research communications
Supramolecular patterns and Hirshfeld surface analysis in the
of bis(2-amino-4-methoxy-6-methylpyrimidinium) isophthalateaDepartment of Chemistry, Government Arts College (Autonomous), Thanthonimalai, Karur 639 005, Tamil Nadu, India, bDepartment of Chemistry, Government Arts College, Tiruchirappalli 620 022, Tamil Nadu, India, and cSchool of Physics, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia
*Correspondence e-mail: manavaibala@gmail.com
In the title molecular salt, 2C6H10N3O+·C8H4O42−, the N atom of each of the two 2-amino-4-methoxy-6-methylpyrimidine molecules lying between the amine and methyl groups has been protonated. The dihedral angles between the pyrimidine rings of the cations and the benzene ring of the succinate dianion are 5.04 (8) and 7.95 (8)°. Each of the cations is linked to the anion through a pair of N—H⋯O(carboxylate) hydrogen bonds, forming cyclic R22(8) ring motifs which are then linked through inversion-related N—H⋯O hydrogen bonds, giving a central R24(8) motif. Peripheral amine N—H⋯O hydrogen-bonding interactions on either side of the succinate anion, also through centrosymmetric R22(8) extensions, form one-dimensional ribbons extending along [211]. The also features π–π stacking interactions between the aromatic rings of the pyrimidine cations [minimum ring centroid separation = 3.6337 (9) Å]. The intermolecular interactions were also investigated using Hirshfeld surface studies and two-dimensional fingerprint images.
Keywords: crystal structure; 2-aminopyrimidines; isophthalates; hydrogen bonding; Hirshfeld surface analysis.
CCDC reference: 1559277
1. Chemical context
Pyrimidine and aminopyrimidine derivatives have useful applications in many fields, for example as pesticides and pharmaceutical agents (Condon et al., 1993), while imazosulfuron, ethirmol and mepanipyrim have been commercialized as agrochemicals (Maeno et al., 1990). Pyrimidine derivatives have also been developed as antiviral agents, such as AZT, which is the most widely used anti-AIDS drug (Gilchrist, 1997). Hydrogen bonding plays a vital role in molecular recognition. It is significant to know the types of hydrogen bonds present to design new materials with highly specific features. Supramolecular chemistry plays a pivotal role in many biological systems and is involved in artificial systems. It refers to the specific relation between two or more molecules through non-covalent interactions such as hydrogen bonding, hydrophobic forces, and π–π interactions. The origin of supramolecular architectures is correlated to the positions and properties of the active groups in molecules (Desiraju, 1989; Steiner, 2002). As part of our recent studies in this field, the synthesis, and Hirshfeld surface analysis of the title salt have been undertaken and are presented herein.
2. Structural commentary
The A and B) and an isophthalate dianion (Fig. 1). The cations and the anion are essentially planar with the dihedral angles between the pyrimidine rings of cation A and cation B and that of the benzene ring of the succinate dianion of 5.04 (8) and 7.96 (8)°, respectively. The pyrimidinium cations are protonated at N1A and N1B, which are present between the amine and methyl groups. The protonation is reflected in an enhancement in bond angles at N1A/N1B [C1A—N1A—C2A = 120.76 (13)°; C1B—N1B—C2B = 120.99 (14)°], when compared with those at the unprotonated atom N3A/N3B [C1A—N3A—C4A = 116.01 (14)°; C1B—N3B—C4B = 116.45 (13)°]. The corresponding angle in neutral 2-amino-4-methoxy-6-methylpyrimidine (Glidewell et al., 2003) is 116.01 (18)°. The bond lengths and angles are normal for the carboxylate groups of the isophthalate anion (Allen et al., 1987).
of the title salt comprises two 2-amino-4-methoxy-6-methylpyrimidinium cations (3. Supramolecular features
In the crystal, the protonated nitrogen atoms (N1A and N1B) and the 2-amino group nitrogen atoms (N2A and N2B) of the cations form two pairs of N—H⋯O hydrogen bonds with carboxyl O-atom acceptors (O3, O5) and (O2, O4), respectively, of the isophalate anion (Table 1 and Fig. 1). These form eight-membered ring motifs with graph-set notation R22(8) on either side of the pyrimidine dianion. The ring units are cyclically linked across a crystalligraphic inversion centre through four N—H⋯O hydrogen bonds [graph set R42(8)], providing a DDAA array of quadruple hydrogen bonds (D = H-atom donor, A = H-atom acceptor) represented by the overall graph-set notation R22(8), R42(8), R22(8), as shown in Fig. 2. The same type of conjoined motif has been reported in the crystal structures of trimethoprim hydrogen glutarate (Robert et al., 2001), 2-amino-4-methoxy-6-methylpyridinium trifluoroacetate (Jeevaraj et al., 2016) and 2-amino-4-methoxy-6-methylpyrimidinium 2-hydroxybenzoate (Jeevaraj et al., 2017).
