1-(4-Fluoro­phen­yl)biguanid-1-ium chloride

Tutughamiarso, M.; Bolte, M.

doi:10.1107/S1600536810037785

organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Page o2648

doi:10.1107/S1600536810037785

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1-(4-Fluorophenyl)biguanid-1-ium chloride

Maya Tutughamiarso ^a and Michael Bolte ^b ^*

^aInstitut für Organische Chemie und Chemische Biologie, Goethe-Universität Frankfurt, Max-von-Laue-Str. 7, 60438 Frankfurt/Main, Germany, and ^bInstitut für Anorganische Chemie, Goethe-Universität Frankfurt, Max-von-Laue-Str. 7, 60438 Frankfurt/Main, Germany
^*Correspondence e-mail: bolte@chemie.uni-frankfurt.de

(Received 15 September 2010; accepted 21 September 2010; online 30 September 2010)

The title compound, C₈H₁₁FN₅⁺·Cl⁻, crystallized with a monoprotonated 1-(4-fluorophenyl)biguanidinium cation and a chloride anion in the asymmetric unit. The biguanidium group is not planar [dihedral angle between the two CN₃ groups = 52.0 (1)°] and is rotated with respect to the phenyl group [τ = 54.3 (3)°]. In the crystal, N—H⋯N hydrogen-bonded centrosymmetric dimers are connected into ribbons, which are further stabilized by N—H⋯Cl interactions, forming a three-dimensional hydrogen-bonded network.

Related literature

For related structures, see: Dalpiaz et al. (1996 ); Portalone et al. (2004 ); LeBel et al. (2005 ). For hydrogen-bond motifs, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₈H₁₁FN₅⁺·Cl⁻
M_r = 231.67
Monoclinic, P 2₁ /n
a = 6.9954 (5) Å
b = 9.2187 (4) Å
c = 16.3149 (11) Å
β = 91.111 (5)°
V = 1051.93 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 173 K
0.40 × 0.40 × 0.20 mm

Data collection

STOE IPDS II two-circle-diffractometer
13661 measured reflections
1966 independent reflections
1605 reflections with I > 2σ(I)
R_int = 0.135

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.095
S = 1.03
1966 reflections
165 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Table 1
Selected bond lengths (Å)

N8—C5	1.429 (2)
N8—C9	1.356 (2)
N9—C9	1.326 (2)
N10—C9	1.332 (2)
N10—C11	1.339 (2)
N12—C11	1.338 (3)
N13—C11	1.325 (3)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N8—H8⋯Clⁱ	0.83 (2)	2.50 (2)	3.2758 (17)	156 (2)
N9—H91⋯Clⁱⁱ	0.88 (3)	2.47 (3)	3.3283 (18)	163 (2)
N9—H92⋯Clⁱ	0.83 (3)	2.46 (3)	3.2358 (19)	155 (3)
N12—H121⋯Cl	0.87 (3)	2.50 (3)	3.3212 (19)	157 (2)
N12—H122⋯Clⁱⁱⁱ	0.88 (3)	2.80 (3)	3.5463 (19)	143 (2)
N13—H131⋯Cl	0.87 (3)	2.58 (3)	3.384 (2)	154 (2)
N13—H132⋯N10^iv	0.87 (3)	2.35 (3)	3.177 (3)	160 (2)
Symmetry codes: (i) x, y-1, z; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (iv) -x+1, -y+1, -z+1.

Data collection: X-AREA (Stoe & Cie, 2001 ); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008 )and XP (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810037785/bx2308sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810037785/bx2308Isup2.hkl

checkCIF report

Comment top

1-(4-Fluorophenyl)biguanid hydrochloride crystallized with a monoprotonated 1-(4-fluorophenyl)biguanidinium cation and a chloride anion in the asymmetric unit. The protonation occurs at the N atom (N8) attached to the phenyl ring (Fig. 1). The biguanidium group is rotated with respect to the phenyl group by the rotation angle τ = 54.3 (3)° [the angle τ is defined as: τ = |ω1 + ω2 ± π|/2, the torsion angles ω1 and ω2 being respectively C4—C5—N8—C9 and C6—C5—N8—C9 (Dalpiaz et al., 1996)]. The planes defined by N8, C9, N9, N10 atoms and by N10, C11, N12, N13 atoms enclose a dihedral angle of 52.0 (1)°. Similar C—N bond lengths lead to the conclusion that the π- electron density is delocalized over the biguanidium group (Tab. 1). Two N—H···N hydrogen bonds stabilize a centrosymmetric dimer, which is further connected to a ribbon by R¹₂(3) N—H···Cl^- interactions (Bernstein et al., 1995; Fig. 2). The sixfold coordinated Cl^- anion forms another two N—H···Cl^- interactions leading to a three-dimensional hydrogen-bonded network.

