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The title compound, 2,4-diamino-5-bromo-7-(2-deoxy-2-fluoro-[beta]-D-ara­bino­furanosyl)-7H-pyrrolo[2,3-d]pyrimidine, C11H13BrFN5O3, shows two conformations of the exocyclic C4'-C5' bond, with the torsion angle [gamma] (O5'-C5'-C4'-C3') being 170.1 (3)° for conformer 1 (occupancy 0.69) and 60.7 (7)° for conformer 2 (occupancy 0.31). The N-glycosylic bond exhibits an anti conformation, with [chi] = -114.8 (4)°. The sugar pucker is N-type (C3'-endo; 3T4), with P = 23.3 (4)° and [tau]m = 36.5 (2)°. The compound forms a three-dimensional network that is stabilized by several inter­molecular hydrogen bonds (N-H...O, O-H...N and N-H...Br).

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107027138/sf3039sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107027138/sf3039Isup2.hkl
Contains datablock I

CCDC reference: 665527

Comment top

The introduction of halogens in components of nucleic acids generally leads to changes in their physical properties and biological activity. Among the various positions, the 7-position of the 7-deazapurine moiety (purine numbering is used throughout) and the 2'-position of the sugar residue are important modification sites (Seela, Chittepu et al., 2005). A series of 7-substituted 7-deazapurine ribonucleosides and 2'-deoxyribonucleosides exhibit antiviral activity against various RNA and DNA viruses, including Herpes simplex virus types 1 and type 2 (HSV-1 and HSV-2) (Bergstrom et al., 1984; De Clercq et al., 1986). The introduction of the 7-bromo substituent increases the polarizability of the nucleobase and enhances base-stacking interactions, thereby stabilizing the DNA duplex structure (Ramzaeva & Seela, 1996; Seela & Thomas, 1995). The 7-bromo substituent decreases the basicity of the title compound, (I) (pKa = 4.77), compared to the non-halogenated compound (pKa = 5.67), as indicated by the lower pKa value. The nuleobase plays an important role in directing the conformation of the sugar moiety.

The introduction of an F atom instead of H into the 2'-position of the sugar moiety of nucleosides enhances the chemical stability and biological activity of nucleosides (Filler & Naqvi, 1979; Marquez et al., 1990; Masood et al., 1990). It leads to a minor change in the size of the molecule but strongly influences the S/N-conformational equilibrium of the pentofuranose ring in solution (He et al., 2003). In order to elucidate the combined influence of bromination at position 7 of 2-amino-2'-deoxytubercidin and the introduction of a 2'-fluoro substituent in the sugar residue, we have synthesized the title compound 2-amino-7-deaza-7-bromo-2'-deoxy-2'-fluoroadenosine, (I), and subjected it to single-crystal X-ray analysis. The synthesis of the title compound was reported previously (Peng & Seela, 2004). The structure of compound (I) is shown in Fig. 1 and selected geometric parameters are summarized in Table 1.

The orientation of the base relative to the sugar moiety (syn/anti) is denoted by the torsion angle χ, which is defined as O4'-C1'-N9—C4 for purine nucleosides (IUPAC-IUB Joint Commission on Biochemical Nomenclature, 1983). The crystal structure of compound (I) exhibits a torsion angle χ of −114.8 (4)°, falling into the anti range. This value is close to those of compound (IIa) (see scheme) [χ = −105.0 (6)°; Seela, Sirivolu et al., 2005] and (III) (see scheme) [χ = −102.5 (6)°; Seela et al., 2006]. The length of the N-glycosylic bond of nucleoside (I) is 1.442 (5) Å, which is similar to compound (IIa) [1.447 (5) Å; Seela, Sirivolu et al., 2005] and (III) [1.464 (6) Å; Seela et al., 2006]. For the sugar moiety, two major twisted conformations are found, denoted north and south. The north (N) conformation refers to the C3'-endo-C2'-exo conformer, whereas the south (S) conformation represents the C2'-endo-C3'-exo conformer [Seela et al., 2000]. The sugar moiety of compound (I) shows an N conformation with a phase angle of pseudorotation P = 23.3 (4)° and the maximum amplitude of puckering τm = 36.5 (2)° (Altona & Sundaralingam, 1972), indicating that the sugar ring adopts an unsymmetrical twist (C3'-endo-C4'-exo; 3T4). Nucleoside (III) shows the same sugar moiety structure as (I) (P = 19.6° and τm = 32.9°; Seela et al., 2006), whereas compound (IIa) exhibits differences in the N conformation [C3'-endo-C2'-exo, between 3T2 and E3, with P = 5.8 (5)° and τm = 30.0 (3)°; Seela, Sirivolu et al., 2005].

