Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229614000825/gz3251sup1.cif | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614000825/gz3251Isup6.cml | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614000825/gz3251Isup6.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614000825/gz3251IIsup7.cml | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614000825/gz3251IIsup7.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614000825/gz3251IIIsup8.cml | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614000825/gz3251IIIsup8.hkl | |
Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229614000825/gz3251IVsup9.cml | |
Structure factor file (CIF format) https://doi.org/10.1107/S2053229614000825/gz3251IVsup9.hkl |
CCDC references: 981325; 981326; 981327; 981328
Theophylline (1,3-dimethylxanthine) is a naturally occurring base that is chemically and structurally related to caffeine and theobromine. Its main medicinal use is in the treatment of asthma symptoms, but in the field of crystal science it is perhaps better known as the model active pharmaceutical ingredient (API) at the heart of many physical-form screening and prediction studies. Three polymorphs have been structurally described (Fucke et al., 2012), as have numerous organic cocrystal forms (see, for example, Fucke et al., 2012; Karki et al., 2007), as well as dimethyl sulfoxide (DMSO) and hydrate solvate forms (Cardin et al., 2007; Sun et al., 2002). The aqueous dissolution profile of theophylline and its transformation to theophylline hydrate has also received much attention (De Smidt et al., 1986; Rodriguez-Hornedo et al., 1992). Additionally, theophylline has been used as a ligand with d-block metals and several such complexes have been structurally characterized (for example, Abuhijleh et al., 2009; Griffith & Amma, 1979; Nolte et al., 2006). Despite this interest, only two structures of simple salt forms where theophyllline acts as a Brønsted base and hence occurs as a protonated cation are known. A perchlorate salt form has been described (Biradha et al., 2010) and, in a relatively early and film-based study that gave a poorly defined structure, an anhydrous hydrochloride form has been described in the space group Pna21 (Koo et al., 1978). This latter form is especially interesting to the pharmaceutical community as hydrochloride salts are the commonest salt form of basic APIs to be commercially exploited (Stahl & Wermuth, 2008). Herein, the structures of the tetrafluoroborate, (I), and hydrated bromide, (III), salts of theophylline are described, as are two new structures of theophylline hydrochloride, an anhydrate, (IV), and a monohydrate, (II). The identity of the previously reported hydrochloride structure is re-assessed in light of these results.
Large colourless crystals of (I), (II) and (III) were obtained using the following general scheme. Theophylline (approximately 0.5 g) was suspended in deionized water (10 ml). The appropriate concentrated acid (HBF4, HCl or HBr) was added in sufficient volume to ensure dissolution of the theophylline. The solutions were filtered and left to evaporate. Crystals of (II) were recovered from solution after approximately 4 d, but crystals of (I) and (III) were only obtained after approximately two weeks. Buist et al. (2013) describe the method used for in situ generation of HCl by reaction of a alcohol solution of an active pharmaceutical ingredient (API) with acetyl chloride. Following this method with methanol and theophylline again gave crystals of (II), but with ethanol as the solvent, suitable colourless crystals of (IV) were deposited directly from the reaction mixture after 48 h.
Crystal data, data collection and structure refinement details are summarized in Table 1. H atoms bound to C atoms were placed geometrically and refined in riding mode, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C) for Csp2 groups, and C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C) for methyl groups. H atoms bound to N atoms were positioned as found by difference syntheses; in (I) and (II), these atoms were refined freely; however, for (III) the N—H distances were restrained to 0.86 (1) Å and for (IV) the H atoms were restrained both to have N—H distances of 0.86 (2) Å and such that Uiso(H) = 1.2Ueq(N). In both hydrates, the H atoms of the water molecules were positioned as found by difference syntheses and were refined with restraints such that the O—H and H···H distances approximated 0.88 (1) and 1.33 (2) Å, respectively, and with Uiso(H) values set at 1.5Ueq(O).
The reaction of an aqueous slurry of theophylline with concentrated tetrafluoroboric acid gave the tetrafluoroborate salt of the protonated theophylline cation, (I) (Fig. 1). This structure has a unit cell that is isomorphous with that of the reported perchlorate salt (Biradha et al., 2010). Both the perchlorate and the tetrafluoroborate salt structures have the same hydrogen-bonding motif involving planar dimeric theophylline units forming a ten-membered ring (Fig. 2 and Table 2). A similar dimeric hydrogen-bonding motif is observed in the structure of theophylline hydrate (Sun et al., 2002). In tetrafluoroborate (I), the tetrahedral counter-ion accepts a hydrogen bond from the second N—H group of the theophylline cation, and thus two anions lie pendant to the theophylline dimer. Note that only one of the four F atoms acts as a hydrogen-bond acceptor, though a second F atom does make a significantly short contact with π geometry through an interaction with the central xanthine C—C bond [F4···C3 = 2.8704 (13) Å]. Again, a similar pendant interaction occurs in the perchlorate structure, indicating that here similarities in the anions shape and general size outweigh any differences that might be expected due to their differing electronic natures. The molecular geometry of the cation in (I), as judged by a comparison of the bond lengths and angles, is also in good agreement with that described for the perchlorate salt. The same is true for the molecular geometries of all the other theophylline cations described herein (see Supporting information).
On reaction of theophylline with concentrated aqueous HCl or HBr, the monohydrates of theophylline hydrochloride, (II) (Fig. 3), and theophylline hydrobromide, (III) (Fig. 4), were obtained. The structures of (II) and (III) are essentially mutually isomorphous and isostructural and are thus described together. With the exception of the H atoms of the methyl groups, all the atoms of the cations of (II) and (III) lie on the mirror plane (Z' = 1/2) in the space group Pnma. The halide ions reside in the same plane, but modeling the water molecules in-plane gave models with elongated displacement ellipsoids for atom O1W. This effect was more pronounced for (III) than for (II). Thus, the water molecules are modeled as being displaced slightly out of plane, that is they are disordered about the mirror. Alternative refinement in the space group Pna21 gives similar models with disorder in the position of the water molecule. The higher-symmetry model is thus prefered. The hydrogen-bonded theophylline dimer observed for the structures with the tetrahedral anions is not seen here. Instead, one N—H group donates a hydrogen bond to the halide anion, whilst the second N—H group donates a hydrogen bond to the water molecule. Both H atoms of the water molecule donate hydrogen bonds, one to the halide and one to atom O2 (Tables 3 and 4). These hydrogen bonds combine to form planar sheets parallel to the ac plane, but they also leave one C═O group of each theophylline that, in contradiction to predictions based on Etter's rules, does not act as a hydrogen-bond acceptor (Etter, 1990). The most significant interactions between adjacent sheets are the close contacts that result from the halides ions lying symmetrically between pairs of xanthine rings, see Fig. 5. For hydrated chloride salt (II), the shortest such contact is C3···Cl' [3.3979 (6) Å], whilst for hydrate bromide salt (III) the equivalent Br interaction distance is 3.4307 (7) Å (symmetry code: -x+1/2, -y+1, z+1/2).
Rather than using aqueous HCl, HCl can be generated in situ by reaction of alcohols with acetyl chloride. This water-free method has been used recently to produce salt forms of weakly basic groups and to obtain nonhydrated forms of salts (Perumalla & Sun, 2012; Buist et al., 2013). Using this technique with theophylline and methanol led only to an alternative preparation of (II). However, with ethanol, an anhydrous phase of theophylline hydrochloride (IV) was isolated and characterized (Fig. 6). The structure is pseudocentrosymmetric and a solution is possible in the higher-symmetry space group C2/c. However, refining with this higher symmetry leads to scrambling of the C═O and N—Me positions, with all C═O and N—Me distances lying between 1.32 and 1.34 Å, and the constituent atoms have poor displacement ellipsoid shapes. An ordered structure of (IV) is thus described in the space group Cc and consists of two crystallographically independent cation and anion pairs (Z' = 2), hereafter ions A and B. The N—H groups of the cations act as hydrogen-bond donors only to the chloride anions (Table 5). These interactions give parallel one-dimensional chains consisting of cation A and Cl2 and of cation B with Cl1. Both chains propagate parallel to the crystallographic c direction. Secondary interactions between chains of cation A and between chains of cation B take the form of stacking interactions between C4N2 rings. The shortest such C···C distances are 3.284 (8) and 2.285 (8) Å. The chains of cation A bind to the chains of cation B through C—H···Cl interactions involving the H atom of the imidazole rings (Table 5). This weak C—H donor is not used to form hydrogen bonds in hydrate (II), presumably because the water H atoms are available and are stronger donors. Unlike the other theopylline salt structures above, theophylline cations that are joined by hydrogen bonding are no longer coplanar, indeed neighbouring imidazole ring planes are now approximately perpendicular [89.8 (2) and 88.7 (2)°]. None of the C═O groups in chloride salt (IV) act as classical hydrogen-bond acceptors, all four form only relatively long interactions with methyl-group H atoms.
