research communications
Crystal structures of the synthetic intermediate 3-[(6-chloro-7H-purin-7-yl)methyl]cyclobutan-1-one, and of two oxetanocin derivatives: 3-[(6-chloro-8,9-dihydro-7H-purin-7-yl)methyl]cyclobutan-1-ol and 3-[(6-chloro-9H-purin-9-yl)methyl]cyclobutan-1-ol
aDepartment of Chemistry, York University, 4700 Keele St., Toronto, ON, M3J 1P3, Canada
*Correspondence e-mail: audette@yorku.ca
The crystal structures of an intermediate, C10H9ClN4O, 3-[(6-chloro-7H-purin-7-yl)methyl]cyclobutan-1-one (I), and two N-7 and N-9 regioisomeric oxetanocin nucleoside analogs, C10H13ClN4O, 3-[(6-chloro-8,9-dihydro-7H-purin-7-yl)methyl]cyclobutan-1-ol (II) and C10H11ClN4O, 3-[(6-chloro-9H-purin-9-yl)methyl]cyclobutan-1-ol (IV), are reported. The crystal structures of the nucleoside analogs confirmed the reduction of the N-7- and N-9-substituted cyclobutanones with LiAl(OtBu)3 to occur with facial selectivity, yielding cis-nucleosides analogs similar to those found in nature. Reduction of the purine ring of the N-7 cyclobutanone to a dihydropurine was observed for compound (II) but not for the purine ring of the N-9 cyclobutanone on formation of compound (IV). In the crystal of (I), molecules are linked by a weak Cl⋯O interaction, forming a 21 helix along [010]. The helices are linked by offset π–π interactions [intercentroid distance = 3.498 (1) Å], forming layers parallel to (101). In the crystal of (II), molecules are linked by pairs of O—H⋯N hydrogen bonds, forming inversion dimers with an R22(8) ring motif. The dimers are linked by O—H⋯N hydrogen bonds, forming chains along [001], which in turn are linked by C—H⋯π and offset π–π interactions [intercentroid distance = 3.509 (1) Å], forming slabs parallel to the ac plane. In the crystal of (IV), molecules are linked by O—H⋯N hydrogen bonds, forming chains along [101]. The chains are linked by C—H⋯N and C—H⋯O hydrogen bonds and C—H⋯π and offset π–π interactions [intercentroid distance = 3.364 (1) Å], forming a supramolecular framework.
1. Chemical context
Derivatives of naturally occurring ). The development of new and different nucleoside analogs is important in combating drug-resistant mutants and increasing therapeutic effectivity. The naturally occurring oxetanocin A, a nucleoside analog, demonstrated efficacy against herpes and HIV (Hoshino et al., 1987). Further exploration of oxetanocin A derivatives such as cyclobut-A and cyclobut-B (Lobucavir) represented an increase in potency and metabolic stability (Hoshino et al., 1987; Bisacchi et al., 1991). The current study focuses on the structural characterization of two nucleoside analogs, (II) and (IV), as well as the purinyl-cyclobutanone intermediate (I), prior to reduction.
are an emerging class of antiviral therapeutics that are used to target tumors, herpes virus and the human immunodeficiency virus (HIV) (De Clercq, 20052. Structural commentary
The molecular structures of compounds (I), (II) and (IV) are illustrated in Figs. 1, 2 and 3, respectively. In compounds (I) and (II) there is a short intramolecular C—H⋯Cl interaction present (Tables 1 and 2, respectively).
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In compound (I) the purine ring is attached to the cyclobutanone unit through atom N7, rendering the attachment cis to the chlorine atom bound to the aromatic ring at the C6 position. The mean plane of the cyclobutane ring (A = C2′–C5′) is inclined to the mean plane of the purine ring system (B = N1/N37N7/N9/C2/C4/C5/C6/C8) by 52.62 (11)°, while the torsion angle N7—C5′—C4′⋯C2′ is ca 125.4°.
Reduction of compound (I) with lithium tri-tert-butoxyaluminum hydride lead to the formation of the oxetanocin derivative compound (II). Here the the mean plane of the cyclobutanol ring (A) is inclined to the mean plane of the purine ring system (B) by 26.37 (15)°, while the torsion angle N7—C5′—C4′⋯C2′ is ca 120.0°. Atoms C6′ and C4′ are positionally disordered and were split giving a refined occupancy ratio for C6′:C6′B and C4′:C4′B of 0.858 (4):0.142 (4) (Fig. 2).
In compound (IV), the cyclobutanol ring is attached to atom N9 of the purine ring (Fig. 3). As a result of the trans positioning of the cyclobutanol unit, there are no intramolecular hydrogen bonds between the chlorine atom and the cyclobutanol or methylene connector as observed in compounds (I) and (II). Here, the mean plane of the cyclobutanol ring (A) is inclined to the mean plane of the purine ring system (B) by 71.20 (13)°, and the torsion angle N7—C5′—C4′⋯C2′ is ca 144.8°.
Reduction of the purine ring of the N-7 cyclobutanone to a dihydropurine was observed for compound (II) but not for the purine ring of the N-9 cyclobutanone on formation of compound (IV). This is confirmed by the values of the bond lengths and bond angles involving atom C8; see Table 3. Similar over-reductions of purine derivatives can be found in the literature, where electron-deficient purines are dearomatized by NaBH4 to a dihydropurine (Aarhus et al., 2014). We speculate the reason for over-reduction of the N-7 ketone may be due to the strain associated with the system. N-7 alkylation forces the chlorine of the purine ring to be oriented towards the cyclobutanone ring, which increases the strain energy of the system. This strain energy is released when the rigid aromatic structure of the purine is reduced to a more flexible dihydropurine (sp2 C8 to sp3 C8). This strained orientation is not observed for the N-9 ketone, hence the integrity of its purine ring is preserved.
3. Supramolecular features
In the crystal of (I), molecules are linked by a weak Cl⋯O interaction [Cl1⋯O1′(−x + 1, y − , −z + ) = 3.180 (2) Å], forming a 21 helix along [010], see Fig. 4. The helices are linked by offset π-π- interactions, forming layers parallel to (101): CgB⋯CgBi = 3.498 (1) Å, CgB is the centroid of the purine ring system, α = 0.00 (5) Å, β = 21.6°, interplanar distance = 3.252 (1) Å, offset = 1.289 Å, symmetry code (i) −x + 2, −y + 1, −z + 1.
In the crystal of (II), molecules are linked by pairs of N—H⋯N hydrogen bonds, forming inversion dimers with an R22(8) ring motif (Table 2 and Fig. 5). The dimers are linked by O—H⋯N hydrogen bonds, forming ribbons along [001], which in turn are linked by C—H⋯π (Table 2) and offset π–π interactions, forming slabs parallel to the ac plane. [Details of the offset π–π interactions: CgB⋯CgBv = 3.498 (1) Å, CgB is the centroid of the purine ring system, α = 0.00 (5) Å, β = 21.6°, interplanar distance = 3.252 (1) Å, offset = 1.289 Å, symmetry code (v) −x + 2, −y + 1, −z + 1.]