In the crystal of (I), two conformations of the exocyclic C4'-C5' bond were found corresponding to occupancies of 0.69 of conformer 1 (Fig. 1a) and 0.31 of conformer 2 (Fig. 1b). The torsion angle γ is defined as O5'1-C5'1-C4'-C3' for conformer 1 and O5'2-C5'2-C4'-C3' for conformer 2. For conformer 1, this torsion angle is 170.1 (3)°, falling into +ap (trans) range. This is close to compounds (IIa) [γ = 172.0 (4)°; Seela, Sirivolu et al.,2005] and (III) [γ = 171.5 (4)°; Seela et al., 2006]. In contrast, the conformer 2 adopts a conformation with γ = 60.7 (7)° representing a +synclinal (gauche) conformation. The base unit of (I) is essentially planar, with an r.m.s. deviation of 0.0201 Å and a maximum deviation of −0.0369 (3) Å for the ring atom C2. The bromo substituent is located −0.0764 (5) Å below the 7-deazapurine plane on the same side as the 2-amino group [−0.0851 (6) Å] whereas the 6-amino group lies 0.0533 (7) Å above the plane.

In contrast to the behavior in solid state, the spatial conformation of the sugar moiety dynamically interconverts between north (N) and south (S) in solution. This ratio was determined from the vicinal 3J (H, H) coupling constants of the 1H NMR spectrum measured in D2O, using the PSEUROT program (van Wijk & Altona, 1993). The population in an aqueous solution of compound (I) is 0.63 S and 0.37 N, whereas for the non-fluorinated nucleoside, (IIc), the populations are shifted towards S (0.71 S and 0.29 N; Peng & Seela, 2004). This shows that the introduction of an F atom in the arabino position of the sugar moiety enhances the population of the N-conformers. In contrast, the related 8-aza compound, (IIb), incorporating an N atom instead of a C atom at position 8, exclusively forms the N conformation (He et al., 2003).

Compound (I) forms a compact three-dimensional network, which is stabilized by hydrogen bonds and stacking interactions (Fig. 2 and Table 2). The nucleobases are arranged head-to-tail. The two conformers 1 and 2, are linked through hydrogen bonds between neighbouring nucleobases and sugar residues. The N2 and N6 amino groups function as H-atom donors and atoms O5' of both conformers act as H-atom acceptors (N2—H2A···O5'1; N2—H2B···O5'1; N6—H6A···O5'2). Further hydrogen bonds connect neighbouring sugar residues and the exocyclic substituents of the nucleobase. Hydrogen bonds are formed between N3 and H5' of conformer 1 (O5'1-H5'1···N3), while atom H5' of conformer 2 forms a hydrogen bond with O3' (O5'2-H5'2···O3'). Both conformers form two further intermolecular hydrogen bonds (O3'-H3A···N1 and N6—H6B···Br7).

Experimental top

Compound (I) was synthesized as described previously (Peng & Seela, 2004) and was crystallized from MeOH (m.p. 470 K). For the diffraction experiment, a single-crystal was fixed at the top of a Lindemann capillary with epoxy resin.

Refinement top

The absolute configuration was obtained from the Flack parameter as well as from the defined configuration of the sugar halide used in the glycosylation reaction.

