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In the title compound, 3-[(4-amino-2-methyl-5-pyrimidin-1-io)methyl]-5-(2-hydroxy­ethyl)-4-methyl­thia­zolium(2+) bis(tetra­fluoro­borate), C12H18N4OS2+·2BF4, the divalent thia­mine cation (in the F conformation) is associated with BF4 anions via two characteristic bridging interactions between the thia­zolium and pyrimidinium rings, i.e. C—H...BF4...pyrimidinium and N—H...BF4...thia­zolium interactions. Thi­amine mol­ecules are linked by N—H...O hydrogen bonds to form a helical chain structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101009222/da1186sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101009222/da1186Isup2.hkl
Contains datablock I

CCDC reference: 173364

Comment top

Thiamine pyrophosphate is a coenzyme for a number of metabolic enzymes (Krampitz, 1969). Studies of the thiamine-anion system as a model for coenzyme-substrate interactions are of interest because, in the reactions catalyzed by thiamine, a substrate anion such as pyruvate directly interacts with thiamine at the C2 site (Breslow, 1958).

Thiamine exists either as a monovalent cation with a quaternary N on the thiazolium moiety or as a divalent one (H-thiamine) with an additional proton at N1' of the pyrimidine ring. It has been observed (Aoki et al., 1991) that in thiamine-anion complexes the anions are associated with thiamine through two types of characteristic bridging interactions, forming host–guest-like anion complexation. Moreover, thiamine molecules themselves form various hydrogen-bonded structures and, together with anions in some cases, build up distinct higher-order supramolecular structures (Aoki et al., 1993, 1999). There are two types of hydrogen-bonded chain structures depending on whether N1' of the pyrimidine moiety is protonated. One type of chain structure incorporates an O53—H···N1' hydrogen bond, such as in N1'-unprotonated thiamine·ClO4·H2O (Kozioł et al., 1987), thiamine(BF4)·H2O (Aoki et al., 1990) and thiamine(PF6)·H2O (Aoki et al., 1988). Another type has an N1'—H···O53 hydrogen bond, as in N1'-protonated H-thiamine·(ClO4)2 (Aoki et al., 1988). These observations led us to further examine (i) the host–guest-like thiamine-anion complexation in H-thiamine(BF4)2, (I), and (ii) whether a chain structure similar to that in H-thiamine(ClO4)2 occurs in (I). \sch

The structure of (I) contains a divalent thiamine cation with N1' protonated and two disordered BF4- ions (denoted A and B), as shown in Fig. 1. The molecular dimensions of thiamine in (I) are in agreement with another known N1'-protonated thiamine (Cramer et al., 1981). The protonation at N1' influences the C2'—N1'—C6' bond angle and the opposite C4'—N4'1 bond length. These values are 119.9 (4)° and 1.318 (5) Å in (I) while they are 115.0 (3)° and 1.337 (4) Å in thiamine·BF4·H2O, which has an N1'-unprotonated pyrimidine ring. The C5 hydroxyethyl side chain folds back towards the thiazolium ring with the torsion angles (Pletcher et al., 1977): ϕ5α (S1—C5—C51—C52) = -67.5 (7)° and ϕ5β (C5—C51—C52—O53) = 64.4 (7)°. This conformation results in a close contact between O53 and the electropositive S1 atom (Jordan, 1974) with O53···S1 = 3.029 (3) Å, which is a common structural feature of thiamine compounds.

