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The title compound, a 1:2 adduct of 18-crown-6 and ammonia, C12H24O6·2NH3, has inversion symmetry. Two ammonia mol­ecules are connected to the crown ether above and below the cyclic plane via N—H...O hydrogen bonds to form a disc-like adduct.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805027364/ob6577sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805027364/ob6577Isup2.hkl
Contains datablock I

CCDC reference: 287679

Key indicators

  • Single-crystal X-ray study
  • T = 100 K
  • Mean [sigma](C-C) = 0.002 Å
  • R factor = 0.048
  • wR factor = 0.123
  • Data-to-parameter ratio = 13.1

checkCIF/PLATON results

No syntax errors found



Alert level C ABSTM02_ALERT_3_C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90 Tmin and Tmax reported: 0.767 0.986 Tmin(prime) and Tmax expected: 0.962 0.986 RR(prime) = 0.797 Please check that your absorption correction is appropriate. PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.80 PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given ....... ? PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.11 Ratio
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 5 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 ALERT type 3 Indicator that the structure quality may be low 2 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

The group of cyclic polyethers, the so called crown ethers, certainly is one of the most useful substance classes in organic, metallorganic and inorganic chemistry. Crown ethers, which are tools to increase the solubility of inorganic salts in organic solvents (Yakshin, 2002), are able to coordinate to charged as well as neutral molecules (Elbasyouny et al., 1983; Huang et al., 1993; Doxsee et al., 2000) and have been used to isolate such unusual compounds as alkalides and electrides (Dye, 1984). The fact that almost every week new crown ether compounds are published confirm this impression. We report here on the title compound, (I), the 1:2 adduct of 18-crown-6 and ammonia, which forms a queue with other solvent–crown ether adducts starting with the water complexes of crown ethers (Newkome et al., 1981; Mootz et al., 1994) over acetonitrile compounds (Mosier-Boss & Popov, 1985; Mosier-Boss, 2005) to adducts containing formamide or nitromethane (Voegtle et al., 1980; de Boer et al., 1982).

Compound (I) has inversion symmetry (Fig. 1). The disc-like building blocks are stacked along the c axis with a tilt angle of 52.4 (s.u.?)° between the plane normal (line between the two N atoms) and the c axis (Fig. 2). The N—H···O hydrogen bonds (Table 1) connect the NH3 molecules with the crown ether. The H···O distances [2.30 (3)–2.43 (3) Å] fit to values recently reported for the {[Li(NH3)4]2[18-crown-6]2+ cation (Wiesler and Korber, 2005).

Experimental top

Crystals of (I) were grown by slow evaporation of a satured solution of 18-crown-6 in liquid ammonia at 195 K.

Refinement top

All H atoms were located from difference maps and refined freely. The C—H and N—H distances are 0.93 (2)–1.01 (2) Å and 0.85 (3)–0.90 (3) Å, respectively.

Computing details top

Data collection: SMART32 (Bruker, 1997); cell refinement: SAINT32 (Bruker, 2003); data reduction: SAINT32; program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: ATOMS (Dowty, 2002); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) with numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. Unlabeled atoms are related to labeled atoms by (−x, −y, 1 − z). Broken lines indicate hydrogen bonds.
[Figure 2] Fig. 2. Packing scheme of (I) projected along the a axis. Broken lines indicate hydrogen bonds.
1,4,7,10,13,16-Hexaoxacyclooctadecane–ammonia (1/2) top
Crystal data top
C12H24O6·2H3NF(000) = 328
Mr = 298.38Dx = 1.203 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.4789 (14) ÅCell parameters from 1983 reflections
b = 7.6632 (14) Åθ = 5.5–59.7°
c = 14.374 (3) ŵ = 0.10 mm1
β = 91.754 (4)°T = 100 K
V = 823.4 (3) Å3Needle, colorless
Z = 20.4 × 0.2 × 0.15 mm
Data collection top
Bruker SMART APEX
diffractometer
1983 independent reflections
Radiation source: fine-focus sealed tube1400 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.056
ω scansθmax = 28.0°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
h = 99
Tmin = 0.767, Tmax = 0.986k = 1010
11143 measured reflectionsl = 1818
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)] = 0.048Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123All H-atom parameters refined
S = 1.05 w = 1/[σ2(Fo2) + (0.0643P)2 + 0.1375P]
where P = (Fo2 + 2Fc2)/3
1983 reflections(Δ/σ)max < 0.001
151 parametersΔρmax = 0.31 e Å3
0 restraintsΔρmin = 0.17 e Å3
Crystal data top
C12H24O6·2H3NV = 823.4 (3) Å3
Mr = 298.38Z = 2
Monoclinic, P21/cMo Kα radiation
a = 7.4789 (14) ŵ = 0.10 mm1
b = 7.6632 (14) ÅT = 100 K
c = 14.374 (3) Å0.4 × 0.2 × 0.15 mm
β = 91.754 (4)°
Data collection top
Bruker SMART APEX
diffractometer
1983 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2003)
1400 reflections with I > 2σ(I)
Tmin = 0.767, Tmax = 0.986Rint = 0.056
11143 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0480 restraints
wR(F2) = 0.123All H-atom parameters refined
S = 1.05Δρmax = 0.31 e Å3
1983 reflectionsΔρmin = 0.17 e Å3
151 parameters
Special details top

