1. Chemical context
Piperazines and substituted piperazines are pharmacophores that can be found in many biologically active compounds across a number of different therapeutic areas (Berkheij, 2005) such as antifungal (Upadhayaya et al., 2004), anti-bacterial, anti-malarial and anti-psychotic agents (Chaudhary et al., 2006). A review on the current pharmacological and toxicological information for piperazine derivatives was described (Elliott, 2011). 4-(4-Nitrophenyl)piperazin-1-ium chloride monohydrate has been used as an intermediate in the synthesis of anticancer drugs, transcriptase inhibitors and antifungal reagents and is also an important reagent for potassium channel openers, which show considerable biomolecular current-voltage rectification characteristics (Lu, 2007). 4-Nitrophenylpiperazine was the starting material in the synthesis and biological evaluation of piperazine containing hydrazone derivatives (Kaya et al., 2016).
Very recently, we have reported the syntheses, crystal structures and Hirshfeld surface analysis of 4-(4-nitrophenyl)piperazin-1-ium trifluoroacetate (Cambridge Structural Database refcode BEYREG) and 4-(4-nitrophenyl)piperazin-1-ium trichloroacetate (BEYRIK) (Shankara Prasad et al., 2023). As part of our ongoing studies in this area, the present paper reports the crystal structure studies and Hirshfeld surface analysis of three salts of 1-(4-nitrophenyl)piperazine with organic acids viz., 4-(4-nitrophenyl)piperazin-1-ium 2-chlorobenzoate, C10H14N3O2+·C7H4ClO2− (1), 4-(4-nitrophenyl)piperazin-1-ium 2-bromobenzoate hemihydrate, C10H14N3O2+·C7H4BrO2−·0.5H2O (2), and 4-(4-nitrophenyl)piperazin-1-ium 2-iodobenzoate hemihydrate, C10H14N3O2+·C7H4IO2−·0.5H2O (3).
2. Structural commentary
Structure 1 consists of a 4-nitropiperazinium cation linked to a 2-chlorobenzoate anion by two N—H⋯O hydrogen bonds (Fig. 1, Table 1), which will be discussed in further detail in the Supramolecular features section of the paper. Both the cation and the anion exhibit whole-ion disorder, which was modeled with two equivalent conformations with occupancies of 0.745 (10)/0.255 (10) and 0.563 (13)/0.437 (13) respectively. When discussing the conformations of the anion and cation, only the major components will be used. In the chlorobenzoate anion, the carboxylate group is significantly twisted with respect to the 2-chlorophenyl ring with a dihedral angle of 76.7 (4)°, which is likely due to the steric interaction between the ortho-chloro substituent and the carboxylate group. Structures 2 and 3 exhibit similar cation conformations, with equivalent dihedral angles of 65.5 (3) and 67.1 (5)°, respectively. Additionally, in all three structures, the 4-nitrophenyl group occupies an equatorial position in its attachment to the piperazinium ring.
D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A | C3—H3A⋯O2i | 0.93 | 2.13 | 2.880 (15) | 137 | N2—H2B⋯O3ii | 0.88 (2) | 1.86 (2) | 2.740 (6) | 172 (3) | N2—H2B⋯O3Aii | 0.88 (2) | 1.73 (2) | 2.590 (13) | 164 (3) | N2—H2C⋯O4 | 0.89 (2) | 1.83 (2) | 2.705 (8) | 169 (3) | N2—H2C⋯O4A | 0.89 (2) | 1.81 (3) | 2.644 (19) | 156 (3) | C8—H8A⋯Cl1iii | 0.97 | 2.82 | 3.629 (5) | 142 | C8—H8A⋯Cl1iv | 0.97 | 2.95 | 3.780 (5) | 144 | C8—H8A⋯Cl1Aiv | 0.97 | 2.88 | 3.643 (12) | 136 | C8—H8B⋯O4Aiv | 0.97 | 2.58 | 3.13 (2) | 116 | C10—H10A⋯O3Aii | 0.97 | 2.65 | 3.285 (19) | 123 | Symmetry codes: (i) ; (ii) ; (iii) ; (iv) . | |
| Figure 1 The molecular structure of 1 with the N—H⋯O hydrogen bond shown as a dashed line. Atomic displacement parameters are at the 30% probability level. |
Since 2 and 3 are isostructural, only 2 will be discussed in detail. This structure consists of a 4-(4-nitrophenyl)piperazin-1-ium cation linked to a 2-bromobenzoate anion by two N—H⋯O hydrogen bonds (Figs. 2 and 3, Tables 2 and 3). Both 2 and 3 contain 0.5 water molecules of crystallization [disordered over two locations with occupancies of 0.276 (3)/0.223 (3) for the iodobenzoate derivative]. Additionally, there is a weak C—H⋯Br interaction accepted by the bromine atom in the 2-bromobezoate anion and a carbon atom in the piperazinium ring, as well as a pair of weak C—H⋯O interactions between adjacent 4-nitrophenyl rings in the 4-(4-nitrophenyl)piperazin-1-ium cation.
D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A | N2—H2A⋯O3 | 0.85 (2) | 1.83 (2) | 2.655 (3) | 164 (2) | N2—H2B⋯O4i | 0.88 (2) | 1.82 (2) | 2.701 (3) | 173 (2) | C2—H2⋯O2ii | 0.93 | 2.50 | 3.307 (4) | 145 | C7—H7B⋯Br1iii | 0.97 | 3.11 | 4.032 (2) | 160 | C10—H10B⋯O1Wi | 0.97 | 2.10 | 3.057 (8) | 169 | Symmetry codes: (i) ; (ii) ; (iii) . | |
D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A | C2—H2⋯I1i | 0.93 | 3.28 | 4.110 (4) | 150 | C3—H3⋯O1ii | 0.93 | 2.53 | 3.347 (7) | 147 | C6—H6⋯I1iii | 0.93 | 3.26 | 3.940 (4) | 132 | C7—H7A⋯O1WA | 0.97 | 2.14 | 3.09 (3) | 167 | C7—H7A⋯O1WB | 0.97 | 2.01 | 2.85 (3) | 145 | N2—H2A⋯O3iv | 0.88 (5) | 1.86 (5) | 2.717 (5) | 164 (5) | N2—H2B⋯O4 | 0.93 (5) | 1.77 (5) | 2.666 (6) | 160 (5) | O1WB—H1W3⋯O3iv | 0.83 (2) | 1.71 (10) | 2.37 (2) | 135 (12) | Symmetry codes: (i) ; (ii) ; (iii) x, y+1, z; (iv) . | |
| Figure 2 The molecular structure of 2 with the N—H⋯O hydrogen bond shown as a dashed line. Atomic displacement parameters are at the 30% probability level. |
| Figure 3 The molecular structure of 3 with the N—H⋯O hydrogen bond shown as a dashed line. Atomic displacement parameters are at the 30% probability level. |
3. Supramolecular features
In the packing of 1, which contains both a disordered cation and anion as well as disordered water of solvation, the discussion will focus solely on the major component. The cation forms an R44(12) loop involving N—H⋯O hydrogen bonds with two adjacent anions and an adjacent cation (symmetry codes: 2 − x, 1 − y, 1 − z; x, 1 + y, z; 1 − x, 1 − y, 1 − z; see Fig. 4 for packing and Fig. 5 for fingerprint plots). There is also a π–π interaction between the nitro group in the cation and the phenyl ring of an adjacent cation [symmetry code: 1 − x, −y, −z; Y⋯Cg distance = 3.488 (18) Å; X—Y⋯Cg: 85.8 (12)°].
| Figure 4 Packing diagram for 1 showing an R44(12) loop of N—H⋯O hydrogen bonds with two cations and two anions (symmetry codes: 2 − x, 1 − y, 1 − z; x, 1 + y, z; 1 − x, 1 − y, 1 − z). Hydrogen bonds shown as dashed lines. |
| Figure 5 Fingerprint plot for 1 showing the N—H⋯O hydrogen bonds as prominent spikes. |
In the packing of 2, two cations and two anions form an R44 (12) loop (Etter et al., 1990) of N—H⋯O hydrogen bonds (symmetry code: 1 − x, −y, −z; see Fig. 6 for packing and Fig. 7 for fingerprint plots). Additionally, there are weak C—H⋯O interactions between adjacent nitrophenyl rings (symmetry code: −x, 1 − y, 1 − z) that form an R22(10) ring (Fig. 6), as well as a weak C—H⋯Br interaction between the piperazine ring and the bromine atom in an adjacent 2-bromobenzoate anion (symmetry code: −1 + x, y, z). The phenyl rings in adjacent cations form π–π interactions with a perpendicular distance between centroids of 3.5332 (11) Å (symmetry code: 1 − x, 1 − y, 1 − z; slippage = 0.737 Å). These are all clearly seen in the fingerprint plot generated by CrystalExplorer (Spackman et al., 2021).
| Figure 6 Packing diagram for 2 showing an R44(12) loop arising from N—H⋯O hydrogen bonds with an adjacent cation and anion (symmetry code: 1 − x, −y, −z) and an R22(10) loop comprised of weak C—H⋯O interactions between adjacent nitrophenyl rings (symmetry code: −x, 1 − y, 1 − z). Hydrogen bonds and C—H⋯O interactions shown as dashed lines. The half occupancy water molecule is omitted for clarity. |
| Figure 7 Fingerprint plot for 2 showing the N—H⋯O hydrogen bonds as prominent spikes. |
In the packing of 3, a pair of cations and a pair of anions form an R44(12) loop linked by N—H⋯O hydrogen bonds (symmetry code: 1 − x, 1 − y, 1 − z; see Fig. 8 for packing and Fig. 9 for fingerprint plots). Additionally, there are weak C—H⋯O interactions between adjacent nitrophenyl rings (symmetry code: 1 − x, 1 − y, −z) that form an R22 (10) ring. This structure contains a partially occupied water molecule close to a center of inversion for which the hydrogen atoms were not able to be located (see Refinement). This species is likely to be involved in hydrogen bonding with an adjacent oxygen atom in the anion (symmetry code: 1 − x, 1 − y, 1 − z) and with the piperazine ring in the cation, forming an R33(10) ring. The phenyl rings in adjacent cations form π–π interactions with a perpendicular distance between centroids of 3.586 (4) Å (symmetry code: −x, 1 − y, −z; slippage = 0.379 Å).
| Figure 8 Packing diagram for 3 showing the same features as Fig. 6. |
| Figure 9 Fingerprint plot for 3 showing the N—H⋯O hydrogen bonding as prominent spikes. |
4. Database survey
Related structures containing the 4-(4-nitrophenyl)piperazin-1-ium cation include 4-(4-nitrophenyl)piperazin-1-ium chloride monohydrate (refcode LIJNAU; Lu, 2007) and 4,6-dimethoxy pyrimidin-2-amine-1-(4-nitrophenyl)piperazine (1:1) (LUDMUU; Wang et al., 2014). Very recently, we have reported the crystal structures of six salts of 1-(4-nitrophenyl)piperazine (NEBVOJ, NEBVUP, NEBWAW, NEBWEA, NEBWIE, NEBWOK; Mahesha et al., 2022a). The syntheses and crystal structures of 4-(4-nitrophenyl)piperazin-1-ium benzoate monohydrate (BEFGIG) and 4-(4-nitrophenyl)piperazin-1-ium 2-carboxy-4,6-dinitrophenolate (BEFGOM) have been reported (Shankara Prasad et al., 2022). A survey of these published derivatives containing the 4-(4-nitrophenyl)piperazin-1-ium cation shows that the most common conformation adopted by the 4-nitrophenyl substituent with respect to the six-membered piperazinium ring is equatorial (LUDMUU, NEBVOJ, NEBVUP, NEBWAW, NEBWEA, NEBWOK, BEFGIG and BEYRIK) with only three adopting the axial conformation (LUDMUU, BEFGOM, and BEYREG). One published structure contains two 4-nitrophenyl cations, with one adopting an equatorial conformation and the other an axial conformation (Mahesha et al., 2022a).
