The low-temperature phase of morpholinium tetra­fluoro­borate

Owczarek, M.; Szklarz, P.; Jakubas, R.; Lis, T.

doi:10.1107/S1600536808004339

organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page o667

doi:10.1107/S1600536808004339

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The low-temperature phase of morpholinium tetrafluoroborate

Magdalena Owczarek,^a Przemyslaw Szklarz,^a ^* Ryszard Jakubas ^a and Tadeusz Lis ^a

^aFaculty of Chemistry, University of Wrocław, F. Joliot-Curie 14, 50-383 Wrocław, Poland
^*Correspondence e-mail: pszklarz@eto.wchuwr.pl

(Received 21 January 2008; accepted 13 February 2008; online 5 March 2008)

The crystal structure of the low-temperature form of the title compound, C₄H₁₀NO⁺·BF₄⁻, was determined at 80 K. Two reversible phase transitions, at 158/158 and 124/126 K (heating/cooling), were detected by differential scanning calorimetry for this compound, and the sequence of phase transitions was subsequently confirmed by single-crystal X-ray diffraction experiments. The asymmetric unit at 80 K consists of three BF₄⁻ tetrahedral anions and three morpholinium cations (Z′ = 3). Hydrogen-bonded morpholinium cations form chains along the [100] direction. The BF₄⁻ anions are connected to these chains by N—H⋯F hydrogen bonds. In the crystal structure, two different layers perpendicular to the [001] direction can be distinguished, which differ in the geometry of the hydrogen bonds between cationic and anionic species.

Related literature

For the crystal structures of morpholinium chlorate(VII) (isostructural with the title compound) and morpholinium hydrogensulfate, see: Grigoriev et al. (2008 ); Yin et al. (2006 ).

Experimental

Crystal data

C₄H₁₀NO⁺·BF₄⁻
M_r = 174.94
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.106 (4) Å
b = 9.417 (4) Å
c = 28.572 (11) Å
V = 2181.0 (16) Å³
Z = 12
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 80 (2) K
0.5 × 0.5 × 0.4 mm

Data collection

Kuma KM-4 CCD κ-geometry diffractometer
Absorption correction: none
20616 measured reflections
4642 independent reflections
3913 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.092
S = 1.13
4642 reflections
298 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯F2	0.92	1.96	2.742 (2)	142
N1—H1D⋯O3ⁱ	0.92	1.96	2.857 (2)	164
N2—H2C⋯F8	0.92	1.96	2.799 (2)	151
N2—H2D⋯O2ⁱⁱ	0.92	1.95	2.842 (2)	164
N3—H3C⋯F9	0.92	1.96	2.742 (2)	141
N3—H3D⋯O1ⁱ	0.92	1.96	2.856 (2)	164
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Versions 1.171. Oxford Diffraction, Abingdon, Oxfordshire, England.]$ ); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2006 $[Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Versions 1.171. Oxford Diffraction, Abingdon, Oxfordshire, England.]$ ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1998 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808004339/gk2132sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808004339/gk2132Isup2.hkl

checkCIF report

Comment top

The morpholinium tetrafluoroborate (I) undergoes two reversible phase transitions at 158/158 K and 124/126 K (heating/cooling). At the room temperature it crystallizes in the orthorhombic space group Pnma with Z'=1. The intermediate phase appeared to be incommensurately modulated. The structure of (I) in the low-temperature phase contains ordered BF₄^- tetrahedral units and morpholinium cations in the chair conformation. The bond distances and angles in the BF₄^- anions and morpholinium cations are in agreement with the expected values. The N–H morpholinium protons are involved in the hydrogen bonds N–H···O (morpholine-morpholine zigzag chains) and N—H···F with BF₄^- anions. The tetrahedral BF₄^- anions occupy voids between morpholinium chains.

The title compound I appeared to be isostructural with morpholinium chlorate(VII) at 100 K (Grigoriev et al., 2008). Both structures are characterized by two independent hydrogen bonded layers and only slight differences in geometry of hydrogen bonds between morpholinium and anionic species are observed.

