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Acta Cryst. (2007). E63, o2966
https://doi.org/10.1107/S1600536807015656
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Hydrogen-bonding patterns in pyrimethamine tetra­fluoro­borate

K. Balasubramani, P. T. Muthiah and D. E. Lynch
The title compound [systematic name: 2,4-diamino-5-(4-chloro­phen­yl)-6-ethyl­pyrimdinium tetra­fluoro­borate], C12H14ClN4+·BF4−, is isomorphous with pyrimethamine perchlorate. The pyrimethamine (PMN) mol­ecule is protonated at one of the pyrimidine N atoms. The protonated N atom and 2-amino group of the PMN cation inter­act with the tetra­fluoro­borate anion through a pair of N—H...F hydrogen bonds [graph set R22(8)]. The inversion-related PMN cations are linked through a pair of N—H...N hydrogen bonds. In addition to the base pairing, the F atoms bridge the 2-amino and 4-amino groups on either side of the paired bases, resulting in a complementary DADA array.
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Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807015656/bt2329sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807015656/bt2329Isup2.hkl
Contains datablock I

CCDC reference: 651480

checkCIF report

Key indicators

  • Single-crystal X-ray study
  • T = 120 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.045
  • wR factor = 0.126
  • Data-to-parameter ratio = 17.2

checkCIF/PLATON results

No syntax errors found




Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         B1


   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check
Comment top

Pyrimethamine [2,4-diamino-5-(p-chlorophenyl)-6-ethylpyrimidine] is an antifolate drug used in anti-malarial chemotherapy (Olliaro, 2001). The crystal structure of pyrimethamine (PMN) itself has been reported from our laboratory (Sethuraman & Muthiah, 2002). The present study has been undertaken to explore the hydrogen bonding patterns involving the PMN cation in a variety of environments. The crystal structures of trimethoprim tetrafluoridoborate (Hemamalini et al., 2005) and PMN dinitrate (Balasubramani et al., 2005) have also been reported from our laboratory.

The asymmetric unit of (I) contains a protonated pyrimethamine (PMN) cation and a tetrafluoridoborate anion (FLUB) (Fig.1). The pyrimethamine molecule is protonated at atom N1 of the pyrimidine moiety, which is evident from the increase in the internal angle at protonated N1 (C2—N1—C6 = 121.99 (14) Å) compared with that at unprotanated atom N3(C2—N3—C4 = 117.90 (15) Å). The dihedral angle between the pyrimidine and benzene planes is 67.79 (8) Å. The torsion angle (C5—C6—C7—C8) is 106.3 (2) Å. The distorted tetrahedral BF4 ion has typical B—F distances.

The protonated atom N1 and the 2-amino group is hydrogen bonded to the F atoms of the tetrafluoridoborate anions (F3 & F4) leading to the formation of a fork-like hydrogen bonding pattern with graph-set notation R22(8) (Etter, 1990; Bernstein et al., 1995). The R22(8) motif is frequently observed in aminopyrimidine carboxylate salts (Lynch & Jones, 2004). Here the tetrafluoridoborate anion mimics the role of the carboxylate group. The PMN cations are centrosymmetrically paired through N—H···N hydrogen bonds involving the 4-amino group and the N3 atom of the unprotonated pyrimidine to form the ring motif R22(8). The pairs further interact with tetrafluoridoborate anion through N—H···F hydrogen bonds. The fluorine atom (F3) connects the 2-amino and 4-amino groups on either side of the paired PMN cation, forming an eight membered hydrogen bonded ring motif with graph set R32(8). This pattern is called a complementary DADA (D is donor and A is acceptor) array of quadruple hydrogen bonds (Fig.2). The DADA array of cyclic hydrogen-bonded ring motifs can be represented by graph set notations R32(8), R22(8) and R32(8). This pattern is similar to that reported in PMN carboxylates (Stanley et al., 2005).

The present crystal structure is isomorphous with pyrimethamine perchlorate (Sethuraman, 2002). This is very interesting from crystal engineering point of view. Since both the anions, (perchlorate and tetrafluoridoborate) have a tetrahedral geometry and similar hydrogen bonding capability (hydrogen bond acceptors). Trimethoprim perchlorate (Muthiah et al., 2002) and trimethoprim tetrafluoridoborate (Hemamalini et al., 2005) are also isomorphous.