Thiamine molecule adopts the usual F conformation in terms of the torsion angles (Pletcher et al., 1977): ϕT (C5'—C35'—N3—C2) = 11.4 (7)°, and ϕP (N3—C35'—C5'—C4') = -82.8 (5)°. Aoki et al. (1993) have noted that when thiamine is in the F form there are two well defined 'anion holes' between the thiazolium and pyrimidine rings. The area denoted 'anion hole I' is occupied by an anion which bridges the two rings through a C2—H···anion···pyrimidine-ring interaction, and 'anion hole II' is occupied by an anion which bridges the two rings through an N4'1-H···anion···thiazolium-ring interaction. In (I), the A anion accepts a hydrogen bond from C2 (C2—H···F3 or C2—H···F2', see Table 3) and makes a close stacking interaction with the pyrimidinium ring (Table 2), thus being located in 'anion hole I'. The B anion lies in 'anion hole II' to form an N4'1-H···F7 or N4'1-H···F6' hydrogen bond (Table 3) and a close contact with the thiazolium ring (Table 2). These two types of thiamine-anion complexation also exist in thiamine(BF4)·H2O in which 'anion hole II' is occupied by a water molecule (Aoki et al., 1990). The anion complexation at 'anion hole I' occurs only for the F conformation but not for the other two energetically favourable conformations, S (ϕT= ±100°, ϕP= ±150°) and V (ϕT= ±90°, ϕP= 90°), thus being peculiar to the F form. On the other hand, the anion complexation at 'anion hole II' is also possible for a thiamine molecule in the S form, but it requires large anions such as CdCl42- (Richardson et al., 1975) and HgCl42- (Hadjiliadis et al., 1983) rather than small anions like ClO4- or BF4-. In the V form, none of these 'anion holes' are available. It therefore appears that thiamine-anion complexation plays an important role in determining molecular conformations, and vice versa.

As expected, a helical chain structure in the 'head-to-tail' fashion is formed along the twofold screw axis in the b direction through N1'-H···O53 hydrogen bonds, where O53 acts as an acceptor, between the pyrimidinium 'head' of a thiamine molecule and the hydroxyethyl 'tail' of the other one (Fig. 2). The repeat period of the helical chain is the length of the b axis (7.565 Å). The A anion is located inside the spiral and is attached to the chain through the C2—H···BF4-···pyrimidinium interaction, as mentioned above. The B anion lies outside of the spiral and interacts with the chain through the N4'1—H···BF4-···thiazolium contact and, at the same time, links two neighbouring chains by N4'1—H···BF4-···H—O53 hydrogen bonds. This chain structure is similar to that in H-thiamine·(ClO4)2 but different from that in thiamine·ClO4·H2O and thiamine·BF4·H2O, where the molecular chain is constructed through O53—H···N1' hydrogen bonds, with longer repeat periods of 11.234 and 11.134 Å, respectively.

It is of interest to note the molecular self-association in thiamine-anion systems. For example, a polymeric chain structure with each anion molecule held between hydrogen-bonded thiamine-thiamine dimers is commonly formed for [PtCl4]2- (Cramer et al., 1988), [PtCl6]2- (Aoki et al., 1993) and [Pt(NO2)4]2- (Hu et al., 2001) anions, while the linear SCN- anion facilitates the formation of a triple helical structure (Hu & Zhang, 1993) in which each helical chain consists of alternate thiamine and anion molecules. Therefore, the higher-order structures in thiamine-anion systems depend on not only the nature of thiamine itself but also that of the anions.

Experimental top

Crystals of (I) were obtained at room temperature by the slow evaporation of an aqueous solution (pH = 2) of thiamine chloride hydrochloride (69.2 mg, 0.2 mmol) and NaBF4 (43.9 mg, 0.4 mmol).

Refinement top

Each of the two BF4- ions is disordered at two positions around the common B atom. The occupancy factors were refined to give 0.538 and 0.462 for anion A and 0.752 and 0.248 for anion B. All H atoms were located from difference Fourier maps and refined isotropically, except for those of methyl groups, which were added at ideal positions.