The room-temperature phase of I is isostructural with the morpholinium hydrogensulfate (Yin et al., 2006). The tetrafluoroborate anions appear to be dynamically disordered in this phase. During the phase transition from modulated to the low temperature phase at 124 K threefold increase of the lattice parameter b is observed.

Related literature top

For the crystal structures of morpholinium chlorate(VII) (isostructural with the title compound) and morpholinium hydrogensulfate, see: Grigoriev et al. (2008); Yin et al. (2006).

Experimental top

The title compound was prepared by reaction of stoichiometric amounts of morpholine and concentrated tetrafluoroboric acid in water. The resulting solid was recrystallized from methanol at room temperature. The crystal for X-ray measurements was slowly cooled from room temperature to 80 K. During cooling, the crystal undergoes phase transition from centrosymmetric (Pnma), through modulated phase, to the non-centrosymmetric P2₁2₁2₁ space group.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2006); cell refinement: CrysAlis CCD (Oxford Diffraction, 2006); data reduction: CrysAlis RED (Oxford Diffraction, 2006); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Asymmetric unit of the title compound with atom labelling scheme. The displacement ellipsoids were drawn at the 50% probability level.
	Fig. 2. Projection of the crystal packing along [100].
	Fig. 3. Two types of chains in the crystal structure of (I). Symmetry codes: (v) 1/2 + x, 1/2 - y, 1 - z; (x) 1 + x, y, z; (xi) 3/2 + x, 1/2 - y,1 - z; (xii) -1/2 + x, 3/2 - y,1 - z; (xiii) -1 + x, y, z; (xiv) -3/2 + x, 3/2 - y, 1 - z.

morpholinium tetrafluoroborate top

Crystal data top

C₄H₁₀NO⁺·BF₄⁻	F(000) = 1080
M_r = 174.94	D_x = 1.598 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 14871 reflections
a = 8.106 (4) Å	θ = 5–34°
b = 9.417 (4) Å	µ = 0.17 mm⁻¹
c = 28.572 (11) Å	T = 80 K
V = 2181.0 (16) Å³	Block, colorless
Z = 12	0.5 × 0.5 × 0.4 mm

Data collection top

Kuma KM-4 CCD κ-geometry diffractometer	3913 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.033
Graphite monochromator	θ_max = 34.3°, θ_min = 4.8°
ω scans	h = −12→9
20616 measured reflections	k = −14→14
4642 independent reflections	l = −44→32

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.092	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.052P)²] where P = (F_o² + 2F_c²)/3
4642 reflections	(Δ/σ)_max = 0.001
298 parameters	Δρ_max = 0.46 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₄H₁₀NO⁺·BF₄⁻	V = 2181.0 (16) Å³
M_r = 174.94	Z = 12
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.106 (4) Å	µ = 0.17 mm⁻¹
b = 9.417 (4) Å	T = 80 K
c = 28.572 (11) Å	0.5 × 0.5 × 0.4 mm

Data collection top

Kuma KM-4 CCD κ-geometry diffractometer	3913 reflections with I > 2σ(I)
20616 measured reflections	R_int = 0.033
4642 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.092	H-atom parameters constrained
S = 1.13	Δρ_max = 0.46 e Å⁻³
4642 reflections	Δρ_min = −0.31 e Å⁻³
298 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