Related literature top

For related literature, see: Balasubramani et al. (2005); Bernstein et al. (1995); Etter (1990); Hemamalini et al. (2005); Lynch & Jones (2004); Muthiah et al. (2002); Olliaro (2001); Sethuraman & Muthiah (2002); Sethuraman (2002); Stanley et al. (2005).

Experimental top

Hot methanolic solution of pyrimethamine (30 mg, Aldrich), and tetrafluoridoboric acid (220 mg of 40% solution; Aldrich) were mixed in a 1:2 molar ratio. The resulting solution was warmed over a water bath for a few minutes and then kept at room temperature for crystallization. After a few days crystals appeared from the mother liquor.

Refinement top

All the H atoms were fixed geometrically and were refined using a riding model. with N—H = 0.86Å and C—H ranging from 0.93 to 0.97Å and with Uiso(H)=1.2Ueq(C,N).

Structure description top

Pyrimethamine [2,4-diamino-5-(p-chlorophenyl)-6-ethylpyrimidine] is an antifolate drug used in anti-malarial chemotherapy (Olliaro, 2001). The crystal structure of pyrimethamine (PMN) itself has been reported from our laboratory (Sethuraman & Muthiah, 2002). The present study has been undertaken to explore the hydrogen bonding patterns involving the PMN cation in a variety of environments. The crystal structures of trimethoprim tetrafluoridoborate (Hemamalini et al., 2005) and PMN dinitrate (Balasubramani et al., 2005) have also been reported from our laboratory.

The asymmetric unit of (I) contains a protonated pyrimethamine (PMN) cation and a tetrafluoridoborate anion (FLUB) (Fig.1). The pyrimethamine molecule is protonated at atom N1 of the pyrimidine moiety, which is evident from the increase in the internal angle at protonated N1 (C2—N1—C6 = 121.99 (14) Å) compared with that at unprotanated atom N3(C2—N3—C4 = 117.90 (15) Å). The dihedral angle between the pyrimidine and benzene planes is 67.79 (8) Å. The torsion angle (C5—C6—C7—C8) is 106.3 (2) Å. The distorted tetrahedral BF4 ion has typical B—F distances.

The protonated atom N1 and the 2-amino group is hydrogen bonded to the F atoms of the tetrafluoridoborate anions (F3 & F4) leading to the formation of a fork-like hydrogen bonding pattern with graph-set notation R22(8) (Etter, 1990; Bernstein et al., 1995). The R22(8) motif is frequently observed in aminopyrimidine carboxylate salts (Lynch & Jones, 2004). Here the tetrafluoridoborate anion mimics the role of the carboxylate group. The PMN cations are centrosymmetrically paired through N—H···N hydrogen bonds involving the 4-amino group and the N3 atom of the unprotonated pyrimidine to form the ring motif R22(8). The pairs further interact with tetrafluoridoborate anion through N—H···F hydrogen bonds. The fluorine atom (F3) connects the 2-amino and 4-amino groups on either side of the paired PMN cation, forming an eight membered hydrogen bonded ring motif with graph set R32(8). This pattern is called a complementary DADA (D is donor and A is acceptor) array of quadruple hydrogen bonds (Fig.2). The DADA array of cyclic hydrogen-bonded ring motifs can be represented by graph set notations R32(8), R22(8) and R32(8). This pattern is similar to that reported in PMN carboxylates (Stanley et al., 2005).

The present crystal structure is isomorphous with pyrimethamine perchlorate (Sethuraman, 2002). This is very interesting from crystal engineering point of view. Since both the anions, (perchlorate and tetrafluoridoborate) have a tetrahedral geometry and similar hydrogen bonding capability (hydrogen bond acceptors). Trimethoprim perchlorate (Muthiah et al., 2002) and trimethoprim tetrafluoridoborate (Hemamalini et al., 2005) are also isomorphous.

For related literature, see: Balasubramani et al. (2005); Bernstein et al. (1995); Etter (1990); Hemamalini et al. (2005); Lynch & Jones (2004); Muthiah et al. (2002); Olliaro (2001); Sethuraman & Muthiah (2002); Sethuraman (2002); Stanley et al. (2005).

Computing details top

Data collection: COLLECT (Hooft, 1998); cell refinement: DENZO (Otwinowski & Minor, 1997) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON.

