—N2—C3—C4 | 62.17 (12) | N3—C8—C9—C10 | 178.94 (10) |
C1—N1—C4—C3 | 54.94 (11) | C8—C9—C10—C5 | 2.44 (18) |
N2—C3—C4—N1 | −58.37 (12) | N2—C5—C10—C9 | 173.84 (11) |
C3—N2—C5—C10 | 162.34 (10) | C6—C5—C10—C9 | −2.92 (17) |
C2—N2—C5—C10 | 15.32 (16) | O3—C11—C12—C13 | −15.24 (14) |
C3—N2—C5—C6 | −21.04 (16) | O4—C11—C12—C13 | 165.46 (9) |
C2—N2—C5—C6 | −168.06 (10) | C11—C12—C13—C14 | 166.06 (8) |
N2—C5—C6—C7 | −175.36 (10) | H6O—O6—C14—O5 | 9.0 (11) |
C10—C5—C6—C7 | 1.39 (16) | H6O—O6—C14—C13 | −172.7 (11) |
C5—C6—C7—C8 | 0.62 (17) | C12—C13—C14—O5 | −11.74 (14) |
C6—C7—C8—C9 | −1.19 (17) | C12—C13—C14—O6 | 169.97 (9) |
C6—C7—C8—N3 | 179.54 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1NA···O3 | 0.934 (15) | 1.793 (16) | 2.7250 (12) | 175.5 (13) |
N1—H1NB···O5i | 0.903 (16) | 1.945 (16) | 2.8127 (12) | 160.5 (13) |
O6—H6O···O4ii | 1.17 (2) | 1.27 (2) | 2.4367 (10) | 176 (2) |
C1—H1A···O6iii | 0.99 | 2.49 | 3.1374 (13) | 123 |
C3—H3A···O5i | 0.99 | 2.59 | 3.3238 (15) | 130 |
C3—H3B···O2iv | 0.99 | 2.51 | 3.4168 (15) | 153 |
C4—H4A···O2v | 0.99 | 2.55 | 3.5053 (15) | 162 |
C4—H4B···O4vi | 0.99 | 2.45 | 3.2354 (13) | 136 |
C10—H10···O4vii | 0.95 | 2.57 | 3.4146 (13) | 149 |
Symmetry codes: (i) −x+1, y+1, −z+1/2; (ii) x, y−1, z; (iii) x, y+1, z; (iv) x, −y+2, z−1/2; (v) −x+1/2, −y+3/2, −z+1; (vi) −x+1, y, −z+1/2; (vii) −x+1, −y+2, −z+1. |
C10H14N3O2+·C7H6NO2−·H2O | Z = 2 |
Mr = 362.38 | F(000) = 384 |
Triclinic, P1 | Dx = 1.439 Mg m−3 |
a = 6.0453 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 7.3930 (3) Å | Cell parameters from 9362 reflections |
c = 19.1439 (6) Å | θ = 2.8–27.5° |
α = 79.482 (2)° | µ = 0.11 mm−1 |
β = 89.215 (1)° | T = 90 K |
γ = 83.967 (1)° | Cut block, pale yellow |
V = 836.55 (6) Å3 | 0.30 × 0.26 × 0.25 mm |
Bruker D8 Venture dual source diffractometer | 3810 independent reflections |
Radiation source: microsource | 3567 reflections with I > 2σ(I) |
Detector resolution: 7.41 pixels mm-1 | Rint = 0.033 |
φ and ω scans | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −7→7 |
Tmin = 0.939, Tmax = 0.971 | k = −9→9 |
34250 measured reflections | l = −23→24 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.098 | w = 1/[σ2(Fo2) + (0.0553P)2 + 0.2799P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
3810 reflections | Δρmax = 0.40 e Å−3 |
260 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | Extinction correction: SHELXL-2019/2 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.060 (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 | ||
O1 | 0.53605 (15) | 0.20260 (13) | 1.00635 (4) | 0.0313 (2) | |
O2 | 0.23072 (15) | 0.38290 (13) | 0.99145 (5) | 0.0317 (2) | |
N1 | 0.76952 (13) | 0.71108 (11) | 0.54685 (4) | 0.01334 (18) | |
H1NA | 0.813 (3) | 0.774 (2) | 0.5028 (9) | 0.034 (4)* | |
H1NB | 0.732 (2) | 0.596 (2) | 0.5393 (7) | 0.023 (3)* | |
N2 | 0.68305 (13) | 0.65351 (11) | 0.69771 (4) | 0.01221 (18) | |
N3 | 0.41469 (16) | 0.32803 (12) | 0.97077 (5) | 0.0193 (2) | |
C1 | 0.57897 (16) | 0.81697 (13) | 0.57606 (5) | 0.0146 (2) | |
H1C | 0.454845 | 0.844383 | 0.541278 | 0.018* | |
H1D | 0.624218 | 0.935914 | 0.584689 | 0.018* | |
C2 | 0.50264 (15) | 0.70618 (13) | 0.64495 (5) | 0.0137 (2) | |
H2A | 0.379688 | 0.780329 | 0.664798 | 0.016* | |
H2B | 0.444540 | 0.592986 | 0.635118 | 0.016* | |
C3 | 0.88481 (15) | 0.56519 (13) | 0.66941 (5) | 0.0143 (2) | |
H3A | 0.857762 | 0.439718 | 0.662658 | 0.017* | |
H3B | 1.007080 | 0.551797 | 0.704450 | 0.017* | |
C4 | 0.95609 (16) | 0.67460 (13) | 0.59914 (5) | 0.0149 (2) | |
H4A | 1.003928 | 0.793496 | 0.606856 | 0.018* | |
H4B | 1.084141 | 0.604189 | 0.580091 | 0.018* | |
C5 | 0.61991 (16) | 0.57294 (13) | 0.76590 (5) | 0.01256 (19) | |
C6 | 0.76269 (16) | 0.43863 (14) | 0.81014 (5) | 0.0167 (2) | |
H6 | 0.905917 | 0.401074 | 0.793498 | 0.020* | |
C7 | 0.69753 (17) | 0.36046 (14) | 0.87753 (5) | 0.0182 (2) | |
H7 | 0.795230 | 0.270086 | 0.907019 | 0.022* | |
C8 | 0.48877 (17) | 0.41525 (13) | 0.90149 (5) | 0.0158 (2) | |
C9 | 0.34481 (17) | 0.54901 (14) | 0.86003 (5) | 0.0170 (2) | |
H9 | 0.202792 | 0.586433 | 0.877573 | 0.020* | |
C10 | 0.41010 (16) | 0.62734 (13) | 0.79291 (5) | 0.0159 (2) | |
H10 | 0.311958 | 0.719530 | 0.764402 | 0.019* | |
O3 | 0.91205 (12) | 0.87584 (10) | 0.41666 (4) | 0.01794 (17) | |
O4 | 0.63869 (13) | 0.73092 (11) | 0.38233 (4) | 0.02436 (19) | |
N4 | 0.99454 (17) | 1.07521 (13) | 0.07778 (5) | 0.0216 (2) | |
H4NA | 0.881 (3) | 1.094 (2) | 0.0482 (9) | 0.039 (4)* | |
H4NB | 1.098 (3) | 1.152 (2) | 0.0683 (9) | 0.036 (4)* | |
C11 | 0.79522 (16) | 0.82924 (13) | 0.36896 (5) | 0.0147 (2) | |
C12 | 0.84904 (15) | 0.89608 (12) | 0.29267 (5) | 0.0132 (2) | |
C13 | 1.04220 (16) | 0.98073 (13) | 0.27286 (5) | 0.0139 (2) | |
