organic compounds
Hydrogen-bonding patterns in trimethoprim tetrafluoroborate
aSchool of Chemistry, Bharathidasan University, Tiruchirappalli 620 024, Tamil Nadu, India, and bFaculty of Health and Life Sciences, Coventry University, Coventry CV1 5FB, England
*Correspondence e-mail: tommtrichy@yahoo.co.in
In the title compound [systematic name: 2,4-diamino-5-(3,4,5-trimethoxybenzyl)pyrimidinium tetrafluoroborate], C14H19N4O3+·BF4−, the trimethoprim (TMP) molecule is protonated at one of the pyrimidine N atoms. The protonated N atom and 2-amine group of the TMP cation interact with the tetrafluoroborate anion through a pair of N—H⋯F hydrogen bonds [graph set R22(8)]. The inversion-related TMP cations are linked through a pair of N—H⋯N hydrogen bonds. The 2-amine group of one TMP cation and the 4-amine group of another cation are bridged by a methoxy O atom, via N—H⋯O hydrogen bonds.
Comment
Trimethoprim [2,4-diamino-5-(3′,4′,5′-trimethoxybenzyl)pyrimidine or TMP] is a well known antifolate drug. It is a potent inhibitor of bacterial dihydrofolate reductase (DHFR) but is less effective against human DHFR. The drug (TMP) in its N1-protonated form inhibits DHFR. The ) and its complexes, for example, trimethoprim monobenzoate benzoic acid (Bettinetti et al., 1985) and trimethoprim acetate (Bryan et al., 1987), have been reported in the literature. The present study has been undertaken to explore the hydrogen-bonding patterns involving the TMP cation in a variety of environments. The crystal structures of TMP sulfate trihydrate (Muthiah et al., 2001), TMP nitrate (Murugesan & Muthiah, 1997) and TMP carboxylates (Stanley et al., 2005) have also been reported from our laboratory.
of trimethoprim (Koetzle & Williams, 1976The contains a protonated trimethoprim (TMP) cation and a tetrafluoroborate anion (FLUB) (Fig. 1). The trimethoprim molecule is protonated at atom N1 of the pyrimidine moiety, which is evident from the increase in the internal angle at protonated N1 [C2—N1—C6 = 120.15 (13)°] compared with that at unprotonated atom N3 [C2—N3—C4 = 118.36 (14)°]. The dihedral angle between the pyrimidine and benzene planes is 84.27 (7)°; the corresponding angle in trimethoprim perchlorate is 83.7 (2)° (Muthiah et al., 2002). The conformation of the trimethoprim cation is described by the two torsion angles C4—C5—C7—C8 and C5—C7—C8—C9, which are 77.84 (19) and −158.03 (14)°, respectively. The distorted tetrahedral BF4 ion has typical B—F distances.
of (I)Atoms F2 and F1 act as acceptors in N—H⋯F interactions (Table 2) with the protonated pyrimidine N1 and 2-amine group of the TMP cation, leading to the formation of a fork-like hydrogen-bonding pattern with graph-set notation R22(8) (Etter, 1990; Bernstein et al., 1995). The R22(8) motif is frequently observed in aminopyrimidine carboxylate salts (Lynch & Jones, 2004). Here the tetrafluoroborate anion mimics the role of the carboxylate group. The TMP cations are paired centrosymmetrically through N4—H4A⋯N3iii and N3⋯H4Aiii—N4iii hydrogen bonds (symmetry codes are given in Table 2). The 2-amine group of one TMP cation and the 4-amine group of another cation (both of these cations being members of a base pair) are bridged by methoxy atom O1, using a pair of N—H⋯O hydrogen bonds, leading to a complementary DADA (D = donor in hydrogen bonds, A = acceptor in hydrogen bonds) array of quadruple hydrogen bonds (Fig. 2). This pattern is similar to that reported in TMP nitrate (Murugesan & Muthiah, 1997), TMP trifluoroacetate (Francis et al., 2002), and TMP salicylate methanol solvate (Panneerselvam et al., 2002). The hydrogen-bonding parameters are listed in Table 2.