	x	y	z	U_iso*/U_eq
B1	0.5748 (2)	−0.38148 (19)	0.66006 (6)	0.0138 (3)
B2	0.38324 (17)	0.16152 (18)	0.50547 (6)	0.0145 (3)
B3	0.5721 (2)	−0.36435 (19)	0.33817 (6)	0.0137 (3)
F1	0.67871 (11)	−0.36736 (13)	0.69879 (3)	0.0272 (2)
F2	0.52308 (13)	−0.24786 (11)	0.64441 (4)	0.0285 (2)
F3	0.43715 (11)	−0.46227 (11)	0.67231 (3)	0.0207 (2)
F4	0.66156 (10)	−0.44725 (10)	0.62384 (3)	0.01512 (17)
F5	0.35554 (13)	0.23160 (12)	0.46328 (3)	0.0258 (2)
F6	0.24001 (11)	0.09601 (11)	0.52149 (4)	0.0257 (2)
F7	0.50716 (11)	0.06012 (10)	0.50017 (4)	0.0244 (2)
F8	0.43192 (12)	0.26312 (10)	0.53898 (3)	0.01994 (19)
F9	0.52566 (14)	−0.23018 (12)	0.35451 (4)	0.0333 (3)
F10	0.67387 (11)	−0.35204 (14)	0.29913 (3)	0.0306 (3)
F11	0.43177 (11)	−0.44221 (11)	0.32671 (3)	0.0222 (2)
F12	0.65993 (10)	−0.43246 (10)	0.37371 (3)	0.01573 (18)
O1	0.69421 (11)	0.25053 (12)	0.67290 (4)	0.0142 (2)
O2	0.23260 (11)	0.76931 (12)	0.49397 (4)	0.0166 (2)
O3	0.69339 (11)	0.26920 (12)	0.32955 (4)	0.0151 (2)
N1	0.45612 (14)	0.02870 (13)	0.66772 (4)	0.0111 (2)
H1C	0.4314	−0.0664	0.6654	0.013*
H1D	0.3585	0.0784	0.6690	0.013*
N2	0.45949 (13)	0.54141 (13)	0.50542 (4)	0.0130 (2)
H2C	0.4778	0.4455	0.5086	0.016*
H2D	0.5599	0.5868	0.5063	0.016*
N3	0.45585 (14)	0.04709 (13)	0.33294 (4)	0.0113 (2)
H3C	0.4306	−0.0480	0.3350	0.014*
H3D	0.3586	0.0971	0.3311	0.014*
C1	0.55316 (17)	0.05500 (16)	0.71154 (5)	0.0133 (3)
H1A	0.6538	−0.0046	0.7117	0.016*
H1B	0.4861	0.0300	0.7393	0.016*
C2	0.60018 (17)	0.21069 (18)	0.71332 (5)	0.0154 (3)
H2A	0.4989	0.2693	0.7149	0.018*
H2B	0.6659	0.2291	0.7419	0.018*
C3	0.59955 (16)	0.22934 (17)	0.63068 (5)	0.0139 (3)
H3A	0.6654	0.2594	0.6032	0.017*
H3B	0.4985	0.2883	0.6318	0.017*
C4	0.55267 (18)	0.07415 (16)	0.62565 (5)	0.0137 (3)
H4A	0.4855	0.0607	0.5970	0.016*
H4B	0.6535	0.0155	0.6228	0.016*
C5	0.35391 (17)	0.59281 (18)	0.54488 (5)	0.0160 (3)
H5A	0.4122	0.5791	0.5750	0.019*
H5B	0.2498	0.5379	0.5459	0.019*
C6	0.31647 (17)	0.74878 (17)	0.53769 (5)	0.0179 (3)
H6A	0.2465	0.7838	0.5636	0.022*
H6B	0.4206	0.8038	0.5378	0.022*
C7	0.33543 (18)	0.72648 (17)	0.45575 (5)	0.0166 (3)
H7A	0.4384	0.7830	0.4560	0.020*
H7B	0.2777	0.7450	0.4258	0.020*
C8	0.37715 (17)	0.56993 (17)	0.45929 (5)	0.0149 (3)
H8A	0.2751	0.5126	0.4567	0.018*
H8B	0.4517	0.5426	0.4334	0.018*
C9	0.54945 (18)	0.09205 (16)	0.37573 (5)	0.0140 (3)
H9A	0.6502	0.0335	0.3791	0.017*
H9B	0.4803	0.0782	0.4039	0.017*
C10	0.59621 (16)	0.24721 (16)	0.37110 (5)	0.0147 (3)
H10A	0.4950	0.3059	0.3695	0.018*
H10B	0.6601	0.2771	0.3989	0.018*
C11	0.60280 (17)	0.22966 (17)	0.28841 (5)	0.0153 (3)
H11A	0.6707	0.2484	0.2603	0.018*