H13 | 1.142098 | 0.996856 | 0.308568 | 0.017* | |
C14 | 1.09049 (16) | 1.04151 (13) | 0.20203 (5) | 0.0155 (2) | |
H14 | 1.223476 | 1.097509 | 0.189691 | 0.019* | |
C15 | 0.94427 (17) | 1.02089 (13) | 0.14843 (5) | 0.0155 (2) | |
C16 | 0.74953 (17) | 0.93703 (14) | 0.16826 (5) | 0.0171 (2) | |
H16 | 0.647635 | 0.923274 | 0.132721 | 0.020* | |
C17 | 0.70465 (16) | 0.87434 (13) | 0.23895 (5) | 0.0154 (2) | |
H17 | 0.573636 | 0.815474 | 0.251325 | 0.019* | |
O1W | 0.29390 (13) | 0.65167 (10) | 0.46397 (4) | 0.01758 (17) | |
H1W1 | 0.183 (3) | 0.730 (2) | 0.4450 (9) | 0.037 (4)* | |
H2W1 | 0.410 (3) | 0.681 (2) | 0.4372 (9) | 0.041 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0317 (5) | 0.0350 (5) | 0.0201 (4) | 0.0004 (4) | 0.0010 (3) | 0.0114 (3) |
O2 | 0.0324 (5) | 0.0330 (5) | 0.0247 (4) | 0.0021 (4) | 0.0150 (3) | 0.0036 (3) |
N1 | 0.0154 (4) | 0.0138 (4) | 0.0104 (4) | −0.0018 (3) | 0.0009 (3) | −0.0012 (3) |
N2 | 0.0114 (4) | 0.0134 (4) | 0.0108 (4) | −0.0001 (3) | 0.0004 (3) | −0.0004 (3) |
N3 | 0.0251 (5) | 0.0189 (4) | 0.0139 (4) | −0.0055 (3) | 0.0030 (3) | −0.0014 (3) |
C1 | 0.0158 (4) | 0.0143 (4) | 0.0125 (4) | 0.0010 (3) | 0.0001 (3) | −0.0009 (3) |
C2 | 0.0121 (4) | 0.0163 (4) | 0.0117 (4) | 0.0005 (3) | −0.0001 (3) | −0.0008 (3) |
C3 | 0.0124 (4) | 0.0168 (4) | 0.0122 (4) | 0.0009 (3) | 0.0014 (3) | −0.0001 (3) |
C4 | 0.0130 (4) | 0.0182 (5) | 0.0128 (4) | −0.0020 (3) | 0.0010 (3) | −0.0009 (3) |
C5 | 0.0148 (4) | 0.0114 (4) | 0.0118 (4) | −0.0027 (3) | 0.0005 (3) | −0.0021 (3) |
C6 | 0.0148 (4) | 0.0189 (5) | 0.0147 (4) | 0.0007 (4) | 0.0013 (3) | −0.0001 (4) |
C7 | 0.0195 (5) | 0.0190 (5) | 0.0141 (4) | 0.0002 (4) | −0.0010 (4) | 0.0013 (4) |
C8 | 0.0214 (5) | 0.0152 (4) | 0.0110 (4) | −0.0049 (4) | 0.0026 (4) | −0.0014 (3) |
C9 | 0.0176 (5) | 0.0160 (5) | 0.0169 (5) | −0.0009 (4) | 0.0046 (4) | −0.0029 (4) |
C10 | 0.0168 (5) | 0.0142 (4) | 0.0151 (4) | 0.0015 (3) | 0.0017 (4) | −0.0003 (3) |
O3 | 0.0217 (4) | 0.0183 (4) | 0.0128 (3) | −0.0012 (3) | 0.0020 (3) | −0.0006 (3) |
O4 | 0.0247 (4) | 0.0269 (4) | 0.0211 (4) | −0.0106 (3) | 0.0074 (3) | 0.0006 (3) |
N4 | 0.0260 (5) | 0.0244 (5) | 0.0130 (4) | −0.0024 (4) | 0.0022 (4) | 0.0000 (3) |
C11 | 0.0151 (4) | 0.0116 (4) | 0.0155 (4) | 0.0021 (3) | 0.0036 (3) | 0.0001 (3) |
C12 | 0.0145 (4) | 0.0107 (4) | 0.0131 (4) | 0.0007 (3) | 0.0023 (3) | −0.0005 (3) |
C13 | 0.0145 (4) | 0.0131 (4) | 0.0141 (4) | −0.0010 (3) | 0.0005 (3) | −0.0027 (3) |
C14 | 0.0151 (4) | 0.0147 (4) | 0.0163 (5) | −0.0030 (3) | 0.0036 (3) | −0.0017 (3) |
C15 | 0.0196 (5) | 0.0125 (4) | 0.0134 (4) | 0.0013 (3) | 0.0025 (3) | −0.0013 (3) |
C16 | 0.0190 (5) | 0.0158 (4) | 0.0163 (5) | −0.0012 (4) | −0.0031 (4) | −0.0027 (4) |
C17 | 0.0136 (4) | 0.0130 (4) | 0.0191 (5) | −0.0019 (3) | 0.0007 (3) | −0.0012 (3) |
O1W | 0.0171 (4) | 0.0180 (4) | 0.0176 (4) | −0.0034 (3) | 0.0037 (3) | −0.0023 (3) |
O1—N3 | 1.2256 (12) | C7—C8 | 1.3827 (14) |
O2—N3 | 1.2288 (12) | C7—H7 | 0.9500 |
N1—C1 | 1.4850 (12) | C8—C9 | 1.3845 (14) |
N1—C4 | 1.4884 (12) | C9—C10 | 1.3801 (13) |
N1—H1NA | 0.936 (17) | C9—H9 | 0.9500 |
N1—H1NB | 0.942 (15) | C10—H10 | 0.9500 |
N2—C5 | 1.3980 (12) | O3—C11 | 1.2787 (13) |
N2—C3 | 1.4668 (12) | O4—C11 | 1.2488 (13) |
N2—C2 | 1.4694 (12) | N4—C15 | 1.3781 (13) |
N3—C8 | 1.4517 (12) | N4—H4NA | 0.879 (18) |
C1—C2 | 1.5137 (12) | N4—H4NB | 0.886 (18) |
C1—H1C | 0.9900 | C11—C12 | 1.4968 (12) |
C1—H1D | 0.9900 | C12—C13 | 1.3978 (13) |
C2—H2A | 0.9900 | C12—C17 | 1.3999 (13) |
C2—H2B | 0.9900 | C13—C14 | 1.3856 (13) |
C3—C4 | 1.5197 (12) | C13—H13 | 0.9500 |
C3—H3A | 0.9900 | C14—C15 | 1.4028 (14) |
C3—H3B | 0.9900 | C14—H14 | 0.9500 |
C4—H4A | 0.9900 | C15—C16 | 1.4034 (14) |
C4—H4B | 0.9900 | C16—C17 | 1.3810 (14) |
C5—C6 | 1.4076 (13) | C16—H16 | 0.9500 |
C5—C10 | 1.4102 (13) | C17—H17 | 0.9500 |
C6—C7 | 1.3838 (13) | O1W—H1W1 | 0.877 (18) |
C6—H6 | 0.9500 | O1W—H2W1 | 0.885 (18) |
C1—N1—C4 | 108.92 (7) | C7—C6—H6 | 119.5 |
C1—N1—H1NA | 111.3 (10) | C5—C6—H6 | 119.5 |
C4—N1—H1NA | 111.3 (10) | C8—C7—C6 | 119.32 (9) |
C1—N1—H1NB | 111.3 (9) | C8—C7—H7 | 120.3 |
C4—N1—H1NB | 107.5 (8) | C6—C7—H7 | 120.3 |
H1NA—N1—H1NB | 106.4 (13) | C7—C8—C9 | 121.45 (9) |
C5—N2—C3 | 116.22 (7) | C7—C8—N3 | 119.79 (9) |
C5—N2—C2 | 115.77 (7) | C9—C8—N3 | 118.74 (9) |
C3—N2—C2 | 112.92 (7) | C10—C9—C8 | 119.20 (9) |
O1—N3—O2 | 122.35 (9) | C10—C9—H9 | 120.4 |
O1—N3—C8 | 119.31 (9) | C8—C9—H9 | 120.4 |
O2—N3—C8 | 118.34 (9) | C9—C10—C5 | 121.17 (9) |
N1—C1—C2 | 110.02 (7) | C9—C10—H10 | 119.4 |
N1—C1—H1C | 109.7 | C5—C10—H10 | 119.4 |
C2—C1—H1C | 109.7 | C15—N4—H4NA | 115.6 (11) |
N1—C1—H1D | 109.7 | C15—N4—H4NB | 116.4 (11) |