Computing details top

Data collection: XSCANS (Siemens, 1994b); cell refinement: XSCANS; data reduction: SHELXTL (Siemens, 1994a); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. H-thiamine·(BF4)2 drawn with 50% probability displacement ellipsoids. Note that the BF4- anions are associated to thiamine at the two 'anion holes' through two types of bridging interactions, C2—H···BF4-···pyrimidinium and N4'1—H···BF4-···thiazolium. Broken lines denote hydrogen bonds.
[Figure 2] Fig. 2. A stereoview of the crystal packing, showing the formation of the helical molecular chain in the b direction. Only those H atoms involved in hydrogen bonds are shown. Minor disordered positions of the BF4- anions are omitted for clarity. Broken lines denote hydrogen bonds.
3-[(4-amino-2-methyl-5-pyrimidinio)methyl]-5-(2-hydroxyethyl)- 4-methylthiazolium(2+) bis(tetrafluoroborate) top
Crystal data top
C12H18N4OS2+·2BF4F(000) = 896
Mr = 439.98Dx = 1.536 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 13.849 (1) ÅCell parameters from 20 reflections
b = 7.565 (1) Åθ = 6.5–11.2°
c = 18.554 (5) ŵ = 0.26 mm1
β = 101.90 (1)°T = 293 K
V = 1902.1 (6) Å3Tabular, colourless
Z = 40.45 × 0.40 × 0.12 mm
Data collection top
Siemens P4
diffractometer
Rint = 0.022
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 1.7°
Graphite monochromatorh = 116
ω scansk = 18
4564 measured reflectionsl = 2221
3348 independent reflections3 standard reflections every 100 reflections
1501 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: difference Fourier map
wR(F2) = 0.124H atoms treated by a mixture of independent and constrained refinement
S = 0.99 w = 1/[σ2(Fo2) + (0.040P)2]
where P = (Fo2 + 2Fc2)/3
3348 reflections(Δ/σ)max = 0.011
377 parametersΔρmax = 0.24 e Å3
41 restraintsΔρmin = 0.19 e Å3
Crystal data top
C12H18N4OS2+·2BF4V = 1902.1 (6) Å3
Mr = 439.98Z = 4
Monoclinic, P21/nMo Kα radiation
a = 13.849 (1) ŵ = 0.26 mm1
b = 7.565 (1) ÅT = 293 K
c = 18.554 (5) Å0.45 × 0.40 × 0.12 mm
β = 101.90 (1)°
Data collection top
Siemens P4
diffractometer
Rint = 0.022
4564 measured reflections3 standard reflections every 100 reflections
3348 independent reflections intensity decay: none
1501 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.05541 restraints
wR(F2) = 0.124H atoms treated by a mixture of independent and constrained refinement
S = 0.99Δρmax = 0.24 e Å3
3348 reflectionsΔρmin = 0.19 e Å3
377 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
S10.86029 (8)0.9675 (2)0.09574 (8)0.0764 (5)
C20.7621 (3)1.1002 (6)0.0884 (3)0.0620 (14)
H20.694 (3)1.052 (6)0.090 (2)0.088 (15)*
N30.7860 (2)1.2677 (5)0.0908 (2)0.0466 (9)