5. Synthesis and crystallization
For the synthesis of salts (1)–(3), a solution of commercially available (from Sigma-Aldrich) 1-(4-nitrophenyl)piperazine (100 mg, 0.483 mmol) in methanol (10 ml) was mixed with equimolar solutions of the appropriate acids in methanol (10 ml) and ethyl acetate (10 ml), viz., 2-chlorobenzoic acid (76 mg, 0.483 mmol) for (1), 2-bromobenzoic acid (97 mg, 0.483 mmol) for (2), and 2-iodobenzoic acid (120 mg, 0.483 mmol) for (3), The resulting solutions were stirred for 15 minutes at room temperature and allowed to stand at the same temperature. X-ray quality crystals were formed on slow evaporation after one week for all compounds, where ethanol:ethylacetate (1:1) was used for crystallization. The melting points are 439–441 K (1), 443–445 K (2) and 451–453 K (3).
6. Refinement
Crystal data, data collection and structure refinement details are summarized in Table 4. For all structures, the hydrogen atoms were located in difference maps and relocated to idealized locations (C—H = 0.93–0.97 Å) and refined as riding with Uiso(H) = 1.2Ueq(C) while the N—H hydrogen atoms were refined isotropically. For 1, in which both the cation and the anion exhibit whole-ion disorder, two equivalent conformations were modeled with occupancies of 0.745 (10)/0.255 (10) and 0.563 (13)/ 0.437 (13) respectively. The water hydrogen atoms were refined isotropically with idealized geometries.
| 1 | 2 | 3 | Crystal data | Chemical formula | C10H14N3O2+·C7H4ClO2− | C10H14N3O2+·C7H4BrO2−·0.5H2O | C10H14N3O2+·C7H4IO2−·0.5H2O | Mr | 363.79 | 417.26 | 928.50 | Crystal system, space group | Triclinic, P | Triclinic, P | Triclinic, P | Temperature (K) | 293 | 293 | 293 | a, b, c (Å) | 6.6073 (5), 8.2708 (5), 16.984 (1) | 7.2570 (5), 9.7772 (6), 14.202 (1) | 7.3949 (6), 9.3440 (8), 14.498 (1) | α, β, γ (°) | 102.385 (6), 91.745 (6), 99.903 (6) | 102.101 (6), 99.534 (6), 110.981 (6) | 104.967 (8), 94.707 (7), 107.430 (8) | V (Å3) | 890.84 (10) | 887.41 (11) | 909.44 (13) | Z | 2 | 2 | 1 | Radiation type | Mo Kα | Mo Kα | Mo Kα | μ (mm−1) | 0.24 | 2.35 | 1.79 | Crystal size (mm) | 0.48 × 0.44 × 0.24 | 0.36 × 0.32 × 0.20 | 0.50 × 0.44 × 0.24 | | Data collection | Diffractometer | Oxford Diffraction Xcalibur CCD | Oxford Diffraction Xcalibur CCD | Oxford Diffraction Xcalibur CCD | Absorption correction | Multi-scan (CrysAlis RED; Oxford Diffraction, 2009) | Multi-scan (CrysAlis RED; Oxford Diffraction, 2009) | Multi-scan (CrysAlis RED; Oxford Diffraction, 2009) | Tmin, Tmax | 0.894, 1.000 | 0.781, 1.000 | 0.697, 1.000 | No. of measured, independent and observed [I > 2σ(I)] reflections | 6637, 3787, 1916 | 6177, 3856, 2478 | 6275, 3904, 2443 | Rint | 0.014 | 0.016 | 0.024 | (sin θ/λ)max (Å−1) | 0.653 | 0.660 | 0.661 | | Refinement | R[F2 > 2σ(F2)], wR(F2), S | 0.065, 0.162, 1.06 | 0.036, 0.084, 0.94 | 0.046, 0.117, 1.02 | No. of reflections | 3787 | 3856 | 3904 | No. of parameters | 357 | 244 | 264 | No. of restraints | 714 | 5 | 13 | H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | Δρmax, Δρmin (e Å−3) | 0.15, −0.15 | 0.51, −0.33 | 0.61, −0.44 | Computer programs: CrysAlis CCD and CrysAlis RED (Oxford Diffraction, 2009), SHELXL2018 (Sheldrick, 2015b), SHELXL2018/3 (Sheldrick, 2015a) and OLEX2 (Dolomanov et al., 2009). | |
Supporting information
For all structures, data collection: CrysAlis CCD (Oxford Diffraction, 2009); cell refinement: CrysAlis RED (Oxford Diffraction, 2009); data reduction: CrysAlis RED (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXL2018 (Sheldrick, 2015b); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015a); molecular graphics: Olex2 1.5 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 1.5 (Dolomanov et al., 2009).
4-(4-Nitrophenyl)piperazin-1-ium 2-chlorobenzoate (1)
top Crystal data top C10H14N3O2+·C7H4ClO2− | Z = 2 |
Mr = 363.79 | F(000) = 380 |
Triclinic, P1 | Dx = 1.356 Mg m−3 |
a = 6.6073 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.2708 (5) Å | Cell parameters from 2365 reflections |
c = 16.984 (1) Å | θ = 2.6–27.6° |
α = 102.385 (6)° | µ = 0.24 mm−1 |
β = 91.745 (6)° | T = 293 K |
γ = 99.903 (6)° | Prism, yellow |
V = 890.84 (10) Å3 | 0.48 × 0.44 × 0.24 mm |
Data collection top Oxford Diffraction Xcalibur CCD diffractometer | 1916 reflections with I > 2σ(I) |
ω scans | Rint = 0.014 |
Absorption correction: multi-scan (CrysalisRed; Oxford Diffraction, 2009) | θmax = 27.7°, θmin = 2.6° |
Tmin = 0.894, Tmax = 1.000 | h = −8→8 |
6637 measured reflections | k = −10→7 |
3787 independent reflections | l = −20→21 |
Refinement top Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.065 | Hydrogen site location: mixed |
wR(F2) = 0.162 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0521P)2 + 0.3137P] where P = (Fo2 + 2Fc2)/3 |
3787 reflections | (Δ/σ)max < 0.001 |
357 parameters | Δρmax = 0.15 e Å−3 |
714 restraints | Δρmin = −0.15 e Å−3 |
Special details top 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
Cl1 | 1.0680 (5) | 0.6989 (5) | 0.5627 (2) | 0.0833 (8) | 0.745 (10) |
O3 | 0.7965 (9) | 1.0649 (9) | 0.6034 (5) | 0.0842 (18) | 0.745 (10) |
O4 | 0.6067 (11) | 0.8100 (10) | 0.5952 (5) | 0.082 (2) | 0.745 (10) |
C11 | 0.9076 (7) | 0.8971 (6) | 0.6843 (2) | 0.0615 (11) | 0.745 (10) |
C12 | 1.0545 (7) | 0.7974 (6) | 0.6616 (3) | 0.0650 (12) | 0.745 (10) |
C13 | 1.1959 (7) | 0.7776 (5) | 0.7195 (3) | 0.0835 (16) | 0.745 (10) |
H13 | 1.294232 | 0.710907 | 0.704298 | 0.100* | 0.745 (10) |
C14 | 1.1905 (8) | 0.8575 (5) | 0.8000 (3) | 0.0943 (18) | 0.745 (10) |
H14 | 1.285124 | 0.844228 | 0.838711 | 0.113* | 0.745 (10) |
C15 | 1.0436 (9) | 0.9572 (6) | 0.8227 (2) | 0.0931 (16) | 0.745 (10) |
H15 | 1.039942 | 1.010634 | 0.876538 | 0.112* | 0.745 (10) |
C16 | 0.9022 (8) | 0.9770 (6) | 0.7648 (3) | 0.0776 (13) | 0.745 (10) |
H16 | 0.803866 | 1.043720 | 0.779953 | 0.093* | 0.745 (10) |
C17 | 0.7612 (19) | 0.9300 (14) | 0.6263 (9) | 0.0666 (17) | 0.745 (10) |
Cl1A | 1.0723 (17) | 0.6949 (14) | 0.5994 (9) | 0.100 (3) | 0.255 (10) |