C2—C1—H1D | 109.7 | H4NA—N4—H4NB | 116.6 (15) |
H1C—C1—H1D | 108.2 | O4—C11—O3 | 123.77 (9) |
N2—C2—C1 | 112.23 (8) | O4—C11—C12 | 118.01 (9) |
N2—C2—H2A | 109.2 | O3—C11—C12 | 118.21 (9) |
C1—C2—H2A | 109.2 | C13—C12—C17 | 118.22 (9) |
N2—C2—H2B | 109.2 | C13—C12—C11 | 121.69 (9) |
C1—C2—H2B | 109.2 | C17—C12—C11 | 120.10 (9) |
H2A—C2—H2B | 107.9 | C14—C13—C12 | 121.14 (9) |
N2—C3—C4 | 112.56 (8) | C14—C13—H13 | 119.4 |
N2—C3—H3A | 109.1 | C12—C13—H13 | 119.4 |
C4—C3—H3A | 109.1 | C13—C14—C15 | 120.42 (9) |
N2—C3—H3B | 109.1 | C13—C14—H14 | 119.8 |
C4—C3—H3B | 109.1 | C15—C14—H14 | 119.8 |
H3A—C3—H3B | 107.8 | N4—C15—C14 | 120.82 (9) |
N1—C4—C3 | 110.60 (8) | N4—C15—C16 | 120.62 (9) |
N1—C4—H4A | 109.5 | C14—C15—C16 | 118.51 (9) |
C3—C4—H4A | 109.5 | C17—C16—C15 | 120.61 (9) |
N1—C4—H4B | 109.5 | C17—C16—H16 | 119.7 |
C3—C4—H4B | 109.5 | C15—C16—H16 | 119.7 |
H4A—C4—H4B | 108.1 | C16—C17—C12 | 121.09 (9) |
N2—C5—C6 | 121.76 (9) | C16—C17—H17 | 119.5 |
N2—C5—C10 | 120.38 (8) | C12—C17—H17 | 119.5 |
C6—C5—C10 | 117.85 (9) | H1W1—O1W—H2W1 | 104.7 (15) |
C7—C6—C5 | 120.98 (9) | ||
C4—N1—C1—C2 | −60.5 (1) | O2—N3—C8—C9 | −3.55 (14) |
C5—N2—C2—C1 | 171.62 (8) | C7—C8—C9—C10 | 0.95 (16) |
C3—N2—C2—C1 | −50.91 (10) | N3—C8—C9—C10 | −177.35 (9) |
N1—C1—C2—N2 | 56.6 (1) | C8—C9—C10—C5 | 0.26 (15) |
C5—N2—C3—C4 | −173.16 (8) | N2—C5—C10—C9 | 179.86 (9) |
C2—N2—C3—C4 | 49.57 (11) | C6—C5—C10—C9 | −1.23 (15) |
C1—N1—C4—C3 | 59.29 (10) | O4—C11—C12—C13 | −169.47 (9) |
N2—C3—C4—N1 | −54.06 (10) | O3—C11—C12—C13 | 10.47 (13) |
C3—N2—C5—C6 | 11.92 (13) | O4—C11—C12—C17 | 10.42 (14) |
C2—N2—C5—C6 | 147.97 (9) | O3—C11—C12—C17 | −169.64 (9) |
C3—N2—C5—C10 | −169.20 (8) | C17—C12—C13—C14 | −0.09 (14) |
C2—N2—C5—C10 | −33.16 (12) | C11—C12—C13—C14 | 179.80 (8) |
N2—C5—C6—C7 | 179.93 (9) | C12—C13—C14—C15 | 0.67 (14) |
C10—C5—C6—C7 | 1.03 (15) | C13—C14—C15—N4 | −177.78 (9) |
C5—C6—C7—C8 | 0.12 (16) | C13—C14—C15—C16 | −0.24 (14) |
C6—C7—C8—C9 | −1.14 (16) | N4—C15—C16—C17 | 176.78 (9) |
C6—C7—C8—N3 | 177.14 (9) | C14—C15—C16—C17 | −0.77 (14) |
O1—N3—C8—C7 | −2.18 (15) | C15—C16—C17—C12 | 1.38 (15) |
O2—N3—C8—C7 | 178.12 (10) | C13—C12—C17—C16 | −0.93 (14) |
O1—N3—C8—C9 | 176.15 (10) | C11—C12—C17—C16 | 179.18 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1NA···O3 | 0.936 (17) | 1.804 (17) | 2.737 (1) | 174.7 (15) |
N1—H1NB···O1Wi | 0.942 (15) | 1.864 (15) | 2.7934 (11) | 168.4 (13) |
N4—H4NA···O1ii | 0.879 (18) | 2.258 (18) | 3.0861 (13) | 156.9 (15) |
N4—H4NB···O2iii | 0.886 (18) | 2.248 (17) | 3.0315 (13) | 147.3 (14) |
O1W—H1W1···O3iv | 0.877 (18) | 1.890 (18) | 2.7569 (11) | 169.7 (16) |
O1W—H2W1···O4 | 0.885 (18) | 1.755 (18) | 2.6388 (11) | 177.2 (17) |
C1—H1C···O1W | 0.99 | 2.50 | 3.2511 (12) | 132 |
C2—H2B···O4i | 0.99 | 2.58 | 3.5572 (13) | 170 |
C4—H4A···O3v | 0.99 | 2.51 | 3.4578 (12) | 161 |
C4—H4B···O1Wvi | 0.99 | 2.53 | 3.2921 (12) | 134 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y+1, z−1; (iii) x+1, y+1, z−1; (iv) x−1, y, z; (v) −x+2, −y+2, −z+1; (vi) x+1, y, z. |
C10H14N3O2+·C8H6ClO2− | Z = 2 |
Mr = 377.82 | F(000) = 396 |
Triclinic, P1 | Dx = 1.451 Mg m−3 |
a = 6.8051 (2) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.3927 (5) Å | Cell parameters from 9810 reflections |
c = 14.3869 (7) Å | θ = 2.6–27.5° |
α = 83.849 (2)° | µ = 0.25 mm−1 |
β = 81.283 (2)° | T = 90 K |
γ = 72.492 (2)° | Rounded block, pale yellow |
V = 865.01 (7) Å3 | 0.28 × 0.24 × 0.22 mm |
Bruker D8 Venture dual source diffractometer | 3954 independent reflections |
Radiation source: microsource | 3617 reflections with I > 2σ(I) |
Detector resolution: 7.41 pixels mm-1 | Rint = 0.034 |
φ and ω scans | θmax = 27.5°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −7→8 |
Tmin = 0.931, Tmax = 0.971 | k = −12→12 |
28796 measured reflections | l = −18→18 |
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)] = 0.029 | Hydrogen site location: mixed |
wR(F2) = 0.074 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0293P)2 + 0.3972P] where P = (Fo2 + 2Fc2)/3 |
3954 reflections | (Δ/σ)max = 0.001 |
243 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
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 | ||
O1 | −0.50792 (15) | 0.72253 (11) | −0.02713 (7) | 0.0316 (2) | |
O2 | −0.25948 (17) | 0.82570 (11) | −0.05317 (7) | 0.0356 (2) | |
N1 | 0.26456 (14) | 0.13828 (11) | 0.41177 (7) | 0.01585 (19) | |
H1NA | 0.325 (2) | 0.0464 (18) | 0.4359 (10) | 0.026 (4)* | |
H1NB | 0.269 (2) | 0.2061 (18) | 0.4542 (11) | 0.032 (4)* | |
N2 | 0.07010 (14) | 0.32686 (10) | 0.26302 (6) | 0.01586 (19) | |
N3 | −0.34059 (17) | 0.73363 (11) | −0.01097 (7) | 0.0227 (2) | |
C1 | 0.38614 (17) | 0.16486 (12) | 0.32016 (8) | 0.0176 (2) | |
