Crystal structure of 2,2-di­phenyl­hydrazinium chloride

Paul, A.K.; Mukherjee, S.; Stoeckli-Evans, H.

doi:10.1107/S1600536814022879

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ISSN: 2056-9890

Volume 70| Part 11| November 2014| Pages 382-384

doi:10.1107/S1600536814022879

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Crystal structure of 2,2-diphenylhydrazinium chloride

Amit Kumal Paul,^a Soma Mukherjee ^a and Helen Stoeckli-Evans ^b ^*

^aDepartment of Environmental Science, University of Kalyani, Kalyani, Nadia 741 235, West Bengal, India, and ^bInstitute of Physics, University of Neuchâtel, rue Emile-Argand 11, CH-2000 Neuchâtel, Switzerland
^*Correspondence e-mail: helen.stoeckli-evans@unine.ch

Edited by A. J. Lough, University of Toronto, Canada (Received 13 October 2014; accepted 17 October 2014; online 24 October 2014)

In the title compound, C₁₂H₁₃N₂⁺·Cl⁻, the chloride salt of 1,1′-diphenylhydrazine, the phenyl rings are inclined to one another by 78.63 (17)°. The N—⁺NH₃ bond lengths is 1.445 (3) Å, and the N—C_phenyl bond lengths are 1.435 (3) and 1.447 (4) Å. In the crystal, molecules are linked via N—H⋯Cl hydrogen bonds, forming chains along [10-1], which enclose two adjacent R⁴₂(6) ring motifs. The chains are reinforced by C—H⋯Cl hydrogen bonds.

Keywords: crystal structure; diphenylhydrazine; hydrazinium; hydrogen bonding.

CCDC reference: 1029761

1. Chemical context

1,1′-Diphenylhydrazine is a `free' hydrazine, viz with an NH₂ group. It has been used as a starting reagent for the preparation of Schiff bases as fluorescent sensors for fluoride (Mukherjee et al., 2014 ), and metal complexes (Stender et al., 2003 ; Clulow et al., 2008 ). The title compound, (I), crystallized out of a reaction of 1,1′-diphenylhydrazine with 2,6-diacetylpyridine in an attempt to prepare the ligand 2,6-diacetylpyridine bis(N,N-diphenylhydrazone). The latter compound is one of a series that has been used to prepare bis(imino)pyridyl iron and cobalt complexes to study the effect of nitrogen substituents on ethylene oligomerization and polymerization (Britovsek et al., 2001 ).

2. Structural commentary

The molecular structure of the title salt, (I), is illustrated in Fig. 1, and selected bond distances and bond angles are given in Table 1. The two phenyl rings (C1–C6 and C7–C12) are inclined to one another by 78.63 (17)°. The N1—N2 bond lengths is 1.445 (3) Å and the N1—C1 and N1—C7 bond lengths are 1.435 (3) and 1.447 (4) Å, respectively. Atom N1 is displaced from the plane of the three connected atoms, (N2/C1/C7), by 0.370 (2) Å, while the sum of the three angles involving atom N1 is 340.9 °. This illustrates clearly the pyramidal nature of the central N atom, N1.

Table 1
Selected geometric parameters (Å, °)

N1—N2	1.445 (3)	N1—C7	1.447 (4)
N1—C1	1.435 (3)

C1—N1—N2	113.4 (2)	N2—N1—C7	111.5 (2)
C1—N1—C7	116.0 (2)

Figure 1
A view of the molecular structure of the title compound with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

3. Supramolecular features

In the crystal of compound (I), molecules are linked via N—H⋯Cl hydrogen bonds, forming chains along [10 $[\overline{1}]$ ], which enclose two adjacent $[R_{2}^{4}]$ (6) ring motifs (Table 2 and Fig. 2). The chains are reinforced by C—H⋯Cl hydrogen bonds (Fig. 3 and Table 2).