C40.8874 (3)1.2973 (6)0.0976 (2)0.0514 (12)
C50.9382 (3)1.1454 (6)0.1006 (2)0.0556 (12)
C410.9253 (3)1.4818 (6)0.1022 (3)0.0764 (15)
H41A0.91331.53810.14780.092*
H41B0.89071.54960.05890.092*
H41C0.99701.48070.10310.092*
C511.0476 (3)1.1195 (9)0.1112 (3)0.071 (2)
H51A1.076 (3)1.237 (7)0.108 (2)0.089 (18)*
H51B1.061 (3)1.039 (6)0.072 (2)0.092 (19)*
C521.0920 (4)1.0447 (10)0.1868 (3)0.076 (2)
H52A1.165 (3)1.033 (6)0.188 (2)0.085 (15)*
H52B1.078 (3)1.124 (6)0.224 (2)0.081 (17)*
O531.0552 (2)0.8716 (6)0.1954 (2)0.0740 (10)
H531.089 (4)0.783 (6)0.176 (3)0.14 (3)*
C35'0.7137 (3)1.4136 (6)0.0881 (3)0.0528 (13)
H35A0.712 (3)1.478 (6)0.042 (2)0.081 (16)*
H35B0.743 (3)1.495 (5)0.1262 (19)0.052 (13)*
N1'0.4992 (3)1.3065 (5)0.1719 (2)0.0593 (11)
H1'0.484 (3)1.307 (6)0.215 (2)0.070 (16)*
C2'0.4354 (3)1.2319 (6)0.1155 (3)0.0545 (12)
N3'0.4534 (2)1.2214 (5)0.0490 (2)0.0554 (10)
C4'0.5417 (3)1.2823 (6)0.0380 (2)0.0512 (11)
C5'0.6144 (3)1.3514 (6)0.0972 (2)0.0468 (11)
C6'0.5886 (3)1.3609 (6)0.1624 (3)0.0539 (12)
H6'0.627 (3)1.402 (5)0.204 (2)0.054 (13)*
C2'10.3424 (3)1.1584 (7)0.1308 (3)0.080 (2)
H21A0.31531.24060.16310.096*
H21B0.35591.04250.15560.096*
H21C0.29391.14310.08390.096*
N4'10.5546 (3)1.2715 (6)0.0303 (2)0.0652 (13)
H41D0.514 (3)1.229 (6)0.062 (2)0.066 (17)*
H41E0.610 (3)1.312 (6)0.049 (2)0.079 (15)*
B10.6254 (5)0.8429 (10)0.2014 (4)0.074 (2)
F10.6361 (15)0.7025 (14)0.2470 (5)0.157 (6)0.538 (12)
F20.5288 (8)0.886 (2)0.1902 (10)0.227 (8)0.538 (12)
F30.6501 (9)0.7912 (13)0.1359 (4)0.108 (5)0.538 (12)
F40.6834 (8)0.9605 (19)0.2405 (6)0.128 (6)0.538 (12)
F1'0.5659 (10)0.7213 (15)0.2179 (7)0.109 (4)0.462 (12)
F2'0.5802 (7)0.9266 (11)0.1393 (4)0.082 (4)0.462 (12)
F3'0.7124 (7)0.7753 (15)0.1906 (14)0.213 (10)0.462 (12)
F4'0.6395 (15)0.9955 (19)0.2462 (9)0.167 (9)0.462 (12)
B20.7827 (5)1.3773 (12)0.1096 (4)0.077 (2)
F50.8093 (5)1.3984 (12)0.1743 (3)0.119 (3)0.752 (9)
F60.8223 (5)1.5208 (8)0.0626 (3)0.130 (3)0.752 (9)
F70.6836 (3)1.4009 (11)0.1203 (4)0.132 (3)0.752 (9)
F80.8041 (8)1.2226 (9)0.0764 (3)0.150 (3)0.752 (9)
F5'0.8725 (11)1.301 (3)0.0782 (9)0.105 (6)0.248 (9)
F6'0.7282 (19)1.448 (4)0.0688 (11)0.165 (12)0.248 (9)
F7'0.7292 (19)1.245 (3)0.1631 (15)0.225 (15)0.248 (9)
F8'0.807 (2)1.510 (4)0.1594 (15)0.24 (2)0.248 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0512 (7)0.0543 (8)0.1232 (12)0.0060 (7)0.0170 (7)0.0063 (9)
C20.040 (3)0.053 (3)0.092 (4)0.002 (2)0.012 (2)0.006 (3)
N30.036 (2)0.049 (2)0.054 (2)0.001 (2)0.006 (2)0.006 (2)
C40.040 (2)0.057 (3)0.055 (3)0.008 (2)0.005 (2)0.001 (2)
C50.042 (2)0.057 (3)0.067 (3)0.002 (3)0.011 (2)0.008 (3)
C410.049 (3)0.068 (4)0.110 (4)0.016 (3)0.011 (3)0.000 (3)