The extension of the A— H⋯O2ii and N2B—H⋯O4i hydrogen bonds in centrosymmetric R42(8) interactions (for symmetry codes, see Table 1). These interactions result in one-dimensional ribbon structures extending along [211] (Fig. 3). The is further stablized by π–π stacking interactions between the aromatic rings of the pyrimidine cations, having centroid–centroid separations Cg⋯Cgiii of 3.6337 (9) for cation B and Cg⋯Cgiv of 3.7260 (9) Å for cation A [symmetry codes: (iii) −x + 2, −y + 1, −z + 1; (iv) −x, −y, −z].
is through lateral duplex N24. Hirshfeld surface analysis
The dnorm parameter takes negative or positive values depending upon whether the intermolecular close contact is shorter or longer than the van der Waals radii, respectively (Spackman & Jayatilaka, 2009; McKinnon et al., 2007). The 3D dnorm surface of the title salt is shown in Fig. 4. Colours are used to illustrate the contribution of intermolecular contacts present in the with red inidicating N—H⋯O interactions. Two-dimensional fingerprint images are depicted in Fig. 5, and from this study it is revealed that the H⋯H interactions present (48.8%) are a major contributor whereas O⋯H/H⋯O (17.9%), C⋯H/H⋯C (13.8%), N⋯H/H⋯N (8.3%), C⋯C (4.1%), C⋯O/O⋯C (2.8%), C⋯N/N⋯C (1.7%), O⋯O (1.1%), O⋯N/N⋯O (0.9%) and N⋯N (0.6%), have significant contribution to the total surface.
5. Database survey
A search of the Cambridge Structural Database (Version 5.37, update February 2014; Groom et al., 2016) for 2-amino-4-methoxy-6-methylpyrimidine yielded only seven structures: VAQSOW, VAQSUC, VAQSEM, VAQSIQ, VAQRUB and VAQSAI (Aakeröy et al., 2003); NUQTOJ (Jasinski et al., 2010).
6. Synthesis and crystallization
The title compound was synthesized in a reaction involving a hot methanolic solution (20 ml) of 2-amino-4-methoxy-6-methylpyrimidine (139 mg, 1.0 mmol) and a hot methanolic solution (20 ml) of isophthalic acid (166 mg, 1.0 mmol). The two solutions were mixed and stirred on a heating magnetic stirrer for few minutes. The colorless solution was cooled and kept at room temperature for slow evaporation. After a few days, the crystals of the title compound suitable for the X-ray analysis appeared, yield 65%.
7. Refinement
Crystal data, data collection and structure . The hydrogen atoms were positioned geometrically (N—H = 0.86 Å and C—H = 0.96 or 0.93 Å) and were refined using a riding model with Uiso(H) = 1.2 Ueq(N or C) or 1.5Ueq(methyl C).
