4-(2-Chloro-ethyl)morpholinium picrate.

The title compound, C(6)H(13)ClNO(+)·C(6)H(2)N(3)O(7) (-), was synthesized from picric acid and 4-(2-chloro-ethyl)morpholine. The crystal structure is stabilized by C-H⋯O and N-H⋯O hydrogen-bond inter-actions.

Related literature

For the homeopathic uses of the metal derivatives of picric acid, see: Maurya et al. (1999 ▶). For the medical applications of ammonium picrate, see: Boericke (1982 ▶) and of morpholine derivatives, see: Lutz et al. (1947 ▶); Hazard et al. (1948 ▶); Raymond et al. (1999 ▶). For a related structure, see: Briggs et al. (2004 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C6H13ClNO+·C6H2N3O7 −

M = 378.72

Triclinic,

a = 8.2063 (4) Å

b = 9.3075 (5) Å

c = 10.2896 (6) Å

α = 93.954 (5)°

β = 95.284 (5)°

γ = 90.376 (4)°

V = 780.65 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.30 mm−1

T = 293 K

0.30 × 0.24 × 0.18 mm

Data collection

Oxford Diffraction Xcalibur diffractometer

Absorption correction: none

8478 measured reflections

4960 independent reflections

3665 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.058

wR(F 2) = 0.179

S = 1.12

4960 reflections

286 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.85 e Å−3

Δρmin = −0.61 e Å−3

Data collection: CrysAlis Pro (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis Pro; data reduction: CrysAlis RED (Oxford Diffraction, 2007 ▶); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows(Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809035405/jh2096sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809035405/jh2096Isup2.hkl

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

C6H13ClNO+·C6H2N3O7−	Z = 2
Mr = 378.72	F(000) = 392
Triclinic, P1	Dx = 1.611 Mg m−3
a = 8.2063 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 9.3075 (5) Å	Cell parameters from 3665 reflections
c = 10.2896 (6) Å	θ = 3.3–32.3°
α = 93.954 (5)°	µ = 0.30 mm−1
β = 95.284 (5)°	T = 293 K
γ = 90.376 (4)°	Rectangular, yellow
V = 780.65 (7) Å3	0.30 × 0.24 × 0.18 mm

Oxford Diffraction Xcalibur diffractometer	Rint = 0.016
ω–2θ scans	θmax = 32.3°, θmin = 3.3°
8478 measured reflections	h = −12→12
4960 independent reflections	k = −8→13
3665 reflections with I > 2σ(I)	l = −14→15

Refinement on F2	0 restraints
Least-squares matrix: full	0 constraints
R[F2 > 2σ(F2)] = 0.058	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.179	w = 1/[σ2(Fo2) + (0.0877P)2 + 0.2886P] where P = (Fo2 + 2Fc2)/3
S = 1.12	(Δ/σ)max < 0.001
4960 reflections	Δρmax = 0.85 e Å−3
286 parameters	Δρmin = −0.60 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.