In 1978, Koo et al. reported a single-crystal structure which they described as anhydrous theophylline hydrochloride [Cambridge Structural Database (CSD; Allen, 2002) refcode THEOPI (Koo et al., 1978)]. However, the unit cell given is not that of anhydrous chloride salt (IV), but instead matches that of the hydrated form (II). The earlier description was based on film data and is rather inaccurate, with an R factor > 12% and no H-atom positions reported. Although the structure is reported as having the space group Pna21, recovery of the atomic positions from the CSD shows that all reported atoms have z coordinates of 0.5. Comparing the structure of (II) with that of THEOPI shows that the cations and anions pack in aan almost manner, the only observable difference being that where the water molecules occur in (II) there is a void in THEOPI (Fig. 8). The diameter of the void is approximately 8.25 Å from N to Cl. Whilst one N—H group of the imidazole ring in THEOPI is in the correct position to form a hydrogen bond with the anion, the second N—H group is oriented towards the void. There is no suitable hydrogen-bond acceptor, such as would be expected for a formally partially positive H atom. Whilst it is possible to have hydrated and anhydrous phases of organic species that have somewhat similar unit cells, dehydration is typically accompanied by a shrinking of the void space previously occupied by water (see, for example, Shankland et al., 2001). The evidence outlined above points towards THEOPI having been wrongly described as an anhydrous phase in the space group Pna21. We believe that it should have been described as the Pnma monohydrate form (II).
For all compounds, data collection: CrysAlis PRO (Oxford Diffraction, 2010); cell refinement: CrysAlis PRO (Oxford Diffraction, 2010); data reduction: CrysAlis PRO (Oxford Diffraction, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008). Molecular graphics: ORTEP-3 for Windows (Farrugia, 2012) and X-SEED (Barbour, 2001) for (I), (II), (IV); ORTEP-3 for Windows (Farrugia, 2012) for (III). For all compounds, software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
Fig. 1. The ion-pair structure of (I), with non-H-atom ellipsoids drawn at the
50% probability level. Fig. 2. The dimeric hydrogen-bonded fragment of (I), showing the pendant nature of the BF4- anions. Fig. 3. The ion-pair structure of (II), with non-H-atom ellipsoids drawn at the 50% probability level. Fig. 4. The ion-pair structure of (III), with non-H atom ellipsoids drawn at the 50% probability level. Fig. 5. The structure of (II), viewed along the b axis, showing two hydrogen-bonded sheets parallel to the ac plane and the position of the anions with respect to the ring systems. The structure of (III) is similar. Fig. 6. The ion-pair structure of (IV), with non-H-atom ellipsoids drawn at the 50% probability level. Fig. 7. Packing diagram for (IV), showing parts of the one-dimensional chains that propagate parallel to the crystallographic c direction. Fig. 8. Packing diagram produced from the atomic coordinates of CSD entry THEOPI (Koo et al., 1978). The void space has been highlighted. |
C7H9N4O2+·BF4− | F(000) = 544 |
Mr = 267.99 | Dx = 1.711 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 7776 reflections |
a = 13.0883 (4) Å | θ = 3.4–29.4° |
b = 6.0413 (1) Å | µ = 0.17 mm−1 |
c = 14.5542 (4) Å | T = 123 K |
β = 115.306 (3)° | Block, colourless |
V = 1040.37 (5) Å3 | 0.30 × 0.12 × 0.10 mm |
Z = 4 |
Oxford Diffraction Xcalibur E diffractometer | 2705 independent reflections |
Radiation source: fine-focus sealed tube | 2366 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
ω scans | θmax = 29.5°, θmin = 3.4° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | h = −17→17 |
Tmin = 0.913, Tmax = 1.000 | k = −7→8 |
14312 measured reflections | l = −19→20 |
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.082 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0316P)2 + 0.5591P] where P = (Fo2 + 2Fc2)/3 |
2705 reflections | (Δ/σ)max < 0.001 |
173 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
C7H9N4O2+·BF4− | V = 1040.37 (5) Å3 |
Mr = 267.99 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.0883 (4) Å | µ = 0.17 mm−1 |
b = 6.0413 (1) Å | T = 123 K |
c = 14.5542 (4) Å | 0.30 × 0.12 × 0.10 mm |
β = 115.306 (3)° |
Oxford Diffraction Xcalibur E diffractometer | 2705 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | 2366 reflections with I > 2σ(I) |
Tmin = 0.913, Tmax = 1.000 | Rint = 0.020 |
14312 measured reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.082 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.05 | Δρmax = 0.40 e Å−3 |
2705 reflections | Δρmin = −0.23 e Å−3 |
173 parameters |
Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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. |
x | y | z | Uiso*/Ueq | ||
F1 | 0.81186 (7) | 0.15621 (14) | 0.34517 (7) | 0.0323 (2) | |
F2 | 0.86001 (7) | 0.08252 (15) | 0.51256 (6) | 0.0339 (2) | |
F3 | 0.85378 (7) | −0.19548 (13) | 0.40440 (6) | 0.02707 (18) | |
F4 | 0.69139 (6) | −0.03528 (14) | 0.39121 (6) | 0.02790 (19) | |
O1 | 0.42131 (7) | 0.24903 (15) | 0.46997 (6) | 0.02036 (19) | |
O2 | 0.33892 (8) | −0.26810 (15) | 0.21988 (7) | 0.0240 (2) | |
N1 | 0.55961 (8) | 0.48102 (17) | 0.37422 (7) | 0.0169 (2) | |
N2 | 0.56503 (8) | 0.34903 (17) | 0.23748 (8) | 0.0174 (2) | |
N3 | 0.38136 (8) | −0.00979 (16) | 0.34439 (7) | 0.01487 (19) | |
N4 | 0.44422 (8) | 0.02592 (16) | 0.21372 (7) | 0.0160 (2) | |
C1 | 0.60316 (10) | 0.5085 (2) | 0.30823 (9) | 0.0189 (2) | |
H1 | 0.6537 | 0.6236 | 0.3105 | 0.023* | |
C2 | 0.49099 (9) | 0.29613 (19) | 0.34591 (8) | 0.0149 (2) | |