C510.043 (3)0.080 (4)0.090 (4)0.010 (3)0.017 (3)0.018 (4)
C520.047 (3)0.096 (5)0.085 (4)0.008 (4)0.012 (3)0.002 (4)
O530.062 (2)0.086 (3)0.079 (2)0.017 (2)0.025 (2)0.013 (2)
C35'0.044 (3)0.049 (3)0.063 (3)0.001 (2)0.006 (3)0.000 (3)
N1'0.051 (2)0.070 (3)0.058 (3)0.002 (2)0.015 (2)0.002 (2)
C2'0.039 (2)0.055 (3)0.069 (3)0.003 (2)0.009 (2)0.000 (3)
N3'0.040 (2)0.064 (3)0.061 (2)0.003 (2)0.006 (2)0.003 (2)
C4'0.048 (3)0.054 (3)0.052 (3)0.008 (2)0.010 (2)0.002 (3)
C5'0.038 (2)0.048 (3)0.051 (3)0.002 (2)0.001 (2)0.005 (2)
C6'0.047 (3)0.060 (3)0.051 (3)0.002 (3)0.001 (3)0.000 (3)
C2'10.055 (3)0.091 (4)0.098 (4)0.010 (3)0.028 (3)0.005 (3)
N4'10.055 (3)0.085 (3)0.053 (3)0.016 (3)0.006 (2)0.009 (3)
B10.063 (4)0.079 (5)0.073 (5)0.000 (5)0.002 (4)0.002 (5)
F10.309 (18)0.088 (6)0.072 (5)0.042 (10)0.031 (8)0.019 (5)
F20.113 (8)0.230 (17)0.299 (18)0.055 (9)0.046 (10)0.033 (14)
F30.144 (9)0.121 (8)0.069 (5)0.060 (8)0.045 (5)0.021 (5)
F40.092 (6)0.195 (15)0.087 (5)0.062 (8)0.005 (4)0.064 (7)
F1'0.132 (9)0.085 (8)0.127 (10)0.039 (8)0.068 (7)0.028 (7)
F2'0.076 (6)0.088 (6)0.067 (5)0.013 (5)0.021 (4)0.021 (5)
F3'0.087 (8)0.096 (8)0.44 (3)0.019 (6)0.017 (11)0.031 (14)
F4'0.26 (2)0.071 (7)0.168 (12)0.017 (11)0.026 (12)0.017 (7)
B20.068 (5)0.101 (6)0.067 (5)0.005 (5)0.024 (4)0.005 (5)
F50.106 (4)0.186 (8)0.071 (3)0.037 (5)0.035 (3)0.015 (4)
F60.147 (5)0.125 (5)0.115 (4)0.036 (4)0.017 (4)0.008 (4)
F70.072 (3)0.202 (8)0.136 (5)0.016 (4)0.052 (3)0.007 (6)
F80.225 (9)0.103 (5)0.105 (4)0.019 (5)0.009 (5)0.016 (4)
F5'0.094 (11)0.093 (14)0.129 (13)0.012 (10)0.028 (10)0.008 (10)
F6'0.19 (3)0.22 (3)0.103 (14)0.05 (2)0.075 (17)0.021 (17)
F7'0.21 (2)0.120 (17)0.33 (4)0.036 (18)0.02 (3)0.02 (2)
F8'0.23 (3)0.27 (4)0.28 (4)0.13 (3)0.19 (3)0.11 (3)
Geometric parameters (Å, º) top
S1—C21.673 (4)N3'—C4'1.361 (5)
S1—C51.715 (4)C4'—N4'11.318 (5)
C2—N31.308 (5)C4'—C5'1.427 (5)
C2—H21.01 (4)C5'—C6'1.332 (6)
N3—C41.403 (5)C6'—H6'0.89 (4)
N3—C35'1.484 (5)C2'1—H21A0.99
C4—C51.342 (5)C2'1—H21B0.99
C4—C411.488 (6)C2'1—H21C0.99
C5—C511.501 (6)N4'1—H41D0.79 (4)
C41—H41A0.99N4'1—H41E0.96 (5)
C41—H41B0.99B1—F1'1.313 (10)
C41—H41C0.99B1—F41.313 (12)
C51—C521.521 (7)B1—F2'1.349 (9)
C51—H51A0.98 (5)B1—F11.347 (11)
C51—H51B0.99 (5)B1—F4'1.413 (15)
C52—O531.426 (7)B1—F31.384 (9)
C52—H52A1.01 (4)B1—F3'1.362 (12)
C52—H52B0.96 (4)B1—F21.350 (11)
O53—H530.93 (3)B2—F6'1.290 (14)
C35'—C5'1.496 (5)B2—F81.327 (9)
C35'—H35A0.97 (4)B2—F51.336 (9)
C35'—H35B0.96 (4)B2—F71.357 (8)
N1'—C2'1.347 (5)B2—F5'1.386 (14)
N1'—C6'1.350 (5)B2—F61.429 (9)
N1'—H1'0.86 (4)B2—F8'1.45 (2)
C2'—N3'1.309 (5)B2—F7'1.49 (2)
C2'—C2'11.483 (6)
S1···O533.029 (3)C2'···F23.117 (17)