In the crystal of (IV), molecules are linked by O—H⋯N hydrogen bonds (Table 3), forming chains along direction [101]. The chains are linked by C—H⋯O and C—H⋯N hydrogen bonds, and C—H⋯π (Table 4) and offset π–π interactions, forming a supramolecular framework (see Fig. 6). [Details of the offset π–π interactions: CgB⋯CgBvi = 3.534 (1) Å, CgB is the centroid of the purine ring system, α = 0.02 (10) Å, β = 17.8°, interplanar distance = 3.364 (1) Å, offset = 1.08 Å, symmetry code (vi) −x + 1, −y + 1, −z. ]
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4. Database survey
A search of the Cambridge Structural Database (CSD, Version 5.40, update February 2019; Groom et al., 2016) found two related structure, viz. 6-chloro-9-(3-hydroxymethyl-3-hydroxycyclobutyl)purine (CSD refcode SOGROV; Boumchita et al., 1991)) and cis-1-bromomethyl-3-(6-chloro-9H-purin-yl)cyclobutanol (ZUMHAQ; Gharbaoui et al., 1995). The coordinates are not available for either structure.
5. Synthesis and crystallization
Synthesis of compounds (I) and (III): Potassium carbonate (12.0 mmol) was added to a solution of (3-oxocyclobutyl)methyl benzoate (10.0 mmol) in methanol (20 ml) and stirred for 1 h at room temperature. Saturated sodium bicarbonate (10.0 ml) was added and stirring continued for an additional 15 min. The solvent was evaporated under vacuum, followed by purification by flash with ethyl acetate, resulting in 3-(hydroxymethyl)cyclobutan-1-one in 70% yield.
3-(Hydroxymethyl)cyclobutan-1-one (1 mmol) was dissolved in 10 ml of dry dichloromethane and cooled to 195 K. Hunig's base (3.2 mmol) was added, followed by trifluoromethanesulfonic anhydride (1 mmol) and the mixture was stirred for 10 min, cooled to 273 K and stirred to obtain the qualitative conversion to (3-oxocyclobutyl)methyl trifluoromethanesulfonate.
The (3-oxocyclobutyl)methyl trifluoromethanesulfonate (5.61 mmol) was added to a mixture containing 6-chloro-7H-purine (5.61 mmol), potassium hydroxide (5.61 mmol), tris[2-(2-methoxyethoxy)ethyl]amine (0.28 mmol), magnesium sulfate (2 g) and anhydrous acetonitrile (100 ml), which was then heated to 333 K for 5 h and cooled to room temperature. The product was purified using 5% methanol and 5% trimethylamine in chloroform, which yielded two UV-active compounds.
The two UV-active compounds were separated using flash H-purin-9-yl)methyl]cyclobutan-1-one (III) and 37% of the N-7 alkylated derivative 3-[(6-chloro-7H-purin-7-yl)methyl]cyclobutan-1-one (I).
with ethyl acetate, giving 51% of the N-9 alkylated derivative; 3-[(6-chloro-9Synthesis of 3-[(6-chloro-8,9-dihydro-7H-purin-7-yl)methyl]cyclobutan-1-ol (II): 3-[(6-Chloro-7H-purin-7-yl)methyl]cyclobutan-1-one (I) (0.21 mmol) in dichloromethane (10 ml) was cooled to 195 K and lithium tri-tert-butoxyaluminum hydride was added. The mixture was cooled to room temperature and sodium borohydride (0.32 mmol) was added and the resulting mixture allowed to stir overnight. Methanol (2 ml) was added and the mixture allowed to stir overnight to convert the over-reduced 3-[(6-chloro-7H-purin-7-yl]methyl)cyclobutanone(I) to 3-[(6-chloro-8,9-dihydro-7H-purin-7-yl)methyl]cyclobutan-1-ol (II).
Synthesis of cis-3-[(6-chloro-9H-purin-9-yl)methyl]cyclobutan-1-ol (IV): 3-[(6-Chloro-9H-purin-9-yl)methyl]cyclobutan-1-one (III) (0.21 mmol) was added to diethyl ether and cooled to 195 K and lithium tri-tert-butoxyaluminum hydride (0.32 mmol) was added. The reaction was allowed to warm to room temperature and left to stir overnight, which provided quantitative conversion to cis-3-[(6-chloro-9H-purin-9-yl)methyl]cyclobutan-1-ol (IV). Crystallization was achieved through evaporation over three days with tetrahydrofuran as the solvent.
Pale-yellow plate-like crystals of (I), suitable for X-ray were obtained by slow evaporation of a solution in dichloromethane and heptane. Colourless plate-like crystals of (II), were obtained by slow evaporation of a solution in methanol, dichloromethane and diethyl ether (1:1:1, 9 ml). Colorless plate-like crystals of (IV), were obtained by slow evaporation of a solution in methanol (3 ml) .
6. Refinement
Crystal data, data collection and structure . For all three compounds, C-bound H atoms were placed in calculated positions and refined as riding: C—H = 0.95–0.99 Å with Uiso(H) = 1.2Ueq(C). For compound (II), the OH and NH H atoms were located in a difference-Fourier map. While the OH H atom was freely refined the NH H atom was refined with a distance restraint: N—H = 0.86 (2) Å. For compound (IV), the OH H atom was located in a difference-Fourier map and freely refined. In compound (II), atoms C6′ and C4′ are positionally disordered and were split giving a refined occupancy ratio for C6′:C6′B and C4′:C4′B of 0.858 (4):0.142 (4). For the final of compound (II) three most disagreeable reflections (31, 32, 70) were omitted, and for the final of compound (IV) four most disagreeable reflections (58, 66, 57, 67) were omitted.