Experimental
Hot aqueous solutions of trimethoprim (145 mg; obtained as a gift sample from Shilpa Antibiotics Ltd) and tetrafluoroboric acid (220 mg of 40% solution; Aldrich) were mixed in a 1:2 molar ratio. The resulting solution was warmed over a water bath for a few minutes and then kept at room temperature for crystallization. After a few days, block-shaped colourless crystals of (I) were obtained.
Crystal data
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Data collection
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Refinement
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All H atoms were placed in idealized locations and were refined using a riding model, with C—H = 0.95–0.99 Å, N—H = 0.88 Å and Uiso(H) = 1.2Ueq(C,N). Two of the F atoms in the BF4 group are disordered over two positions, and the occupancy factors for the disordered positions F3A/F3B and F4A/F4B were refined to 0.60 (2)/0.40 (2). Similarity restraints were applied to distances involving disordered atoms.
Data collection: COLLECT (Hooft, 1998); cell DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.
Supporting information
https://doi.org/10.1107/S1600536805036615/ci6673sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536805036615/ci6673Isup2.hkl
Data collection: COLLECT (Hooft, 1998); cell
DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.C14H19N4O3+·BF4− | Z = 2 |
Mr = 378.14 | F(000) = 392 |
Triclinic, P1 | Dx = 1.518 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.4105 (3) Å | Cell parameters from 3811 reflections |
b = 9.5397 (2) Å | θ = 3.0–27.6° |
c = 10.1276 (4) Å | µ = 0.14 mm−1 |
α = 88.564 (2)° | T = 120 K |
β = 73.253 (2)° | Block, colourless |
γ = 72.304 (2)° | 0.18 × 0.16 × 0.09 mm |
V = 827.48 (5) Å3 |
Bruker–Nonius KappaCCD area-detector diffractometer | 3193 reflections with I > 2σ(I) |
Radiation source: Bruker–Nonius FR591 rotating anode | Rint = 0.041 |
Graphite monochromator | θmax = 27.6°, θmin = 3.0° |
φ and ω scans | h = −12→12 |
18185 measured reflections | k = −12→12 |
3811 independent reflections | l = −13→13 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.132 | w = 1/[σ2(Fo2) + (0.0644P)2 + 0.2497P] where P = (Fo2 + 2Fc2)/3 |
S = 1.15 | (Δ/σ)max = 0.001 |
3811 reflections | Δρmax = 0.61 e Å−3 |
255 parameters | Δρmin = −0.52 e Å−3 |
6 restraints | Extinction correction: SHELXL97, FC*=KFC[1+0.001XFC2Λ3/SIN(2Θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.133 (9) |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
