Synthesis, structural elucidation, characterization and theoretical DFT study of 1-(o-tol­yl)biguanidium chloride

Kaabi, K.; Klai, K.; Wenger, E.; Jelsch, C.; Lefebvre, F.; Nasr, C.B.

doi:10.1107/S2053229620006336

Synthesis, structural elucidation, characterization and theoretical DFT study of 1-(o-tolyl)biguanidium chloride

K. Kaabi, K. Klai, E. Wenger, C. Jelsch, F. Lefebvre and C. B. Nasr

The structure of the new salt 1-(o-tolyl)biguanidium chloride, C₉H₁₄N₅⁺·Cl⁻, has been determined by single-crystal X-ray diffraction. The salt crystallizes in the monoclinic space group C2/c. In this structure, the chloride and biguanidium hydrophilic ions are mostly connected to each other via N—H

N and N—H

Cl hydrogen bonds to form layers parallel to the ab plane around y = $1 \over 3$ and y = $2 \over 3$ . The 2-methylbenzyl groups form layers between these layers around y = 0 and y = $1 \over 2$ , with the methyl group forming C—H

π interactions with the aromatic ring. Intermolecular interactions on the Hirshfeld surface were investigated in terms of contact enrichment and electrostatic energy, and confirm the role of strong hydrogen bonds along with hydrophobic interactions. A correlation between electrostatic energy and contact enrichment is found only for the strongly attractive (N—H

Cl⁻) and repulsive contacts. Electrostatic energies between ions reveal that the interacting biguanidium cation pairs are repulsive and that the crystal is maintained by attractive cation

Cl⁻ dimers. The vibrational absorption bands were identified by IR spectroscopy.

Keywords: hydrogen bonding; IR spectroscopy; crystal structure; Hirshfeld surface; contact enrichment ratio; electrostatic potential; biguanidium.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2053229620006336/ku3263sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S2053229620006336/ku3263Isup2.hkl Contains datablock I
	Portable Document Format (PDF) file https://doi.org/10.1107/S2053229620006336/ku3263sup3.pdf IR spectroscopy information and spectra, plus additional packing diagrams
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2053229620006336/ku3263Isup4.cml Supplementary material

CCDC reference: 1877569

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2015); cell refinement: CrysAlis PRO (Rigaku OD, 2015); data reduction: CrysAlis PRO (Rigaku OD, 2015); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL (Sheldrick, 2008, 2015b) and MoPro (Jelsch et al., 2005); molecular graphics: DIAMOND (Brandenburg, 1998).

2-[Amino(iminiumyl)methyl]-1-(2-methylphenyl)guanidine chloride top

Crystal data top

C₉H₁₄N₅⁺·Cl⁻	F(000) = 960
M_r = 227.68	D_x = 1.293 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 8409 reflections
a = 18.4640 (7) Å	θ = 3.7–32.4°
b = 13.7652 (6) Å	µ = 0.30 mm⁻¹
c = 9.3158 (3) Å	T = 110 K
β = 98.847 (4)°	Prism, white
V = 2339.54 (16) Å³	0.23 × 0.15 × 0.04 mm
Z = 8

Data collection top

Agilent SuperNova Dual Source diffractometer with an Atlas detector	3970 independent reflections
Radiation source: fine-focus sealed tube	2840 reflections with > 2.0σ(I)
Mirror monochromator	R_int = 0.063
ω scans	θ_max = 31.9°, θ_min = 3.7°
Absorption correction: multi-scan (CrysAlis PRO; Rigaku OD, 2015)	h = −27→27
T_min = 0.850, T_max = 1.000	k = −19→20
29979 measured reflections	l = −13→13

Refinement top

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)] = 0.057	Hydrogen site location: difference Fourier map
wR(F²) = 0.065	All H-atom parameters refined
S = 0.97	w = 1/[2.1*σ²(F_o²)]
3970 reflections	(Δ/σ)_max = −0.002
192 parameters	Δρ_max = 0.64 e Å⁻³
47 restraints	Δρ_min = −0.40 e Å⁻³

Special details top

Refinement. Refinement of F² against reflections. The threshold expression of F² > 2sigma(F²) is used for calculating R-factors(gt) 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.

