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The crystal structure of the title compound, C2H10N2O2+·2Cl, is built up from one 2-hydroxy­ethyl­hydrazinium(2+) cation and two Cl anions. The mol­ecular structure is stabilized by O—H...Cl and N—H...Cl hydrogen bonds. The crystal structure is stabilized by one N—H...O and three N—H...Cl inter­actions, and the three-dimensional network of hydrogen bonds stabilizes the crystal packing. All five hydrazinium H atoms are involved in hydrogen bonds to Cl anions. The Cl...H contact distances range from 2.122 (15) to 2.809 (14) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105007183/dn1076sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270105007183/dn1076Isup2.hkl
Contains datablock I

CCDC reference: 273063

Comment top

Hydrogen bonding plays a key role in molecular recognition and the engineering of organic solids (Desiraju, 1989; Melendez & Hamilton, 1998). The design of highly specific solid-state compounds is of considerable significance in organic chemistry, due to their important applications in the development of new optical, magnetic and electronic systems (Lehn, 1992).

The structure of the title compound, (I), is presented in Fig. 1, and selected bond distances and angles are given in Table 1. The asymmetric unit contains one protonated 2-hydroxyethylhydrazinium cation and two Cl counter-anions. Atoms N1 and N2 exhibit approximately ideal tetrahedral geometry, with average angles of 109.45 (13) and 109.48 (13)°, respectively.

Hydrogen bonds are abundant in this structure, as might be expected from the structural formula and the liability of amino groups to act as donor. In fact, five different N—H···Cl bonds are found, with H···Cl distances ranging from 2.122 (15) to 2.809 (14) Å. The shortest, N2—H42···Cl2 [2.122 (15) Å], has a nearly linear contact angle [171.1 (13)°]. According to Balmer et al. (2001), this bond is the strongest among those found for N—H···Cl contacts. Table 2 gives the details of the hydrogen-bond geometry of (I). The H atoms on N1 and N2, with the exception of H31, have only one hydrogen bond, while atom H31 forms a three-centre interaction with two Cl atoms. Our investigation shows that the 2-hydroxyethylhydrazinium cation is linked to the two Cl anions through O1—H1···Cl1 [O1···Cl1 3.0874 (7) Å] and N1—H31···Cl1 [N1···Cl1 3.4104 (8) Å] hydrogen bonds, resulting in the formation of cyclic seven-membered hydrogen-bonded rings, and an N2—H41···Cl2 [N2···Cl2 3.0701 (8) Å] hydrogen bond (Fig. 1).

The 2-hydroxyethylhydrazinium dichloride units are arranged in such a way as to form a two-dimensional network via O—H···Cl and N—H···Cl interactions, which develop parallel to the bc plane. There is also another N—H···Cl interaction, which connects two symmetry-related planar networks (Fig. 2). The N1—H31···O1 interaction builds an approximately zigzag chain, which develops parallel to the c axis (Fig. 3). Importantly, the N1—H32···Cl1 and N2—H43···Cl1 interactions link symmetry-related such zigzag chains to build up a two-dimensional network as a layer, which includes R66(20) rings (Bernstein et al., 1995) and develops parallel to the bc plane (Fig. 4).

Four independent halogen–halogen contacts in each structure provide the more striking examples of secondary interactions (Table 3). The halogen–halogen interactions form zigzag-like roofs interconnected by Cl···Cl contacts (Fig. 5). In the doubly protonated 2-hydroxyethylhydrazine moiety, the average C2—N1 [1.502 (2) Å], C1—O1 [1.429 (2) Å] and N1—N2 [1.449 (2) Å] distances (Table 1) are in good agreement with the normal values (Orpen et al., 1992; Demir et al., 2002; Parkins et al., 2001).

Experimental top

HCl [aqueous, 37% (w/w), 0.93 ml, 30 mmol] was added dropwise to 2-hydroxyethylhydrazine (1.01 ml, 15 mmol) in ether (20 ml) and the resulting solution was stirred for 15 min at 293 K. Colourless single crystals of (I) were obtained by slow evaporation of the solvent, and these crystals were dried in air (m.p. 406–408 K).

Refinement top

H atoms were located in a difference map and refined isotropically, with N—H = 0.86 (2)–0.94 (2), O—H = 0.83 (2) and C—H = 0.94 (2)–0.98 (2) Å, and with Uiso(H) values in the range 0.015 (3)–0.030 (4) Å2.