O1 | −0.22859 (13) | 0.61645 (12) | 0.66705 (11) | 0.0221 (3) | |
O2 | −0.06715 (14) | 0.72735 (13) | 0.78897 (11) | 0.0248 (3) | |
O3 | 0.15105 (13) | 0.84755 (12) | 0.64102 (11) | 0.0235 (3) | |
N1 | 0.28278 (15) | 0.96385 (14) | −0.00878 (13) | 0.0199 (4) | |
N2 | 0.53520 (16) | 0.86442 (15) | −0.15031 (14) | 0.0246 (4) | |
N3 | 0.40722 (15) | 0.70767 (14) | −0.03325 (13) | 0.0195 (4) | |
N4 | 0.28298 (16) | 0.55383 (14) | 0.09004 (15) | 0.0238 (4) | |
C2 | 0.40794 (18) | 0.84404 (17) | −0.06383 (15) | 0.0190 (4) | |
C4 | 0.27950 (18) | 0.68998 (17) | 0.05895 (15) | 0.0186 (4) | |
C5 | 0.14285 (18) | 0.81297 (17) | 0.12055 (15) | 0.0182 (4) | |
C6 | 0.15165 (18) | 0.94728 (17) | 0.08297 (16) | 0.0192 (4) | |
C7 | −0.00296 (17) | 0.79327 (17) | 0.21807 (16) | 0.0199 (4) | |
C8 | −0.00211 (17) | 0.76276 (16) | 0.36594 (15) | 0.0185 (4) | |
C9 | −0.10785 (17) | 0.69467 (16) | 0.44282 (16) | 0.0190 (4) | |
C10 | −0.12541 (17) | 0.68018 (16) | 0.58268 (16) | 0.0188 (4) | |
C11 | −0.03807 (18) | 0.73361 (16) | 0.64772 (16) | 0.0196 (4) | |
C12 | 0.07051 (18) | 0.79892 (16) | 0.56898 (16) | 0.0196 (4) | |
C13 | 0.08929 (18) | 0.81245 (17) | 0.42804 (16) | 0.0194 (4) | |
C14 | −0.3298 (2) | 0.57224 (19) | 0.60493 (18) | 0.0266 (5) | |
C15 | 0.0542 (2) | 0.62255 (19) | 0.83157 (18) | 0.0298 (5) | |
C16 | 0.28441 (19) | 0.8868 (2) | 0.56058 (18) | 0.0266 (5) | |
F1 | 0.56011 (11) | 0.15397 (11) | 0.78546 (10) | 0.0272 (3) | |
F2 | 0.30228 (12) | 0.24550 (11) | 0.90592 (11) | 0.0322 (3) | |
F3A | 0.3745 (7) | 0.1814 (13) | 0.6750 (7) | 0.083 (2) | 0.60 (2) |
F4A | 0.4213 (9) | 0.3796 (4) | 0.7583 (15) | 0.083 (2) | 0.60 (2) |
B1 | 0.4133 (2) | 0.23827 (19) | 0.7771 (2) | 0.0276 (6) | |
F3B | 0.3813 (8) | 0.1471 (6) | 0.6919 (6) | 0.0282 (16) | 0.40 (2) |
F4B | 0.4046 (11) | 0.3723 (5) | 0.7221 (6) | 0.0322 (16) | 0.40 (2) |
H1 | 0.28620 | 1.05250 | −0.03210 | 0.0240* | |
H2A | 0.61790 | 0.78820 | −0.18670 | 0.0300* | |
H2B | 0.53670 | 0.95420 | −0.17110 | 0.0300* | |
H4A | 0.36650 | 0.47940 | 0.05090 | 0.0290* | |
H4B | 0.20180 | 0.53760 | 0.14980 | 0.0290* | |
H6 | 0.06490 | 1.03210 | 0.12110 | 0.0230* | |
H7A | −0.02500 | 0.71090 | 0.17900 | 0.0240* | |
H7B | −0.09060 | 0.88360 | 0.22080 | 0.0240* | |
H9 | −0.16780 | 0.65820 | 0.39950 | 0.0230* | |
H13 | 0.16410 | 0.85550 | 0.37460 | 0.0230* | |
H14A | −0.39000 | 0.65770 | 0.56720 | 0.0320* | |
H14B | −0.40140 | 0.53330 | 0.67510 | 0.0320* | |
