Morpholinium hydrogen chloranilate methanol monosolvate.

In the crystal structure of the title compound, C(4)H(10)NO(+)·C(6)HCl(2)O(4) (-)·CH(4)O, the components are held together by bifurcated O-H⋯(O,O), O-H⋯(O,Cl) and N-H⋯(O,O) hydrogen bonds into a centrosymmetric 2+2+2 aggregate. The aggregates are further connected by another bifurcated N-H⋯(O, O) hydrogen bond, forming a double-tape structure along the b axis. A weak C-H⋯O inter-action is observed between the tapes.

Related literature

For a related structure, see: Ishida & Kashino (1999 ▶). For 35Cl nuclear quadrupole resonance studies on proton-transfer in chloranilic acid–organic base systems, see: Ikeda et al. (2005 ▶); Asaji, Hoshino et al. (2010 ▶); Asaji, Seliger et al. (2010 ▶).

Experimental

Crystal data

C4H10NO+·C6HCl2O4 −·CH4O

M = 328.15

Triclinic,

a = 9.11845 (17) Å

b = 9.39881 (17) Å

c = 9.96935 (18) Å

α = 107.8089 (7)°

β = 107.5510 (7)°

γ = 110.2398 (7)°

V = 679.25 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.50 mm−1

T = 170 K

0.45 × 0.41 × 0.30 mm

Data collection

Rigaku R-AXIS RAPID II diffractometer

Absorption correction: numerical (NUMABS; Higashi, 1999 ▶) T min = 0.817, T max = 0.860

17817 measured reflections

3928 independent reflections

3636 reflections with I > 2σ(I)

R int = 0.025

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.077

S = 1.08

3928 reflections

197 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.51 e Å−3

Δρmin = −0.28 e Å−3

Data collection: PROCESS-AUTO (Rigaku/MSC, 2004 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) General, I. DOI: 10.1107/S1600536811047891/lh5377sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811047891/lh5377Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811047891/lh5377Isup3.cml

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

C4H10NO+·C6HCl2O4−·CH4O	Z = 2
Mr = 328.15	F(000) = 340.00
Triclinic, P1	Dx = 1.604 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71075 Å
a = 9.11845 (17) Å	Cell parameters from 16546 reflections
b = 9.39881 (17) Å	θ = 3.6–30.1°
c = 9.96935 (18) Å	µ = 0.50 mm−1
α = 107.8089 (7)°	T = 170 K
β = 107.5510 (7)°	Block, brown
γ = 110.2398 (7)°	0.45 × 0.41 × 0.30 mm
V = 679.25 (2) Å3

Rigaku R-AXIS RAPID II diffractometer	3636 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm-1	Rint = 0.025
ω scans	θmax = 30.0°
Absorption correction: numerical (NUMABS; Higashi, 1999)	h = −12→12
Tmin = 0.817, Tmax = 0.860	k = −13→13
17817 measured reflections	l = −14→14
3928 independent reflections

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ2(Fo2) + (0.0459P)2 + 0.1482P] where P = (Fo2 + 2Fc2)/3
3928 reflections	(Δ/σ)max = 0.001
197 parameters	Δρmax = 0.51 e Å−3
0 restraints	Δρmin = −0.28 e Å−3

