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The asymmetric unit of the title compound, C12H28N2O4+·2Cl, contains one half of a centrosymmetric cation and one anion. In the crystal structure, inter­molecular N—H...Cl hydrogen bonds result in the formation of a supra­molecular structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680703807X/hk2305sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680703807X/hk2305Isup2.hkl
Contains datablock I

CCDC reference: 662410

Key indicators

  • Single-crystal X-ray study
  • T = 120 K
  • R factor = 0.030
  • wR factor = 0.066
  • Data-to-parameter ratio = 18.8

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Comment top

In recent years, there has been considerable interest in proton transfer systems and their structures (Smith et al., 1999; Zafar et al., 2000). Several proton transfer systems using 1,10-diaza-18-crown-6, with proton donor molecules, such as [(H2DA18C6)I2·2H2O], (II), (Chekhlov, 2005), [(H2DA18C6)(C2HO4)2], (III), and [(H2DA18C6)2(C2O4)2·2H2O], (IV), (Chekhlov, 2000), [(H2DA18C6)(picrate)2], (V), (Chekhlov, 2001), [(H2DA18C6)(HPTD)2], (VI), (Simonov et al., 2003), [(H2DA18C6)(PD)2·(H2O)4], (VII), and [(H2DA18C6)(PS)2·(H2O)2], (VIII), (Fonari et al., 2004), [(H2DA18C6)(CCl3COO)2(CCl3COOH)2], (IX), (Chekhlov et al., 1994), [(H2DA18C6)(CCl3COO)2], (X), (Chekhlov & Martynov, 1998) and {[H2DA18C6][(ArSO2)2N]2}, (XI), (Moers et al., 2000), [where H2DA18C6 is 1,10-Diazonia-18-crown-6, C2O4 is oxalate, HPTD is (4Z,5E)-pyrimidine-2,4,5,6(1H,3H)-tetraone 4,5-dioxime anion, PD is 2-(2-methylphenyl)-2H-[1,2,3]triazolo[4,5-d] pyrimidine-5,7(4H,6H)-dione 3-oxide anion, PS is 6-amino-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-5-yl- sulfamate and (ArSO2)2N is bis(4-chlorobenzenesulfonyl)imide] have been synthesized and characterized by single-crystal X-ray diffraction methods. We report herein the synthesis and crystal structure of the title compound, (I).

The asymmetric unit of (I), (Fig. 1), contains one half centrosymmetric cation and one anion. The bond lengths and angles in good agreement with the corresponding values in (II), (IX) and (X).

In the crystal structure, intermolecular N—H···Cl [H1c···Cl1i = 2.23 (2) Å, N1···Cl1i = 3.11 (1) Å, N1—H1c···Cl1i = 176.0 (3)° and H1dc···Cl1ii = 2.19 (2) Å, N1···Cl1ii = 3.11 (2) Å, N1—H1d···Cl1ii = 174.0 (2)°; symmetry codes: (i) 3/2 - x, 1/2 + y, 1/2 - z; (ii) x, 1 + y, z] hydrogen bonds seem to be effective in the stabilization of the structure, resulting in the formation of a supramolecular structure (Fig. 2).

Related literature top

For related literature, see: Smith et al. (1999); Zafar et al. (2000); Chekhlov et al. (1994); Chekhlov & Martynov (1998); Chekhlov (2000, 2001, 2005); Simonov et al. (2003); Fonari et al. (2004); Moers et al. (2000).

Experimental top

1,10-diaza-18-crown-6 (0.12 g, 0.45 mmol) was added to a solution of HCl (0.1 M, 10 ml) and the resulting colorless solution was stirred at 323 K for 2 h. Then, it was left to evaporate slowly at room temperature. The milky precipitated product was recrystallized from EtOH in two weeks (yield; 0.13 g, 84.7%, m.p. 468–471 K).

Refinement top

H6A, H6B (for CH2) and H1C, H1D (for NH2) were located in difference syntheses and refined isotropically [C—H = 0.970 (17) and 0.979 (16) Å, Uiso(H) = 0.26 (4) and 0.19 (4) Å2; N—H = 0.888 (18) and 0.926 (18) Å, Uiso(H) = 0.26 (4) and 0.31 (4) Å2]. The remaining H atoms were positioned geometrically, with C—H = 0.97 Å for methylene H, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).