Related literature top

For related structures, see: Dalpiaz et al. (1996); Portalone et al. (2004); LeBel et al. (2005). For hydrogen-bond motifs, see: Bernstein et al. (1995).

Experimental top

Single crystals of title compound were obtained by cocrystallization of the commercially available 1-(4-fluorophenyl)biguanid hydrochloride (2.6 mg) and propylthiouracil (1.1 mg) from methanol (50 µL) at room temperature.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA (Stoe & Cie, 2001); data reduction: X-AREA (Stoe & Cie, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008)and XP (Sheldrick, 2008); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. A perspective view of the title compound, showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. The dashed line indicates the N—H···Cl^- interactions.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

1-(4-Fluorophenyl)biguanid-1-ium chloride top

Crystal data top

C₈H₁₁FN₅⁺·Cl⁻	F(000) = 480
M_r = 231.67	D_x = 1.463 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 8763 reflections
a = 6.9954 (5) Å	θ = 3.3–26.0°
b = 9.2187 (4) Å	µ = 0.35 mm⁻¹
c = 16.3149 (11) Å	T = 173 K
β = 91.111 (5)°	Block, colourless
V = 1051.93 (11) Å³	0.40 × 0.40 × 0.20 mm
Z = 4

Data collection top

STOE IPDS II two-circle- diffractometer	1605 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.135
Graphite monochromator	θ_max = 25.6°, θ_min = 3.3°
ω scans	h = −8→8
13661 measured reflections	k = −11→11
1966 independent reflections	l = −19→19

Refinement top

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)] = 0.039	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.095	w = 1/[σ²(F_o²) + (0.0521P)²] where P = (F_o² + 2F_c²)/3
S = 1.03	(Δ/σ)_max < 0.001
1966 reflections	Δρ_max = 0.22 e Å⁻³
165 parameters	Δρ_min = −0.24 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.008 (2)

Crystal data top

C₈H₁₁FN₅⁺·Cl⁻	V = 1051.93 (11) Å³
M_r = 231.67	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.9954 (5) Å	µ = 0.35 mm⁻¹
b = 9.2187 (4) Å	T = 173 K
c = 16.3149 (11) Å	0.40 × 0.40 × 0.20 mm
β = 91.111 (5)°

Data collection top

STOE IPDS II two-circle- diffractometer	1605 reflections with I > 2σ(I)
13661 measured reflections	R_int = 0.135
1966 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.095	H atoms treated by a mixture of independent and constrained refinement
S = 1.03	Δρ_max = 0.22 e Å⁻³
1966 reflections	Δρ_min = −0.24 e Å⁻³
165 parameters

