1. Chemical context
Crystal engineering, the conception and synthesis of molecular solid-state structures, is fundamentally based upon the discernment and subsequent exploitation of intermolecular interactions (Desiraju, 1989) Thus, primarily non-covalent bonding is used to achieve the organization of molecules and ions in the solid state in order to produce materials with desired properties. One molecule that has been used that has multiple acceptor sites is hexamethylenetetramine (hmta), and it has been shown to act as a hydrogen-bond acceptor for alcohol or carboxylic acid donors (Lemmerer, 2011). Interestingly, hmta has four equivalent N atoms but there are very few reported co-crystals or salts that use all four. Examples that use all four N atoms in neutral hydrogen bonding are seen with alcohols (MacLean et al., 1999), whereas the vast majority of molecular complexes with hmta show it acting as a twofold acceptor (Li et al., 2001). However, if protonation does occur, then it is usually confined to only one site being protonated (Lemmerer et al., 2012). 2-Chloro-4-nitrobenzoic (2c4nH) acid has been used extensively in making co-crystals and salts using pyridine as an acceptor (Lemmerer et al., 2010, 2015) and has been chosen to be the hydrogen-bond donor/acid. The experimental pKa of hmta is 4.89 (Cooney et al., 1986), and the calculated pKa of 2c4nH is 2.04 (Lemmerer et al., 2015). Childs et al. (2007) postulated that for 0 < ΔpKa < 3, either a neutral co-crystal or salt can form, and that the crystalline environment can influence which one is favoured. In general, however, for ΔpKa values > 3 and < 0, a salt or co-crystal, respectively, is formed (Lemmerer et al., 2015). Hence, it is postulated that proton transfer will occur for a solution containing hmta and 2c4nH. In this work, we will make molecular salts using a 1:1 or 1:2 ratio of hmta with 2c4nH to see if two N atoms sites can be protonated. The four salts synthesized and reported here are: (hmtaH+)·(NH4+)(2c4nH−)2, (I), (hmtaH+)·(2c4nH−)2, (II) and (hmtaH+)·(2c4nH−), (IIIa) and (IIIb).
2. Structural commentary
The asymmetric units and atom-labelling schemes are shown in Fig. 1, together with their displacement ellipsoids for all four salts. A noteworthy asymmetric unit is the one for salts (I) and (II). In salt (I), there is the expected simple hmtaH+ cation and 2c4n− pair that are hydrogen bonded to each other using a charge-assisted N+—H⋯O− hydrogen bond (Table 1). However, an NH4+ ammonium cation is included in the asymmetric unit and its charge is balanced by a second 2c4n− anion. The NH4+ cation's appearance is not unique as it has been reported in the literature that hmta can decompose to form NH4 and formaldehyde (Lough et al., 2000), especially if the crystallization takes place slowly and in the presence of an acid. From a crystallographic standpoint, the 2:1 molecular salt (II) features half of an hmtaH+ cation crystallizing along a mirror plane at y = 1/4 and a fully occupied 2c4nH anion. In the difference-Fourier map, there is clear evidence that the N1 atom on a special position (0.485286 0.250000 0.494001) is protonated and hence has a half positive charge. However, the carboxylic acid group of 2c4nH has bond lengths typical of being neutral and clearly shows an acidic H atom, H2, located near O1 in the difference-Fourier map. Combined, this means that H1 acts as a bifurcated donor to two 2-chloro-4-nitrobenzoic molecules (Table 2), which themselves share the hydrogen atom H2. Molecular salts (IIIa) and (IIIb) both have a 1:1 ratio and are polymorphs of each other. Both have charge-assisted N+—H⋯O− hydrogen bonds (Tables 3 and 4) between the two ions but differ in their packing as described further below.
D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A | N1—H1⋯O1 | 0.94 (2) | 1.71 (2) | 2.6564 (18) | 177 (2) | N1A—H1A⋯O2 | 0.94 (2) | 1.89 (2) | 2.817 (2) | 168 (2) | N1A—H2A⋯O5 | 0.93 (2) | 1.87 (2) | 2.784 (2) | 167 (2) | N1A—H3A⋯O5i | 0.91 (2) | 1.90 (2) | 2.803 (2) | 171 (2) | N1A—H4A⋯O6ii | 1.02 (2) | 1.73 (2) | 2.747 (2) | 173 (2) | Symmetry codes: (i) ; (ii) x, y+1, z. | |
D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A | N1—H1⋯O2 | 0.92 (3) | 2.12 (2) | 2.7667 (15) | 126 (1) | | |
D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A | N1—H1⋯O1 | 1.00 (3) | 1.60 (3) | 2.599 (2) | 173 (3) | | |
D—H⋯A | D—H | H⋯A | D⋯A | D—H⋯A | N1—H1⋯O1 | 0.90 (2) | 1.80 (2) | 2.6911 (17) | 175.7 (19) | | |
| Figure 1 Perspective views of compounds (I)–(IIIb), showing the atom-numbering schemes. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Atoms with superscript (i) are at symmetry position (x, −y + , z). The dashed lines indicate the symmetry-independent N+—H⋯O− hydrogen bonds. |
3. Supramolecular features
The packing of salt (I) consists of clearly separated layers of hydrophobic and hydrophillic layers. All good hydrogen-bond donors are used (Table1, Fig. 2a). The NH4+ cation forms a hydrogen-bonded ring using two carboxylate groups and this ring repeats along the b-axis direction. The ring can be described as R43(8) and is a common feature in ammonium carboxylate salts (Lemmerer & Fernandes, 2012). This ladder is then surrounded by a 2c4n− anion that hydrogen bonds to the hmta+ cation. Overall, the hydrophilic layer consists of the cationic NH part of hmtaH+, NH4+ and the carboxylate CO2− part of 2c4n− (Fig. 3a). Salt (II) consists only of the hmtaH+ and 2c4n− anion in a 1:2 ratio. However, it appears crystallographically that only one complete proton transfer has taken place, and that on average, each of the 2c4n anions has released half a proton each to the N atom (labelled H1) and that the other half proton (labelled as H2) is located in between the two anions. Hence, only one N atom on hmta has been protonated, and subsequently, two 2c4n− anions are behaving as acceptors from a single N—H group (Fig. 1). Overall, the same layering of hydrophilic and hydrophobic parts occurs, where the cationic and anionic parts are located in the same ac plane. Salts (IIIa) and (IIIb) have identical asymmetric units with a 2:1 ratio of hmtaH+ and 2c4n−, in contrast to the previous two salts. The only significant difference is in the relative packing of these ion pairs. In (IIIa), the pairs pack anti-parallel (Fig. 3c), and in (IIIb), parallel (Fig. 3d).
| Figure 2 (a) Detailed view of the five hydrogen bonds formed by the cations and anions in (I). (b) The hydrogen-bonded ladder formed between the NH4+ cation and carboxylate anion forming a repeating R43(8) motif. Hydrogen bonds are shown as dashed red lines. |
| Figure 3 The packing diagrams for all four salts. Note the different packing arrangement of the two 1:1 dimorphs (IIIa) and (IIIb). |
4. Database survey
Up to now, there are only 36 structures of singly protonated hmtaH+ molecular salts in the Cambridge Structural Database (CSD, Version 5.38; Groom et al., 2016), together with any organic or inorganic counter-anion. Only one structure has the hmta doubly protonated (FOQZIW; Zaręba et al., 2014). Co-crystals of hmta in a 1:1 or 1:2 ratio with carboxylic acids are much more numerous (45). Ultimately, it has been shown that even with an excess of 2c4n, the hmta molecule only allows itself to be protonated once.
5. Synthesis and crystallization
All chemicals were purchased from commercial sources (Sigma Aldrich) and used as received without further purification. Crystals were grown via the slow evaporation method, under ambient conditions, of alcoholic solutions. For (I) and (II), these crystals crystallized out concomitantly from a 1:2 ratio, and (IIIa) and (IIIb), concomitantly from a 1:1 molar ratio. The morphology of the yellow-tinted crystals are shown in Fig. 4. Detailed masses and volumes are as follows. For (I) and (II): hexamethylenetetramine (0.050 g, 0.375 mmol) and 2-chloro-4-nitrobenzoic acid acid (0.072 g, 0.375 mmol) in methanol (5 mL); for (IIIa) and (IIIb): hexamethylenetetramine (0.050 g, 0.375 mmol) and 2-chloro-4-nitrobenzoic acid acid (0.144 g, 0.750 mmol) in ethanol (5 mL).
| Figure 4 The morphologies of the four title salts: (I) block, (II) plate, (IIIa) thick needles and (IIIb) prism. |
Crystal data, data collection and structure refinement details are summarized in Table 5. For all compounds, the C-bound H atoms were placed geometrically (C—H bond lengths of 0.99 (ethylene CH2), and 0.95 (Ar—H) Å) and refined as riding with Uiso(H) = 1.2Ueq(C). The N–bound H atoms were located in difference-Fourier maps and their coordinates and isotropic displacement parameters allowed to refine freely. The O–bound H atom in (II) was located in the difference-Fourier map and refined as riding with Uiso(H) = 1.5Ueq(O).