A single crystal was carefully selected under a polarizing microscope in order to perform its structural analysis. X-ray diffraction data were collected on a SuperNova (Dual, Cu at zero Atlas) diffractometer at 110 K, using graphite-monochromated Mo Kα = 0.71073 Å radiation. The structure was solved using a direct method with the SHELXT program The structure was refined using the full-matrix least-squares procedure using the SHELXL program (Sheldrick, 2008; Sheldrick 2015). The drawings were made with Diamond (Brandenburg, 1998). Crystal data and experimental parameters used for the intensity data collection are summarized in Table 1.

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

	x	y	z	U_iso*/U_eq
Cl	0.414821 (13)	0.88578 (2)	−0.04433 (3)	0.01974 (2)
N2	0.33610 (4)	0.78604 (6)	0.42786 (10)	0.01757 (7)
N3	0.30580 (4)	0.81756 (7)	0.65219 (9)	0.01997 (8)
H1	0.3193 (6)	0.8406 (9)	0.756 (10)	0.0244 (2)*
H2	0.257 (10)	0.7853 (8)	0.6192 (12)	0.0244 (2)*
N4	0.36565 (5)	0.75392 (7)	0.20089 (10)	0.01987 (8)
H4	0.3785 (6)	0.7843 (8)	0.109 (10)	0.0244 (2)*
N5	0.39543 (5)	0.90299 (7)	0.29973 (9)	0.02277 (8)
H3	0.3896 (7)	0.957 (10)	0.3710 (9)	0.0280 (3)*
H5	0.4122 (6)	0.9204 (8)	0.204 (10)	0.0279 (3)*
N6	0.41948 (5)	0.86368 (8)	0.61097 (9)	0.02504 (8)
H6	0.4310 (6)	0.8816 (9)	0.718 (10)	0.0302 (3)*
H7	0.460 (10)	0.8615 (10)	0.5498 (9)	0.0302 (3)*
C7	0.35465 (5)	0.82389 (8)	0.56102 (12)	0.01720 (8)
C8	0.36674 (5)	0.81496 (8)	0.31484 (12)	0.01704 (8)
C9	0.35099 (6)	0.65283 (8)	0.20189 (13)	0.02048 (9)
C1	0.39317 (6)	0.59042 (9)	0.29875 (14)	0.02626 (11)
C2	0.29635 (6)	0.61761 (8)	0.09368 (13)	0.02776 (11)
H8	0.2707 (5)	0.667 (10)	0.0104 (8)	0.0335 (3)*
C3	0.28159 (7)	0.51917 (10)	0.08305 (15)	0.03686 (13)
H9	0.240 (10)	0.4912 (5)	−0.0010 (9)	0.0449 (4)*
C4	0.37666 (7)	0.49095 (9)	0.28582 (15)	0.03765 (14)
H14	0.410 (10)	0.4425 (4)	0.3608 (9)	0.0464 (5)*
C6	0.45508 (6)	0.62439 (8)	0.40909 (13)	0.03502 (12)
H10	0.4772 (4)	0.692 (10)	0.3770 (9)	0.0523 (5)*
H11	0.499 (10)	0.5723 (4)	0.4226 (10)	0.0523 (5)*
H12	0.4374 (4)	0.6349 (7)	0.513 (10)	0.0522 (5)*
C5	0.32202 (8)	0.45601 (8)	0.17956 (18)	0.04085 (15)
H13	0.3110 (6)	0.379 (10)	0.1731 (12)	0.0506 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl	0.02111 (12)	0.02624 (15)	0.01251 (14)	0.00064 (10)	0.00457 (9)	0.00235 (11)
N2	0.0193 (4)	0.0218 (5)	0.0124 (5)	−0.0053 (4)	0.0050 (3)	−0.0019 (4)
N3	0.0189 (4)	0.0286 (6)	0.0135 (5)	−0.0043 (4)	0.0061 (4)	−0.0024 (4)
N4	0.0276 (5)	0.0197 (5)	0.0135 (5)	−0.0037 (4)	0.0070 (4)	−0.0023 (4)
N5	0.0334 (5)	0.0224 (5)	0.0140 (5)	−0.0096 (4)	0.0085 (4)	−0.0021 (4)
N6	0.0196 (4)	0.0427 (7)	0.0132 (5)	−0.0091 (4)	0.0040 (4)	−0.0041 (5)
C7	0.0177 (5)	0.0217 (6)	0.0128 (6)	−0.0026 (4)	0.0044 (4)	−0.0013 (5)
C8	0.0193 (5)	0.0187 (6)	0.0136 (6)	−0.0030 (4)	0.0040 (4)	−0.0014 (5)
C9	0.0228 (5)	0.0209 (6)	0.0198 (6)	−0.0025 (4)	0.0097 (4)	−0.0023 (5)
C1	0.0272 (6)	0.0225 (6)	0.0309 (7)	0.0004 (5)	0.0100 (5)	0.0019 (6)
C2	0.0296 (6)	0.0275 (7)	0.0267 (7)	−0.0071 (5)	0.0061 (5)	−0.0101 (6)
C3	0.0390 (7)	0.0318 (8)	0.0411 (9)	−0.0097 (6)	0.0104 (6)	−0.0136 (7)
C4	0.0437 (8)	0.0253 (7)	0.0470 (10)	0.0036 (6)	0.0164 (7)	0.0058 (7)
C6	0.0337 (7)	0.0381 (8)	0.0322 (8)	0.0062 (6)	0.0015 (6)	0.0058 (6)
C5	0.0487 (8)	0.0216 (7)	0.0554 (11)	−0.0071 (6)	0.0184 (7)	−0.0103 (7)