Computing details top

Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997), CAMERON (Watkin et al., 1993) and PLUTON (Spek, 1998); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. A view of the structure of (I), with the atom-numbering scheme. Displacement ellipsoids are darwn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A packing diagram for (I).
[Figure 3] Fig. 3. The zigzag chain parallel to the c axis built up by N—H···O interactions. Cl atoms have been omitted for clarity. [Symmetry codes: (i) x, −y + 3/2, z + 1/2; (vi) x, 3/2 − y, 1/2 − z.]
[Figure 4] Fig. 4. The two-dimensional network, including the R66(20) rings built up by N—H···Cl interactions. [Symmetry codes: (i) x, 3/2 − y, z − 1/2; (ii) 1 − x, y − 1/2, −z + 1/2; (iii) 1 − x, 1 − y, −z; (iv) 2 − x, y + 1/2, −z + 1/2; (v) x, 3/2 − y, 1/2 + z; (vi) x, 1/2 − y, 1/2 + z]
[Figure 5] Fig. 5. The halogen–halogen interactions forming zigzag-like roofs interconnected by Cl···Cl contacts.
2-Hydroxyethylhydrazinium dichloride top
Crystal data top
C2H10N2O2+·2ClF(000) = 312
Mr = 149.02Dx = 1.571 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 11440 reflections
a = 10.2367 (9) Åθ = 2.8–29.4°
b = 8.4158 (6) ŵ = 0.93 mm1
c = 7.5111 (7) ÅT = 150 K
β = 103.208 (7)°Shapeless, colourless
V = 629.96 (9) Å30.54 × 0.50 × 0.43 mm
Z = 4
Data collection top
Stoe IPDS-II
diffractometer
1678 independent reflections
Radiation source: fine-focus sealed tube1625 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.077
Detector resolution: 6.67 pixels mm-1θmax = 29.1°, θmin = 3.2°
rotation method scansh = 1313
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)
k = 1111
Tmin = 0.680, Tmax = 0.735l = 1010
11440 measured reflections
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)] = 0.019Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.050All H-atom parameters refined
S = 1.17 w = 1/[σ2(Fo2) + (0.0248P)2 + 0.1595P]
where P = (Fo2 + 2Fc2)/3
1678 reflections(Δ/σ)max = 0.001
104 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.24 e Å3
Crystal data top
C2H10N2O2+·2ClV = 629.96 (9) Å3
Mr = 149.02Z = 4
Monoclinic, P21/cMo Kα radiation
a = 10.2367 (9) ŵ = 0.93 mm1
b = 8.4158 (6) ÅT = 150 K
c = 7.5111 (7) Å0.54 × 0.50 × 0.43 mm
β = 103.208 (7)°
Data collection top
Stoe IPDS-II
diffractometer
1678 independent reflections
Absorption correction: integration
(X-RED32; Stoe & Cie, 2002)
1625 reflections with I > 2σ(I)
Tmin = 0.680, Tmax = 0.735Rint = 0.077
11440 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0190 restraints
wR(F2) = 0.050All H-atom parameters refined
S = 1.17Δρmax = 0.31 e Å3
1678 reflectionsΔρmin = 0.24 e Å3
104 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
C10.71821 (9)0.61221 (11)0.54054 (12)0.01471 (17)
C20.80446 (9)0.53938 (11)0.42411 (12)0.01263 (17)
N10.72172 (7)0.49533 (9)0.23861 (10)0.01046 (14)
N20.80584 (7)0.43367 (9)0.12342 (10)0.01086 (14)
O10.67849 (7)0.76998 (8)0.48174 (9)0.01514 (14)
Cl10.42289 (2)0.68909 (3)0.18828 (3)0.01514 (7)
Cl21.03755 (2)0.67097 (2)0.15246 (3)0.01381 (7)
H10.6031 (17)0.764 (2)0.411 (2)0.030 (4)*
H110.7758 (13)0.6167 (17)0.6645 (18)0.019 (3)*
H120.6416 (14)0.5456 (17)0.5414 (19)0.022 (3)*
H210.8750 (13)0.6121 (16)0.4098 (18)0.015 (3)*
H220.8457 (13)0.4459 (17)0.4768 (18)0.019 (3)*
H310.6791 (14)0.5740 (17)0.1803 (19)0.021 (3)*
H320.6598 (14)0.4161 (17)0.2489 (19)0.023 (3)*
H410.8646 (14)0.5063 (18)0.1082 (19)0.025 (3)*
H420.8514 (14)0.3496 (17)0.179 (2)0.021 (3)*
H430.7533 (14)0.4053 (17)0.0204 (19)0.019 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0189 (4)0.0132 (4)0.0131 (4)0.0002 (3)0.0060 (3)0.0013 (3)
C20.0135 (4)0.0133 (4)0.0098 (4)0.0015 (3)0.0001 (3)0.0020 (3)
N10.0103 (3)0.0105 (3)0.0106 (3)0.0009 (3)0.0022 (3)0.0007 (3)
N20.0117 (3)0.0107 (3)0.0103 (3)0.0003 (3)0.0028 (3)0.0015 (3)
O10.0127 (3)0.0126 (3)0.0182 (3)0.0015 (2)0.0005 (2)0.0043 (2)
Cl10.01252 (11)0.01620 (11)0.01517 (11)0.00083 (7)0.00001 (8)0.00335 (7)
Cl20.01437 (11)0.01321 (11)0.01439 (11)0.00396 (7)0.00437 (8)0.00269 (7)
Geometric parameters (Å, º) top
C1—O11.429 (2)N1—N21.449 (2)
C1—C21.5076 (12)N1—H310.86 (2)
C1—H110.98 (2)N1—H320.94 (2)
C1—H120.966 (14)N2—H410.883 (15)
C2—N11.502 (2)N2—H420.895 (15)
C2—H210.971 (13)N2—H430.869 (14)
C2—H220.94 (2)O1—H10.83 (2)
O1—C1—C2111.20 (7)N2—N1—H31105.9 (9)
O1—C1—H11108.9 (8)C2—N1—H31113.4 (9)
C2—C1—H11105.2 (8)N2—N1—H32107.5 (9)
O1—C1—H12111.6 (8)C2—N1—H32110.4 (9)
C2—C1—H12110.6 (8)H31—N1—H32108.5 (12)
H11—C1—H12109.1 (12)N1—N2—H41110.2 (9)
N1—C2—C1110.94 (7)N1—N2—H42108.9 (9)
N1—C2—H21109.2 (8)H41—N2—H42107.9 (12)
C1—C2—H21110.9 (8)N1—N2—H43107.4 (9)
N1—C2—H22106.8 (8)H41—N2—H43112.2 (13)
C1—C2—H22111.4 (8)H42—N2—H43110.3 (13)
H21—C2—H22107.5 (11)C1—O1—H1107.6 (12)
N2—N1—C2110.86 (6)
O1—C1—C2—N173.52 (9)C1—C2—N1—N2176.77 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···Cl10.833 (17)2.278 (17)3.0874 (7)164.1 (15)
N1—H31···O1i0.856 (15)1.986 (14)2.7257 (10)144.0 (13)
N1—H31···Cl10.856 (15)2.809 (14)3.4104 (8)128.7 (11)
N1—H32···Cl1ii0.935 (15)2.185 (15)3.0832 (8)160.9 (12)
N2—H43···Cl1iii0.869 (14)2.246 (15)3.0864 (8)162.4 (12)
N2—H41···Cl20.883 (15)2.213 (15)3.0701 (8)163.6 (13)
N2—H42···Cl2iv0.895 (15)2.122 (15)3.0098 (8)171.1 (13)
Symmetry codes: (i) x, y+3/2, z1/2; (ii) x+1, y1/2, z+1/2; (iii) x+1, y+1, z; (iv) x+2, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC2H10N2O2+·2Cl
Mr149.02
Crystal system, space groupMonoclinic, P21/c
Temperature (K)150
a, b, c (Å)10.2367 (9), 8.4158 (6), 7.5111 (7)
β (°) 103.208 (7)
V3)629.96 (9)
Z4
Radiation typeMo Kα
µ (mm1)0.93
Crystal size (mm)0.54 × 0.50 × 0.43
Data collection
DiffractometerStoe IPDS-II
diffractometer
Absorption correctionIntegration
(X-RED32; Stoe & Cie, 2002)
Tmin, Tmax0.680, 0.735
No. of measured, independent and
observed [I > 2σ(I)] reflections
11440, 1678, 1625
Rint0.077
(sin θ/λ)max1)0.684
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.019, 0.050, 1.17
No. of reflections1678
No. of parameters104
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.31, 0.24