details are summarized in Table 2
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Supporting information
CCDC reference: 1559277
https://doi.org/10.1107/S2056989017013950/zs2389sup1.cif
contains datablocks global, I, 1. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989017013950/zs2389Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989017013950/zs2389Isup3.cml
Data collection: APEX2 (Bruker, 2004); cell
XPREP (Bruker, 2004); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2015 (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).2C6H10N3O+·C8H4O42− | Z = 2 |
Mr = 444.45 | F(000) = 468 |
Triclinic, P1 | Dx = 1.344 Mg m−3 |
a = 8.1346 (3) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 8.2092 (3) Å | Cell parameters from 5061 reflections |
c = 17.2340 (6) Å | θ = 2.4–27.5° |
α = 92.4728 (12)° | µ = 0.10 mm−1 |
β = 91.3245 (13)° | T = 296 K |
γ = 107.0413 (12)° | Block, colourless |
V = 1098.54 (7) Å3 | 0.62 × 0.42 × 0.35 mm |
Bruker Kappa APEXII CCD diffractometer | 3717 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.028 |
ω and φ scans | θmax = 27.5°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Bruker, 2004) | h = −10→10 |
Tmin = 0.893, Tmax = 0.920 | k = −10→10 |
36645 measured reflections | l = −22→22 |
5061 independent reflections |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
wR(F2) = 0.151 | w = 1/[σ2(Fo2) + (0.0712P)2 + 0.2201P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.009 |
5060 reflections | Δρmax = 0.21 e Å−3 |
293 parameters | Δρmin = −0.19 e Å−3 |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
x | y | z | Uiso*/Ueq | ||
N1A | −0.01236 (16) | 0.13584 (16) | 0.12598 (7) | 0.0429 (3) | |
H1A | 0.055899 | 0.227779 | 0.147811 | 0.051* | |
N1B | 0.79527 (16) | 0.53363 (16) | 0.52792 (7) | 0.0432 (3) | |
H1B | 0.740866 | 0.559370 | 0.489182 | 0.052* | |
N2B | 0.92978 (19) | 0.81823 (16) | 0.55416 (8) | 0.0538 (4) | |
H2B1 | 1.001350 | 0.900179 | 0.581201 | 0.065* | |
H2B2 | 0.872417 | 0.840238 | 0.515499 | 0.065* | |
N2A | −0.0872 (2) | 0.29572 (17) | 0.03446 (8) | 0.0598 (4) | |
H2A1 | −0.146357 | 0.305927 | −0.006085 | 0.072* | |
H2A2 | −0.015998 | 0.384548 | 0.057300 | 0.072* | |
N3B | 0.99869 (17) | 0.62724 (16) | 0.63248 (7) | 0.0429 (3) | |
N3A | −0.21746 (17) | 0.00644 (16) | 0.02535 (8) | 0.0467 (3) | |
O1B | 1.05403 (17) | 0.42661 (15) | 0.70799 (7) | 0.0586 (3) | |
O1A | −0.33778 (18) | −0.28258 (16) | 0.02360 (9) | 0.0717 (4) | |
O2 | 0.16941 (18) | 0.57355 (16) | 0.10408 (8) | 0.0695 (4) | |
O3 | 0.21834 (16) | 0.39923 (14) | 0.18953 (7) | 0.0589 (3) | |
O4 | 0.79842 (17) | 0.88112 (15) | 0.41293 (7) | 0.0643 (4) | |