H11B	0.5014	0.2878	0.2862	0.018*
C12	0.55689 (17)	0.07375 (16)	0.29006 (5)	0.0132 (3)
H12A	0.4929	0.0480	0.2618	0.016*
H12B	0.6580	0.0148	0.2908	0.016*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
B1	0.0138 (6)	0.0131 (8)	0.0143 (7)	−0.0009 (6)	−0.0009 (5)	−0.0013 (6)
B2	0.0134 (5)	0.0142 (7)	0.0158 (7)	0.0010 (5)	−0.0013 (5)	−0.0011 (7)
B3	0.0145 (6)	0.0128 (8)	0.0139 (7)	−0.0011 (6)	−0.0002 (5)	0.0014 (6)
F1	0.0194 (4)	0.0478 (7)	0.0145 (4)	−0.0065 (5)	−0.0016 (3)	−0.0079 (5)
F2	0.0373 (5)	0.0128 (5)	0.0353 (6)	0.0082 (4)	0.0082 (4)	0.0009 (4)
F3	0.0151 (4)	0.0218 (5)	0.0251 (4)	−0.0049 (4)	0.0030 (4)	0.0001 (4)
F4	0.0160 (4)	0.0152 (4)	0.0142 (4)	0.0024 (3)	0.0004 (3)	−0.0005 (4)
F5	0.0338 (5)	0.0305 (6)	0.0131 (4)	0.0110 (5)	−0.0033 (4)	0.0005 (4)
F6	0.0173 (4)	0.0230 (5)	0.0369 (5)	−0.0078 (4)	0.0042 (4)	−0.0056 (5)
F7	0.0200 (4)	0.0197 (5)	0.0334 (5)	0.0079 (3)	0.0017 (4)	0.0011 (5)
F8	0.0288 (4)	0.0143 (5)	0.0167 (4)	−0.0052 (4)	−0.0058 (3)	0.0007 (4)
F9	0.0418 (6)	0.0122 (5)	0.0458 (6)	0.0099 (5)	−0.0112 (5)	−0.0032 (5)
F10	0.0210 (5)	0.0571 (8)	0.0137 (4)	−0.0115 (5)	0.0012 (3)	0.0090 (5)
F11	0.0148 (4)	0.0249 (5)	0.0270 (5)	−0.0056 (4)	−0.0027 (4)	0.0019 (5)
F12	0.0179 (4)	0.0160 (4)	0.0133 (4)	0.0026 (3)	−0.0011 (3)	0.0001 (4)
O1	0.0122 (4)	0.0166 (5)	0.0138 (4)	−0.0041 (4)	−0.0018 (3)	0.0007 (4)
O2	0.0128 (3)	0.0165 (5)	0.0205 (5)	0.0050 (4)	−0.0019 (4)	−0.0021 (5)
O3	0.0126 (4)	0.0160 (5)	0.0166 (5)	−0.0042 (4)	0.0008 (3)	−0.0005 (4)
N1	0.0105 (5)	0.0092 (5)	0.0136 (5)	−0.0006 (4)	−0.0003 (4)	−0.0004 (5)
N2	0.0112 (4)	0.0094 (5)	0.0185 (6)	0.0002 (4)	−0.0001 (4)	0.0012 (5)
N3	0.0113 (5)	0.0096 (5)	0.0130 (5)	−0.0005 (4)	0.0011 (4)	0.0011 (5)
C1	0.0156 (6)	0.0139 (7)	0.0105 (5)	−0.0015 (5)	−0.0007 (5)	−0.0001 (6)
C2	0.0165 (6)	0.0172 (7)	0.0124 (6)	−0.0027 (5)	−0.0005 (4)	−0.0031 (6)
C3	0.0152 (6)	0.0147 (7)	0.0116 (6)	−0.0018 (5)	−0.0009 (4)	0.0012 (6)
C4	0.0176 (6)	0.0129 (7)	0.0105 (5)	−0.0011 (5)	0.0009 (5)	−0.0016 (6)
C5	0.0139 (5)	0.0237 (8)	0.0104 (5)	−0.0020 (6)	−0.0014 (5)	−0.0003 (6)
C6	0.0158 (6)	0.0199 (8)	0.0182 (6)	0.0020 (6)	−0.0018 (5)	−0.0080 (6)
C7	0.0170 (6)	0.0169 (7)	0.0159 (6)	0.0017 (5)	0.0001 (5)	0.0053 (6)
C8	0.0175 (6)	0.0152 (7)	0.0120 (6)	0.0014 (5)	0.0019 (5)	−0.0019 (6)
C9	0.0167 (6)	0.0144 (7)	0.0109 (5)	0.0009 (5)	−0.0001 (5)	0.0012 (6)
C10	0.0157 (6)	0.0141 (7)	0.0144 (6)	−0.0009 (5)	0.0004 (4)	−0.0019 (6)
C11	0.0161 (6)	0.0162 (7)	0.0135 (6)	−0.0027 (5)	0.0014 (4)	0.0019 (6)
C12	0.0140 (5)	0.0153 (7)	0.0103 (5)	−0.0011 (5)	0.0008 (5)	−0.0010 (6)