H14C | −0.26680 | 0.49570 | 0.53040 | 0.0320* | |
H15A | 0.07690 | 0.52510 | 0.78690 | 0.0360* | |
H15B | 0.02010 | 0.61800 | 0.93220 | 0.0360* | |
H15C | 0.14860 | 0.65310 | 0.80480 | 0.0360* | |
H16A | 0.35430 | 0.80460 | 0.49390 | 0.0320* | |
H16B | 0.34000 | 0.90840 | 0.62190 | 0.0320* | |
H16C | 0.25000 | 0.97420 | 0.51100 | 0.0320* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0211 (6) | 0.0236 (6) | 0.0208 (6) | −0.0100 (5) | −0.0018 (5) | 0.0043 (4) |
O2 | 0.0277 (6) | 0.0273 (6) | 0.0159 (6) | −0.0064 (5) | −0.0036 (5) | 0.0030 (4) |
O3 | 0.0241 (6) | 0.0297 (6) | 0.0193 (6) | −0.0123 (5) | −0.0059 (5) | 0.0008 (4) |
N1 | 0.0206 (7) | 0.0182 (6) | 0.0204 (7) | −0.0069 (5) | −0.0045 (5) | 0.0037 (5) |
N2 | 0.0212 (7) | 0.0191 (7) | 0.0281 (7) | −0.0068 (5) | 0.0014 (6) | 0.0036 (5) |
N3 | 0.0195 (7) | 0.0190 (6) | 0.0183 (6) | −0.0064 (5) | −0.0026 (5) | 0.0019 (5) |
N4 | 0.0194 (7) | 0.0195 (7) | 0.0271 (7) | −0.0058 (5) | 0.0008 (6) | 0.0036 (5) |
C2 | 0.0205 (8) | 0.0214 (8) | 0.0162 (7) | −0.0079 (6) | −0.0054 (6) | 0.0016 (6) |
C4 | 0.0189 (7) | 0.0219 (8) | 0.0163 (7) | −0.0081 (6) | −0.0054 (6) | 0.0024 (6) |
C5 | 0.0178 (7) | 0.0233 (8) | 0.0142 (7) | −0.0071 (6) | −0.0048 (6) | 0.0016 (6) |
C6 | 0.0173 (7) | 0.0224 (8) | 0.0168 (7) | −0.0051 (6) | −0.0043 (6) | 0.0008 (6) |
C7 | 0.0162 (7) | 0.0239 (8) | 0.0185 (7) | −0.0066 (6) | −0.0032 (6) | 0.0010 (6) |
C8 | 0.0158 (7) | 0.0184 (7) | 0.0174 (7) | −0.0027 (6) | −0.0017 (6) | 0.0007 (5) |
C9 | 0.0161 (7) | 0.0175 (7) | 0.0218 (8) | −0.0046 (6) | −0.0039 (6) | 0.0005 (6) |
C10 | 0.0166 (7) | 0.0152 (7) | 0.0202 (8) | −0.0035 (6) | −0.0003 (6) | 0.0023 (6) |
C11 | 0.0196 (7) | 0.0187 (7) | 0.0162 (7) | −0.0032 (6) | −0.0016 (6) | 0.0011 (5) |
C12 | 0.0170 (7) | 0.0188 (7) | 0.0208 (8) | −0.0038 (6) | −0.0042 (6) | 0.0000 (6) |
C13 | 0.0162 (7) | 0.0210 (7) | 0.0189 (7) | −0.0058 (6) | −0.0018 (6) | 0.0012 (6) |
C14 | 0.0245 (8) | 0.0283 (9) | 0.0282 (9) | −0.0136 (7) | −0.0040 (7) | 0.0029 (7) |
C15 | 0.0392 (10) | 0.0273 (9) | 0.0239 (9) | −0.0084 (7) | −0.0132 (8) | 0.0054 (7) |
C16 | 0.0216 (8) | 0.0341 (9) | 0.0254 (8) | −0.0124 (7) | −0.0045 (7) | −0.0010 (7) |
F1 | 0.0221 (5) | 0.0325 (5) | 0.0288 (5) | −0.0086 (4) | −0.0101 (4) | 0.0049 (4) |
F2 | 0.0281 (6) | 0.0300 (5) | 0.0319 (6) | −0.0094 (4) | 0.0015 (4) | 0.0051 (4) |
F3A | 0.0294 (18) | 0.177 (6) | 0.0344 (18) | −0.012 (3) | −0.0181 (14) | 0.006 (3) |