O5 | 0.64086 (15) | 0.61013 (14) | 0.40389 (7) | 0.0555 (3) | |
C1B | 0.90804 (19) | 0.65930 (18) | 0.57191 (8) | 0.0410 (3) | |
C1A | −0.10574 (19) | 0.14466 (19) | 0.06145 (9) | 0.0425 (3) | |
C2B | 0.7665 (2) | 0.36687 (19) | 0.54402 (9) | 0.0456 (4) | |
C2A | −0.0249 (2) | −0.0166 (2) | 0.15691 (10) | 0.0487 (4) | |
C3B | 0.8530 (2) | 0.3293 (2) | 0.60541 (10) | 0.0515 (4) | |
H3BA | 0.836264 | 0.217138 | 0.618682 | 0.062* | |
C3A | −0.1312 (3) | −0.1589 (2) | 0.12097 (12) | 0.0605 (5) | |
H3AA | −0.139979 | −0.266164 | 0.139045 | 0.073* | |
C4B | 0.9690 (2) | 0.4660 (2) | 0.64837 (9) | 0.0454 (4) | |
C4A | −0.2281 (2) | −0.1402 (2) | 0.05555 (10) | 0.0517 (4) | |
C5B | 0.6421 (2) | 0.2386 (2) | 0.49067 (12) | 0.0607 (5) | |
H5BA | 0.532723 | 0.261138 | 0.490466 | 0.091* | |
H5BB | 0.628885 | 0.126229 | 0.508184 | 0.091* | |
H5BC | 0.684565 | 0.246030 | 0.439034 | 0.091* | |
C5A | 0.0783 (3) | −0.0105 (3) | 0.23016 (12) | 0.0660 (5) | |
H5AA | 0.193899 | 0.060400 | 0.224298 | 0.099* | |
H5AB | 0.079853 | −0.123711 | 0.241133 | 0.099* | |
H5AC | 0.027678 | 0.035789 | 0.272238 | 0.099* | |
C6B | 1.1837 (3) | 0.5631 (2) | 0.74878 (11) | 0.0634 (5) | |
H6BA | 1.237028 | 0.517871 | 0.789506 | 0.095* | |
H6BB | 1.131620 | 0.644482 | 0.770828 | 0.095* | |
H6BC | 1.269111 | 0.618162 | 0.713223 | 0.095* | |
C6A | −0.4472 (3) | −0.2673 (3) | −0.04086 (14) | 0.0779 (6) | |
H6AA | −0.527231 | −0.376790 | −0.054897 | 0.117* | |
H6AB | −0.378123 | −0.226479 | −0.084393 | 0.117* | |
H6AC | −0.509236 | −0.188282 | −0.026269 | 0.117* | |
C7 | 0.2483 (2) | 0.5433 (2) | 0.16146 (9) | 0.0436 (4) | |
C8 | 0.38688 (18) | 0.68720 (19) | 0.20172 (8) | 0.0389 (3) | |
C9 | 0.4277 (2) | 0.8500 (2) | 0.17444 (9) | 0.0472 (4) | |
H9A | 0.372680 | 0.869938 | 0.129514 | 0.057* | |
C10 | 0.5503 (2) | 0.9830 (2) | 0.21387 (10) | 0.0553 (4) | |
H10A | 0.577106 | 1.092201 | 0.195488 | 0.066* | |
C11 | 0.6331 (2) | 0.9540 (2) | 0.28053 (10) | 0.0476 (4) | |
H11A | 0.714413 | 1.044147 | 0.307115 | 0.057* | |
C12 | 0.59580 (18) | 0.79158 (19) | 0.30793 (8) | 0.0391 (3) | |
C13 | 0.47164 (18) | 0.65826 (19) | 0.26823 (8) | 0.0389 (3) | |
H13A | 0.445286 | 0.548907 | 0.286444 | 0.047* | |
C14 | 0.68577 (19) | 0.7582 (2) | 0.38013 (9) | 0.0431 (3) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1A | 0.0455 (7) | 0.0362 (7) | 0.0437 (7) | 0.0074 (5) | −0.0061 (5) | 0.0030 (5) |
N1B | 0.0458 (7) | 0.0367 (7) | 0.0409 (7) | 0.0029 (5) | −0.0040 (5) | 0.0018 (5) |
N2B | 0.0680 (9) | 0.0341 (7) | 0.0506 (8) | 0.0035 (6) | −0.0239 (7) | 0.0028 (6) |
N2A | 0.0728 (10) | 0.0390 (7) | 0.0543 (8) | −0.0031 (7) | −0.0290 (7) | 0.0093 (6) |