C3 | 0.49637 (9) | 0.21386 (19) | 0.26086 (8) | 0.0146 (2) | |
C4 | 0.43007 (9) | 0.18602 (19) | 0.39354 (8) | 0.0147 (2) | |
C5 | 0.38509 (9) | −0.09502 (19) | 0.25639 (8) | 0.0163 (2) | |
C6 | 0.31646 (10) | −0.1429 (2) | 0.38539 (9) | 0.0185 (2) | |
H6A | 0.3229 | −0.0773 | 0.4492 | 0.028* | |
H6B | 0.3463 | −0.2942 | 0.3980 | 0.028* | |
H6C | 0.2368 | −0.1460 | 0.3363 | 0.028* | |
C7 | 0.45279 (12) | −0.0565 (2) | 0.12200 (9) | 0.0238 (3) | |
H7A | 0.4207 | 0.0532 | 0.0675 | 0.036* | |
H7B | 0.4110 | −0.1958 | 0.1003 | 0.036* | |
H7C | 0.5324 | −0.0816 | 0.1372 | 0.036* | |
B1 | 0.80447 (12) | 0.0062 (2) | 0.41456 (10) | 0.0199 (3) | |
H1N | 0.5721 (14) | 0.569 (3) | 0.4264 (13) | 0.033 (4)* | |
H2N | 0.5852 (14) | 0.333 (3) | 0.1866 (13) | 0.033 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.0403 (5) | 0.0270 (4) | 0.0402 (5) | 0.0049 (4) | 0.0275 (4) | 0.0107 (4) |
F2 | 0.0350 (4) | 0.0393 (5) | 0.0286 (4) | −0.0084 (4) | 0.0148 (4) | −0.0115 (4) |
F3 | 0.0370 (4) | 0.0249 (4) | 0.0289 (4) | 0.0093 (3) | 0.0233 (3) | 0.0061 (3) |
F4 | 0.0221 (4) | 0.0308 (4) | 0.0334 (4) | −0.0010 (3) | 0.0144 (3) | −0.0003 (3) |
O1 | 0.0239 (4) | 0.0233 (4) | 0.0176 (4) | −0.0045 (3) | 0.0125 (3) | −0.0056 (3) |
O2 | 0.0298 (5) | 0.0190 (4) | 0.0252 (4) | −0.0078 (4) | 0.0135 (4) | −0.0075 (4) |
N1 | 0.0187 (5) | 0.0161 (5) | 0.0169 (4) | −0.0031 (4) | 0.0086 (4) | −0.0036 (4) |
N2 | 0.0198 (5) | 0.0185 (5) | 0.0174 (5) | −0.0015 (4) | 0.0113 (4) | −0.0013 (4) |
N3 | 0.0149 (4) | 0.0155 (5) | 0.0155 (4) | −0.0011 (3) | 0.0078 (4) | −0.0011 (4) |
N4 | 0.0189 (5) | 0.0160 (5) | 0.0146 (4) | −0.0012 (4) | 0.0086 (4) | −0.0032 (4) |
C1 | 0.0194 (5) | 0.0188 (6) | 0.0199 (5) | −0.0032 (4) | 0.0098 (4) | −0.0011 (4) |
C2 | 0.0153 (5) | 0.0149 (5) | 0.0147 (5) | −0.0008 (4) | 0.0066 (4) | −0.0019 (4) |
C3 | 0.0141 (5) | 0.0153 (5) | 0.0146 (5) | 0.0013 (4) | 0.0064 (4) | 0.0002 (4) |
C4 | 0.0132 (5) | 0.0156 (5) | 0.0149 (5) | 0.0007 (4) | 0.0055 (4) | −0.0006 (4) |
C5 | 0.0150 (5) | 0.0164 (5) | 0.0163 (5) | 0.0010 (4) | 0.0054 (4) | −0.0010 (4) |
C6 | 0.0180 (5) | 0.0178 (6) | 0.0226 (6) | −0.0025 (4) | 0.0115 (4) | 0.0009 (4) |
C7 | 0.0365 (7) | 0.0216 (6) | 0.0186 (5) | −0.0008 (5) | 0.0166 (5) | −0.0054 (5) |
B1 | 0.0219 (6) | 0.0201 (6) | 0.0221 (6) | 0.0008 (5) | 0.0135 (5) | 0.0001 (5) |
F1—B1 | 1.3908 (16) | N3—C6 | 1.4689 (14) |
F2—B1 | 1.3744 (16) | N4—C3 | 1.3511 (15) |
F3—B1 | 1.4158 (16) | N4—C5 | 1.3890 (15) |
F4—B1 | 1.3925 (16) | N4—C7 | 1.4733 (14) |
O1—C4 | 1.2266 (13) | C1—H1 | 0.9500 |
O2—C5 | 1.2110 (14) | C2—C3 | 1.3634 (15) |
N1—C1 | 1.3203 (15) | C2—C4 | 1.4253 (15) |
N1—C2 | 1.3812 (15) | C6—H6A | 0.9800 |
N1—H1N | 0.883 (18) | C6—H6B | 0.9800 |
N2—C1 | 1.3412 (15) | C6—H6C | 0.9800 |
N2—C3 | 1.3608 (14) | C7—H7A | 0.9800 |
N2—H2N | 0.892 (17) | C7—H7B | 0.9800 |
N3—C4 | 1.3883 (14) | C7—H7C | 0.9800 |
N3—C5 | 1.4005 (14) | ||
C1—N1—C2 | 108.22 (10) | N3—C4—C2 | 112.09 (9) |
C1—N1—H1N | 124.8 (11) | O2—C5—N4 | 121.80 (10) |
C2—N1—H1N | 127.0 (11) | O2—C5—N3 | 120.86 (11) |
C1—N2—C3 | 107.94 (10) | N4—C5—N3 | 117.35 (10) |
C1—N2—H2N | 124.9 (11) | N3—C6—H6A | 109.5 |
C3—N2—H2N | 127.1 (11) | N3—C6—H6B | 109.5 |
C4—N3—C5 | 126.63 (9) | H6A—C6—H6B | 109.5 |
C4—N3—C6 | 118.36 (9) | N3—C6—H6C | 109.5 |
C5—N3—C6 | 114.99 (9) | H6A—C6—H6C | 109.5 |
C3—N4—C5 | 118.17 (9) | H6B—C6—H6C | 109.5 |
C3—N4—C7 | 121.77 (10) | N4—C7—H7A | 109.5 |
C5—N4—C7 | 120.01 (10) | N4—C7—H7B | 109.5 |
N1—C1—N2 | 109.47 (10) | H7A—C7—H7B | 109.5 |
N1—C1—H1 | 125.3 | N4—C7—H7C | 109.5 |
N2—C1—H1 | 125.3 | H7A—C7—H7C | 109.5 |
C3—C2—N1 | 106.63 (10) | H7B—C7—H7C | 109.5 |
C3—C2—C4 | 121.89 (10) | F2—B1—F1 | 111.40 (11) |
N1—C2—C4 | 131.30 (10) | F2—B1—F4 | 110.43 (10) |
N4—C3—N2 | 128.43 (10) | F1—B1—F4 | 109.67 (11) |
N4—C3—C2 | 123.81 (10) | F2—B1—F3 | 109.55 (11) |
N2—C3—C2 | 107.71 (10) | F1—B1—F3 | 107.97 (10) |
O1—C4—N3 | 122.10 (10) | F4—B1—F3 | 107.71 (11) |
O1—C4—C2 | 125.79 (11) | ||
C2—N1—C1—N2 | 0.33 (14) | C6—N3—C4—O1 | 0.68 (16) |
C3—N2—C1—N1 | −1.05 (14) | C5—N3—C4—C2 | −2.02 (15) |
C1—N1—C2—C3 | 0.52 (13) | C6—N3—C4—C2 | 179.50 (10) |
C1—N1—C2—C4 | 175.59 (12) | C3—C2—C4—O1 | 179.94 (11) |
C5—N4—C3—N2 | 174.85 (11) | N1—C2—C4—O1 | 5.5 (2) |
C7—N4—C3—N2 | −2.56 (18) | C3—C2—C4—N3 | 1.18 (15) |
C5—N4—C3—C2 | −2.47 (16) | N1—C2—C4—N3 | −173.26 (11) |
C7—N4—C3—C2 | −179.88 (11) | C3—N4—C5—O2 | −177.95 (11) |
C1—N2—C3—N4 | −176.30 (11) | C7—N4—C5—O2 | −0.49 (17) |
C1—N2—C3—C2 | 1.36 (13) | C3—N4—C5—N3 | 1.61 (15) |
N1—C2—C3—N4 | 176.65 (10) | C7—N4—C5—N3 | 179.07 (10) |
C4—C2—C3—N4 | 1.01 (17) | C4—N3—C5—O2 | −179.75 (11) |
N1—C2—C3—N2 | −1.15 (12) | C6—N3—C5—O2 | −1.22 (15) |
C4—C2—C3—N2 | −176.79 (10) | C4—N3—C5—N4 | 0.69 (16) |
C5—N3—C4—O1 | 179.16 (11) | C6—N3—C5—N4 | 179.22 (10) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O1i | 0.883 (18) | 1.838 (18) | 2.7165 (13) | 172.7 (16) |
N2—H2N···F3ii | 0.892 (17) | 1.823 (18) | 2.7094 (12) | 172.2 (16) |
N2—H2N···F1ii | 0.892 (17) | 2.525 (17) | 3.0239 (13) | 115.9 (14) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+3/2, y+1/2, −z+1/2. |
C7H9N4O2+·Cl−·H2O | F(000) = 488 |
Mr = 234.65 | Dx = 1.531 Mg m−3 |
Orthorhombic, Pnma | Cu Kα radiation, λ = 1.54180 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 715 reflections |
a = 13.8664 (7) Å | θ = 3.9–71.5° |
b = 6.4623 (3) Å | µ = 3.33 mm−1 |
c = 11.3634 (6) Å | T = 123 K |
V = 1018.26 (9) Å3 | Fragment from plate, colourless |
Z = 4 | 0.28 × 0.18 × 0.04 mm |
Oxford Diffraction Gemini S diffractometer | 1090 independent reflections |
Radiation source: fine-focus sealed tube | 1077 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.017 |