N1'···F2'3.188 (11)C6'···F43.495 (16)
C2'···F2'3.031 (11)C4···F63.377 (7)
N3'···F2'3.106 (9)C2···F83.359 (9)
C4'···F2'3.263 (8)N3···F83.183 (7)
C5'···F2'3.364 (9)C4···F83.247 (7)
C6'···F2'3.312 (10)C5···F83.472 (8)
N1'···F4'3.179 (19)C4···F5'3.226 (18)
C6'···F4'3.178 (17)C5···F5'3.460 (18)
N1'···F23.217 (17)N3···F6'3.21 (2)
C2—S1—C591.5 (2)C2'—N3'—C4'118.2 (4)
N3—C2—S1112.5 (3)N4'1—C4'—N3'115.3 (4)
N3—C2—H2125 (3)N4'1—C4'—C5'123.2 (4)
S1—C2—H2122 (3)N3'—C4'—C5'121.5 (4)
C2—N3—C4113.5 (4)C6'—C5'—C4'116.1 (4)
C2—N3—C35'123.8 (3)C6'—C5'—C35'120.7 (4)
C4—N3—C35'122.7 (4)C4'—C5'—C35'123.2 (4)
C5—C4—N3111.9 (4)C5'—C6'—N1'121.8 (4)
C5—C4—C41128.8 (4)C5'—C6'—H6'125 (2)
N3—C4—C41119.3 (4)N1'—C6'—H6'114 (2)
C4—C5—C51128.6 (5)C2'—C2'1—H21A109.5
C4—C5—S1110.6 (3)C2'—C2'1—H21B109.5
C51—C5—S1120.8 (4)H21A—C2'1—H21B109.5
C4—C41—H41A109.5C2'—C2'1—H21C109.5
C4—C41—H41B109.5H21A—C2'1—H21C109.5
H41A—C41—H41B109.5H21B—C2'1—H21C109.5
C4—C41—H41C109.5C4'—N4'1—H41D122 (3)
H41A—C41—H41C109.5C4'—N4'1—H41E127 (3)
H41B—C41—H41C109.5H41D—N4'1—H41E111 (4)
C5—C51—C52112.0 (4)F1'—B1—F2'109.0 (8)
C5—C51—H51A106 (3)F4—B1—F1102.2 (10)
C52—C51—H51A108 (3)F1'—B1—F4'116.9 (10)
C5—C51—H51B108 (3)F2'—B1—F4'95.9 (10)
C52—C51—H51B111 (3)F4—B1—F3116.4 (8)
H51A—C51—H51B112 (4)F1—B1—F3108.3 (8)
O53—C52—C51111.0 (5)F1'—B1—F3'112.9 (9)
O53—C52—H52A107 (3)F2'—B1—F3'108.7 (11)
C51—C52—H52A105 (2)F4'—B1—F3'112.0 (10)
O53—C52—H52B112 (3)F4—B1—F2113.3 (9)
C51—C52—H52B109 (3)F1—B1—F2105.2 (11)
H52A—C52—H52B113 (4)F3—B1—F2110.5 (9)
C52—O53—H53114 (4)F8—B2—F5116.5 (7)
N3—C35'—C5'113.0 (4)F8—B2—F7107.8 (8)
N3—C35'—H35A107 (3)F5—B2—F7108.1 (6)
C5'—C35'—H35A114 (2)F6'—B2—F5'120.6 (13)
N3—C35'—H35B106 (2)F8—B2—F6111.5 (6)
C5'—C35'—H35B112 (2)F5—B2—F6108.4 (7)
H35A—C35'—H35B104 (3)F7—B2—F6103.8 (7)
C2'—N1'—C6'119.9 (4)F6'—B2—F8'109.2 (16)
C2'—N1'—H1'118 (3)F5'—B2—F8'104.4 (12)
C6'—N1'—H1'122 (3)F6'—B2—F7'113.4 (15)
N3'—C2'—N1'122.4 (4)F5'—B2—F7'106.2 (12)
N3'—C2'—C2'1119.9 (4)F8'—B2—F7'100.9 (14)
N1'—C2'—C2'1117.7 (4)
S1—C5—C51—C5267.5 (7)C2—N3—C35'—C5'11.4 (7)
C5—C51—C52—O5364.4 (7)N3—C35'—C5'—C4'82.8 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···F31.01 (4)2.29 (4)3.035 (8)130 (3)
C2—H2···F21.01 (4)2.20 (4)3.154 (11)156 (3)
N41—H41D···F2i0.79 (4)2.09 (5)2.875 (8)169 (4)
N41—H41D···F3i0.79 (4)2.41 (4)3.132 (12)153 (4)
N41—H41E···F70.96 (5)1.94 (5)2.859 (7)158 (4)
N41—H41E···F60.96 (5)2.02 (5)2.96 (3)165 (4)
N1—H1···O53ii0.86 (4)1.92 (4)2.763 (6)166 (4)
O53—H53···F5iii0.93 (3)1.97 (4)2.855 (8)157 (5)
O53—H53···F5iii0.93 (3)2.09 (5)2.886 (16)143 (5)
Symmetry codes: (i) x+1, y+2, z; (ii) x+3/2, y+1/2, z+1/2; (iii) x+2, y+2, z.