Geometric parameters (Å, º) top

N2—C8	1.3306 (13)	C9—C1	1.3938 (16)
N2—C7	1.3405 (14)	C9—C2	1.3986 (15)
N3—C7	1.3335 (12)	C1—C4	1.4039 (17)
N3—H1	1.01 (9)	C1—C6	1.4902 (17)
N3—H2	1.01 (16)	C2—C3	1.3826 (16)
N4—C8	1.3516 (14)	C2—H8	1.08 (9)
N4—C9	1.4179 (14)	C3—C5	1.384 (2)
N4—H4	1.01 (8)	C3—H9	1.08 (11)
N5—C8	1.3385 (13)	C4—C5	1.3863 (19)
N5—H3	1.01 (10)	C4—H14	1.08 (9)
N5—H5	1.01 (9)	C6—H11	1.08 (14)
N6—C7	1.3334 (13)	C6—H10	1.08 (12)
N6—H7	1.02 (15)	C6—H12	1.08 (9)
N6—H6	1.02 (9)	C5—H13	1.08 (14)

C8—N2—C7	122.46 (8)	C9—C1—C4	116.95 (10)
C7—N3—H1	120 (4)	C9—C1—C6	123.10 (9)
C7—N3—H2	120 (8)	C4—C1—C6	119.91 (10)
H1—N3—H2	120 (2)	C9—C2—C3	120.24 (10)
C8—N4—C9	125.79 (8)	C9—C2—H8	119 (3)
C8—N4—H4	115 (4)	C3—C2—H8	120 (7)
C9—N4—H4	118.7 (6)	C2—C3—C5	119.24 (10)
C8—N5—H3	121 (7)	C2—C3—H9	121 (2)
C8—N5—H5	119 (1)	C5—C3—H9	120 (4)
H3—N5—H5	119 (4)	C1—C4—C5	121.61 (11)
C7—N6—H7	120 (9)	C1—C4—H14	117 (2)
C7—N6—H6	119 (1)	C5—C4—H14	122 (6)
H7—N6—H6	120 (4)	C1—C6—H11	111 (7)
N2—C7—N6	124.79 (8)	C1—C6—H10	111 (2)
N2—C7—N3	117.54 (8)	C1—C6—H12	111 (3)
N6—C7—N3	117.61 (8)	H11—C6—H10	107 (6)
N4—C8—N2	118.60 (8)	H11—C6—H12	108 (4)
N4—C8—N5	116.01 (8)	H10—C6—H12	108 (2)
N2—C8—N5	125.27 (8)	C3—C5—C4	120.43 (11)
N4—C9—C1	121.39 (9)	C3—C5—H13	120 (5)
N4—C9—C2	116.92 (9)	C4—C5—H13	119 (3)
C1—C9—C2	121.48 (10)