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N⋯Cl1ⁱ	0.92 (3)	2.31 (3)	3.208 (3)	165 (3)
N2—H2N⋯Cl1ⁱⁱ	0.96 (3)	2.23 (3)	3.167 (3)	167 (3)
N2—H3N⋯Cl1ⁱⁱⁱ	0.86 (4)	2.30 (4)	3.154 (3)	175 (3)
C2—H2⋯Cl1ⁱ	0.95	2.96	3.696 (3)	135
Symmetry codes: (i) $[x, -y+1, z+{\script{1\over 2}}]$ ; (ii) $[x, -y+2, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 2
A partial view normal to (10 $[\overline{1}]$ ) of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 2

for details; C-bound H atoms have been omitted for clarity).

Figure 3
A view along the b axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 2

for details; C-bound H atoms not involved in hydrogen bonding have been omitted for clarity).

4. Database survey

A search of the Cambridge Structural Database (Version 5.35, last update May 2014; Groom & Allen, 2014 ) yielded only two hits for the sub-structure 1,1′-diphenylhydrazine: viz. 1,1′-diphenylhydrazinium dicyanogold(I) monohydrate (II) (Stender et al., 2003) and 1,1′-diphenylhydrazine (III) itself (Clulow et al., 2008).

The structure of salt (II) is very similar to that of the title compound, (I). The two phenyl rings are inclined to one another by 80.04 (19)° compared to 78.63 (17)° in (I). The bond lengths and angles involving the central N atom are also very similar to those in (I). The central N atom is displaced by 0.358 (3) Å from the plane of the three attached N and C atoms, and the sum of their bond angles is 342.0°, indicating clearly the pyramidal nature of the central N atom, as in (I).

In 1,1′-diphenylhydrazine (III), which crystallized with two independent molecules per asymmetric unit, the phenyl rings are inclined to one another by only 58.39 (2) and 52.30 (9)°, and the N—NH₂ bond lengths are 1.418 (2) and 1.411 (3) Å. The central N atoms are displaced by 0.1199 (17) and 0.0828 (19) Å from the planes of the three attached N and C atoms, with the sums of their bond angles being 357.85 and 358.97°. This confirms the trigonal–planar conformation of the central N atom.

In the crystal of compound (II), molecules are linked by N—H⋯N, N—H⋯O and O—H⋯N hydrogen bonds, forming two-dimensional networks parallel to (001). These sheets are linked via C—H⋯π interactions, forming a three-dimensional structure. In the crystal of compound (III), there are no hydrogen bonds present with only weak C—H⋯π interactions linking the molecules to form chains along [100]. There are no π–π interactions present in the crystal structures of any of the three compounds.

5. Synthesis and crystallization

Brown block-like crystals of the title compound were obtained during an attempt to prepare the ligand 2,6-diacetylpyridine bis(N,N-diphenylhydrazone) by a condensation reaction involving 1,1′-diphenylhydrazinium hydrochloride and 2,6-diacetylpyridine in methanol.

6. Refinement details

Crystal data, data collection and structure refinement details are summarized in Table 3. The ammonium H atoms were located in a difference Fourier map and freely refined. The C-bound H atoms were included in calculated positions and treated as riding atoms: C—H = 0.95 Å with U_iso(H) = 1.2U_eq(C).

Table 3
Experimental details

Crystal data
Chemical formula	C₁₂H₁₃N₂⁺·Cl⁻
M_r	220.69
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	21.341 (3), 5.3728 (4), 19.940 (3)
β (°)	98.291 (10)
V (Å³)	2262.4 (5)
Z	8
Radiation type	Mo Kα
μ (mm⁻¹)	0.31
Crystal size (mm)	0.45 × 0.35 × 0.25

Data collection
Diffractometer	STOE IPDS 2
Absorption correction	Multi-scan (MULscanABS in PLATON; Spek, 2009 )
T_min, T_max	0.578, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7392, 2140, 1517
R_int	0.120
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.141, 0.93
No. of reflections	2140
No. of parameters	148
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.47
Computer programs: X-AREA and X-RED32 (Stoe & Cie, 2009 ), SHELXS2013 and SHELXL2013 (Sheldrick, 2008 ), PLATON (Spek, 2009), Mercury (Macrae et al., 2008 ), and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1029761