F4A | 0.036 (2) | 0.041 (2) | 0.137 (6) | −0.0033 (16) | 0.015 (4) | 0.052 (3) |
B1 | 0.0211 (9) | 0.0302 (10) | 0.0292 (10) | −0.0077 (8) | −0.0052 (8) | 0.0113 (8) |
F3B | 0.027 (2) | 0.028 (3) | 0.037 (3) | −0.0106 (13) | −0.0177 (18) | −0.0065 (15) |
F4B | 0.038 (3) | 0.025 (2) | 0.027 (3) | −0.0061 (16) | −0.0042 (15) | 0.0111 (15) |
F1—B1 | 1.397 (2) | C5—C7 | 1.503 (2) |
F2—B1 | 1.405 (2) | C5—C6 | 1.347 (2) |
F3A—B1 | 1.365 (8) | C7—C8 | 1.520 (2) |
F3B—B1 | 1.392 (7) | C8—C9 | 1.393 (2) |
F4A—B1 | 1.379 (5) | C8—C13 | 1.391 (2) |
F4B—B1 | 1.371 (5) | C9—C10 | 1.386 (2) |
O1—C10 | 1.377 (2) | C10—C11 | 1.397 (2) |
O1—C14 | 1.443 (2) | C11—C12 | 1.400 (2) |
O2—C11 | 1.3802 (19) | C12—C13 | 1.394 (2) |
O2—C15 | 1.435 (2) | C6—H6 | 0.95 |
O3—C16 | 1.435 (2) | C7—H7A | 0.99 |
O3—C12 | 1.368 (2) | C7—H7B | 0.99 |
N1—C2 | 1.356 (2) | C9—H9 | 0.95 |
N1—C6 | 1.364 (2) | C13—H13 | 0.95 |
N2—C2 | 1.330 (2) | C14—H14B | 0.98 |
N3—C2 | 1.331 (2) | C14—H14A | 0.98 |
N3—C4 | 1.347 (2) | C14—H14C | 0.98 |
N4—C4 | 1.322 (2) | C15—H15B | 0.98 |
N1—H1 | 0.88 | C15—H15A | 0.98 |
N2—H2B | 0.88 | C15—H15C | 0.98 |
N2—H2A | 0.88 | C16—H16C | 0.98 |
N4—H4A | 0.88 | C16—H16A | 0.98 |
N4—H4B | 0.88 | C16—H16B | 0.98 |
C4—C5 | 1.441 (2) | ||
F1···C16i | 3.368 (2) | C9···H15Aiii | 3.0620 |
F1···C2i | 2.9212 (18) | C9···H14C | 2.7394 |
F1···N1i | 3.0584 (17) | C9···H16Cvii | 3.0218 |
F1···N3i | 2.9986 (17) | C10···H2Avi | 2.7763 |
F1···N2ii | 2.8851 (17) | C11···H2Avi | 3.0749 |
F1···C4i | 3.136 (2) | C12···H14Ciii | 2.8703 |
F1···C5i | 3.302 (2) | C12···H15C | 2.8987 |
F1···C6i | 3.239 (2) | C13···H16C | 2.7550 |
F2···N1ii | 2.8445 (17) | C13···H16A | 2.7409 |
F3A···C16i | 3.288 (8) | C13···H14Ciii | 2.9945 |
F3A···C9iii | 2.995 (9) | C14···H2Avi | 2.8183 |
F3A···C7iii | 3.282 (8) | C14···H4Biii | 3.0896 |
F3B···C16iv | 3.318 (7) | C14···H9 | 2.4843 |
F3B···C7iii | 3.279 (8) | C16···H7Bvii | 2.9178 |
F3B···C16i | 3.365 (7) | C16···H13 | 2.5261 |
F3B···C9iii | 3.213 (7) | B1···H16Ai | 2.9217 |
F4B···C15 | 3.323 (8) | B1···H1ii | 2.8443 |
F1···H16Ai | 2.7629 | B1···H2Bii | 2.7082 |
F1···H2Bii | 2.0078 | H1···H2B | 2.2865 |
F1···H13i | 2.6100 | H1···F2viii | 1.9656 |
F2···H1ii | 1.9656 | H1···B1viii | 2.8443 |
F3A···H9iii | 2.3818 | H2A···O2ix | 2.7789 |
F3A···H14Aiii | 2.8522 | H2A···O1ix | 2.1012 |
F3A···H7Biii | 2.8258 | H2A···C10ix | 2.7763 |
F3A···H16Ai | 2.6715 | H2A···C11ix | 3.0749 |
F3A···H16Biv | 2.8039 | H2A···C14ix | 2.8183 |
