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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 64| Part 1| January 2008| Page o330
https://doi.org/10.1107/S1600536807066974

Redetermination of phenyl­hydrazinium chloride

Geraldo M. de Lima,a James L. Wardella and William T. A. Harrisonb*

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[Koo, C. H. (1965). Bull. Chem. Soc. Jpn, 38, 286.]). 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[Koo, C. H. (1965). Bull. Chem. Soc. Jpn, 38, 286.]). For a related structure, see: Hammerl et al. (2001[Hammerl, A., Holl, G., Kaiser, M., Klapötke, T. M., Mayer, P., Nöth, H. & Warchhold, M. (2001). Z. Anorg. Allg. Chem. 627, 1477-1482.]). For reference structural data, see: Allen et al. (1987[Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 1, pp. S1-19.]).

[Scheme 1]

Experimental

Crystal data

  • C6H9N2+·Cl−

  • Mr = 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[Bruker (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.874, Tmax = 0.995

  • 3891 measured reflections

  • 1288 independent reflections

  • 1073 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.57 e Å−3

  • Δρmin = −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[Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.]); cell refinement: SCALEPACK (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]); data reduction: DENZO (Otwinowski & Minor, 1997[Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307-326. New York: Academic Press.]), SCALEPACK and SORTAV (Blessing, 1995[Blessing, R. H. (1995). Acta Cryst. A51, 33-38.]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997[Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.]); molecular graphics: ORTEP-3 (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]); 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).

Refinement top

The N-bound H atoms were located in a difference map and their positions were freely refined with the constraint Uiso(H) = 1.2Ueq(N). The C-bound H atoms were placed in calculated positions (C—H = 0.93 Å) and refined as riding with Uiso(H) = 1.2Ueq(C).

Structure description 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).