O3A | 0.741 (3) | 1.065 (3) | 0.6227 (13) | 0.082 (4) | 0.255 (10) |
O4A | 0.654 (3) | 0.785 (3) | 0.5841 (13) | 0.073 (4) | 0.255 (10) |
C11A | 0.877 (2) | 0.906 (2) | 0.7016 (7) | 0.066 (2) | 0.255 (10) |
C12A | 1.030 (2) | 0.8078 (18) | 0.6923 (8) | 0.069 (2) | 0.255 (10) |
C13A | 1.1458 (19) | 0.7951 (16) | 0.7596 (10) | 0.083 (2) | 0.255 (10) |
H13A | 1.247604 | 0.729405 | 0.753378 | 0.099* | 0.255 (10) |
C14A | 1.110 (2) | 0.8807 (17) | 0.8362 (8) | 0.092 (3) | 0.255 (10) |
H14A | 1.187433 | 0.872219 | 0.881231 | 0.111* | 0.255 (10) |
C15A | 0.958 (2) | 0.9790 (17) | 0.8455 (7) | 0.090 (3) | 0.255 (10) |
H15A | 0.933424 | 1.036208 | 0.896755 | 0.108* | 0.255 (10) |
C16A | 0.841 (2) | 0.9916 (19) | 0.7782 (8) | 0.081 (2) | 0.255 (10) |
H16A | 0.739583 | 1.057381 | 0.784426 | 0.097* | 0.255 (10) |
C17A | 0.735 (7) | 0.904 (5) | 0.617 (3) | 0.067 (3) | 0.255 (10) |
O1A | 0.437 (2) | 0.1420 (17) | −0.0678 (8) | 0.143 (4) | 0.437 (13) |
O2A | 0.725 (2) | 0.2969 (18) | −0.0749 (8) | 0.127 (3) | 0.437 (13) |
N3A | 0.575 (2) | 0.2519 (16) | −0.0385 (7) | 0.105 (2) | 0.437 (13) |
C1A | 0.548 (2) | 0.5327 (19) | 0.1991 (6) | 0.071 (2) | 0.437 (13) |
C2A | 0.713 (2) | 0.5730 (16) | 0.1536 (7) | 0.085 (3) | 0.437 (13) |
H2 | 0.820154 | 0.661738 | 0.175667 | 0.102* | 0.437 (13) |
C3A | 0.7186 (17) | 0.4807 (15) | 0.0753 (7) | 0.089 (3) | 0.437 (13) |
H3 | 0.829021 | 0.507621 | 0.044865 | 0.107* | 0.437 (13) |
C4A | 0.5589 (19) | 0.3480 (14) | 0.0424 (5) | 0.086 (2) | 0.437 (13) |
C5A | 0.3939 (18) | 0.3077 (15) | 0.0878 (7) | 0.093 (2) | 0.437 (13) |
H5 | 0.287089 | 0.218996 | 0.065773 | 0.112* | 0.437 (13) |
C6A | 0.389 (2) | 0.4001 (18) | 0.1662 (7) | 0.089 (2) | 0.437 (13) |
H6 | 0.278218 | 0.373111 | 0.196576 | 0.107* | 0.437 (13) |
O1 | 0.5473 (18) | 0.1306 (13) | −0.0808 (7) | 0.144 (3) | 0.563 (13) |
O2 | 0.836 (2) | 0.2893 (15) | −0.0755 (6) | 0.161 (4) | 0.563 (13) |
N3 | 0.675 (2) | 0.2455 (14) | −0.0465 (6) | 0.109 (3) | 0.563 (13) |
C1 | 0.5784 (18) | 0.5063 (14) | 0.1894 (4) | 0.070 (2) | 0.563 (13) |
C2 | 0.7641 (16) | 0.5504 (13) | 0.1562 (5) | 0.089 (3) | 0.563 (13) |
H2A | 0.866018 | 0.635336 | 0.185813 | 0.107* | 0.563 (13) |
C3 | 0.7975 (15) | 0.4676 (12) | 0.0787 (5) | 0.095 (2) | 0.563 (13) |
H3A | 0.921692 | 0.497043 | 0.056517 | 0.114* | 0.563 (13) |
C4 | 0.6452 (15) | 0.3406 (11) | 0.0345 (4) | 0.086 (2) | 0.563 (13) |
C5 | 0.4595 (14) | 0.2966 (11) | 0.0676 (5) | 0.087 (2) | 0.563 (13) |
H5A | 0.357591 | 0.211638 | 0.038029 | 0.105* | 0.563 (13) |
C6 | 0.4261 (15) | 0.3794 (13) | 0.1451 (5) | 0.0822 (19) | 0.563 (13) |
H6A | 0.301914 | 0.349929 | 0.167326 | 0.099* | 0.563 (13) |
N1 | 0.5532 (4) | 0.5957 (3) | 0.27470 (16) | 0.0768 (8) | |
N2 | 0.5064 (4) | 0.7717 (3) | 0.43581 (17) | 0.0675 (7) | |
H2B | 0.417 (4) | 0.834 (3) | 0.4252 (17) | 0.081* | |
H2C | 0.530 (5) | 0.795 (4) | 0.4892 (11) | 0.081* | |
C7 | 0.3683 (5) | 0.5526 (4) | 0.3162 (2) | 0.0921 (11) | |
H7A | 0.313237 | 0.433276 | 0.297924 | 0.110* | |
H7B | 0.264769 | 0.614262 | 0.302794 | 0.110* | |
C8 | 0.4136 (5) | 0.5935 (3) | 0.4054 (2) | 0.0858 (10) | |
H8A | 0.286923 | 0.568239 | 0.431384 | 0.103* | |
H8B | 0.506956 | 0.523703 | 0.419185 | 0.103* | |
C9 | 0.6955 (5) | 0.8126 (4) | 0.3947 (2) | 0.0899 (11) | |
H9A | 0.796744 | 0.749561 | 0.408843 | 0.108* | |
H9B | 0.752465 | 0.931538 | 0.412976 | 0.108* | |
C10 | 0.6532 (6) | 0.7714 (4) | 0.3053 (2) | 0.0929 (11) | |
H10A | 0.565368 | 0.844595 | 0.290746 | 0.111* | |
H10B | 0.781839 | 0.792344 | 0.279945 | 0.111* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Cl1 | 0.0608 (8) | 0.0760 (9) | 0.0980 (18) | 0.0096 (6) | 0.0027 (12) | −0.0109 (13) |
O3 | 0.056 (3) | 0.069 (2) | 0.139 (4) | 0.019 (2) | 0.014 (3) | 0.041 (3) |
O4 | 0.048 (3) | 0.077 (3) | 0.115 (4) | 0.000 (2) | 0.000 (3) | 0.018 (2) |
C11 | 0.053 (2) | 0.0330 (18) | 0.092 (3) | −0.0025 (16) | 0.002 (2) | 0.0088 (19) |
C12 | 0.058 (2) | 0.0400 (19) | 0.088 (3) | 0.0002 (16) | −0.009 (2) | 0.003 (2) |
C13 | 0.087 (3) | 0.050 (2) | 0.108 (4) | 0.015 (2) | −0.016 (3) | 0.007 (3) |
C14 | 0.110 (4) | 0.069 (3) | 0.096 (4) | 0.012 (3) | −0.029 (3) | 0.009 (3) |
C15 | 0.107 (4) | 0.064 (3) | 0.097 (3) | 0.002 (3) | −0.004 (3) | 0.004 (2) |
C16 | 0.077 (3) | 0.049 (2) | 0.101 (3) | 0.007 (2) | 0.009 (2) | 0.009 (2) |
C17 | 0.047 (4) | 0.048 (4) | 0.101 (4) | 0.007 (3) | 0.010 (3) | 0.009 (3) |
Cl1A | 0.071 (3) | 0.079 (3) | 0.140 (6) | 0.017 (2) | 0.020 (5) | −0.004 (5) |
O3A | 0.064 (8) | 0.063 (5) | 0.128 (9) | 0.024 (6) | 0.017 (7) | 0.030 (6) |
O4A | 0.048 (8) | 0.062 (6) | 0.104 (7) | 0.005 (6) | 0.004 (6) | 0.014 (5) |
C11A | 0.057 (4) | 0.038 (4) | 0.099 (4) | 0.005 (3) | 0.001 (4) | 0.009 (4) |
C12A | 0.063 (4) | 0.039 (4) | 0.098 (4) | 0.004 (3) | −0.007 (4) | 0.009 (4) |
C13A | 0.085 (4) | 0.054 (4) | 0.103 (5) | 0.011 (4) | −0.015 (4) | 0.010 (4) |
C14A | 0.096 (5) | 0.068 (5) | 0.105 (5) | 0.009 (5) | −0.010 (5) | 0.009 (5) |
C15A | 0.089 (6) | 0.066 (5) | 0.106 (5) | 0.001 (4) | 0.000 (5) | 0.011 (5) |
C16A | 0.080 (5) | 0.054 (4) | 0.101 (4) | 0.001 (4) | 0.002 (4) | 0.008 (4) |
C17A | 0.051 (5) | 0.047 (5) | 0.102 (5) | 0.011 (4) | 0.006 (4) | 0.015 (5) |
O1A | 0.145 (8) | 0.134 (6) | 0.107 (6) | −0.007 (6) | −0.031 (6) | −0.035 (5) |
O2A | 0.135 (7) | 0.122 (6) | 0.103 (6) | 0.019 (6) | 0.005 (6) | −0.019 (5) |
N3A | 0.117 (5) | 0.090 (4) | 0.089 (4) | 0.007 (5) | −0.014 (4) | −0.007 (3) |
C1A | 0.090 (5) | 0.033 (4) | 0.080 (4) | 0.002 (4) | −0.014 (3) | −0.001 (3) |
C2A | 0.095 (5) | 0.053 (4) | 0.091 (4) | −0.005 (4) | −0.014 (4) | −0.001 (3) |
C3A | 0.094 (5) | 0.072 (4) | 0.087 (4) | −0.001 (4) | −0.010 (4) | 0.004 (3) |
C4A | 0.104 (5) | 0.068 (3) | 0.074 (3) | 0.001 (4) | −0.018 (4) | −0.001 (3) |
C5A | 0.112 (5) | 0.071 (4) | 0.077 (5) | −0.009 (4) | −0.017 (4) | 0.000 (4) |
C6A | 0.107 (5) | 0.063 (4) | 0.079 (5) | −0.006 (4) | −0.017 (4) | −0.001 (4) |
O1 | 0.146 (7) | 0.123 (4) | 0.116 (5) | −0.016 (5) | −0.006 (5) | −0.043 (4) |