Geometric parameters (Å, º) top

B1—F3	1.3950 (19)	C1—C2	1.516 (2)
B1—F4	1.3964 (19)	C1—H1A	0.9900
B1—F1	1.3971 (18)	C1—H1B	0.9900
B1—F2	1.400 (2)	C2—H2A	0.9900
B2—F6	1.3921 (18)	C2—H2B	0.9900
B2—F5	1.3926 (19)	C3—C4	1.517 (2)
B2—F7	1.3942 (18)	C3—H3A	0.9900
B2—F8	1.4098 (19)	C3—H3B	0.9900
B3—F10	1.3919 (18)	C4—H4A	0.9900
B3—F11	1.3926 (19)	C4—H4B	0.9900
B3—F12	1.3962 (19)	C5—C6	1.514 (2)
B3—F9	1.399 (2)	C5—H5A	0.9900
O1—C2	1.4338 (18)	C5—H5B	0.9900
O1—C3	1.4435 (17)	C6—H6A	0.9900
O2—C7	1.4318 (18)	C6—H6B	0.9900
O2—C6	1.4354 (18)	C7—C8	1.516 (2)
O3—C11	1.4350 (18)	C7—H7A	0.9900
O3—C10	1.4397 (18)	C7—H7B	0.9900
N1—C4	1.4968 (18)	C8—H8A	0.9900
N1—C1	1.4992 (17)	C8—H8B	0.9900
N1—H1C	0.9200	C9—C10	1.515 (2)
N1—H1D	0.9200	C9—H9A	0.9900
N2—C5	1.4960 (18)	C9—H9B	0.9900
N2—C8	1.5014 (18)	C10—H10A	0.9900
N2—H2C	0.9200	C10—H10B	0.9900
N2—H2D	0.9200	C11—C12	1.515 (2)
N3—C12	1.4950 (17)	C11—H11A	0.9900
N3—C9	1.4998 (18)	C11—H11B	0.9900
N3—H3C	0.9200	C12—H12A	0.9900
N3—H3D	0.9200	C12—H12B	0.9900