Experimental. Data collection is performed with three batch runs at ϕ = 0.00 ° (603 frames), at ϕ = 120.00 ° (603 frames) and at ϕ = 240.00 (603 frames). Frame width = 0.30 \& in ω. Data is merged, corrected for decay, and treated with multi-scan absorption corrections.

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
N10.1463 (2)0.1279 (2)0.58096 (11)0.0252 (3)
O10.01313 (14)0.30332 (14)0.39576 (7)0.0203 (3)
O20.23196 (13)0.03940 (14)0.34328 (7)0.0192 (3)
O30.30709 (14)0.22309 (15)0.48313 (8)0.0218 (3)
C10.1842 (2)0.3831 (2)0.39192 (13)0.0251 (4)
C20.0663 (2)0.2966 (2)0.30783 (11)0.0210 (4)
C30.2485 (2)0.2170 (2)0.31875 (12)0.0208 (4)
C40.4015 (2)0.0399 (2)0.36075 (12)0.0218 (4)
C50.3739 (2)0.2234 (2)0.39212 (11)0.0222 (4)
C60.2540 (2)0.3912 (2)0.51192 (13)0.0243 (4)
H110.192 (3)0.034 (4)0.5601 (17)0.051 (7)*
H220.042 (3)0.091 (3)0.6038 (16)0.050 (7)*
H330.109 (3)0.180 (3)0.5289 (18)0.047 (7)*
H1A0.176 (2)0.501 (3)0.3660 (13)0.027 (5)*
H1B0.260 (2)0.315 (2)0.3502 (13)0.024 (5)*
H2A0.076 (2)0.413 (2)0.2819 (13)0.022 (4)*
H2B0.010 (3)0.231 (3)0.2632 (13)0.027 (5)*
H3A0.318 (2)0.278 (2)0.3675 (13)0.022 (4)*
H3B0.303 (2)0.227 (2)0.2615 (14)0.026 (5)*
H4A0.463 (2)0.029 (2)0.4077 (12)0.018 (4)*
H4B0.465 (2)0.038 (2)0.3027 (13)0.021 (4)*
H5A0.292 (2)0.282 (2)0.3493 (12)0.018 (4)*
H5B0.490 (2)0.288 (2)0.3926 (13)0.026 (5)*
H6A0.160 (3)0.438 (2)0.4673 (13)0.028 (5)*
H6B0.354 (2)0.467 (2)0.5127 (12)0.022 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0203 (7)0.0309 (9)0.0244 (8)0.0000 (7)0.0002 (6)0.0011 (7)
O10.0155 (5)0.0248 (6)0.0208 (6)0.0039 (4)0.0030 (4)0.0028 (4)
O20.0122 (5)0.0200 (6)0.0254 (6)0.0006 (4)0.0028 (4)0.0015 (4)
O30.0198 (6)0.0240 (6)0.0219 (6)0.0021 (5)0.0034 (4)0.0006 (5)
C10.0175 (8)0.0273 (9)0.0305 (9)0.0056 (7)0.0020 (7)0.0096 (8)
C20.0249 (8)0.0198 (8)0.0186 (8)0.0002 (7)0.0037 (6)0.0029 (6)
C30.0189 (8)0.0223 (9)0.0214 (8)0.0022 (7)0.0064 (6)0.0001 (7)
C40.0136 (7)0.0287 (9)0.0232 (9)0.0016 (7)0.0034 (6)0.0005 (7)
C50.0192 (8)0.0253 (9)0.0221 (8)0.0048 (7)0.0019 (6)0.0003 (6)
C60.0174 (7)0.0213 (9)0.0346 (10)0.0051 (7)0.0069 (7)0.0042 (7)
Geometric parameters (Å, º) top
N1—H110.85 (3)C2—H2A0.972 (19)
N1—H220.90 (3)C2—H2B0.98 (2)
N1—H330.89 (3)C3—H3A0.982 (18)
O1—C21.4137 (19)C3—H3B0.93 (2)
O1—C11.4178 (19)C4—C51.493 (2)
O2—C31.412 (2)C4—H4A0.963 (18)
O2—C41.4212 (18)C4—H4B0.972 (18)
O3—C61.414 (2)C5—H5A0.967 (18)
O3—C51.4146 (19)C5—H5B1.001 (19)
C1—C6i1.494 (2)C6—C1i1.494 (2)
C1—H1A0.98 (2)C6—H6A1.005 (19)
C1—H1B0.964 (19)C6—H6B0.946 (19)
C2—C31.497 (2)
H11—N1—H22103 (2)O2—C3—H3B110.0 (11)
H11—N1—H33102 (2)C2—C3—H3B107.1 (11)
H22—N1—H33101 (2)H3A—C3—H3B110.9 (15)
C2—O1—C1112.59 (12)O2—C4—C5108.99 (13)
C3—O2—C4111.80 (12)O2—C4—H4A107.3 (10)
C6—O3—C5112.29 (13)C5—C4—H4A111.8 (11)
O1—C1—C6i108.81 (14)O2—C4—H4B107.3 (10)
O1—C1—H1A110.4 (10)C5—C4—H4B110.6 (10)
C6i—C1—H1A109.9 (11)H4A—C4—H4B110.7 (15)
O1—C1—H1B107.6 (11)O3—C5—C4109.47 (13)
C6i—C1—H1B112.5 (11)O3—C5—H5A110.8 (10)
H1A—C1—H1B107.7 (15)C4—C5—H5A109.7 (10)
O1—C2—C3109.09 (13)O3—C5—H5B109.1 (11)
O1—C2—H2A110.3 (11)C4—C5—H5B109.9 (10)
C3—C2—H2A109.7 (11)H5A—C5—H5B107.8 (14)
O1—C2—H2B110.7 (11)O3—C6—C1i110.03 (14)
C3—C2—H2B111.6 (11)O3—C6—H6A109.5 (11)
H2A—C2—H2B105.5 (16)C1i—C6—H6A110.3 (11)
O2—C3—C2109.39 (13)O3—C6—H6B109.5 (11)
O2—C3—H3A109.4 (11)C1i—C6—H6B108.2 (11)
C2—C3—H3A110.1 (10)H6A—C6—H6B109.3 (15)
Symmetry code: (i) x, y, z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H33···O10.89 (3)2.30 (3)3.181 (2)175 (2)
N1—H22···O2i0.90 (3)2.42 (3)3.320 (2)174 (2)
N1—H11···O30.85 (3)2.43 (3)3.281 (2)173 (2)
Symmetry code: (i) x, y, z+1.