Computer programs: X-AREA (Stoe & Cie, 2002), X-AREA, X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), CAMERON (Watkin et al., 1993) and PLUTON (Spek, 1998), WinGX (Farrugia, 1999).

Selected geometric parameters (Å, º) top
C1—O11.429 (2)N1—N21.449 (2)
C2—N11.502 (2)
O1—C1—C2111.20 (7)N2—N1—C2110.86 (6)
N1—C2—C1110.94 (7)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O1—H1···Cl10.833 (17)2.278 (17)3.0874 (7)164.1 (15)
N1—H31···O1i0.856 (15)1.986 (14)2.7257 (10)144.0 (13)
N1—H31···Cl10.856 (15)2.809 (14)3.4104 (8)128.7 (11)
N1—H32···Cl1ii0.935 (15)2.185 (15)3.0832 (8)160.9 (12)
N2—H43···Cl1iii0.869 (14)2.246 (15)3.0864 (8)162.4 (12)
N2—H41···Cl20.883 (15)2.213 (15)3.0701 (8)163.6 (13)
N2—H42···Cl2iv0.895 (15)2.122 (15)3.0098 (8)171.1 (13)
Symmetry codes: (i) x, y+3/2, z1/2; (ii) x+1, y1/2, z+1/2; (iii) x+1, y+1, z; (iv) x+2, y1/2, z+1/2.
Cl···Cl contacts for (I) (Å) top
Cl1···Cl1v3.8930 (5)Cl1···Cl2vi3.8949 (5)
Cl2···Cl2vii3.6487 (3)Cl2···Cl2v3.9842 (5)
Symmetry codes: (v) x, −y + 3/2, z − 1/2; (vi) x − 1, y, z; (vii) −x, −y + 1, z.
 

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