F3—B1—F4	110.30 (13)	H3A—C3—H3B	108.1
F3—B1—F1	109.61 (13)	N1—C4—C3	109.29 (11)
F4—B1—F1	109.00 (12)	N1—C4—H4A	109.8
F3—B1—F2	109.32 (13)	C3—C4—H4A	109.8
F4—B1—F2	108.22 (13)	N1—C4—H4B	109.8
F1—B1—F2	110.37 (14)	C3—C4—H4B	109.8
F6—B2—F5	111.11 (12)	H4A—C4—H4B	108.3
F6—B2—F7	109.46 (13)	N2—C5—C6	109.05 (12)
F5—B2—F7	110.28 (12)	N2—C5—H5A	109.9
F6—B2—F8	108.12 (12)	C6—C5—H5A	109.9
F5—B2—F8	108.14 (13)	N2—C5—H5B	109.9
F7—B2—F8	109.69 (11)	C6—C5—H5B	109.9
F10—B3—F11	109.85 (13)	H5A—C5—H5B	108.3
F10—B3—F12	108.61 (13)	O2—C6—C5	110.10 (12)
F11—B3—F12	110.21 (13)	O2—C6—H6A	109.6
F10—B3—F9	110.60 (14)	C5—C6—H6A	109.6
F11—B3—F9	109.52 (13)	O2—C6—H6B	109.6
F12—B3—F9	108.03 (13)	C5—C6—H6B	109.6
C2—O1—C3	110.75 (10)	H6A—C6—H6B	108.2
C7—O2—C6	110.50 (10)	O2—C7—C8	110.66 (12)
C11—O3—C10	110.98 (10)	O2—C7—H7A	109.5
C4—N1—C1	110.43 (11)	C8—C7—H7A	109.5
C4—N1—H1C	109.6	O2—C7—H7B	109.5
C1—N1—H1C	109.6	C8—C7—H7B	109.5
C4—N1—H1D	109.6	H7A—C7—H7B	108.1
C1—N1—H1D	109.6	N2—C8—C7	109.38 (12)
H1C—N1—H1D	108.1	N2—C8—H8A	109.8
C5—N2—C8	110.45 (10)	C7—C8—H8A	109.8
C5—N2—H2C	109.6	N2—C8—H8B	109.8
C8—N2—H2C	109.6	C7—C8—H8B	109.8
C5—N2—H2D	109.6	H8A—C8—H8B	108.2
C8—N2—H2D	109.6	N3—C9—C10	109.12 (12)
H2C—N2—H2D	108.1	N3—C9—H9A	109.9
C12—N3—C9	110.09 (11)	C10—C9—H9A	109.9
C12—N3—H3C	109.6	N3—C9—H9B	109.9
C9—N3—H3C	109.6	C10—C9—H9B	109.9
C12—N3—H3D	109.6	H9A—C9—H9B	108.3
C9—N3—H3D	109.6	O3—C10—C9	110.34 (12)
H3C—N3—H3D	108.2	O3—C10—H10A	109.6
N1—C1—C2	108.65 (11)	C9—C10—H10A	109.6
N1—C1—H1A	110.0	O3—C10—H10B	109.6
C2—C1—H1A	110.0	C9—C10—H10B	109.6
N1—C1—H1B	110.0	H10A—C10—H10B	108.1
C2—C1—H1B	110.0	O3—C11—C12	110.59 (12)
H1A—C1—H1B	108.3	O3—C11—H11A	109.5
O1—C2—C1	111.08 (12)	C12—C11—H11A	109.5
O1—C2—H2A	109.4	O3—C11—H11B	109.5
C1—C2—H2A	109.4	C12—C11—H11B	109.5
O1—C2—H2B	109.4	H11A—C11—H11B	108.1
C1—C2—H2B	109.4	N3—C12—C11	108.82 (11)
H2A—C2—H2B	108.0	N3—C12—H12A	109.9
O1—C3—C4	110.22 (12)	C11—C12—H12A	109.9
O1—C3—H3A	109.6	N3—C12—H12B	109.9
C4—C3—H3A	109.6	C11—C12—H12B	109.9
O1—C3—H3B	109.6	H12A—C12—H12B	108.3
C4—C3—H3B	109.6