H1A | 0.395730 | 0.086035 | 0.277758 | 0.021* | |
H1B | 0.528798 | 0.159661 | 0.330426 | 0.021* | |
C2 | 0.28355 (16) | 0.31715 (12) | 0.27444 (8) | 0.0172 (2) | |
H2A | 0.283868 | 0.396692 | 0.314290 | 0.021* | |
H2B | 0.362111 | 0.331786 | 0.212161 | 0.021* | |
C3 | −0.05253 (16) | 0.30313 (12) | 0.35323 (7) | 0.0156 (2) | |
H3A | −0.195330 | 0.309614 | 0.342459 | 0.019* | |
H3B | −0.061304 | 0.382276 | 0.395239 | 0.019* | |
C4 | 0.04638 (16) | 0.15129 (12) | 0.39986 (8) | 0.0156 (2) | |
H4A | −0.033315 | 0.138579 | 0.462142 | 0.019* | |
H4B | 0.044013 | 0.071645 | 0.360567 | 0.019* | |
C5 | −0.02922 (16) | 0.43171 (12) | 0.19619 (7) | 0.0151 (2) | |
C6 | −0.21686 (17) | 0.42157 (12) | 0.17151 (8) | 0.0176 (2) | |
H6 | −0.273862 | 0.345143 | 0.201503 | 0.021* | |
C7 | −0.31899 (17) | 0.52046 (12) | 0.10471 (8) | 0.0183 (2) | |
H7 | −0.446340 | 0.513477 | 0.089059 | 0.022* | |
C8 | −0.23292 (18) | 0.63078 (12) | 0.06044 (7) | 0.0177 (2) | |
C9 | −0.04689 (18) | 0.64229 (12) | 0.08123 (8) | 0.0185 (2) | |
H9 | 0.011220 | 0.716896 | 0.049151 | 0.022* | |
C10 | 0.05405 (17) | 0.54344 (12) | 0.14959 (8) | 0.0168 (2) | |
H10 | 0.181000 | 0.551621 | 0.164951 | 0.020* | |
Cl1 | 1.20054 (4) | −0.01622 (3) | 0.85294 (2) | 0.02223 (8) | |
O3 | 0.31330 (12) | 0.34221 (9) | 0.51721 (6) | 0.01836 (17) | |
O4 | 0.60380 (12) | 0.15406 (8) | 0.52384 (6) | 0.01855 (17) | |
C11 | 0.48457 (16) | 0.27847 (11) | 0.54780 (7) | 0.0141 (2) | |
C12 | 0.54892 (18) | 0.36457 (12) | 0.61677 (8) | 0.0187 (2) | |
H12A | 0.600482 | 0.444591 | 0.580440 | 0.022* | |
H12B | 0.424032 | 0.413504 | 0.659594 | 0.022* | |
C13 | 0.71304 (17) | 0.27174 (12) | 0.67559 (8) | 0.0160 (2) | |
C14 | 0.65746 (17) | 0.19582 (12) | 0.75951 (8) | 0.0176 (2) | |
H14 | 0.514929 | 0.204580 | 0.779430 | 0.021* | |
C15 | 0.80586 (18) | 0.10768 (12) | 0.81460 (8) | 0.0179 (2) | |
H15 | 0.765725 | 0.057433 | 0.871881 | 0.022* | |
C16 | 1.01349 (17) | 0.09451 (12) | 0.78437 (8) | 0.0166 (2) | |
C17 | 1.07373 (17) | 0.16949 (12) | 0.70198 (8) | 0.0176 (2) | |
H17 | 1.216498 | 0.160159 | 0.682282 | 0.021* | |
C18 | 0.92272 (17) | 0.25871 (12) | 0.64834 (8) | 0.0171 (2) | |
H18 | 0.963297 | 0.311542 | 0.592260 | 0.021* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0330 (5) | 0.0302 (5) | 0.0312 (5) | −0.0051 (4) | −0.0172 (4) | 0.0068 (4) |
O2 | 0.0498 (6) | 0.0257 (5) | 0.0320 (5) | −0.0142 (4) | −0.0119 (4) | 0.0144 (4) |
N1 | 0.0159 (4) | 0.0129 (4) | 0.0185 (5) | −0.0027 (4) | −0.0054 (4) | 0.0004 (4) |
N2 | 0.0133 (4) | 0.0189 (5) | 0.0153 (4) | −0.0052 (3) | −0.0029 (3) | 0.0026 (3) |
N3 | 0.0318 (6) | 0.0165 (5) | 0.0170 (5) | −0.0019 (4) | −0.0061 (4) | 0.0004 (4) |
C1 | 0.0143 (5) | 0.0182 (5) | 0.0198 (5) | −0.0033 (4) | −0.0026 (4) | −0.0023 (4) |
C2 | 0.0144 (5) | 0.0203 (5) | 0.0178 (5) | −0.0062 (4) | −0.0037 (4) | 0.0007 (4) |
C3 | 0.0148 (5) | 0.0160 (5) | 0.0147 (5) | −0.0033 (4) | −0.0019 (4) | 0.0012 (4) |
C4 | 0.0162 (5) | 0.0141 (5) | 0.0175 (5) | −0.0053 (4) | −0.0043 (4) | 0.0004 (4) |
C5 | 0.0168 (5) | 0.0150 (5) | 0.0127 (5) | −0.0033 (4) | −0.0017 (4) | −0.0017 (4) |
C6 | 0.0188 (5) | 0.0176 (5) | 0.0173 (5) | −0.0073 (4) | −0.0033 (4) | 0.0019 (4) |
C7 | 0.0177 (5) | 0.0195 (5) | 0.0174 (5) | −0.0043 (4) | −0.0041 (4) | −0.0007 (4) |
C8 | 0.0242 (6) | 0.0138 (5) | 0.0124 (5) | −0.0012 (4) | −0.0031 (4) | −0.0005 (4) |
C9 | 0.0267 (6) | 0.0138 (5) | 0.0153 (5) | −0.0073 (4) | −0.0002 (4) | −0.0017 (4) |
C10 | 0.0195 (5) | 0.0168 (5) | 0.0158 (5) | −0.0072 (4) | −0.0021 (4) | −0.0027 (4) |
Cl1 | 0.02364 (15) | 0.02014 (14) | 0.02045 (14) | −0.00019 (11) | −0.00884 (10) | 0.00015 (10) |
O3 | 0.0165 (4) | 0.0167 (4) | 0.0219 (4) | −0.0031 (3) | −0.0066 (3) | −0.0009 (3) |
O4 | 0.0207 (4) | 0.0131 (4) | 0.0216 (4) | −0.0023 (3) | −0.0063 (3) | −0.0023 (3) |
C11 | 0.0171 (5) | 0.0121 (5) | 0.0138 (5) | −0.0064 (4) | −0.0022 (4) | 0.0024 (4) |
C12 | 0.0220 (5) | 0.0131 (5) | 0.0216 (6) | −0.0029 (4) | −0.0082 (4) | −0.0023 (4) |
C13 | 0.0202 (5) | 0.0116 (5) | 0.0173 (5) | −0.0042 (4) | −0.0055 (4) | −0.0035 (4) |
C14 | 0.0174 (5) | 0.0155 (5) | 0.0209 (5) | −0.0053 (4) | −0.0024 (4) | −0.0036 (4) |
C15 | 0.0232 (5) | 0.0144 (5) | 0.0167 (5) | −0.0064 (4) | −0.0025 (4) | −0.0005 (4) |
C16 | 0.0199 (5) | 0.0127 (5) | 0.0170 (5) | −0.0019 (4) | −0.0066 (4) | −0.0024 (4) |
C17 | 0.0175 (5) | 0.0186 (5) | 0.0181 (5) | −0.0061 (4) | −0.0026 (4) | −0.0038 (4) |
C18 | 0.0226 (5) | 0.0156 (5) | 0.0149 (5) | −0.0076 (4) | −0.0032 (4) | −0.0014 (4) |
O1—N3 | 1.2322 (14) | C7—C8 | 1.3904 (16) |
O2—N3 | 1.2224 (14) | C7—H7 | 0.9500 |
N1—C1 | 1.4857 (14) | C8—C9 | 1.3812 (16) |
N1—C4 | 1.4873 (13) | C9—C10 | 1.3880 (16) |
N1—H1NA | 0.894 (16) | C9—H9 | 0.9500 |