| (I) | (II) | (IIIa) | (IIIb) | Crystal data | Chemical formula | H4N+·C6H13N4+·2C7H3ClNO4− | 0.5C6H13N4+·C7H3.50ClNO4− | C6H13N4+·C7H3ClNO4− | C6H13N4+·C7H3ClNO4− | Mr | 560.35 | 543.32 | 341.76 | 341.76 | Crystal system, space group | Monoclinic, C2/c | Orthorhombic, Pnma | Monoclinic, Cc | Monoclinic, P21/c | Temperature (K) | 173 | 173 | 173 | 173 | a, b, c (Å) | 33.6032 (8), 6.0235 (1), 28.0229 (7) | 8.2777 (2), 19.7942 (5), 13.5331 (4) | 5.9049 (1), 21.9330 (4), 12.0194 (2) | 12.0663 (2), 19.5741 (4), 6.6473 (1) | α, β, γ (°) | 90, 121.007 (1), 90 | 90, 90, 90 | 90, 103.445 (1), 90 | 90, 105.820 (1), 90 | V (Å3) | 4861.56 (19) | 2217.40 (10) | 1514.00 (5) | 1510.54 (5) | Z | 8 | 4 | 4 | 4 | Radiation type | Mo Kα | Mo Kα | Mo Kα | Mo Kα | μ (mm−1) | 0.33 | 0.36 | 0.28 | 0.28 | Crystal size (mm) | 0.36 × 0.19 × 0.05 | 0.49 × 0.22 × 0.17 | 0.43 × 0.36 × 0.16 | 0.34 × 0.34 × 0.09 | | Data collection | Diffractometer | Bruker D8 Venture Photon CCD area detector | Bruker D8 Venture Photon CCD area detector | Bruker D8 Venture Photon CCD area detector | Bruker D8 Venture Photon CCD area detector | Absorption correction | Integration (XPREP; Bruker, 2016) | Integration (XPREP; Bruker, 2016) | Integration (XPREP; Bruker, 2016) | Integration (XPREP; Bruker, 2016) | Tmin, Tmax | 0.927, 0.986 | 0.887, 0.954 | 0.914, 0.978 | 0.921, 0.981 | No. of measured, independent and observed [I > 2σ(I)] reflections | 16830, 5858, 4131 | 20018, 2749, 2269 | 19814, 3644, 3487 | 26282, 3650, 3027 | Rint | 0.047 | 0.037 | 0.047 | 0.052 | | Refinement | R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.093, 0.95 | 0.031, 0.084, 1.06 | 0.026, 0.066, 1.07 | 0.039, 0.109, 1.05 | No. of reflections | 5858 | 2749 | 3644 | 3650 | No. of parameters | 354 | 173 | 212 | 212 | No. of restraints | 0 | 0 | 2 | 0 | 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 | H atoms treated by a mixture of independent and constrained refinement | Δρmax, Δρmin (e Å−3) | 0.29, −0.34 | 0.27, −0.23 | 0.15, −0.16 | 0.55, −0.32 | Absolute structure | – | – | Flack x determined using 1663 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) | – | Absolute structure parameter | – | – | −0.010 (19) | – | Computer programs: APEX3, SAINT-Plus and XPREP (Bruker 2016), SHELXS97 (Sheldrick, 2015), SHELXL2017/1 (Sheldrick, 2015), ORTEPIII for Windows and WinGX publication routines (Farrugia, 2012) and DIAMOND (Brandenburg & Berndt, 1999). | |
Supporting information
For all structures, data collection: APEX3 (Bruker, 2016); cell refinement: SAINT-Plus (Bruker, 2016); data reduction: SAINT-Plus and XPREP (Bruker 2016); program(s) used to solve structure: SHELXS97 (Sheldrick, 2015); program(s) used to refine structure: SHELXL2017/1 (Sheldrick, 2015); molecular graphics: ORTEP-III for Windows (Farrugia, 2012) and DIAMOND (Brandenburg & Berndt, 1999); software used to prepare material for publication: WinGX publication routines (Farrugia, 2012).
Ammonium hexamethylenetetraminium bis(2-chloro-4-nitro-benzoate) (I)
top Crystal data top H4N+·C6H13N4+·2C7H3ClNO4− | F(000) = 2320 |
Mr = 560.35 | Dx = 1.531 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 4303 reflections |
a = 33.6032 (8) Å | θ = 2.4–26.5° |
b = 6.0235 (1) Å | µ = 0.33 mm−1 |
c = 28.0229 (7) Å | T = 173 K |
β = 121.007 (1)° | Plate, yellow |
V = 4861.56 (19) Å3 | 0.36 × 0.19 × 0.05 mm |
Z = 8 | |
Data collection top Bruker D8 Venture Photon CCD area detector diffractometer | 4131 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
ω scans | θmax = 28.0°, θmin = 1.4° |
Absorption correction: integration (XPREP; Bruker, 2016) | h = −44→42 |
Tmin = 0.927, Tmax = 0.986 | k = −7→7 |
16830 measured reflections | l = −34→37 |
5858 independent reflections | |
Refinement top Refinement on F2 | 0 constraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.093 | w = 1/[σ2(Fo2) + (0.0425P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.95 | (Δ/σ)max < 0.001 |
5858 reflections | Δρmax = 0.29 e Å−3 |
354 parameters | Δρmin = −0.34 e Å−3 |
0 restraints | |
Special details top Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 2007) |
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 | |
C1 | 0.12646 (7) | 0.8962 (3) | 0.25907 (8) | 0.0436 (5) | |
H1B | 0.124511 | 0.734282 | 0.263614 | 0.052* | |
H1C | 0.15024 | 0.92274 | 0.248896 | 0.052* | |
C2 | 0.14211 (6) | 1.2486 (3) | 0.30330 (8) | 0.0376 (4) | |
H2B | 0.152064 | 1.326005 | 0.338888 | 0.045* | |
H2C | 0.165633 | 1.27754 | 0.292835 | 0.045* | |
C3 | 0.08364 (7) | 1.2276 (3) | 0.20814 (7) | 0.0322 (4) | |
H3B | 0.106877 | 1.25849 | 0.197318 | 0.039* | |
H3C | 0.053299 | 1.285973 | 0.178539 | 0.039* | |
C4 | 0.06273 (6) | 1.2897 (3) | 0.27554 (7) | 0.0340 (4) | |
H4B | 0.032214 | 1.348363 | 0.246406 | 0.041* | |
H4C | 0.071612 | 1.367283 | 0.310805 | 0.041* | |
C5 | 0.10396 (8) | 0.9702 (4) | 0.32528 (8) | 0.0538 (6) | |
H5A | 0.101801 | 0.808914 | 0.330395 | 0.065* | |
H5B | 0.113292 | 1.044666 | 0.361035 | 0.065* | |
C6 | 0.04479 (7) | 0.9401 (3) | 0.23067 (8) | 0.0417 (5) | |
H6A | 0.013988 | 0.994563 | 0.201219 | 0.05* | |
H6B | 0.042317 | 0.778576 | 0.235157 | 0.05* | |
N1 | 0.08009 (5) | 0.9820 (2) | 0.21368 (6) | 0.0298 (3) | |
N2 | 0.13960 (6) | 1.0090 (3) | 0.31095 (6) | 0.0436 (4) | |
N3 | 0.09712 (5) | 1.3374 (2) | 0.26001 (6) | 0.0293 (3) | |
N4 | 0.05840 (6) | 1.0525 (3) | 0.28254 (6) | 0.0400 (4) | |
H1 | 0.0698 (7) | 0.909 (3) | 0.1795 (9) | 0.055 (6)* | |
C7 | 0.06854 (5) | 0.5904 (3) | 0.05877 (6) | 0.0239 (3) | |
C8 | 0.08353 (5) | 0.3865 (3) | 0.05022 (6) | 0.0242 (3) | |
C9 | 0.07300 (5) | 0.3194 (3) | −0.00250 (6) | 0.0254 (4) | |
H9 | 0.082512 | 0.178213 | −0.008152 | 0.03* | |
C10 | 0.04844 (5) | 0.4631 (3) | −0.04620 (6) | 0.0272 (4) | |
C11 | 0.03282 (6) | 0.6669 (3) | −0.04007 (7) | 0.0304 (4) | |
H11 | 0.015947 | 0.76348 | −0.07092 | 0.037* | |
C12 | 0.04261 (5) | 0.7252 (3) | 0.01254 (7) | 0.0283 (4) | |
H12 | 0.031212 | 0.86257 | 0.017342 | 0.034* | |
C13 | 0.08027 (6) | 0.6776 (3) | 0.11575 (7) | 0.0263 (4) | |
N5 | 0.03893 (5) | 0.3921 (3) | −0.10143 (6) | 0.0344 (4) | |
O1 | 0.04796 (4) | 0.7787 (2) | 0.11648 (5) | 0.0392 (3) | |
O2 | 0.12006 (4) | 0.6506 (2) | 0.15595 (5) | 0.0360 (3) | |
O3 | 0.02132 (5) | 0.5272 (3) | −0.13945 (5) | 0.0491 (4) | |
O4 | 0.04925 (4) | 0.2028 (2) | −0.10660 (5) | 0.0442 (4) | |
Cl1 | 0.11490 (2) | 0.19844 (7) | 0.10370 (2) | 0.03492 (12) | |