details are summarized in Table 5
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Supporting information
https://doi.org/10.1107/S2056989019004432/zp2033sup1.cif
contains datablocks global, I, II, IV. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989019004432/zp2033Isup2.hkl
Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989019004432/zp2033IIsup3.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989019004432/zp2033IIsup5.cml
For all structures, data collection: CrysAlis PRO (Rigaku OD, 2018); cell
CrysAlis PRO (Rigaku OD, 2018); data reduction: CrysAlis PRO (Rigaku OD, 2018); program(s) used to solve structure: SHELXS (Sheldrick, 2008); program(s) used to refine structure: SHELXL (Sheldrick, 2015); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009), PLATON (Spek, 2009) and publCIF (Westrip, 2010).C10H9ClN4O | F(000) = 488 |
Mr = 236.66 | Dx = 1.555 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.9736 (5) Å | Cell parameters from 9903 reflections |
b = 6.8854 (4) Å | θ = 3.3–32.6° |
c = 12.2746 (5) Å | µ = 0.36 mm−1 |
β = 92.938 (4)° | T = 110 K |
V = 1010.63 (8) Å3 | Plate, pale_yellow |
Z = 4 | 0.43 × 0.21 × 0.04 mm |
Bruker APEXII CCD diffractometer | 2508 independent reflections |
Radiation source: sealed X-ray tube | 2217 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
ω scans | θmax = 28.3°, θmin = 3.3° |
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2018) | h = −15→15 |
Tmin = 0.661, Tmax = 1.000 | k = −9→9 |
35539 measured reflections | l = −16→16 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.111 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0508P)2 + 0.9477P] where P = (Fo2 + 2Fc2)/3 |
2508 reflections | (Δ/σ)max < 0.001 |
145 parameters | Δρmax = 0.60 e Å−3 |
0 restraints | Δρmin = −0.28 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 | ||
Cl1 | 0.70136 (4) | 0.21385 (7) | 0.52904 (4) | 0.02685 (14) | |
N1 | 0.81306 (13) | 0.2530 (2) | 0.35301 (12) | 0.0230 (3) | |
N3 | 0.93051 (12) | 0.5196 (2) | 0.30500 (11) | 0.0219 (3) | |
N7 | 0.84068 (11) | 0.6388 (2) | 0.56456 (11) | 0.0183 (3) | |
N9 | 0.95030 (12) | 0.7744 (2) | 0.44062 (12) | 0.0216 (3) | |
O1' | 0.43878 (13) | 0.6449 (3) | 0.76126 (16) | 0.0503 (5) | |
C2' | 0.53242 (16) | 0.6753 (3) | 0.73657 (17) | 0.0303 (4) | |
C3' | 0.64220 (16) | 0.7042 (3) | 0.80129 (15) | 0.0297 (4) | |
H3'A | 0.670598 | 0.585740 | 0.839075 | 0.036* | |
H3'B | 0.642461 | 0.816481 | 0.851695 | 0.036* | |
C4' | 0.69801 (14) | 0.7464 (3) | 0.69174 (14) | 0.0215 (4) | |
H4' | 0.720328 | 0.885805 | 0.685533 | 0.026* | |
C5' | 0.58520 (15) | 0.7032 (3) | 0.62724 (16) | 0.0297 (4) | |
H5'A | 0.554763 | 0.814870 | 0.584483 | 0.036* | |
H5'B | 0.586295 | 0.584132 | 0.582080 | 0.036* | |
C6' | 0.79428 (14) | 0.6106 (3) | 0.67259 (12) | 0.0198 (3) | |
H6'A | 0.854160 | 0.632156 | 0.729957 | 0.024* | |
H6'B | 0.768262 | 0.474799 | 0.678746 | 0.024* | |
C2 | 0.88240 (14) | 0.3491 (3) | 0.28787 (13) | 0.0230 (4) | |
H2 | 0.898377 | 0.285913 | 0.221649 | 0.028* | |
C4 | 0.90857 (13) | 0.6006 (3) | 0.40103 (13) | 0.0183 (3) | |
C5 | 0.83895 (13) | 0.5123 (2) | 0.47653 (12) | 0.0176 (3) | |
C6 | 0.79181 (14) | 0.3358 (3) | 0.44645 (13) | 0.0198 (3) | |
C8 | 0.90917 (14) | 0.7900 (3) | 0.53629 (14) | 0.0205 (3) | |
H8 | 0.925073 | 0.897356 | 0.583167 | 0.025* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0305 (2) | 0.0264 (2) | 0.0241 (2) | −0.00833 (17) | 0.00535 (16) | 0.00170 (17) |
N1 | 0.0231 (7) | 0.0246 (8) | 0.0213 (7) | 0.0002 (6) | 0.0002 (6) | −0.0029 (6) |
N3 | 0.0215 (7) | 0.0272 (8) | 0.0173 (7) | 0.0026 (6) | 0.0046 (5) | 0.0014 (6) |
N7 | 0.0202 (7) | 0.0202 (7) | 0.0146 (6) | 0.0007 (5) | 0.0030 (5) | 0.0009 (5) |
N9 | 0.0213 (7) | 0.0210 (7) | 0.0229 (7) | −0.0006 (6) | 0.0036 (5) | 0.0027 (6) |
O1' | 0.0302 (8) | 0.0585 (12) | 0.0639 (11) | −0.0075 (8) | 0.0186 (8) | 0.0010 (9) |
C2' | 0.0257 (9) | 0.0282 (10) | 0.0377 (10) | 0.0011 (7) | 0.0102 (8) | −0.0006 (8) |
