The low-temperature phase of morpholinium tetra-fluoro-borate.

The crystal structure of the low-temperature form of the title compound, C(4)H(10)NO(+)·BF(4) (-), 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 BF(4) (-) tetra-hedral anions and three morpholinium cations (Z' = 3). Hydrogen-bonded morpholinium cations form chains along the [100] direction. The BF(4) (-) 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 = 174.94

Orthorhombic,

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[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.092

S = 1.13

4642 reflections

298 parameters

H-atom parameters constrained

Δρmax = 0.46 e Å−3

Δρmin = −0.31 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis CCD; 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.

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

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

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

C4H10NO+·BF4–	F000 = 1080
Mr = 174.94	Dx = 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 = 5–34º
b = 9.417 (4) Å	µ = 0.17 mm−1
c = 28.572 (11) Å	T = 80 (2) K
V = 2181.0 (16) Å3	Block, colorless
Z = 12	0.5 × 0.5 × 0.4 mm

Kuma KM-4 CCD κ-geometry diffractometer	3913 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.033
Monochromator: graphite	θmax = 34.3º
T = 80(2) K	θmin = 4.8º
ω scans	h = −12→9
Absorption correction: none	k = −14→14
20616 measured reflections	l = −44→32
4642 independent reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037	H-atom parameters constrained
wR(F2) = 0.092	w = 1/[σ2(Fo2) + (0.052P)2] where P = (Fo2 + 2Fc2)/3
S = 1.13	(Δ/σ)max = 0.001
4642 reflections	Δρmax = 0.46 e Å−3
298 parameters	Δρmin = −0.31 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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)

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···F10iv	0.99	2.39	3.337 (2)	160
C3—H3A···F5v	0.99	2.45	3.413 (2)	165
C5—H5A···F4vi	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···F12vi	0.99	2.41	3.352 (2)	159
C9—H9B···F5	0.99	2.45	3.233 (2)	136
C11—H11A···F1vii	0.99	2.41	3.373 (2)	163
C12—H12A···F10viii	0.99	2.40	3.237 (2)	142
C12—H12B···F3ix	0.99	2.54	3.429 (2)	149

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) ; (ii) .