Atom O5' shows a rather large displacement parameter. This resulted from two different positions (1 and 2) of atom O5'. It is in agreement with the bond lengths and angles. Consequently, two site-occupancy factors, K1 and K2, were introduced, with K2 = 1 - K1.

All H atoms were found in a difference Fourier synthesis. In order to maximize the data/parameter ratio, the H atoms were placed in geometrically idealized positions with C—H = 0.93–0.98 Å and N—H 0.86 Å (using AFIX 93) and constrained to ride on their parent atoms with Uiso(H)= 1.2Ueq(C)= Ueq(N). The OH groups were refined as rigid groups allowed to rotate but not tip (using AFIX 147) with O—H= 0.82 Å and U(H) = 1.5Ueq(O).

Computing details top

Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS (Siemens, 1996); data reduction: SHELXTL (Sheldrick, 1997); program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 1997) and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. Perspective views of (a) conformer 1 [occupancy 0.690 (7)] and (b) conformer 2 [occupancy 0.310 (7)] of compound (I), showing the atomic numbering. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as spheres of arbitrary size.
[Figure 2] Fig. 2. The crystal packing of (I), showing the intermolecular hydrogen-bonding network (projection parallel to the b axis). Only H atoms involved in hydrogen bonding are shown.
2,4-diamino-7-(2-deoxy-2-fluoro-β-D-arabinofuranosyl)-5-bromo-7H- pyrrolo[2,3-d]pyrimidine top
Crystal data top
C11H13BrFN5O3F(000) = 728
Mr = 362.17Dx = 1.807 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 44 reflections
a = 7.7618 (14) Åθ = 4.8–13.0°
b = 9.688 (2) ŵ = 3.12 mm1
c = 17.707 (3) ÅT = 293 K
V = 1331.6 (5) Å3Block, colourless
Z = 40.4 × 0.4 × 0.2 mm
Data collection top
Bruker P4
diffractometer
2221 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.027
Graphite monochromatorθmax = 30.0°, θmin = 2.3°
2θ/ω scansh = 110
Absorption correction: ψ scan
(XSCANS; Siemens, 1996)
k = 131
Tmin = 0.479, Tmax = 0.791l = 241
2872 measured reflections3 standard reflections every 97 reflections
2687 independent reflections intensity decay: none
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.040 w = 1/[σ2(Fo2) + (0.0596P)2 + 0.6193P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.106(Δ/σ)max = 0.001
S = 1.03Δρmax = 0.60 e Å3
2687 reflectionsΔρmin = 0.78 e Å3