O2 | 0.144 (7) | 0.150 (5) | 0.140 (5) | −0.011 (6) | 0.036 (5) | −0.051 (4) |
N3 | 0.125 (6) | 0.090 (4) | 0.088 (4) | −0.008 (5) | −0.003 (4) | −0.008 (3) |
C1 | 0.090 (4) | 0.033 (3) | 0.082 (3) | 0.007 (3) | −0.017 (3) | 0.006 (3) |
C2 | 0.099 (5) | 0.059 (4) | 0.092 (3) | −0.004 (4) | −0.003 (3) | −0.004 (3) |
C3 | 0.103 (5) | 0.074 (3) | 0.090 (3) | −0.005 (4) | −0.005 (4) | −0.002 (3) |
C4 | 0.105 (5) | 0.068 (3) | 0.076 (3) | 0.004 (4) | −0.012 (3) | 0.004 (2) |
C5 | 0.108 (5) | 0.068 (3) | 0.069 (4) | −0.010 (3) | −0.015 (3) | 0.002 (3) |
C6 | 0.101 (4) | 0.058 (3) | 0.070 (4) | −0.011 (3) | −0.012 (3) | −0.001 (3) |
N1 | 0.0767 (17) | 0.0420 (12) | 0.099 (2) | −0.0114 (11) | −0.0042 (15) | 0.0076 (13) |
N2 | 0.0543 (15) | 0.0425 (12) | 0.103 (2) | 0.0079 (10) | 0.0018 (15) | 0.0101 (14) |
C7 | 0.079 (2) | 0.0508 (17) | 0.127 (3) | −0.0174 (16) | −0.006 (2) | 0.0043 (19) |
C8 | 0.086 (2) | 0.0425 (16) | 0.121 (3) | −0.0017 (15) | 0.014 (2) | 0.0099 (17) |
C9 | 0.061 (2) | 0.074 (2) | 0.111 (3) | −0.0155 (16) | 0.0106 (19) | −0.0102 (19) |
C10 | 0.096 (3) | 0.0543 (18) | 0.105 (3) | −0.0236 (17) | 0.011 (2) | −0.0043 (18) |
Geometric parameters (Å, º) top Cl1—C12 | 1.715 (3) | C3A—C4A | 1.3900 |
Cl1—H8Ai | 2.953 (5) | C3A—H3 | 0.9300 |
O3—C17 | 1.247 (14) | C4A—C5A | 1.3900 |
O4—C17 | 1.304 (10) | C5A—C6A | 1.3900 |
C11—C12 | 1.3900 | C5A—H5 | 0.9300 |
C11—C16 | 1.3900 | C6A—H6 | 0.9300 |
C11—C17 | 1.458 (15) | O1—N3 | 1.189 (9) |
C12—C13 | 1.3900 | O2—N3 | 1.216 (10) |
C13—C14 | 1.3900 | N3—C4 | 1.468 (8) |
C13—H13 | 0.9300 | C1—C2 | 1.3900 |
C14—C15 | 1.3900 | C1—C6 | 1.3900 |
C14—H14 | 0.9300 | C1—N1 | 1.507 (7) |
C15—C16 | 1.3900 | C2—C3 | 1.3900 |
C15—H15 | 0.9300 | C2—H2A | 0.9300 |
C16—H16 | 0.9300 | C3—C4 | 1.3900 |
Cl1A—C12A | 1.711 (4) | C3—H3A | 0.9300 |
O3A—C17A | 1.31 (4) | C4—C5 | 1.3900 |
O4A—C17A | 1.06 (4) | C5—C6 | 1.3900 |
C11A—C12A | 1.3900 | C5—H5A | 0.9300 |
C11A—C16A | 1.3900 | C6—H6A | 0.9300 |
C11A—C17A | 1.68 (4) | N1—C7 | 1.459 (4) |
C12A—C13A | 1.3900 | N1—C10 | 1.464 (3) |
C13A—C14A | 1.3900 | N2—C8 | 1.469 (3) |
C13A—H13A | 0.9300 | N2—C9 | 1.474 (4) |
C14A—C15A | 1.3900 | N2—H2B | 0.882 (17) |
C14A—H14A | 0.9300 | N2—H2C | 0.889 (17) |
C15A—C16A | 1.3900 | C7—C8 | 1.488 (5) |
C15A—H15A | 0.9300 | C7—H7A | 0.9700 |
C16A—H16A | 0.9300 | C7—H7B | 0.9700 |
O1A—N3A | 1.182 (10) | C8—H8A | 0.9700 |
O2A—N3A | 1.235 (12) | C8—H8B | 0.9700 |
N3A—C4A | 1.448 (9) | C9—C10 | 1.490 (5) |
C1A—N1 | 1.275 (9) | C9—H9A | 0.9700 |
C1A—C2A | 1.3900 | C9—H9B | 0.9700 |
C1A—C6A | 1.3900 | C10—H10A | 0.9700 |
C2A—C3A | 1.3900 | C10—H10B | 0.9700 |
C2A—H2 | 0.9300 | | |
| | | |
C12—Cl1—H8Ai | 92.6 (2) | C4A—C5A—H5 | 120.0 |
C12—C11—C16 | 120.0 | C5A—C6A—C1A | 120.0 |
C12—C11—C17 | 122.9 (6) | C5A—C6A—H6 | 120.0 |
C16—C11—C17 | 117.0 (6) | C1A—C6A—H6 | 120.0 |
C11—C12—C13 | 120.0 | O1—N3—O2 | 122.6 (9) |
C11—C12—Cl1 | 121.34 (18) | O1—N3—C4 | 120.6 (8) |
C13—C12—Cl1 | 118.66 (18) | O2—N3—C4 | 116.9 (7) |
C14—C13—C12 | 120.0 | C2—C1—C6 | 120.0 |
C14—C13—H13 | 120.0 | C2—C1—N1 | 117.8 (6) |
C12—C13—H13 | 120.0 | C6—C1—N1 | 122.1 (6) |
C13—C14—C15 | 120.0 | C1—C2—C3 | 120.0 |
C13—C14—H14 | 120.0 | C1—C2—H2A | 120.0 |
C15—C14—H14 | 120.0 | C3—C2—H2A | 120.0 |
C14—C15—C16 | 120.0 | C4—C3—C2 | 120.0 |
C14—C15—H15 | 120.0 | C4—C3—H3A | 120.0 |
C16—C15—H15 | 120.0 | C2—C3—H3A | 120.0 |
C15—C16—C11 | 120.0 | C3—C4—C5 | 120.0 |
C15—C16—H16 | 120.0 | C3—C4—N3 | 122.1 (5) |
C11—C16—H16 | 120.0 | C5—C4—N3 | 117.9 (5) |
O3—C17—O4 | 122.2 (12) | C4—C5—C6 | 120.0 |
O3—C17—C11 | 119.3 (7) | C4—C5—H5A | 120.0 |
O4—C17—C11 | 118.2 (10) | C6—C5—H5A | 120.0 |
C12A—C11A—C16A | 120.0 | C5—C6—C1 | 120.0 |
C12A—C11A—C17A | 116.6 (17) | C5—C6—H6A | 120.0 |
C16A—C11A—C17A | 123.3 (17) | C1—C6—H6A | 120.0 |
C11A—C12A—C13A | 120.0 | C1A—N1—C7 | 117.5 (7) |
C11A—C12A—Cl1A | 121.3 (4) | C1A—N1—C10 | 118.6 (7) |
C13A—C12A—Cl1A | 118.7 (4) | C7—N1—C10 | 111.7 (3) |
C14A—C13A—C12A | 120.0 | C7—N1—C1 | 121.9 (5) |
C14A—C13A—H13A | 120.0 | C10—N1—C1 | 120.3 (5) |
C12A—C13A—H13A | 120.0 | C8—N2—C9 | 109.7 (2) |
C13A—C14A—C15A | 120.0 | C8—N2—H2B | 108 (2) |
C13A—C14A—H14A | 120.0 | C9—N2—H2B | 109.3 (19) |
C15A—C14A—H14A | 120.0 | C8—N2—H2C | 111 (2) |
C16A—C15A—C14A | 120.0 | C9—N2—H2C | 112 (2) |
C16A—C15A—H15A | 120.0 | H2B—N2—H2C | 107 (3) |
C14A—C15A—H15A | 120.0 | N1—C7—C8 | 111.2 (3) |
C15A—C16A—C11A | 120.0 | N1—C7—H7A | 109.4 |
C15A—C16A—H16A | 120.0 | C8—C7—H7A | 109.4 |
C11A—C16A—H16A | 120.0 | N1—C7—H7B | 109.4 |
O4A—C17A—O3A | 140 (4) | C8—C7—H7B | 109.4 |
O4A—C17A—C11A | 118 (4) | H7A—C7—H7B | 108.0 |
O3A—C17A—C11A | 101 (2) | N2—C8—C7 | 111.6 (3) |
O1A—N3A—O2A | 123.5 (11) | N2—C8—H8A | 109.3 |
O1A—N3A—C4A | 118.5 (10) | C7—C8—H8A | 109.3 |
O2A—N3A—C4A | 117.8 (10) | N2—C8—H8B | 109.3 |
N1—C1A—C2A | 121.6 (9) | C7—C8—H8B | 109.3 |
N1—C1A—C6A | 117.4 (9) | H8A—C8—H8B | 108.0 |
C2A—C1A—C6A | 120.0 | N2—C9—C10 | 111.3 (3) |
C1A—C2A—C3A | 120.0 | N2—C9—H9A | 109.4 |
C1A—C2A—H2 | 120.0 | C10—C9—H9A | 109.4 |
C3A—C2A—H2 | 120.0 | N2—C9—H9B | 109.4 |
C4A—C3A—C2A | 120.0 | C10—C9—H9B | 109.4 |
C4A—C3A—H3 | 120.0 | H9A—C9—H9B | 108.0 |
C2A—C3A—H3 | 120.0 | N1—C10—C9 | 111.9 (3) |
C3A—C4A—C5A | 120.0 | N1—C10—H10A | 109.2 |
C3A—C4A—N3A | 118.0 (6) | C9—C10—H10A | 109.2 |
C5A—C4A—N3A | 122.0 (6) | N1—C10—H10B | 109.2 |
C6A—C5A—C4A | 120.0 | C9—C10—H10B | 109.2 |
C6A—C5A—H5 | 120.0 | H10A—C10—H10B | 107.9 |
| | | |
C16—C11—C12—C13 | 0.0 | O1A—N3A—C4A—C5A | 4.2 (16) |
C17—C11—C12—C13 | 177.0 (7) | O2A—N3A—C4A—C5A | 179.5 (10) |
C16—C11—C12—Cl1 | −179.2 (4) | C3A—C4A—C5A—C6A | 0.0 |
C17—C11—C12—Cl1 | −2.3 (6) | N3A—C4A—C5A—C6A | 177.9 (10) |
H8Ai—Cl1—C12—C11 | −77.7 | C4A—C5A—C6A—C1A | 0.0 |
H8Ai—Cl1—C12—C13 | 103.1 | N1—C1A—C6A—C5A | −169.0 (13) |
C11—C12—C13—C14 | 0.0 | C2A—C1A—C6A—C5A | 0.0 |
Cl1—C12—C13—C14 | 179.2 (4) | C6—C1—C2—C3 | 0.0 |
C12—C13—C14—C15 | 0.0 | N1—C1—C2—C3 | 177.8 (9) |
C13—C14—C15—C16 | 0.0 | C1—C2—C3—C4 | 0.0 |