C3' | 0.0284 (9) | 0.0409 (12) | 0.0207 (8) | 0.0025 (8) | 0.0091 (7) | 0.0002 (8) |
C4' | 0.0198 (8) | 0.0263 (9) | 0.0187 (8) | 0.0019 (6) | 0.0046 (6) | 0.0022 (6) |
C5' | 0.0215 (8) | 0.0425 (12) | 0.0251 (9) | 0.0037 (8) | 0.0000 (7) | −0.0010 (8) |
C6' | 0.0228 (8) | 0.0253 (9) | 0.0116 (7) | 0.0016 (7) | 0.0033 (6) | 0.0011 (6) |
C2 | 0.0229 (8) | 0.0301 (9) | 0.0162 (7) | 0.0041 (7) | 0.0021 (6) | −0.0038 (7) |
C4 | 0.0177 (7) | 0.0204 (8) | 0.0168 (7) | 0.0022 (6) | 0.0003 (6) | 0.0037 (6) |
C5 | 0.0179 (7) | 0.0213 (8) | 0.0135 (7) | 0.0035 (6) | 0.0004 (6) | 0.0011 (6) |
C6 | 0.0195 (7) | 0.0223 (8) | 0.0175 (7) | 0.0007 (6) | 0.0015 (6) | 0.0039 (6) |
C8 | 0.0205 (7) | 0.0176 (8) | 0.0232 (8) | 0.0009 (6) | −0.0014 (6) | −0.0022 (6) |
Cl1—C6 | 1.7372 (17) | C3'—H3'A | 0.9900 |
N1—C6 | 1.317 (2) | C3'—H3'B | 0.9900 |
N1—C2 | 1.354 (2) | C4'—C6' | 1.512 (2) |
N3—C2 | 1.320 (2) | C4'—C5' | 1.559 (2) |
N3—C4 | 1.342 (2) | C4'—H4' | 1.0000 |
N7—C8 | 1.381 (2) | C5'—H5'A | 0.9900 |
N7—C5 | 1.387 (2) | C5'—H5'B | 0.9900 |
N7—C6' | 1.4765 (19) | C6'—H6'A | 0.9900 |
N9—C8 | 1.301 (2) | C6'—H6'B | 0.9900 |
N9—C4 | 1.376 (2) | C2—H2 | 0.9500 |
O1'—C2' | 1.195 (2) | C4—C5 | 1.415 (2) |
C2'—C3' | 1.514 (3) | C5—C6 | 1.382 (2) |
C2'—C5' | 1.524 (3) | C8—H8 | 0.9500 |
C3'—C4' | 1.559 (2) | ||
C6—N1—C2 | 117.04 (16) | C2'—C5'—H5'B | 114.0 |
C2—N3—C4 | 113.96 (15) | C4'—C5'—H5'B | 114.0 |
C8—N7—C5 | 105.24 (13) | H5'A—C5'—H5'B | 111.2 |
C8—N7—C6' | 125.49 (14) | N7—C6'—C4' | 112.54 (14) |
C5—N7—C6' | 128.74 (15) | N7—C6'—H6'A | 109.1 |
C8—N9—C4 | 104.09 (14) | C4'—C6'—H6'A | 109.1 |
O1'—C2'—C3' | 133.7 (2) | N7—C6'—H6'B | 109.1 |
O1'—C2'—C5' | 133.0 (2) | C4'—C6'—H6'B | 109.1 |
C3'—C2'—C5' | 93.29 (14) | H6'A—C6'—H6'B | 107.8 |
C2'—C3'—C4' | 88.33 (14) | N3—C2—N1 | 128.03 (16) |
C2'—C3'—H3'A | 113.9 | N3—C2—H2 | 116.0 |
C4'—C3'—H3'A | 113.9 | N1—C2—H2 | 116.0 |
C2'—C3'—H3'B | 113.9 | N3—C4—N9 | 126.01 (15) |
C4'—C3'—H3'B | 113.9 | N3—C4—C5 | 123.02 (16) |
H3'A—C3'—H3'B | 111.1 | N9—C4—C5 | 110.96 (14) |
C6'—C4'—C5' | 116.77 (16) | C6—C5—N7 | 138.56 (15) |
C6'—C4'—C3' | 112.49 (15) | C6—C5—C4 | 116.68 (15) |
C5'—C4'—C3' | 90.22 (14) | N7—C5—C4 | 104.75 (14) |
C6'—C4'—H4' | 111.9 | N1—C6—C5 | 121.22 (16) |
C5'—C4'—H4' | 111.9 | N1—C6—Cl1 | 116.95 (14) |
C3'—C4'—H4' | 111.9 | C5—C6—Cl1 | 121.83 (13) |
C2'—C5'—C4' | 87.96 (14) | N9—C8—N7 | 114.95 (15) |
C2'—C5'—H5'A | 114.0 | N9—C8—H8 | 122.5 |
C4'—C5'—H5'A | 114.0 | N7—C8—H8 | 122.5 |
O1'—C2'—C3'—C4' | −175.7 (3) | C8—N7—C5—C6 | 179.2 (2) |
C5'—C2'—C3'—C4' | 3.32 (16) | C6'—N7—C5—C6 | 7.2 (3) |
C2'—C3'—C4'—C6' | −122.53 (16) | C8—N7—C5—C4 | 0.10 (17) |
C2'—C3'—C4'—C5' | −3.24 (16) | C6'—N7—C5—C4 | −171.83 (15) |
O1'—C2'—C5'—C4' | 175.7 (3) | N3—C4—C5—C6 | −0.8 (2) |
C3'—C2'—C5'—C4' | −3.32 (16) | N9—C4—C5—C6 | −179.83 (14) |
C6'—C4'—C5'—C2' | 118.72 (16) | N3—C4—C5—N7 | 178.47 (15) |
C3'—C4'—C5'—C2' | 3.22 (15) | N9—C4—C5—N7 | −0.52 (18) |
C8—N7—C6'—C4' | 76.0 (2) | C2—N1—C6—C5 | −0.4 (2) |
C5—N7—C6'—C4' | −113.61 (19) | C2—N1—C6—Cl1 | 179.16 (13) |
C5'—C4'—C6'—N7 | 72.5 (2) | N7—C5—C6—N1 | −177.58 (18) |
C3'—C4'—C6'—N7 | 174.86 (15) | C4—C5—C6—N1 | 1.4 (2) |
C4—N3—C2—N1 | 2.1 (3) | N7—C5—C6—Cl1 | 2.9 (3) |
C6—N1—C2—N3 | −1.5 (3) | C4—C5—C6—Cl1 | −178.08 (12) |
C2—N3—C4—N9 | 178.09 (16) | C4—N9—C8—N7 | −0.70 (19) |
C2—N3—C4—C5 | −0.8 (2) | C5—N7—C8—N9 | 0.4 (2) |
C8—N9—C4—N3 | −178.22 (16) | C6'—N7—C8—N9 | 172.66 (15) |
C8—N9—C4—C5 | 0.74 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
C6′—H6′B···Cl1 | 0.99 | 2.66 | 3.407 (2) | 132 |
C4′—H4′···Cl1i | 1.00 | 2.97 | 3.7889 (19) | 140 |
C6′—H6′B···N1ii | 0.99 | 2.68 | 3.343 (2) | 124 |
Symmetry codes: (i) x, y+1, z; (ii) x, −y+1/2, z+1/2. |
C10H13ClN4O | Z = 2 |
Mr = 240.69 | F(000) = 252 |
Triclinic, P1 | Dx = 1.488 Mg m−3 |
a = 6.1101 (4) Å | Cu Kα radiation, λ = 1.54184 Å |
b = 8.6075 (5) Å | Cell parameters from 8605 reflections |
c = 11.0083 (7) Å | θ = 4.3–65.4° |
α = 68.957 (6)° | µ = 3.03 mm−1 |