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
Cl1	1.01275 (3)	0.30381 (3)	0.86968 (3)	0.02809 (7)
Cl2	0.20309 (3)	0.06793 (3)	0.53010 (3)	0.02191 (7)
O1	0.71379 (10)	0.00021 (10)	0.82390 (9)	0.02629 (15)
O2	0.84595 (9)	0.45763 (9)	0.70404 (9)	0.02291 (14)
O3	0.50528 (8)	0.35907 (8)	0.55923 (8)	0.01801 (13)
O4	0.37147 (9)	−0.10742 (9)	0.67309 (9)	0.02464 (15)
O5	0.58600 (10)	0.31839 (10)	−0.00604 (8)	0.02641 (15)
O6	0.80802 (9)	0.70163 (9)	0.66544 (10)	0.02655 (16)
N1	0.52494 (12)	0.35047 (11)	0.26136 (10)	0.02167 (16)
C1	0.67022 (12)	0.08381 (11)	0.76387 (10)	0.01785 (16)
C2	0.79228 (11)	0.23463 (11)	0.77003 (11)	0.01801 (16)
C3	0.73479 (11)	0.32094 (10)	0.70050 (10)	0.01635 (15)
C4	0.54246 (11)	0.26734 (10)	0.61815 (9)	0.01450 (15)
C5	0.42266 (11)	0.12427 (11)	0.61394 (10)	0.01582 (15)
C6	0.47242 (11)	0.02420 (11)	0.67825 (10)	0.01687 (16)
C7	0.70652 (13)	0.42900 (12)	0.27855 (11)	0.02421 (18)
H7A	0.7887	0.4300	0.3706	0.029*
H7B	0.7451	0.5482	0.2962	0.029*
C8	0.70673 (13)	0.32531 (13)	0.12851 (12)	0.02324 (18)
H8A	0.8263	0.3774	0.1376	0.028*
H8B	0.6745	0.2081	0.1150	0.028*
C9	0.41236 (13)	0.23401 (14)	−0.02607 (12)	0.0271 (2)
H9A	0.3830	0.1173	−0.0391	0.033*
H9B	0.3285	0.2242	−0.1231	0.033*
C10	0.39445 (13)	0.33079 (14)	0.11517 (12)	0.02451 (19)
H10A	0.4149	0.4445	0.1240	0.029*
H10B	0.2742	0.2678	0.1012	0.029*
C11	0.98148 (13)	0.84290 (14)	0.75821 (14)	0.0311 (2)
H11A	1.0434	0.8324	0.8508	0.047*
H11B	0.9754	0.9493	0.7933	0.047*
H11C	1.0448	0.8441	0.6943	0.047*
H1A	0.520 (2)	0.414 (2)	0.3435 (19)	0.036 (4)*
H1B	0.4968 (19)	0.252 (2)	0.2566 (17)	0.032 (4)*
H2	0.801 (2)	0.512 (2)	0.675 (2)	0.052 (5)*
H6	0.750 (2)	0.718 (2)	0.609 (2)	0.041 (4)*

	U11	U22	U33	U12	U13	U23
Cl1	0.01597 (11)	0.02532 (12)	0.03726 (14)	0.00939 (9)	0.00314 (9)	0.01727 (10)
Cl2	0.01479 (10)	0.02700 (12)	0.02709 (12)	0.01005 (8)	0.00953 (8)	0.01609 (9)
O1	0.0255 (3)	0.0270 (3)	0.0347 (4)	0.0155 (3)	0.0119 (3)	0.0222 (3)
O2	0.0153 (3)	0.0180 (3)	0.0339 (4)	0.0068 (2)	0.0065 (3)	0.0162 (3)
O3	0.0178 (3)	0.0170 (3)	0.0206 (3)	0.0095 (2)	0.0066 (2)	0.0109 (2)
O4	0.0229 (3)	0.0235 (3)	0.0338 (4)	0.0104 (3)	0.0144 (3)	0.0198 (3)
O5	0.0241 (3)	0.0382 (4)	0.0223 (3)	0.0151 (3)	0.0135 (3)	0.0172 (3)
O6	0.0189 (3)	0.0227 (3)	0.0357 (4)	0.0082 (3)	0.0056 (3)	0.0194 (3)
N1	0.0300 (4)	0.0218 (4)	0.0196 (4)	0.0145 (3)	0.0139 (3)	0.0120 (3)
C1	0.0194 (4)	0.0179 (4)	0.0189 (4)	0.0104 (3)	0.0084 (3)	0.0103 (3)
C2	0.0146 (3)	0.0170 (4)	0.0213 (4)	0.0081 (3)	0.0051 (3)	0.0098 (3)
C3	0.0149 (3)	0.0146 (3)	0.0176 (4)	0.0069 (3)	0.0054 (3)	0.0073 (3)
C4	0.0151 (3)	0.0144 (3)	0.0138 (3)	0.0080 (3)	0.0058 (3)	0.0061 (3)
C5	0.0136 (3)	0.0175 (4)	0.0174 (4)	0.0079 (3)	0.0068 (3)	0.0091 (3)
C6	0.0189 (4)	0.0177 (4)	0.0178 (4)	0.0099 (3)	0.0098 (3)	0.0097 (3)
C7	0.0239 (4)	0.0213 (4)	0.0209 (4)	0.0078 (3)	0.0067 (3)	0.0091 (3)
C8	0.0207 (4)	0.0261 (4)	0.0258 (4)	0.0119 (3)	0.0115 (4)	0.0137 (4)
C9	0.0212 (4)	0.0362 (5)	0.0194 (4)	0.0123 (4)	0.0092 (4)	0.0096 (4)
C10	0.0269 (4)	0.0327 (5)	0.0238 (4)	0.0191 (4)	0.0145 (4)	0.0159 (4)
C11	0.0194 (4)	0.0250 (5)	0.0430 (6)	0.0080 (4)	0.0068 (4)	0.0192 (4)