Figures top
[Figure 1] Fig. 1. A view of (I), with the atom-labelling scheme and 50% probability displacement ellipsoids
[Figure 2] Fig. 2. A view of the hydrogen-bonded supramolecular chain in (I) Symmetry codes:(i)2 - x,y - 1/2,3/2 - z;(ii)1 - x,-y,1 - z;(iii)x - 1,1/2 - y,z - 1/2
'2,4-diamino-5-(p-chlorophenyl)-6-ethylpyrimidinium tetrafluoridoborate' top
Crystal data top
C12H14ClN4+·BF4−F(000) = 688
Mr = 336.53Dx = 1.491 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 3445 reflections
a = 8.3042 (2) Åθ = 2.1–27.6°
b = 13.2529 (4) ŵ = 0.30 mm−1
c = 13.7368 (4) ÅT = 120 K
β = 97.326 (2)°Block, colourless
V = 1499.46 (7) Å30.25 × 0.20 × 0.15 mm
Z = 4
Data collection top
Bruker–Nonius KappaCCD
diffractometer		3436 independent reflections
Radiation source: Bruker–Nonius FR591 rotating anode2654 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
Detector resolution: 9.091 pixels mm-1θmax = 27.6°, θmin = 2.1°
φ&ω scansh = −10→10
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		k = −16→17
Tmin = 0.929, Tmax = 0.957l = −17→15
13025 measured reflections
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)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.0697P)2 + 0.5139P]
where P = (Fo2 + 2Fc2)/3
3436 reflections(Δ/σ)max < 0.001
200 parametersΔρmax = 0.51 e Å−3
0 restraintsΔρmin = −0.44 e Å−3
Crystal data top
C12H14ClN4+·BF4−V = 1499.46 (7) Å3
Mr = 336.53Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.3042 (2) ŵ = 0.30 mm−1
b = 13.2529 (4) ÅT = 120 K
c = 13.7368 (4) Å0.25 × 0.20 × 0.15 mm
β = 97.326 (2)°
Data collection top
Bruker–Nonius KappaCCD
diffractometer		3436 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)		2654 reflections with I > 2σ(I)
Tmin = 0.929, Tmax = 0.957Rint = 0.033
13025 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.126H-atom parameters constrained
S = 1.07Δρmax = 0.51 e Å−3
3436 reflectionsΔρmin = −0.44 e Å−3
200 parameters
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All e.s.d.'s are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl10.20890 (6)0.30756 (4)−0.01027 (3)0.0335 (2)
N10.81272 (17)0.24830 (10)0.51009 (10)0.0187 (4)
N20.86615 (18)0.13132 (11)0.63404 (11)0.0229 (4)
N30.67182 (17)0.09490 (11)0.50368 (11)0.0180 (4)
N40.47915 (17)0.06149 (11)0.37458 (11)0.0204 (4)
C20.7825 (2)0.15724 (13)0.54826 (13)0.0181 (5)
C40.5906 (2)0.12414 (12)0.41709 (12)0.0167 (5)
C50.6199 (2)0.21960 (12)0.37222 (13)0.0169 (5)
C60.7337 (2)0.28059 (12)0.42153 (13)0.0176 (5)
C70.7823 (2)0.38326 (13)0.39047 (14)0.0223 (5)
C80.7174 (3)0.46708 (14)0.45136 (16)0.0309 (6)
C90.5242 (2)0.24697 (13)0.27664 (12)0.0178 (5)
C100.4071 (2)0.32305 (14)0.27008 (14)0.0227 (5)
C110.3121 (2)0.34435 (14)0.18187 (14)0.0245 (5)
C120.3328 (2)0.28714 (14)0.09990 (14)0.0231 (5)