ω scans | θmax = 73.0°, θmin = 7.5° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | h = −11→17 |
Tmin = 0.542, Tmax = 1.000 | k = −7→7 |
3701 measured reflections | l = −11→14 |
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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0478P)2 + 0.3984P] where P = (Fo2 + 2Fc2)/3 |
1090 reflections | (Δ/σ)max < 0.001 |
106 parameters | Δρmax = 0.34 e Å−3 |
3 restraints | Δρmin = −0.32 e Å−3 |
C7H9N4O2+·Cl−·H2O | V = 1018.26 (9) Å3 |
Mr = 234.65 | Z = 4 |
Orthorhombic, Pnma | Cu Kα radiation |
a = 13.8664 (7) Å | µ = 3.33 mm−1 |
b = 6.4623 (3) Å | T = 123 K |
c = 11.3634 (6) Å | 0.28 × 0.18 × 0.04 mm |
Oxford Diffraction Gemini S diffractometer | 1090 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | 1077 reflections with I > 2σ(I) |
Tmin = 0.542, Tmax = 1.000 | Rint = 0.017 |
3701 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 3 restraints |
wR(F2) = 0.081 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.12 | Δρmax = 0.34 e Å−3 |
1090 reflections | Δρmin = −0.32 e Å−3 |
106 parameters |
Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cl1 | 0.23401 (3) | 0.2500 | 0.03516 (4) | 0.02111 (18) | |
O1 | 0.42178 (9) | 0.2500 | 0.32625 (11) | 0.0258 (3) | |
O2 | 0.36175 (11) | 0.2500 | 0.72153 (12) | 0.0331 (4) | |
N1 | 0.20282 (11) | 0.2500 | 0.29566 (14) | 0.0183 (3) | |
N2 | 0.10821 (11) | 0.2500 | 0.44846 (14) | 0.0193 (3) | |
N3 | 0.39025 (11) | 0.2500 | 0.52517 (13) | 0.0186 (3) | |
N4 | 0.23095 (11) | 0.2500 | 0.60187 (14) | 0.0184 (3) | |
C1 | 0.11223 (13) | 0.2500 | 0.33042 (16) | 0.0207 (4) | |
H1 | 0.0579 | 0.2500 | 0.2796 | 0.025* | |
C2 | 0.26060 (12) | 0.2500 | 0.39409 (16) | 0.0163 (4) | |
C3 | 0.20037 (13) | 0.2500 | 0.48881 (16) | 0.0165 (4) | |
C4 | 0.36339 (13) | 0.2500 | 0.40650 (16) | 0.0178 (4) | |
C5 | 0.32902 (14) | 0.2500 | 0.62224 (16) | 0.0213 (4) | |
C6 | 0.49388 (14) | 0.2500 | 0.55447 (17) | 0.0264 (4) | |
H6A | 0.5319 | 0.2500 | 0.4817 | 0.040* | |
H6B | 0.5093 | 0.1262 | 0.6006 | 0.040* | 0.50 |
H6C | 0.5093 | 0.3738 | 0.6006 | 0.040* | 0.50 |
C7 | 0.16252 (15) | 0.2500 | 0.70028 (17) | 0.0279 (4) | |
H7A | 0.1981 | 0.2500 | 0.7748 | 0.042* | |
H7B | 0.1219 | 0.1262 | 0.6959 | 0.042* | 0.50 |
H7C | 0.1219 | 0.3738 | 0.6959 | 0.042* | 0.50 |
O1W | −0.05899 (12) | 0.258 (8) | 0.55938 (16) | 0.034 (2) | 0.50 |
H1W | −0.080 (2) | 0.233 (12) | 0.6309 (14) | 0.051* | 0.50 |
H2W | −0.1110 (18) | 0.226 (9) | 0.519 (2) | 0.051* | 0.50 |
H1N | 0.219 (2) | 0.2500 | 0.219 (3) | 0.041 (7)* | |
H2N | 0.061 (2) | 0.2500 | 0.488 (2) | 0.030 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0230 (3) | 0.0252 (3) | 0.0151 (3) | 0.000 | 0.00115 (14) | 0.000 |
O1 | 0.0160 (6) | 0.0414 (8) | 0.0200 (7) | 0.000 | 0.0031 (5) | 0.000 |
O2 | 0.0301 (7) | 0.0534 (9) | 0.0157 (7) | 0.000 | −0.0051 (6) | 0.000 |
N1 | 0.0176 (7) | 0.0237 (8) | 0.0137 (7) | 0.000 | −0.0008 (6) | 0.000 |
N2 | 0.0136 (7) | 0.0255 (8) | 0.0188 (8) | 0.000 | 0.0023 (6) | 0.000 |
N3 | 0.0147 (7) | 0.0238 (8) | 0.0175 (8) | 0.000 | −0.0015 (6) | 0.000 |
N4 | 0.0195 (8) | 0.0233 (8) | 0.0123 (7) | 0.000 | 0.0028 (5) | 0.000 |
C1 | 0.0168 (8) | 0.0263 (9) | 0.0191 (9) | 0.000 | −0.0022 (7) | 0.000 |
C2 | 0.0168 (8) | 0.0183 (8) | 0.0139 (8) | 0.000 | 0.0003 (6) | 0.000 |
C3 | 0.0165 (8) | 0.0167 (8) | 0.0162 (8) | 0.000 | 0.0007 (7) | 0.000 |
C4 | 0.0167 (8) | 0.0206 (8) | 0.0160 (8) | 0.000 | −0.0015 (6) | 0.000 |
C5 | 0.0229 (9) | 0.0243 (9) | 0.0166 (9) | 0.000 | −0.0021 (7) | 0.000 |
C6 | 0.0166 (9) | 0.0374 (11) | 0.0252 (9) | 0.000 | −0.0058 (7) | 0.000 |
C7 | 0.0246 (9) | 0.0436 (12) | 0.0156 (8) | 0.000 | 0.0057 (7) | 0.000 |
O1W | 0.0180 (7) | 0.061 (6) | 0.0242 (8) | 0.002 (4) | 0.0063 (6) | 0.007 (7) |
O1—C4 | 1.220 (2) | N4—C7 | 1.467 (2) |
O2—C5 | 1.216 (2) | C1—H1 | 0.9500 |
N1—C1 | 1.317 (2) | C2—C3 | 1.362 (2) |
N1—C2 | 1.376 (2) | C2—C4 | 1.432 (2) |
N1—H1N | 0.90 (3) | C6—H6A | 0.9800 |
N2—C1 | 1.342 (2) | C6—H6B | 0.9800 |
N2—C3 | 1.358 (2) | C6—H6C | 0.9800 |
N2—H2N | 0.80 (3) | C7—H7A | 0.9800 |
N3—C5 | 1.392 (2) | C7—H7B | 0.9800 |
N3—C4 | 1.399 (2) | C7—H7C | 0.9800 |
N3—C6 | 1.475 (2) | O1W—H1W | 0.879 (10) |
N4—C3 | 1.353 (2) | O1W—H2W | 0.880 (10) |
N4—C5 | 1.379 (2) | ||
C1—N1—C2 | 108.15 (16) | N2—C3—C2 | 108.07 (16) |
C1—N1—H1N | 122.0 (19) | O1—C4—N3 | 122.96 (16) |
C2—N1—H1N | 129.8 (19) | O1—C4—C2 | 125.95 (17) |
C1—N2—C3 | 107.36 (16) | N3—C4—C2 | 111.09 (15) |
C1—N2—H2N | 126.5 (19) | O2—C5—N4 | 121.57 (17) |
C3—N2—H2N | 126.1 (19) | O2—C5—N3 | 120.50 (17) |
C5—N3—C4 | 126.97 (15) | N4—C5—N3 | 117.93 (16) |
C5—N3—C6 | 114.54 (15) | N3—C6—H6A | 109.5 |
C4—N3—C6 | 118.48 (15) | N3—C6—H6B | 109.5 |
C3—N4—C5 | 117.92 (15) | H6A—C6—H6B | 109.5 |
C3—N4—C7 | 121.42 (15) | N3—C6—H6C | 109.5 |
C5—N4—C7 | 120.66 (15) | H6A—C6—H6C | 109.5 |
N1—C1—N2 | 109.84 (16) | H6B—C6—H6C | 109.5 |
N1—C1—H1 | 125.1 | N4—C7—H7A | 109.5 |
N2—C1—H1 | 125.1 | N4—C7—H7B | 109.5 |
C3—C2—N1 | 106.58 (16) | H7A—C7—H7B | 109.5 |
C3—C2—C4 | 122.16 (16) | N4—C7—H7C | 109.5 |
N1—C2—C4 | 131.27 (16) | H7A—C7—H7C | 109.5 |
N4—C3—N2 | 128.01 (16) | H7B—C7—H7C | 109.5 |
N4—C3—C2 | 123.92 (16) | H1W—O1W—H2W | 99 (2) |
C2—N1—C1—N2 | 0.0 | C6—N3—C4—O1 | 0.0 |
C3—N2—C1—N1 | 0.0 | C5—N3—C4—C2 | 0.0 |
C1—N1—C2—C3 | 0.0 | C6—N3—C4—C2 | 180.0 |
C1—N1—C2—C4 | 180.0 | C3—C2—C4—O1 | 180.0 |
C5—N4—C3—N2 | 180.0 | N1—C2—C4—O1 | 0.0 |
C7—N4—C3—N2 | 0.0 | C3—C2—C4—N3 | 0.0 |
C5—N4—C3—C2 | 0.0 | N1—C2—C4—N3 | 180.0 |
C7—N4—C3—C2 | 180.0 | C3—N4—C5—O2 | 180.0 |
C1—N2—C3—N4 | 180.0 | C7—N4—C5—O2 | 0.0 |
C1—N2—C3—C2 | 0.0 | C3—N4—C5—N3 | 0.0 |
N1—C2—C3—N4 | 180.0 | C7—N4—C5—N3 | 180.0 |
C4—C2—C3—N4 | 0.0 | C4—N3—C5—O2 | 180.0 |
N1—C2—C3—N2 | 0.0 | C6—N3—C5—O2 | 0.0 |