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
[Figure 1] 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
Mr = 144.60Dx = 1.396 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1173 reflections
a = 3.8223 (5) Åθ = 2.9–27.5°
b = 30.461 (5) ŵ = 0.46 mm−1
c = 6.0121 (10) ÅT = 120 K
β = 100.686 (6)°Blade, colourless
V = 687.86 (18) Å30.30 × 0.07 × 0.01 mm
Z = 4
Data collection top
Nonius KappaCCD
diffractometer		1288 independent reflections
Radiation source: fine-focus sealed tube1073 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.053
ω and φ scansθmax = 26.0°, θmin = 3.5°
Absorption correction: multi-scan
(SADABS; Bruker, 2003)		h = −4→4
Tmin = 0.874, Tmax = 0.995k = −35→37
3891 measured reflectionsl = −6→7
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)] = 0.072Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.212H atoms treated by a mixture of independent and constrained refinement
S = 1.12 w = 1/[σ2(Fo2) + (0.0789P)2 + 3.5247P]
where P = (Fo2 + 2Fc2)/3
1288 reflections(Δ/σ)max = 0.001
94 parametersΔρmax = 0.57 e Å−3
0 restraintsΔρmin = −0.62 e Å−3
Crystal data top
C6H9N2+·Cl−V = 687.86 (18) Å3
Mr = 144.60Z = 4
Monoclinic, P21/nMo Kα radiation
a = 3.8223 (5) ŵ = 0.46 mm−1
b = 30.461 (5) ÅT = 120 K
c = 6.0121 (10) Å0.30 × 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)
Tmin = 0.874, Tmax = 0.995Rint = 0.053
3891 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0720 restraints
wR(F2) = 0.212H atoms treated by a mixture of independent and constrained refinement
S = 1.12Δρmax = 0.57 e Å−3
1288 reflectionsΔρmin = −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
xyzUiso*/Ueq
C10.2381 (11)0.12905 (16)0.7787 (9)0.0198 (11)
C20.1470 (12)0.10308 (16)0.9478 (9)0.0230 (11)
H2A0.07950.11611.07710.028*
C30.1557 (13)0.05785 (17)0.9259 (9)0.0244 (11)
H3A0.09390.03981.04160.029*
C40.2530 (13)0.03857 (17)0.7383 (9)0.0268 (12)
H4A0.25740.00750.72450.032*
C50.3432 (13)0.06488 (17)0.5721 (9)0.0253 (12)
H50.41200.05190.44320.030*
C60.3349 (12)0.11030 (16)0.5904 (9)0.0212 (11)
H60.39550.12830.47410.025*
N10.1991 (10)0.17567 (13)0.8023 (7)0.0195 (9)
H10.262 (15)0.1852 (18)0.947 (11)0.023*
N20.4198 (11)0.20052 (14)0.6761 (8)0.0204 (10)
H20.384 (15)0.234 (2)0.707 (10)0.031*
H30.303 (17)0.1992 (18)0.532 (12)0.031*
H40.652 (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
U11U22U33U12U13U23
C10.013 (2)0.021 (2)0.023 (3)0.0028 (17)−0.0015 (19)0.0009 (19)
C20.017 (2)0.024 (3)0.026 (3)−0.0009 (18)−0.002 (2)0.002 (2)
C30.024 (3)0.025 (3)0.024 (3)−0.0042 (19)0.003 (2)0.007 (2)
C40.026 (3)0.021 (3)0.034 (3)0.003 (2)0.006 (2)0.001 (2)
C50.021 (3)0.025 (3)0.030 (3)−0.001 (2)0.003 (2)−0.002 (2)
C60.014 (2)0.024 (2)0.025 (3)0.0012 (18)0.0011 (19)0.000 (2)
N10.018 (2)0.022 (2)0.017 (2)−0.0013 (15)0.0005 (17)−0.0011 (17)
N20.013 (2)0.022 (2)0.025 (3)0.0040 (16)−0.0003 (17)0.0046 (18)
Cl10.0187 (6)0.0199 (6)0.0182 (7)−0.0015 (4)0.0015 (4)−0.0010 (4)
Geometric parameters (Å, º) top
C1—C61.378 (7)C5—C61.389 (7)
C1—C21.383 (7)C5—H50.9500
C1—N11.438 (6)C6—H60.9500
C2—C31.385 (7)N1—N21.449 (6)
C2—H2A0.9500N1—H10.90 (6)
C3—C41.382 (8)N2—H21.04 (6)
C3—H3A0.9500N2—H30.90 (7)
C4—C51.374 (8)N2—H40.93 (6)
C4—H4A0.9500
C6—C1—C2120.6 (5)C6—C5—H5119.6
C6—C1—N1122.6 (4)C1—C6—C5119.4 (5)
C2—C1—N1116.6 (4)C1—C6—H6120.3
C1—C2—C3119.0 (5)C5—C6—H6120.3
C1—C2—H2A120.5C1—N1—N2112.5 (4)
C3—C2—H2A120.5C1—N1—H1113 (4)
C4—C3—C2121.0 (5)N2—N1—H1105 (4)
C4—C3—H3A119.5N1—N2—H2108 (3)
C2—C3—H3A119.5N1—N2—H3104 (4)
C5—C4—C3119.2 (5)H2—N2—H399 (5)
C5—C4—H4A120.4N1—N2—H4109 (4)
C3—C4—H4A120.4H2—N2—H4116 (5)
C4—C5—C6120.7 (5)H3—N2—H4120 (6)
C4—C5—H5119.6
C6—C1—C2—C30.2 (7)C2—C1—C6—C5−0.5 (7)
N1—C1—C2—C3175.6 (4)N1—C1—C6—C5−175.5 (4)
C1—C2—C3—C4−0.1 (7)C4—C5—C6—C10.6 (7)
C2—C3—C4—C50.2 (7)C6—C1—N1—N2−27.3 (6)
C3—C4—C5—C6−0.5 (7)C2—C1—N1—N2157.5 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H4···N1i0.93 (6)2.11 (6)3.031 (6)173 (5)
N1—H1···Cl1ii0.90 (6)2.49 (6)3.256 (4)142 (5)
N2—H2···Cl1iii1.04 (6)2.04 (6)3.079 (4)176 (5)
N2—H3···Cl10.90 (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 formulaC6H9N2+·Cl−
Mr144.60
Crystal system, space groupMonoclinic, 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)
Z4
Radiation typeMo Kα
µ (mm−1)0.46
Crystal size (mm)0.30 × 0.07 × 0.01
Data collection
DiffractometerNonius KappaCCD
Absorption correctionMulti-scan
(SADABS; Bruker, 2003)
Tmin, Tmax0.874, 0.995
No. of measured, independent and
observed [I > 2σ(I)] reflections		3891, 1288, 1073
Rint0.053
(sin θ/λ)max (Å−1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.072, 0.212, 1.12
No. of reflections1288
No. of parameters94
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (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···AD—HH···AD···AD—H···A
N2—H4···N1i0.93 (6)2.11 (6)3.031 (6)173 (5)
N1—H1···Cl1ii0.90 (6)2.49 (6)3.256 (4)142 (5)
N2—H2···Cl1iii1.04 (6)2.04 (6)3.079 (4)176 (5)
N2—H3···Cl10.90 (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

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 1, pp. S1–19.  CrossRef Google Scholar
 First citationBlessing, R. H. (1995). Acta Cryst. A51, 33–38.  CrossRef CAS Web of Science IUCr Journals Google Scholar
 First citationBruker (2003). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
 First citationHammerl, A., Holl, G., Kaiser, M., Klapötke, T. M., Mayer, P., Nöth, H. & Warchhold, M. (2001). Z. Anorg. Allg. Chem. 627, 1477–1482.  Web of Science CSD CrossRef CAS Google Scholar
 First citationKoo, C. H. (1965). Bull. Chem. Soc. Jpn, 38, 286.  CrossRef Web of Science Google Scholar
 First citationNonius (1998). COLLECT. Nonius BV, Delft, The Netherlands.  Google Scholar
 First citationOtwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.  Google Scholar
 First citationSheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.  Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 64| Part 1| January 2008| Page o330
https://doi.org/10.1107/S1600536807066974
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