Special details top

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

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
F1	1.1564 (2)	0.20564 (19)	0.36588 (9)	0.0508 (4)
C2	1.0273 (3)	0.1954 (3)	0.42677 (13)	0.0300 (5)
C3	0.8876 (3)	0.0914 (2)	0.41942 (13)	0.0269 (4)
H3	0.8799	0.0298	0.3728	0.032*
C4	0.7580 (3)	0.0793 (2)	0.48238 (12)	0.0217 (4)
H4	0.6598	0.0083	0.4791	0.026*
C5	0.7707 (3)	0.16967 (19)	0.54979 (11)	0.0186 (4)
C6	0.9161 (3)	0.2732 (2)	0.55575 (13)	0.0240 (4)
H6	0.9266	0.3338	0.6027	0.029*
C7	1.0446 (3)	0.2868 (2)	0.49308 (15)	0.0307 (5)
H7	1.1430	0.3578	0.4957	0.037*
N8	0.6343 (2)	0.15622 (17)	0.61347 (10)	0.0210 (4)
H8	0.611 (3)	0.075 (3)	0.6328 (15)	0.021 (6)*
C9	0.5280 (3)	0.26846 (19)	0.64102 (12)	0.0184 (4)
N9	0.4158 (3)	0.2418 (2)	0.70383 (11)	0.0259 (4)
H91	0.325 (4)	0.301 (3)	0.7203 (17)	0.035 (7)*
H92	0.411 (4)	0.159 (4)	0.7249 (19)	0.043 (8)*
N10	0.5351 (2)	0.39359 (16)	0.60039 (10)	0.0212 (4)
C11	0.5124 (2)	0.5212 (2)	0.63811 (12)	0.0197 (4)
N12	0.5563 (3)	0.5444 (2)	0.71722 (11)	0.0243 (4)
H121	0.562 (4)	0.634 (3)	0.7336 (16)	0.035 (7)*
H122	0.632 (4)	0.480 (3)	0.7417 (17)	0.037 (7)*
N13	0.4489 (3)	0.63199 (19)	0.59356 (12)	0.0259 (4)
H131	0.448 (4)	0.718 (3)	0.6155 (17)	0.035 (7)*
H132	0.423 (4)	0.618 (3)	0.5418 (19)	0.036 (7)*
Cl	0.48546 (6)	0.89909 (5)	0.73525 (3)	0.02180 (17)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
F1	0.0368 (8)	0.0794 (11)	0.0369 (8)	−0.0062 (7)	0.0206 (6)	−0.0049 (7)
C2	0.0218 (10)	0.0440 (12)	0.0245 (11)	0.0048 (9)	0.0080 (8)	0.0022 (9)
C3	0.0235 (9)	0.0357 (11)	0.0214 (10)	0.0108 (9)	−0.0021 (7)	−0.0060 (9)
C4	0.0184 (8)	0.0200 (9)	0.0265 (10)	0.0043 (7)	−0.0029 (7)	−0.0025 (8)
C5	0.0211 (9)	0.0160 (8)	0.0186 (9)	0.0053 (7)	0.0014 (7)	0.0024 (7)
C6	0.0251 (10)	0.0210 (9)	0.0259 (10)	0.0010 (8)	−0.0004 (8)	−0.0029 (8)
C7	0.0255 (10)	0.0304 (11)	0.0362 (12)	−0.0037 (9)	0.0028 (9)	0.0013 (9)
N8	0.0296 (9)	0.0119 (7)	0.0218 (8)	0.0036 (6)	0.0079 (7)	0.0022 (7)
C9	0.0213 (9)	0.0155 (9)	0.0183 (9)	0.0025 (7)	−0.0002 (7)	−0.0011 (7)
N9	0.0322 (10)	0.0164 (8)	0.0295 (10)	0.0056 (7)	0.0122 (8)	0.0029 (7)
N10	0.0305 (8)	0.0148 (7)	0.0182 (8)	0.0048 (6)	0.0030 (6)	0.0008 (6)
C11	0.0180 (9)	0.0171 (9)	0.0243 (10)	0.0019 (7)	0.0045 (7)	0.0020 (7)
N12	0.0361 (10)	0.0155 (8)	0.0211 (9)	0.0034 (8)	−0.0017 (7)	−0.0006 (7)
N13	0.0392 (10)	0.0150 (8)	0.0234 (10)	0.0055 (7)	−0.0048 (7)	0.0006 (7)
Cl	0.0265 (3)	0.0155 (2)	0.0235 (3)	−0.00112 (17)	0.00391 (17)	0.00160 (17)

Geometric parameters (Å, º) top

F1—C2	1.359 (2)	N8—H8	0.83 (2)
C2—C3	1.373 (3)	N9—C9	1.326 (2)
C2—C7	1.375 (3)	N10—C9	1.332 (2)
C3—C4	1.388 (3)	N9—H91	0.88 (3)
C3—H3	0.9500	N9—H92	0.83 (3)
C4—C5	1.381 (3)	N10—C11	1.339 (2)
C4—H4	0.9500	N12—C11	1.338 (3)
C5—C6	1.397 (3)	N13—C11	1.325 (3)
N8—C5	1.429 (2)	N12—H121	0.87 (3)
C6—C7	1.380 (3)	N12—H122	0.88 (3)
C6—H6	0.9500	N13—H131	0.87 (3)
C7—H7	0.9500	N13—H132	0.87 (3)
N8—C9	1.356 (2)

F1—C2—C3	117.8 (2)	C9—N8—H8	116.9 (15)
F1—C2—C7	118.9 (2)	C5—N8—H8	119.4 (15)
C3—C2—C7	123.26 (19)	N9—C9—N10	125.00 (17)
C2—C3—C4	117.75 (19)	N9—C9—N8	116.83 (17)
C2—C3—H3	121.1	N10—C9—N8	118.04 (17)
C4—C3—H3	121.1	C9—N9—H91	124.2 (17)
C5—C4—C3	120.55 (18)	C9—N9—H92	121 (2)
C5—C4—H4	119.7	H91—N9—H92	113 (3)
C3—C4—H4	119.7	C9—N10—C11	121.78 (16)
C4—C5—C6	120.18 (17)	N13—C11—N12	118.33 (18)
C4—C5—N8	119.54 (17)	N13—C11—N10	117.81 (19)
C6—C5—N8	120.28 (17)	N12—C11—N10	123.82 (17)
C7—C6—C5	119.64 (19)	C11—N12—H121	117.2 (18)
C7—C6—H6	120.2	C11—N12—H122	117.0 (17)
C5—C6—H6	120.2	H121—N12—H122	118 (3)
C2—C7—C6	118.6 (2)	C11—N13—H131	119.0 (19)
C2—C7—H7	120.7	C11—N13—H132	118.7 (17)
C6—C7—H7	120.7	H131—N13—H132	122 (3)
C9—N8—C5	123.55 (16)

