Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270105007183/dn1076sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270105007183/dn1076Isup2.hkl |
CCDC reference: 273063
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).
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.
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).
C2H10N2O2+·2Cl− | F(000) = 312 |
Mr = 149.02 | Dx = 1.571 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 11440 reflections |
a = 10.2367 (9) Å | θ = 2.8–29.4° |
b = 8.4158 (6) Å | µ = 0.93 mm−1 |
c = 7.5111 (7) Å | T = 150 K |
β = 103.208 (7)° | Shapeless, colourless |
V = 629.96 (9) Å3 | 0.54 × 0.50 × 0.43 mm |
Z = 4 |
Stoe IPDS-II diffractometer | 1678 independent reflections |
Radiation source: fine-focus sealed tube | 1625 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.077 |
Detector resolution: 6.67 pixels mm-1 | θmax = 29.1°, θmin = 3.2° |
rotation method scans | h = −13→13 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −11→11 |
Tmin = 0.680, Tmax = 0.735 | l = −10→10 |
11440 measured reflections |
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)] = 0.019 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.050 | All 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 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C2H10N2O2+·2Cl− | V = 629.96 (9) Å3 |
Mr = 149.02 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.2367 (9) Å | µ = 0.93 mm−1 |
b = 8.4158 (6) Å | T = 150 K |
c = 7.5111 (7) Å | 0.54 × 0.50 × 0.43 mm |
β = 103.208 (7)° |
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 = 0.735 | Rint = 0.077 |
11440 measured reflections |
R[F2 > 2σ(F2)] = 0.019 | 0 restraints |
wR(F2) = 0.050 | All H-atom parameters refined |
S = 1.17 | Δρmax = 0.31 e Å−3 |
1678 reflections | Δρmin = −0.24 e Å−3 |
104 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.71821 (9) | 0.61221 (11) | 0.54054 (12) | 0.01471 (17) | |
C2 | 0.80446 (9) | 0.53938 (11) | 0.42411 (12) | 0.01263 (17) | |
N1 | 0.72172 (7) | 0.49533 (9) | 0.23861 (10) | 0.01046 (14) | |
N2 | 0.80584 (7) | 0.43367 (9) | 0.12342 (10) | 0.01086 (14) | |
O1 | 0.67849 (7) | 0.76998 (8) | 0.48174 (9) | 0.01514 (14) | |
Cl1 | 0.42289 (2) | 0.68909 (3) | 0.18828 (3) | 0.01514 (7) | |
Cl2 | 1.03755 (2) | 0.67097 (2) | 0.15246 (3) | 0.01381 (7) | |
H1 | 0.6031 (17) | 0.764 (2) | 0.411 (2) | 0.030 (4)* | |
H11 | 0.7758 (13) | 0.6167 (17) | 0.6645 (18) | 0.019 (3)* | |
H12 | 0.6416 (14) | 0.5456 (17) | 0.5414 (19) | 0.022 (3)* | |
H21 | 0.8750 (13) | 0.6121 (16) | 0.4098 (18) | 0.015 (3)* | |
H22 | 0.8457 (13) | 0.4459 (17) | 0.4768 (18) | 0.019 (3)* | |
H31 | 0.6791 (14) | 0.5740 (17) | 0.1803 (19) | 0.021 (3)* | |
H32 | 0.6598 (14) | 0.4161 (17) | 0.2489 (19) | 0.023 (3)* | |
H41 | 0.8646 (14) | 0.5063 (18) | 0.1082 (19) | 0.025 (3)* | |
H42 | 0.8514 (14) | 0.3496 (17) | 0.179 (2) | 0.021 (3)* | |
H43 | 0.7533 (14) | 0.4053 (17) | 0.0204 (19) | 0.019 (3)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0189 (4) | 0.0132 (4) | 0.0131 (4) | 0.0002 (3) | 0.0060 (3) | −0.0013 (3) |
C2 | 0.0135 (4) | 0.0133 (4) | 0.0098 (4) | 0.0015 (3) | −0.0001 (3) | −0.0020 (3) |
N1 | 0.0103 (3) | 0.0105 (3) | 0.0106 (3) | 0.0009 (3) | 0.0022 (3) | −0.0007 (3) |
N2 | 0.0117 (3) | 0.0107 (3) | 0.0103 (3) | 0.0003 (3) | 0.0028 (3) | −0.0015 (3) |
O1 | 0.0127 (3) | 0.0126 (3) | 0.0182 (3) | 0.0015 (2) | −0.0005 (2) | −0.0043 (2) |
Cl1 | 0.01252 (11) | 0.01620 (11) | 0.01517 (11) | 0.00083 (7) | 0.00001 (8) | −0.00335 (7) |
