Acetyl­ene–ammonia–18-crown-6 (1/2/1)

Grassl, T.; Hamberger, M.; Korber, N.

doi:10.1107/S1600536812038792

organic compounds

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Volume 68| Part 10| October 2012| Page o2933

https://doi.org/10.1107/S1600536812038792

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Acetylene–ammonia–18-crown-6 (1/2/1)

Tobias Grassl,^a Markus Hamberger ^a and Nikolaus Korber ^a ^*

^aInstitut für Anorganische Chemie, Universität Regensburg, Universitätsstrasse 31, 93053 Regensburg, Germany
^*Correspondence e-mail: nikolaus.korber@chemie.uni-regensburg.de

(Received 27 July 2012; accepted 10 September 2012; online 15 September 2012)

The title compound, C₂H₂·C₁₂H₂₄O₆·2NH₃, was formed by co-crystallization of 18-crown-6 and acetylene in liquid ammonia. The 18-crown-6 molecule has threefold rotoinversion symmetry. The acteylene molecule lies on the threefold axis and the whole molecule is generated by an inversion center. The two ammonia molecules are also located on the threefold axis and are related by inversion symmetry. In the crystal, the ammonia molecules are located below and above the crown ether plane and are connected by intermolecular N—H⋯O hydrogen bonds. The acetylene molecules are additionally linked by weak C—H⋯N interactions into chains that propagate in the direction of the crystallographic c axis. The 18-crown-6 molecule [occupancy ratio 0.830 (4):0.170 (4)] is disordered and was refined using a split model.

Related literature

For weak intermolecular interactions such as hydrogen bonds and their application in crystal engineering, see: Desiraju (2002 , 2007 ); Boese et al. (2003 , 2009 ); Kirchner et al. (2004 ); Steiner (2002 )

Experimental

Crystal data

C₂H₂·C₁₂H₂₄O₆·2NH₃
M_r = 324.42
Trigonal, $[R \overline 3]$
a = 11.8915 (1) Å
c = 11.5736 (2) Å
V = 1417.33 (3) Å³
Z = 3
Cu Kα radiation
μ = 0.73 mm⁻¹
T = 123 K
0.1 × 0.1 × 0.1 mm

Data collection

Oxford Diffraction SuperNova diffractometer
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012 ), based on expressions derived by Clark & Reid (1995 )] T_min = 0.798, T_max = 0.841
5835 measured reflections
640 independent reflections
598 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.100
S = 1.11
640 reflections
53 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.88	2.40	3.2709 (12)	171
N1—H1A⋯O1A	0.88	2.43	3.270 (4)	159
C1—H1⋯N1	0.95	2.34	3.292 (2)	180

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: olex2.solve (Bourhis et al., 2012 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: DIAMOND (Brandenburg & Putz, H, 2011 ); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812038792/nc2288sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812038792/nc2288Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812038792/nc2288Isup3.mol

Supporting information file. DOI: https://doi.org/10.1107/S1600536812038792/nc2288Isup4.cml

checkCIF report

Comment top

The crystal structure of the title compound was determined in the course of investigations regarding the reactivity of acetylene in liquid ammonia.

In the crystal structure the acetylene molecule shows moderate hydrogen bonding in axial direction to an ammonia molecule on each side with a H···N distance of 2.3422 (15) Å and a C—H···N angle of 180°. Two ammonia molecules are located below and above the crown ether plane, bound by hydrogen bonds to the oxygen atoms in the ring (Fig. 1 and Fig. 2). Both ammonia molecules are connected to 18-crown-6 via three hydrogen bonds each with a H···O distance of 2.40 Å and a N—H···O angle of 171.0° for the crown ether part with a site occupation factor of 0.83 and with a H···O distance of 2.43 Å and a N—H···O angle of 159.4° for the crown ether part with a site occupation factor of 0.17 (Fig. 2 and Table 1).This arrangement leads to one-dimensional strands along the crystallographic c-axis, that are packed in a kind of hexagonal closest arrangement (Fig. 3). The formation of hydrogen bonds between acetylene and ammonia molecules as well as the interaction of ammonia molecules with the crown ether is essential to stabilize the fugitive acetylene molecule in the solid state as was shown previously by Boese et al. (Boese et al., 2009) in C₂H₂*NH₃. Due to the absence of stronger intermolecular interactions the optimization of hydrogen bonds is the driving force for the axial stacking of the molecules along the crystallographic c-axis. This can also be observed in acetylene containing material such as co-crystallized C₂H₂*NH₃ (Boese et al., 2009) and co-crystals of acetylene and acetone/DMSO (Boese et al., 2003) or azacycles (Kirchner et al., 2004).

