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Acta Crystallogr Sect E Struct Rep Online. 2008 February 1; 64(Pt 2): o390.
Published online 2008 January 9. doi:  10.1107/S1600536807068134
PMCID: PMC2960441

Morpholinium perchlorate

Abstract

In the title salt, C4H10NO+·ClO4 , which has three independent formula units, the cations are linked into chains along [100] by N—H(...)O hydrogen bonds. Each cation acts both as a donor and as an acceptor, and every cation makes one N—H(...)O hydrogen bond with a ClO4 anion. The crystal studied was an inversion twin.

Related literature

See Grigoriev et al. (2007 [triangle]) for the structure of morpholinium tetra­oxidorhenate(VII).

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Object name is e-64-0o390-scheme1.jpg

Experimental

Crystal data

  • C4H10NO+·ClO4
  • M r = 187.58
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o390-efi1.jpg
  • a = 8.1515 (3) Å
  • b = 9.5435 (4) Å
  • c = 28.9022 (12) Å
  • V = 2248.41 (16) Å3
  • Z = 12
  • Mo Kα radiation
  • μ = 0.49 mm−1
  • T = 100 (2) K
  • 0.24 × 0.20 × 0.16 mm

Data collection

  • Bruker Kappa APEXII area-detector diffractometer
  • Absorption correction: none
  • 31159 measured reflections
  • 6453 independent reflections
  • 5928 reflections with I > 2σ(I)
  • R int = 0.038

Refinement

  • R[F 2 > 2σ(F 2)] = 0.025
  • wR(F 2) = 0.062
  • S = 1.03
  • 6453 reflections
  • 323 parameters
  • 6 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.30 e Å−3
  • Δρmin = −0.32 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 2793 Friedel pairs
  • Flack parameter: 0.42 (3)

Data collection: APEX2 (Bruker, 2006 [triangle]); cell refinement: SAINT-Plus (Bruker, 1998 [triangle]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a [triangle]); molecular graphics: SHELXTL (Sheldrick, 1997b [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807068134/ng2409sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807068134/ng2409Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

supplementary crystallographic information

Comment

The title compound, (I) (Fig. 1), contains slightly distorted tetrahedral ClO4- anions with Cl—O distances from 1.4353 (11) to 1.4496 (10) Å. Morpholinium cations have chair conformation.

The structure of (I) can be described as alternating cationic and anionic layers parallel to the (013) plane (Fig. 2).

Every morpholinium cation acts as proton donor in two hydrogen bonds, acceptors being O atoms of another morpholinium cation and ClO4- anion (Fig. 3, Table 1).

Morpholinium tetraoxidochlorate(VII) contains three independent formula units, which make two different types of zigzag chains in the [100] direction by N—H···O hydrogen bonds between cations (Fig. 3). The first type is formed by one formula unit and the second type is formed by two remaining formula units. As it is nseen in Fig. 3, two types of chains have different orientation of ClO4- anions.

The structure of morpholinium tetraoxidorhenate(VII) (Grigoriev et al., 2007) also contains alternating cationic and anionic layers with hydrogen bonds in perpendicular direction. But in contrast to (I), O atoms of morpholinium in (C4H10NO)[ReO4] do not participate in hydrogen-bonding.

Experimental

Synthesis of (I) was carried out as a neutralization reaction by dissolution of stoichiometric quantity of morpholine under intensive stirring in 0.92 M water solution of HClO4 at room temperature, followed by evaporation of the resulting solution at temperature 323 K.

Refinement

The H atoms of CH2 groups were refined in idealized geometrical positions with displacement parameters being equal to 1.2 times Ueq of the attached C atoms. The H atoms of NH2 were located on difference Fourier map and refined with displacement parameters being equal to 1.2 times Ueq of the attached N atoms and N—H distances restrained to 0.88 (1) Å.

The Flack parameter was explicitly refined. The absolute structure was selected on the basis of the lower Flack parameter; the structure is a racemic twin.

Figures

Fig. 1.
A view of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are represented by circles of arbitrary size. Dashed lines indicate the hydrogen-bonding interaction.
Fig. 2.
The unit cell of (I).
Fig. 3.
The comparison of two different types of chains.