C14—C15—C16—C11 | 0.0 | C2—C3—C4—C5 | 0.0 |
C12—C11—C16—C15 | 0.0 | C2—C3—C4—N3 | −177.9 (8) |
C17—C11—C16—C15 | −177.1 (6) | O1—N3—C4—C3 | 175.2 (11) |
C12—C11—C17—O3 | −99.0 (12) | O2—N3—C4—C3 | −4.2 (14) |
C16—C11—C17—O3 | 78.0 (14) | O1—N3—C4—C5 | −2.8 (15) |
C12—C11—C17—O4 | 75.1 (13) | O2—N3—C4—C5 | 177.8 (10) |
C16—C11—C17—O4 | −107.8 (11) | C3—C4—C5—C6 | 0.0 |
C16A—C11A—C12A—C13A | 0.0 | N3—C4—C5—C6 | 178.0 (8) |
C17A—C11A—C12A—C13A | −176.2 (19) | C4—C5—C6—C1 | 0.0 |
C16A—C11A—C12A—Cl1A | 177.7 (12) | C2—C1—C6—C5 | 0.0 |
C17A—C11A—C12A—Cl1A | 1.5 (19) | N1—C1—C6—C5 | −177.7 (9) |
C11A—C12A—C13A—C14A | 0.0 | C2A—C1A—N1—C7 | 176.8 (6) |
Cl1A—C12A—C13A—C14A | −177.7 (12) | C6A—C1A—N1—C7 | −14.3 (11) |
C12A—C13A—C14A—C15A | 0.0 | C2A—C1A—N1—C10 | 37.6 (12) |
C13A—C14A—C15A—C16A | 0.0 | C6A—C1A—N1—C10 | −153.6 (5) |
C14A—C15A—C16A—C11A | 0.0 | C2—C1—N1—C7 | −176.9 (4) |
C12A—C11A—C16A—C15A | 0.0 | C6—C1—N1—C7 | 0.9 (9) |
C17A—C11A—C16A—C15A | 176 (2) | C2—C1—N1—C10 | 32.7 (8) |
C12A—C11A—C17A—O4A | 57 (5) | C6—C1—N1—C10 | −149.5 (5) |
C16A—C11A—C17A—O4A | −119 (4) | C1A—N1—C7—C8 | 164.1 (9) |
C12A—C11A—C17A—O3A | −132 (2) | C10—N1—C7—C8 | −54.0 (4) |
C16A—C11A—C17A—O3A | 52 (3) | C1—N1—C7—C8 | 153.4 (6) |
N1—C1A—C2A—C3A | 168.6 (14) | C9—N2—C8—C7 | −57.1 (4) |
C6A—C1A—C2A—C3A | 0.0 | N1—C7—C8—N2 | 56.4 (4) |
C1A—C2A—C3A—C4A | 0.0 | C8—N2—C9—C10 | 56.2 (4) |
C2A—C3A—C4A—C5A | 0.0 | C1A—N1—C10—C9 | −164.9 (9) |
C2A—C3A—C4A—N3A | −178.0 (10) | C7—N1—C10—C9 | 53.6 (4) |
O1A—N3A—C4A—C3A | −177.9 (12) | C1—N1—C10—C9 | −153.2 (6) |
O2A—N3A—C4A—C3A | −2.6 (14) | N2—C9—C10—N1 | −55.0 (4) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Hydrogen-bond geometry (Å, º) top D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3A···O2ii | 0.93 | 2.13 | 2.880 (15) | 137 |
N2—H2B···O3iii | 0.88 (2) | 1.86 (2) | 2.740 (6) | 172 (3) |
N2—H2B···O3Aiii | 0.88 (2) | 1.73 (2) | 2.590 (13) | 164 (3) |
N2—H2C···O4 | 0.89 (2) | 1.83 (2) | 2.705 (8) | 169 (3) |
N2—H2C···O4A | 0.89 (2) | 1.81 (3) | 2.644 (19) | 156 (3) |
C8—H8A···Cl1iv | 0.97 | 2.82 | 3.629 (5) | 142 |
C8—H8A···Cl1i | 0.97 | 2.95 | 3.780 (5) | 144 |
C8—H8A···Cl1Ai | 0.97 | 2.88 | 3.643 (12) | 136 |
C8—H8B···O4Ai | 0.97 | 2.58 | 3.13 (2) | 116 |
C10—H10A···O3Aiii | 0.97 | 2.65 | 3.285 (19) | 123 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+2, −y+1, −z; (iii) −x+1, −y+2, −z+1; (iv) x−1, y, z. |
4-(4-Nitrophenyl)piperazin-1-ium 2-bromobenzoate hemihydrate (2)
top Crystal data top C10H14N3O2+·C7H4BrO2−·0.5H2O | Z = 2 |
Mr = 417.26 | F(000) = 426 |
Triclinic, P1 | Dx = 1.562 Mg m−3 |
a = 7.2570 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.7772 (6) Å | Cell parameters from 2832 reflections |
c = 14.202 (1) Å | θ = 3.0–27.9° |
α = 102.101 (6)° | µ = 2.35 mm−1 |
β = 99.534 (6)° | T = 293 K |
γ = 110.981 (6)° | Prism, brown |
V = 887.41 (11) Å3 | 0.36 × 0.32 × 0.20 mm |
Data collection top Oxford Diffraction Xcalibur CCD diffractometer | 2478 reflections with I > 2σ(I) |
ω scans | Rint = 0.016 |
Absorption correction: multi-scan (CrysalisRed; Oxford Diffraction, 2009) | θmax = 28.0°, θmin = 3.0° |
Tmin = 0.781, Tmax = 1.000 | h = −9→9 |
6177 measured reflections | k = −12→12 |
3856 independent reflections | l = −11→18 |
Refinement top Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.036 | Hydrogen site location: mixed |
wR(F2) = 0.084 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0444P)2] where P = (Fo2 + 2Fc2)/3 |
3856 reflections | (Δ/σ)max < 0.001 |
244 parameters | Δρmax = 0.51 e Å−3 |
5 restraints | Δρmin = −0.33 e Å−3 |
Special details top 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
O1 | 0.4472 (3) | 0.9088 (2) | 0.57716 (16) | 0.0866 (7) | |
O2 | 0.1466 (4) | 0.7360 (3) | 0.53813 (19) | 0.0965 (8) | |
N1 | 0.5490 (3) | 0.3809 (2) | 0.27923 (14) | 0.0452 (5) | |
N2 | 0.6259 (3) | 0.1873 (2) | 0.12301 (15) | 0.0462 (5) | |
H2A | 0.686 (3) | 0.132 (3) | 0.1015 (18) | 0.055* | |
H2B | 0.556 (3) | 0.198 (3) | 0.0700 (14) | 0.055* | |
N3 | 0.3218 (4) | 0.7818 (3) | 0.53126 (16) | 0.0593 (6) | |
C1 | 0.3797 (4) | 0.6788 (3) | 0.46525 (17) | 0.0447 (6) | |
C2 | 0.2487 (4) | 0.5276 (3) | 0.4245 (2) | 0.0540 (7) | |
H2 | 0.123215 | 0.491207 | 0.439437 | 0.065* | |
C3 | 0.3015 (4) | 0.4304 (3) | 0.36200 (19) | 0.0518 (6) | |
H3 | 0.209824 | 0.328530 | 0.333702 | 0.062* | |
C4 | 0.4910 (3) | 0.4806 (2) | 0.33958 (16) | 0.0399 (5) | |
C5 | 0.6204 (4) | 0.6357 (3) | 0.38273 (19) | 0.0493 (6) | |
H5 | 0.746350 | 0.673689 | 0.368381 | 0.059* | |
C6 | 0.5675 (4) | 0.7326 (3) | 0.44508 (18) | 0.0505 (6) | |
H6 | 0.657730 | 0.834750 | 0.473932 | 0.061* | |
C7 | 0.3935 (4) | 0.2306 (3) | 0.2201 (2) | 0.0611 (8) | |
H7A | 0.307731 | 0.241586 | 0.164666 | 0.073* | |
H7B | 0.307496 | 0.187484 | 0.261102 | 0.073* | |
C8 | 0.4847 (5) | 0.1232 (3) | 0.1806 (2) | 0.0676 (8) | |
H8A | 0.557431 | 0.102503 | 0.235884 | 0.081* | |
H8B | 0.376210 | 0.026977 | 0.138441 | 0.081* | |
C9 | 0.7856 (4) | 0.3349 (3) | 0.1852 (2) | 0.0781 (10) | |
H9A | 0.874756 | 0.378980 | 0.145729 | 0.094* | |
H9B | 0.867453 | 0.319121 | 0.239824 | 0.094* | |
C10 | 0.6991 (5) | 0.4438 (3) | 0.2265 (3) | 0.0808 (10) | |
H10A | 0.809491 | 0.536313 | 0.271886 | 0.097* | |
H10B | 0.635383 | 0.471694 | 0.172320 | 0.097* | |
Br1 | 0.92610 (5) | −0.00832 (3) | 0.31967 (2) | 0.06679 (14) | |
O3 | 0.8488 (3) | 0.0263 (3) | 0.09269 (16) | 0.0782 (6) | |
O4 | 0.6156 (3) | −0.2125 (3) | 0.03302 (17) | 0.0860 (7) | |
C11 | 0.9379 (3) | −0.1685 (3) | 0.12893 (18) | 0.0438 (6) | |
C12 | 1.0135 (4) | −0.1304 (3) | 0.23087 (19) | 0.0469 (6) | |
C13 | 1.1536 (4) | −0.1827 (3) | 0.2715 (2) | 0.0609 (7) | |
H13 | 1.201561 | −0.157757 | 0.340436 | 0.073* | |
C14 | 1.2204 (4) | −0.2701 (3) | 0.2107 (3) | 0.0671 (8) | |
H14 | 1.316352 | −0.303199 | 0.238116 | 0.080* | |
C15 | 1.1471 (4) | −0.3102 (3) | 0.1086 (2) | 0.0630 (8) | |
H15 | 1.193664 | −0.369875 | 0.067067 | 0.076* | |
C16 | 1.0048 (4) | −0.2615 (3) | 0.0683 (2) | 0.0545 (7) | |
