Redetermination of phenyl­hydrazinium chloride

Lima, G.M. de; Wardell, J.L.; Harrison, W.T.A.

doi:10.1107/S1600536807066974

organic compounds

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Volume 64| Part 1| January 2008| Page o330

https://doi.org/10.1107/S1600536807066974

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Redetermination of phenylhydrazinium chloride

Geraldo M. de Lima,^a James L. Wardell ^a and William T. A. Harrison ^b ^*

^aDepartamento de Quimica, UFMG, Campus - Pampulha, 31270-901 Belo Horizonte, Minas Gerais, Brazil, and ^bDepartment of Chemistry, University of Aberdeen, Meston Walk, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: w.harrison@abdn.ac.uk

(Received 5 December 2007; accepted 14 December 2007; online 21 December 2007)

In the redetermined structure [Koo (1965 ). Bull. Chem. Soc. Jpn, 38, 286] of the title compound, C₆H₉N₂⁺·Cl⁻, the H atoms have been located and the hydrogen-bonding scheme established. A series of N—H⋯Cl and N—H⋯N hydrogen bonds leads to a layered network parallel to the (010) plane.

Related literature

For the earlier structure determination, see: Koo (1965). For a related structure, see: Hammerl et al. (2001 ). For reference structural data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₆H₉N₂⁺·Cl⁻
M_r = 144.60
Monoclinic, P 2₁ /n
a = 3.8223 (5) Å
b = 30.461 (5) Å
c = 6.0121 (10) Å
β = 100.686 (6)°
V = 687.86 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.46 mm⁻¹
T = 120 (2) K
0.30 × 0.07 × 0.01 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.874, T_max = 0.995
3891 measured reflections
1288 independent reflections
1073 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.072
wR(F²) = 0.212
S = 1.12
1288 reflections
94 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.62 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H4⋯N1ⁱ	0.93 (6)	2.11 (6)	3.031 (6)	173 (5)
N1—H1⋯Cl1ⁱⁱ	0.90 (6)	2.49 (6)	3.256 (4)	142 (5)
N2—H2⋯Cl1ⁱⁱⁱ	1.04 (6)	2.04 (6)	3.079 (4)	176 (5)
N2—H3⋯Cl1	0.90 (7)	2.35 (7)	3.187 (5)	154 (6)
Symmetry codes: (i) x+1, y, z; (ii) x+1, y, z+1; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: DENZO (Otwinowski & Minor, 1997), SCALEPACK and SORTAV (Blessing, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536807066974/bt2663sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807066974/bt2663Isup2.hkl

checkCIF report

Comment top

The structure of the title compound, (I), was established by Koo (1965), but no hydrogen atoms were located. The hydrogen bonding pattern in the crystal of (I) cannot be established based on geometrical placement of the H atoms because roatation of the terminal –NH₃⁺ group leads to different plausible arrangements for the hydrogen bonds. Here, the redetermined structure of (I), including the H atom positions is presented (Fig. 1), and the hydrogen bonding scheme is definitively established.

In (I), atoms N1 and N2 deviate from the C1—C6 ring plane by -0.098 (4)Å and 0.418 (4) Å, respectively. The bond-angle sum for N1 is 331°, indicative of sp³ hybridization for this atom. Otherwise, the geometrical paramaters for (I) may be regarded as normal (Allen et al., 1987).

The crystal packing for (I) is influenced by cation-to-cation N—H···N and cation-to-anion N—H···Cl hydrogen bonds (Table 1). The former of these leads to [100] chains in the crystal. One of the H···Cl separations is unusually short, with H···Cl = 2.04 (6) Å, which possibly correlates with the its long N—H separation of 1.04 (6) Å. Together, the hydrogen bonds lead to sheets parallel to the (010) plane (Fig. 2).

Only one other crystal structure containing the phenylhydrazinium cation has been determined (Hammerl et al., 2001), which has similar geometrical paramaters to those in (I).

Related literature top

For the previous structure, see: Koo (1965). For a related structure, see: Hammerl et al. (2001). For reference structural data, see: Allen et al. (1987).

Experimental top

The title compound was prepared by dropwise addition of concentrated hydrochloric acid (1 equivalent) to an ethanolic solution of phenylhydrazine. The product, which appreared on standing, was collected and colourless blades of (I) were recrystallized from EtOH, m.p 525–528 K (decomp).

Structure description top

Only one other crystal structure containing the phenylhydrazinium cation has been determined (Hammerl et al., 2001), which has similar geometrical paramaters to those in (I).