C14 | 0.22494 (5) | 0.1024 (3) | 0.09588 (6) | 0.0241 (3) | |
C15 | 0.18721 (5) | 0.0359 (3) | 0.04462 (6) | 0.0232 (3) | |
C16 | 0.17243 (6) | 0.1593 (3) | −0.00290 (7) | 0.0258 (4) | |
H16 | 0.146226 | 0.11506 | −0.037342 | 0.031* | |
C17 | 0.19690 (6) | 0.3500 (3) | 0.00099 (6) | 0.0268 (4) | |
C18 | 0.23531 (6) | 0.4187 (3) | 0.05009 (7) | 0.0296 (4) | |
H18 | 0.252105 | 0.547679 | 0.051372 | 0.035* | |
C19 | 0.24862 (6) | 0.2941 (3) | 0.09738 (7) | 0.0278 (4) | |
H19 | 0.274601 | 0.340546 | 0.131781 | 0.033* | |
C20 | 0.24019 (5) | −0.0227 (3) | 0.14930 (7) | 0.0279 (4) | |
N6 | 0.17928 (6) | 0.4903 (3) | −0.04867 (6) | 0.0377 (4) | |
O5 | 0.24220 (5) | 0.0883 (2) | 0.18852 (5) | 0.0463 (4) | |
O6 | 0.24993 (4) | −0.22222 (19) | 0.15110 (5) | 0.0353 (3) | |
O7 | 0.20330 (6) | 0.6416 (3) | −0.04802 (6) | 0.0652 (5) | |
O8 | 0.14019 (5) | 0.4528 (3) | −0.08803 (5) | 0.0594 (4) | |
Cl2 | 0.15515 (2) | −0.19840 (7) | 0.03935 (2) | 0.03327 (12) | |
N1A | 0.21195 (6) | 0.5093 (3) | 0.19658 (7) | 0.0301 (3) | |
H1A | 0.1800 (8) | 0.543 (3) | 0.1788 (8) | 0.046 (6)* | |
H2A | 0.2175 (7) | 0.365 (4) | 0.1897 (8) | 0.045 (6)* | |
H4A | 0.2269 (7) | 0.617 (4) | 0.1824 (8) | 0.056 (6)* | |
H3A | 0.2251 (7) | 0.522 (3) | 0.2341 (9) | 0.046 (6)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0376 (10) | 0.0339 (10) | 0.0426 (11) | 0.0118 (9) | 0.0088 (9) | −0.0071 (9) |
C2 | 0.0293 (9) | 0.0417 (11) | 0.0359 (10) | −0.0049 (8) | 0.0125 (8) | −0.0159 (8) |
C3 | 0.0407 (10) | 0.0352 (10) | 0.0257 (8) | 0.0047 (8) | 0.0207 (8) | 0.0023 (7) |
C4 | 0.0335 (9) | 0.0428 (11) | 0.0288 (9) | 0.0015 (8) | 0.0183 (8) | −0.0080 (8) |
C5 | 0.0782 (16) | 0.0458 (13) | 0.0310 (10) | −0.0021 (12) | 0.0235 (11) | 0.0110 (9) |
C6 | 0.0423 (11) | 0.0425 (11) | 0.0428 (11) | −0.0186 (9) | 0.0237 (9) | −0.0145 (9) |
N1 | 0.0286 (7) | 0.0305 (8) | 0.0267 (7) | −0.0013 (6) | 0.0117 (6) | −0.0103 (6) |
N2 | 0.0404 (9) | 0.0420 (10) | 0.0291 (8) | 0.0126 (8) | 0.0040 (7) | −0.0011 (7) |
N3 | 0.0364 (8) | 0.0255 (7) | 0.0299 (7) | −0.0010 (6) | 0.0198 (7) | −0.0040 (6) |
N4 | 0.0465 (9) | 0.0495 (10) | 0.0296 (8) | −0.0157 (8) | 0.0237 (8) | −0.0066 (7) |
C7 | 0.0206 (7) | 0.0273 (9) | 0.0279 (8) | −0.0059 (7) | 0.0153 (7) | −0.0069 (7) |
C8 | 0.0239 (8) | 0.0257 (8) | 0.0243 (8) | −0.0042 (7) | 0.0135 (7) | −0.0017 (7) |
C9 | 0.0245 (8) | 0.0282 (9) | 0.0266 (8) | −0.0042 (7) | 0.0155 (7) | −0.0075 (7) |
C10 | 0.0206 (8) | 0.0387 (10) | 0.0217 (8) | −0.0050 (7) | 0.0106 (7) | −0.0063 (7) |
C11 | 0.0234 (8) | 0.0356 (10) | 0.0270 (8) | −0.0008 (7) | 0.0092 (7) | 0.0013 (7) |
C12 | 0.0228 (8) | 0.0278 (9) | 0.0334 (9) | −0.0001 (7) | 0.0139 (7) | −0.0046 (7) |
C13 | 0.0302 (9) | 0.0237 (9) | 0.0310 (9) | −0.0076 (7) | 0.0201 (8) | −0.0086 (7) |
N5 | 0.0237 (7) | 0.0551 (10) | 0.0224 (7) | −0.0012 (7) | 0.0105 (6) | −0.0038 (7) |
O1 | 0.0282 (6) | 0.0513 (8) | 0.0410 (7) | −0.0063 (6) | 0.0198 (6) | −0.0237 (6) |
O2 | 0.0354 (7) | 0.0425 (7) | 0.0260 (6) | 0.0049 (6) | 0.0129 (6) | −0.0074 (5) |
O3 | 0.0473 (8) | 0.0709 (10) | 0.0260 (7) | 0.0071 (7) | 0.0166 (6) | 0.0067 (7) |
O4 | 0.0400 (8) | 0.0593 (9) | 0.0312 (7) | 0.0072 (7) | 0.0170 (6) | −0.0145 (6) |
Cl1 | 0.0519 (3) | 0.0274 (2) | 0.0269 (2) | 0.0028 (2) | 0.0213 (2) | 0.00014 (17) |
C14 | 0.0230 (8) | 0.0225 (8) | 0.0256 (8) | 0.0026 (7) | 0.0117 (7) | −0.0020 (7) |
C15 | 0.0234 (8) | 0.0197 (8) | 0.0294 (8) | −0.0030 (6) | 0.0157 (7) | −0.0046 (7) |
C16 | 0.0247 (8) | 0.0294 (9) | 0.0229 (8) | −0.0031 (7) | 0.0119 (7) | −0.0062 (7) |
C17 | 0.0310 (9) | 0.0280 (9) | 0.0232 (8) | −0.0024 (7) | 0.0153 (7) | −0.0009 (7) |
C18 | 0.0317 (9) | 0.0272 (9) | 0.0319 (9) | −0.0083 (7) | 0.0179 (8) | −0.0023 (7) |
C19 | 0.0230 (8) | 0.0277 (9) | 0.0254 (8) | −0.0040 (7) | 0.0071 (7) | −0.0035 (7) |
C20 | 0.0233 (8) | 0.0273 (9) | 0.0280 (9) | 0.0004 (7) | 0.0096 (7) | 0.0024 (7) |
N6 | 0.0480 (10) | 0.0392 (9) | 0.0260 (8) | −0.0087 (8) | 0.0191 (7) | −0.0007 (7) |
O5 | 0.0737 (10) | 0.0317 (7) | 0.0230 (6) | 0.0127 (7) | 0.0174 (7) | 0.0018 (6) |
O6 | 0.0391 (7) | 0.0249 (6) | 0.0444 (7) | 0.0065 (5) | 0.0233 (6) | 0.0058 (6) |
O7 | 0.0738 (11) | 0.0669 (10) | 0.0432 (8) | −0.0364 (9) | 0.0217 (8) | 0.0112 (8) |
O8 | 0.0607 (10) | 0.0618 (10) | 0.0288 (7) | −0.0197 (8) | 0.0039 (7) | 0.0090 (7) |
Cl2 | 0.0287 (2) | 0.0269 (2) | 0.0405 (2) | −0.00875 (17) | 0.01514 (19) | −0.00310 (18) |
N1A | 0.0353 (9) | 0.0268 (8) | 0.0231 (8) | −0.0002 (7) | 0.0114 (7) | −0.0008 (7) |
Geometric parameters (Å, º) top C1—N2 | 1.452 (2) | C9—H9 | 0.95 |
C1—N1 | 1.507 (2) | C10—C11 | 1.380 (2) |
C1—H1B | 0.99 | C10—N5 | 1.473 (2) |
C1—H1C | 0.99 | C11—C12 | 1.380 (2) |
C2—N3 | 1.467 (2) | C11—H11 | 0.95 |
C2—N2 | 1.468 (2) | C12—H12 | 0.95 |
C2—H2B | 0.99 | C13—O2 | 1.237 (2) |
C2—H2C | 0.99 | C13—O1 | 1.254 (2) |
C3—N3 | 1.441 (2) | N5—O4 | 1.222 (2) |
C3—N1 | 1.498 (2) | N5—O3 | 1.2243 (19) |
C3—H3B | 0.99 | C14—C19 | 1.391 (2) |
C3—H3C | 0.99 | C14—C15 | 1.398 (2) |
C4—N3 | 1.458 (2) | C14—C20 | 1.510 (2) |
C4—N4 | 1.460 (2) | C15—C16 | 1.375 (2) |
C4—H4B | 0.99 | C15—Cl2 | 1.7349 (16) |
C4—H4C | 0.99 | C16—C17 | 1.384 (2) |
C5—N4 | 1.461 (3) | C16—H16 | 0.95 |
C5—N2 | 1.465 (3) | C17—C18 | 1.379 (2) |
C5—H5A | 0.99 | C17—N6 | 1.467 (2) |
C5—H5B | 0.99 | C18—C19 | 1.382 (2) |
C6—N4 | 1.448 (2) | C18—H18 | 0.95 |
C6—N1 | 1.510 (2) | C19—H19 | 0.95 |
C6—H6A | 0.99 | C20—O6 | 1.2399 (19) |
C6—H6B | 0.99 | C20—O5 | 1.258 (2) |
N1—H1 | 0.94 (2) | N6—O7 | 1.2113 (19) |
C7—C12 | 1.391 (2) | N6—O8 | 1.2247 (19) |
C7—C8 | 1.394 (2) | N1A—H1A | 0.94 (2) |
C7—C13 | 1.527 (2) | N1A—H2A | 0.93 (2) |
C8—C9 | 1.390 (2) | N1A—H4A | 1.02 (2) |
C8—Cl1 | 1.7357 (16) | N1A—H3A | 0.91 (2) |
C9—C10 | 1.374 (2) | | |
| | | |
N2—C1—N1 | 109.47 (14) | C8—C7—C13 | 124.12 (15) |
N2—C1—H1B | 109.8 | C9—C8—C7 | 121.47 (15) |
N1—C1—H1B | 109.8 | C9—C8—Cl1 | 115.88 (13) |
N2—C1—H1C | 109.8 | C7—C8—Cl1 | 122.62 (12) |
N1—C1—H1C | 109.8 | C10—C9—C8 | 118.11 (15) |
H1B—C1—H1C | 108.2 | C10—C9—H9 | 120.9 |
N3—C2—N2 | 111.53 (14) | C8—C9—H9 | 120.9 |
N3—C2—H2B | 109.3 | C9—C10—C11 | 122.78 (15) |
N2—C2—H2B | 109.3 | C9—C10—N5 | 117.32 (15) |
N3—C2—H2C | 109.3 | C11—C10—N5 | 119.90 (15) |
N2—C2—H2C | 109.3 | C12—C11—C10 | 117.57 (16) |
H2B—C2—H2C | 108 | C12—C11—H11 | 121.2 |
N3—C3—N1 | 110.42 (14) | C10—C11—H11 | 121.2 |
N3—C3—H3B | 109.6 | C11—C12—C7 | 122.45 (16) |