N1—H1NB | 0.937 (16) | C10—H10 | 0.9500 |
N2—C5 | 1.3945 (14) | Cl1—C16 | 1.7434 (11) |
N2—C2 | 1.4610 (13) | O3—C11 | 1.2609 (13) |
N2—C3 | 1.4670 (13) | O4—C11 | 1.2545 (13) |
N3—C8 | 1.4544 (14) | C11—C12 | 1.5319 (15) |
C1—C2 | 1.5175 (15) | C12—C13 | 1.5055 (15) |
C1—H1A | 0.9900 | C12—H12A | 0.9900 |
C1—H1B | 0.9900 | C12—H12B | 0.9900 |
C2—H2A | 0.9900 | C13—C18 | 1.3930 (16) |
C2—H2B | 0.9900 | C13—C14 | 1.3959 (16) |
C3—C4 | 1.5137 (14) | C14—C15 | 1.3901 (15) |
C3—H3A | 0.9900 | C14—H14 | 0.9500 |
C3—H3B | 0.9900 | C15—C16 | 1.3860 (16) |
C4—H4A | 0.9900 | C15—H15 | 0.9500 |
C4—H4B | 0.9900 | C16—C17 | 1.3844 (16) |
C5—C10 | 1.4014 (15) | C17—C18 | 1.3920 (15) |
C5—C6 | 1.4084 (15) | C17—H17 | 0.9500 |
C6—C7 | 1.3755 (15) | C18—H18 | 0.9500 |
C6—H6 | 0.9500 | ||
C1—N1—C4 | 111.22 (8) | C5—C6—H6 | 119.4 |
C1—N1—H1NA | 108.7 (10) | C6—C7—C8 | 118.96 (10) |
C4—N1—H1NA | 109.3 (10) | C6—C7—H7 | 120.5 |
C1—N1—H1NB | 109.4 (10) | C8—C7—H7 | 120.5 |
C4—N1—H1NB | 110.8 (10) | C9—C8—C7 | 121.62 (10) |
H1NA—N1—H1NB | 107.3 (13) | C9—C8—N3 | 119.78 (10) |
C5—N2—C2 | 118.82 (9) | C7—C8—N3 | 118.58 (10) |
C5—N2—C3 | 117.88 (9) | C8—C9—C10 | 119.14 (10) |
C2—N2—C3 | 112.05 (8) | C8—C9—H9 | 120.4 |
O2—N3—O1 | 123.01 (10) | C10—C9—H9 | 120.4 |
O2—N3—C8 | 118.49 (10) | C9—C10—C5 | 120.73 (10) |
O1—N3—C8 | 118.5 (1) | C9—C10—H10 | 119.6 |
N1—C1—C2 | 110.44 (9) | C5—C10—H10 | 119.6 |
N1—C1—H1A | 109.6 | O4—C11—O3 | 124.59 (10) |
C2—C1—H1A | 109.6 | O4—C11—C12 | 119.40 (9) |
N1—C1—H1B | 109.6 | O3—C11—C12 | 115.99 (9) |
C2—C1—H1B | 109.6 | C13—C12—C11 | 115.29 (9) |
H1A—C1—H1B | 108.1 | C13—C12—H12A | 108.5 |
N2—C2—C1 | 109.47 (9) | C11—C12—H12A | 108.5 |
N2—C2—H2A | 109.8 | C13—C12—H12B | 108.5 |
C1—C2—H2A | 109.8 | C11—C12—H12B | 108.5 |
N2—C2—H2B | 109.8 | H12A—C12—H12B | 107.5 |
C1—C2—H2B | 109.8 | C18—C13—C14 | 118.25 (10) |
H2A—C2—H2B | 108.2 | C18—C13—C12 | 121.49 (10) |
N2—C3—C4 | 110.37 (9) | C14—C13—C12 | 120.26 (10) |
N2—C3—H3A | 109.6 | C15—C14—C13 | 121.52 (10) |
C4—C3—H3A | 109.6 | C15—C14—H14 | 119.2 |
N2—C3—H3B | 109.6 | C13—C14—H14 | 119.2 |
C4—C3—H3B | 109.6 | C16—C15—C14 | 118.74 (10) |
H3A—C3—H3B | 108.1 | C16—C15—H15 | 120.6 |
N1—C4—C3 | 109.74 (9) | C14—C15—H15 | 120.6 |
N1—C4—H4A | 109.7 | C17—C16—C15 | 121.2 (1) |
C3—C4—H4A | 109.7 | C17—C16—Cl1 | 119.80 (9) |
N1—C4—H4B | 109.7 | C15—C16—Cl1 | 119.00 (9) |
C3—C4—H4B | 109.7 | C16—C17—C18 | 119.24 (10) |
H4A—C4—H4B | 108.2 | C16—C17—H17 | 120.4 |
N2—C5—C10 | 122.74 (10) | C18—C17—H17 | 120.4 |
N2—C5—C6 | 118.81 (10) | C17—C18—C13 | 121.03 (10) |
C10—C5—C6 | 118.39 (10) | C17—C18—H18 | 119.5 |
C7—C6—C5 | 121.12 (10) | C13—C18—H18 | 119.5 |
C7—C6—H6 | 119.4 | ||
C4—N1—C1—C2 | 56.92 (11) | O1—N3—C8—C7 | 2.59 (15) |
C5—N2—C2—C1 | −158.61 (9) | C7—C8—C9—C10 | −1.54 (17) |
C3—N2—C2—C1 | 58.37 (11) | N3—C8—C9—C10 | 179.95 (10) |
N1—C1—C2—N2 | −56.83 (11) | C8—C9—C10—C5 | 0.95 (16) |
C5—N2—C3—C4 | 157.89 (9) | N2—C5—C10—C9 | 177.79 (10) |
C2—N2—C3—C4 | −58.71 (11) | C6—C5—C10—C9 | 0.44 (16) |
C1—N1—C4—C3 | −56.34 (11) | O4—C11—C12—C13 | −20.24 (15) |
N2—C3—C4—N1 | 56.40 (11) | O3—C11—C12—C13 | 161.46 (10) |
C2—N2—C5—C10 | −10.02 (15) | C11—C12—C13—C18 | 94.64 (12) |
C3—N2—C5—C10 | 130.87 (11) | C11—C12—C13—C14 | −85.23 (13) |
C2—N2—C5—C6 | 167.32 (10) | C18—C13—C14—C15 | −0.76 (16) |
C3—N2—C5—C6 | −51.78 (14) | C12—C13—C14—C15 | 179.12 (10) |
N2—C5—C6—C7 | −178.76 (10) | C13—C14—C15—C16 | −0.64 (16) |
C10—C5—C6—C7 | −1.30 (16) | C14—C15—C16—C17 | 1.28 (16) |
C5—C6—C7—C8 | 0.76 (17) | C14—C15—C16—Cl1 | −179.84 (8) |
C6—C7—C8—C9 | 0.69 (17) | C15—C16—C17—C18 | −0.50 (16) |
C6—C7—C8—N3 | 179.21 (10) | Cl1—C16—C17—C18 | −179.38 (8) |
O2—N3—C8—C9 | 2.19 (16) | C16—C17—C18—C13 | −0.95 (16) |
O1—N3—C8—C9 | −178.86 (10) | C14—C13—C18—C17 | 1.56 (15) |
O2—N3—C8—C7 | −176.36 (11) | C12—C13—C18—C17 | −178.32 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1NA···O4i | 0.894 (16) | 1.848 (16) | 2.7252 (12) | 166.3 (14) |
N1—H1NB···O3 | 0.937 (16) | 1.765 (17) | 2.6903 (12) | 169.0 (15) |
C4—H4A···O4ii | 0.99 | 2.46 | 3.2539 (14) | 137 |
C7—H7···O1iii | 0.95 | 2.59 | 3.2256 (15) | 124 |
C12—H12A···O3iv | 0.99 | 2.49 | 3.4710 (14) | 173 |
C15—H15···O2v | 0.95 | 2.37 | 3.1944 (15) | 146 |
C18—H18···O3vi | 0.95 | 2.55 | 3.2644 (15) | 132 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) x−1, y, z; (iii) −x−1, −y+1, −z; (iv) −x+1, −y+1, −z+1; (v) x+1, y−1, z+1; (vi) x+1, y, z. |
C10H14N3O2+·C7F5O2− | Z = 2 |
Mr = 419.31 | F(000) = 428 |
Triclinic, P1 | Dx = 1.649 Mg m−3 |
a = 5.9779 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 11.3934 (8) Å | Cell parameters from 9830 reflections |
c = 12.9312 (9) Å | θ = 2.8–27.5° |
α = 75.754 (2)° | µ = 0.15 mm−1 |