C4—C2—C3—N2 | 180.0 | C4—N3—C5—N4 | 0.0 |
C5—N3—C4—O1 | 180.0 | C6—N3—C5—N4 | 180.0 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Cl1 | 0.90 (3) | 2.10 (3) | 2.9915 (17) | 171 (3) |
N2—H2N···O1W | 0.80 (3) | 1.85 (3) | 2.639 (3) | 172 (3) |
O1W—H1W···O2i | 0.88 (1) | 1.86 (2) | 2.722 (2) | 165 (7) |
O1W—H2W···Cl1ii | 0.88 (1) | 2.24 (2) | 3.065 (2) | 156 (5) |
Symmetry codes: (i) x−1/2, y, −z+3/2; (ii) x−1/2, y, −z+1/2. |
C7H9N4O2+·Br−·H2O | F(000) = 560 |
Mr = 279.11 | Dx = 1.735 Mg m−3 |
Orthorhombic, Pnma | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2n | Cell parameters from 3572 reflections |
a = 14.0120 (5) Å | θ = 2.9–29.9° |
b = 6.6151 (3) Å | µ = 3.84 mm−1 |
c = 11.5297 (4) Å | T = 123 K |
V = 1068.70 (7) Å3 | Prism, colourless |
Z = 4 | 0.22 × 0.12 × 0.08 mm |
Oxford Diffraction Xcalibur E diffractometer | 1553 independent reflections |
Radiation source: fine-focus sealed tube | 1378 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ω scans | θmax = 29.9°, θmin = 3.4° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | h = −18→18 |
Tmin = 0.943, Tmax = 1.000 | k = −9→9 |
7635 measured reflections | l = −15→15 |
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)] = 0.025 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.058 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0245P)2 + 0.5427P] where P = (Fo2 + 2Fc2)/3 |
1553 reflections | (Δ/σ)max = 0.001 |
106 parameters | Δρmax = 0.36 e Å−3 |
5 restraints | Δρmin = −0.48 e Å−3 |
C7H9N4O2+·Br−·H2O | V = 1068.70 (7) Å3 |
Mr = 279.11 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 14.0120 (5) Å | µ = 3.84 mm−1 |
b = 6.6151 (3) Å | T = 123 K |
c = 11.5297 (4) Å | 0.22 × 0.12 × 0.08 mm |
Oxford Diffraction Xcalibur E diffractometer | 1553 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | 1378 reflections with I > 2σ(I) |
Tmin = 0.943, Tmax = 1.000 | Rint = 0.033 |
7635 measured reflections |
R[F2 > 2σ(F2)] = 0.025 | 5 restraints |
wR(F2) = 0.058 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.36 e Å−3 |
1553 reflections | Δρmin = −0.48 e Å−3 |
106 parameters |
Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Br1 | 0.238793 (17) | 0.2500 | 0.030738 (19) | 0.01977 (9) | |
O1 | 0.42192 (12) | 0.2500 | 0.32740 (15) | 0.0270 (4) | |
O2 | 0.36669 (15) | 0.2500 | 0.71829 (16) | 0.0376 (5) | |
N1 | 0.20447 (15) | 0.2500 | 0.30119 (17) | 0.0178 (4) | |
N2 | 0.11254 (14) | 0.2500 | 0.45350 (17) | 0.0187 (4) | |
N3 | 0.39277 (14) | 0.2500 | 0.52399 (17) | 0.0198 (4) | |
N4 | 0.23609 (14) | 0.2500 | 0.60213 (17) | 0.0187 (4) | |
C1 | 0.11501 (17) | 0.2500 | 0.3368 (2) | 0.0207 (5) | |
H1 | 0.0606 | 0.2500 | 0.2877 | 0.025* | |
C2 | 0.26338 (16) | 0.2500 | 0.3970 (2) | 0.0163 (5) | |
C3 | 0.20478 (17) | 0.2500 | 0.4915 (2) | 0.0159 (4) | |
C4 | 0.36473 (17) | 0.2500 | 0.4072 (2) | 0.0183 (5) | |
C5 | 0.33321 (18) | 0.2500 | 0.6207 (2) | 0.0214 (5) | |
C6 | 0.49547 (18) | 0.2500 | 0.5505 (2) | 0.0294 (6) | |
H6A | 0.5320 | 0.2500 | 0.4780 | 0.044* | |
H6B | 0.5114 | 0.1290 | 0.5956 | 0.044* | 0.50 |
H6C | 0.5114 | 0.3710 | 0.5956 | 0.044* | 0.50 |
C7 | 0.16970 (19) | 0.2500 | 0.6999 (2) | 0.0277 (6) | |
H7A | 0.2057 | 0.2500 | 0.7728 | 0.042* | |
H7B | 0.1294 | 0.1290 | 0.6962 | 0.042* | 0.50 |
H7C | 0.1294 | 0.3710 | 0.6962 | 0.042* | 0.50 |
O1W | −0.04826 (17) | 0.221 (2) | 0.5711 (2) | 0.032 (3) | 0.50 |
H1W | −0.094 (2) | 0.286 (7) | 0.535 (3) | 0.048* | 0.50 |
H2W | −0.057 (2) | 0.280 (7) | 0.6387 (19) | 0.048* | 0.50 |
H1N | 0.225 (2) | 0.2500 | 0.2308 (12) | 0.036 (9)* | |
H2N | 0.0595 (13) | 0.2500 | 0.490 (2) | 0.033 (9)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.02056 (13) | 0.02542 (14) | 0.01334 (12) | 0.000 | 0.00125 (9) | 0.000 |
O1 | 0.0164 (9) | 0.0446 (12) | 0.0198 (9) | 0.000 | 0.0042 (7) | 0.000 |
O2 | 0.0272 (11) | 0.0694 (16) | 0.0162 (9) | 0.000 | −0.0072 (8) | 0.000 |
N1 | 0.0172 (10) | 0.0250 (11) | 0.0113 (9) | 0.000 | −0.0008 (8) | 0.000 |
N2 | 0.0120 (9) | 0.0293 (12) | 0.0149 (9) | 0.000 | 0.0020 (8) | 0.000 |
N3 | 0.0125 (9) | 0.0284 (12) | 0.0183 (10) | 0.000 | −0.0023 (8) | 0.000 |
N4 | 0.0167 (10) | 0.0269 (11) | 0.0125 (9) | 0.000 | 0.0017 (8) | 0.000 |
C1 | 0.0166 (12) | 0.0277 (14) | 0.0176 (11) | 0.000 | −0.0029 (9) | 0.000 |
C2 | 0.0162 (11) | 0.0204 (11) | 0.0122 (10) | 0.000 | 0.0011 (8) | 0.000 |
C3 | 0.0148 (11) | 0.0178 (11) | 0.0150 (10) | 0.000 | −0.0005 (9) | 0.000 |
C4 | 0.0178 (12) | 0.0210 (12) | 0.0161 (11) | 0.000 | −0.0010 (9) | 0.000 |
C5 | 0.0202 (12) | 0.0290 (14) | 0.0152 (11) | 0.000 | −0.0016 (9) | 0.000 |
C6 | 0.0152 (12) | 0.0447 (18) | 0.0284 (14) | 0.000 | −0.0056 (10) | 0.000 |
C7 | 0.0232 (13) | 0.0463 (17) | 0.0136 (11) | 0.000 | 0.0033 (9) | 0.000 |
O1W | 0.0173 (10) | 0.058 (8) | 0.0209 (10) | −0.0022 (18) | 0.0038 (8) | −0.005 (2) |
O1—C4 | 1.220 (3) | N4—C7 | 1.461 (3) |
O2—C5 | 1.219 (3) | C1—H1 | 0.9500 |
N1—C1 | 1.319 (3) | C2—C3 | 1.364 (3) |
N1—C2 | 1.379 (3) | C2—C4 | 1.425 (3) |
N1—H1N | 0.860 (10) | C6—H6A | 0.9800 |
N2—C1 | 1.345 (3) | C6—H6B | 0.9800 |
N2—C3 | 1.365 (3) | C6—H6C | 0.9800 |
N2—H2N | 0.855 (10) | C7—H7A | 0.9800 |
N3—C5 | 1.393 (3) | C7—H7B | 0.9800 |
N3—C4 | 1.403 (3) | C7—H7C | 0.9800 |
N3—C6 | 1.471 (3) | O1W—H1W | 0.882 (10) |
N4—C3 | 1.349 (3) | O1W—H2W | 0.880 (10) |
N4—C5 | 1.378 (3) | ||
C1—N1—C2 | 108.6 (2) | C2—C3—N2 | 108.3 (2) |
C1—N1—H1N | 127 (2) | O1—C4—N3 | 122.7 (2) |
C2—N1—H1N | 124 (2) | O1—C4—C2 | 126.4 (2) |
C1—N2—C3 | 107.2 (2) | N3—C4—C2 | 111.0 (2) |
C1—N2—H2N | 121 (2) | O2—C5—N4 | 121.5 (2) |
C3—N2—H2N | 132 (2) | O2—C5—N3 | 120.6 (2) |
C5—N3—C4 | 126.9 (2) | N4—C5—N3 | 117.9 (2) |
C5—N3—C6 | 114.8 (2) | N3—C6—H6A | 109.5 |
C4—N3—C6 | 118.3 (2) | N3—C6—H6B | 109.5 |