Crystal data

C4H10NO+·ClO4F000 = 1176
Mr = 187.58Dx = 1.662 Mg m3
Orthorhombic, P212121Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 7054 reflections
a = 8.1515 (3) Åθ = 2.3–30.0º
b = 9.5435 (4) ŵ = 0.49 mm1
c = 28.9022 (12) ÅT = 100 (2) K
V = 2248.41 (16) Å3Fragment, colourless
Z = 120.24 × 0.20 × 0.16 mm

Data collection

Bruker KappaAPEXII area-detector diffractometer5928 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.038
Monochromator: graphiteθmax = 30.0º
T = 100(2) Kθmin = 2.3º
ω and [var phi] scansh = −11→11
Absorption correction: none (SADABS; Sheldrick, 2004?)k = −13→13
31159 measured reflectionsl = −40→40
6453 independent reflections

Refinement

Refinement on F2Hydrogen site location: mixed
Least-squares matrix: fullH atoms treated by a mixture of independent and constrained refinement
R[F2 > 2σ(F2)] = 0.025  w = 1/[σ2(Fo2) + (0.0368P)2 + 0.1234P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.062(Δ/σ)max = 0.001
S = 1.03Δρmax = 0.30 e Å3
6453 reflectionsΔρmin = −0.32 e Å3
323 parametersExtinction correction: none
6 restraintsAbsolute structure: Flack (1983), 2793 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.42 (3)
Secondary atom site location: difference Fourier map

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 (Å2)