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536814022879/lh5735sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814022879/lh5735Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814022879/lh5735Isup3.cml

checkCIF report

Chemical context top

1,1'-Diphenylhydrazine is a "free" hydrazine, viz with an NH₂ group. It has been used as a starting reagent for the preparation of Schiff bases as fluorescent sensors for fluoride (Mukherjee et al., 2014), and metal complexes (Stender et al., 2003; Clulow et al., 2008). The title compound, (I), crystallized out of a reaction of 1,1'-diphenylhydrazine with 2,6-diacetylpyridine in an attempt to prepare the ligand 2,6-diacetylpyridine bis(N,N-diphenylhydrazone). The latter compound is one of a series that has been used to prepare bis(imino)pyridyl iron and cobalt complexes to study the effect of nitrogen substituents on ethylene oligomerization and polymerization (Britovsek et al., 2001).

Structural commentary top

Supramolecular features top

In the crystal of compound (I), molecules are linked via N—H···Cl hydrogen bonds, forming chains along [101], which enclose two adjacent R⁴₂(6) ring motifs (Table 2 and Fig. 2). The chains are reinforced by C—H···Cl hydrogen bonds (Fig. 3 and Table 2).

Database survey top

A search of the Cambridge Structural Database (Version 5.35, last update May 2014; Groom & Allen, 2014) yielded only two hits for the sub-structure 1,1'-diphenylhydrazine: viz. 1,1'-diphenylhydrazinium dicyanogold(I) monohydrate (II) (Stender et al., 2003) and 1,1'-diphenylhydrazine (III) itself (Clulow et al., 2008).

In 1,1'-diphenylhydrazine (III), which crystallized with two independent molecules per asymmetric unit, the phenyl rings are inclined to one another by only 58.39 (2) and 52.30 (9)°, and the N—NH₂ bond lengths are 1.418 (2) and 1.411 (3) Å. The central N atoms are displaced by 0.1199 (17) and 0.0828 (19) Å from the planes of the three attached N and C atoms, with the sums of their bond angles being 357.85 and 358.97°. This confirms the trigonal–planar conformation of the central N atom.

In the crystal of compound (II), molecules are linked by N—H···N, N—H···O and O—H···N hydrogen bonds, forming two-dimensional networks parallel to (001). These sheets are linked via C—H···π interactions, forming a three-dimensional structure. In the crystal of compound (III), there are no hydrogen bonds present with only weak C—H···π interactions linking the molecules to form chains along [100]. There are no π–π interactions present in the crystal structures of any of the three compounds.

Synthesis and crystallization top

Brown block-like crystals of the title compound were obtained during an attempt to prepare the ligand 2,6-diacetylpyridine bis(N,N-diphenylhydrazone) by a condensation reaction involving 1,1'-diphenylhydrazinium hydrochloride and 2,6-diacetylpyridine in methanol.

Refinement details top

Related literature top

For related literature, see: Groom & Allen (2014); Britovsek et al. (2001); Clulow et al. (2008); Mukherjee et al. (2014); Stender et al. (2003).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2009); cell refinement: X-AREA (Stoe & Cie, 2009); data reduction: X-RED32 (Stoe & Cie, 2009); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

A view of the molecular structure of the title compound with atom labelling. Displacement ellipsoids are drawn at the 50% probability level.

A partial view normal to (101) of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 2 for details; C-bound H atoms have been omitted for clarity).

A view along the b axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 2 for details; C-bound H atoms not involved in hydrogen bonding have been omitted for clarity).

2,2-Diphenylhydrazinium chloride top

Crystal data top

C₁₂H₁₃N₂⁺·Cl⁻	F(000) = 928
M_r = 220.69	D_x = 1.296 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 21.341 (3) Å	Cell parameters from 5046 reflections
b = 5.3728 (4) Å	θ = 1.9–26.0°
c = 19.940 (3) Å	µ = 0.31 mm⁻¹
β = 98.291 (10)°	T = 173 K
V = 2262.4 (5) Å³	Block, brown
Z = 8	0.45 × 0.35 × 0.25 mm