Cl1—C2	1.7168 (9)	C2—C3	1.3536 (11)
Cl2—C5	1.7246 (8)	C3—C4	1.5069 (11)
O1—C1	1.2221 (11)	C4—C5	1.3874 (11)
O2—C3	1.3148 (10)	C5—C6	1.4107 (11)
O2—H2	0.825 (19)	C7—C8	1.5161 (13)
O3—C4	1.2630 (10)	C7—H7A	0.9900
O4—C6	1.2349 (11)	C7—H7B	0.9900
O5—C9	1.4211 (12)	C8—H8A	0.9900
O5—C8	1.4219 (12)	C8—H8B	0.9900
O6—C11	1.4260 (12)	C9—C10	1.5148 (13)
O6—H6	0.740 (17)	C9—H9A	0.9900
N1—C10	1.4870 (12)	C9—H9B	0.9900
N1—C7	1.4904 (13)	C10—H10A	0.9900
N1—H1A	0.876 (16)	C10—H10B	0.9900
N1—H1B	0.853 (16)	C11—H11A	0.9800
C1—C2	1.4373 (12)	C11—H11B	0.9800
C1—C6	1.5413 (12)	C11—H11C	0.9800
C3—O2—H2	113.5 (13)	C8—C7—H7A	110.0
C9—O5—C8	109.92 (7)	N1—C7—H7B	110.0
C11—O6—H6	111.7 (13)	C8—C7—H7B	110.0
C10—N1—C7	111.68 (7)	H7A—C7—H7B	108.4
C10—N1—H1A	109.0 (10)	O5—C8—C7	110.97 (8)
C7—N1—H1A	109.8 (10)	O5—C8—H8A	109.4
C10—N1—H1B	108.2 (10)	C7—C8—H8A	109.4
C7—N1—H1B	109.5 (10)	O5—C8—H8B	109.4
H1A—N1—H1B	108.6 (14)	C7—C8—H8B	109.4
O1—C1—C2	123.92 (8)	H8A—C8—H8B	108.0
O1—C1—C6	117.69 (8)	O5—C9—C10	110.93 (8)
C2—C1—C6	118.39 (7)	O5—C9—H9A	109.5
C3—C2—C1	120.81 (8)	C10—C9—H9A	109.5
C3—C2—Cl1	120.88 (7)	O5—C9—H9B	109.5
C1—C2—Cl1	118.31 (6)	C10—C9—H9B	109.5
O2—C3—C2	120.97 (8)	H9A—C9—H9B	108.0
O2—C3—C4	117.02 (7)	N1—C10—C9	109.27 (8)
C2—C3—C4	122.00 (8)	N1—C10—H10A	109.8
O3—C4—C5	125.78 (8)	C9—C10—H10A	109.8
O3—C4—C3	116.12 (7)	N1—C10—H10B	109.8
C5—C4—C3	118.10 (7)	C9—C10—H10B	109.8
C4—C5—C6	123.01 (8)	H10A—C10—H10B	108.3
C4—C5—Cl2	118.77 (6)	O6—C11—H11A	109.5
C6—C5—Cl2	118.20 (6)	O6—C11—H11B	109.5
O4—C6—C5	125.85 (8)	H11A—C11—H11B	109.5
O4—C6—C1	116.53 (8)	O6—C11—H11C	109.5
C5—C6—C1	117.61 (7)	H11A—C11—H11C	109.5
N1—C7—C8	108.60 (8)	H11B—C11—H11C	109.5
N1—C7—H7A	110.0
O1—C1—C2—C3	179.84 (9)	C3—C4—C5—Cl2	176.39 (6)