C130.4498 (2)0.21222 (14)0.10388 (13)0.0227 (5)
C140.5453 (2)0.19232 (13)0.19203 (14)0.0213 (5)
F11.15948 (13)0.43382 (8)0.76949 (8)0.0282 (3)
F20.88796 (16)0.45512 (11)0.73877 (14)0.0630 (6)
F30.99045 (17)0.29803 (9)0.77354 (10)0.0464 (5)
F41.01944 (16)0.37203 (10)0.62986 (9)0.0469 (5)
B11.0123 (3)0.38982 (16)0.73014 (16)0.0249 (6)
H10.883500.287200.542200.0220*
H2A0.848300.074200.660400.0270*
H2B0.937900.171700.663000.0270*
H4A0.461400.005100.402300.0240*
H4B0.424400.077100.319200.0240*
H7A0.741500.393300.321800.0270*
H7B0.899800.387300.397200.0270*
H8A0.600800.465800.442000.0460*
H8B0.754600.531300.430800.0460*
H8C0.755800.456800.519600.0460*
H100.392500.360100.325800.0270*
H110.235900.396100.177800.0290*
H130.464100.175600.047900.0270*
H140.624100.142200.195000.0260*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0249 (3)0.0522 (3)0.0218 (3)−0.0043 (2)−0.0031 (2)0.0113 (2)
N10.0171 (7)0.0176 (7)0.0205 (8)−0.0039 (6)−0.0016 (6)−0.0009 (6)
N20.0238 (8)0.0214 (7)0.0215 (8)−0.0038 (6)−0.0051 (6)0.0029 (6)
N30.0169 (7)0.0174 (7)0.0192 (7)−0.0004 (6)0.0000 (6)0.0006 (6)
N40.0220 (8)0.0178 (7)0.0199 (8)−0.0042 (6)−0.0026 (6)0.0027 (6)
C20.0164 (8)0.0181 (8)0.0197 (9)0.0006 (7)0.0020 (7)−0.0002 (7)
C40.0155 (8)0.0165 (8)0.0185 (8)0.0018 (6)0.0033 (6)−0.0009 (6)
C50.0167 (8)0.0169 (8)0.0174 (8)0.0009 (6)0.0030 (7)0.0005 (6)
C60.0167 (8)0.0171 (8)0.0194 (8)0.0016 (6)0.0039 (7)0.0014 (6)
C70.0235 (9)0.0196 (8)0.0237 (9)−0.0036 (7)0.0023 (7)0.0029 (7)
C80.0388 (11)0.0187 (9)0.0359 (11)−0.0012 (8)0.0069 (9)0.0018 (8)
C90.0169 (8)0.0174 (8)0.0191 (9)−0.0028 (6)0.0018 (7)0.0028 (7)
C100.0231 (9)0.0231 (9)0.0221 (9)0.0010 (7)0.0031 (7)−0.0004 (7)
C110.0207 (9)0.0249 (9)0.0274 (10)0.0020 (7)0.0009 (7)0.0053 (8)
C120.0190 (9)0.0299 (10)0.0198 (9)−0.0062 (7)0.0003 (7)0.0072 (7)
C130.0228 (9)0.0285 (9)0.0173 (9)−0.0053 (8)0.0040 (7)−0.0001 (7)
C140.0197 (9)0.0218 (8)0.0228 (9)−0.0008 (7)0.0039 (7)0.0009 (7)
F10.0239 (6)0.0281 (6)0.0297 (6)−0.0050 (4)−0.0072 (5)−0.0034 (5)
F20.0286 (7)0.0495 (9)0.1086 (14)0.0075 (6)0.0004 (8)−0.0334 (9)
F30.0533 (8)0.0382 (7)0.0464 (9)−0.0196 (6)0.0009 (7)0.0058 (6)
F40.0515 (8)0.0565 (9)0.0311 (7)−0.0261 (7)−0.0013 (6)−0.0129 (6)
B10.0215 (10)0.0245 (10)0.0280 (12)−0.0011 (8)−0.0001 (9)−0.0071 (9)
Geometric parameters (Å, º) top
Cl1—C121.7393 (19)C5—C61.357 (2)
F1—B11.399 (3)C6—C71.497 (2)
F2—B11.364 (3)C7—C81.529 (3)
F3—B11.377 (2)C9—C101.396 (2)
F4—B11.406 (3)C9—C141.399 (2)
N1—C61.375 (2)C10—C111.388 (3)
N1—C21.352 (2)C11—C121.386 (3)
N2—C21.334 (2)C12—C131.385 (3)
N3—C21.326 (2)C13—C141.386 (3)
N3—C41.347 (2)C7—H7A0.9700
N4—C41.323 (2)C7—H7B0.9698
N1—H10.8601C8—H8A0.9605
N2—H2A0.8601C8—H8B0.9601
N2—H2B0.8598C8—H8C0.9606
N4—H4A0.8600C10—H100.9302
N4—H4B0.8603C11—H110.9300