F3B···H16Biv | 2.5723 | H2B···F1viii | 2.0078 |
F3B···H2Bii | 2.6183 | H2B···B1viii | 2.7082 |
F3B···H7Biii | 2.7261 | H2B···H1 | 2.2865 |
F3B···H9iii | 2.6571 | H2B···F3Bviii | 2.6183 |
F3B···H16Ai | 2.8106 | H4A···N3x | 2.2886 |
F4A···H14Bv | 2.5018 | H4A···H4Ax | 2.5725 |
F4B···H16Ai | 2.7889 | H4B···C7 | 2.5689 |
F4B···H15A | 2.8661 | H4B···C14iii | 3.0896 |
F4B···H14Bv | 2.6619 | H4B···O1iii | 2.3604 |
O1···N2vi | 2.9345 (18) | H4B···C8 | 2.8977 |
O1···O2 | 2.6600 (18) | H4B···H7A | 2.2117 |
O1···N4iii | 2.9210 (18) | H6···O2vii | 2.4983 |
O2···O3 | 2.7108 (18) | H6···H7B | 2.3462 |
O2···C6vii | 3.171 (2) | H6···O3vii | 2.6741 |
O2···O1 | 2.6600 (18) | H7A···H4B | 2.2117 |
O3···C15 | 3.022 (2) | H7A···N4 | 2.7165 |
O3···O2 | 2.7108 (18) | H7A···H15Aiii | 2.4411 |
O1···H4Biii | 2.3604 | H7A···H9 | 2.3813 |
O1···H2Avi | 2.1012 | H7A···H15Bxiii | 2.5464 |
O2···H6vii | 2.4983 | H7B···H6 | 2.3462 |
O2···H2Avi | 2.7789 | H7B···O3vii | 2.7738 |
O3···H15C | 2.4582 | H7B···C16vii | 2.9178 |
O3···H7Bvii | 2.7738 | H7B···F3Aiii | 2.8258 |
O3···H6vii | 2.6741 | H7B···F3Biii | 2.7261 |
N1···F2viii | 2.8445 (17) | H9···H14A | 2.2838 |
N1···F1i | 3.0584 (17) | H9···H14C | 2.2565 |
N2···F1viii | 2.8851 (17) | H9···C14 | 2.4843 |
N2···O1ix | 2.9345 (18) | H9···H7A | 2.3813 |
N3···F1i | 2.9986 (17) | H9···F3Biii | 2.6571 |
N3···N4x | 3.121 (2) | H9···F3Aiii | 2.3818 |
N4···O1iii | 2.9210 (18) | H9···H15Aiii | 2.3830 |
N4···C14iii | 3.385 (2) | H13···H16A | 2.3638 |
N4···N3x | 3.121 (2) | H13···C5 | 2.6875 |
N4···C8 | 3.418 (2) | H13···C6 | 3.0840 |
N3···H4Ax | 2.2886 | H13···C16 | 2.5261 |
N4···H14Biii | 2.9079 | H13···H16C | 2.2633 |
N4···H7A | 2.7165 | H13···F1i | 2.6100 |
C2···F1i | 2.9212 (18) | H14A···C9 | 2.7167 |
C4···F1i | 3.136 (2) | H14A···F3Aiii | 2.8522 |
C5···F1i | 3.302 (2) | H14A···H9 | 2.2838 |
C6···C6xi | 3.594 (2) | H14B···F4Bxiv | 2.6619 |
C6···O2vii | 3.171 (2) | H14B···F4Axiv | 2.5018 |
C6···F1i | 3.239 (2) | H14B···N4iii | 2.9079 |
C7···F3Aiii | 3.282 (8) | H14C···H9 | 2.2565 |
C7···F3Biii | 3.279 (8) | H14C···C9 | 2.7394 |
C8···C16vii | 3.518 (2) | H14C···C12iii | 2.8703 |
C8···N4 | 3.418 (2) | H14C···C13iii | 2.9945 |
C9···F3Aiii | 2.995 (9) | H15A···F4B | 2.8661 |
C9···F3Biii | 3.213 (7) | H15A···C9iii | 3.0620 |
C9···C10iii | 3.552 (2) | H15A···H7Aiii | 2.4411 |
C10···C9iii | 3.552 (2) | H15A···H9iii | 2.3830 |
C12···C13vii | 3.549 (2) | H15B···H7Axv | 2.5464 |
C13···C12vii | 3.549 (2) | H15C···O3 | 2.4582 |