N1—C3—H3B | 109.6 | C11—C12—H12 | 118.8 |
N3—C3—H3C | 109.6 | C7—C12—H12 | 118.8 |
N1—C3—H3C | 109.6 | O2—C13—O1 | 125.97 (15) |
H3B—C3—H3C | 108.1 | O2—C13—C7 | 118.86 (15) |
N3—C4—N4 | 112.46 (14) | O1—C13—C7 | 115.12 (15) |
N3—C4—H4B | 109.1 | O4—N5—O3 | 123.84 (15) |
N4—C4—H4B | 109.1 | O4—N5—C10 | 118.31 (15) |
N3—C4—H4C | 109.1 | O3—N5—C10 | 117.85 (16) |
N4—C4—H4C | 109.1 | C19—C14—C15 | 118.09 (15) |
H4B—C4—H4C | 107.8 | C19—C14—C20 | 119.18 (14) |
N4—C5—N2 | 112.37 (15) | C15—C14—C20 | 122.72 (14) |
N4—C5—H5A | 109.1 | C16—C15—C14 | 121.59 (15) |
N2—C5—H5A | 109.1 | C16—C15—Cl2 | 117.30 (12) |
N4—C5—H5B | 109.1 | C14—C15—Cl2 | 121.01 (13) |
N2—C5—H5B | 109.1 | C15—C16—C17 | 117.97 (15) |
H5A—C5—H5B | 107.9 | C15—C16—H16 | 121 |
N4—C6—N1 | 110.20 (14) | C17—C16—H16 | 121 |
N4—C6—H6A | 109.6 | C18—C17—C16 | 122.72 (15) |
N1—C6—H6A | 109.6 | C18—C17—N6 | 119.13 (15) |
N4—C6—H6B | 109.6 | C16—C17—N6 | 118.04 (14) |
N1—C6—H6B | 109.6 | C17—C18—C19 | 117.93 (15) |
H6A—C6—H6B | 108.1 | C17—C18—H18 | 121 |
C3—N1—C1 | 108.86 (14) | C19—C18—H18 | 121 |
C3—N1—C6 | 108.38 (14) | C18—C19—C14 | 121.64 (15) |
C1—N1—C6 | 108.37 (15) | C18—C19—H19 | 119.2 |
C3—N1—H1 | 111.0 (13) | C14—C19—H19 | 119.2 |
C1—N1—H1 | 112.1 (13) | O6—C20—O5 | 125.82 (16) |
C6—N1—H1 | 108.0 (13) | O6—C20—C14 | 118.14 (15) |
C1—N2—C5 | 109.25 (17) | O5—C20—C14 | 116.04 (14) |
C1—N2—C2 | 108.94 (16) | O7—N6—O8 | 123.31 (16) |
C5—N2—C2 | 108.27 (16) | O7—N6—C17 | 118.61 (15) |
C3—N3—C4 | 108.97 (14) | O8—N6—C17 | 118.03 (15) |
C3—N3—C2 | 108.73 (14) | H1A—N1A—H2A | 112.6 (17) |
C4—N3—C2 | 108.61 (14) | H1A—N1A—H4A | 108.4 (17) |
C6—N4—C4 | 108.95 (14) | H2A—N1A—H4A | 108.8 (17) |
C6—N4—C5 | 108.66 (16) | H1A—N1A—H3A | 109.6 (17) |
C4—N4—C5 | 107.91 (15) | H2A—N1A—H3A | 106.8 (17) |
C12—C7—C8 | 117.56 (15) | H4A—N1A—H3A | 110.7 (17) |
C12—C7—C13 | 118.28 (14) | | |
| | | |
N3—C3—N1—C1 | −58.93 (19) | N5—C10—C11—C12 | 179.91 (15) |
N3—C3—N1—C6 | 58.74 (18) | C10—C11—C12—C7 | 2.2 (2) |
N2—C1—N1—C3 | 58.6 (2) | C8—C7—C12—C11 | −2.1 (2) |
N2—C1—N1—C6 | −59.1 (2) | C13—C7—C12—C11 | 175.80 (15) |
N4—C6—N1—C3 | −58.4 (2) | C12—C7—C13—O2 | −136.62 (16) |
N4—C6—N1—C1 | 59.64 (19) | C8—C7—C13—O2 | 41.1 (2) |
N1—C1—N2—C5 | 58.9 (2) | C12—C7—C13—O1 | 41.0 (2) |
N1—C1—N2—C2 | −59.2 (2) | C8—C7—C13—O1 | −141.29 (16) |
N4—C5—N2—C1 | −60.0 (2) | C9—C10—N5—O4 | 6.9 (2) |
N4—C5—N2—C2 | 58.6 (2) | C11—C10—N5—O4 | −173.10 (15) |
N3—C2—N2—C1 | 60.8 (2) | C9—C10—N5—O3 | −172.66 (15) |
N3—C2—N2—C5 | −57.87 (19) | C11—C10—N5—O3 | 7.3 (2) |
N1—C3—N3—C4 | −59.01 (18) | C19—C14—C15—C16 | −2.5 (2) |
N1—C3—N3—C2 | 59.21 (19) | C20—C14—C15—C16 | 176.37 (15) |
N4—C4—N3—C3 | 59.83 (18) | C19—C14—C15—Cl2 | −178.82 (12) |
N4—C4—N3—C2 | −58.46 (18) | C20—C14—C15—Cl2 | 0.0 (2) |
N2—C2—N3—C3 | −60.51 (19) | C14—C15—C16—C17 | 1.8 (2) |
N2—C2—N3—C4 | 57.93 (19) | Cl2—C15—C16—C17 | 178.27 (12) |
N1—C6—N4—C4 | 58.2 (2) | C15—C16—C17—C18 | 0.6 (3) |
N1—C6—N4—C5 | −59.1 (2) | C15—C16—C17—N6 | −175.74 (15) |
N3—C4—N4—C6 | −59.57 (19) | C16—C17—C18—C19 | −2.1 (3) |
N3—C4—N4—C5 | 58.23 (19) | N6—C17—C18—C19 | 174.17 (16) |
N2—C5—N4—C6 | 59.7 (2) | C17—C18—C19—C14 | 1.4 (3) |
N2—C5—N4—C4 | −58.3 (2) | C15—C14—C19—C18 | 0.8 (2) |
C12—C7—C8—C9 | −0.1 (2) | C20—C14—C19—C18 | −178.03 (16) |
C13—C7—C8—C9 | −177.82 (15) | C19—C14—C20—O6 | −124.75 (17) |
C12—C7—C8—Cl1 | −178.35 (12) | C15—C14—C20—O6 | 56.4 (2) |
C13—C7—C8—Cl1 | 3.9 (2) | C19—C14—C20—O5 | 54.6 (2) |
C7—C8—C9—C10 | 2.0 (2) | C15—C14—C20—O5 | −124.17 (18) |
Cl1—C8—C9—C10 | −179.62 (12) | C18—C17—N6—O7 | 12.8 (3) |
C8—C9—C10—C11 | −1.9 (2) | C16—C17—N6—O7 | −170.81 (17) |
C8—C9—C10—N5 | 178.06 (14) | C18—C17—N6—O8 | −164.69 (17) |
C9—C10—C11—C12 | −0.1 (2) | C16—C17—N6—O8 | 11.7 (2) |
Hydrogen-bond geometry (Å, º) top D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.94 (2) | 1.71 (2) | 2.6564 (18) | 177 (2) |
N1A—H1A···O2 | 0.94 (2) | 1.89 (2) | 2.817 (2) | 168 (2) |
N1A—H2A···O5 | 0.93 (2) | 1.87 (2) | 2.784 (2) | 167 (2) |
N1A—H3A···O5i | 0.91 (2) | 1.90 (2) | 2.803 (2) | 171 (2) |
N1A—H4A···O6ii | 1.02 (2) | 1.73 (2) | 2.747 (2) | 173 (2) |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) x, y+1, z. |
Hexamethylenetetraminium hydrogen bis(2-chloro-4-nitro-benzoate) (II)
top Crystal data top C6H13N4+·C14H7Cl2N2O8− | F(000) = 1120 |
Mr = 543.32 | Dx = 1.627 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 7712 reflections |
a = 8.2777 (2) Å | θ = 2.9–28.3° |
b = 19.7942 (5) Å | µ = 0.36 mm−1 |
c = 13.5331 (4) Å | T = 173 K |
V = 2217.40 (10) Å3 | Block, yellow |
Z = 4 | 0.49 × 0.22 × 0.17 mm |
Data collection top Bruker D8 Venture Photon CCD area detector diffractometer | 2269 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
ω scans | θmax = 28.0°, θmin = 1.8° |
Absorption correction: integration (XPREP; Bruker, 2016) | h = −9→10 |
Tmin = 0.887, Tmax = 0.954 | k = −26→26 |
20018 measured reflections | l = −15→17 |
2749 independent reflections | |
Refinement top Refinement on F2 | 0 constraints |
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) = 0.084 | w = 1/[σ2(Fo2) + (0.0459P)2 + 0.3817P] where P = (Fo2 + 2Fc2)/3 |
S = 1.06 | (Δ/σ)max = 0.001 |
2749 reflections | Δρmax = 0.27 e Å−3 |
173 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | |
Special details top Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 2016) |
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 | 0.5362 (2) | 0.25 | 0.60139 (15) | 0.0293 (4) | |
H1A | 0.602402 | 0.209478 | 0.615413 | 0.035* | 0.5 |
H1B | 0.602403 | 0.290522 | 0.615413 | 0.035* | 0.5 |
C2 | 0.29732 (18) | 0.31010 (6) | 0.64113 (11) | 0.0316 (3) | |
H2A | 0.201625 | 0.3107 | 0.684998 | 0.038* | |
H2B | 0.361744 | 0.351156 | 0.655045 | 0.038* | |
C3 | 0.38433 (16) | 0.31232 (7) | 0.47447 (11) | 0.0302 (3) | |
H3A | 0.449124 | 0.353372 | 0.487692 | 0.036* | |
H3B | 0.350359 | 0.313181 | 0.404342 | 0.036* | |
C4 | 0.1490 (2) | 0.25 | 0.51788 (16) | 0.0317 (4) | |
H4A | 0.051092 | 0.249999 | 0.559915 | 0.038* | |
H4B | 0.113777 | 0.25 | 0.447969 | 0.038* | |
N1 | 0.48529 (18) | 0.25 | 0.49400 (12) | 0.0266 (3) | |
N2 | 0.3952 (2) | 0.25 | 0.66325 (12) | 0.0298 (3) | |
N3 | 0.24353 (13) | 0.31154 (5) | 0.53769 (9) | 0.0284 (2) | |
H1 | 0.575 (3) | 0.25 | 0.4540 (19) | 0.050 (7)* | |
C5 | 0.91417 (14) | 0.41404 (6) | 0.36290 (9) | 0.0225 (2) | |
C6 | 0.84727 (14) | 0.47610 (6) | 0.38838 (9) | 0.0224 (3) | |