H16 | 0.952495 | −0.291267 | −0.000611 | 0.065* | |
C17 | 0.7895 (5) | −0.1121 (4) | 0.0817 (2) | 0.0564 (7) | |
O1W | 0.5508 (9) | −0.5202 (7) | −0.0662 (6) | 0.138 (2) | 0.5 |
H1W1 | 0.435882 | −0.430124 | −0.060307 | 0.207* | 0.5 |
H1W2 | 0.458306 | −0.629327 | −0.042348 | 0.207* | 0.5 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0975 (16) | 0.0587 (13) | 0.0842 (15) | 0.0191 (13) | 0.0368 (13) | −0.0055 (11) |
O2 | 0.0777 (15) | 0.0870 (16) | 0.1195 (19) | 0.0333 (13) | 0.0502 (15) | 0.0009 (14) |
N1 | 0.0415 (11) | 0.0324 (10) | 0.0568 (12) | 0.0109 (9) | 0.0146 (10) | 0.0093 (9) |
N2 | 0.0471 (13) | 0.0423 (12) | 0.0490 (12) | 0.0236 (10) | 0.0069 (10) | 0.0080 (10) |
N3 | 0.0699 (17) | 0.0574 (15) | 0.0511 (13) | 0.0261 (14) | 0.0222 (13) | 0.0119 (11) |
C1 | 0.0523 (15) | 0.0453 (14) | 0.0398 (13) | 0.0228 (13) | 0.0121 (12) | 0.0143 (11) |
C2 | 0.0445 (14) | 0.0516 (15) | 0.0666 (17) | 0.0165 (13) | 0.0229 (13) | 0.0177 (13) |
C3 | 0.0435 (15) | 0.0382 (13) | 0.0670 (17) | 0.0108 (12) | 0.0159 (13) | 0.0112 (12) |
C4 | 0.0384 (13) | 0.0357 (12) | 0.0452 (13) | 0.0148 (11) | 0.0067 (11) | 0.0149 (10) |
C5 | 0.0413 (14) | 0.0372 (13) | 0.0630 (16) | 0.0100 (11) | 0.0163 (12) | 0.0105 (12) |
C6 | 0.0506 (15) | 0.0378 (13) | 0.0524 (15) | 0.0121 (12) | 0.0083 (13) | 0.0066 (11) |
C7 | 0.0520 (16) | 0.0403 (14) | 0.0762 (18) | 0.0041 (13) | 0.0293 (15) | 0.0039 (13) |
C8 | 0.088 (2) | 0.0366 (14) | 0.0735 (18) | 0.0160 (15) | 0.0382 (17) | 0.0111 (13) |
C9 | 0.0509 (17) | 0.0548 (17) | 0.101 (2) | 0.0095 (14) | 0.0262 (17) | −0.0155 (16) |
C10 | 0.075 (2) | 0.0370 (15) | 0.125 (3) | 0.0103 (14) | 0.061 (2) | 0.0078 (16) |
Br1 | 0.0855 (2) | 0.05620 (19) | 0.05928 (19) | 0.02352 (16) | 0.03290 (16) | 0.01687 (13) |
O3 | 0.1037 (16) | 0.0759 (15) | 0.0967 (15) | 0.0672 (14) | 0.0419 (13) | 0.0421 (12) |
O4 | 0.0686 (14) | 0.1081 (18) | 0.0862 (15) | 0.0493 (15) | −0.0021 (13) | 0.0322 (14) |
C11 | 0.0435 (13) | 0.0383 (13) | 0.0501 (14) | 0.0172 (11) | 0.0089 (12) | 0.0154 (11) |
C12 | 0.0479 (14) | 0.0379 (13) | 0.0538 (15) | 0.0126 (12) | 0.0135 (12) | 0.0194 (11) |
C13 | 0.0569 (17) | 0.0535 (16) | 0.0625 (17) | 0.0141 (15) | 0.0009 (15) | 0.0236 (14) |
C14 | 0.0530 (17) | 0.0570 (18) | 0.094 (2) | 0.0271 (15) | 0.0038 (17) | 0.0318 (17) |
C15 | 0.0583 (17) | 0.0508 (16) | 0.088 (2) | 0.0320 (15) | 0.0202 (16) | 0.0180 (15) |
C16 | 0.0564 (16) | 0.0532 (16) | 0.0554 (15) | 0.0288 (14) | 0.0108 (13) | 0.0107 (13) |
C17 | 0.067 (2) | 0.076 (2) | 0.0507 (15) | 0.0494 (18) | 0.0227 (15) | 0.0258 (15) |
O1W | 0.118 (4) | 0.096 (4) | 0.197 (7) | 0.036 (4) | 0.044 (4) | 0.046 (4) |
Geometric parameters (Å, º) top O1—N3 | 1.204 (3) | C8—H8A | 0.9700 |
O2—N3 | 1.216 (3) | C8—H8B | 0.9700 |
N1—C4 | 1.387 (3) | C9—C10 | 1.487 (4) |
N1—C10 | 1.452 (3) | C9—H9A | 0.9700 |
N1—C7 | 1.456 (3) | C9—H9B | 0.9700 |
N2—C9 | 1.461 (3) | C10—H10A | 0.9700 |
N2—C8 | 1.465 (3) | C10—H10B | 0.9700 |
N2—H2A | 0.846 (16) | Br1—C12 | 1.896 (2) |
N2—H2B | 0.881 (16) | O3—C17 | 1.230 (3) |
N3—C1 | 1.452 (3) | O4—C17 | 1.254 (3) |
C1—C2 | 1.370 (3) | C11—C12 | 1.378 (3) |
C1—C6 | 1.376 (3) | C11—C16 | 1.389 (3) |
C2—C3 | 1.363 (3) | C11—C17 | 1.502 (4) |
C2—H2 | 0.9300 | C12—C13 | 1.389 (4) |
C3—C4 | 1.400 (3) | C13—C14 | 1.355 (4) |
C3—H3 | 0.9300 | C13—H13 | 0.9300 |
C4—C5 | 1.399 (3) | C14—C15 | 1.377 (4) |
C5—C6 | 1.361 (3) | C14—H14 | 0.9300 |
C5—H5 | 0.9300 | C15—C16 | 1.375 (4) |
C6—H6 | 0.9300 | C15—H15 | 0.9300 |
C7—C8 | 1.492 (3) | C16—H16 | 0.9300 |
C7—H7A | 0.9700 | O1W—H1W1 | 1.4134 |
C7—H7B | 0.9700 | O1W—H1W2 | 1.1905 |
| | | |
C4—N1—C10 | 118.22 (18) | C7—C8—H8A | 109.4 |
C4—N1—C7 | 118.65 (17) | N2—C8—H8B | 109.4 |
C10—N1—C7 | 112.0 (2) | C7—C8—H8B | 109.4 |
C9—N2—C8 | 109.6 (2) | H8A—C8—H8B | 108.0 |
C9—N2—H2A | 106.7 (16) | N2—C9—C10 | 112.0 (2) |
C8—N2—H2A | 114.7 (17) | N2—C9—H9A | 109.2 |
C9—N2—H2B | 110.9 (17) | C10—C9—H9A | 109.2 |
C8—N2—H2B | 108.5 (16) | N2—C9—H9B | 109.2 |
H2A—N2—H2B | 106 (2) | C10—C9—H9B | 109.2 |
O1—N3—O2 | 122.2 (2) | H9A—C9—H9B | 107.9 |
O1—N3—C1 | 119.5 (2) | N1—C10—C9 | 112.8 (2) |
O2—N3—C1 | 118.3 (2) | N1—C10—H10A | 109.0 |
C2—C1—C6 | 120.1 (2) | C9—C10—H10A | 109.0 |
C2—C1—N3 | 119.9 (2) | N1—C10—H10B | 109.0 |
C6—C1—N3 | 120.0 (2) | C9—C10—H10B | 109.0 |
C3—C2—C1 | 120.2 (2) | H10A—C10—H10B | 107.8 |
C3—C2—H2 | 119.9 | C12—C11—C16 | 118.0 (2) |
C1—C2—H2 | 119.9 | C12—C11—C17 | 122.6 (2) |
C2—C3—C4 | 121.4 (2) | C16—C11—C17 | 119.3 (2) |
C2—C3—H3 | 119.3 | C11—C12—C13 | 120.8 (2) |
C4—C3—H3 | 119.3 | C11—C12—Br1 | 121.09 (19) |
N1—C4—C5 | 121.73 (19) | C13—C12—Br1 | 118.1 (2) |
N1—C4—C3 | 121.6 (2) | C14—C13—C12 | 120.0 (3) |
C5—C4—C3 | 116.6 (2) | C14—C13—H13 | 120.0 |
C6—C5—C4 | 121.9 (2) | C12—C13—H13 | 120.0 |
C6—C5—H5 | 119.0 | C13—C14—C15 | 120.4 (3) |
C4—C5—H5 | 119.0 | C13—C14—H14 | 119.8 |
C5—C6—C1 | 119.7 (2) | C15—C14—H14 | 119.8 |
C5—C6—H6 | 120.2 | C16—C15—C14 | 119.7 (3) |
C1—C6—H6 | 120.2 | C16—C15—H15 | 120.2 |
N1—C7—C8 | 112.2 (2) | C14—C15—H15 | 120.2 |
N1—C7—H7A | 109.2 | C15—C16—C11 | 121.0 (3) |
C8—C7—H7A | 109.2 | C15—C16—H16 | 119.5 |
N1—C7—H7B | 109.2 | C11—C16—H16 | 119.5 |
C8—C7—H7B | 109.2 | O3—C17—O4 | 126.0 (3) |
H7A—C7—H7B | 107.9 | O3—C17—C11 | 117.9 (3) |
N2—C8—C7 | 111.3 (2) | O4—C17—C11 | 116.2 (3) |
N2—C8—H8A | 109.4 | H1W1—O1W—H1W2 | 105.4 |
| | | |
O1—N3—C1—C2 | 170.2 (3) | N1—C7—C8—N2 | −55.5 (3) |
O2—N3—C1—C2 | −9.8 (4) | C8—N2—C9—C10 | −56.2 (3) |
O1—N3—C1—C6 | −8.7 (4) | C4—N1—C10—C9 | 165.9 (2) |
O2—N3—C1—C6 | 171.2 (3) | C7—N1—C10—C9 | −50.6 (4) |
C6—C1—C2—C3 | −1.4 (4) | N2—C9—C10—N1 | 53.6 (4) |
N3—C1—C2—C3 | 179.7 (2) | C16—C11—C12—C13 | 0.5 (4) |
C1—C2—C3—C4 | 1.4 (4) | C17—C11—C12—C13 | −178.8 (2) |
C10—N1—C4—C5 | −26.0 (3) | C16—C11—C12—Br1 | −178.41 (17) |
C7—N1—C4—C5 | −167.1 (2) | C17—C11—C12—Br1 | 2.4 (3) |
C10—N1—C4—C3 | 155.3 (3) | C11—C12—C13—C14 | 1.2 (4) |
C7—N1—C4—C3 | 14.2 (3) | Br1—C12—C13—C14 | −179.9 (2) |
C2—C3—C4—N1 | 177.4 (2) | C12—C13—C14—C15 | −1.3 (4) |