Related literature top

For weak intermolecular interactions such as hydrogen bonds and their application in crystal engineering, see: Desiraju (2002, 2007); Boese et al. (2003, 2009); Kirchner et al. (2004); Steiner (2002)

Experimental top

0.039 g(1.0 mmol) potassium and 0.264 g(1.00 mmol)18-crown-6 were placed under argon atmosphere in a baked-out reaction vessel and 30 ml of dry liquid ammonia were condensed. The mixture was stored at 236 K for one week to ensure that all substances were completely dissolved. Afterwards an excess of acetylene gas was fed into the solution until the colour changed from deep blue to colourless. Colourless crystals of the title compound were obtained after further storage at 236 K for nine month. Well soluble potassium hydrogen acetylide KC₂H remained in solution.

Structure description top

The crystal structure of the title compound was determined in the course of investigations regarding the reactivity of acetylene in liquid ammonia.

For weak intermolecular interactions such as hydrogen bonds and their application in crystal engineering, see: Desiraju (2002, 2007); Boese et al. (2003, 2009); Kirchner et al. (2004); Steiner (2002)

Computing details top

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: olex2.solve (Bourhis et al., 2012); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, H, 2011); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. : Crystal structure of the title compound with labeling and displacement ellipsoids drawn at the 50% probability level. Disordering is shown as full and open bonds. Symmetry codes: (i) 2/3 - x, 4/3 - y, 1/3 - z; (ii) -1/3 + y, 1/3 - x + y, 4/3 - z; (iii) 2/3 + x-y, 1/3 + x, 4/3 - z.
	Fig. 2. : Crystal structure with view along the b-axis showing the hydrogen bonding interactions. Displacement ellipsoids are drawn at the 50% probability level and disorder is shown as full and open bonds.
	Fig. 3. : Projection of the unit cell along the crystallographic c-axis. Displacement ellipsoids are drawn at the 50% probability level and disorder is shown as full and open bonds

Ethyne–ammonia–1,4,7,10,13,16-hexaoxacyclooctadecane (1/2/1) top

Crystal data top

C₂H₂·C₁₂H₂₄O₆·2NH₃	D_x = 1.140 Mg m⁻³
M_r = 324.42	Cu Kα radiation, λ = 1.54184 Å
Trigonal, R3	Cell parameters from 3585 reflections
Hall symbol: -R 3	θ = 5.8–73.3°
a = 11.8915 (1) Å	µ = 0.73 mm⁻¹
c = 11.5736 (2) Å	T = 123 K
V = 1417.33 (3) Å³	Block, clear colourless
Z = 3	0.1 × 0.1 × 0.1 mm
F(000) = 534

Data collection top

Oxford Diffraction SuperNova diffractometer	640 independent reflections
Radiation source: fine-focus sealed tube	598 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
ω scans	θ_max = 73.3°, θ_min = 5.8°
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012), based on expressions derived by Clark & Reid (1995)]	h = −14→14
T_min = 0.798, T_max = 0.841	k = −14→14
5835 measured reflections	l = −14→14