β = 83.799 (5)° | T = 110 K |
γ = 87.189 (5)° | Plate, colorless |
V = 537.15 (6) Å3 | 0.44 × 0.30 × 0.12 mm |
Bruker–Nonius Kappa CCD diffractometer | 1793 independent reflections |
Radiation source: sealed X-ray tube, Enhance (Cu) X-ray Source | 1681 reflections with I > 2σ(I) |
Detector resolution: 7.9 pixels mm-1 | Rint = 0.028 |
ω scans | θmax = 66.0°, θmin = 4.3° |
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2018) | h = −7→5 |
Tmin = 0.771, Tmax = 1.000 | k = −10→10 |
9261 measured reflections | l = −13→12 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.037 | Hydrogen site location: mixed |
wR(F2) = 0.098 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0479P)2 + 0.5464P] where P = (Fo2 + 2Fc2)/3 |
1793 reflections | (Δ/σ)max < 0.001 |
160 parameters | Δρmax = 0.71 e Å−3 |
1 restraint | Δρmin = −0.27 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 | Occ. (<1) | |
Cl1 | 0.16834 (8) | 0.41808 (6) | 0.40624 (5) | 0.02598 (19) | |
N1 | 0.4817 (3) | 0.2850 (2) | 0.28999 (16) | 0.0208 (4) | |
C2 | 0.6669 (3) | 0.2012 (3) | 0.28642 (19) | 0.0208 (4) | |
H2 | 0.719070 | 0.193795 | 0.204161 | 0.025* | |
N3 | 0.7920 (3) | 0.1241 (2) | 0.38609 (16) | 0.0201 (4) | |
C4 | 0.7122 (3) | 0.1387 (2) | 0.49898 (19) | 0.0181 (4) | |
C5 | 0.5139 (3) | 0.2254 (2) | 0.51675 (19) | 0.0175 (4) | |
C6 | 0.4064 (3) | 0.2984 (2) | 0.40720 (19) | 0.0185 (4) | |
N7 | 0.4843 (3) | 0.2163 (2) | 0.64573 (16) | 0.0195 (4) | |
C8 | 0.6671 (3) | 0.1184 (3) | 0.71453 (19) | 0.0217 (4) | |
H8A | 0.750275 | 0.184768 | 0.750830 | 0.026* | |
H8B | 0.612778 | 0.016417 | 0.786389 | 0.026* | |
N9 | 0.8027 (3) | 0.0776 (2) | 0.61286 (16) | 0.0212 (4) | |
H9 | 0.916 (3) | 0.018 (3) | 0.627 (2) | 0.021 (6)* | |
O1' | 0.1576 (3) | 0.2578 (2) | 1.12373 (14) | 0.0278 (4) | |
H1' | 0.256 (5) | 0.284 (4) | 1.161 (3) | 0.045 (8)* | |
C2' | 0.2169 (4) | 0.3455 (3) | 0.9900 (2) | 0.0273 (5) | |
H2' | 0.230429 | 0.466833 | 0.973632 | 0.033* | |
C3' | 0.4091 (4) | 0.2873 (3) | 0.9160 (2) | 0.0346 (6) | |
H3'1 | 0.446403 | 0.167641 | 0.956402 | 0.041* | |
H3'2 | 0.541933 | 0.356932 | 0.895749 | 0.041* | |
C5' | 0.0629 (4) | 0.3203 (3) | 0.8985 (2) | 0.0277 (5) | |
H5'1 | −0.044286 | 0.412524 | 0.866879 | 0.033* | |
H5'2 | −0.011259 | 0.211215 | 0.933326 | 0.033* | |
C4' | 0.2642 (4) | 0.3281 (3) | 0.7998 (2) | 0.0240 (6) | 0.858 (4) |
H4' | 0.288618 | 0.445876 | 0.739504 | 0.029* | 0.858 (4) |
C6' | 0.2716 (4) | 0.2157 (3) | 0.7213 (2) | 0.0229 (6) | 0.858 (4) |
H6'1 | 0.239112 | 0.100518 | 0.781565 | 0.027* | 0.858 (4) |
H6'2 | 0.155181 | 0.251106 | 0.660680 | 0.027* | 0.858 (4) |
C4'B | 0.246 (3) | 0.216 (2) | 0.8417 (15) | 0.0240 (6) | 0.142 (4) |
H4'B | 0.228733 | 0.092243 | 0.870206 | 0.029* | 0.142 (4) |
C6'B | 0.332 (3) | 0.308 (2) | 0.7043 (15) | 0.0229 (6) | 0.142 (4) |
H6'3 | 0.206224 | 0.345077 | 0.650824 | 0.027* | 0.142 (4) |
H6'4 | 0.406521 | 0.409522 | 0.701360 | 0.027* | 0.142 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0222 (3) | 0.0321 (3) | 0.0240 (3) | 0.0101 (2) | −0.0049 (2) | −0.0110 (2) |
N1 | 0.0227 (9) | 0.0239 (9) | 0.0162 (8) | 0.0000 (7) | −0.0018 (7) | −0.0078 (7) |
C2 | 0.0227 (11) | 0.0255 (10) | 0.0158 (10) | −0.0004 (8) | 0.0012 (8) | −0.0104 (8) |
N3 | 0.0198 (9) | 0.0244 (9) | 0.0173 (8) | 0.0013 (7) | 0.0010 (7) | −0.0100 (7) |
C4 | 0.0171 (10) | 0.0192 (10) | 0.0186 (10) | −0.0008 (8) | −0.0003 (8) | −0.0080 (8) |
C5 | 0.0181 (10) | 0.0193 (9) | 0.0166 (10) | −0.0025 (8) | 0.0006 (8) | −0.0087 (8) |
C6 | 0.0168 (10) | 0.0204 (10) | 0.0192 (10) | 0.0014 (8) | −0.0004 (8) | −0.0087 (8) |
N7 | 0.0173 (9) | 0.0277 (9) | 0.0155 (8) | 0.0057 (7) | −0.0014 (7) | −0.0109 (7) |
C8 | 0.0212 (11) | 0.0293 (11) | 0.0176 (10) | 0.0059 (8) | −0.0036 (8) | −0.0121 (8) |
N9 | 0.0181 (9) | 0.0294 (10) | 0.0181 (9) | 0.0094 (7) | −0.0038 (7) | −0.0114 (7) |
O1' | 0.0275 (9) | 0.0394 (9) | 0.0177 (7) | 0.0028 (7) | −0.0043 (6) | −0.0115 (7) |