Structure description top

In recent years, there has been considerable interest in proton transfer systems and their structures (Smith et al., 1999; Zafar et al., 2000). Several proton transfer systems using 1,10-diaza-18-crown-6, with proton donor molecules, such as [(H2DA18C6)I2·2H2O], (II), (Chekhlov, 2005), [(H2DA18C6)(C2HO4)2], (III), and [(H2DA18C6)2(C2O4)2·2H2O], (IV), (Chekhlov, 2000), [(H2DA18C6)(picrate)2], (V), (Chekhlov, 2001), [(H2DA18C6)(HPTD)2], (VI), (Simonov et al., 2003), [(H2DA18C6)(PD)2·(H2O)4], (VII), and [(H2DA18C6)(PS)2·(H2O)2], (VIII), (Fonari et al., 2004), [(H2DA18C6)(CCl3COO)2(CCl3COOH)2], (IX), (Chekhlov et al., 1994), [(H2DA18C6)(CCl3COO)2], (X), (Chekhlov & Martynov, 1998) and {[H2DA18C6][(ArSO2)2N]2}, (XI), (Moers et al., 2000), [where H2DA18C6 is 1,10-Diazonia-18-crown-6, C2O4 is oxalate, HPTD is (4Z,5E)-pyrimidine-2,4,5,6(1H,3H)-tetraone 4,5-dioxime anion, PD is 2-(2-methylphenyl)-2H-[1,2,3]triazolo[4,5-d] pyrimidine-5,7(4H,6H)-dione 3-oxide anion, PS is 6-amino-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-5-yl- sulfamate and (ArSO2)2N is bis(4-chlorobenzenesulfonyl)imide] have been synthesized and characterized by single-crystal X-ray diffraction methods. We report herein the synthesis and crystal structure of the title compound, (I).

The asymmetric unit of (I), (Fig. 1), contains one half centrosymmetric cation and one anion. The bond lengths and angles in good agreement with the corresponding values in (II), (IX) and (X).

In the crystal structure, intermolecular N—H···Cl [H1c···Cl1i = 2.23 (2) Å, N1···Cl1i = 3.11 (1) Å, N1—H1c···Cl1i = 176.0 (3)° and H1dc···Cl1ii = 2.19 (2) Å, N1···Cl1ii = 3.11 (2) Å, N1—H1d···Cl1ii = 174.0 (2)°; symmetry codes: (i) 3/2 - x, 1/2 + y, 1/2 - z; (ii) x, 1 + y, z] hydrogen bonds seem to be effective in the stabilization of the structure, resulting in the formation of a supramolecular structure (Fig. 2).