Experimental details

Crystal data
Chemical formulaC12H18N4OS2+·2BF4
Mr439.98
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)13.849 (1), 7.565 (1), 18.554 (5)
β (°) 101.90 (1)
V3)1902.1 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.26
Crystal size (mm)0.45 × 0.40 × 0.12
Data collection
DiffractometerSiemens P4
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
4564, 3348, 1501
Rint0.022
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.124, 0.99
No. of reflections3348
No. of parameters377
No. of restraints41
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.24, 0.19

Computer programs: XSCANS (Siemens, 1994b), XSCANS, SHELXTL (Siemens, 1994a), SHELXTL.

Selected geometric parameters (Å, º) top
S1—C21.673 (4)N1'—C2'1.347 (5)
S1—C51.715 (4)N1'—C6'1.350 (5)
C2—N31.308 (5)C2'—N3'1.309 (5)
N3—C41.403 (5)N3'—C4'1.361 (5)
N3—C35'1.484 (5)C4'—N4'11.318 (5)
C4—C51.342 (5)C4'—C5'1.427 (5)
C35'—C5'1.496 (5)C5'—C6'1.332 (6)
N1'···F2'3.188 (11)C2'···F23.117 (17)
C2'···F2'3.031 (11)C4···F63.377 (7)
N3'···F2'3.106 (9)N3···F83.183 (7)
N1'···F4'3.179 (19)C4···F83.247 (7)
C6'···F4'3.178 (17)C4···F5'3.226 (18)
N1'···F23.217 (17)N3···F6'3.21 (2)
C2—S1—C591.5 (2)C2'—N1'—C6'119.9 (4)
N3—C2—S1112.5 (3)N3'—C2'—N1'122.4 (4)
C2—N3—C4113.5 (4)C2'—N3'—C4'118.2 (4)
C2—N3—C35'123.8 (3)N3'—C4'—C5'121.5 (4)
C4—N3—C35'122.7 (4)C6'—C5'—C4'116.1 (4)
C5—C4—N3111.9 (4)C6'—C5'—C35'120.7 (4)
C4—C5—S1110.6 (3)C4'—C5'—C35'123.2 (4)
N3—C35'—C5'113.0 (4)C5'—C6'—N1'121.8 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C2—H2···F31.01 (4)2.29 (4)3.035 (8)130 (3)
C2—H2···F2'1.01 (4)2.20 (4)3.154 (11)156 (3)
N4'1—H41D···F2'i0.79 (4)2.09 (5)2.875 (8)169 (4)
N4'1—H41D···F3i0.79 (4)2.41 (4)3.132 (12)153 (4)
N4'1—H41E···F70.96 (5)1.94 (5)2.859 (7)158 (4)
N4'1—H41E···F6'0.96 (5)2.02 (5)2.96 (3)165 (4)
N1'—H1'···O53ii0.86 (4)1.92 (4)2.763 (6)166 (4)
O53—H53···F5iii0.93 (3)1.97 (4)2.855 (8)157 (5)
O53—H53···F5'iii0.93 (3)2.09 (5)2.886 (16)143 (5)
Symmetry codes: (i) x+1, y+2, z; (ii) x+3/2, y+1/2, z+1/2; (iii) x+2, y+2, z.
 

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