C2' | 0.0286 (12) | 0.0371 (12) | 0.0179 (10) | −0.0017 (9) | −0.0008 (9) | −0.0119 (9) |
C3' | 0.0257 (12) | 0.0522 (15) | 0.0340 (13) | 0.0000 (11) | −0.0030 (10) | −0.0253 (12) |
C5' | 0.0250 (11) | 0.0400 (13) | 0.0215 (11) | 0.0119 (9) | −0.0052 (9) | −0.0157 (10) |
C4' | 0.0258 (13) | 0.0263 (14) | 0.0205 (12) | 0.0035 (11) | 0.0002 (10) | −0.0104 (11) |
C6' | 0.0164 (12) | 0.0341 (16) | 0.0216 (12) | 0.0011 (11) | 0.0000 (10) | −0.0147 (11) |
C4'B | 0.0258 (13) | 0.0263 (14) | 0.0205 (12) | 0.0035 (11) | 0.0002 (10) | −0.0104 (11) |
C6'B | 0.0164 (12) | 0.0341 (16) | 0.0216 (12) | 0.0011 (11) | 0.0000 (10) | −0.0147 (11) |
Cl1—C6 | 1.739 (2) | C2'—C3' | 1.524 (3) |
N1—C2 | 1.317 (3) | C2'—C5' | 1.527 (3) |
N1—C6 | 1.365 (3) | C2'—H2' | 1.0000 |
C2—N3 | 1.355 (3) | C3'—C4' | 1.561 (3) |
C2—H2 | 0.9500 | C3'—C4'B | 1.626 (16) |
N3—C4 | 1.332 (3) | C3'—H3'1 | 0.9900 |
C4—N9 | 1.342 (3) | C3'—H3'2 | 0.9900 |
C4—C5 | 1.424 (3) | C5'—C4' | 1.537 (3) |
C5—C6 | 1.366 (3) | C5'—C4'B | 1.616 (15) |
C5—N7 | 1.386 (2) | C5'—H5'1 | 0.9900 |
N7—C6'B | 1.440 (15) | C5'—H5'2 | 0.9900 |
N7—C6' | 1.465 (3) | C4'—C6' | 1.508 (3) |
N7—C8 | 1.471 (3) | C4'—H4' | 1.0000 |
C8—N9 | 1.455 (3) | C6'—H6'1 | 0.9900 |
C8—H8A | 0.9900 | C6'—H6'2 | 0.9900 |
C8—H8B | 0.9900 | C4'B—C6'B | 1.48 (2) |
N9—H9 | 0.833 (17) | C4'B—H4'B | 1.0000 |
O1'—C2' | 1.407 (3) | C6'B—H6'3 | 0.9900 |
O1'—H1' | 0.84 (3) | C6'B—H6'4 | 0.9900 |
C2—N1—C6 | 116.73 (17) | C2'—C3'—H3'1 | 114.0 |
N1—C2—N3 | 127.76 (18) | C4'—C3'—H3'1 | 114.0 |
N1—C2—H2 | 116.1 | C2'—C3'—H3'2 | 114.0 |
N3—C2—H2 | 116.1 | C4'—C3'—H3'2 | 114.0 |
C4—N3—C2 | 113.74 (17) | H3'1—C3'—H3'2 | 111.2 |
N3—C4—N9 | 126.70 (19) | C2'—C5'—C4' | 88.64 (17) |
N3—C4—C5 | 124.39 (18) | C2'—C5'—C4'B | 92.8 (6) |
N9—C4—C5 | 108.91 (17) | C2'—C5'—H5'1 | 113.9 |
C6—C5—N7 | 136.29 (19) | C4'—C5'—H5'1 | 113.9 |
C6—C5—C4 | 115.33 (18) | C2'—C5'—H5'2 | 113.9 |
N7—C5—C4 | 108.35 (17) | C4'—C5'—H5'2 | 113.9 |
N1—C6—C5 | 122.04 (18) | H5'1—C5'—H5'2 | 111.1 |
N1—C6—Cl1 | 115.38 (15) | C6'—C4'—C5' | 118.5 (2) |
C5—C6—Cl1 | 122.56 (15) | C6'—C4'—C3' | 120.1 (2) |
C5—N7—C6'B | 128.7 (6) | C5'—C4'—C3' | 87.40 (17) |
C5—N7—C6' | 125.55 (17) | C6'—C4'—H4' | 109.7 |
C5—N7—C8 | 108.55 (16) | C5'—C4'—H4' | 109.7 |
C6'B—N7—C8 | 121.7 (6) | C3'—C4'—H4' | 109.7 |
C6'—N7—C8 | 118.33 (17) | N7—C6'—C4' | 113.3 (2) |
N9—C8—N7 | 103.41 (15) | N7—C6'—H6'1 | 108.9 |
N9—C8—H8A | 111.1 | C4'—C6'—H6'1 | 108.9 |
N7—C8—H8A | 111.1 | N7—C6'—H6'2 | 108.9 |
N9—C8—H8B | 111.1 | C4'—C6'—H6'2 | 108.9 |
N7—C8—H8B | 111.1 | H6'1—C6'—H6'2 | 107.7 |
H8A—C8—H8B | 109.0 | C6'B—C4'B—C5' | 112.7 (13) |
C4—N9—C8 | 110.76 (17) | C6'B—C4'B—C3' | 99.0 (12) |
C4—N9—H9 | 125.9 (17) | C5'—C4'B—C3' | 82.6 (7) |
C8—N9—H9 | 123.2 (17) | C6'B—C4'B—H4'B | 118.5 |
C2'—O1'—H1' | 103 (2) | C5'—C4'B—H4'B | 118.5 |
O1'—C2'—C3' | 121.1 (2) | C3'—C4'B—H4'B | 118.5 |
O1'—C2'—C5' | 114.52 (18) | N7—C6'B—C4'B | 115.0 (14) |
C3'—C2'—C5' | 89.12 (16) | N7—C6'B—H6'3 | 108.5 |
O1'—C2'—H2' | 110.1 | C4'B—C6'B—H6'3 | 108.5 |
C3'—C2'—H2' | 110.1 | N7—C6'B—H6'4 | 108.5 |
C5'—C2'—H2' | 110.1 | C4'B—C6'B—H6'4 | 108.5 |
C2'—C3'—C4' | 87.87 (18) | H6'3—C6'B—H6'4 | 107.5 |
C2'—C3'—C4'B | 92.5 (5) | ||
C6—N1—C2—N3 | 0.8 (3) | N7—C8—N9—C4 | −1.3 (2) |
N1—C2—N3—C4 | −0.3 (3) | O1'—C2'—C3'—C4' | 138.2 (2) |
C2—N3—C4—N9 | −178.94 (19) | C5'—C2'—C3'—C4' | 19.78 (18) |
C2—N3—C4—C5 | 0.4 (3) | O1'—C2'—C3'—C4'B | 105.1 (6) |
N3—C4—C5—C6 | −1.1 (3) | C5'—C2'—C3'—C4'B | −13.3 (6) |
N9—C4—C5—C6 | 178.36 (17) | O1'—C2'—C5'—C4' | −144.2 (2) |
N3—C4—C5—N7 | −179.35 (17) | C3'—C2'—C5'—C4' | −20.09 (19) |
N9—C4—C5—N7 | 0.1 (2) | O1'—C2'—C5'—C4'B | −110.7 (6) |
C2—N1—C6—C5 | −1.6 (3) | C3'—C2'—C5'—C4'B | 13.4 (6) |
C2—N1—C6—Cl1 | 177.14 (14) | C2'—C5'—C4'—C6' | 142.7 (2) |
N7—C5—C6—N1 | 179.3 (2) | C2'—C5'—C4'—C3' | 19.62 (18) |
C4—C5—C6—N1 | 1.6 (3) | C2'—C3'—C4'—C6' | −141.4 (2) |
N7—C5—C6—Cl1 | 0.7 (3) | C2'—C3'—C4'—C5' | −19.66 (18) |
C4—C5—C6—Cl1 | −176.96 (14) | C5—N7—C6'—C4' | −135.6 (2) |