xyzUiso*/Ueq
Cl10.57617 (4)−0.38371 (3)0.659062 (11)0.01229 (6)
Cl20.37184 (4)0.16395 (3)0.506534 (10)0.01225 (6)
Cl30.57257 (4)−0.35661 (3)0.339378 (11)0.01296 (7)
O10.68287 (14)−0.37350 (14)0.69869 (4)0.0261 (3)
O20.53026 (15)−0.24599 (12)0.64345 (5)0.0297 (3)
O30.43207 (14)−0.46173 (11)0.67131 (4)0.0207 (2)
O40.66220 (12)−0.45314 (11)0.62201 (3)0.0157 (2)
O50.34519 (14)0.23379 (12)0.46318 (4)0.0237 (2)
O60.22474 (13)0.09516 (12)0.52183 (4)0.0246 (2)
O70.50117 (12)0.06236 (11)0.50191 (4)0.0248 (2)
O80.41766 (13)0.26762 (11)0.54084 (4)0.0189 (2)
O90.53099 (16)−0.22094 (13)0.35767 (5)0.0342 (3)
O100.67421 (14)−0.34228 (16)0.29901 (4)0.0321 (3)
O110.42568 (14)−0.43179 (12)0.32752 (4)0.0236 (2)
O120.66235 (13)−0.43202 (11)0.37422 (3)0.0168 (2)
O130.69481 (11)0.24689 (11)0.67280 (4)0.0155 (2)
O140.22067 (11)0.76837 (11)0.49220 (3)0.0171 (2)
O150.69469 (12)0.27281 (11)0.32867 (4)0.0165 (2)
N10.45845 (14)0.02905 (12)0.66878 (4)0.0119 (2)
H1C0.434 (2)−0.0603 (10)0.6668 (6)0.014*
H1D0.3666 (14)0.0755 (16)0.6699 (6)0.014*
N20.44656 (13)0.54724 (12)0.50755 (4)0.0135 (2)
H2C0.5419 (14)0.5912 (16)0.5086 (6)0.016*
H2D0.462 (2)0.4558 (10)0.5114 (6)0.016*
N30.45865 (14)0.05497 (12)0.33319 (4)0.0122 (2)
H3C0.3684 (15)0.1049 (17)0.3313 (6)0.015*
H3D0.440 (2)−0.0347 (10)0.3344 (6)0.015*
C10.55582 (18)0.05548 (15)0.71163 (5)0.0144 (3)
H1A0.492 (2)0.0284 (19)0.7388 (6)0.017*
H1B0.646 (2)0.0006 (19)0.7113 (6)0.017*
C20.60347 (17)0.20873 (15)0.71312 (5)0.0164 (3)
H2A0.50330.26710.71510.020*
H2B0.67050.22680.74110.020*
C30.59875 (17)0.22590 (15)0.63150 (5)0.0143 (3)
H3A0.66280.25560.60410.017*
H3B0.49810.28380.63300.017*
C40.55258 (18)0.07310 (14)0.62683 (5)0.0144 (3)
H4A0.48470.05940.59880.017*
H4B0.65280.01530.62370.017*
C50.33638 (17)0.60033 (17)0.54496 (5)0.0167 (3)
H5A0.39050.58940.57540.020*
H5B0.23310.54580.54530.020*
C60.29959 (18)0.75241 (16)0.53623 (5)0.0188 (3)
H6A0.22730.78890.56100.023*
H6B0.40280.80700.53670.023*
C70.32779 (17)0.72437 (16)0.45577 (5)0.0164 (3)
H7A0.42930.78130.45640.020*
H7B0.27360.73950.42550.020*
C80.37108 (18)0.57105 (15)0.46105 (4)0.0148 (3)
H8A0.27100.51310.45780.018*
H8B0.44920.54310.43650.018*
C90.55216 (18)0.10032 (15)0.37512 (4)0.0150 (3)
H9A0.65210.04230.37860.018*
H9B0.48370.08790.40310.018*
C100.59916 (17)0.25284 (15)0.36984 (5)0.0162 (3)
H10A0.49880.31100.36820.019*
H10B0.66340.28320.39710.019*
C110.60345 (17)0.23347 (15)0.28832 (5)0.0168 (3)