C13···C13vii | 3.598 (2) | H15C···C12 | 2.8987 |
C14···N4iii | 3.385 (2) | H16A···F3Bi | 2.8106 |
C15···O3 | 3.022 (2) | H16A···C13 | 2.7409 |
C15···F4B | 3.323 (8) | H16A···H13 | 2.3638 |
C16···F3Bxii | 3.318 (7) | H16A···F1i | 2.7629 |
C16···F1i | 3.368 (2) | H16A···F3Ai | 2.6715 |
C16···C8vii | 3.518 (2) | H16A···B1i | 2.9217 |
C16···F3Bi | 3.365 (7) | H16A···F4Bi | 2.7889 |
C16···F3Ai | 3.288 (8) | H16B···F3Axii | 2.8039 |
C5···H13 | 2.6875 | H16B···F3Bxii | 2.5723 |
C6···H13 | 3.0840 | H16C···C13 | 2.7550 |
C7···H4B | 2.5689 | H16C···H13 | 2.2633 |
C8···H4B | 2.8977 | H16C···C8vii | 2.8661 |
C8···H16Cvii | 2.8661 | H16C···C9vii | 3.0218 |
C9···H14A | 2.7167 | ||
C10—O1—C14 | 116.47 (12) | C5—C6—H6 | 119.38 |
C11—O2—C15 | 114.69 (13) | C5—C7—H7A | 108.05 |
C12—O3—C16 | 116.53 (12) | C5—C7—H7B | 108.02 |
C2—N1—C6 | 120.15 (13) | C8—C7—H7A | 108.05 |
C2—N3—C4 | 118.36 (14) | C8—C7—H7B | 107.99 |
C2—N1—H1 | 119.95 | H7A—C7—H7B | 107.29 |
C6—N1—H1 | 119.90 | C8—C9—H9 | 120.04 |
C2—N2—H2A | 120.02 | C10—C9—H9 | 120.05 |
H2A—N2—H2B | 120.02 | C8—C13—H13 | 120.08 |
C2—N2—H2B | 119.96 | C12—C13—H13 | 120.19 |
H4A—N4—H4B | 120.02 | O1—C14—H14A | 109.47 |
C4—N4—H4A | 119.95 | O1—C14—H14B | 109.44 |
C4—N4—H4B | 120.03 | O1—C14—H14C | 109.52 |
N2—C2—N3 | 119.35 (15) | H14A—C14—H14B | 109.44 |
N1—C2—N2 | 118.59 (14) | H14A—C14—H14C | 109.50 |
N1—C2—N3 | 122.06 (15) | H14B—C14—H14C | 109.47 |
N3—C4—C5 | 122.06 (14) | O2—C15—H15A | 109.52 |
N4—C4—C5 | 120.69 (15) | O2—C15—H15B | 109.46 |
N3—C4—N4 | 117.24 (15) | O2—C15—H15C | 109.45 |
C4—C5—C6 | 116.06 (15) | H15A—C15—H15B | 109.47 |
C6—C5—C7 | 121.62 (15) | H15A—C15—H15C | 109.46 |
C4—C5—C7 | 122.30 (14) | H15B—C15—H15C | 109.47 |
N1—C6—C5 | 121.27 (15) | O3—C16—H16A | 109.46 |
C5—C7—C8 | 117.06 (14) | O3—C16—H16B | 109.48 |
C7—C8—C9 | 117.45 (15) | O3—C16—H16C | 109.46 |
C7—C8—C13 | 122.04 (14) | H16A—C16—H16B | 109.47 |
C9—C8—C13 | 120.24 (14) | H16A—C16—H16C | 109.47 |
C8—C9—C10 | 119.91 (15) | H16B—C16—H16C | 109.48 |
O1—C10—C9 | 123.88 (15) | F1—B1—F2 | 108.92 (14) |
O1—C10—C11 | 115.49 (14) | F1—B1—F3A | 111.4 (4) |
C9—C10—C11 | 120.61 (15) | F1—B1—F4A | 105.5 (4) |
O2—C11—C12 | 121.87 (15) | F1—B1—F3B | 102.4 (3) |
C10—C11—C12 | 119.09 (14) | F1—B1—F4B | 116.1 (5) |
O2—C11—C10 | 118.96 (15) | F2—B1—F3A | 111.0 (3) |
O3—C12—C11 | 115.08 (14) | F2—B1—F4A | 105.9 (6) |
C11—C12—C13 | 120.37 (16) | F2—B1—F3B | 104.3 (3) |
O3—C12—C13 | 124.55 (15) | F2—B1—F4B | 114.0 (3) |