C7 | 0.93805 (15) | 0.53490 (6) | 0.38801 (9) | 0.0236 (3) | |
H7 | 0.890704 | 0.577243 | 0.403921 | 0.028* | |
C8 | 1.09962 (15) | 0.52991 (6) | 0.36376 (9) | 0.0240 (3) | |
C9 | 1.17365 (15) | 0.46922 (6) | 0.34177 (9) | 0.0259 (3) | |
H9 | 1.286207 | 0.46701 | 0.328452 | 0.031* | |
C10 | 1.07902 (15) | 0.41200 (6) | 0.33976 (9) | 0.0254 (3) | |
H10 | 1.126815 | 0.370043 | 0.322226 | 0.03* | |
C11 | 0.82257 (15) | 0.34800 (6) | 0.36070 (10) | 0.0263 (3) | |
N4 | 1.19475 (14) | 0.59237 (5) | 0.35791 (8) | 0.0290 (2) | |
O1 | 0.85862 (14) | 0.31125 (5) | 0.28588 (7) | 0.0377 (3) | |
H2 | 0.83408 | 0.270874 | 0.297686 | 0.057* | 0.5 |
O2 | 0.72967 (12) | 0.33353 (5) | 0.42674 (8) | 0.0413 (3) | |
O3 | 1.33995 (11) | 0.58735 (5) | 0.34060 (9) | 0.0404 (3) | |
O4 | 1.12464 (12) | 0.64612 (5) | 0.36731 (9) | 0.0407 (3) | |
Cl1 | 0.64344 (4) | 0.48455 (2) | 0.41656 (3) | 0.03169 (11) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0282 (9) | 0.0237 (8) | 0.0360 (10) | 0 | −0.0040 (8) | 0 |
C2 | 0.0363 (7) | 0.0243 (6) | 0.0343 (7) | 0.0015 (5) | 0.0073 (6) | −0.0047 (5) |
C3 | 0.0284 (7) | 0.0277 (6) | 0.0344 (7) | 0.0016 (5) | 0.0039 (5) | 0.0090 (5) |
C4 | 0.0231 (9) | 0.0317 (9) | 0.0404 (11) | 0 | 0.0011 (8) | 0 |
N1 | 0.0220 (7) | 0.0262 (7) | 0.0316 (8) | 0 | 0.0065 (6) | 0 |
N2 | 0.0383 (9) | 0.0237 (7) | 0.0276 (8) | 0 | 0.0015 (7) | 0 |
N3 | 0.0249 (5) | 0.0251 (5) | 0.0351 (6) | 0.0026 (4) | 0.0046 (5) | 0.0028 (4) |
C5 | 0.0238 (6) | 0.0242 (6) | 0.0194 (5) | 0.0018 (5) | 0.0011 (5) | 0.0031 (5) |
C6 | 0.0199 (6) | 0.0278 (6) | 0.0196 (6) | 0.0041 (5) | 0.0017 (4) | 0.0025 (5) |
C7 | 0.0265 (6) | 0.0238 (6) | 0.0207 (6) | 0.0049 (5) | −0.0003 (5) | 0.0013 (5) |
C8 | 0.0261 (6) | 0.0253 (6) | 0.0207 (6) | −0.0015 (5) | 0.0003 (5) | 0.0021 (5) |
C9 | 0.0216 (6) | 0.0316 (6) | 0.0244 (6) | 0.0032 (5) | 0.0035 (5) | 0.0023 (5) |
C10 | 0.0261 (6) | 0.0237 (6) | 0.0262 (6) | 0.0065 (5) | 0.0041 (5) | 0.0015 (5) |
C11 | 0.0265 (6) | 0.0243 (6) | 0.0281 (7) | 0.0030 (5) | −0.0003 (5) | 0.0030 (5) |
N4 | 0.0302 (6) | 0.0292 (6) | 0.0277 (6) | −0.0029 (5) | 0.0015 (5) | 0.0026 (4) |
O1 | 0.0618 (7) | 0.0215 (5) | 0.0299 (5) | −0.0019 (4) | 0.0082 (5) | 0.0000 (4) |
O2 | 0.0399 (6) | 0.0337 (5) | 0.0503 (7) | −0.0100 (5) | 0.0201 (5) | −0.0041 (5) |
O3 | 0.0273 (5) | 0.0398 (6) | 0.0541 (7) | −0.0066 (4) | 0.0075 (4) | 0.0006 (5) |
O4 | 0.0406 (6) | 0.0248 (5) | 0.0566 (7) | −0.0009 (4) | 0.0045 (5) | −0.0009 (5) |
Cl1 | 0.02016 (16) | 0.03606 (19) | 0.0388 (2) | 0.00424 (12) | 0.00556 (12) | −0.00421 (14) |
Geometric parameters (Å, º) top C1—N2 | 1.436 (2) | C5—C6 | 1.3909 (17) |
C1—N1 | 1.513 (2) | C5—C10 | 1.4006 (17) |
C1—H1A | 0.99 | C5—C11 | 1.5115 (17) |
C1—H1B | 0.99 | C6—C7 | 1.3854 (17) |
C2—N3 | 1.4693 (19) | C6—Cl1 | 1.7378 (12) |
C2—N2 | 1.4703 (16) | C7—C8 | 1.3806 (17) |
C2—H2A | 0.99 | C7—H7 | 0.95 |
C2—H2B | 0.99 | C8—C9 | 1.3811 (17) |
C3—N3 | 1.4460 (16) | C8—N4 | 1.4679 (16) |
C3—N1 | 1.5132 (15) | C9—C10 | 1.3775 (18) |
C3—H3A | 0.99 | C9—H9 | 0.95 |
C3—H3B | 0.99 | C10—H10 | 0.95 |
C4—N3i | 1.4725 (14) | C11—O2 | 1.2133 (16) |
C4—N3 | 1.4725 (14) | C11—O1 | 1.2820 (16) |
C4—H4A | 0.99 | N4—O4 | 1.2185 (14) |
C4—H4B | 0.99 | N4—O3 | 1.2286 (14) |
N1—H1 | 0.92 (3) | O1—H2 | 0.84 |
| | | |
N2—C1—N1 | 109.51 (14) | C1—N2—C2i | 109.21 (10) |
N2—C1—H1A | 109.8 | C2—N2—C2i | 108.03 (15) |
N1—C1—H1A | 109.8 | C3—N3—C2 | 108.64 (11) |
N2—C1—H1B | 109.8 | C3—N3—C4 | 109.24 (12) |
N1—C1—H1B | 109.8 | C2—N3—C4 | 108.57 (12) |
H1A—C1—H1B | 108.2 | C6—C5—C10 | 117.96 (11) |
N3—C2—N2 | 112.13 (11) | C6—C5—C11 | 124.68 (10) |
N3—C2—H2A | 109.2 | C10—C5—C11 | 117.34 (11) |
N2—C2—H2A | 109.2 | C7—C6—C5 | 121.67 (11) |
N3—C2—H2B | 109.2 | C7—C6—Cl1 | 116.53 (9) |
N2—C2—H2B | 109.2 | C5—C6—Cl1 | 121.73 (9) |
H2A—C2—H2B | 107.9 | C8—C7—C6 | 117.79 (11) |
N3—C3—N1 | 109.46 (11) | C8—C7—H7 | 121.1 |
N3—C3—H3A | 109.8 | C6—C7—H7 | 121.1 |
N1—C3—H3A | 109.8 | C7—C8—C9 | 122.90 (12) |
N3—C3—H3B | 109.8 | C7—C8—N4 | 118.18 (11) |
N1—C3—H3B | 109.8 | C9—C8—N4 | 118.88 (11) |
H3A—C3—H3B | 108.2 | C10—C9—C8 | 117.86 (11) |
N3i—C4—N3 | 111.64 (14) | C10—C9—H9 | 121.1 |
N3i—C4—H4A | 109.3 | C8—C9—H9 | 121.1 |
N3—C4—H4A | 109.3 | C9—C10—C5 | 121.73 (11) |
N3i—C4—H4B | 109.3 | C9—C10—H10 | 119.1 |
N3—C4—H4B | 109.3 | C5—C10—H10 | 119.1 |
H4A—C4—H4B | 108 | O2—C11—O1 | 126.54 (12) |
C1—N1—C3 | 108.75 (10) | O2—C11—C5 | 120.51 (12) |
C1—N1—C3i | 108.75 (10) | O1—C11—C5 | 112.92 (11) |
C3—N1—C3i | 109.21 (14) | O4—N4—O3 | 123.81 (11) |
C1—N1—H1 | 110.0 (16) | O4—N4—C8 | 118.31 (10) |
C3—N1—H1 | 110.1 (8) | O3—N4—C8 | 117.83 (11) |
C3i—N1—H1 | 110.1 (8) | C11—O1—H2 | 109.5 |
C1—N2—C2 | 109.21 (10) | | |
| | | |
N2—C1—N1—C3 | 59.41 (9) | C5—C6—C7—C8 | −1.59 (18) |
N2—C1—N1—C3i | −59.42 (9) | Cl1—C6—C7—C8 | −178.61 (9) |
N3—C3—N1—C1 | −59.65 (14) | C6—C7—C8—C9 | −1.09 (19) |
N3—C3—N1—C3i | 58.89 (18) | C6—C7—C8—N4 | 176.73 (11) |
N1—C1—N2—C2 | −58.97 (10) | C7—C8—C9—C10 | 3.08 (19) |
N1—C1—N2—C2i | 58.97 (10) | N4—C8—C9—C10 | −174.73 (11) |
N3—C2—N2—C1 | 60.31 (15) | C8—C9—C10—C5 | −2.47 (19) |
N3—C2—N2—C2i | −58.36 (18) | C6—C5—C10—C9 | −0.04 (19) |
N1—C3—N3—C2 | 59.30 (14) | C11—C5—C10—C9 | −178.59 (11) |
N1—C3—N3—C4 | −58.98 (15) | C6—C5—C11—O2 | −43.34 (19) |
N2—C2—N3—C3 | −60.24 (14) | C10—C5—C11—O2 | 135.11 (14) |
N2—C2—N3—C4 | 58.46 (15) | C6—C5—C11—O1 | 138.58 (13) |
N3i—C4—N3—C3 | 60.40 (19) | C10—C5—C11—O1 | −42.97 (16) |
N3i—C4—N3—C2 | −57.92 (18) | C7—C8—N4—O4 | −5.45 (18) |
C10—C5—C6—C7 | 2.13 (18) | C9—C8—N4—O4 | 172.47 (12) |
C11—C5—C6—C7 | −179.43 (11) | C7—C8—N4—O3 | 176.84 (12) |
C10—C5—C6—Cl1 | 179.00 (9) | C9—C8—N4—O3 | −5.24 (18) |
C11—C5—C6—Cl1 | −2.56 (18) | | |
Symmetry code: (i) x, −y+1/2, z. |
Hydrogen-bond geometry (Å, º) top D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O2 | 0.92 (3) | 2.12 (2) | 2.7667 (15) | 126 (1) |
Hexamethylenetetraminium 2-chloro-4-nitro-benzoate (IIIa)
top Crystal data top C6H13N4+·C7H3ClNO4− | F(000) = 712 |
Mr = 341.76 | Dx = 1.499 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C -2yc | Cell parameters from 8081 reflections |
a = 5.9049 (1) Å | θ = 2.6–28.2° |
b = 21.9330 (4) Å | µ = 0.28 mm−1 |
c = 12.0194 (2) Å | T = 173 K |
β = 103.445 (1)° | Block, yellow |
V = 1514.00 (5) Å3 | 0.43 × 0.36 × 0.16 mm |
Z = 4 | |
Data collection top Bruker D8 Venture Photon CCD area detector diffractometer | 3487 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