205 parametersExtinction correction: SHELXTL (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.0106 (14)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), with 460 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.005 (12)
Crystal data top
C11H13BrFN5O3V = 1331.6 (5) Å3
Mr = 362.17Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 7.7618 (14) ŵ = 3.12 mm1
b = 9.688 (2) ÅT = 293 K
c = 17.707 (3) Å0.4 × 0.4 × 0.2 mm
Data collection top
Bruker P4
diffractometer
2221 reflections with I > 2σ(I)
Absorption correction: ψ scan
(XSCANS; Siemens, 1996)
Rint = 0.027
Tmin = 0.479, Tmax = 0.7913 standard reflections every 97 reflections
2872 measured reflections intensity decay: none
2687 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.040H-atom parameters constrained
wR(F2) = 0.106Δρmax = 0.60 e Å3
S = 1.03Δρmin = 0.78 e Å3
2687 reflectionsAbsolute structure: Flack (1983), with 460 Friedel pairs
205 parametersAbsolute structure parameter: 0.005 (12)
1 restraint
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
N10.1289 (5)0.2176 (3)1.17059 (18)0.0379 (8)
C20.1043 (5)0.0791 (4)1.1735 (2)0.0334 (8)
N20.0856 (5)0.0244 (4)1.24418 (17)0.0448 (9)
H2A0.07260.06321.24970.054*
H2B0.08680.07751.28310.054*
N30.1012 (4)0.0092 (3)1.11538 (16)0.0319 (7)
C40.1166 (5)0.0545 (4)1.0487 (2)0.0316 (8)
C50.1358 (6)0.1959 (4)1.0365 (2)0.0352 (8)
C60.1447 (6)0.2773 (4)1.1025 (2)0.0354 (7)
N60.1678 (7)0.4144 (4)1.0992 (2)0.0530 (9)
H6A0.17210.46211.14010.064*
H6B0.17820.45461.05610.064*
C70.1390 (6)0.2154 (3)0.9561 (2)0.0367 (8)
Br70.15974 (8)0.38288 (4)0.90405 (2)0.05348 (17)
C80.1262 (7)0.0898 (4)0.92320 (19)0.0429 (10)
H8A0.12680.07280.87150.051*
N90.1119 (5)0.0095 (3)0.97942 (17)0.0378 (8)
C1'0.0872 (5)0.1555 (4)0.9679 (2)0.0324 (7)
H1'0.08400.20221.01690.039*
C2'0.2240 (5)0.2235 (4)0.9181 (2)0.0347 (8)
H2'0.25020.31580.93760.042*
F2'0.3740 (3)0.1461 (3)0.91499 (15)0.0506 (6)
C3'0.1399 (5)0.2360 (3)0.84091 (18)0.0317 (7)
H3'0.15100.14860.81350.038*
O3'0.2044 (4)0.3456 (3)0.79619 (16)0.0439 (7)
H3'A0.25280.31400.75880.066*
C4'0.0478 (5)0.2595 (4)0.86277 (18)0.0291 (7)
H4'0.06540.35710.87500.035*
O4'0.0725 (4)0.1771 (3)0.92965 (14)0.0385 (6)
C5'10.1749 (7)0.2161 (4)0.8035 (2)0.0404 (9)0.690 (7)
H5110.16460.27760.76050.049*0.690 (7)
H5120.14580.12380.78650.049*0.690 (7)
O5'10.3436 (6)0.2167 (4)0.8280 (2)0.0407 (11)0.690 (7)
H5'10.36420.29000.84940.061*0.690 (7)
C5'20.1749 (7)0.2161 (4)0.8035 (2)0.0404 (9)0.310 (7)
H5210.29100.23600.82060.049*0.310 (7)
H5220.15450.26780.75740.049*0.310 (7)