C6—C5—N7—C6'B | −10.1 (10) | C8—N7—C6'—C4' | 78.4 (3) |
C4—C5—N7—C6'B | 167.6 (10) | C5'—C4'—C6'—N7 | −171.4 (2) |
C6—C5—N7—C6' | 32.6 (4) | C3'—C4'—C6'—N7 | −66.6 (3) |
C4—C5—N7—C6' | −149.7 (2) | C2'—C5'—C4'B—C6'B | −109.4 (12) |
C6—C5—N7—C8 | −178.7 (2) | C2'—C5'—C4'B—C3' | −12.7 (6) |
C4—C5—N7—C8 | −0.9 (2) | C2'—C3'—C4'B—C6'B | 124.6 (10) |
C5—N7—C8—N9 | 1.3 (2) | C2'—C3'—C4'B—C5' | 12.7 (6) |
C6'B—N7—C8—N9 | −168.2 (9) | C5—N7—C6'B—C4'B | 146.2 (9) |
C6'—N7—C8—N9 | 152.69 (18) | C8—N7—C6'B—C4'B | −46.6 (16) |
N3—C4—N9—C8 | −179.79 (18) | C5'—C4'B—C6'B—N7 | −175.7 (10) |
C5—C4—N9—C8 | 0.8 (2) | C3'—C4'B—C6'B—N7 | 98.5 (13) |
Cg1 is the centroid of ring N1/C2/N3/C4/C5/C6. |
D—H···A | D—H | H···A | D···A | D—H···A |
C6′—H6′2···Cl1 | 0.99 | 2.64 | 3.390 (3) | 132 |
N9—H9···N3i | 0.83 (2) | 2.14 (2) | 2.952 (2) | 166 (2) |
O1′—H1′···N1ii | 0.84 (3) | 2.09 (3) | 2.909 (2) | 164 (3) |
C4′—H4′···Cg1iii | 0.99 | 2.87 | 3.857 (3) | 170 |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) x, y, z+1; (iii) −x+1, −y+1, −z+1. |
C10H11ClN4O | F(000) = 496 |
Mr = 238.68 | Dx = 1.482 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54178 Å |
a = 12.7276 (8) Å | Cell parameters from 4964 reflections |
b = 5.9725 (4) Å | θ = 4.0–64.9° |
c = 14.819 (1) Å | µ = 3.04 mm−1 |
β = 108.250 (3)° | T = 110 K |
V = 1069.81 (12) Å3 | Plate, colourless |
Z = 4 | 0.50 × 0.21 × 0.07 mm |
Bruker APEXII CCD diffractometer | 1732 independent reflections |
Radiation source: sealed X-ray tube | 1569 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.045 |
Detector resolution: 7.9 pixels mm-1 | θmax = 64.9°, θmin = 4.0° |
ω scans | h = −14→14 |
Absorption correction: numerical (CrysAlisPro; Rigaku OD, 2018) | k = −4→7 |
Tmin = 0.043, Tmax = 0.741 | l = −17→17 |
7078 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0599P)2 + 1.4189P] where P = (Fo2 + 2Fc2)/3 |
1732 reflections | (Δ/σ)max < 0.001 |
146 parameters | Δρmax = 0.35 e Å−3 |
0 restraints | Δρmin = −0.31 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 | ||
Cl1 | 0.65978 (4) | 0.22748 (10) | 0.21719 (4) | 0.0258 (2) | |
O1' | −0.06577 (11) | 0.5696 (3) | −0.19248 (10) | 0.0233 (4) | |
H1' | −0.067187 | 0.456986 | −0.226798 | 0.035* | |
N3 | 0.44729 (14) | 0.7995 (3) | 0.06539 (12) | 0.0218 (4) | |
N1 | 0.61729 (14) | 0.5895 (3) | 0.11346 (12) | 0.0196 (4) | |
N7 | 0.39848 (13) | 0.3289 (3) | 0.19580 (12) | 0.0199 (4) | |
N9 | 0.30402 (13) | 0.6280 (3) | 0.11873 (11) | 0.0186 (4) | |
C4 | 0.40817 (16) | 0.6422 (4) | 0.11001 (13) | 0.0178 (5) | |
C5 | 0.46564 (16) | 0.4569 (4) | 0.15808 (13) | 0.0168 (5) | |
C3' | 0.12604 (16) | 0.5194 (4) | −0.07173 (14) | 0.0201 (5) | |
H3'A | 0.090406 | 0.436047 | −0.031431 | 0.024* | |
H3'B | 0.179230 | 0.424010 | −0.090614 | 0.024* | |
C6 | 0.57424 (16) | 0.4399 (4) | 0.15774 (13) | 0.0180 (5) | |
C8 | 0.30351 (16) | 0.4385 (4) | 0.16970 (14) | 0.0192 (5) | |
H8 | 0.240264 | 0.389301 | 0.185165 | 0.023* | |
C2 | 0.55210 (18) | 0.7598 (4) | 0.07007 (15) | 0.0223 (5) | |
H2 | 0.584609 | 0.865250 | 0.038801 | 0.027* | |
C2' | 0.04431 (16) | 0.6477 (4) | −0.15487 (14) | 0.0177 (5) | |
H2' | 0.077386 | 0.673588 | −0.206946 | 0.021* | |
C4' | 0.17237 (18) | 0.7495 (4) | −0.03173 (15) | 0.0216 (5) | |
H4' | 0.231950 | 0.796287 | −0.058547 | 0.026* | |
C6' | 0.21115 (17) | 0.7800 (4) | 0.07552 (15) | 0.0208 (5) | |
H6'A | 0.234806 | 0.936928 | 0.091463 | 0.025* | |
H6'B | 0.149539 | 0.747512 | 0.100968 | 0.025* | |
C5' | 0.05979 (17) | 0.8537 (4) | −0.09087 (15) | 0.0217 (5) | |
H5'A | 0.005170 | 0.866225 | −0.056036 | 0.026* | |
H5'B | 0.066593 | 0.996160 | −0.122717 | 0.026* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0169 (3) | 0.0313 (4) | 0.0291 (3) | 0.0052 (2) | 0.0069 (2) | 0.0101 (2) |
O1' | 0.0144 (7) | 0.0311 (10) | 0.0231 (8) | −0.0006 (6) | 0.0037 (6) | −0.0095 (7) |
N3 | 0.0217 (9) | 0.0229 (11) | 0.0184 (9) | −0.0037 (8) | 0.0027 (7) | 0.0013 (8) |