For the previous structure, see: Koo (1965). For a related structure, see: Hammerl et al. (2001). For reference structural data, see: Allen et al. (1987).

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997), and SORTAV (Blessing, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top

Fig. 1. View of the molecular structure of (I) showing 50% displacement ellipsoids. The H atoms are drawn as spheres of arbitrary radius and the hydrogen bond is shown as a double-dashed line.

phenylhydrazinium chloride top

Crystal data top

C₆H₉N₂⁺·Cl⁻	F(000) = 304
M_r = 144.60	D_x = 1.396 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1173 reflections
a = 3.8223 (5) Å	θ = 2.9–27.5°
b = 30.461 (5) Å	µ = 0.46 mm⁻¹
c = 6.0121 (10) Å	T = 120 K
β = 100.686 (6)°	Blade, colourless
V = 687.86 (18) Å³	0.30 × 0.07 × 0.01 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	1288 independent reflections
Radiation source: fine-focus sealed tube	1073 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
ω and φ scans	θ_max = 26.0°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −4→4
T_min = 0.874, T_max = 0.995	k = −35→37
3891 measured reflections	l = −6→7

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)] = 0.072	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.212	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.0789P)² + 3.5247P] where P = (F_o² + 2F_c²)/3
1288 reflections	(Δ/σ)_max = 0.001
94 parameters	Δρ_max = 0.57 e Å⁻³
0 restraints	Δρ_min = −0.62 e Å⁻³

Crystal data top

C₆H₉N₂⁺·Cl⁻	V = 687.86 (18) Å³
M_r = 144.60	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 3.8223 (5) Å	µ = 0.46 mm⁻¹
b = 30.461 (5) Å	T = 120 K
c = 6.0121 (10) Å	0.30 × 0.07 × 0.01 mm
β = 100.686 (6)°

Data collection top

Nonius KappaCCD diffractometer	1288 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	1073 reflections with I > 2σ(I)
T_min = 0.874, T_max = 0.995	R_int = 0.053
3891 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.072	0 restraints
wR(F²) = 0.212	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	Δρ_max = 0.57 e Å⁻³
1288 reflections	Δρ_min = −0.62 e Å⁻³
94 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
C1	0.2381 (11)	0.12905 (16)	0.7787 (9)	0.0198 (11)
C2	0.1470 (12)	0.10308 (16)	0.9478 (9)	0.0230 (11)
H2A	0.0795	0.1161	1.0771	0.028*
C3	0.1557 (13)	0.05785 (17)	0.9259 (9)	0.0244 (11)
H3A	0.0939	0.0398	1.0416	0.029*
C4	0.2530 (13)	0.03857 (17)	0.7383 (9)	0.0268 (12)
H4A	0.2574	0.0075	0.7245	0.032*
C5	0.3432 (13)	0.06488 (17)	0.5721 (9)	0.0253 (12)
H5	0.4120	0.0519	0.4432	0.030*
C6	0.3349 (12)	0.11030 (16)	0.5904 (9)	0.0212 (11)
H6	0.3955	0.1283	0.4741	0.025*
N1	0.1991 (10)	0.17567 (13)	0.8023 (7)	0.0195 (9)
H1	0.262 (15)	0.1852 (18)	0.947 (11)	0.023*
N2	0.4198 (11)	0.20052 (14)	0.6761 (8)	0.0204 (10)
H2	0.384 (15)	0.234 (2)	0.707 (10)	0.031*
H3	0.303 (17)	0.1992 (18)	0.532 (12)	0.031*
H4	0.652 (17)	0.190 (2)	0.712 (10)	0.031*
Cl1	−0.2104 (3)	0.20115 (4)	0.2468 (2)	0.0192 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.013 (2)	0.021 (2)	0.023 (3)	0.0028 (17)	−0.0015 (19)	0.0009 (19)
C2	0.017 (2)	0.024 (3)	0.026 (3)	−0.0009 (18)	−0.002 (2)	0.002 (2)
C3	0.024 (3)	0.025 (3)	0.024 (3)	−0.0042 (19)	0.003 (2)	0.007 (2)
C4	0.026 (3)	0.021 (3)	0.034 (3)	0.003 (2)	0.006 (2)	0.001 (2)
C5	0.021 (3)	0.025 (3)	0.030 (3)	−0.001 (2)	0.003 (2)	−0.002 (2)
C6	0.014 (2)	0.024 (2)	0.025 (3)	0.0012 (18)	0.0011 (19)	0.000 (2)
N1	0.018 (2)	0.022 (2)	0.017 (2)	−0.0013 (15)	0.0005 (17)	−0.0011 (17)
N2	0.013 (2)	0.022 (2)	0.025 (3)	0.0040 (16)	−0.0003 (17)	0.0046 (18)
Cl1	0.0187 (6)	0.0199 (6)	0.0182 (7)	−0.0015 (4)	0.0015 (4)	−0.0010 (4)