For related literature, see: Smith et al. (1999); Zafar et al. (2000); Chekhlov et al. (1994); Chekhlov & Martynov (1998); Chekhlov (2000, 2001, 2005); Simonov et al. (2003); Fonari et al. (2004); Moers et al. (2000).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [symmetry code a: 2 - x, -y, 1 - z].
[Figure 2] Fig. 2. A partial packing diagram of (I). Hydrogen bonds are shown as dashed lines.
1,10-Diazonia-18-crown-6 dichloride top
Crystal data top
C12H28N2O42+·2ClF(000) = 360
Mr = 335.26Dx = 1.321 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2000 reflections
a = 9.5461 (19) Åθ = 2.5–22.5°
b = 5.6297 (11) ŵ = 0.40 mm1
c = 15.688 (3) ÅT = 120 K
β = 90.70 (3)°Needle, colorless
V = 843.0 (3) Å30.35 × 0.10 × 0.05 mm
Z = 2
Data collection top
Stoe IPDSII
diffractometer
2012 independent reflections
Radiation source: fine-focus sealed tube1811 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
Detector resolution: 0.15 mm pixels mm-1θmax = 27.9°, θmin = 2.5°
rotation method scansh = 1212
Absorption correction: numerical
(shape of crystal determined optically)
k = 77
Tmin = 0.950, Tmax = 0.980l = 2020
6928 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)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066H atoms treated by a mixture of independent and constrained refinement
S = 1.13 w = 1/[σ2(Fo2) + (0.0217P)2 + 0.3926P]
where P = (Fo2 + 2Fc2)/3
2012 reflections(Δ/σ)max = 0.011
107 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.18 e Å3
Crystal data top
C12H28N2O42+·2ClV = 843.0 (3) Å3
Mr = 335.26Z = 2
Monoclinic, P21/nMo Kα radiation
a = 9.5461 (19) ŵ = 0.40 mm1
b = 5.6297 (11) ÅT = 120 K
c = 15.688 (3) Å0.35 × 0.10 × 0.05 mm
β = 90.70 (3)°
Data collection top
Stoe IPDSII
diffractometer
2012 independent reflections
Absorption correction: numerical
(shape of crystal determined optically)
1811 reflections with I > 2σ(I)
Tmin = 0.950, Tmax = 0.980Rint = 0.027
6928 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.066H atoms treated by a mixture of independent and constrained refinement
S = 1.13Δρmax = 0.31 e Å3
2012 reflectionsΔρmin = 0.18 e Å3
107 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
Cl10.57203 (3)0.11647 (5)0.317180 (18)0.01755 (9)
O11.11725 (9)0.01497 (16)0.39337 (5)0.01855 (19)
O20.77044 (9)0.43864 (16)0.54459 (5)0.01715 (19)
N10.83570 (11)0.42244 (18)0.35935 (6)0.0150 (2)
H1C0.7629 (18)0.332 (3)0.3449 (10)0.026 (4)*
H1D0.8705 (18)0.479 (3)0.3084 (11)0.031 (4)*
C11.02583 (13)0.1255 (2)0.34187 (7)0.0171 (2)
H1A0.96270.02560.30880.021*
H1B1.07880.22430.30310.021*
C20.94521 (12)0.2770 (2)0.40406 (8)0.0159 (2)
H2A0.90090.17530.44580.019*
H2B1.00960.38160.43420.019*
C30.78311 (13)0.6312 (2)0.40907 (8)0.0177 (2)
H3A0.73160.73610.37100.021*
H3B0.86240.71890.43210.021*
C40.68918 (12)0.5579 (2)0.48138 (8)0.0180 (2)
H4A0.64540.69720.50590.022*
H4B0.61580.45360.46010.022*
C50.69032 (13)0.2846 (2)0.59700 (8)0.0191 (3)
H5A0.63900.17160.56190.023*
H5B0.62350.37590.62960.023*
C60.78945 (13)0.1554 (2)0.65629 (8)0.0188 (3)
H6A0.7348 (17)0.054 (3)0.6930 (10)0.026 (4)*
H6B0.8432 (16)0.267 (3)0.6918 (10)0.019 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.01650 (14)0.01926 (15)0.01685 (14)0.00181 (11)0.00086 (9)0.00161 (11)