β = 81.670 (2)° | T = 90 K |
γ = 87.717 (2)° | Tablet, pale yellow |
V = 844.63 (9) Å3 | 0.21 × 0.17 × 0.05 mm |
Bruker D8 Venture dual source diffractometer | 3882 independent reflections |
Radiation source: microsource | 3456 reflections with I > 2σ(I) |
Detector resolution: 7.41 pixels mm-1 | Rint = 0.034 |
φ and ω scans | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Krause et al., 2015) | h = −7→7 |
Tmin = 0.914, Tmax = 0.959 | k = −14→14 |
38650 measured reflections | l = −16→16 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.031 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.082 | w = 1/[σ2(Fo2) + (0.0359P)2 + 0.419P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
3882 reflections | Δρmax = 0.36 e Å−3 |
269 parameters | Δρmin = −0.22 e Å−3 |
0 restraints | Extinction correction: SHELXL-2019/2 (Sheldrick 2015b), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.008 (2) |
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 | ||
O1 | 0.43180 (17) | 0.17458 (10) | −0.07590 (8) | 0.0322 (2) | |
O2 | 0.41598 (17) | 0.36577 (10) | −0.07776 (8) | 0.0315 (2) | |
N1 | 1.18846 (17) | 0.19065 (9) | 0.40887 (8) | 0.0156 (2) | |
H1NA | 1.080 (3) | 0.1911 (13) | 0.4679 (12) | 0.019* | |
H1NB | 1.331 (3) | 0.1841 (13) | 0.4282 (12) | 0.019* | |
N2 | 1.23887 (16) | 0.20731 (9) | 0.18180 (8) | 0.0164 (2) | |
N3 | 0.49963 (18) | 0.26345 (11) | −0.05166 (8) | 0.0241 (2) | |
C1 | 1.16518 (19) | 0.30898 (10) | 0.32993 (9) | 0.0170 (2) | |
H1C | 1.215721 | 0.375464 | 0.357861 | 0.020* | |
H1D | 1.004664 | 0.323501 | 0.319507 | 0.020* | |
C2 | 1.30775 (19) | 0.30694 (11) | 0.22310 (9) | 0.0178 (2) | |
H2A | 1.290093 | 0.384788 | 0.170238 | 0.021* | |
H2B | 1.469162 | 0.297174 | 0.233008 | 0.021* | |
C3 | 1.2830 (2) | 0.09221 (11) | 0.25697 (9) | 0.0178 (2) | |
H3A | 1.445777 | 0.085880 | 0.264569 | 0.021* | |
H3B | 1.244024 | 0.023963 | 0.228146 | 0.021* | |
C4 | 1.1436 (2) | 0.08444 (10) | 0.36671 (9) | 0.0175 (2) | |
H4A | 0.980836 | 0.082092 | 0.360358 | 0.021* | |
H4B | 1.181938 | 0.008818 | 0.417856 | 0.021* | |
C5 | 1.04949 (19) | 0.22037 (11) | 0.12889 (9) | 0.0153 (2) | |
C6 | 0.9588 (2) | 0.12034 (11) | 0.10325 (9) | 0.0182 (2) | |
H6 | 1.021849 | 0.042104 | 0.126884 | 0.022* | |
C7 | 0.7802 (2) | 0.13394 (12) | 0.04448 (10) | 0.0198 (2) | |
H7 | 0.721386 | 0.065866 | 0.027385 | 0.024* | |
C8 | 0.68749 (19) | 0.24811 (12) | 0.01068 (9) | 0.0189 (2) | |
C9 | 0.7691 (2) | 0.34801 (11) | 0.03565 (9) | 0.0188 (2) | |
H9 | 0.702687 | 0.425476 | 0.012554 | 0.023* | |
C10 | 0.9478 (2) | 0.33452 (11) | 0.09439 (9) | 0.0174 (2) | |
H10 | 1.003224 | 0.403213 | 0.111854 | 0.021* | |
O3 | 0.86075 (13) | 0.21817 (8) | 0.56526 (7) | 0.01998 (19) | |
O4 | 0.61190 (14) | 0.17431 (8) | 0.46723 (7) | 0.01912 (19) | |
C11 | 0.66662 (18) | 0.21484 (10) | 0.54141 (9) | 0.0144 (2) | |
C12 | 0.48004 (18) | 0.26637 (10) | 0.61162 (9) | 0.0142 (2) | |
C13 | 0.29057 (19) | 0.2006 (1) | 0.66651 (9) | 0.0144 (2) | |
C14 | 0.12144 (19) | 0.2486 (1) | 0.72922 (9) | 0.0152 (2) | |
C15 | 0.13793 (19) | 0.36674 (11) | 0.73547 (9) | 0.0164 (2) | |
C16 | 0.3259 (2) | 0.43432 (10) | 0.68299 (10) | 0.0171 (2) | |
C17 | 0.49472 (19) | 0.38314 (10) | 0.62342 (9) | 0.0161 (2) | |
F1 | 0.26874 (12) | 0.08537 (6) | 0.66068 (6) | 0.01959 (16) | |
F2 | −0.05531 (12) | 0.18192 (6) | 0.78430 (6) | 0.02050 (16) | |
F3 | −0.02700 (12) | 0.41607 (7) | 0.79314 (6) | 0.02259 (17) | |
F4 | 0.34328 (13) | 0.54896 (7) | 0.69035 (6) | 0.02478 (18) | |
F5 | 0.67401 (12) | 0.45273 (6) | 0.57274 (6) | 0.02176 (17) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0272 (5) | 0.0461 (6) | 0.0283 (5) | −0.0045 (4) | −0.0106 (4) | −0.0137 (4) |
O2 | 0.0268 (5) | 0.0417 (6) | 0.0257 (5) | 0.0087 (4) | −0.0111 (4) | −0.0048 (4) |
N1 | 0.0123 (4) | 0.0197 (5) | 0.0159 (5) | 0.0007 (4) | −0.0026 (4) | −0.0061 (4) |
N2 | 0.0159 (5) | 0.0176 (5) | 0.0165 (5) | −0.0003 (4) | −0.0035 (4) | −0.0052 (4) |
N3 | 0.0183 (5) | 0.0382 (7) | 0.0158 (5) | 0.0003 (4) | −0.0032 (4) | −0.0061 (5) |
C1 | 0.0166 (5) | 0.0159 (5) | 0.0201 (6) | −0.0007 (4) | −0.0034 (4) | −0.0066 (4) |
C2 | 0.0161 (5) | 0.0190 (6) | 0.0187 (6) | −0.0038 (4) | −0.0026 (4) | −0.0049 (4) |
C3 | 0.0182 (5) | 0.0184 (6) | 0.0186 (6) | 0.0051 (4) | −0.0053 (4) | −0.0070 (4) |
C4 | 0.0182 (5) | 0.0156 (5) | 0.0189 (6) | 0.0005 (4) | −0.0041 (4) | −0.0040 (4) |
C5 | 0.0140 (5) | 0.0193 (6) | 0.0121 (5) | −0.0005 (4) | 0.0003 (4) | −0.0041 (4) |
C6 | 0.0188 (6) | 0.0178 (6) | 0.0181 (5) | 0.0002 (4) | −0.0020 (4) | −0.0050 (4) |
C7 | 0.0193 (6) | 0.0242 (6) | 0.0172 (5) | −0.0033 (5) | −0.0012 (4) | −0.0078 (5) |
C8 | 0.0144 (5) | 0.0292 (6) | 0.0130 (5) | −0.0004 (5) | −0.0024 (4) | −0.0044 (5) |