C4—C51.441 (2)C13—H130.9297
C5—C91.490 (2)C14—H140.9297
Cl1···F3i3.2791 (14)C14···N43.154 (2)
Cl1···N1ii3.4183 (15)C2···H4Axi3.0892
Cl1···N4iii3.3846 (15)C4···H4Axi3.0901
Cl1···C4iii3.5593 (17)C6···H13vii3.0584
Cl1···H1ii3.1457C8···H12.9502
F1···N4iv2.8561 (18)C9···H4B2.4941
F1···C7v3.348 (2)C9···H7A2.6677
F1···N2vi2.9537 (18)C10···H7A2.9291
F3···C6vii3.297 (2)C11···H2Bii3.0924
F3···Cl1viii3.2791 (14)C13···H8Bxiii2.9412
F3···N23.019 (2)C14···H4B2.6151
F4···C8v3.345 (3)B1···H2Avi3.0213
F4···N12.7609 (19)B1···H12.9924
F1···H2Avi2.0997H1···C82.9502
F1···H7Av2.7859H1···B12.9924
F1···H4Biv2.2235H1···F41.9083
F2···H11ix2.5612H1···Cl1iv3.1457
F2···H14vii2.5476H1···H2B2.2604
F3···H2B2.2650H1···H7B2.4113
F4···H11.9083H1···H8C2.4878
F4···H2B2.7916H2A···B1x3.0213
F4···H8Bv2.5011H2A···H7Avii2.5277
F4···H8C2.7393H2A···F1x2.0997
N1···Cl1iv3.4183 (15)H2B···F32.2650
N1···F42.7609 (19)H2B···F42.7916
N2···F33.019 (2)H2B···H12.2604
N2···F1x2.9537 (18)H2B···C11iv3.0924
N3···N4xi3.033 (2)H4A···C2xi3.0892
N4···Cl1vii3.3846 (15)H4A···C4xi3.0901
N4···N3xi3.033 (2)H4A···N3xi2.2389
N4···C143.154 (2)H4B···C92.4941
N4···F1ii2.8561 (18)H4B···C142.6151
N1···H8C2.8092H4B···F1ii2.2235
N2···H7Avii2.9174H7A···N2iii2.9174
N3···H4Axi2.2389H7A···C92.6677
C2···C14vii3.570 (2)H7A···H2Aiii2.5277
C2···C13vii3.428 (2)H7A···F1v2.7859
C4···Cl1vii3.5593 (17)H7A···C102.9291
C6···F3iii3.297 (2)H7B···H12.4113
C7···C103.430 (2)H8B···C13xii2.9412
C7···F1v3.348 (2)H8B···F4v2.5011
C8···F4v3.345 (3)H8C···F42.7393
C8···C13xii3.576 (3)H8C···N12.8092
C10···C73.430 (2)H8C···H12.4878
C13···C8xiii3.576 (3)H11···F2ix2.5612
C13···C2iii3.428 (2)H13···C6iii3.0584
C14···C2iii3.570 (2)H14···F2iii2.5476
C2—N1—C6121.99 (14)Cl1—C12—C13118.68 (14)
C2—N3—C4117.90 (15)C11—C12—C13121.26 (17)
C2—N1—H1118.99C12—C13—C14119.42 (17)
C6—N1—H1119.02C9—C14—C13120.60 (16)
C2—N2—H2A120.01C6—C7—H7A109.18
C2—N2—H2B120.03C6—C7—H7B109.12
H2A—N2—H2B119.97C8—C7—H7A109.18
H4A—N4—H4B119.96C8—C7—H7B109.16
C4—N4—H4A119.99H7A—C7—H7B107.91
C4—N4—H4B120.04C7—C8—H8A109.48
N1—C2—N3121.94 (16)C7—C8—H8B109.51
N2—C2—N3119.97 (16)C7—C8—H8C109.54
N1—C2—N2118.09 (15)H8A—C8—H8B109.45
N3—C4—N4116.91 (15)H8A—C8—H8C109.37
N3—C4—C5122.49 (15)H8B—C8—H8C109.49
N4—C4—C5120.59 (15)C9—C10—H10119.41
C4—C5—C6117.00 (16)C11—C10—H10119.46
C4—C5—C9119.35 (15)C10—C11—H11120.60
C6—C5—C9123.64 (15)C12—C11—H11120.56
N1—C6—C5118.66 (15)C12—C13—H13120.29
N1—C6—C7114.81 (14)C14—C13—H13120.28
C5—C6—C7126.52 (16)C9—C14—H14119.69
C6—C7—C8112.20 (15)C13—C14—H14119.71
C5—C9—C10121.44 (15)F1—B1—F2109.61 (16)
C5—C9—C14119.78 (15)F1—B1—F3110.97 (17)
C10—C9—C14118.70 (16)F1—B1—F4107.73 (17)
C9—C10—C11121.13 (17)F2—B1—F3112.33 (19)
C10—C11—C12118.84 (16)F2—B1—F4108.57 (18)
Cl1—C12—C11120.05 (14)F3—B1—F4107.48 (16)
C6—N1—C2—N2179.16 (15)C4—C5—C6—N1−0.2 (2)