Refinement top

Refinement on F²	Primary atom site location: iterative
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.100	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0481P)² + 0.8298P] where P = (F_o² + 2F_c²)/3
640 reflections	(Δ/σ)_max < 0.001
53 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₂H₂·C₁₂H₂₄O₆·2NH₃	Z = 3
M_r = 324.42	Cu Kα radiation
Trigonal, R3	µ = 0.73 mm⁻¹
a = 11.8915 (1) Å	T = 123 K
c = 11.5736 (2) Å	0.1 × 0.1 × 0.1 mm
V = 1417.33 (3) Å³

Data collection top

Oxford Diffraction SuperNova diffractometer	640 independent reflections
Absorption correction: analytical [CrysAlis PRO (Agilent, 2012), based on expressions derived by Clark & Reid (1995)]	598 reflections with I > 2σ(I)
T_min = 0.798, T_max = 0.841	R_int = 0.032
5835 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	0 restraints
wR(F²) = 0.100	H-atom parameters constrained
S = 1.11	Δρ_max = 0.18 e Å⁻³
640 reflections	Δρ_min = −0.19 e Å⁻³
53 parameters

Special details top

Experimental. Absorption correction: Crysalis Pro, Agilent Technologies, Version 1.171.35.21, Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R. C. Clark & J. S. Reid (1995).

Crystal mounting in perfluorether

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
O1	0.34988 (11)	0.43774 (10)	0.64475 (7)	0.0298 (4)	0.830 (4)
C2	0.23519 (11)	0.32279 (10)	0.67833 (11)	0.0387 (4)
H2AA	0.2314	0.3164	0.7637	0.046*	0.830 (4)
H2AB	0.2375	0.2463	0.6476	0.046*	0.830 (4)
H2BC	0.1912	0.2473	0.7309	0.046*	0.170 (4)
H2BD	0.2225	0.2880	0.5987	0.046*	0.170 (4)
C3	0.46325 (13)	0.45185 (13)	0.69816 (12)	0.0344 (4)	0.830 (4)
H3B	0.4711	0.3743	0.6819	0.041*	0.830 (4)
H3A	0.4568	0.4586	0.7829	0.041*	0.830 (4)
O1A	0.4390 (5)	0.5013 (5)	0.6463 (3)	0.0254 (17)	0.170 (4)
C3A	0.3587 (6)	0.3803 (6)	0.7006 (6)	0.0312 (12)	0.17
H3AB	0.3905	0.3206	0.6786	0.037*	0.170 (4)
H3AA	0.3700	0.3934	0.7852	0.037*	0.170 (4)
N1	0.3333	0.6667	0.50242 (13)	0.0330 (4)
H1A	0.3430	0.6046	0.5340	0.040*
C1	0.3333	0.6667	0.21796 (16)	0.0289 (4)
H1	0.3333	0.6667	0.3000	0.035*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0306 (8)	0.0310 (6)	0.0287 (5)	0.0160 (5)	0.0010 (4)	0.0042 (4)
C2	0.0397 (7)	0.0276 (6)	0.0487 (7)	0.0168 (5)	0.0111 (5)	0.0046 (4)
C3	0.0379 (8)	0.0347 (7)	0.0359 (8)	0.0220 (7)	−0.0045 (5)	−0.0002 (5)
O1A	0.027 (3)	0.029 (3)	0.022 (2)	0.016 (2)	−0.0035 (16)	0.0004 (17)
C3A	0.027 (3)	0.029 (3)	0.040 (3)	0.016 (3)	−0.002 (2)	0.000 (3)
N1	0.0363 (6)	0.0363 (6)	0.0263 (7)	0.0182 (3)	0.000	0.000
C1	0.0257 (5)	0.0257 (5)	0.0351 (8)	0.0129 (3)	0.000	0.000