Cl2 | 0.01437 (11) | 0.01321 (11) | 0.01439 (11) | −0.00396 (7) | 0.00437 (8) | −0.00269 (7) |
C1—O1 | 1.429 (2) | N1—N2 | 1.449 (2) |
C1—C2 | 1.5076 (12) | N1—H31 | 0.86 (2) |
C1—H11 | 0.98 (2) | N1—H32 | 0.94 (2) |
C1—H12 | 0.966 (14) | N2—H41 | 0.883 (15) |
C2—N1 | 1.502 (2) | N2—H42 | 0.895 (15) |
C2—H21 | 0.971 (13) | N2—H43 | 0.869 (14) |
C2—H22 | 0.94 (2) | O1—H1 | 0.83 (2) |
O1—C1—C2 | 111.20 (7) | N2—N1—H31 | 105.9 (9) |
O1—C1—H11 | 108.9 (8) | C2—N1—H31 | 113.4 (9) |
C2—C1—H11 | 105.2 (8) | N2—N1—H32 | 107.5 (9) |
O1—C1—H12 | 111.6 (8) | C2—N1—H32 | 110.4 (9) |
C2—C1—H12 | 110.6 (8) | H31—N1—H32 | 108.5 (12) |
H11—C1—H12 | 109.1 (12) | N1—N2—H41 | 110.2 (9) |
N1—C2—C1 | 110.94 (7) | N1—N2—H42 | 108.9 (9) |
N1—C2—H21 | 109.2 (8) | H41—N2—H42 | 107.9 (12) |
C1—C2—H21 | 110.9 (8) | N1—N2—H43 | 107.4 (9) |
N1—C2—H22 | 106.8 (8) | H41—N2—H43 | 112.2 (13) |
C1—C2—H22 | 111.4 (8) | H42—N2—H43 | 110.3 (13) |
H21—C2—H22 | 107.5 (11) | C1—O1—H1 | 107.6 (12) |
N2—N1—C2 | 110.86 (6) | ||
O1—C1—C2—N1 | −73.52 (9) | C1—C2—N1—N2 | 176.77 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···Cl1 | 0.833 (17) | 2.278 (17) | 3.0874 (7) | 164.1 (15) |
N1—H31···O1i | 0.856 (15) | 1.986 (14) | 2.7257 (10) | 144.0 (13) |
N1—H31···Cl1 | 0.856 (15) | 2.809 (14) | 3.4104 (8) | 128.7 (11) |
N1—H32···Cl1ii | 0.935 (15) | 2.185 (15) | 3.0832 (8) | 160.9 (12) |
N2—H43···Cl1iii | 0.869 (14) | 2.246 (15) | 3.0864 (8) | 162.4 (12) |
N2—H41···Cl2 | 0.883 (15) | 2.213 (15) | 3.0701 (8) | 163.6 (13) |
N2—H42···Cl2iv | 0.895 (15) | 2.122 (15) | 3.0098 (8) | 171.1 (13) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z; (iv) −x+2, y−1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C2H10N2O2+·2Cl− |
Mr | 149.02 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 150 |
a, b, c (Å) | 10.2367 (9), 8.4158 (6), 7.5111 (7) |
β (°) | 103.208 (7) |
V (Å3) | 629.96 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.93 |
Crystal size (mm) | 0.54 × 0.50 × 0.43 |
Data collection | |
Diffractometer | Stoe IPDS-II diffractometer |
Absorption correction | Integration (X-RED32; Stoe & Cie, 2002) |
Tmin, Tmax | 0.680, 0.735 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 11440, 1678, 1625 |
Rint | 0.077 |
(sin θ/λ)max (Å−1) | 0.684 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.019, 0.050, 1.17 |
No. of reflections | 1678 |
No. of parameters | 104 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 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).
C1—O1 | 1.429 (2) | N1—N2 | 1.449 (2) |
C2—N1 | 1.502 (2) | ||
O1—C1—C2 | 111.20 (7) | N2—N1—C2 | 110.86 (6) |
N1—C2—C1 | 110.94 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···Cl1 | 0.833 (17) | 2.278 (17) | 3.0874 (7) | 164.1 (15) |
N1—H31···O1i | 0.856 (15) | 1.986 (14) | 2.7257 (10) | 144.0 (13) |
N1—H31···Cl1 | 0.856 (15) | 2.809 (14) | 3.4104 (8) | 128.7 (11) |
N1—H32···Cl1ii | 0.935 (15) | 2.185 (15) | 3.0832 (8) | 160.9 (12) |
N2—H43···Cl1iii | 0.869 (14) | 2.246 (15) | 3.0864 (8) | 162.4 (12) |
N2—H41···Cl2 | 0.883 (15) | 2.213 (15) | 3.0701 (8) | 163.6 (13) |
N2—H42···Cl2iv | 0.895 (15) | 2.122 (15) | 3.0098 (8) | 171.1 (13) |
Symmetry codes: (i) x, −y+3/2, z−1/2; (ii) −x+1, y−1/2, −z+1/2; (iii) −x+1, −y+1, −z; (iv) −x+2, y−1/2, −z+1/2. |
Cl1···Cl1v | 3.8930 (5) | Cl1···Cl2vi | 3.8949 (5) |
Cl2···Cl2vii | 3.6487 (3) | Cl2···Cl2v | 3.9842 (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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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).