N3B | 0.0522 (7) | 0.0362 (7) | 0.0371 (6) | 0.0081 (5) | −0.0031 (5) | 0.0036 (5) |
N3A | 0.0479 (7) | 0.0383 (7) | 0.0468 (7) | 0.0024 (6) | −0.0024 (6) | −0.0007 (6) |
O1B | 0.0770 (8) | 0.0444 (7) | 0.0530 (7) | 0.0152 (6) | −0.0096 (6) | 0.0127 (5) |
O1A | 0.0745 (9) | 0.0378 (7) | 0.0886 (10) | −0.0031 (6) | −0.0095 (8) | −0.0065 (6) |
O2 | 0.0835 (9) | 0.0479 (7) | 0.0617 (8) | −0.0022 (6) | −0.0408 (7) | 0.0097 (6) |
O3 | 0.0671 (8) | 0.0410 (6) | 0.0575 (7) | 0.0003 (5) | −0.0270 (6) | 0.0067 (5) |
O4 | 0.0736 (8) | 0.0427 (7) | 0.0608 (7) | −0.0046 (6) | −0.0352 (6) | 0.0032 (5) |
O5 | 0.0626 (7) | 0.0425 (6) | 0.0511 (7) | 0.0008 (5) | −0.0204 (5) | 0.0053 (5) |
C1B | 0.0473 (8) | 0.0342 (7) | 0.0371 (7) | 0.0055 (6) | −0.0010 (6) | 0.0008 (6) |
C1A | 0.0447 (8) | 0.0376 (8) | 0.0408 (8) | 0.0055 (6) | −0.0031 (6) | 0.0015 (6) |
C2B | 0.0465 (8) | 0.0344 (8) | 0.0488 (9) | 0.0005 (6) | 0.0089 (7) | 0.0004 (6) |
C2A | 0.0509 (9) | 0.0431 (9) | 0.0538 (9) | 0.0152 (7) | 0.0031 (7) | 0.0114 (7) |
C3B | 0.0630 (10) | 0.0332 (8) | 0.0540 (9) | 0.0064 (7) | 0.0052 (8) | 0.0082 (7) |
C3A | 0.0695 (11) | 0.0369 (9) | 0.0731 (12) | 0.0117 (8) | −0.0006 (9) | 0.0108 (8) |
C4B | 0.0552 (9) | 0.0393 (8) | 0.0408 (8) | 0.0112 (7) | 0.0056 (7) | 0.0078 (6) |
C4A | 0.0518 (9) | 0.0378 (8) | 0.0591 (10) | 0.0038 (7) | 0.0044 (8) | −0.0025 (7) |
C5B | 0.0604 (10) | 0.0429 (9) | 0.0657 (11) | −0.0034 (8) | −0.0003 (9) | −0.0058 (8) |
C5A | 0.0691 (12) | 0.0608 (11) | 0.0697 (12) | 0.0200 (9) | −0.0108 (10) | 0.0205 (10) |
C6B | 0.0791 (12) | 0.0531 (10) | 0.0561 (10) | 0.0177 (9) | −0.0205 (9) | 0.0053 (8) |
C6A | 0.0690 (12) | 0.0590 (12) | 0.0871 (15) | −0.0055 (10) | −0.0173 (11) | −0.0166 (11) |
C7 | 0.0466 (8) | 0.0404 (8) | 0.0394 (8) | 0.0073 (6) | −0.0112 (6) | 0.0004 (6) |
C8 | 0.0378 (7) | 0.0383 (8) | 0.0379 (7) | 0.0076 (6) | −0.0033 (6) | −0.0007 (6) |
C9 | 0.0502 (8) | 0.0441 (8) | 0.0442 (8) | 0.0097 (7) | −0.0116 (7) | 0.0046 (7) |
C10 | 0.0610 (10) | 0.0372 (8) | 0.0610 (10) | 0.0041 (7) | −0.0126 (8) | 0.0094 (7) |
C11 | 0.0473 (8) | 0.0369 (8) | 0.0515 (9) | 0.0029 (6) | −0.0118 (7) | −0.0022 (7) |
C12 | 0.0366 (7) | 0.0401 (8) | 0.0384 (7) | 0.0086 (6) | −0.0031 (6) | −0.0008 (6) |
C13 | 0.0389 (7) | 0.0357 (7) | 0.0387 (7) | 0.0065 (6) | −0.0051 (6) | 0.0003 (6) |
C14 | 0.0425 (8) | 0.0407 (8) | 0.0412 (8) | 0.0062 (6) | −0.0088 (6) | −0.0018 (6) |
N1A—C1A | 1.3488 (19) | C3B—C4B | 1.405 (2) |
N1A—C2A | 1.359 (2) | C3B—H3BA | 0.9300 |
N1A—H1A | 0.8600 | C3A—C4A | 1.400 (3) |
N1B—C1B | 1.3514 (19) | C3A—H3AA | 0.9300 |