O5'20.159 (2)0.0754 (9)0.7891 (5)0.050 (3)0.310 (7)
H5'20.16620.06160.74350.076*0.310 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.047 (2)0.0335 (15)0.0333 (15)0.0020 (16)0.0008 (14)0.0056 (12)
C20.033 (2)0.0385 (19)0.0291 (16)0.0005 (15)0.0000 (14)0.0029 (14)
N20.063 (2)0.0452 (18)0.0265 (14)0.0091 (19)0.0050 (15)0.0039 (14)
N30.0395 (17)0.0294 (14)0.0269 (13)0.0005 (13)0.0007 (11)0.0006 (11)
C40.044 (2)0.0271 (15)0.0239 (14)0.0009 (15)0.0008 (14)0.0030 (13)
C50.045 (2)0.0298 (15)0.0308 (16)0.0003 (17)0.0024 (16)0.0007 (13)
C60.0367 (18)0.0302 (16)0.0393 (17)0.0005 (17)0.0031 (19)0.0043 (15)
N60.081 (3)0.0315 (14)0.0459 (17)0.008 (2)0.003 (2)0.0057 (15)
C70.052 (2)0.0264 (15)0.0315 (16)0.0015 (17)0.0028 (18)0.0049 (13)
Br70.0885 (4)0.02863 (18)0.0433 (2)0.0020 (2)0.0004 (2)0.00803 (16)
C80.074 (3)0.0301 (16)0.0242 (15)0.0019 (19)0.0020 (17)0.0027 (13)
N90.065 (2)0.0241 (13)0.0246 (13)0.0026 (15)0.0012 (14)0.0003 (11)
C1'0.0441 (19)0.0263 (15)0.0267 (15)0.0019 (15)0.0049 (15)0.0020 (12)
C2'0.0403 (18)0.0264 (16)0.0374 (19)0.0023 (15)0.0028 (15)0.0031 (14)
F2'0.0401 (12)0.0477 (13)0.0639 (16)0.0064 (11)0.0081 (12)0.0014 (12)
C3'0.0446 (19)0.0226 (14)0.0279 (14)0.0024 (17)0.0043 (15)0.0000 (12)
O3'0.0610 (19)0.0328 (13)0.0380 (14)0.0096 (14)0.0163 (13)0.0044 (11)
C4'0.0405 (18)0.0220 (14)0.0249 (14)0.0013 (15)0.0012 (14)0.0014 (12)
O4'0.0407 (13)0.0480 (15)0.0266 (11)0.0003 (14)0.0015 (11)0.0094 (12)
C5'10.053 (2)0.0388 (19)0.0294 (16)0.003 (2)0.0036 (19)0.0005 (14)
O5'10.036 (2)0.040 (2)0.046 (2)0.007 (2)0.003 (2)0.0023 (17)
C5'20.053 (2)0.0388 (19)0.0294 (16)0.003 (2)0.0036 (19)0.0005 (14)
O5'20.087 (8)0.034 (4)0.030 (4)0.020 (6)0.003 (5)0.004 (3)
Geometric parameters (Å, º) top
N1—C61.343 (5)C1'—O4'1.428 (5)
N1—C21.356 (5)C1'—C2'1.530 (5)
C2—N31.340 (5)C1'—H1'0.9800
C2—N21.366 (5)C2'—F2'1.386 (4)
N2—H2A0.8600C2'—C3'1.519 (5)
N2—H2B0.8600C2'—H2'0.9800
N3—C41.337 (5)C3'—O3'1.416 (4)
C4—N91.375 (5)C3'—C4'1.524 (5)
C4—C51.395 (5)C3'—H3'0.9800
C5—C61.411 (5)O3'—H3'A0.8200
C5—C71.436 (5)C4'—O4'1.441 (4)
C6—N61.342 (5)C4'—C5'11.500 (5)
N6—H6A0.8600C4'—H4'0.9800
N6—H6B0.8600C5'1—O5'11.380 (7)
C7—C81.353 (5)C5'1—H5110.9700
C7—Br71.873 (3)C5'1—H5120.9700
C8—N91.389 (4)O5'1—H5'10.8200
C8—H8A0.9300O5'2—H5'20.8200
N9—C1'1.442 (5)
C6—N1—C2118.3 (3)N9—C1'—C2'114.4 (3)
N3—C2—N1127.2 (4)O4'—C1'—H1'109.3
N3—C2—N2117.0 (3)N9—C1'—H1'109.3
N1—C2—N2115.7 (3)C2'—C1'—H1'109.3
C2—N2—H2A120.0F2'—C2'—C3'111.7 (3)