C2—C3—C4—C5 | −1.3 (4) | C13—C14—C15—C16 | −0.2 (4) |
N1—C4—C5—C6 | −177.4 (2) | C14—C15—C16—C11 | 1.9 (4) |
C3—C4—C5—C6 | 1.4 (4) | C12—C11—C16—C15 | −2.0 (4) |
C4—C5—C6—C1 | −1.4 (4) | C17—C11—C16—C15 | 177.2 (3) |
C2—C1—C6—C5 | 1.4 (4) | C12—C11—C17—O3 | 65.2 (3) |
N3—C1—C6—C5 | −179.6 (2) | C16—C11—C17—O3 | −114.1 (3) |
C4—N1—C7—C8 | −165.1 (2) | C12—C11—C17—O4 | −115.8 (3) |
C10—N1—C7—C8 | 51.5 (3) | C16—C11—C17—O4 | 64.9 (3) |
C9—N2—C8—C7 | 57.1 (3) | | |
Hydrogen-bond geometry (Å, º) top D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2A···O3 | 0.85 (2) | 1.83 (2) | 2.655 (3) | 164 (2) |
N2—H2B···O4i | 0.88 (2) | 1.82 (2) | 2.701 (3) | 173 (2) |
C2—H2···O2ii | 0.93 | 2.50 | 3.307 (4) | 145 |
C7—H7B···Br1iii | 0.97 | 3.11 | 4.032 (2) | 160 |
C10—H10B···O1Wi | 0.97 | 2.10 | 3.057 (8) | 169 |
Symmetry codes: (i) −x+1, −y, −z; (ii) −x, −y+1, −z+1; (iii) x−1, y, z. |
4-(4-Nitrophenyl)piperazin-1-ium 2-iodobenzoate hemihydrate (3)
top Crystal data top C10H14N3O2+·C7H4IO2−·0.5H2O | Z = 1 |
Mr = 928.50 | F(000) = 462 |
Triclinic, P1 | Dx = 1.695 Mg m−3 |
a = 7.3949 (6) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.3440 (8) Å | Cell parameters from 2991 reflections |
c = 14.498 (1) Å | θ = 3.0–28.0° |
α = 104.967 (8)° | µ = 1.79 mm−1 |
β = 94.707 (7)° | T = 293 K |
γ = 107.430 (8)° | Prism, orange |
V = 909.44 (13) Å3 | 0.50 × 0.44 × 0.24 mm |
Data collection top Oxford Diffraction Xcalibur CCD diffractometer | 2443 reflections with I > 2σ(I) |
ω scans | Rint = 0.024 |
Absorption correction: multi-scan (CrysalisRed; Oxford Diffraction, 2009) | θmax = 28.0°, θmin = 3.0° |
Tmin = 0.697, Tmax = 1.000 | h = −9→9 |
6275 measured reflections | k = −9→12 |
3904 independent reflections | l = −19→11 |
Refinement top Refinement on F2 | Primary atom site location: dual |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.046 | Hydrogen site location: mixed |
wR(F2) = 0.117 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0514P)2 + 0.5457P] where P = (Fo2 + 2Fc2)/3 |
3904 reflections | (Δ/σ)max < 0.001 |
264 parameters | Δρmax = 0.61 e Å−3 |
13 restraints | Δρmin = −0.44 e Å−3 |
Special details top 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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
C1 | 0.1376 (6) | 0.6393 (4) | 0.1581 (3) | 0.0555 (10) | |
C2 | −0.0631 (7) | 0.5730 (5) | 0.1440 (3) | 0.0687 (12) | |
H2 | −0.116914 | 0.503974 | 0.178262 | 0.082* | |
C3 | −0.1822 (7) | 0.6059 (6) | 0.0822 (4) | 0.0724 (13) | |
H3 | −0.314731 | 0.558330 | 0.073932 | 0.087* | |
C4 | −0.1064 (7) | 0.7096 (5) | 0.0318 (3) | 0.0636 (11) | |
C5 | 0.0897 (7) | 0.7763 (6) | 0.0429 (3) | 0.0723 (13) | |
H5 | 0.141500 | 0.845343 | 0.008346 | 0.087* | |
C6 | 0.2093 (7) | 0.7419 (5) | 0.1044 (3) | 0.0667 (12) | |
H6 | 0.341659 | 0.787923 | 0.110643 | 0.080* | |
C7 | 0.4418 (7) | 0.7234 (7) | 0.2667 (5) | 0.0957 (18) | |
H7A | 0.418923 | 0.802683 | 0.317971 | 0.115* | |
H7B | 0.499045 | 0.773784 | 0.220487 | 0.115* | |
C8 | 0.5801 (7) | 0.6593 (7) | 0.3092 (4) | 0.0927 (17) | |
H8A | 0.619508 | 0.592894 | 0.257190 | 0.111* | |
H8B | 0.693988 | 0.745578 | 0.346016 | 0.111* | |
C9 | 0.3145 (8) | 0.4451 (6) | 0.3207 (4) | 0.0897 (16) | |
H9A | 0.256781 | 0.389355 | 0.364560 | 0.108* | |
H9B | 0.340842 | 0.370385 | 0.267916 | 0.108* | |
C10 | 0.1766 (7) | 0.5111 (6) | 0.2811 (4) | 0.0835 (15) | |
H10A | 0.061412 | 0.425824 | 0.244767 | 0.100* | |
H10B | 0.139797 | 0.577245 | 0.334373 | 0.100* | |
C11 | 0.8424 (6) | 0.2081 (5) | 0.3805 (3) | 0.0609 (11) | |
C12 | 0.8206 (6) | 0.1340 (5) | 0.2821 (3) | 0.0635 (12) | |
C13 | 0.9344 (9) | 0.0414 (6) | 0.2499 (4) | 0.0850 (16) | |
H13 | 0.920205 | −0.009287 | 0.184112 | 0.102* | |
C14 | 1.0663 (9) | 0.0254 (7) | 0.3150 (5) | 0.0919 (17) | |
H14 | 1.143373 | −0.034148 | 0.292932 | 0.110* | |
C15 | 1.0857 (8) | 0.0952 (7) | 0.4112 (5) | 0.0857 (15) | |
H15 | 1.174200 | 0.082483 | 0.455149 | 0.103* | |
C16 | 0.9743 (7) | 0.1845 (6) | 0.4432 (4) | 0.0769 (13) | |
H16 | 0.987579 | 0.231020 | 0.509488 | 0.092* | |
C17 | 0.7295 (7) | 0.3142 (7) | 0.4194 (3) | 0.0746 (13) | |
I1 | 0.61864 (5) | 0.15483 (4) | 0.18127 (2) | 0.08807 (17) | |
N1 | 0.2589 (5) | 0.6027 (4) | 0.2184 (3) | 0.0622 (9) | |
N2 | 0.4954 (6) | 0.5683 (5) | 0.3724 (3) | 0.0686 (10) | |
H2A | 0.482 (7) | 0.635 (6) | 0.424 (4) | 0.082* | |
H2B | 0.596 (7) | 0.539 (6) | 0.396 (4) | 0.082* | |
N3 | −0.2340 (7) | 0.7474 (5) | −0.0316 (3) | 0.0825 (12) | |
O1 | −0.4061 (7) | 0.6959 (6) | −0.0342 (4) | 0.1259 (16) | |
O2 | −0.1641 (7) | 0.8273 (6) | −0.0819 (3) | 0.1165 (14) | |
O3 | 0.6139 (6) | 0.2673 (6) | 0.4715 (3) | 0.1206 (15) | |
O4 | 0.7641 (6) | 0.4395 (5) | 0.4000 (3) | 0.0969 (11) | |
O1WA | 0.426 (5) | 0.976 (3) | 0.449 (2) | 0.154 (7) | 0.224 (3) |
H1W1 | 0.396 (13) | 1.048 (8) | 0.483 (6) | 0.231* | 0.224 (3) |
H1W2 | 0.470 (14) | 1.011 (10) | 0.406 (4) | 0.231* | 0.224 (3) |
O1WB | 0.507 (4) | 0.935 (3) | 0.4569 (19) | 0.149 (6) | 0.276 (3) |
H1W3 | 0.427 (8) | 0.892 (15) | 0.486 (6) | 0.224* | 0.276 (3) |
H1W4 | 0.604 (7) | 0.916 (12) | 0.475 (10) | 0.224* | 0.276 (3) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.061 (2) | 0.043 (2) | 0.057 (2) | 0.0145 (19) | 0.023 (2) | 0.0061 (18) |
C2 | 0.068 (3) | 0.062 (3) | 0.076 (3) | 0.014 (2) | 0.020 (2) | 0.027 (2) |
C3 | 0.065 (3) | 0.065 (3) | 0.079 (3) | 0.012 (2) | 0.017 (2) | 0.017 (2) |
C4 | 0.078 (3) | 0.057 (3) | 0.049 (2) | 0.021 (2) | 0.015 (2) | 0.0047 (19) |
C5 | 0.083 (3) | 0.071 (3) | 0.063 (3) | 0.017 (2) | 0.026 (2) | 0.026 (2) |
C6 | 0.062 (3) | 0.067 (3) | 0.067 (3) | 0.010 (2) | 0.018 (2) | 0.025 (2) |
C7 | 0.067 (3) | 0.082 (3) | 0.140 (5) | 0.007 (3) | 0.005 (3) | 0.062 (3) |
C8 | 0.063 (3) | 0.124 (4) | 0.113 (4) | 0.029 (3) | 0.024 (3) | 0.073 (4) |
C9 | 0.098 (4) | 0.081 (3) | 0.091 (4) | 0.015 (3) | 0.013 (3) | 0.047 (3) |
C10 | 0.069 (3) | 0.090 (4) | 0.094 (3) | 0.009 (3) | 0.018 (3) | 0.051 (3) |
C11 | 0.066 (3) | 0.056 (2) | 0.063 (2) | 0.022 (2) | 0.024 (2) | 0.016 (2) |