N2—C8—N4—C9	−16.30 (15)	C8—N4—C9—C2	127.35 (15)
N2—C8—N4—H4	166 (2)	C9—C1—C4—C5	1.41 (17)
N2—C8—N5—H3	−8 (4)	C9—C1—C4—H14	180 (9)
N2—C8—N5—H5	−173 (3)	C9—C1—C6—H11	−143 (9)
N2—C7—N6—H7	−5 (4)	C9—C1—C6—H10	−24 (1)
N2—C7—N6—H6	−171 (2)	C9—C1—C6—H12	96 (5)
N2—C7—N3—H1	175 (2)	C9—C2—C3—C5	−0.72 (17)
N2—C7—N3—H2	0 (5)	C9—C2—C3—H9	−179 (10)
N3—C7—N2—C8	156.67 (15)	C1—C9—C2—C3	1.78 (17)
N3—C7—N6—H7	172 (4)	C1—C9—C2—H8	−170 (1)
N3—C7—N6—H6	6 (2)	C1—C4—C5—C3	−0.44 (19)
H1—N3—C7—N6	−2 (2)	C1—C4—C5—H13	180 (1)
H2—N3—C7—N6	−178 (5)	C2—C9—C1—C4	−2.07 (16)
N4—C8—N2—C7	157.09 (14)	C2—C9—C1—C6	175.84 (17)
N4—C8—N5—H3	168 (4)	C2—C3—C5—C4	0.07 (19)
N4—C8—N5—H5	3 (2)	C2—C3—C5—H13	180 (1)
N4—C9—C1—C4	−176.71 (15)	H8—C2—C3—C5	171 (2)
N4—C9—C1—C6	1.20 (15)	H8—C2—C3—H9	−7 (11)
N4—C9—C2—C3	176.65 (15)	C3—C5—C4—H14	−179 (10)
N4—C9—C2—H8	4 (2)	H9—C3—C5—C4	179 (13)
H4—N4—C8—N5	−10 (2)	H9—C3—C5—H13	−2 (13)
H4—N4—C9—C1	120 (2)	C4—C1—C6—H11	35 (9)
H4—N4—C9—C2	−55 (2)	C4—C1—C6—H10	154 (1)
N5—C8—N4—C9	167.49 (15)	C4—C1—C6—H12	−86 (5)
N5—C8—N2—C7	−27.08 (15)	H14—C4—C1—C6	2 (13)
N6—C7—N2—C8	−26.32 (16)	H14—C4—C5—H13	2 (13)
C8—N4—C9—C1	−57.78 (16)	C6—C1—C4—C5	−176.57 (18)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···Cl	1.01 (8)	2.17 (7)	3.1584 (9)	163 (1)
N5—H5···Cl	1.01 (9)	2.37 (9)	3.2880 (9)	150 (6)
N6—H7···N5	1.02 (15)	2.52 (6)	2.9156 (13)	103 (5)
C6—H10···C8	1.08 (12)	2.65 (9)	3.1420 (15)	108 (5)
N3—H1···Clⁱ	1.01 (9)	2.44 (6)	3.3431 (9)	148 (4)
N6—H6···Clⁱ	1.02 (9)	2.28 (9)	3.2398 (9)	157 (1)
N5—H3···Clⁱⁱ	1.01 (10)	2.32 (13)	3.2454 (9)	150 (3)
N6—H7···Clⁱⁱⁱ	1.02 (15)	2.34 (18)	3.2284 (9)	146 (11)
N3—H2···N2^iv	1.01 (16)	1.96 (15)	2.9754 (12)	174 (1)