C3—N4—C5 | 117.9 (2) | H6A—C6—H6B | 109.5 |
C3—N4—C7 | 121.5 (2) | N3—C6—H6C | 109.5 |
C5—N4—C7 | 120.6 (2) | H6A—C6—H6C | 109.5 |
N1—C1—N2 | 109.6 (2) | H6B—C6—H6C | 109.5 |
N1—C1—H1 | 125.2 | N4—C7—H7A | 109.5 |
N2—C1—H1 | 125.2 | N4—C7—H7B | 109.5 |
C3—C2—N1 | 106.2 (2) | H7A—C7—H7B | 109.5 |
C3—C2—C4 | 122.3 (2) | N4—C7—H7C | 109.5 |
N1—C2—C4 | 131.5 (2) | H7A—C7—H7C | 109.5 |
N4—C3—C2 | 124.0 (2) | H7B—C7—H7C | 109.5 |
N4—C3—N2 | 127.7 (2) | H1W—O1W—H2W | 96 (2) |
C2—N1—C1—N2 | 0.0 | C6—N3—C4—O1 | 0.0 |
C3—N2—C1—N1 | 0.0 | C5—N3—C4—C2 | 0.0 |
C1—N1—C2—C3 | 0.0 | C6—N3—C4—C2 | 180.0 |
C1—N1—C2—C4 | 180.0 | C3—C2—C4—O1 | 180.0 |
C5—N4—C3—C2 | 0.0 | N1—C2—C4—O1 | 0.0 |
C7—N4—C3—C2 | 180.0 | C3—C2—C4—N3 | 0.0 |
C5—N4—C3—N2 | 180.0 | N1—C2—C4—N3 | 180.0 |
C7—N4—C3—N2 | 0.0 | C3—N4—C5—O2 | 180.0 |
N1—C2—C3—N4 | 180.0 | C7—N4—C5—O2 | 0.0 |
C4—C2—C3—N4 | 0.0 | C3—N4—C5—N3 | 0.0 |
N1—C2—C3—N2 | 0.0 | C7—N4—C5—N3 | 180.0 |
C4—C2—C3—N2 | 180.0 | C4—N3—C5—O2 | 180.0 |
C1—N2—C3—N4 | 180.0 | C6—N3—C5—O2 | 0.0 |
C1—N2—C3—C2 | 0.0 | C4—N3—C5—N4 | 0.0 |
C5—N3—C4—O1 | 180.0 | C6—N3—C5—N4 | 180.0 |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Br1 | 0.86 (1) | 2.32 (1) | 3.1551 (19) | 166 (3) |
N2—H2N···O1W | 0.86 (1) | 1.79 (1) | 2.637 (3) | 174 (1) |
O1W—H2W···O2i | 0.88 (1) | 1.97 (3) | 2.712 (3) | 140 (4) |
O1W—H1W···Br1ii | 0.88 (1) | 2.47 (3) | 3.212 (3) | 143 (4) |
Symmetry codes: (i) x−1/2, y, −z+3/2; (ii) x−1/2, y, −z+1/2. |
C7H9N4O2+·Cl− | F(000) = 896 |
Mr = 216.63 | Dx = 1.598 Mg m−3 |
Monoclinic, Cc | Cu Kα radiation, λ = 1.54180 Å |
Hall symbol: C -2yc | Cell parameters from 2617 reflections |
a = 32.081 (3) Å | θ = 3.5–73.6° |
b = 4.5028 (3) Å | µ = 3.63 mm−1 |
c = 12.8256 (10) Å | T = 123 K |
β = 103.524 (9)° | Rod, colourless |
V = 1801.3 (3) Å3 | 0.33 × 0.08 × 0.04 mm |
Z = 8 |
Oxford Diffraction Gemini S diffractometer | 3230 independent reflections |
Radiation source: fine-focus sealed tube | 2966 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
ω scans | θmax = 73.8°, θmin = 5.7° |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | h = −39→38 |
Tmin = 0.697, Tmax = 1.000 | k = −3→5 |
6692 measured reflections | l = −15→15 |
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)] = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.130 | w = 1/[σ2(Fo2) + (0.0677P)2 + 2.7204P] where P = (Fo2 + 2Fc2)/3 |
S = 1.07 | (Δ/σ)max = 0.001 |
3230 reflections | Δρmax = 0.48 e Å−3 |
270 parameters | Δρmin = −0.26 e Å−3 |
6 restraints | Absolute structure: Flack (1983), 1431 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.28 (3) |
C7H9N4O2+·Cl− | V = 1801.3 (3) Å3 |
Mr = 216.63 | Z = 8 |
Monoclinic, Cc | Cu Kα radiation |
a = 32.081 (3) Å | µ = 3.63 mm−1 |
b = 4.5028 (3) Å | T = 123 K |
c = 12.8256 (10) Å | 0.33 × 0.08 × 0.04 mm |
β = 103.524 (9)° |
Oxford Diffraction Gemini S diffractometer | 3230 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | 2966 reflections with I > 2σ(I) |
Tmin = 0.697, Tmax = 1.000 | Rint = 0.037 |
6692 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.130 | Δρmax = 0.48 e Å−3 |
S = 1.07 | Δρmin = −0.26 e Å−3 |
3230 reflections | Absolute structure: Flack (1983), 1431 Friedel pairs |
270 parameters | Absolute structure parameter: 0.28 (3) |
6 restraints |
Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.40 (release 27-08-2010 CrysAlis171 .NET) (compiled Aug 27 2010,11:50:40) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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. |
x | y | z | Uiso*/Ueq | ||
Cl1 | 0.45718 (3) | 0.9707 (3) | 0.79706 (7) | 0.0269 (3) | |
Cl2 | 0.37986 (3) | 0.9789 (3) | 0.99217 (7) | 0.0273 (3) | |
O1 | 0.77059 (13) | 1.1342 (10) | 0.4567 (3) | 0.0353 (9) | |
O2 | 0.70844 (13) | 0.4278 (11) | 0.6295 (3) | 0.0386 (10) | |
O3 | 0.56058 (13) | 1.1302 (9) | 0.5127 (3) | 0.0333 (9) | |
O4 | 0.62989 (12) | 0.6861 (9) | 0.8257 (3) | 0.0333 (9) | |
N1 | 0.84949 (14) | 1.0771 (11) | 0.6409 (4) | 0.0255 (10) | |
H1N | 0.8570 (17) | 1.227 (8) | 0.608 (4) | 0.031* | |
N2 | 0.85034 (14) | 0.7663 (10) | 0.7711 (3) | 0.0253 (10) | |
H2N | 0.8583 (17) | 0.649 (10) | 0.826 (3) | 0.030* | |
N3 | 0.73984 (14) | 0.7781 (11) | 0.5429 (4) | 0.0282 (10) | |
N4 | 0.77748 (16) | 0.5600 (10) | 0.7066 (4) | 0.0261 (10) | |
N5 | 0.48493 (14) | 0.7281 (10) | 0.5198 (3) | 0.0257 (9) | |
H3N | 0.4747 (17) | 0.800 (11) | 0.455 (2) | 0.031* | |
N6 | 0.48836 (14) | 0.4180 (11) | 0.6518 (3) | 0.0242 (9) | |
H4N | 0.4791 (16) | 0.317 (10) | 0.700 (3) | 0.029* | |
N7 | 0.59565 (15) | 0.8915 (12) | 0.6657 (4) | 0.0271 (9) | |
N8 | 0.56160 (15) | 0.5338 (10) | 0.7531 (4) | 0.0253 (11) | |
C1 | 0.87221 (18) | 0.9721 (11) | 0.7320 (5) | 0.0243 (12) | |
H1 | 0.9004 | 1.0346 | 0.7655 | 0.029* | |
C2 | 0.81038 (17) | 0.9267 (13) | 0.6185 (4) | 0.0243 (11) | |
C3 | 0.81109 (16) | 0.7366 (12) | 0.6999 (4) | 0.0230 (10) | |
C4 | 0.77353 (18) | 0.9665 (12) | 0.5314 (4) | 0.0245 (12) | |
C5 | 0.73991 (18) | 0.5780 (14) | 0.6249 (5) | 0.0266 (11) | |
C6 | 0.70002 (18) | 0.8011 (14) | 0.4597 (4) | 0.0349 (13) | |
H6A | 0.6774 | 0.8837 | 0.4908 | 0.052* | |
H6B | 0.6915 | 0.6033 | 0.4304 | 0.052* | |
H6C | 0.7045 | 0.9314 | 0.4021 | 0.052* | |
C7 | 0.77826 (17) | 0.3596 (12) | 0.7959 (4) | 0.0280 (10) | |
H7A | 0.7664 | 0.4606 | 0.8501 | 0.042* | |
H7B | 0.8079 | 0.3001 | 0.8276 | 0.042* | |
H7C | 0.7611 | 0.1831 | 0.7701 | 0.042* | |
C8 | 0.4636 (2) | 0.5198 (12) | 0.5585 (5) | 0.0275 (13) | |
H8 | 0.4355 | 0.4527 | 0.5260 | 0.033* | |
C9 | 0.52468 (16) | 0.7610 (11) | 0.5888 (4) | 0.0219 (10) | |
C10 | 0.52639 (18) | 0.5665 (12) | 0.6721 (4) | 0.0231 (11) | |
C11 | 0.55974 (19) | 0.9490 (11) | 0.5820 (5) | 0.0239 (11) | |