C12 | 0.073 (3) | 0.042 (2) | 0.066 (3) | 0.008 (2) | 0.028 (2) | 0.0089 (19) |
C13 | 0.110 (4) | 0.056 (3) | 0.085 (3) | 0.026 (3) | 0.048 (3) | 0.004 (2) |
C14 | 0.097 (4) | 0.073 (3) | 0.125 (5) | 0.044 (3) | 0.051 (4) | 0.035 (3) |
C15 | 0.082 (3) | 0.086 (4) | 0.110 (4) | 0.039 (3) | 0.033 (3) | 0.046 (3) |
C16 | 0.085 (3) | 0.089 (3) | 0.072 (3) | 0.040 (3) | 0.031 (3) | 0.031 (3) |
C17 | 0.073 (3) | 0.079 (3) | 0.064 (3) | 0.032 (3) | 0.012 (2) | 0.000 (2) |
I1 | 0.0918 (3) | 0.0799 (2) | 0.0696 (2) | 0.00239 (18) | 0.00710 (17) | 0.01674 (16) |
N1 | 0.061 (2) | 0.057 (2) | 0.071 (2) | 0.0143 (17) | 0.0198 (18) | 0.0276 (17) |
N2 | 0.073 (2) | 0.081 (3) | 0.065 (2) | 0.038 (2) | 0.0256 (19) | 0.025 (2) |
N3 | 0.092 (3) | 0.082 (3) | 0.063 (2) | 0.019 (2) | 0.002 (2) | 0.019 (2) |
O1 | 0.091 (3) | 0.159 (4) | 0.138 (4) | 0.035 (3) | 0.005 (3) | 0.075 (3) |
O2 | 0.116 (3) | 0.134 (4) | 0.100 (3) | 0.022 (3) | 0.003 (2) | 0.064 (3) |
O3 | 0.119 (3) | 0.124 (3) | 0.130 (3) | 0.058 (3) | 0.075 (3) | 0.019 (3) |
O4 | 0.106 (3) | 0.077 (2) | 0.116 (3) | 0.051 (2) | 0.018 (2) | 0.020 (2) |
O1WA | 0.208 (17) | 0.155 (15) | 0.160 (13) | 0.119 (12) | 0.070 (15) | 0.070 (12) |
O1WB | 0.210 (16) | 0.145 (13) | 0.161 (12) | 0.123 (11) | 0.079 (14) | 0.069 (11) |
Geometric parameters (Å, º) top C1—N1 | 1.377 (5) | C10—H10A | 0.9700 |
C1—C6 | 1.398 (6) | C10—H10B | 0.9700 |
C1—C2 | 1.401 (6) | C11—C16 | 1.384 (7) |
C2—C3 | 1.359 (7) | C11—C12 | 1.387 (6) |
C2—H2 | 0.9300 | C11—C17 | 1.511 (7) |
C3—C4 | 1.376 (6) | C12—C13 | 1.403 (7) |
C3—H3 | 0.9300 | C12—I1 | 2.090 (5) |
C4—C5 | 1.373 (6) | C13—C14 | 1.369 (8) |
C4—N3 | 1.443 (7) | C13—H13 | 0.9300 |
C5—C6 | 1.367 (7) | C14—C15 | 1.354 (8) |
C5—H5 | 0.9300 | C14—H14 | 0.9300 |
C6—H6 | 0.9300 | C15—C16 | 1.365 (7) |
C7—N1 | 1.454 (6) | C15—H15 | 0.9300 |
C7—C8 | 1.496 (7) | C16—H16 | 0.9300 |
C7—H7A | 0.9700 | C17—O4 | 1.232 (6) |
C7—H7B | 0.9700 | C17—O3 | 1.243 (6) |
C8—N2 | 1.461 (6) | N2—H2A | 0.88 (5) |
C8—H8A | 0.9700 | N2—H2B | 0.93 (5) |
C8—H8B | 0.9700 | N3—O1 | 1.212 (6) |
C9—N2 | 1.465 (7) | N3—O2 | 1.212 (6) |
C9—C10 | 1.487 (7) | O1WA—H1W1 | 0.82 (2) |
C9—H9A | 0.9700 | O1WA—H1W2 | 0.82 (2) |
C9—H9B | 0.9700 | O1WB—H1W3 | 0.83 (2) |
C10—N1 | 1.453 (5) | O1WB—H1W4 | 0.82 (2) |
| | | |
N1—C1—C6 | 121.4 (4) | N1—C10—H10B | 109.3 |
N1—C1—C2 | 122.6 (4) | C9—C10—H10B | 109.3 |
C6—C1—C2 | 115.9 (4) | H10A—C10—H10B | 107.9 |
C3—C2—C1 | 122.4 (4) | C16—C11—C12 | 118.0 (4) |
C3—C2—H2 | 118.8 | C16—C11—C17 | 120.1 (4) |
C1—C2—H2 | 118.8 | C12—C11—C17 | 121.9 (4) |
C2—C3—C4 | 120.0 (4) | C11—C12—C13 | 119.3 (5) |
C2—C3—H3 | 120.0 | C11—C12—I1 | 121.3 (3) |
C4—C3—H3 | 120.0 | C13—C12—I1 | 119.4 (4) |
C5—C4—C3 | 119.5 (5) | C14—C13—C12 | 120.1 (5) |
C5—C4—N3 | 120.9 (4) | C14—C13—H13 | 119.9 |
C3—C4—N3 | 119.6 (4) | C12—C13—H13 | 119.9 |
C6—C5—C4 | 120.5 (4) | C15—C14—C13 | 120.8 (5) |
C6—C5—H5 | 119.8 | C15—C14—H14 | 119.6 |
C4—C5—H5 | 119.8 | C13—C14—H14 | 119.6 |
C5—C6—C1 | 121.7 (4) | C14—C15—C16 | 119.4 (6) |
C5—C6—H6 | 119.2 | C14—C15—H15 | 120.3 |
C1—C6—H6 | 119.2 | C16—C15—H15 | 120.3 |
N1—C7—C8 | 112.7 (4) | C15—C16—C11 | 122.3 (5) |
N1—C7—H7A | 109.1 | C15—C16—H16 | 118.9 |
C8—C7—H7A | 109.1 | C11—C16—H16 | 118.9 |
N1—C7—H7B | 109.1 | O4—C17—O3 | 126.3 (5) |
C8—C7—H7B | 109.1 | O4—C17—C11 | 118.0 (5) |
H7A—C7—H7B | 107.8 | O3—C17—C11 | 115.6 (5) |
N2—C8—C7 | 111.8 (4) | C1—N1—C10 | 118.7 (4) |
N2—C8—H8A | 109.3 | C1—N1—C7 | 117.8 (3) |
C7—C8—H8A | 109.3 | C10—N1—C7 | 111.5 (4) |
N2—C8—H8B | 109.3 | C8—N2—C9 | 110.3 (4) |
C7—C8—H8B | 109.3 | C8—N2—H2A | 107 (3) |
H8A—C8—H8B | 107.9 | C9—N2—H2A | 114 (3) |
N2—C9—C10 | 111.7 (4) | C8—N2—H2B | 104 (3) |
N2—C9—H9A | 109.3 | C9—N2—H2B | 119 (3) |
C10—C9—H9A | 109.3 | H2A—N2—H2B | 102 (5) |
N2—C9—H9B | 109.3 | O1—N3—O2 | 122.4 (5) |
C10—C9—H9B | 109.3 | O1—N3—C4 | 119.3 (5) |
H9A—C9—H9B | 107.9 | O2—N3—C4 | 118.3 (5) |
N1—C10—C9 | 111.8 (4) | H1W1—O1WA—H1W2 | 103 (3) |
N1—C10—H10A | 109.3 | H1W3—O1WB—H1W4 | 103 (3) |
C9—C10—H10A | 109.3 | | |
| | | |
N1—C1—C2—C3 | −178.0 (4) | C12—C11—C16—C15 | 1.9 (7) |
C6—C1—C2—C3 | −0.1 (6) | C17—C11—C16—C15 | −177.1 (5) |
C1—C2—C3—C4 | −1.0 (7) | C16—C11—C17—O4 | 111.4 (5) |
C2—C3—C4—C5 | 1.5 (7) | C12—C11—C17—O4 | −67.5 (6) |
C2—C3—C4—N3 | −178.2 (4) | C16—C11—C17—O3 | −66.2 (6) |
C3—C4—C5—C6 | −0.8 (7) | C12—C11—C17—O3 | 114.9 (5) |
N3—C4—C5—C6 | 178.8 (4) | C6—C1—N1—C10 | 172.5 (4) |
C4—C5—C6—C1 | −0.3 (7) | C2—C1—N1—C10 | −9.7 (6) |
N1—C1—C6—C5 | 178.7 (4) | C6—C1—N1—C7 | 32.9 (6) |
C2—C1—C6—C5 | 0.8 (6) | C2—C1—N1—C7 | −149.3 (5) |
N1—C7—C8—N2 | −53.1 (7) | C9—C10—N1—C1 | 164.4 (4) |
N2—C9—C10—N1 | 56.1 (6) | C9—C10—N1—C7 | −53.6 (6) |
C16—C11—C12—C13 | −1.3 (6) | C8—C7—N1—C1 | −165.4 (4) |
C17—C11—C12—C13 | 177.7 (4) | C8—C7—N1—C10 | 52.3 (7) |
C16—C11—C12—I1 | 177.8 (3) | C7—C8—N2—C9 | 54.3 (7) |
C17—C11—C12—I1 | −3.3 (6) | C10—C9—N2—C8 | −56.0 (6) |
C11—C12—C13—C14 | −0.4 (7) | C5—C4—N3—O1 | −174.4 (5) |
I1—C12—C13—C14 | −179.5 (4) | C3—C4—N3—O1 | 5.2 (7) |
C12—C13—C14—C15 | 1.6 (8) | C5—C4—N3—O2 | 7.1 (7) |
C13—C14—C15—C16 | −1.0 (8) | C3—C4—N3—O2 | −173.3 (5) |
C14—C15—C16—C11 | −0.7 (8) | | |
Hydrogen-bond geometry (Å, º) top D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2···I1i | 0.93 | 3.28 | 4.110 (4) | 150 |
C3—H3···O1ii | 0.93 | 2.53 | 3.347 (7) | 147 |
C6—H6···I1iii | 0.93 | 3.26 | 3.940 (4) | 132 |
C7—H7A···O1WA | 0.97 | 2.14 | 3.09 (3) | 167 |
C7—H7A···O1WB | 0.97 | 2.01 | 2.85 (3) | 145 |
N2—H2A···O3iv | 0.88 (5) | 1.86 (5) | 2.717 (5) | 164 (5) |
N2—H2B···O4 | 0.93 (5) | 1.77 (5) | 2.666 (6) | 160 (5) |
O1WB—H1W3···O3iv | 0.83 (2) | 1.71 (10) | 2.37 (2) | 135 (12) |
Symmetry codes: (i) x−1, y, z; (ii) −x−1, −y+1, −z; (iii) x, y+1, z; (iv) −x+1, −y+1, −z+1. |
Acknowledgements
One of the authors (HJS) is grateful to the University of Mysore for research facilities. HSY thanks UGC for a BSR Faculty fellowship for three years.
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