C6—C1—C2—C3	−0.87 (13)	C4—C5—C6—O4	−177.30 (9)
O1—C1—C2—Cl1	−0.89 (13)	Cl2—C5—C6—O4	4.08 (13)
C6—C1—C2—Cl1	178.40 (6)	C4—C5—C6—C1	3.11 (12)
C1—C2—C3—O2	−179.07 (8)	Cl2—C5—C6—C1	−175.50 (6)
Cl1—C2—C3—O2	1.68 (13)	O1—C1—C6—O4	−1.84 (12)
C1—C2—C3—C4	1.85 (13)	C2—C1—C6—O4	178.82 (8)
Cl1—C2—C3—C4	−177.40 (6)	O1—C1—C6—C5	177.79 (8)
O2—C3—C4—O3	0.18 (11)	C2—C1—C6—C5	−1.55 (12)
C2—C3—C4—O3	179.29 (8)	C10—N1—C7—C8	−53.98 (10)
O2—C3—C4—C5	−179.49 (8)	C9—O5—C8—C7	−62.82 (10)
C2—C3—C4—C5	−0.38 (12)	N1—C7—C8—O5	58.10 (10)
O3—C4—C5—C6	178.14 (8)	C8—O5—C9—C10	62.10 (11)
C3—C4—C5—C6	−2.22 (12)	C7—N1—C10—C9	53.70 (11)
O3—C4—C5—Cl2	−3.25 (12)	O5—C9—C10—N1	−57.15 (11)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3	0.878 (18)	2.391 (18)	3.0069 (12)	127.5 (16)
N1—H1A···O3i	0.878 (18)	2.180 (19)	2.9255 (13)	142.5 (16)
N1—H1B···O1ii	0.852 (19)	2.170 (19)	2.9207 (14)	146.9 (17)
N1—H1B···O4ii	0.852 (19)	2.233 (19)	2.9277 (14)	138.7 (16)
O2—H2···O3	0.82 (2)	2.26 (2)	2.6605 (12)	110.6 (16)
O2—H2···O6	0.82 (2)	1.79 (2)	2.5564 (13)	153.4 (19)
O6—H6···Cl2i	0.742 (19)	2.761 (19)	3.3342 (9)	136.0 (18)
O6—H6···O3i	0.742 (19)	2.119 (19)	2.7812 (12)	149 (2)
C8—H8A···O2iii	0.99	2.51	3.4115 (15)	152

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3	0.878 (18)	2.391 (18)	3.0069 (12)	127.5 (16)
N1—H1A⋯O3i	0.878 (18)	2.180 (19)	2.9255 (13)	142.5 (16)
N1—H1B⋯O1ii	0.852 (19)	2.170 (19)	2.9207 (14)	146.9 (17)
N1—H1B⋯O4ii	0.852 (19)	2.233 (19)	2.9277 (14)	138.7 (16)
O2—H2⋯O3	0.82 (2)	2.26 (2)	2.6605 (12)	110.6 (16)
O2—H2⋯O6	0.82 (2)	1.79 (2)	2.5564 (13)	153.4 (19)
O6—H6⋯Cl2i	0.742 (19)	2.761 (19)	3.3342 (9)	136.0 (18)
O6—H6⋯O3i	0.742 (19)	2.119 (19)	2.7812 (12)	149 (2)
C8—H8A⋯O2iii	0.99	2.51	3.4115 (15)	152

Symmetry codes: (i) ; (ii) ; (iii) .