F1—C2—C3—C4	178.81 (18)	C5—C6—C7—C2	−1.1 (3)
C7—C2—C3—C4	0.2 (3)	C4—C5—N8—C9	−125.8 (2)
C2—C3—C4—C5	0.1 (3)	C6—C5—N8—C9	54.3 (3)
C3—C4—C5—C6	−0.9 (3)	C5—N8—C9—N9	−176.00 (18)
C3—C4—C5—N8	179.33 (16)	C5—N8—C9—N10	8.0 (3)
C4—C5—C6—C7	1.4 (3)	N9—C9—N10—C11	34.9 (3)
N8—C5—C6—C7	−178.78 (18)	N8—C9—N10—C11	−149.46 (18)
F1—C2—C7—C6	−178.25 (19)	C9—N10—C11—N13	−154.64 (18)
C3—C2—C7—C6	0.3 (3)	C9—N10—C11—N12	27.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N8—H8···Clⁱ	0.83 (2)	2.50 (2)	3.2758 (17)	156 (2)
N9—H91···Clⁱⁱ	0.88 (3)	2.47 (3)	3.3283 (18)	163 (2)
N9—H92···Clⁱ	0.83 (3)	2.46 (3)	3.2358 (19)	155 (3)
N12—H121···Cl	0.87 (3)	2.50 (3)	3.3212 (19)	157 (2)
N12—H122···Clⁱⁱⁱ	0.88 (3)	2.80 (3)	3.5463 (19)	143 (2)
N13—H131···Cl	0.87 (3)	2.58 (3)	3.384 (2)	154 (2)
N13—H132···N10^iv	0.87 (3)	2.35 (3)	3.177 (3)	160 (2)

Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, y−1/2, −z+3/2; (iii) −x+3/2, y−1/2, −z+3/2; (iv) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₈H₁₁FN₅⁺·Cl⁻
M_r	231.67
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	6.9954 (5), 9.2187 (4), 16.3149 (11)
β (°)	91.111 (5)
V (Å³)	1051.93 (11)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.35
Crystal size (mm)	0.40 × 0.40 × 0.20

Data collection
Diffractometer	STOE IPDS II two-circle- diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	13661, 1966, 1605
R_int	0.135
(sin θ/λ)_max (Å⁻¹)	0.608

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.095, 1.03
No. of reflections	1966
No. of parameters	165
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.22, −0.24

Computer programs: X-AREA (Stoe & Cie, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Mercury (Macrae et al., 2008)and XP (Sheldrick, 2008), publCIF (Westrip, 2010).

Selected bond lengths (Å) top

N8—C5	1.429 (2)	N10—C11	1.339 (2)
N8—C9	1.356 (2)	N12—C11	1.338 (3)
N9—C9	1.326 (2)	N13—C11	1.325 (3)
N10—C9	1.332 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N8—H8···Clⁱ	0.83 (2)	2.50 (2)	3.2758 (17)	156 (2)
N9—H91···Clⁱⁱ	0.88 (3)	2.47 (3)	3.3283 (18)	163 (2)
N9—H92···Clⁱ	0.83 (3)	2.46 (3)	3.2358 (19)	155 (3)
N12—H121···Cl	0.87 (3)	2.50 (3)	3.3212 (19)	157 (2)
N12—H122···Clⁱⁱⁱ	0.88 (3)	2.80 (3)	3.5463 (19)	143 (2)
N13—H131···Cl	0.87 (3)	2.58 (3)	3.384 (2)	154 (2)
N13—H132···N10^iv	0.87 (3)	2.35 (3)	3.177 (3)	160 (2)

Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, y−1/2, −z+3/2; (iii) −x+3/2, y−1/2, −z+3/2; (iv) −x+1, −y+1, −z+1.

Acknowledgements

We thank Professor Dr E. Egert (Goethe-Universität Frankfurt, Germany) for helpful discussions.

References

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