Geometric parameters (Å, º) top

C1—C6	1.378 (7)	C5—C6	1.389 (7)
C1—C2	1.383 (7)	C5—H5	0.9500
C1—N1	1.438 (6)	C6—H6	0.9500
C2—C3	1.385 (7)	N1—N2	1.449 (6)
C2—H2A	0.9500	N1—H1	0.90 (6)
C3—C4	1.382 (8)	N2—H2	1.04 (6)
C3—H3A	0.9500	N2—H3	0.90 (7)
C4—C5	1.374 (8)	N2—H4	0.93 (6)
C4—H4A	0.9500

C6—C1—C2	120.6 (5)	C6—C5—H5	119.6
C6—C1—N1	122.6 (4)	C1—C6—C5	119.4 (5)
C2—C1—N1	116.6 (4)	C1—C6—H6	120.3
C1—C2—C3	119.0 (5)	C5—C6—H6	120.3
C1—C2—H2A	120.5	C1—N1—N2	112.5 (4)
C3—C2—H2A	120.5	C1—N1—H1	113 (4)
C4—C3—C2	121.0 (5)	N2—N1—H1	105 (4)
C4—C3—H3A	119.5	N1—N2—H2	108 (3)
C2—C3—H3A	119.5	N1—N2—H3	104 (4)
C5—C4—C3	119.2 (5)	H2—N2—H3	99 (5)
C5—C4—H4A	120.4	N1—N2—H4	109 (4)
C3—C4—H4A	120.4	H2—N2—H4	116 (5)
C4—C5—C6	120.7 (5)	H3—N2—H4	120 (6)
C4—C5—H5	119.6

C6—C1—C2—C3	0.2 (7)	C2—C1—C6—C5	−0.5 (7)
N1—C1—C2—C3	175.6 (4)	N1—C1—C6—C5	−175.5 (4)
C1—C2—C3—C4	−0.1 (7)	C4—C5—C6—C1	0.6 (7)
C2—C3—C4—C5	0.2 (7)	C6—C1—N1—N2	−27.3 (6)
C3—C4—C5—C6	−0.5 (7)	C2—C1—N1—N2	157.5 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H4···N1ⁱ	0.93 (6)	2.11 (6)	3.031 (6)	173 (5)
N1—H1···Cl1ⁱⁱ	0.90 (6)	2.49 (6)	3.256 (4)	142 (5)
N2—H2···Cl1ⁱⁱⁱ	1.04 (6)	2.04 (6)	3.079 (4)	176 (5)
N2—H3···Cl1	0.90 (7)	2.35 (7)	3.187 (5)	154 (6)

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

Experimental details

Crystal data
Chemical formula	C₆H₉N₂⁺·Cl⁻
M_r	144.60
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	120
a, b, c (Å)	3.8223 (5), 30.461 (5), 6.0121 (10)
β (°)	100.686 (6)
V (Å³)	687.86 (18)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.46
Crystal size (mm)	0.30 × 0.07 × 0.01

Data collection
Diffractometer	Nonius KappaCCD
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.874, 0.995
No. of measured, independent and observed [I > 2σ(I)] reflections	3891, 1288, 1073
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.072, 0.212, 1.12
No. of reflections	1288
No. of parameters	94
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.62

Computer programs: COLLECT (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), and SORTAV (Blessing, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H4···N1ⁱ	0.93 (6)	2.11 (6)	3.031 (6)	173 (5)
N1—H1···Cl1ⁱⁱ	0.90 (6)	2.49 (6)	3.256 (4)	142 (5)
N2—H2···Cl1ⁱⁱⁱ	1.04 (6)	2.04 (6)	3.079 (4)	176 (5)
N2—H3···Cl1	0.90 (7)	2.35 (7)	3.187 (5)	154 (6)

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

Acknowledgements

The authors thank the EPSRC UK National Crystallography Service (University of Southampton) for the data collection.

References

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