C4—N1—C1—C2	56.30 (14)	C6—O2—C7—C8	61.49 (15)
C3—O1—C2—C1	61.00 (14)	C5—N2—C8—C7	54.94 (14)
N1—C1—C2—O1	−58.22 (14)	O2—C7—C8—N2	−57.26 (14)
C2—O1—C3—C4	−60.55 (14)	C12—N3—C9—C10	57.02 (14)
C1—N1—C4—C3	−56.75 (15)	C11—O3—C10—C9	60.49 (15)
O1—C3—C4—N1	58.12 (14)	N3—C9—C10—O3	−58.07 (14)
C8—N2—C5—C6	−55.96 (14)	C10—O3—C11—C12	−60.89 (14)
C7—O2—C6—C5	−62.45 (15)	C9—N3—C12—C11	−57.07 (14)
N2—C5—C6—O2	59.27 (14)	O3—C11—C12—N3	58.66 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···F2	0.92	1.96	2.742 (2)	142
N1—H1D···O3ⁱ	0.92	1.96	2.857 (2)	164
N2—H2C···F8	0.92	1.96	2.799 (2)	151
N2—H2D···O2ⁱⁱ	0.92	1.95	2.842 (2)	164
N3—H3C···F9	0.92	1.96	2.742 (2)	141
N3—H3D···O1ⁱ	0.92	1.96	2.856 (2)	164
C1—H1B···F1ⁱⁱⁱ	0.99	2.42	3.261 (2)	143
C2—H2B···F10^iv	0.99	2.39	3.337 (2)	160
C3—H3A···F5^v	0.99	2.45	3.413 (2)	165
C5—H5A···F4^vi	0.99	2.47	3.384 (2)	154
C5—H5B···F7ⁱ	0.99	2.54	3.410 (2)	147
C6—H6A···F12ⁱ	0.99	2.38	3.318 (2)	158
C8—H8B···F12^vi	0.99	2.41	3.352 (2)	159
C9—H9B···F5	0.99	2.45	3.233 (2)	136
C11—H11A···F1^vii	0.99	2.41	3.373 (2)	163
C12—H12A···F10^viii	0.99	2.40	3.237 (2)	142
C12—H12B···F3^ix	0.99	2.54	3.429 (2)	149

Symmetry codes: (i) x−1/2, −y+1/2, −z+1; (ii) x+1/2, −y+3/2, −z+1; (iii) −x+1, y+1/2, −z+3/2; (iv) −x+3/2, −y, z+1/2; (v) x+1/2, −y+1/2, −z+1; (vi) x, y+1, z; (vii) −x+3/2, −y, z−1/2; (viii) −x+1, y+1/2, −z+1/2; (ix) x+1/2, −y−1/2, −z+1.

Experimental details

Crystal data
Chemical formula	C₄H₁₀NO⁺·BF₄⁻
M_r	174.94
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	80
a, b, c (Å)	8.106 (4), 9.417 (4), 28.572 (11)
V (Å³)	2181.0 (16)
Z	12
Radiation type	Mo Kα
µ (mm⁻¹)	0.17
Crystal size (mm)	0.5 × 0.5 × 0.4

Data collection
Diffractometer	Kuma KM-4 CCD κ-geometry diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	20616, 4642, 3913
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.794

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.092, 1.13
No. of reflections	4642
No. of parameters	298
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.46, −0.31

Computer programs: CrysAlis CCD (Oxford Diffraction, 2006), CrysAlis RED (Oxford Diffraction, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1998).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···F2	0.92	1.96	2.742 (2)	142.1
N1—H1D···O3ⁱ	0.92	1.96	2.857 (2)	163.6
N2—H2C···F8	0.92	1.96	2.799 (2)	150.9
N2—H2D···O2ⁱⁱ	0.92	1.95	2.842 (2)	163.5
N3—H3C···F9	0.92	1.96	2.742 (2)	141.4
N3—H3D···O1ⁱ	0.92	1.96	2.856 (2)	163.8

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

References

Brandenburg, K. (1998). DIAMOND. University of Bonn, Germany. Google Scholar
Grigoriev, M. S., German, K. E. & Maruk, A. Y. (2008). Acta Cryst. E64, o390. Web of Science CSD CrossRef IUCr Journals Google Scholar
Oxford Diffraction (2006). CrysAlis CCD and CrysAlis RED. Versions 1.171. Oxford Diffraction, Abingdon, Oxfordshire, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yin, C.-X., Huo, F.-J. & Yang, P. (2006). Acta Cryst. E62, o2084–o2085. Web of Science CSD CrossRef IUCr Journals Google Scholar

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Volume 64| Part 4| April 2008| Page o667

doi:10.1107/S1600536808004339

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