Data collection top

STOE IPDS 2 diffractometer	2140 independent reflections
Radiation source: fine-focus sealed tube	1517 reflections with I > 2σ(I)
Plane graphite monochromator	R_int = 0.120
ϕ + ω scans	θ_max = 25.6°, θ_min = 1.9°
Absorption correction: multi-scan (MULscanABS in PLATON; Spek, 2009)	h = −24→25
T_min = 0.578, T_max = 1.000	k = −6→5
7392 measured reflections	l = −24→24

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: mixed
wR(F²) = 0.141	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	w = 1/[σ²(F_o²) + (0.0794P)²] where P = (F_o² + 2F_c²)/3
2140 reflections	(Δ/σ)_max < 0.001
148 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.47 e Å⁻³

Crystal data top

C₁₂H₁₃N₂⁺·Cl⁻	V = 2262.4 (5) Å³
M_r = 220.69	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 21.341 (3) Å	µ = 0.31 mm⁻¹
b = 5.3728 (4) Å	T = 173 K
c = 19.940 (3) Å	0.45 × 0.35 × 0.25 mm
β = 98.291 (10)°

Data collection top

STOE IPDS 2 diffractometer	2140 independent reflections
Absorption correction: multi-scan (MULscanABS in PLATON; Spek, 2009)	1517 reflections with I > 2σ(I)
T_min = 0.578, T_max = 1.000	R_int = 0.120
7392 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.141	H atoms treated by a mixture of independent and constrained refinement
S = 0.93	Δρ_max = 0.30 e Å⁻³
2140 reflections	Δρ_min = −0.47 e Å⁻³
148 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.

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

	x	y	z	U_iso*/U_eq
N1	0.14173 (10)	0.9765 (4)	0.38714 (11)	0.0284 (5)
N2	0.17735 (12)	0.9687 (5)	0.45449 (12)	0.0296 (5)
H1N	0.1692 (14)	0.834 (6)	0.4807 (14)	0.032 (8)*
H2N	0.1695 (15)	1.113 (6)	0.4803 (14)	0.034 (8)*
H3N	0.217 (2)	0.982 (7)	0.4537 (17)	0.046 (10)*
C1	0.15920 (13)	0.7846 (5)	0.34332 (13)	0.0282 (6)
C2	0.20210 (14)	0.5967 (5)	0.36467 (14)	0.0312 (6)
H2	0.2207	0.5880	0.4108	0.037*
C3	0.21793 (14)	0.4209 (5)	0.31865 (14)	0.0345 (7)
H3	0.2470	0.2917	0.3336	0.041*
C4	0.19146 (15)	0.4339 (6)	0.25115 (15)	0.0376 (7)
H4	0.2025	0.3151	0.2196	0.045*
C5	0.14855 (14)	0.6226 (6)	0.23008 (14)	0.0357 (7)
H5	0.1301	0.6317	0.1838	0.043*
C6	0.13236 (14)	0.7966 (5)	0.27525 (14)	0.0336 (6)
H6	0.1030	0.9246	0.2601	0.040*
C7	0.07462 (14)	1.0052 (5)	0.38918 (15)	0.0334 (7)
C8	0.04095 (15)	0.8348 (7)	0.42154 (16)	0.0438 (8)
H8	0.0617	0.6955	0.4442	0.053*
C9	−0.02370 (18)	0.8694 (9)	0.42060 (19)	0.0622 (11)
H9	−0.0474	0.7536	0.4427	0.075*
C10	−0.05343 (18)	1.0729 (10)	0.3874 (2)	0.0708 (14)
H10	−0.0976	1.0975	0.3870	0.085*
C11	−0.0194 (2)	1.2384 (9)	0.3551 (3)	0.0798 (15)
H11	−0.0405	1.3756	0.3317	0.096*
C12	0.04547 (17)	1.2096 (7)	0.3560 (2)	0.0561 (10)
H12	0.0691	1.3272	0.3344	0.067*
Cl1	0.17516 (3)	0.53583 (13)	0.04013 (3)	0.0316 (2)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0175 (11)	0.0303 (12)	0.0360 (12)	0.0013 (9)	−0.0004 (9)	−0.0032 (9)
N2	0.0203 (13)	0.0317 (13)	0.0361 (13)	−0.0011 (11)	0.0012 (10)	−0.0047 (11)
C1	0.0192 (14)	0.0282 (14)	0.0376 (14)	−0.0040 (11)	0.0052 (11)	−0.0018 (11)
C2	0.0271 (15)	0.0305 (15)	0.0363 (14)	−0.0017 (12)	0.0055 (12)	0.0028 (11)
C3	0.0308 (17)	0.0290 (15)	0.0460 (16)	0.0025 (12)	0.0128 (13)	0.0030 (12)
C4	0.0348 (18)	0.0366 (16)	0.0441 (16)	−0.0056 (14)	0.0148 (13)	−0.0082 (13)
C5	0.0291 (16)	0.0414 (16)	0.0363 (15)	−0.0084 (13)	0.0039 (12)	−0.0036 (12)
C6	0.0255 (15)	0.0348 (15)	0.0401 (15)	−0.0010 (12)	0.0036 (12)	0.0034 (12)
C7	0.0203 (14)	0.0348 (16)	0.0433 (15)	0.0017 (12)	−0.0013 (11)	−0.0123 (12)
C8	0.0226 (16)	0.057 (2)	0.0510 (18)	−0.0017 (15)	0.0043 (13)	−0.0060 (15)
C9	0.031 (2)	0.096 (3)	0.062 (2)	−0.008 (2)	0.0132 (17)	−0.025 (2)
C10	0.0222 (19)	0.102 (4)	0.084 (3)	0.008 (2)	−0.0050 (18)	−0.050 (3)
C11	0.041 (2)	0.067 (3)	0.120 (4)	0.024 (2)	−0.026 (2)	−0.027 (3)
C12	0.036 (2)	0.045 (2)	0.082 (3)	0.0090 (16)	−0.0091 (17)	−0.0038 (18)
Cl1	0.0232 (4)	0.0334 (4)	0.0381 (4)	0.0010 (3)	0.0044 (3)	0.0008 (3)