ω scans | θmax = 28.0°, θmin = 1.9° |
Absorption correction: integration (XPREP; Bruker, 2016) | h = −7→7 |
Tmin = 0.914, Tmax = 0.978 | k = −28→28 |
19814 measured reflections | l = −15→15 |
3644 independent reflections | |
Refinement top Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.026 | w = 1/[σ2(Fo2) + (0.0432P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.066 | (Δ/σ)max = 0.001 |
S = 1.07 | Δρmax = 0.15 e Å−3 |
3644 reflections | Δρmin = −0.16 e Å−3 |
212 parameters | Absolute structure: Flack x determined using 1663 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
2 restraints | Absolute structure parameter: −0.010 (19) |
0 constraints | |
Special details top Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 2007) |
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 | |
C1 | 1.0080 (3) | 0.72838 (9) | 0.47292 (17) | 0.0302 (4) | |
H1A | 1.096685 | 0.737124 | 0.551861 | 0.036* | |
H1B | 1.049816 | 0.686893 | 0.452137 | 0.036* | |
C2 | 0.9342 (4) | 0.75914 (10) | 0.27795 (17) | 0.0319 (4) | |
H2A | 0.976526 | 0.788891 | 0.224231 | 0.038* | |
H2B | 0.976087 | 0.717955 | 0.25558 | 0.038* | |
C3 | 0.6207 (3) | 0.71808 (8) | 0.34676 (16) | 0.0286 (4) | |
H3A | 0.658855 | 0.676431 | 0.325098 | 0.034* | |
H3B | 0.451188 | 0.719959 | 0.341854 | 0.034* | |
C4 | 0.6238 (4) | 0.82334 (9) | 0.3026 (2) | 0.0350 (4) | |
H4A | 0.661827 | 0.853586 | 0.248535 | 0.042* | |
H4B | 0.454371 | 0.825696 | 0.297832 | 0.042* | |
C5 | 1.0013 (4) | 0.83387 (9) | 0.4256 (2) | 0.0391 (5) | |
H5A | 1.088446 | 0.843625 | 0.504334 | 0.047* | |
H5B | 1.045272 | 0.864199 | 0.3733 | 0.047* | |
C6 | 0.6902 (4) | 0.79500 (9) | 0.49725 (19) | 0.0343 (4) | |
H6A | 0.521113 | 0.797405 | 0.493412 | 0.041* | |
H6B | 0.774748 | 0.804796 | 0.576425 | 0.041* | |
N1 | 0.7517 (3) | 0.73145 (7) | 0.46727 (14) | 0.0260 (3) | |
N2 | 1.0680 (3) | 0.77256 (8) | 0.39466 (16) | 0.0320 (4) | |
N3 | 0.6820 (3) | 0.76185 (7) | 0.26875 (14) | 0.0291 (3) | |
N4 | 0.7511 (3) | 0.83861 (7) | 0.41911 (17) | 0.0347 (4) | |
H1 | 0.701 (5) | 0.7025 (12) | 0.521 (3) | 0.047 (7)* | |
C7 | 0.4837 (3) | 0.55022 (8) | 0.59523 (16) | 0.0247 (4) | |
C8 | 0.5755 (3) | 0.51846 (8) | 0.69629 (15) | 0.0235 (3) | |
C9 | 0.4580 (3) | 0.47118 (8) | 0.73393 (16) | 0.0242 (3) | |
H9 | 0.523206 | 0.449697 | 0.802544 | 0.029* | |
C10 | 0.2400 (3) | 0.45652 (8) | 0.66667 (17) | 0.0252 (4) | |
C11 | 0.1378 (3) | 0.48766 (9) | 0.56796 (17) | 0.0317 (4) | |
H11 | −0.014186 | 0.477454 | 0.525556 | 0.038* | |
C12 | 0.2629 (4) | 0.53414 (9) | 0.53253 (18) | 0.0330 (4) | |
H12 | 0.196649 | 0.555527 | 0.463953 | 0.04* | |
C13 | 0.6155 (3) | 0.60098 (8) | 0.55257 (15) | 0.0258 (4) | |
N5 | 0.1104 (3) | 0.40717 (7) | 0.70493 (14) | 0.0282 (3) | |
O1 | 0.5964 (3) | 0.65311 (6) | 0.59380 (14) | 0.0443 (4) | |
O2 | 0.7254 (2) | 0.58844 (6) | 0.48014 (12) | 0.0323 (3) | |
O3 | −0.0851 (3) | 0.39514 (8) | 0.64851 (16) | 0.0452 (4) | |
O4 | 0.2033 (3) | 0.37964 (7) | 0.79287 (13) | 0.0393 (4) | |
Cl1 | 0.84686 (7) | 0.53900 (2) | 0.77974 (4) | 0.03201 (12) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0260 (10) | 0.0383 (10) | 0.0253 (9) | 0.0055 (8) | 0.0038 (7) | 0.0053 (8) |
C2 | 0.0363 (11) | 0.0347 (10) | 0.0284 (10) | 0.0076 (8) | 0.0149 (9) | 0.0089 (8) |
C3 | 0.0262 (9) | 0.0276 (9) | 0.0304 (10) | −0.0036 (7) | 0.0035 (7) | −0.0036 (7) |
C4 | 0.0320 (11) | 0.0278 (9) | 0.0429 (11) | 0.0092 (8) | 0.0043 (9) | 0.0053 (8) |
C5 | 0.0335 (11) | 0.0321 (10) | 0.0508 (13) | −0.0118 (8) | 0.0079 (10) | −0.0032 (9) |
C6 | 0.0374 (11) | 0.0320 (10) | 0.0378 (11) | 0.0008 (8) | 0.0176 (9) | −0.0103 (8) |
N1 | 0.0294 (8) | 0.0256 (7) | 0.0248 (8) | −0.0012 (6) | 0.0100 (6) | −0.0006 (6) |
N2 | 0.0205 (8) | 0.0382 (8) | 0.0382 (9) | 0.0007 (7) | 0.0087 (7) | 0.0060 (7) |
N3 | 0.0308 (9) | 0.0275 (8) | 0.0268 (8) | 0.0046 (6) | 0.0019 (7) | 0.0034 (6) |
N4 | 0.0359 (9) | 0.0230 (7) | 0.0457 (10) | −0.0005 (6) | 0.0109 (8) | −0.0045 (7) |
C7 | 0.0301 (10) | 0.0238 (8) | 0.0201 (8) | 0.0006 (7) | 0.0056 (7) | −0.0003 (6) |
C8 | 0.0224 (8) | 0.0240 (7) | 0.0225 (8) | −0.0004 (7) | 0.0015 (7) | −0.0022 (6) |
C9 | 0.0260 (9) | 0.0231 (8) | 0.0220 (8) | −0.0001 (6) | 0.0024 (7) | 0.0014 (6) |
C10 | 0.0271 (9) | 0.0227 (8) | 0.0250 (9) | −0.0025 (6) | 0.0044 (7) | −0.0014 (6) |
C11 | 0.0287 (10) | 0.0369 (10) | 0.0252 (9) | −0.0044 (8) | −0.0023 (8) | 0.0008 (8) |
C12 | 0.0360 (11) | 0.0365 (10) | 0.0225 (9) | −0.0033 (8) | −0.0012 (8) | 0.0061 (7) |
C13 | 0.0310 (9) | 0.0267 (8) | 0.0191 (8) | −0.0010 (7) | 0.0046 (7) | 0.0019 (6) |
N5 | 0.0291 (8) | 0.0235 (7) | 0.0310 (8) | −0.0044 (6) | 0.0048 (7) | −0.0034 (6) |
O1 | 0.0744 (12) | 0.0273 (7) | 0.0427 (9) | −0.0096 (7) | 0.0370 (9) | −0.0058 (6) |
O2 | 0.0353 (8) | 0.0317 (7) | 0.0331 (7) | 0.0026 (5) | 0.0147 (6) | 0.0024 (6) |
O3 | 0.0341 (8) | 0.0444 (8) | 0.0503 (9) | −0.0169 (7) | −0.0039 (7) | 0.0037 (7) |
O4 | 0.0414 (9) | 0.0321 (7) | 0.0410 (9) | −0.0084 (6) | 0.0027 (7) | 0.0114 (6) |
Cl1 | 0.0265 (2) | 0.0358 (2) | 0.0297 (2) | −0.00838 (18) | −0.00158 (16) | 0.00365 (19) |
Geometric parameters (Å, º) top C1—N2 | 1.450 (3) | C6—N1 | 1.505 (2) |
C1—N1 | 1.501 (3) | C6—H6A | 0.99 |
C1—H1A | 0.99 | C6—H6B | 0.99 |
C1—H1B | 0.99 | N1—H1 | 1.00 (3) |
C2—N3 | 1.469 (3) | C7—C12 | 1.392 (3) |
C2—N2 | 1.471 (3) | C7—C8 | 1.396 (3) |
C2—H2A | 0.99 | C7—C13 | 1.514 (2) |
C2—H2B | 0.99 | C8—C9 | 1.381 (3) |
C3—N3 | 1.445 (2) | C8—Cl1 | 1.7405 (18) |
C3—N1 | 1.504 (2) | C9—C10 | 1.390 (3) |
C3—H3A | 0.99 | C9—H9 | 0.95 |
C3—H3B | 0.99 | C10—C11 | 1.380 (3) |
C4—N4 | 1.466 (3) | C10—N5 | 1.460 (2) |
C4—N3 | 1.472 (3) | C11—C12 | 1.383 (3) |
C4—H4A | 0.99 | C11—H11 | 0.95 |
C4—H4B | 0.99 | C12—H12 | 0.95 |
C5—N4 | 1.466 (3) | C13—O2 | 1.232 (2) |
C5—N2 | 1.473 (3) | C13—O1 | 1.262 (2) |
C5—H5A | 0.99 | N5—O3 | 1.224 (2) |
C5—H5B | 0.99 | N5—O4 | 1.230 (2) |
C6—N4 | 1.443 (3) | | |
| | | |
N2—C1—N1 | 109.65 (15) | C3—N1—C6 | 108.21 (15) |
N2—C1—H1A | 109.7 | C1—N1—H1 | 113.2 (17) |
N1—C1—H1A | 109.7 | C3—N1—H1 | 109.4 (17) |
N2—C1—H1B | 109.7 | C6—N1—H1 | 107.9 (15) |
N1—C1—H1B | 109.7 | C1—N2—C2 | 109.08 (16) |
H1A—C1—H1B | 108.2 | C1—N2—C5 | 109.07 (17) |
N3—C2—N2 | 111.95 (15) | C2—N2—C5 | 107.93 (17) |
N3—C2—H2A | 109.2 | C3—N3—C2 | 109.06 (15) |
N2—C2—H2A | 109.2 | C3—N3—C4 | 108.64 (15) |
N3—C2—H2B | 109.2 | C2—N3—C4 | 108.30 (17) |