H11A0.67040.25100.26030.020*
H11B0.50290.29130.28620.020*
C120.55698 (18)0.07970 (14)0.29050 (5)0.0146 (3)
H12A0.49200.05390.26290.018*
H12B0.65720.02110.29110.018*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.01222 (14)0.01077 (13)0.01386 (13)−0.00072 (11)0.00049 (11)−0.00074 (11)
Cl20.01095 (11)0.01167 (13)0.01412 (13)0.00027 (10)−0.00132 (11)−0.00073 (11)
Cl30.01248 (14)0.01263 (14)0.01377 (13)−0.00160 (11)−0.00006 (11)0.00151 (11)
O10.0178 (5)0.0441 (8)0.0165 (5)−0.0076 (5)−0.0015 (4)−0.0063 (5)
O20.0395 (7)0.0108 (5)0.0389 (7)0.0094 (5)0.0117 (5)0.0024 (5)
O30.0130 (4)0.0230 (5)0.0262 (5)−0.0054 (4)0.0027 (4)0.0000 (4)
O40.0170 (5)0.0146 (5)0.0155 (4)0.0036 (4)0.0009 (4)−0.0010 (4)
O50.0302 (6)0.0260 (6)0.0150 (5)0.0064 (5)−0.0028 (4)0.0020 (4)
O60.0154 (5)0.0216 (6)0.0368 (6)−0.0073 (4)0.0043 (4)−0.0036 (5)
O70.0189 (5)0.0193 (5)0.0361 (6)0.0093 (4)0.0022 (5)0.0007 (5)
O80.0271 (5)0.0143 (5)0.0153 (5)−0.0058 (4)−0.0048 (4)−0.0006 (4)
O90.0453 (8)0.0124 (5)0.0449 (8)0.0121 (5)−0.0133 (6)−0.0033 (5)
O100.0233 (6)0.0579 (9)0.0150 (5)−0.0133 (6)0.0023 (4)0.0081 (6)
O110.0126 (5)0.0272 (6)0.0311 (6)−0.0067 (4)−0.0034 (4)0.0013 (5)
O120.0195 (5)0.0152 (5)0.0158 (4)0.0042 (4)−0.0018 (4)0.0001 (4)
O130.0128 (4)0.0172 (5)0.0166 (5)−0.0049 (4)−0.0022 (4)0.0006 (4)
O140.0143 (4)0.0174 (5)0.0196 (5)0.0057 (4)−0.0010 (4)−0.0015 (4)
O150.0129 (5)0.0185 (5)0.0181 (5)−0.0061 (4)0.0007 (4)−0.0014 (4)
N10.0104 (5)0.0102 (5)0.0152 (5)0.0001 (4)−0.0003 (4)−0.0012 (4)
N20.0108 (5)0.0101 (5)0.0195 (6)0.0003 (4)−0.0001 (4)0.0018 (4)
N30.0115 (6)0.0092 (5)0.0159 (5)0.0000 (4)0.0008 (4)0.0014 (4)
C10.0158 (7)0.0162 (7)0.0112 (6)−0.0004 (5)−0.0004 (5)0.0012 (5)
C20.0180 (7)0.0167 (7)0.0145 (6)−0.0036 (5)−0.0015 (5)−0.0027 (5)
C30.0163 (7)0.0131 (6)0.0133 (6)−0.0010 (5)−0.0013 (5)0.0009 (5)
C40.0187 (7)0.0127 (6)0.0118 (6)0.0001 (5)−0.0002 (5)−0.0013 (5)
C50.0146 (6)0.0244 (7)0.0109 (5)−0.0002 (5)0.0002 (5)0.0009 (5)
C60.0183 (7)0.0210 (8)0.0170 (7)0.0030 (5)−0.0020 (5)−0.0072 (6)
C70.0159 (6)0.0181 (7)0.0152 (6)0.0024 (5)0.0017 (5)0.0045 (5)
C80.0166 (6)0.0156 (7)0.0123 (6)0.0012 (5)0.0026 (5)−0.0010 (5)
C90.0174 (7)0.0180 (7)0.0097 (5)0.0004 (5)0.0004 (5)0.0014 (5)
C100.0169 (7)0.0156 (7)0.0161 (6)−0.0014 (5)0.0009 (5)−0.0024 (5)
C110.0169 (7)0.0185 (7)0.0150 (6)−0.0038 (5)0.0000 (5)0.0031 (5)
C120.0156 (6)0.0167 (7)0.0116 (6)−0.0013 (5)0.0011 (5)−0.0009 (5)