Geometric parameters (Å, º) top

N1—N2	1.445 (3)	C5—C6	1.376 (4)
N1—C1	1.435 (3)	C5—H5	0.9500
N1—C7	1.447 (4)	C6—H6	0.9500
N2—H1N	0.92 (3)	C7—C8	1.380 (5)
N2—H2N	0.96 (3)	C7—C12	1.383 (4)
N2—H3N	0.86 (4)	C8—C9	1.390 (5)
C1—C2	1.388 (4)	C8—H8	0.9500
C1—C6	1.397 (4)	C9—C10	1.384 (7)
C2—C3	1.392 (4)	C9—H9	0.9500
C2—H2	0.9500	C10—C11	1.365 (7)
C3—C4	1.384 (4)	C10—H10	0.9500
C3—H3	0.9500	C11—C12	1.392 (6)
C4—C5	1.390 (4)	C11—H11	0.9500
C4—H4	0.9500	C12—H12	0.9500

C1—N1—N2	113.4 (2)	C4—C5—H5	119.5
C1—N1—C7	116.0 (2)	C5—C6—C1	119.9 (3)
N2—N1—C7	111.5 (2)	C5—C6—H6	120.1
N1—N2—H1N	115.5 (19)	C1—C6—H6	120.1
N1—N2—H2N	111.5 (18)	C8—C7—C12	121.5 (3)
H1N—N2—H2N	106 (3)	C8—C7—N1	121.8 (3)
N1—N2—H3N	112 (2)	C12—C7—N1	116.8 (3)
H1N—N2—H3N	110 (3)	C7—C8—C9	119.2 (4)
H2N—N2—H3N	101 (3)	C7—C8—H8	120.4
C2—C1—C6	119.5 (3)	C9—C8—H8	120.4
C2—C1—N1	123.6 (2)	C10—C9—C8	119.9 (4)
C6—C1—N1	116.9 (2)	C10—C9—H9	120.1
C1—C2—C3	120.2 (3)	C8—C9—H9	120.1
C1—C2—H2	119.9	C11—C10—C9	120.1 (4)
C3—C2—H2	119.9	C11—C10—H10	119.9
C4—C3—C2	120.2 (3)	C9—C10—H10	119.9
C4—C3—H3	119.9	C10—C11—C12	121.2 (4)
C2—C3—H3	119.9	C10—C11—H11	119.4
C3—C4—C5	119.3 (3)	C12—C11—H11	119.4
C3—C4—H4	120.4	C7—C12—C11	118.2 (4)
C5—C4—H4	120.4	C7—C12—H12	120.9
C6—C5—C4	120.9 (3)	C11—C12—H12	120.9
C6—C5—H5	119.5