N1B—C2B | 1.361 (2) | C5B—H5BA | 0.9600 |
N1B—H1B | 0.8600 | C5B—H5BB | 0.9600 |
N2B—C1B | 1.3149 (19) | C5B—H5BC | 0.9600 |
N2B—H2B1 | 0.8600 | C5A—H5AA | 0.9600 |
N2B—H2B2 | 0.8600 | C5A—H5AB | 0.9600 |
N2A—C1A | 1.312 (2) | C5A—H5AC | 0.9600 |
N2A—H2A1 | 0.8600 | C6B—H6BA | 0.9600 |
N2A—H2A2 | 0.8600 | C6B—H6BB | 0.9600 |
N3B—C4B | 1.3166 (19) | C6B—H6BC | 0.9600 |
N3B—C1B | 1.3433 (19) | C6A—H6AA | 0.9600 |
N3A—C4A | 1.312 (2) | C6A—H6AB | 0.9600 |
N3A—C1A | 1.3450 (19) | C6A—H6AC | 0.9600 |
O1B—C4B | 1.3284 (19) | C7—C8 | 1.503 (2) |
O1B—C6B | 1.438 (2) | C8—C9 | 1.385 (2) |
O1A—C4A | 1.333 (2) | C8—C13 | 1.389 (2) |
O1A—C6A | 1.440 (3) | C9—C10 | 1.384 (2) |
O2—C7 | 1.2394 (18) | C9—H9A | 0.9300 |
O3—C7 | 1.2565 (19) | C10—C11 | 1.383 (2) |
O4—C14 | 1.2500 (18) | C10—H10A | 0.9300 |
O5—C14 | 1.2522 (19) | C11—C12 | 1.384 (2) |
C2B—C3B | 1.353 (2) | C11—H11A | 0.9300 |
C2B—C5B | 1.492 (2) | C12—C13 | 1.3934 (19) |
C2A—C3A | 1.348 (3) | C12—C14 | 1.505 (2) |
C2A—C5A | 1.491 (2) | C13—H13A | 0.9300 |
C1A—N1A—C2A | 120.76 (13) | H5BA—C5B—H5BC | 109.5 |
C1A—N1A—H1A | 119.6 | H5BB—C5B—H5BC | 109.5 |
C2A—N1A—H1A | 119.6 | C2A—C5A—H5AA | 109.5 |
C1B—N1B—C2B | 120.99 (14) | C2A—C5A—H5AB | 109.5 |
C1B—N1B—H1B | 119.5 | H5AA—C5A—H5AB | 109.5 |
C2B—N1B—H1B | 119.5 | C2A—C5A—H5AC | 109.5 |
C1B—N2B—H2B1 | 120.0 | H5AA—C5A—H5AC | 109.5 |
C1B—N2B—H2B2 | 120.0 | H5AB—C5A—H5AC | 109.5 |
H2B1—N2B—H2B2 | 120.0 | O1B—C6B—H6BA | 109.5 |
C1A—N2A—H2A1 | 120.0 | O1B—C6B—H6BB | 109.5 |
C1A—N2A—H2A2 | 120.0 | H6BA—C6B—H6BB | 109.5 |
H2A1—N2A—H2A2 | 120.0 | O1B—C6B—H6BC | 109.5 |
C4B—N3B—C1B | 116.45 (13) | H6BA—C6B—H6BC | 109.5 |
C4A—N3A—C1A | 116.01 (14) | H6BB—C6B—H6BC | 109.5 |
C4B—O1B—C6B | 117.64 (13) | O1A—C6A—H6AA | 109.5 |
C4A—O1A—C6A | 117.94 (15) | O1A—C6A—H6AB | 109.5 |
N2B—C1B—N3B | 119.21 (13) | H6AA—C6A—H6AB | 109.5 |
N2B—C1B—N1B | 118.44 (14) | O1A—C6A—H6AC | 109.5 |
N3B—C1B—N1B | 122.34 (14) | H6AA—C6A—H6AC | 109.5 |
N2A—C1A—N3A | 119.59 (14) | H6AB—C6A—H6AC | 109.5 |
N2A—C1A—N1A | 117.70 (13) | O2—C7—O3 | 124.16 (14) |
N3A—C1A—N1A | 122.70 (14) | O2—C7—C8 | 118.79 (14) |
C3B—C2B—N1B | 118.51 (14) | O3—C7—C8 | 117.04 (13) |
C3B—C2B—C5B | 125.04 (15) | C9—C8—C13 | 119.47 (13) |
N1B—C2B—C5B | 116.44 (15) | C9—C8—C7 | 120.64 (13) |
C3A—C2A—N1A | 118.38 (16) | C13—C8—C7 | 119.86 (13) |
C3A—C2A—C5A | 125.42 (16) | C10—C9—C8 | 120.16 (14) |
N1A—C2A—C5A | 116.17 (15) | C10—C9—H9A | 119.9 |
C2B—C3B—C4B | 117.56 (15) | C8—C9—H9A | 119.9 |
C2B—C3B—H3BA | 121.2 | C11—C10—C9 | 120.19 (15) |
C4B—C3B—H3BA | 121.2 | C11—C10—H10A | 119.9 |
C2A—C3A—C4A | 117.88 (16) | C9—C10—H10A | 119.9 |