C8—C13—C12 | 119.73 (15) | F3A—B1—F4A | 113.8 (7) |
N1—C6—H6 | 119.35 | F3B—B1—F4B | 109.9 (4) |
C14—O1—C10—C9 | −4.2 (2) | C6—C5—C7—C8 | −103.87 (18) |
C14—O1—C10—C11 | 174.71 (14) | C5—C7—C8—C13 | 27.9 (2) |
C15—O2—C11—C10 | 109.92 (17) | C5—C7—C8—C9 | −158.03 (14) |
C15—O2—C11—C12 | −73.51 (19) | C13—C8—C9—C10 | 1.9 (2) |
C16—O3—C12—C11 | 167.55 (14) | C7—C8—C13—C12 | 171.44 (14) |
C16—O3—C12—C13 | −13.3 (2) | C7—C8—C9—C10 | −172.26 (14) |
C6—N1—C2—N3 | 1.2 (2) | C9—C8—C13—C12 | −2.4 (2) |
C6—N1—C2—N2 | −178.38 (15) | C8—C9—C10—C11 | 0.1 (2) |
C2—N1—C6—C5 | −0.2 (2) | C8—C9—C10—O1 | 179.02 (14) |
C4—N3—C2—N1 | −2.3 (2) | C9—C10—C11—O2 | 175.11 (14) |
C4—N3—C2—N2 | 177.29 (15) | O1—C10—C11—C12 | 179.46 (13) |
C2—N3—C4—N4 | −178.46 (15) | O1—C10—C11—O2 | −3.9 (2) |
C2—N3—C4—C5 | 2.5 (2) | C9—C10—C11—C12 | −1.6 (2) |
N4—C4—C5—C6 | 179.43 (16) | O2—C11—C12—O3 | 3.7 (2) |
N3—C4—C5—C7 | 176.87 (15) | O2—C11—C12—C13 | −175.57 (14) |
N3—C4—C5—C6 | −1.5 (2) | C10—C11—C12—O3 | −179.77 (14) |
N4—C4—C5—C7 | −2.2 (2) | C10—C11—C12—C13 | 1.0 (2) |
C7—C5—C6—N1 | −178.02 (15) | O3—C12—C13—C8 | −178.17 (14) |
C4—C5—C6—N1 | 0.4 (2) | C11—C12—C13—C8 | 1.0 (2) |
C4—C5—C7—C8 | 77.84 (19) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, y−1, z+1; (iii) −x, −y+1, −z+1; (iv) x, y−1, z; (v) x+1, y, z; (vi) x−1, y, z+1; (vii) −x, −y+2, −z+1; (viii) x, y+1, z−1; (ix) x+1, y, z−1; (x) −x+1, −y+1, −z; (xi) −x, −y+2, −z; (xii) x, y+1, z; (xiii) x, y, z−1; (xiv) x−1, y, z; (xv) x, y, z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···F2viii | 0.88 | 1.97 | 2.8445 (17) | 177 |
N2—H2A···O1ix | 0.88 | 2.10 | 2.9345 (18) | 158 |
N2—H2B···F1viii | 0.88 | 2.01 | 2.8851 (17) | 174 |
N4—H4A···N3x | 0.88 | 2.29 | 3.121 (2) | 158 |
N4—H4B···O1iii | 0.88 | 2.36 | 2.9210 (18) | 122 |
C6—H6···O2vii | 0.95 | 2.50 | 3.171 (2) | 128 |
C9—H9···F3Aiii | 0.95 | 2.38 | 2.995 (9) | 122 |
C14—H14B···F4Axiv | 0.98 | 2.50 | 3.414 (10) | 155 |
C15—H15C···O3 | 0.98 | 2.46 | 3.022 (2) | 116 |
Symmetry codes: (iii) −x, −y+1, −z+1; (vii) −x, −y+2, −z+1; (viii) x, y+1, z−1; (ix) x+1, y, z−1; (x) −x+1, −y+1, −z; (xiv) x−1, y, z. |
Acknowledgements
MH thanks the Council of Scientific and Industrial Research (CSIR), India, for the award of a Senior Research Fellowship (SRF) [reference No. 9/475(123)/2004-EMR-I]. DL thanks the EPSRC National Crystallography Service (Southampton, England) for X-ray data collection.
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