C12 | 0.59735 (16) | 0.7021 (12) | 0.7535 (4) | 0.0252 (10) | |
C13 | 0.6351 (2) | 1.0532 (14) | 0.6672 (5) | 0.0339 (13) | |
H13A | 0.6589 | 0.9122 | 0.6740 | 0.051* | |
H13B | 0.6412 | 1.1901 | 0.7283 | 0.051* | |
H13C | 0.6319 | 1.1659 | 0.6005 | 0.051* | |
C14 | 0.56211 (17) | 0.3378 (13) | 0.8448 (4) | 0.0278 (11) | |
H14A | 0.5428 | 0.1696 | 0.8216 | 0.042* | |
H14B | 0.5526 | 0.4488 | 0.9007 | 0.042* | |
H14C | 0.5913 | 0.2643 | 0.8734 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl1 | 0.0303 (7) | 0.0274 (6) | 0.0232 (7) | −0.0055 (5) | 0.0067 (5) | −0.0023 (5) |
Cl2 | 0.0302 (7) | 0.0294 (6) | 0.0218 (6) | 0.0045 (5) | 0.0048 (5) | 0.0013 (5) |
O1 | 0.040 (2) | 0.032 (2) | 0.0298 (19) | −0.0018 (16) | 0.0002 (15) | 0.0048 (16) |
O2 | 0.036 (2) | 0.043 (2) | 0.036 (2) | −0.0124 (18) | 0.0075 (17) | −0.0027 (18) |
O3 | 0.041 (2) | 0.0287 (19) | 0.0310 (18) | −0.0042 (16) | 0.0107 (15) | 0.0028 (15) |
O4 | 0.0327 (17) | 0.0333 (19) | 0.0301 (19) | −0.0001 (15) | −0.0005 (14) | 0.0047 (16) |
N1 | 0.026 (2) | 0.023 (2) | 0.026 (2) | −0.0027 (19) | 0.0049 (18) | −0.0002 (19) |
N2 | 0.028 (2) | 0.026 (2) | 0.020 (2) | −0.0019 (18) | 0.0021 (17) | 0.0040 (18) |
N3 | 0.028 (2) | 0.029 (2) | 0.025 (2) | −0.0011 (18) | 0.0011 (17) | −0.0040 (17) |
N4 | 0.029 (2) | 0.025 (2) | 0.024 (2) | 0.0012 (19) | 0.0063 (19) | 0.0015 (19) |
N5 | 0.025 (2) | 0.025 (2) | 0.024 (2) | 0.0004 (18) | 0.0004 (17) | 0.0006 (18) |
N6 | 0.028 (2) | 0.024 (2) | 0.020 (2) | 0.001 (2) | 0.0057 (18) | 0.0029 (19) |
N7 | 0.032 (2) | 0.023 (2) | 0.027 (2) | −0.0049 (18) | 0.0088 (18) | −0.0031 (18) |
N8 | 0.030 (3) | 0.023 (2) | 0.022 (3) | −0.0001 (17) | 0.005 (2) | 0.0020 (17) |
C1 | 0.024 (3) | 0.024 (3) | 0.022 (3) | 0.0011 (19) | 0.000 (2) | −0.006 (2) |
C2 | 0.024 (3) | 0.027 (3) | 0.022 (3) | 0.002 (2) | 0.005 (2) | −0.001 (2) |
C3 | 0.027 (2) | 0.019 (2) | 0.022 (2) | 0.0030 (19) | 0.0036 (18) | −0.0011 (19) |
C4 | 0.027 (3) | 0.026 (3) | 0.020 (3) | 0.001 (2) | 0.004 (2) | −0.003 (2) |
C5 | 0.023 (2) | 0.028 (2) | 0.027 (3) | 0.002 (2) | 0.0027 (19) | −0.007 (2) |
C6 | 0.034 (3) | 0.037 (3) | 0.029 (3) | 0.005 (2) | −0.003 (2) | −0.007 (2) |
C7 | 0.034 (3) | 0.021 (2) | 0.030 (2) | −0.0013 (19) | 0.010 (2) | 0.0015 (19) |
C8 | 0.028 (3) | 0.026 (3) | 0.030 (3) | −0.0004 (19) | 0.009 (3) | 0.005 (2) |
C9 | 0.024 (2) | 0.017 (2) | 0.024 (3) | −0.0007 (19) | 0.0064 (19) | −0.0005 (19) |
C10 | 0.029 (3) | 0.017 (2) | 0.024 (3) | −0.003 (2) | 0.008 (2) | −0.003 (2) |
C11 | 0.030 (3) | 0.020 (2) | 0.023 (3) | −0.004 (2) | 0.009 (2) | −0.008 (2) |
C12 | 0.026 (2) | 0.022 (2) | 0.028 (2) | 0.0015 (19) | 0.0059 (19) | 0.002 (2) |
C13 | 0.034 (3) | 0.030 (3) | 0.039 (3) | −0.007 (2) | 0.010 (2) | 0.000 (2) |
C14 | 0.036 (2) | 0.025 (3) | 0.022 (2) | 0.0017 (19) | 0.0050 (19) | 0.0010 (18) |
O1—C4 | 1.205 (7) | N7—C12 | 1.404 (7) |
O2—C5 | 1.228 (7) | N7—C13 | 1.458 (7) |
O3—C11 | 1.211 (7) | N8—C10 | 1.352 (7) |
O4—C12 | 1.225 (6) | N8—C12 | 1.373 (7) |
N1—C1 | 1.313 (7) | N8—C14 | 1.468 (7) |
N1—C2 | 1.395 (7) | C1—H1 | 0.9500 |
N1—H1N | 0.86 (2) | C2—C3 | 1.346 (8) |
N2—C1 | 1.329 (8) | C2—C4 | 1.436 (7) |
N2—C3 | 1.379 (6) | C6—H6A | 0.9800 |
N2—H2N | 0.866 (19) | C6—H6B | 0.9800 |
N3—C5 | 1.385 (7) | C6—H6C | 0.9800 |
N3—C4 | 1.409 (8) | C7—H7A | 0.9800 |
N3—C6 | 1.464 (6) | C7—H7B | 0.9800 |
N4—C3 | 1.358 (7) | C7—H7C | 0.9800 |
N4—C5 | 1.402 (8) | C8—H8 | 0.9500 |
N4—C7 | 1.454 (7) | C9—C10 | 1.373 (7) |
N5—C8 | 1.324 (7) | C9—C11 | 1.427 (7) |
N5—C9 | 1.380 (6) | C13—H13A | 0.9800 |
N5—H3N | 0.883 (19) | C13—H13B | 0.9800 |
N6—C8 | 1.351 (7) | C13—H13C | 0.9800 |
N6—C10 | 1.362 (7) | C14—H14A | 0.9800 |
N6—H4N | 0.872 (19) | C14—H14B | 0.9800 |
N7—C11 | 1.403 (7) | C14—H14C | 0.9800 |
C1—N1—C2 | 107.1 (5) | N3—C6—H6A | 109.5 |
C1—N1—H1N | 124 (4) | N3—C6—H6B | 109.5 |
C2—N1—H1N | 128 (4) | H6A—C6—H6B | 109.5 |
C1—N2—C3 | 107.4 (4) | N3—C6—H6C | 109.5 |
C1—N2—H2N | 130 (4) | H6A—C6—H6C | 109.5 |
C3—N2—H2N | 122 (4) | H6B—C6—H6C | 109.5 |
C5—N3—C4 | 127.3 (4) | N4—C7—H7A | 109.5 |
C5—N3—C6 | 116.5 (5) | N4—C7—H7B | 109.5 |
C4—N3—C6 | 116.2 (5) | H7A—C7—H7B | 109.5 |
C3—N4—C5 | 118.4 (5) | N4—C7—H7C | 109.5 |
C3—N4—C7 | 123.1 (5) | H7A—C7—H7C | 109.5 |
C5—N4—C7 | 118.5 (5) | H7B—C7—H7C | 109.5 |
C8—N5—C9 | 108.4 (5) | N5—C8—N6 | 108.9 (5) |
C8—N5—H3N | 120 (4) | N5—C8—H8 | 125.5 |
C9—N5—H3N | 131 (4) | N6—C8—H8 | 125.5 |
C8—N6—C10 | 108.5 (5) | C10—C9—N5 | 107.1 (5) |
C8—N6—H4N | 125 (4) | C10—C9—C11 | 122.5 (5) |
C10—N6—H4N | 124 (4) | N5—C9—C11 | 130.4 (5) |
C11—N7—C12 | 126.7 (5) | N8—C10—N6 | 130.1 (5) |
C11—N7—C13 | 118.3 (5) | N8—C10—C9 | 122.8 (5) |
C12—N7—C13 | 115.0 (5) | N6—C10—C9 | 107.0 (5) |
C10—N8—C12 | 119.4 (5) | O3—C11—N7 | 122.0 (5) |
C10—N8—C14 | 122.1 (5) | O3—C11—C9 | 126.7 (5) |
C12—N8—C14 | 118.4 (4) | N7—C11—C9 | 111.2 (5) |
N1—C1—N2 | 110.8 (5) | O4—C12—N8 | 122.3 (5) |
N1—C1—H1 | 124.6 | O4—C12—N7 | 120.6 (5) |
N2—C1—H1 | 124.6 | N8—C12—N7 | 117.1 (4) |
C3—C2—N1 | 107.4 (5) | N7—C13—H13A | 109.5 |
C3—C2—C4 | 123.0 (5) | N7—C13—H13B | 109.5 |
N1—C2—C4 | 129.5 (5) | H13A—C13—H13B | 109.5 |
C2—C3—N4 | 123.5 (5) | N7—C13—H13C | 109.5 |
C2—C3—N2 | 107.4 (5) | H13A—C13—H13C | 109.5 |
N4—C3—N2 | 129.1 (5) | H13B—C13—H13C | 109.5 |
O1—C4—N3 | 122.7 (5) | N8—C14—H14A | 109.5 |
O1—C4—C2 | 126.4 (6) | N8—C14—H14B | 109.5 |
N3—C4—C2 | 110.8 (5) | H14A—C14—H14B | 109.5 |
O2—C5—N3 | 122.6 (5) | N8—C14—H14C | 109.5 |
O2—C5—N4 | 120.4 (5) | H14A—C14—H14C | 109.5 |
N3—C5—N4 | 117.0 (5) | H14B—C14—H14C | 109.5 |
C2—N1—C1—N2 | −0.8 (6) | C9—N5—C8—N6 | 0.6 (6) |
C3—N2—C1—N1 | 0.4 (6) | C10—N6—C8—N5 | −0.1 (7) |
C1—N1—C2—C3 | 0.9 (6) | C8—N5—C9—C10 | −0.9 (6) |