N1 | 0.0194 (9) | 0.0206 (10) | 0.0183 (8) | −0.0042 (8) | 0.0051 (7) | −0.0005 (8) |
N7 | 0.0155 (9) | 0.0260 (11) | 0.0177 (8) | −0.0011 (8) | 0.0045 (7) | 0.0024 (8) |
N9 | 0.0142 (8) | 0.0232 (11) | 0.0160 (8) | 0.0021 (8) | 0.0013 (7) | −0.0017 (8) |
C4 | 0.0169 (10) | 0.0206 (12) | 0.0129 (9) | −0.0030 (9) | 0.0004 (8) | −0.0016 (8) |
C5 | 0.0156 (9) | 0.0207 (12) | 0.0121 (9) | −0.0022 (8) | 0.0014 (7) | −0.0014 (8) |
C3' | 0.0188 (10) | 0.0231 (12) | 0.0177 (10) | 0.0034 (9) | 0.0045 (8) | −0.0013 (9) |
C6 | 0.0160 (10) | 0.0219 (12) | 0.0134 (9) | −0.0010 (9) | 0.0006 (8) | −0.0002 (9) |
C8 | 0.0159 (10) | 0.0234 (13) | 0.0177 (9) | −0.0013 (9) | 0.0045 (8) | 0.0003 (9) |
C2 | 0.0230 (11) | 0.0232 (13) | 0.0193 (10) | −0.0064 (9) | 0.0047 (9) | 0.0015 (9) |
C2' | 0.0134 (9) | 0.0220 (12) | 0.0165 (10) | 0.0005 (9) | 0.0031 (8) | −0.0007 (9) |
C4' | 0.0186 (11) | 0.0249 (13) | 0.0194 (11) | 0.0010 (9) | 0.0035 (9) | 0.0009 (9) |
C6' | 0.0193 (11) | 0.0209 (12) | 0.0194 (10) | 0.0043 (9) | 0.0021 (8) | 0.0000 (9) |
C5' | 0.0206 (10) | 0.0223 (13) | 0.0185 (10) | 0.0032 (9) | 0.0011 (8) | 0.0001 (9) |
Cl1—C6 | 1.723 (2) | C3'—C2' | 1.544 (3) |
O1'—C2' | 1.415 (2) | C3'—H3'A | 0.9900 |
O1'—H1' | 0.8400 | C3'—H3'B | 0.9900 |
N3—C4 | 1.332 (3) | C8—H8 | 0.9500 |
N3—C2 | 1.335 (3) | C2—H2 | 0.9500 |
N1—C6 | 1.325 (3) | C2'—C5' | 1.528 (3) |
N1—C2 | 1.342 (3) | C2'—H2' | 1.0000 |
N7—C8 | 1.321 (3) | C4'—C6' | 1.520 (3) |
N7—C5 | 1.388 (3) | C4'—C5' | 1.556 (3) |
N9—C8 | 1.362 (3) | C4'—H4' | 1.0000 |
N9—C4 | 1.374 (3) | C6'—H6'A | 0.9900 |
N9—C6' | 1.469 (3) | C6'—H6'B | 0.9900 |
C4—C5 | 1.393 (3) | C5'—H5'A | 0.9900 |
C5—C6 | 1.388 (3) | C5'—H5'B | 0.9900 |
C3'—C4' | 1.539 (3) | ||
C2'—O1'—H1' | 109.5 | N3—C2—H2 | 116.0 |
C4—N3—C2 | 111.81 (19) | N1—C2—H2 | 116.0 |
C6—N1—C2 | 117.32 (17) | O1'—C2'—C5' | 115.42 (17) |
C8—N7—C5 | 103.39 (18) | O1'—C2'—C3' | 119.16 (18) |
C8—N9—C4 | 106.00 (17) | C5'—C2'—C3' | 88.88 (16) |
C8—N9—C6' | 127.78 (17) | O1'—C2'—H2' | 110.6 |
C4—N9—C6' | 126.10 (18) | C5'—C2'—H2' | 110.6 |
N3—C4—N9 | 127.7 (2) | C3'—C2'—H2' | 110.6 |
N3—C4—C5 | 126.60 (19) | C6'—C4'—C3' | 118.02 (19) |
N9—C4—C5 | 105.69 (18) | C6'—C4'—C5' | 118.75 (18) |
C6—C5—N7 | 134.5 (2) | C3'—C4'—C5' | 88.05 (16) |
C6—C5—C4 | 114.87 (19) | C6'—C4'—H4' | 110.1 |
N7—C5—C4 | 110.64 (17) | C3'—C4'—H4' | 110.1 |
C4'—C3'—C2' | 86.87 (17) | C5'—C4'—H4' | 110.1 |
C4'—C3'—H3'A | 114.2 | N9—C6'—C4' | 109.58 (17) |
C2'—C3'—H3'A | 114.2 | N9—C6'—H6'A | 109.8 |
C4'—C3'—H3'B | 114.2 | C4'—C6'—H6'A | 109.8 |
C2'—C3'—H3'B | 114.2 | N9—C6'—H6'B | 109.8 |
H3'A—C3'—H3'B | 111.3 | C4'—C6'—H6'B | 109.8 |
N1—C6—C5 | 121.3 (2) | H6'A—C6'—H6'B | 108.2 |
N1—C6—Cl1 | 117.18 (15) | C2'—C5'—C4' | 86.82 (16) |
C5—C6—Cl1 | 121.52 (16) | C2'—C5'—H5'A | 114.2 |
N7—C8—N9 | 114.28 (18) | C4'—C5'—H5'A | 114.2 |
N7—C8—H8 | 122.9 | C2'—C5'—H5'B | 114.2 |
N9—C8—H8 | 122.9 | C4'—C5'—H5'B | 114.2 |
N3—C2—N1 | 128.1 (2) | H5'A—C5'—H5'B | 111.3 |
Cg1 is the centroid of ring N1/C2/N3/C4/C5/C6. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1′—H1′···N7i | 0.84 | 2.03 | 2.853 (3) | 168 |
C8—H8···O1′ii | 0.95 | 2.27 | 3.148 (2) | 153 |
C2—H2···N3iii | 0.95 | 2.48 | 3.311 (3) | 146 |
C2′—H2′···Cg1iv | 0.99 | 2.84 | 3.628 (2) | 136 |
Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) −x, −y+1, −z; (iii) −x+1, −y+2, −z; (iv) x−3/2, −y+1/2, z−3/2. |
Bond/angle | (I) | (II) | (IV) |
C8—N7 | 1.381 (2) | 1.471 (3) | 1.362 (3) |
C8—N9 | 1.301 (2) | 1.455 (3) | 1.321 (3) |
N7—C8—N9 | 114.95 (15) | 103.41 (15) | 114.28 (18) |
Footnotes
‡Contributed equally to this work.
Acknowledgements
The authors are grateful to Dr Paul Doyle of the Department of Chemistry X-ray Facility at University of Western Ontario for assistance with the data collection.
Funding information
Funding for this research was provided by: Natural Sciences and Engineering Research Council of Canada (grant No. RGPIN-06218-2014 to Gerald F. Audette).
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