C9 | 0.0175 (5) | 0.0213 (6) | 0.0152 (5) | 0.0020 (4) | −0.0003 (4) | −0.0015 (4) |
C10 | 0.0177 (5) | 0.0179 (6) | 0.0164 (5) | −0.0012 (4) | −0.0009 (4) | −0.0045 (4) |
O3 | 0.0124 (4) | 0.0296 (5) | 0.0211 (4) | 0.0009 (3) | −0.0036 (3) | −0.0115 (4) |
O4 | 0.0153 (4) | 0.0250 (4) | 0.0208 (4) | 0.0024 (3) | −0.0047 (3) | −0.0118 (3) |
C11 | 0.0136 (5) | 0.0136 (5) | 0.0159 (5) | 0.0003 (4) | −0.0021 (4) | −0.0032 (4) |
C12 | 0.0131 (5) | 0.0164 (5) | 0.0141 (5) | 0.0010 (4) | −0.0041 (4) | −0.0043 (4) |
C13 | 0.0154 (5) | 0.0130 (5) | 0.0160 (5) | 0.0000 (4) | −0.0051 (4) | −0.0040 (4) |
C14 | 0.0134 (5) | 0.0180 (6) | 0.0133 (5) | −0.0025 (4) | −0.0017 (4) | −0.0019 (4) |
C15 | 0.0152 (5) | 0.0201 (6) | 0.0149 (5) | 0.0035 (4) | −0.0017 (4) | −0.0069 (4) |
C16 | 0.0192 (6) | 0.0138 (5) | 0.0205 (6) | 0.0002 (4) | −0.0043 (4) | −0.0073 (4) |
C17 | 0.0134 (5) | 0.0172 (5) | 0.0176 (5) | −0.0032 (4) | −0.0017 (4) | −0.0037 (4) |
F1 | 0.0192 (3) | 0.0132 (3) | 0.0269 (4) | −0.0020 (3) | −0.0013 (3) | −0.0067 (3) |
F2 | 0.0171 (3) | 0.0219 (4) | 0.0199 (4) | −0.0052 (3) | 0.0037 (3) | −0.0033 (3) |
F3 | 0.0201 (4) | 0.0244 (4) | 0.0240 (4) | 0.0027 (3) | 0.0036 (3) | −0.0115 (3) |
F4 | 0.0244 (4) | 0.0158 (4) | 0.0366 (4) | −0.0012 (3) | −0.0006 (3) | −0.0131 (3) |
F5 | 0.0171 (3) | 0.0186 (4) | 0.0291 (4) | −0.0062 (3) | 0.0024 (3) | −0.0071 (3) |
O1—N3 | 1.2304 (15) | C6—C7 | 1.3806 (17) |
O2—N3 | 1.2376 (15) | C6—H6 | 0.9500 |
N1—C4 | 1.4922 (15) | C7—C8 | 1.3866 (18) |
N1—C1 | 1.4926 (15) | C7—H7 | 0.9500 |
N1—H1NA | 0.929 (15) | C8—C9 | 1.3814 (18) |
N1—H1NB | 0.915 (16) | C9—C10 | 1.3810 (17) |
N2—C5 | 1.3902 (14) | C9—H9 | 0.9500 |
N2—C2 | 1.4638 (14) | C10—H10 | 0.9500 |
N2—C3 | 1.4675 (15) | O3—C11 | 1.2475 (14) |
N3—C8 | 1.4556 (15) | O4—C11 | 1.2496 (14) |
C1—C2 | 1.5193 (16) | C11—C12 | 1.5263 (15) |
C1—H1C | 0.9900 | C12—C17 | 1.3836 (16) |
C1—H1D | 0.9900 | C12—C13 | 1.3860 (16) |
C2—H2A | 0.9900 | C13—F1 | 1.3459 (13) |
C2—H2B | 0.9900 | C13—C14 | 1.3841 (16) |
C3—C4 | 1.5225 (16) | C14—F2 | 1.3343 (13) |
C3—H3A | 0.9900 | C14—C15 | 1.3764 (16) |
C3—H3B | 0.9900 | C15—F3 | 1.3391 (13) |
C4—H4A | 0.9900 | C15—C16 | 1.3807 (17) |
C4—H4B | 0.9900 | C16—F4 | 1.3418 (13) |
C5—C10 | 1.4106 (16) | C16—C17 | 1.3788 (16) |
C5—C6 | 1.4107 (16) | C17—F5 | 1.3473 (13) |
C4—N1—C1 | 113.04 (9) | C10—C5—C6 | 117.61 (10) |
C4—N1—H1NA | 107.8 (9) | C7—C6—C5 | 121.27 (11) |
C1—N1—H1NA | 106.1 (9) | C7—C6—H6 | 119.4 |
C4—N1—H1NB | 109.5 (9) | C5—C6—H6 | 119.4 |
C1—N1—H1NB | 109.6 (9) | C6—C7—C8 | 119.25 (11) |
H1NA—N1—H1NB | 110.9 (13) | C6—C7—H7 | 120.4 |
C5—N2—C2 | 119.8 (1) | C8—C7—H7 | 120.4 |
C5—N2—C3 | 120.24 (10) | C9—C8—C7 | 121.24 (11) |
C2—N2—C3 | 108.81 (9) | C9—C8—N3 | 119.10 (11) |
O1—N3—O2 | 123.20 (11) | C7—C8—N3 | 119.66 (11) |
O1—N3—C8 | 118.67 (11) | C10—C9—C8 | 119.56 (11) |
O2—N3—C8 | 118.13 (11) | C10—C9—H9 | 120.2 |
N1—C1—C2 | 109.46 (9) | C8—C9—H9 | 120.2 |
N1—C1—H1C | 109.8 | C9—C10—C5 | 121.06 (11) |
C2—C1—H1C | 109.8 | C9—C10—H10 | 119.5 |
N1—C1—H1D | 109.8 | C5—C10—H10 | 119.5 |
C2—C1—H1D | 109.8 | O3—C11—O4 | 126.84 (11) |
H1C—C1—H1D | 108.2 | O3—C11—C12 | 115.21 (10) |
N2—C2—C1 | 110.54 (9) | O4—C11—C12 | 117.95 (10) |
N2—C2—H2A | 109.5 | C17—C12—C13 | 116.73 (10) |
C1—C2—H2A | 109.5 | C17—C12—C11 | 120.47 (10) |
N2—C2—H2B | 109.5 | C13—C12—C11 | 122.8 (1) |
C1—C2—H2B | 109.5 | F1—C13—C14 | 117.97 (10) |
H2A—C2—H2B | 108.1 | F1—C13—C12 | 119.72 (10) |
N2—C3—C4 | 110.32 (9) | C14—C13—C12 | 122.31 (10) |
N2—C3—H3A | 109.6 | F2—C14—C15 | 119.71 (10) |
C4—C3—H3A | 109.6 | F2—C14—C13 | 121.1 (1) |
N2—C3—H3B | 109.6 | C15—C14—C13 | 119.19 (10) |
C4—C3—H3B | 109.6 | F3—C15—C14 | 120.17 (10) |
H3A—C3—H3B | 108.1 | F3—C15—C16 | 119.85 (10) |
N1—C4—C3 | 110.66 (9) | C14—C15—C16 | 119.98 (10) |
N1—C4—H4A | 109.5 | F4—C16—C17 | 120.49 (10) |
C3—C4—H4A | 109.5 | F4—C16—C15 | 119.94 (10) |
N1—C4—H4B | 109.5 | C17—C16—C15 | 119.57 (11) |
C3—C4—H4B | 109.5 | F5—C17—C16 | 117.56 (10) |
H4A—C4—H4B | 108.1 | F5—C17—C12 | 120.25 (10) |
N2—C5—C10 | 121.43 (10) | C16—C17—C12 | 122.14 (11) |
N2—C5—C6 | 120.9 (1) | ||
C4—N1—C1—C2 | −52.11 (12) | O4—C11—C12—C17 | −124.65 (12) |
C5—N2—C2—C1 | 80.27 (13) | O3—C11—C12—C13 | −124.39 (12) |
C3—N2—C2—C1 | −63.65 (12) | O4—C11—C12—C13 | 55.62 (15) |
N1—C1—C2—N2 | 58.10 (12) | C17—C12—C13—F1 | −178.3 (1) |
C5—N2—C3—C4 | −81.76 (12) | C11—C12—C13—F1 | 1.44 (16) |
C2—N2—C3—C4 | 61.97 (12) | C17—C12—C13—C14 | 0.83 (16) |
C1—N1—C4—C3 | 51.34 (12) | C11—C12—C13—C14 | −179.43 (10) |
N2—C3—C4—N1 | −55.67 (12) | F1—C13—C14—F2 | 1.56 (16) |
C2—N2—C5—C10 | 13.05 (16) | C12—C13—C14—F2 | −177.59 (10) |
C3—N2—C5—C10 | 152.87 (10) | F1—C13—C14—C15 | −179.14 (10) |