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

Analysis of contacts on the Hirshfeld surface. Reciprocal contacts X···Y and Y···X are merged. The second line shows the chemical content on the surface. The % of contact types between chemical species are given in the next five lines, followed by their enrichment ratios. The major contacts, as well as the most enriched ones, are highlighted in bold. The lower part of the table give the contact enrichment when the N atom with lone pair Nlp is distinguished from the other N—H/NH₂ atoms top

Atom	Hn	C	N	Cl	Hc
Surface %	27.3	19.3	8.1	15.5	29.8
Hn	4.4
C	6.4	5.0		% contacts
N	4.9	1.1	0
Cl	27.3	1.2	1.2	0.2
Hc	7.8	18.7	7.1	3.8	11.0
Hn	0.58
C	0.62	1.43		Enrichment
N	1.24	0.42	0
Cl	2.92	0.19	0.48	0.08
Hc	0.48	1.69	1.68	0.38	1.25

Atom	Hn	C	Nlp	Nh	Cl	Hc
Nlp	2.37	0.05	0	0	0	0.98
Nh	0.39	0.36	0	0	0.88	2.24

Comparison between C—N bond distances in 1-(o-tolyl)biguanidium and metformin chloride (Niranjana et al., 2017) top

1-(o-Tolyl)biguanidium chloride	Metformin chloride
N6—C7	1.3334 (13)	N5—C4	1.3398 (3)
N3—C7	1.3335 (13)	N4—C4	1.3407 (4)
N2—C7	1.3407 (13)	N3—C4	1.3332 (3)
N2—C8	1.3307 (13)	C4—N3	1.3332 (3)
N5—C8	1.3385 (13)	N2—C3	1.3372 (4)
N4—C8	1.3516 (14)	N1—C3	1.3376 (4)
N4—C9	1.4180 (14)	N1—C1(CH₃)	1.4590 (4)
		N1—C2(CH₃)	1.4566 (5)

Electrostatic energy (kJ mol-1) between the TBG⁺ cations and the neighbouring cations in direct contact. The summation was performed by attributing a coefficient 1/2 to the involutional symmetry operators σ and a unitary weight to the others top

	Symmetry code	Energy	Coefficient
TBG⁺···Cl^-	x, y, z	-385	1/2
	x, y, z+1	-410	1
	x, -y+2, z+1/2	-369	1
	-x+1, y, -z+1/2	-369	1/2
	x, -y+1, z-1/2	126	1
	-x+1, y, -z+1/2	216	1/2
TBG⁺···TBG⁺	-x+1, y, -z+3/2	245	1/2
	-x+1, -y+1, -z+1	135	1/2
	-x+1/2, y-1/2, -z+1/2	138	1
	-x+1/2, -y+3/2, -z	141	1/2
	-x+1/2, -y+3/2, -z+1	60	1/2
Sum		-472

Calculated energies of the possible cations obtained by protonation of 1-(o-tolyl)biguanide top

Structure	Absolute energy (Ha)	Relative energy versus structure 6 (kJ mol^-1)
1	-624.898406392	230
2	-624.903083434	216
3	-624.916688817	182
4	-624.954584111	83
5	-624.966125315	52
6	-624.986333171	0
7	-624.964705612	55

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Synthesis, structural elucidation, characterization and theoretical DFT study of 1-(o-tol­yl)biguanidium chloride

Supporting information

Synthesis, structural elucidation, characterization and theoretical DFT study of 1-(o-tolyl)biguanidium chloride