C2—N2—H2B120.0F2'—C2'—C1'111.9 (3)
H2A—N2—H2B120.0C3'—C2'—C1'104.7 (3)
C4—N3—C2112.4 (3)F2'—C2'—H2'109.5
N3—C4—N9125.2 (3)C3'—C2'—H2'109.5
N3—C4—C5126.8 (3)C1'—C2'—H2'109.5
N9—C4—C5107.9 (3)O3'—C3'—C2'114.2 (3)
C4—C5—C6115.2 (3)O3'—C3'—C4'111.6 (3)
C4—C5—C7106.5 (3)C2'—C3'—C4'101.2 (3)
C6—C5—C7138.3 (4)O3'—C3'—H3'109.8
N6—C6—N1118.6 (4)C2'—C3'—H3'109.8
N6—C6—C5121.6 (4)C4'—C3'—H3'109.8
N1—C6—C5119.9 (3)C3'—O3'—H3'A109.5
C6—N6—H6A120.0O4'—C4'—C5'1109.4 (3)
C6—N6—H6B120.0O4'—C4'—C3'104.7 (3)
H6A—N6—H6B120.0C5'1—C4'—C3'114.1 (3)
C8—C7—C5107.9 (3)O4'—C4'—H4'109.5
C8—C7—Br7125.0 (3)C5'1—C4'—H4'109.5
C5—C7—Br7127.1 (3)C3'—C4'—H4'109.5
C7—C8—N9108.7 (3)C1'—O4'—C4'110.8 (3)
C7—C8—H8A125.7O5'1—C5'1—C4'113.8 (3)
N9—C8—H8A125.7O5'1—C5'1—H511108.8
C4—N9—C8109.0 (3)C4'—C5'1—H511108.8
C4—N9—C1'124.9 (3)O5'1—C5'1—H512108.8
C8—N9—C1'126.0 (3)C4'—C5'1—H512108.8
O4'—C1'—N9109.1 (3)H511—C5'1—H512107.7
O4'—C1'—C2'105.4 (3)
C6—N1—C2—N33.3 (7)C7—C8—N9—C40.3 (5)
C6—N1—C2—N2178.8 (4)C7—C8—N9—C1'176.8 (4)
N1—C2—N3—C43.4 (6)C4—N9—C1'—O4'114.8 (4)
N2—C2—N3—C4178.6 (4)C8—N9—C1'—O4'61.8 (5)
C2—N3—C4—N9177.7 (4)C4—N9—C1'—C2'127.5 (4)
C2—N3—C4—C50.6 (6)C8—N9—C1'—C2'55.9 (6)
N3—C4—C5—C62.0 (7)O4'—C1'—C2'—F2'140.6 (3)
N9—C4—C5—C6179.4 (4)N9—C1'—C2'—F2'20.8 (4)
N3—C4—C5—C7177.4 (4)O4'—C1'—C2'—C3'19.5 (3)
N9—C4—C5—C71.2 (6)N9—C1'—C2'—C3'100.3 (3)
C2—N1—C6—N6179.5 (5)F2'—C2'—C3'—O3'85.6 (4)
C2—N1—C6—C50.1 (6)C1'—C2'—C3'—O3'153.1 (3)
C4—C5—C6—N6178.2 (5)F2'—C2'—C3'—C4'154.3 (3)
C7—C5—C6—N62.6 (10)C1'—C2'—C3'—C4'33.1 (3)
C4—C5—C6—N12.3 (6)O3'—C3'—C4'—O4'157.1 (3)
C7—C5—C6—N1177.0 (6)C2'—C3'—C4'—O4'35.2 (3)
C4—C5—C7—C81.3 (6)O3'—C3'—C4'—C5'183.3 (4)
C6—C5—C7—C8179.4 (6)C2'—C3'—C4'—C5'1154.8 (3)
C4—C5—C7—Br7179.3 (3)N9—C1'—O4'—C4'126.6 (3)
C6—C5—C7—Br70.0 (10)C2'—C1'—O4'—C4'3.3 (4)
C5—C7—C8—N91.0 (6)C5'1—C4'—O4'—C1'147.5 (3)
Br7—C7—C8—N9179.6 (3)C3'—C4'—O4'—C1'24.8 (3)
N3—C4—N9—C8178.0 (4)O4'—C4'—C5'1—O5'153.2 (5)
C5—C4—N9—C80.6 (5)C3'—C4'—C5'1—O5'1170.1 (3)
N3—C4—N9—C1'0.9 (7)C3'—C4'—C5'1—O5'260.7 (7)
C5—C4—N9—C1'177.7 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O51i0.862.623.290 (6)136
N2—H2B···O51ii0.862.453.034 (6)126
N6—H6A···O52iii0.862.122.857 (10)143
N6—H6B···Br70.862.783.469 (4)138
O3—H3A···N1iv0.822.042.857 (4)175
O51—H51···N3v0.822.062.871 (5)169
O52—H52···O3vi0.822.232.714 (9)118
Symmetry codes: (i) x+1/2, y+1/2, z+2; (ii) x1/2, y, z+1/2; (iii) x+1/2, y1/2, z+2; (iv) x+1/2, y, z1/2; (v) x1/2, y+1/2, z+2; (vi) x, y1/2, z+3/2.