Geometric parameters (Å, °)

Cl1—O31.4351 (11)C1—C21.514 (2)
Cl1—O21.4391 (12)C1—H1A0.975 (18)
Cl1—O41.4415 (10)C1—H1B0.900 (18)
Cl1—O11.4415 (11)C2—H2A0.9900
Cl2—O51.4359 (11)C2—H2B0.9900
Cl2—O61.4367 (11)C3—C41.5121 (19)
Cl2—O71.4385 (10)C3—H3A0.9900
Cl2—O81.4496 (10)C3—H3B0.9900
Cl3—O111.4374 (11)C4—H4A0.9900
Cl3—O101.4376 (11)C4—H4B0.9900
Cl3—O121.4379 (10)C5—C61.503 (2)
Cl3—O91.4390 (13)C5—H5A0.9900
O13—C21.4301 (17)C5—H5B0.9900
O13—C31.4415 (16)C6—H6A0.9900
O14—C71.4308 (16)C6—H6B0.9900
O14—C61.4342 (17)C7—C81.513 (2)
O15—C111.4333 (17)C7—H7A0.9900
O15—C101.4349 (17)C7—H7B0.9900
N1—C11.4926 (17)C8—H8A0.9900
N1—C41.4951 (17)C8—H8B0.9900
N1—H1C0.877 (9)C9—C101.513 (2)
N1—H1D0.871 (9)C9—H9A0.9900
N2—C51.4943 (18)C9—H9B0.9900
N2—C81.4955 (17)C10—H10A0.9900
N2—H2C0.884 (9)C10—H10B0.9900
N2—H2D0.889 (9)C11—C121.5169 (19)
N3—C121.4903 (17)C11—H11A0.9900
N3—C91.4956 (18)C11—H11B0.9900
N3—H3C0.878 (9)C12—H12A0.9900
N3—H3D0.870 (9)C12—H12B0.9900
O3—Cl1—O2109.78 (7)H3A—C3—H3B108.2
O3—Cl1—O4110.06 (6)N1—C4—C3109.05 (11)
O2—Cl1—O4108.26 (7)N1—C4—H4A109.9
O3—Cl1—O1109.45 (7)C3—C4—H4A109.9
O2—Cl1—O1110.14 (8)N1—C4—H4B109.9
O4—Cl1—O1109.14 (7)C3—C4—H4B109.9
O5—Cl2—O6110.75 (7)H4A—C4—H4B108.3
O5—Cl2—O7110.04 (7)N2—C5—C6109.01 (12)
O6—Cl2—O7109.41 (7)N2—C5—H5A109.9
O5—Cl2—O8108.60 (7)C6—C5—H5A109.9
O6—Cl2—O8108.45 (7)N2—C5—H5B109.9
O7—Cl2—O8109.55 (7)C6—C5—H5B109.9
O11—Cl3—O10109.51 (7)H5A—C5—H5B108.3
O11—Cl3—O12109.94 (7)O14—C6—C5109.94 (12)
O10—Cl3—O12108.83 (7)O14—C6—H6A109.7
O11—Cl3—O9109.91 (8)C5—C6—H6A109.7
O10—Cl3—O9110.39 (9)O14—C6—H6B109.7
O12—Cl3—O9108.24 (7)C5—C6—H6B109.7
C2—O13—C3110.89 (10)H6A—C6—H6B108.2
C7—O14—C6110.37 (10)O14—C7—C8110.61 (11)
C11—O15—C10111.00 (10)O14—C7—H7A109.5
C1—N1—C4110.64 (10)C8—C7—H7A109.5
C1—N1—H1C109.7 (11)O14—C7—H7B109.5
C4—N1—H1C109.6 (11)C8—C7—H7B109.5
C1—N1—H1D109.9 (11)H7A—C7—H7B108.1
C4—N1—H1D109.2 (11)N2—C8—C7109.49 (11)
H1C—N1—H1D107.8 (16)N2—C8—H8A109.8
C5—N2—C8110.58 (10)C7—C8—H8A109.8
C5—N2—H2C110.1 (11)N2—C8—H8B109.8
C8—N2—H2C108.7 (11)C7—C8—H8B109.8
C5—N2—H2D109.2 (11)H8A—C8—H8B108.2
C8—N2—H2D108.7 (11)N3—C9—C10109.02 (11)
H2C—N2—H2D109.6 (15)N3—C9—H9A109.9
C12—N3—C9110.54 (11)C10—C9—H9A109.9
C12—N3—H3C108.1 (11)N3—C9—H9B109.9
C9—N3—H3C108.8 (11)C10—C9—H9B109.9
C12—N3—H3D106.5 (11)H9A—C9—H9B108.3
C9—N3—H3D109.9 (12)O15—C10—C9110.41 (11)
H3C—N3—H3D113.0 (17)O15—C10—H10A109.6
N1—C1—C2108.86 (11)C9—C10—H10A109.6
N1—C1—H1A109.9 (10)O15—C10—H10B109.6
C2—C1—H1A111.7 (11)C9—C10—H10B109.6
N1—C1—H1B109.0 (11)H10A—C10—H10B108.1
C2—C1—H1B110.8 (12)O15—C11—C12110.44 (12)
H1A—C1—H1B106.5 (15)O15—C11—H11A109.6
O13—C2—C1110.88 (11)C12—C11—H11A109.6
O13—C2—H2A109.5O15—C11—H11B109.6
C1—C2—H2A109.5C12—C11—H11B109.6
O13—C2—H2B109.5H11A—C11—H11B108.1
C1—C2—H2B109.5N3—C12—C11108.78 (11)
H2A—C2—H2B108.1N3—C12—H12A109.9
O13—C3—C4110.07 (11)C11—C12—H12A109.9
O13—C3—H3A109.6N3—C12—H12B109.9
C4—C3—H3A109.6C11—C12—H12B109.9
O13—C3—H3B109.6H12A—C12—H12B108.3
C4—C3—H3B109.6
C4—N1—C1—C256.08 (15)C6—O14—C7—C861.45 (14)
C3—O13—C2—C160.92 (15)C5—N2—C8—C754.51 (14)
N1—C1—C2—O13−57.76 (15)O14—C7—C8—N2−56.81 (14)
C2—O13—C3—C4−61.05 (15)C12—N3—C9—C1056.67 (14)
C1—N1—C4—C3−56.79 (15)C11—O15—C10—C960.83 (14)
O13—C3—C4—N158.36 (14)N3—C9—C10—O15−57.92 (14)
C8—N2—C5—C6−56.06 (14)C10—O15—C11—C12−61.04 (14)
C7—O14—C6—C5−62.99 (15)C9—N3—C12—C11−56.71 (15)
N2—C5—C6—O1459.76 (15)O15—C11—C12—N358.34 (15)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1C···O20.877 (9)2.051 (13)2.7872 (16)141.0 (15)
N1—H1D···O15i0.871 (9)2.015 (10)2.8642 (15)164.7 (16)
N2—H2C···O14ii0.884 (9)1.980 (10)2.8441 (14)165.5 (16)
N2—H2D···O80.889 (9)2.020 (11)2.8465 (15)154.1 (15)
N3—H3C···O13i0.878 (9)2.004 (10)2.8690 (15)168.0 (17)
N3—H3D···O90.870 (9)2.039 (13)2.7895 (17)143.9 (16)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: NG2409).

References

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  • Bruker (2006). APEX2 Bruker AXS Inc., Madison, Wisconsin, USA.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Grigoriev, M. S., German, K. E. & Maruk, A. Y. (2007). Acta Cryst. E63, m2355.
  • Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97 University of Göttingen, Germany.
  • Sheldrick, G. M. (1997b). SHELXTL Version 5.10. Bruker AXS Inc., Madison, Wisconsin, USA.

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