Experimental details

Crystal data
Chemical formulaC12H24O6·2H3N
Mr298.38
Crystal system, space groupMonoclinic, P21/c
Temperature (K)100
a, b, c (Å)7.4789 (14), 7.6632 (14), 14.374 (3)
β (°) 91.754 (4)
V3)823.4 (3)
Z2
Radiation typeMo Kα
µ (mm1)0.10
Crystal size (mm)0.4 × 0.2 × 0.15
Data collection
DiffractometerBruker SMART APEX
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2003)
Tmin, Tmax0.767, 0.986
No. of measured, independent and
observed [I > 2σ(I)] reflections
11143, 1983, 1400
Rint0.056
(sin θ/λ)max1)0.660
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.048, 0.123, 1.05
No. of reflections1983
No. of parameters151
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.31, 0.17

Computer programs: SMART32 (Bruker, 1997), SAINT32 (Bruker, 2003), SAINT32, SHELXTL (Sheldrick, 2000), SHELXTL, ATOMS (Dowty, 2002).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H33···O10.89 (3)2.30 (3)3.181 (2)175 (2)
N1—H22···O2i0.90 (3)2.42 (3)3.320 (2)174 (2)
N1—H11···O30.85 (3)2.43 (3)3.281 (2)173 (2)
Symmetry code: (i) x, y, z+1.
 

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