1,10-Diazo­nia-18-crown-6 dichloride

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.

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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S1. Comment

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

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).

S2. Experimental

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).

S3. Refinement

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, U_iso(H) = 0.26 (4) and 0.19 (4) Ų; N—H = 0.888 (18) and 0.926 (18) Å, U_iso(H) = 0.26 (4) and 0.31 (4) Ų]. 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 U_iso(H) = 1.2U_eq(C).

Computing details

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

	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].
	Fig. 2. A partial packing diagram of (I). Hydrogen bonds are shown as dashed lines.

1,10-Diazonia-18-crown-6 dichloride

Crystal data

C12H28N2O4^2+·2Cl^−	F(000) = 360
Mr = 335.26	Dx = 1.321 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2000 reflections
a = 9.5461 (19) Å	θ = 2.5–22.5°
b = 5.6297 (11) Å	µ = 0.40 mm^−1
c = 15.688 (3) Å	T = 120 K
β = 90.70 (3)°	Needle, colorless
V = 843.0 (3) Å^3	0.35 × 0.10 × 0.05 mm
Z = 2

Data collection

Stoe IPDSII diffractometer	2012 independent reflections
Radiation source: fine-focus sealed tube	1811 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.027
Detector resolution: 0.15 mm pixels mm^-1	θmax = 27.9°, θmin = 2.5°
rotation method scans	h = −12→12
Absorption correction: numerical (shape of crystal determined optically)	k = −7→7
Tmin = 0.950, Tmax = 0.980	l = −20→20
6928 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.066	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ^2(Fo^2) + (0.0217P)^2 + 0.3926P] where P = (Fo^2 + 2Fc^2)/3
2012 reflections	(Δ/σ)max = 0.011
107 parameters	Δρmax = 0.31 e Å^−3
0 restraints	Δρmin = −0.18 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.57203 (3)	0.11647 (5)	0.317180 (18)	0.01755 (9)
O1	1.11725 (9)	−0.01497 (16)	0.39337 (5)	0.01855 (19)
O2	0.77044 (9)	0.43864 (16)	0.54459 (5)	0.01715 (19)
N1	0.83570 (11)	0.42244 (18)	0.35935 (6)	0.0150 (2)
H1C	0.7629 (18)	0.332 (3)	0.3449 (10)	0.026 (4)*
H1D	0.8705 (18)	0.479 (3)	0.3084 (11)	0.031 (4)*
C1	1.02583 (13)	0.1255 (2)	0.34187 (7)	0.0171 (2)
H1A	0.9627	0.0256	0.3088	0.021*
H1B	1.0788	0.2243	0.3031	0.021*
C2	0.94521 (12)	0.2770 (2)	0.40406 (8)	0.0159 (2)
H2A	0.9009	0.1753	0.4458	0.019*
H2B	1.0096	0.3816	0.4342	0.019*
C3	0.78311 (13)	0.6312 (2)	0.40907 (8)	0.0177 (2)
H3A	0.7316	0.7361	0.3710	0.021*
H3B	0.8624	0.7189	0.4321	0.021*
C4	0.68918 (12)	0.5579 (2)	0.48138 (8)	0.0180 (2)
H4A	0.6454	0.6972	0.5059	0.022*
H4B	0.6158	0.4536	0.4601	0.022*
C5	0.69032 (13)	0.2846 (2)	0.59700 (8)	0.0191 (3)
H5A	0.6390	0.1716	0.5619	0.023*
H5B	0.6235	0.3759	0.6296	0.023*
C6	0.78945 (13)	0.1554 (2)	0.65629 (8)	0.0188 (3)
H6A	0.7348 (17)	0.054 (3)	0.6930 (10)	0.026 (4)*
H6B	0.8432 (16)	0.267 (3)	0.6918 (10)	0.019 (4)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.01650 (14)	0.01926 (15)	0.01685 (14)	−0.00181 (11)	−0.00086 (9)	−0.00161 (11)
O1	0.0203 (4)	0.0203 (4)	0.0151 (4)	0.0079 (4)	0.0013 (3)	0.0012 (3)
O2	0.0145 (4)	0.0191 (4)	0.0179 (4)	−0.0001 (3)	−0.0012 (3)	0.0042 (3)
N1	0.0140 (5)	0.0162 (5)	0.0149 (5)	−0.0006 (4)	−0.0024 (4)	0.0021 (4)
C1	0.0186 (5)	0.0179 (6)	0.0149 (5)	0.0031 (5)	−0.0003 (4)	0.0021 (5)
C2	0.0152 (5)	0.0172 (6)	0.0153 (5)	0.0033 (5)	−0.0021 (4)	0.0003 (5)
C3	0.0197 (6)	0.0132 (5)	0.0201 (6)	0.0028 (5)	−0.0026 (4)	0.0019 (5)
C4	0.0152 (5)	0.0190 (6)	0.0197 (6)	0.0048 (5)	−0.0012 (4)	0.0000 (5)
C5	0.0149 (5)	0.0205 (6)	0.0221 (6)	0.0013 (5)	0.0042 (4)	0.0029 (5)
C6	0.0186 (6)	0.0213 (6)	0.0166 (5)	0.0039 (5)	0.0053 (5)	0.0019 (5)