C2A—C3A—H3AA | 121.1 | C10—C11—C12 | 120.42 (14) |
C4A—C3A—H3AA | 121.1 | C10—C11—H11A | 119.8 |
N3B—C4B—O1B | 119.14 (14) | C12—C11—H11A | 119.8 |
N3B—C4B—C3B | 124.12 (15) | C11—C12—C13 | 119.16 (13) |
O1B—C4B—C3B | 116.73 (14) | C11—C12—C14 | 120.92 (13) |
N3A—C4A—O1A | 119.48 (17) | C13—C12—C14 | 119.91 (13) |
N3A—C4A—C3A | 124.20 (15) | C8—C13—C12 | 120.59 (14) |
O1A—C4A—C3A | 116.31 (16) | C8—C13—H13A | 119.7 |
C2B—C5B—H5BA | 109.5 | C12—C13—H13A | 119.7 |
C2B—C5B—H5BB | 109.5 | O4—C14—O5 | 124.55 (14) |
H5BA—C5B—H5BB | 109.5 | O4—C14—C12 | 117.59 (14) |
C2B—C5B—H5BC | 109.5 | O5—C14—C12 | 117.85 (13) |
C4B—N3B—C1B—N2B | 178.73 (15) | C1A—N3A—C4A—C3A | −0.4 (3) |
C4B—N3B—C1B—N1B | −1.7 (2) | C6A—O1A—C4A—N3A | −3.3 (3) |
C2B—N1B—C1B—N2B | −179.43 (14) | C6A—O1A—C4A—C3A | 176.28 (18) |
C2B—N1B—C1B—N3B | 1.0 (2) | C2A—C3A—C4A—N3A | 2.5 (3) |
C4A—N3A—C1A—N2A | 179.66 (16) | C2A—C3A—C4A—O1A | −176.97 (17) |
C4A—N3A—C1A—N1A | −1.6 (2) | O2—C7—C8—C9 | −1.1 (2) |
C2A—N1A—C1A—N2A | −179.80 (15) | O3—C7—C8—C9 | 179.99 (15) |
C2A—N1A—C1A—N3A | 1.4 (2) | O2—C7—C8—C13 | 177.05 (15) |
C1B—N1B—C2B—C3B | 0.2 (2) | O3—C7—C8—C13 | −1.9 (2) |
C1B—N1B—C2B—C5B | −178.77 (14) | C13—C8—C9—C10 | −0.9 (2) |
C1A—N1A—C2A—C3A | 0.8 (2) | C7—C8—C9—C10 | 177.20 (15) |
C1A—N1A—C2A—C5A | −177.42 (15) | C8—C9—C10—C11 | 0.3 (3) |
N1B—C2B—C3B—C4B | −0.6 (2) | C9—C10—C11—C12 | 0.8 (3) |
C5B—C2B—C3B—C4B | 178.30 (16) | C10—C11—C12—C13 | −1.1 (2) |
N1A—C2A—C3A—C4A | −2.6 (3) | C10—C11—C12—C14 | 179.64 (15) |
C5A—C2A—C3A—C4A | 175.43 (18) | C9—C8—C13—C12 | 0.6 (2) |
C1B—N3B—C4B—O1B | −179.52 (14) | C7—C8—C13—C12 | −177.54 (14) |
C1B—N3B—C4B—C3B | 1.3 (2) | C11—C12—C13—C8 | 0.4 (2) |
C6B—O1B—C4B—N3B | −4.3 (2) | C14—C12—C13—C8 | 179.69 (14) |
C6B—O1B—C4B—C3B | 174.96 (16) | C11—C12—C14—O4 | −2.0 (2) |
C2B—C3B—C4B—N3B | −0.1 (3) | C13—C12—C14—O4 | 178.71 (15) |
C2B—C3B—C4B—O1B | −179.39 (15) | C11—C12—C14—O5 | 176.88 (15) |
C1A—N3A—C4A—O1A | 179.08 (15) | C13—C12—C14—O5 | −2.4 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2B—H2B1···O4i | 0.86 | 2.04 | 2.8150 (19) | 150 |
N1A—H1A···O3 | 0.86 | 1.74 | 2.5921 (17) | 171 |
N1B—H1B···O5 | 0.86 | 1.79 | 2.6448 (17) | 175 |
N2B—H2B2···O4 | 0.86 | 1.93 | 2.7648 (19) | 164 |
N2A—H2A1···O2ii | 0.86 | 2.03 | 2.805 (2) | 150 |
N2A—H2A2···O2 | 0.86 | 1.95 | 2.803 (2) | 172 |
Symmetry codes: (i) −x+2, −y+2, −z+1; (ii) −x, −y+1, −z. |
Footnotes
‡Thomson Reuters ResearcherID: A-5599-2009.
Funding information
KB and PS thank the Department of Science and Technology (DST-SERB), grant No. SB/FT/CS-058/2013, New Delhi, India, for financial support.
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