C1—N1—C2—C4 | 177.0 (6) | C8—N5—C9—C11 | 178.1 (6) |
N1—C2—C3—N4 | 177.7 (5) | C12—N8—C10—N6 | 176.7 (6) |
C4—C2—C3—N4 | 1.4 (9) | C14—N8—C10—N6 | −7.4 (9) |
N1—C2—C3—N2 | −0.7 (6) | C12—N8—C10—C9 | 0.5 (8) |
C4—C2—C3—N2 | −177.1 (5) | C14—N8—C10—C9 | 176.4 (5) |
C5—N4—C3—C2 | −0.5 (8) | C8—N6—C10—N8 | −177.2 (6) |
C7—N4—C3—C2 | −178.7 (5) | C8—N6—C10—C9 | −0.4 (7) |
C5—N4—C3—N2 | 177.5 (5) | N5—C9—C10—N8 | 177.8 (5) |
C7—N4—C3—N2 | −0.7 (9) | C11—C9—C10—N8 | −1.3 (9) |
C1—N2—C3—C2 | 0.2 (6) | N5—C9—C10—N6 | 0.8 (6) |
C1—N2—C3—N4 | −178.1 (6) | C11—C9—C10—N6 | −178.3 (5) |
C5—N3—C4—O1 | 179.9 (5) | C12—N7—C11—O3 | 175.4 (5) |
C6—N3—C4—O1 | −1.4 (8) | C13—N7—C11—O3 | −1.0 (8) |
C5—N3—C4—C2 | 0.3 (8) | C12—N7—C11—C9 | −7.0 (8) |
C6—N3—C4—C2 | 179.0 (4) | C13—N7—C11—C9 | 176.6 (5) |
C3—C2—C4—O1 | 179.3 (6) | C10—C9—C11—O3 | −178.4 (5) |
N1—C2—C4—O1 | 3.8 (10) | N5—C9—C11—O3 | 2.7 (9) |
C3—C2—C4—N3 | −1.1 (8) | C10—C9—C11—N7 | 4.1 (7) |
N1—C2—C4—N3 | −176.7 (5) | N5—C9—C11—N7 | −174.8 (5) |
C4—N3—C5—O2 | 178.1 (6) | C10—N8—C12—O4 | 178.6 (5) |
C6—N3—C5—O2 | −0.7 (8) | C14—N8—C12—O4 | 2.6 (8) |
C4—N3—C5—N4 | 0.4 (9) | C10—N8—C12—N7 | −2.8 (8) |
C6—N3—C5—N4 | −178.3 (4) | C14—N8—C12—N7 | −178.9 (5) |
C3—N4—C5—O2 | −178.0 (5) | C11—N7—C12—O4 | −174.8 (5) |
C7—N4—C5—O2 | 0.3 (8) | C13—N7—C12—O4 | 1.7 (8) |
C3—N4—C5—N3 | −0.3 (7) | C11—N7—C12—N8 | 6.6 (8) |
C7—N4—C5—N3 | 178.0 (5) | C13—N7—C12—N8 | −176.9 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Cl2i | 0.86 (2) | 2.23 (2) | 3.074 (5) | 164 (5) |
N2—H2N···Cl2ii | 0.87 (2) | 2.22 (2) | 3.058 (4) | 163 (5) |
N5—H3N···Cl1iii | 0.88 (2) | 2.22 (2) | 3.099 (5) | 171 (5) |
N6—H4N···Cl1iv | 0.87 (2) | 2.21 (2) | 3.066 (5) | 166 (5) |
C1—H1···Cl1v | 0.95 | 2.64 | 3.479 (5) | 147 |
C8—H8···Cl2vi | 0.95 | 2.61 | 3.452 (6) | 149 |
Symmetry codes: (i) x+1/2, −y+5/2, z−1/2; (ii) x+1/2, y−1/2, z; (iii) x, −y+2, z−1/2; (iv) x, y−1, z; (v) x+1/2, y+1/2, z; (vi) x, −y+1, z−1/2. |
Experimental details
(I) | (II) | (III) | (IV) | |
Crystal data | ||||
Chemical formula | C7H9N4O2+·BF4− | C7H9N4O2+·Cl−·H2O | C7H9N4O2+·Br−·H2O | C7H9N4O2+·Cl− |
Mr | 267.99 | 234.65 | 279.11 | 216.63 |
Crystal system, space group | Monoclinic, P21/n | Orthorhombic, Pnma | Orthorhombic, Pnma | Monoclinic, Cc |
Temperature (K) | 123 | 123 | 123 | 123 |
a, b, c (Å) | 13.0883 (4), 6.0413 (1), 14.5542 (4) | 13.8664 (7), 6.4623 (3), 11.3634 (6) | 14.0120 (5), 6.6151 (3), 11.5297 (4) | 32.081 (3), 4.5028 (3), 12.8256 (10) |
α, β, γ (°) | 90, 115.306 (3), 90 | 90, 90, 90 | 90, 90, 90 | 90, 103.524 (9), 90 |
V (Å3) | 1040.37 (5) | 1018.26 (9) | 1068.70 (7) | 1801.3 (3) |
Z | 4 | 4 | 4 | 8 |
Radiation type | Mo Kα | Cu Kα | Mo Kα | Cu Kα |
µ (mm−1) | 0.17 | 3.33 | 3.84 | 3.63 |
Crystal size (mm) | 0.30 × 0.12 × 0.10 | 0.28 × 0.18 × 0.04 | 0.22 × 0.12 × 0.08 | 0.33 × 0.08 × 0.04 |
Data collection | ||||
Diffractometer | Oxford Diffraction Xcalibur E diffractometer | Oxford Diffraction Gemini S diffractometer | Oxford Diffraction Xcalibur E diffractometer | Oxford Diffraction Gemini S diffractometer |
Absorption correction | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) | Multi-scan (CrysAlis PRO; Oxford Diffraction, 2010) |
Tmin, Tmax | 0.913, 1.000 | 0.542, 1.000 | 0.943, 1.000 | 0.697, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 14312, 2705, 2366 | 3701, 1090, 1077 | 7635, 1553, 1378 | 6692, 3230, 2966 |
Rint | 0.020 | 0.017 | 0.033 | 0.037 |
(sin θ/λ)max (Å−1) | 0.692 | 0.620 | 0.702 | 0.623 |
Refinement | ||||
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.082, 1.05 | 0.029, 0.081, 1.12 | 0.025, 0.058, 1.07 | 0.048, 0.130, 1.07 |
No. of reflections | 2705 | 1090 | 1553 | 3230 |
No. of parameters | 173 | 106 | 106 | 270 |
No. of restraints | 0 | 3 | 5 | 6 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.40, −0.23 | 0.34, −0.32 | 0.36, −0.48 | 0.48, −0.26 |
Absolute structure | ? | ? | ? | Flack (1983), 1431 Friedel pairs |
Absolute structure parameter | ? | ? | ? | 0.28 (3) |
Computer programs: CrysAlis PRO (Oxford Diffraction, 2010), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012) and X-SEED (Barbour, 2001), ORTEP-3 for Windows (Farrugia, 2012).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···O1i | 0.883 (18) | 1.838 (18) | 2.7165 (13) | 172.7 (16) |
N2—H2N···F3ii | 0.892 (17) | 1.823 (18) | 2.7094 (12) | 172.2 (16) |
N2—H2N···F1ii | 0.892 (17) | 2.525 (17) | 3.0239 (13) | 115.9 (14) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+3/2, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Cl1 | 0.90 (3) | 2.10 (3) | 2.9915 (17) | 171 (3) |
N2—H2N···O1W | 0.80 (3) | 1.85 (3) | 2.639 (3) | 172 (3) |
O1W—H1W···O2i | 0.879 (10) | 1.86 (2) | 2.722 (2) | 165 (7) |
O1W—H2W···Cl1ii | 0.880 (10) | 2.24 (2) | 3.065 (2) | 156 (5) |
Symmetry codes: (i) x−1/2, y, −z+3/2; (ii) x−1/2, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Br1 | 0.860 (10) | 2.315 (13) | 3.1551 (19) | 166 (3) |
N2—H2N···O1W | 0.855 (10) | 1.785 (11) | 2.637 (3) | 173.5 (12) |
O1W—H2W···O2i | 0.880 (10) | 1.97 (3) | 2.712 (3) | 140 (4) |
O1W—H1W···Br1ii | 0.882 (10) | 2.47 (3) | 3.212 (3) | 143 (4) |
Symmetry codes: (i) x−1/2, y, −z+3/2; (ii) x−1/2, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1N···Cl2i | 0.86 (2) | 2.23 (2) | 3.074 (5) | 164 (5) |
N2—H2N···Cl2ii | 0.866 (19) | 2.22 (2) | 3.058 (4) | 163 (5) |
N5—H3N···Cl1iii | 0.883 (19) | 2.22 (2) | 3.099 (5) | 171 (5) |
N6—H4N···Cl1iv | 0.872 (19) | 2.21 (2) | 3.066 (5) | 166 (5) |
C1—H1···Cl1v | 0.95 | 2.64 | 3.479 (5) | 147 |
C8—H8···Cl2vi | 0.95 | 2.61 | 3.452 (6) | 149 |
Symmetry codes: (i) x+1/2, −y+5/2, z−1/2; (ii) x+1/2, y−1/2, z; (iii) x, −y+2, z−1/2; (iv) x, y−1, z; (v) x+1/2, y+1/2, z; (vi) x, −y+1, z−1/2. |