Geometric parameters (Å, º)

C1—O1	1.4223 (15)	C4—H4A	0.9700
C1—C2	1.5132 (16)	C4—H4B	0.9700
C1—H1A	0.9700	C5—O2	1.4243 (15)
C1—H1B	0.9700	C5—C6	1.5060 (18)
C2—N1	1.4958 (15)	C5—H5A	0.9700
C2—H2A	0.9700	C5—H5B	0.9700
C2—H2B	0.9700	C6—O1^i	1.4290 (14)
C3—N1	1.5003 (16)	C6—H6A	0.970 (17)
C3—C4	1.5119 (17)	C6—H6B	0.979 (16)
C3—H3A	0.9700	N1—H1C	0.888 (18)
C3—H3B	0.9700	N1—H1D	0.926 (18)
C4—O2	1.4203 (15)	O1—C6^i	1.4290 (14)
O1—C1—C2	105.10 (9)	C3—C4—H4B	109.8
O1—C1—H1A	110.7	H4A—C4—H4B	108.3
C2—C1—H1A	110.7	O2—C5—C6	108.23 (10)
O1—C1—H1B	110.7	O2—C5—H5A	110.1
C2—C1—H1B	110.7	C6—C5—H5A	110.1
H1A—C1—H1B	108.8	O2—C5—H5B	110.1
N1—C2—C1	111.36 (10)	C6—C5—H5B	110.1
N1—C2—H2A	109.4	H5A—C5—H5B	108.4
C1—C2—H2A	109.4	O1^i—C6—C5	108.75 (10)
N1—C2—H2B	109.4	O1^i—C6—H6A	109.9 (10)
C1—C2—H2B	109.4	C5—C6—H6A	108.3 (10)
H2A—C2—H2B	108.0	O1^i—C6—H6B	109.8 (9)
N1—C3—C4	112.45 (10)	C5—C6—H6B	111.3 (9)
N1—C3—H3A	109.1	H6A—C6—H6B	108.8 (13)
C4—C3—H3A	109.1	C2—N1—C3	114.92 (9)
N1—C3—H3B	109.1	C2—N1—H1C	110.3 (11)
C4—C3—H3B	109.1	C3—N1—H1C	108.3 (11)
H3A—C3—H3B	107.8	C2—N1—H1D	109.8 (11)
O2—C4—C3	109.21 (10)	C3—N1—H1D	107.6 (11)
O2—C4—H4A	109.8	H1C—N1—H1D	105.4 (15)
C3—C4—H4A	109.8	C1—O1—C6^i	112.34 (9)
O2—C4—H4B	109.8	C4—O2—C5	113.48 (9)
O1—C1—C2—N1	−175.53 (9)	C4—C3—N1—C2	−73.04 (13)
N1—C3—C4—O2	68.74 (13)	C2—C1—O1—C6^i	−174.95 (10)
O2—C5—C6—O1^i	−62.08 (13)	C3—C4—O2—C5	−156.73 (10)
C1—C2—N1—C3	−161.13 (10)	C6—C5—O2—C4	175.61 (10)

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···Cl1	0.89 (2)	2.23 (2)	3.1144 (12)	175.7 (14)
N1—H1D···Cl1^ii	0.93 (2)	2.19 (2)	3.1142 (12)	174.0 (2)

Symmetry code: (ii) −x+3/2, y+1/2, −z+1/2.