N2—C2—H2B | 109.2 | C6—N4—C5 | 108.62 (17) |
H2A—C2—H2B | 107.9 | C6—N4—C4 | 108.69 (16) |
N3—C3—N1 | 110.18 (15) | C5—N4—C4 | 108.72 (18) |
N3—C3—H3A | 109.6 | C12—C7—C8 | 118.04 (17) |
N1—C3—H3A | 109.6 | C12—C7—C13 | 119.58 (16) |
N3—C3—H3B | 109.6 | C8—C7—C13 | 122.38 (17) |
N1—C3—H3B | 109.6 | C9—C8—C7 | 122.48 (17) |
H3A—C3—H3B | 108.1 | C9—C8—Cl1 | 118.08 (14) |
N4—C4—N3 | 111.86 (15) | C7—C8—Cl1 | 119.43 (14) |
N4—C4—H4A | 109.2 | C8—C9—C10 | 116.82 (17) |
N3—C4—H4A | 109.2 | C8—C9—H9 | 121.6 |
N4—C4—H4B | 109.2 | C10—C9—H9 | 121.6 |
N3—C4—H4B | 109.2 | C11—C10—C9 | 123.11 (17) |
H4A—C4—H4B | 107.9 | C11—C10—N5 | 118.76 (17) |
N4—C5—N2 | 112.12 (16) | C9—C10—N5 | 118.09 (16) |
N4—C5—H5A | 109.2 | C10—C11—C12 | 118.13 (18) |
N2—C5—H5A | 109.2 | C10—C11—H11 | 120.9 |
N4—C5—H5B | 109.2 | C12—C11—H11 | 120.9 |
N2—C5—H5B | 109.2 | C11—C12—C7 | 121.37 (18) |
H5A—C5—H5B | 107.9 | C11—C12—H12 | 119.3 |
N4—C6—N1 | 110.32 (15) | C7—C12—H12 | 119.3 |
N4—C6—H6A | 109.6 | O2—C13—O1 | 126.16 (17) |
N1—C6—H6A | 109.6 | O2—C13—C7 | 118.14 (16) |
N4—C6—H6B | 109.6 | O1—C13—C7 | 115.67 (16) |
N1—C6—H6B | 109.6 | O3—N5—O4 | 123.01 (17) |
H6A—C6—H6B | 108.1 | O3—N5—C10 | 118.76 (16) |
C1—N1—C3 | 108.81 (15) | O4—N5—C10 | 118.23 (15) |
C1—N1—C6 | 109.14 (15) | | |
| | | |
N2—C1—N1—C3 | 59.36 (19) | N3—C4—N4—C5 | 57.9 (2) |
N2—C1—N1—C6 | −58.5 (2) | C12—C7—C8—C9 | 1.7 (3) |
N3—C3—N1—C1 | −59.28 (19) | C13—C7—C8—C9 | −178.40 (17) |
N3—C3—N1—C6 | 59.19 (19) | C12—C7—C8—Cl1 | −177.75 (15) |
N4—C6—N1—C1 | 59.0 (2) | C13—C7—C8—Cl1 | 2.2 (2) |
N4—C6—N1—C3 | −59.2 (2) | C7—C8—C9—C10 | −0.6 (3) |
N1—C1—N2—C2 | −59.2 (2) | Cl1—C8—C9—C10 | 178.85 (14) |
N1—C1—N2—C5 | 58.5 (2) | C8—C9—C10—C11 | −1.5 (3) |
N3—C2—N2—C1 | 59.7 (2) | C8—C9—C10—N5 | −179.32 (16) |
N3—C2—N2—C5 | −58.7 (2) | C9—C10—C11—C12 | 2.5 (3) |
N4—C5—N2—C1 | −60.1 (2) | N5—C10—C11—C12 | −179.77 (18) |
N4—C5—N2—C2 | 58.3 (2) | C10—C11—C12—C7 | −1.3 (3) |
N1—C3—N3—C2 | 58.6 (2) | C8—C7—C12—C11 | −0.7 (3) |
N1—C3—N3—C4 | −59.30 (19) | C13—C7—C12—C11 | 179.37 (18) |
N2—C2—N3—C3 | −59.3 (2) | C12—C7—C13—O2 | −83.2 (2) |
N2—C2—N3—C4 | 58.8 (2) | C8—C7—C13—O2 | 96.9 (2) |
N4—C4—N3—C3 | 60.2 (2) | C12—C7—C13—O1 | 95.1 (2) |
N4—C4—N3—C2 | −58.1 (2) | C8—C7—C13—O1 | −84.8 (2) |
N1—C6—N4—C5 | −58.8 (2) | C11—C10—N5—O3 | −0.3 (3) |
N1—C6—N4—C4 | 59.3 (2) | C9—C10—N5—O3 | 177.59 (18) |
N2—C5—N4—C6 | 59.9 (2) | C11—C10—N5—O4 | 179.86 (18) |
N2—C5—N4—C4 | −58.2 (2) | C9—C10—N5—O4 | −2.3 (3) |
N3—C4—N4—C6 | −60.2 (2) | | |
Hydrogen-bond geometry (Å, º) top D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 1.00 (3) | 1.60 (3) | 2.599 (2) | 173 (3) |
Hexamethylenetetraminium 2-chloro-4-nitro-benzoate (IIIb)
top Crystal data top C6H13N4+·C7H3ClNO4− | F(000) = 712 |
Mr = 341.76 | Dx = 1.503 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 8173 reflections |
a = 12.0663 (2) Å | θ = 2.7–28.3° |
b = 19.5741 (4) Å | µ = 0.28 mm−1 |
c = 6.6473 (1) Å | T = 173 K |
β = 105.820 (1)° | Flint, yellow |
V = 1510.54 (5) Å3 | 0.34 × 0.34 × 0.09 mm |
Z = 4 | |
Data collection top Bruker D8 Venture Photon CCD area detector diffractometer | 3027 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.052 |
ω scans | θmax = 28°, θmin = 1.8° |
Absorption correction: integration (XPREP; Bruker, 2016) | h = −15→15 |
Tmin = 0.921, Tmax = 0.981 | k = −25→25 |
26282 measured reflections | l = −7→8 |
3650 independent reflections | |
Refinement top Refinement on F2 | 0 constraints |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.039 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.109 | w = 1/[σ2(Fo2) + (0.054P)2 + 0.5922P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
3650 reflections | Δρmax = 0.55 e Å−3 |
212 parameters | Δρmin = −0.32 e Å−3 |
0 restraints | |
Special details top Experimental. Numerical integration absorption corrections based on indexed crystal faces were applied using the XPREP routine (Bruker, 2016) |
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 | |
C1 | 0.47109 (13) | 0.06841 (8) | 0.8298 (2) | 0.0271 (3) | |
H1A | 0.476631 | 0.018936 | 0.803213 | 0.033* | |
H1B | 0.546088 | 0.08373 | 0.921587 | 0.033* | |
C2 | 0.37372 (14) | 0.15425 (8) | 0.9693 (2) | 0.0276 (3) | |
H2A | 0.313223 | 0.162548 | 1.041406 | 0.033* | |
H2B | 0.447916 | 0.170366 | 1.062001 | 0.033* | |
C3 | 0.43573 (13) | 0.18246 (7) | 0.6683 (2) | 0.0244 (3) | |
H3A | 0.510444 | 0.199335 | 0.757087 | 0.029* | |
H3B | 0.417076 | 0.208139 | 0.534971 | 0.029* | |
C4 | 0.23625 (12) | 0.16842 (8) | 0.6381 (2) | 0.0266 (3) | |
H4A | 0.17462 | 0.176786 | 0.707533 | 0.032* | |
H4B | 0.216747 | 0.19411 | 0.50475 | 0.032* | |
C5 | 0.27060 (14) | 0.05744 (8) | 0.7927 (3) | 0.0286 (3) | |
H5A | 0.274979 | 0.008016 | 0.764242 | 0.034* | |
H5B | 0.208987 | 0.064229 | 0.863228 | 0.034* | |
C6 | 0.32952 (12) | 0.08285 (8) | 0.4889 (2) | 0.0243 (3) | |
H6A | 0.310535 | 0.107689 | 0.354087 | 0.029* | |
H6B | 0.333422 | 0.033463 | 0.459442 | 0.029* | |
N1 | 0.44482 (11) | 0.10695 (6) | 0.6253 (2) | 0.0224 (3) | |
N2 | 0.38141 (12) | 0.08021 (6) | 0.9327 (2) | 0.0272 (3) | |
N3 | 0.34674 (10) | 0.19364 (6) | 0.77319 (19) | 0.0236 (3) | |
N4 | 0.24105 (10) | 0.09499 (6) | 0.5939 (2) | 0.0253 (3) | |
H1 | 0.5012 (17) | 0.0994 (10) | 0.563 (3) | 0.034 (5)* | |
C7 | 0.75647 (12) | 0.14049 (7) | 0.3243 (2) | 0.0245 (3) | |
C8 | 0.86231 (13) | 0.10840 (7) | 0.4116 (2) | 0.0250 (3) | |
C9 | 0.95324 (12) | 0.11511 (8) | 0.3214 (3) | 0.0283 (3) | |
H9 | 1.025178 | 0.093435 | 0.380783 | 0.034* | |
C10 | 0.93535 (13) | 0.15426 (8) | 0.1431 (2) | 0.0291 (3) | |
C11 | 0.83262 (14) | 0.18678 (8) | 0.0513 (3) | 0.0312 (3) | |
H11 | 0.822882 | 0.213174 | −0.072295 | 0.037* | |
C12 | 0.74455 (13) | 0.17962 (8) | 0.1452 (3) | 0.0295 (3) | |
H12 | 0.673439 | 0.202156 | 0.085609 | 0.035* | |
C13 | 0.65228 (13) | 0.13753 (8) | 0.4116 (3) | 0.0276 (3) | |
N5 | 1.03144 (12) | 0.16391 (9) | 0.0488 (2) | 0.0407 (4) | |
O1 | 0.61912 (11) | 0.08068 (6) | 0.4561 (2) | 0.0409 (3) | |
O2 | 0.60096 (11) | 0.19263 (6) | 0.4134 (2) | 0.0434 (3) | |
O3 | 1.02236 (14) | 0.20679 (8) | −0.0877 (3) | 0.0594 (4) | |
O4 | 1.11599 (12) | 0.12771 (11) | 0.1120 (2) | 0.0706 (6) | |
Cl1 | 0.88646 (4) | 0.06116 (2) | 0.64016 (6) | 0.03601 (13) | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.0267 (7) | 0.0216 (7) | 0.0312 (8) | 0.0035 (6) | 0.0047 (6) | 0.0047 (6) |