Geometric parameters (Å, º) top

O1—C2	1.4196 (15)	C3—H3B	0.9900
O1—C3	1.4148 (18)	C3—H3A	0.9900
C2—H2AA	0.9900	O1A—C2ⁱⁱ	1.446 (5)
C2—H2AB	0.9900	O1A—C3A	1.416 (8)
C2—H2BC	0.9900	C3A—H3AB	0.9900
C2—H2BD	0.9900	C3A—H3AA	0.9900
C2—C3ⁱ	1.4698 (18)	N1—H1A	0.8810
C2—O1Aⁱ	1.446 (5)	C1—C1ⁱⁱⁱ	1.187 (4)
C2—C3A	1.298 (6)	C1—H1	0.9500
C3—C2ⁱⁱ	1.4698 (18)

C3—O1—C2	113.22 (10)	C3A—C2—H2BC	107.5
O1—C2—H2AA	109.4	C3A—C2—H2BD	107.5
O1—C2—H2AB	109.4	C3A—C2—C3ⁱ	152.4 (3)
O1—C2—H2BC	149.2	C3A—C2—O1Aⁱ	119.3 (3)
O1—C2—H2BD	91.2	O1—C3—C2ⁱⁱ	110.55 (11)
O1—C2—C3ⁱ	111.27 (10)	O1—C3—H3B	109.5
O1—C2—O1Aⁱ	89.71 (18)	O1—C3—H3A	109.5
H2AA—C2—H2AB	108.0	C2ⁱⁱ—C3—H3B	109.5
H2BC—C2—H2BD	107.0	C2ⁱⁱ—C3—H3A	109.5
C3ⁱ—C2—H2AA	109.4	H3B—C3—H3A	108.1
C3ⁱ—C2—H2AB	109.4	C3A—O1A—C2ⁱⁱ	122.5 (4)
C3ⁱ—C2—H2BC	97.7	C2—C3A—O1A	117.3 (5)
C3ⁱ—C2—H2BD	74.6	C2—C3A—H3AB	108.0
O1Aⁱ—C2—H2AA	87.6	C2—C3A—H3AA	108.0
O1Aⁱ—C2—H2AB	148.6	O1A—C3A—H3AB	108.0
O1Aⁱ—C2—H2BC	107.5	O1A—C3A—H3AA	108.0
O1Aⁱ—C2—H2BD	107.5	H3AB—C3A—H3AA	107.2
C3A—C2—H2AA	80.7	C1ⁱⁱⁱ—C1—H1	180.0
C3A—C2—H2AB	90.6

Symmetry codes: (i) y−1/3, −x+y+1/3, −z+4/3; (ii) x−y+2/3, x+1/3, −z+4/3; (iii) −x+2/3, −y+4/3, −z+1/3.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.88	2.40	3.2709 (12)	171
N1—H1A···O1A	0.88	2.43	3.270 (4)	159
C1—H1···N1	0.95	2.34	3.292 (2)	180

Experimental details

Crystal data
Chemical formula	C₂H₂·C₁₂H₂₄O₆·2NH₃
M_r	324.42
Crystal system, space group	Trigonal, R3
Temperature (K)	123
a, c (Å)	11.8915 (1), 11.5736 (2)
V (Å³)	1417.33 (3)
Z	3
Radiation type	Cu Kα
µ (mm⁻¹)	0.73
Crystal size (mm)	0.1 × 0.1 × 0.1

Data collection
Diffractometer	Oxford Diffraction SuperNova
Absorption correction	Analytical [CrysAlis PRO (Agilent, 2012), based on expressions derived by Clark & Reid (1995)]
T_min, T_max	0.798, 0.841
No. of measured, independent and observed [I > 2σ(I)] reflections	5835, 640, 598
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.621

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.100, 1.11
No. of reflections	640
No. of parameters	53
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.19

Computer programs: CrysAlis PRO (Agilent, 2012), olex2.solve (Bourhis et al., 2012), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, H, 2011), OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.88	2.40	3.2709 (12)	171.0
N1—H1A···O1A	0.88	2.43	3.270 (4)	159.4
C1—H1···N1	0.95	2.34	3.292 (2)	180.0

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 10| October 2012| Page o2933

https://doi.org/10.1107/S1600536812038792

Open

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