N2—N1—C1—C2	5.2 (4)	C1—N1—C7—C8	72.9 (3)
C7—N1—C1—C2	−125.8 (3)	N2—N1—C7—C8	−59.0 (3)
N2—N1—C1—C6	−172.7 (2)	C1—N1—C7—C12	−105.9 (3)
C7—N1—C1—C6	56.3 (3)	N2—N1—C7—C12	122.2 (3)
C6—C1—C2—C3	−0.4 (4)	C12—C7—C8—C9	0.1 (5)
N1—C1—C2—C3	−178.2 (2)	N1—C7—C8—C9	−178.7 (3)
C1—C2—C3—C4	0.7 (4)	C7—C8—C9—C10	0.1 (5)
C2—C3—C4—C5	−0.6 (4)	C8—C9—C10—C11	0.5 (6)
C3—C4—C5—C6	0.3 (4)	C9—C10—C11—C12	−1.3 (6)
C4—C5—C6—C1	0.0 (4)	C8—C7—C12—C11	−0.8 (5)
C2—C1—C6—C5	0.1 (4)	N1—C7—C12—C11	178.0 (3)
N1—C1—C6—C5	178.1 (2)	C10—C11—C12—C7	1.4 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N···Cl1ⁱ	0.92 (3)	2.31 (3)	3.208 (3)	165 (3)
N2—H2N···Cl1ⁱⁱ	0.96 (3)	2.23 (3)	3.167 (3)	167 (3)
N2—H3N···Cl1ⁱⁱⁱ	0.86 (4)	2.30 (4)	3.154 (3)	175 (3)
C2—H2···Cl1ⁱ	0.95	2.96	3.696 (3)	135

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

Selected geometric parameters (Å, º) top

N1—N2	1.445 (3)	N1—C7	1.447 (4)
N1—C1	1.435 (3)

C1—N1—N2	113.4 (2)	N2—N1—C7	111.5 (2)
C1—N1—C7	116.0 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N···Cl1ⁱ	0.92 (3)	2.31 (3)	3.208 (3)	165 (3)
N2—H2N···Cl1ⁱⁱ	0.96 (3)	2.23 (3)	3.167 (3)	167 (3)
N2—H3N···Cl1ⁱⁱⁱ	0.86 (4)	2.30 (4)	3.154 (3)	175 (3)
C2—H2···Cl1ⁱ	0.95	2.96	3.696 (3)	135

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₃N₂⁺·Cl⁻
M_r	220.69
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	21.341 (3), 5.3728 (4), 19.940 (3)
β (°)	98.291 (10)
V (Å³)	2262.4 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.45 × 0.35 × 0.25

Data collection
Diffractometer	STOE IPDS 2 diffractometer
Absorption correction	Multi-scan (MULscanABS in PLATON; Spek, 2009)
T_min, T_max	0.578, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	7392, 2140, 1517
R_int	0.120
(sin θ/λ)_max (Å⁻¹)	0.609

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.141, 0.93
No. of reflections	2140
No. of parameters	148
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.47

Computer programs: X-AREA (Stoe & Cie, 2009), X-RED32 (Stoe & Cie, 2009), SHELXS2013 (Sheldrick, 2008), PLATON (Spek, 2009) and Mercury (Macrae et al., 2008), SHELXL2013 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Acknowledgements

Financial support from the CSIR, UGC, DST–FIST and DST–PURSE, New Delhi, and the Indo Swiss Joint Research Program (ISJRP) for Joint Utilization of Advanced Facilities (JUAF) are gratefully acknowledged. We are also grateful to the University of Kalyani for providing infrastructural facilities, and to the XRD Application Laboratory, CSEM, Neuchâtel, Switzerland, for access to the X-ray diffraction equipment.

References

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