C2 | 0.0346 (8) | 0.0249 (7) | 0.0237 (7) | −0.0002 (6) | 0.0088 (6) | −0.0012 (6) |
C3 | 0.0265 (7) | 0.0156 (6) | 0.0333 (8) | −0.0003 (5) | 0.0116 (6) | 0.0010 (6) |
C4 | 0.0223 (7) | 0.0268 (7) | 0.0310 (8) | 0.0051 (6) | 0.0076 (6) | −0.0002 (6) |
C5 | 0.0312 (8) | 0.0241 (7) | 0.0346 (8) | −0.0056 (6) | 0.0160 (6) | −0.0001 (6) |
C6 | 0.0247 (7) | 0.0239 (7) | 0.0249 (7) | −0.0001 (6) | 0.0077 (6) | −0.0021 (6) |
N1 | 0.0216 (6) | 0.0179 (6) | 0.0298 (6) | 0.0015 (4) | 0.0110 (5) | 0.0020 (5) |
N2 | 0.0350 (7) | 0.0222 (6) | 0.0247 (6) | 0.0002 (5) | 0.0090 (5) | 0.0032 (5) |
N3 | 0.0265 (6) | 0.0191 (6) | 0.0269 (6) | 0.0014 (5) | 0.0103 (5) | 0.0004 (5) |
N4 | 0.0209 (6) | 0.0260 (6) | 0.0292 (6) | −0.0003 (5) | 0.0072 (5) | −0.0023 (5) |
C7 | 0.0198 (7) | 0.0216 (7) | 0.0329 (8) | −0.0033 (5) | 0.0089 (6) | −0.0067 (6) |
C8 | 0.0231 (7) | 0.0239 (7) | 0.0273 (7) | −0.0025 (6) | 0.0058 (6) | −0.0041 (6) |
C9 | 0.0181 (7) | 0.0333 (8) | 0.0325 (8) | 0.0000 (6) | 0.0054 (6) | −0.0070 (6) |
C10 | 0.0225 (7) | 0.0356 (8) | 0.0317 (8) | −0.0050 (6) | 0.0115 (6) | −0.0082 (7) |
C11 | 0.0305 (8) | 0.0309 (8) | 0.0334 (8) | −0.0023 (6) | 0.0103 (7) | 0.0014 (7) |
C12 | 0.0233 (7) | 0.0280 (8) | 0.0368 (8) | 0.0020 (6) | 0.0076 (6) | −0.0010 (6) |
C13 | 0.0219 (7) | 0.0274 (8) | 0.0359 (8) | −0.0027 (6) | 0.0117 (6) | −0.0060 (6) |
N5 | 0.0271 (7) | 0.0621 (10) | 0.0355 (8) | −0.0076 (7) | 0.0129 (6) | −0.0112 (7) |
O1 | 0.0368 (7) | 0.0242 (6) | 0.0723 (9) | −0.0010 (5) | 0.0331 (6) | −0.0005 (6) |
O2 | 0.0391 (7) | 0.0293 (6) | 0.0702 (9) | 0.0047 (5) | 0.0291 (7) | 0.0018 (6) |
O3 | 0.0622 (9) | 0.0590 (9) | 0.0723 (11) | −0.0087 (7) | 0.0443 (8) | 0.0089 (8) |
O4 | 0.0281 (7) | 0.1466 (18) | 0.0404 (8) | 0.0219 (9) | 0.0149 (6) | 0.0116 (9) |
Cl1 | 0.0355 (2) | 0.0380 (2) | 0.0323 (2) | −0.00006 (17) | 0.00555 (16) | 0.00463 (16) |
Geometric parameters (Å, º) top C1—N2 | 1.448 (2) | C6—N1 | 1.5140 (19) |
C1—N1 | 1.5105 (19) | C6—H6A | 0.99 |
C1—H1A | 0.99 | C6—H6B | 0.99 |
C1—H1B | 0.99 | N1—H1 | 0.90 (2) |
C2—N3 | 1.4724 (19) | C7—C12 | 1.390 (2) |
C2—N2 | 1.4766 (19) | C7—C8 | 1.399 (2) |
C2—H2A | 0.99 | C7—C13 | 1.522 (2) |
C2—H2B | 0.99 | C8—C9 | 1.393 (2) |
C3—N3 | 1.4475 (18) | C8—Cl1 | 1.7340 (16) |
C3—N1 | 1.5150 (18) | C9—C10 | 1.378 (2) |
C3—H3A | 0.99 | C9—H9 | 0.95 |
C3—H3B | 0.99 | C10—C11 | 1.379 (2) |
C4—N4 | 1.4714 (19) | C10—N5 | 1.473 (2) |
C4—N3 | 1.4746 (19) | C11—C12 | 1.379 (2) |
C4—H4A | 0.99 | C11—H11 | 0.95 |
C4—H4B | 0.99 | C12—H12 | 0.95 |
C5—N4 | 1.469 (2) | C13—O1 | 1.2454 (19) |
C5—N2 | 1.474 (2) | C13—O2 | 1.2454 (19) |
C5—H5A | 0.99 | N5—O3 | 1.219 (2) |
C5—H5B | 0.99 | N5—O4 | 1.219 (2) |
C6—N4 | 1.4454 (19) | | |
| | | |
N2—C1—N1 | 110.18 (11) | C6—N1—C3 | 108.36 (11) |
N2—C1—H1A | 109.6 | C1—N1—H1 | 109.4 (12) |
N1—C1—H1A | 109.6 | C6—N1—H1 | 111.2 (12) |
N2—C1—H1B | 109.6 | C3—N1—H1 | 110.4 (12) |
N1—C1—H1B | 109.6 | C1—N2—C5 | 108.64 (12) |
H1A—C1—H1B | 108.1 | C1—N2—C2 | 108.84 (12) |
N3—C2—N2 | 112.14 (12) | C5—N2—C2 | 108.28 (12) |
N3—C2—H2A | 109.2 | C3—N3—C2 | 109.46 (12) |
N2—C2—H2A | 109.2 | C3—N3—C4 | 108.80 (12) |
N3—C2—H2B | 109.2 | C2—N3—C4 | 107.99 (11) |
N2—C2—H2B | 109.2 | C6—N4—C5 | 108.79 (12) |
H2A—C2—H2B | 107.9 | C6—N4—C4 | 109.36 (11) |
N3—C3—N1 | 109.86 (11) | C5—N4—C4 | 108.80 (12) |
N3—C3—H3A | 109.7 | C12—C7—C8 | 118.18 (14) |
N1—C3—H3A | 109.7 | C12—C7—C13 | 116.36 (13) |
N3—C3—H3B | 109.7 | C8—C7—C13 | 125.45 (14) |
N1—C3—H3B | 109.7 | C9—C8—C7 | 121.08 (14) |
H3A—C3—H3B | 108.2 | C9—C8—Cl1 | 117.62 (12) |
N4—C4—N3 | 111.73 (11) | C7—C8—Cl1 | 121.27 (12) |
N4—C4—H4A | 109.3 | C10—C9—C8 | 117.76 (14) |
N3—C4—H4A | 109.3 | C10—C9—H9 | 121.1 |
N4—C4—H4B | 109.3 | C8—C9—H9 | 121.1 |
N3—C4—H4B | 109.3 | C9—C10—C11 | 123.26 (14) |
H4A—C4—H4B | 107.9 | C9—C10—N5 | 118.72 (14) |
N4—C5—N2 | 111.88 (12) | C11—C10—N5 | 118.00 (15) |
N4—C5—H5A | 109.2 | C12—C11—C10 | 117.61 (15) |
N2—C5—H5A | 109.2 | C12—C11—H11 | 121.2 |
N4—C5—H5B | 109.2 | C10—C11—H11 | 121.2 |
N2—C5—H5B | 109.2 | C11—C12—C7 | 122.11 (14) |
H5A—C5—H5B | 107.9 | C11—C12—H12 | 118.9 |
N4—C6—N1 | 109.79 (12) | C7—C12—H12 | 118.9 |
N4—C6—H6A | 109.7 | O1—C13—O2 | 125.36 (14) |
N1—C6—H6A | 109.7 | O1—C13—C7 | 118.49 (13) |
N4—C6—H6B | 109.7 | O2—C13—C7 | 115.79 (14) |
N1—C6—H6B | 109.7 | O3—N5—O4 | 123.66 (16) |
H6A—C6—H6B | 108.2 | O3—N5—C10 | 118.92 (15) |
C1—N1—C6 | 108.45 (11) | O4—N5—C10 | 117.42 (16) |
C1—N1—C3 | 109.01 (11) | | |
| | | |
N2—C1—N1—C6 | −58.92 (15) | N3—C4—N4—C5 | 58.67 (15) |
N2—C1—N1—C3 | 58.86 (15) | C12—C7—C8—C9 | −0.3 (2) |
N4—C6—N1—C1 | 59.13 (15) | C13—C7—C8—C9 | −178.99 (14) |
N4—C6—N1—C3 | −59.07 (14) | C12—C7—C8—Cl1 | 177.65 (11) |
N3—C3—N1—C1 | −58.31 (15) | C13—C7—C8—Cl1 | −1.0 (2) |
N3—C3—N1—C6 | 59.54 (15) | C7—C8—C9—C10 | −0.2 (2) |
N1—C1—N2—C5 | 58.93 (15) | Cl1—C8—C9—C10 | −178.17 (12) |
N1—C1—N2—C2 | −58.77 (15) | C8—C9—C10—C11 | 0.1 (2) |
N4—C5—N2—C1 | −60.34 (15) | C8—C9—C10—N5 | 178.05 (14) |
N4—C5—N2—C2 | 57.72 (16) | C9—C10—C11—C12 | 0.4 (2) |
N3—C2—N2—C1 | 59.64 (16) | N5—C10—C11—C12 | −177.55 (14) |
N3—C2—N2—C5 | −58.29 (16) | C10—C11—C12—C7 | −0.9 (2) |
N1—C3—N3—C2 | 58.23 (15) | C8—C7—C12—C11 | 0.9 (2) |
N1—C3—N3—C4 | −59.57 (15) | C13—C7—C12—C11 | 179.66 (14) |
N2—C2—N3—C3 | −59.64 (16) | C12—C7—C13—O1 | 131.29 (16) |
N2—C2—N3—C4 | 58.66 (16) | C8—C7—C13—O1 | −50.0 (2) |
N4—C4—N3—C3 | 60.13 (15) | C12—C7—C13—O2 | −42.2 (2) |
N4—C4—N3—C2 | −58.59 (15) | C8—C7—C13—O2 | 136.53 (17) |
N1—C6—N4—C5 | −59.65 (15) | C9—C10—N5—O3 | −168.41 (16) |
N1—C6—N4—C4 | 59.06 (15) | C11—C10—N5—O3 | 9.7 (2) |
N2—C5—N4—C6 | 60.87 (15) | C9—C10—N5—O4 | 12.0 (2) |
N2—C5—N4—C4 | −58.19 (15) | C11—C10—N5—O4 | −169.91 (17) |
N3—C4—N4—C6 | −60.04 (16) | | |
Hydrogen-bond geometry (Å, º) top D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.90 (2) | 1.80 (2) | 2.6911 (17) | 175.7 (19) |
Acknowledgements
This material is based upon work supported financially by the University of the Witwatersrand Friedel Sellschop Grant and the Molecular Sciences Institute. The National Research Foundation National Equipment Programme (UID: 78572) is thanked for financing the purchase of the single-crystal diffractometer. Any opinions, findings and conclusions or recommendations expressed in this material are those of the authors and therefore the NRF does not accept any liability in regard thereto.
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