O10.0203 (4)0.0203 (4)0.0151 (4)0.0079 (4)0.0013 (3)0.0012 (3)
O20.0145 (4)0.0191 (4)0.0179 (4)0.0001 (3)0.0012 (3)0.0042 (3)
N10.0140 (5)0.0162 (5)0.0149 (5)0.0006 (4)0.0024 (4)0.0021 (4)
C10.0186 (5)0.0179 (6)0.0149 (5)0.0031 (5)0.0003 (4)0.0021 (5)
C20.0152 (5)0.0172 (6)0.0153 (5)0.0033 (5)0.0021 (4)0.0003 (5)
C30.0197 (6)0.0132 (5)0.0201 (6)0.0028 (5)0.0026 (4)0.0019 (5)
C40.0152 (5)0.0190 (6)0.0197 (6)0.0048 (5)0.0012 (4)0.0000 (5)
C50.0149 (5)0.0205 (6)0.0221 (6)0.0013 (5)0.0042 (4)0.0029 (5)
C60.0186 (6)0.0213 (6)0.0166 (5)0.0039 (5)0.0053 (5)0.0019 (5)
Geometric parameters (Å, º) top
C1—O11.4223 (15)C4—H4A0.9700
C1—C21.5132 (16)C4—H4B0.9700
C1—H1A0.9700C5—O21.4243 (15)
C1—H1B0.9700C5—C61.5060 (18)
C2—N11.4958 (15)C5—H5A0.9700
C2—H2A0.9700C5—H5B0.9700
C2—H2B0.9700C6—O1i1.4290 (14)
C3—N11.5003 (16)C6—H6A0.970 (17)
C3—C41.5119 (17)C6—H6B0.979 (16)
C3—H3A0.9700N1—H1C0.888 (18)
C3—H3B0.9700N1—H1D0.926 (18)
C4—O21.4203 (15)O1—C6i1.4290 (14)
O1—C1—C2105.10 (9)C3—C4—H4B109.8
O1—C1—H1A110.7H4A—C4—H4B108.3
C2—C1—H1A110.7O2—C5—C6108.23 (10)
O1—C1—H1B110.7O2—C5—H5A110.1
C2—C1—H1B110.7C6—C5—H5A110.1
H1A—C1—H1B108.8O2—C5—H5B110.1
N1—C2—C1111.36 (10)C6—C5—H5B110.1
N1—C2—H2A109.4H5A—C5—H5B108.4
C1—C2—H2A109.4O1i—C6—C5108.75 (10)
N1—C2—H2B109.4O1i—C6—H6A109.9 (10)
C1—C2—H2B109.4C5—C6—H6A108.3 (10)
H2A—C2—H2B108.0O1i—C6—H6B109.8 (9)
N1—C3—C4112.45 (10)C5—C6—H6B111.3 (9)
N1—C3—H3A109.1H6A—C6—H6B108.8 (13)
C4—C3—H3A109.1C2—N1—C3114.92 (9)
N1—C3—H3B109.1C2—N1—H1C110.3 (11)
C4—C3—H3B109.1C3—N1—H1C108.3 (11)
H3A—C3—H3B107.8C2—N1—H1D109.8 (11)
O2—C4—C3109.21 (10)C3—N1—H1D107.6 (11)
O2—C4—H4A109.8H1C—N1—H1D105.4 (15)
C3—C4—H4A109.8C1—O1—C6i112.34 (9)
O2—C4—H4B109.8C4—O2—C5113.48 (9)
O1—C1—C2—N1175.53 (9)C4—C3—N1—C273.04 (13)
N1—C3—C4—O268.74 (13)C2—C1—O1—C6i174.95 (10)
O2—C5—C6—O1i62.08 (13)C3—C4—O2—C5156.73 (10)
C1—C2—N1—C3161.13 (10)C6—C5—O2—C4175.61 (10)
Symmetry code: (i) x+2, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···Cl10.89 (2)2.23 (2)3.1144 (12)175.7 (14)
N1—H1D···Cl1ii0.93 (2)2.19 (2)3.1142 (12)174.0 (2)
Symmetry code: (ii) x+3/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC12H28N2O42+·2Cl
Mr335.26
Crystal system, space groupMonoclinic, P21/n
Temperature (K)120
a, b, c (Å)9.5461 (19), 5.6297 (11), 15.688 (3)
β (°) 90.70 (3)
V3)843.0 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.40
Crystal size (mm)0.35 × 0.10 × 0.05
Data collection
DiffractometerStoe IPDSII
Absorption correctionNumerical
(shape of crystal determined optically)
Tmin, Tmax0.950, 0.980
No. of measured, independent and
observed [I > 2σ(I)] reflections
6928, 2012, 1811
Rint0.027
(sin θ/λ)max1)0.658
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.030, 0.066, 1.13
No. of reflections2012
No. of parameters107
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.31, 0.18

Computer programs: X-AREA (Stoe & Cie, 2005), X-AREA, X-RED (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1C···Cl10.89 (2)2.23 (2)3.1144 (12)175.7 (14)
N1—H1D···Cl1i0.93 (2)2.19 (2)3.1142 (12)174.0 (2)
Symmetry code: (i) x+3/2, y+1/2, z+1/2.
 

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