C6—N1—C2—N3−1.8 (3)C4—C5—C9—C14−66.9 (2)
C2—N1—C6—C51.3 (2)C6—C5—C9—C10−69.2 (2)
C2—N1—C6—C7−179.94 (15)C6—C5—C9—C14114.1 (2)
C4—N3—C2—N11.1 (2)C5—C6—C7—C8106.3 (2)
C4—N3—C2—N2−179.85 (15)N1—C6—C7—C8−72.4 (2)
C2—N3—C4—N4−179.05 (15)C5—C9—C10—C11−176.36 (16)
C2—N3—C4—C50.0 (2)C14—C9—C10—C110.4 (3)
N4—C4—C5—C9−0.5 (2)C5—C9—C14—C13175.67 (16)
N3—C4—C5—C6−0.4 (2)C10—C9—C14—C13−1.1 (3)
N3—C4—C5—C9−179.53 (15)C9—C10—C11—C121.3 (3)
N4—C4—C5—C6178.56 (16)C10—C11—C12—C13−2.4 (3)
C9—C5—C6—N1178.87 (15)C10—C11—C12—Cl1176.78 (14)
C9—C5—C6—C70.2 (3)C11—C12—C13—C141.6 (3)
C4—C5—C9—C10109.79 (19)Cl1—C12—C13—C14−177.51 (14)
C4—C5—C6—C7−178.82 (16)C12—C13—C14—C90.1 (3)
Symmetry codes: (i) x−1, y, z−1; (ii) x−1, −y+1/2, z−1/2; (iii) x, −y+1/2, z−1/2; (iv) x+1, −y+1/2, z+1/2; (v) −x+2, −y+1, −z+1; (vi) −x+2, y+1/2, −z+3/2; (vii) x, −y+1/2, z+1/2; (viii) x+1, y, z+1; (ix) −x+1, −y+1, −z+1; (x) −x+2, y−1/2, −z+3/2; (xi) −x+1, −y, −z+1; (xii) −x+1, y+1/2, −z+1/2; (xiii) −x+1, y−1/2, −z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···F40.861.912.7609 (19)171
N2—H2A···F1x0.862.102.9537 (18)172
N2—H2B···F30.862.273.019 (2)146
N4—H4A···N3xi0.862.243.033 (2)154
N4—H4B···F1ii0.862.222.8561 (18)130
C8—H8B···F4v0.962.503.345 (3)147
C14—H14···F2iii0.932.553.444 (2)162
Symmetry codes: (ii) x−1, −y+1/2, z−1/2; (iii) x, −y+1/2, z−1/2; (v) −x+2, −y+1, −z+1; (x) −x+2, y−1/2, −z+3/2; (xi) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formulaC12H14ClN4+·BF4−
Mr336.53
Crystal system, space groupMonoclinic, P21/c
Temperature (K)120
a, b, c (Å)8.3042 (2), 13.2529 (4), 13.7368 (4)
β (°) 97.326 (2)
V (Å3)1499.46 (7)
Z4
Radiation typeMo Kα
µ (mm−1)0.30
Crystal size (mm)0.25 × 0.20 × 0.15
Data collection
DiffractometerBruker–Nonius KappaCCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.929, 0.957
No. of measured, independent and
observed [I > 2σ(I)] reflections		13025, 3436, 2654
Rint0.033
(sin θ/λ)max (Å−1)0.651
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.126, 1.07
No. of reflections3436
No. of parameters200
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.51, −0.44

Computer programs: COLLECT (Hooft, 1998), DENZO (Otwinowski & Minor, 1997) and COLLECT, DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), PLATON.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···F40.861.912.7609 (19)171
N2—H2A···F1i0.862.102.9537 (18)172
N2—H2B···F30.862.273.019 (2)146
N4—H4A···N3ii0.862.243.033 (2)154
N4—H4B···F1iii0.862.222.8561 (18)130
C8—H8B···F4iv0.962.503.345 (3)147
C14—H14···F2v0.932.553.444 (2)162
Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) −x+1, −y, −z+1; (iii) x−1, −y+1/2, z−1/2; (iv) −x+2, −y+1, −z+1; (v) x, −y+1/2, z−1/2.
 

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