Experimental details

Crystal data
Chemical formulaC11H13BrFN5O3
Mr362.17
Crystal system, space groupOrthorhombic, P212121
Temperature (K)293
a, b, c (Å)7.7618 (14), 9.688 (2), 17.707 (3)
V3)1331.6 (5)
Z4
Radiation typeMo Kα
µ (mm1)3.12
Crystal size (mm)0.4 × 0.4 × 0.2
Data collection
DiffractometerBruker P4
diffractometer
Absorption correctionψ scan
(XSCANS; Siemens, 1996)
Tmin, Tmax0.479, 0.791
No. of measured, independent and
observed [I > 2σ(I)] reflections
2872, 2687, 2221
Rint0.027
(sin θ/λ)max1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.040, 0.106, 1.03
No. of reflections2687
No. of parameters205
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.60, 0.78
Absolute structureFlack (1983), with 460 Friedel pairs
Absolute structure parameter0.005 (12)

Computer programs: XSCANS (Siemens, 1996), SHELXTL (Sheldrick, 1997) and PLATON (Spek, 2003).

Selected geometric parameters (Å, º) top
C2—N21.366 (5)N9—C1'1.442 (5)
C6—N61.342 (5)C2'—F2'1.386 (4)
C7—Br71.873 (3)C5'1—O5'11.380 (7)
N1—C2—N2115.7 (3)N9—C1'—C2'114.4 (3)
N6—C6—N1118.6 (4)F2'—C2'—C3'111.7 (3)
C8—C7—Br7125.0 (3)F2'—C2'—C1'111.9 (3)
C5—C7—Br7127.1 (3)O4'—C4'—C5'1109.4 (3)
C4—N9—C1'124.9 (3)O5'1—C5'1—C4'113.8 (3)
O4'—C1'—N9109.1 (3)
C6—N1—C2—N33.3 (7)C1'—C2'—C3'—C4'33.1 (3)
C7—C5—C6—N62.6 (10)C2'—C3'—C4'—O4'35.2 (3)
C6—C5—C7—Br70.0 (10)C2'—C3'—C4'—C5'1154.8 (3)
C4—N9—C1'—O4'114.8 (4)N9—C1'—O4'—C4'126.6 (3)
C8—N9—C1'—O4'61.8 (5)C2'—C1'—O4'—C4'3.3 (4)
O4'—C1'—C2'—F2'140.6 (3)C5'1—C4'—O4'—C1'147.5 (3)
N9—C1'—C2'—F2'20.8 (4)C3'—C4'—O4'—C1'24.8 (3)
O4'—C1'—C2'—C3'19.5 (3)O4'—C4'—C5'1—O5'153.2 (5)
N9—C1'—C2'—C3'100.3 (3)C3'—C4'—C5'1—O5'1170.1 (3)
F2'—C2'—C3'—O3'85.6 (4)C3'—C4'—C5'1—O5'260.7 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O5'1i0.862.623.290 (6)135.6
N2—H2B···O5'1ii0.862.453.034 (6)125.5
N6—H6A···O5'2iii0.862.122.857 (10)143.1
N6—H6B···Br70.862.783.469 (4)137.7
O3'—H3'A···N1iv0.822.042.857 (4)174.6
O5'1—H5'1···N3v0.822.062.871 (5)169.3
O5'2—H5'2···O3'vi0.822.232.714 (9)118.3
Symmetry codes: (i) x+1/2, y+1/2, z+2; (ii) x1/2, y, z+1/2; (iii) x+1/2, y1/2, z+2; (iv) x+1/2, y, z1/2; (v) x1/2, y+1/2, z+2; (vi) x, y1/2, z+3/2.
 

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