C2—N2—C5—C6 | −170.03 (10) | C12—C13—C14—C15 | 1.72 (17) |
C3—N2—C5—C6 | −30.21 (15) | F2—C14—C15—F3 | −2.64 (16) |
N2—C5—C6—C7 | −175.64 (11) | C13—C14—C15—F3 | 178.05 (10) |
C10—C5—C6—C7 | 1.39 (17) | F2—C14—C15—C16 | 176.77 (10) |
C5—C6—C7—C8 | −0.41 (18) | C13—C14—C15—C16 | −2.54 (17) |
C6—C7—C8—C9 | −0.66 (18) | F3—C15—C16—F4 | 0.33 (17) |
C6—C7—C8—N3 | 179.78 (10) | C14—C15—C16—F4 | −179.08 (10) |
O1—N3—C8—C9 | 178.16 (11) | F3—C15—C16—C17 | −179.76 (10) |
O2—N3—C8—C9 | −1.79 (16) | C14—C15—C16—C17 | 0.83 (17) |
O1—N3—C8—C7 | −2.27 (17) | F4—C16—C17—F5 | −0.70 (17) |
O2—N3—C8—C7 | 177.78 (11) | C15—C16—C17—F5 | 179.4 (1) |
C7—C8—C9—C10 | 0.68 (17) | F4—C16—C17—C12 | −178.25 (10) |
N3—C8—C9—C10 | −179.75 (10) | C15—C16—C17—C12 | 1.85 (18) |
C8—C9—C10—C5 | 0.35 (17) | C13—C12—C17—F5 | 179.89 (10) |
N2—C5—C10—C9 | 175.65 (10) | C11—C12—C17—F5 | 0.15 (16) |
C6—C5—C10—C9 | −1.36 (17) | C13—C12—C17—C16 | −2.62 (17) |
O3—C11—C12—C17 | 55.33 (15) | C11—C12—C17—C16 | 177.63 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1NA···O3 | 0.929 (15) | 1.754 (16) | 2.6723 (13) | 169.4 (14) |
N1—H1NB···O4i | 0.915 (16) | 1.816 (16) | 2.7310 (13) | 178.8 (14) |
C1—H1C···F5ii | 0.99 | 2.49 | 3.4813 (14) | 177 |
C1—H1D···F4iii | 0.99 | 2.49 | 3.3996 (14) | 153 |
C4—H4B···O3iv | 0.99 | 2.56 | 3.3421 (15) | 136 |
C6—H6···F2v | 0.95 | 2.54 | 3.4536 (15) | 161 |
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+1, −z+1; (iii) −x+1, −y+1, −z+1; (iv) −x+2, −y, −z+1; (v) −x+1, −y, −z+1. |
Acknowledgements
One of the authors (V) is grateful to the DST–PURSE Project, Vijnana Bhavana, UOM for providing research facilities. HSY thanks UGC for a BSR Faculty fellowship for three years.
Funding information
Funding for this research was provided by: NSF (MRI CHE1625732) and the University of Kentucky (Bruker D8 Venture diffractometer).
References
Ayeni, A. O., Watkins, G. M. & Hosten, E. C. (2019). Bull. Chem. Soc. Ethiop. 33, 341–348. CAS Google Scholar
Berkheij, M., van der Sluis, L., Sewing, C., den Boer, D. J., Terpstra, J. W., Hiemstra, H., Iwema Bakker, W. I., van den Hoogenband, A. & van Maarseveen, J. H. (2005). Tetrahedron Lett. 46, 2369–2371. Web of Science CrossRef CAS Google Scholar
Bhardwaj, M., Ai, Q., Parkin, S. R. & Grossman, R. B. (2020). Acta Cryst. E76, 77–81. Web of Science CSD CrossRef IUCr Journals Google Scholar
Bruker (2016). APEX3. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chaudhary, P., Kumar, R., Verma, K., Singh, D., Yadav, V., Chhillar, A. K., Sharma, G. L. & Chandra, R. (2006). Bioorg. Med. Chem. 14, 1819–1826. Web of Science CrossRef PubMed CAS Google Scholar
Fábry, J. (2018). Acta Cryst. E74, 1344–1357. Web of Science CSD CrossRef IUCr Journals 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
Gupta, S., Pandey, D., Mandalapu, D., Bala, V., Sharma, V., Shukla, M., Yadav, S. K., Singh, N., Jaiswal, S., Maikhuri, J. P., Lal, J., Siddiqi, M. I., Gupta, G. & Sharma, V. L. (2016). Med. Chem. Commun. 7, 2111–2121. Web of Science CrossRef CAS Google Scholar
Kaya, B., Ozkay, Y., Temel, H. E. & Kaplancikli, Z. A. (2016). J. Chem. 5878410. Google Scholar
Kharb, R., Bansal, K. & Sharma, A. K. (2012). Der Pharma Chem. 4, 2470–2488. CAS Google Scholar
König, O., Bürgi, H.-B., Armbruster, T., Hulliger, J. & Weber, T. (1997). J. Am. Chem. Soc. 119, 10632–10640. 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
Lu, Y.-X. (2007). Acta Cryst. E63, o3611. Web of Science CSD CrossRef IUCr Journals Google Scholar
Mahesha, N., Kiran Kumar, H., Yathirajan, H. S., Foro, S., Abdelbaky, M. S. M. & Garcia-Granda, S. (2022). Acta Cryst. E78, 510–518. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rehman, Z., Shah, A., Muhammad, N., Ali, S., Qureshi, R., Meetsma, A. & Butler, I. S. (2009). Eur. J. Med. Chem. 44, 3986–3993. Web of Science CSD CrossRef PubMed CAS Google Scholar
Shankara Prasad, H. J., Devaraju, Vinaya, Yathirajan, H. S., Parkin, S. R. & Glidewell, C. (2022). Acta Cryst. E78, 840–845. 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
Upadhayaya, P. S., Sinha, N., Jain, S., Kishore, N., Chandra, R. & Arora, S. K. (2004). Bioorg. Med. Chem. 12, 2225–2238. Web of Science CrossRef PubMed CAS Google Scholar
Wang, X.-Y., Wang, M.-Z., Guo, F.-J., Sun, J. & Qian, S.-S. (2014). Z. Kristallogr. Cryst. Mat. 229, 97–98. CAS Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wodtke, R., Steinberg, J., Köckerling, M., Löser, R. & Mamat, C. (2018). RSC Adv. 8, 40921–40933. Web of Science CSD CrossRef CAS PubMed Google Scholar
Zhang, R.-H., Guo, H.-Y., Deng, H., Li, J. & Quan, Z.-S. (2021). J. Enzyme Inhib. Med. Chem. 36, 1165–1197. Web of Science CrossRef CAS PubMed Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.