	x	y	z	Uiso*/Ueq
H8B	−0.178 (3)	−0.150 (3)	0.786 (2)	0.035 (6)*
H9B	−0.286 (3)	0.146 (3)	0.883 (3)	0.041 (6)*
H4	0.386 (3)	0.587 (2)	0.610 (2)	0.033 (6)*
H9A	−0.401 (3)	0.024 (3)	0.793 (2)	0.036 (6)*
H10A	−0.331 (3)	0.311 (3)	0.731 (2)	0.039 (6)*
H2	0.299 (3)	0.541 (3)	0.972 (3)	0.042 (7)*
H11A	−0.135 (3)	−0.023 (3)	0.548 (2)	0.040 (6)*
H12A	−0.241 (3)	0.215 (3)	0.532 (3)	0.049 (7)*
H8A	−0.102 (3)	−0.044 (2)	0.887 (3)	0.033 (6)*
H11B	−0.300 (3)	−0.076 (3)	0.597 (2)	0.037 (6)*
H7B	0.087 (4)	−0.208 (3)	0.791 (3)	0.058 (8)*
H12B	−0.355 (4)	0.101 (3)	0.435 (3)	0.055 (8)*
H7A	0.069 (3)	−0.121 (3)	0.678 (3)	0.052 (7)*
H10B	−0.504 (4)	0.259 (3)	0.757 (3)	0.052 (7)*
H4'	−0.106 (3)	0.125 (3)	0.743 (2)	0.037 (6)*
Cl	0.22010 (6)	0.00390 (7)	0.83918 (7)	0.0572 (2)
N4	−0.18045 (17)	0.05189 (15)	0.73274 (15)	0.0277 (3)
C8	−0.1068 (2)	−0.0703 (2)	0.8042 (2)	0.0333 (4)
C9	−0.3282 (2)	0.1067 (2)	0.7962 (2)	0.0343 (4)
O8	−0.4535 (2)	0.1794 (2)	0.58892 (18)	0.0535 (4)
C11	−0.2318 (2)	0.0085 (2)	0.5915 (2)	0.0365 (4)
C10	−0.4054 (3)	0.2269 (2)	0.7217 (3)	0.0469 (5)
C7	0.0592 (2)	−0.1150 (2)	0.7678 (2)	0.0405 (4)
C12	−0.3138 (3)	0.1338 (3)	0.5261 (2)	0.0465 (5)
C5	0.2198 (2)	0.43814 (18)	0.62764 (19)	0.0308 (3)
N2	0.47503 (19)	0.70058 (17)	0.84556 (19)	0.0374 (4)
C2	0.2800 (2)	0.51646 (19)	0.8933 (2)	0.0325 (4)
O1	0.0317 (2)	0.25764 (19)	0.67334 (16)	0.0543 (5)
C4	0.3325 (2)	0.54510 (18)	0.6696 (2)	0.0318 (4)
C3	0.3613 (2)	0.58362 (18)	0.80201 (19)	0.0310 (4)
C1	0.1667 (2)	0.40844 (18)	0.85050 (19)	0.0311 (4)
C6	0.1275 (2)	0.35914 (19)	0.71437 (19)	0.0330 (4)
N3	0.0845 (2)	0.34768 (17)	0.95407 (18)	0.0384 (4)
N1	0.1924 (2)	0.40692 (18)	0.48624 (17)	0.0389 (4)
O5	0.5335 (2)	0.76658 (17)	0.76105 (19)	0.0541 (4)
O2	−0.0347 (2)	0.2682 (2)	0.92512 (19)	0.0603 (5)
O4	0.5057 (2)	0.73018 (19)	0.96342 (19)	0.0542 (4)
O3	0.1342 (2)	0.3801 (2)	1.06775 (18)	0.0568 (5)
O7	0.0693 (3)	0.3444 (3)	0.4397 (2)	0.0808 (7)
O6	0.2896 (3)	0.4530 (3)	0.4174 (2)	0.0902 (8)

	U11	U22	U33	U12	U13	U23
Cl	0.0304 (2)	0.0661 (4)	0.0743 (5)	−0.0029 (2)	0.0023 (2)	0.0011 (3)
N4	0.0240 (6)	0.0286 (6)	0.0314 (7)	−0.0047 (5)	0.0033 (5)	0.0069 (5)
C8	0.0287 (8)	0.0346 (9)	0.0378 (10)	−0.0009 (7)	0.0032 (7)	0.0116 (7)
C9	0.0269 (8)	0.0356 (9)	0.0411 (10)	−0.0010 (6)	0.0065 (7)	0.0041 (7)
O8	0.0401 (8)	0.0624 (10)	0.0567 (11)	0.0076 (7)	−0.0100 (7)	0.0140 (8)
C11	0.0333 (9)	0.0426 (10)	0.0330 (9)	−0.0036 (7)	0.0009 (7)	0.0027 (7)
C10	0.0431 (11)	0.0402 (10)	0.0573 (14)	0.0088 (9)	0.0011 (10)	0.0067 (9)
C7	0.0340 (9)	0.0425 (10)	0.0449 (12)	0.0056 (8)	0.0033 (8)	0.0012 (9)
C12	0.0446 (11)	0.0585 (13)	0.0362 (11)	−0.0044 (10)	−0.0058 (9)	0.0152 (9)
C5	0.0287 (7)	0.0271 (7)	0.0367 (9)	−0.0030 (6)	0.0012 (6)	0.0057 (6)
N2	0.0289 (7)	0.0288 (7)	0.0537 (11)	−0.0048 (6)	0.0011 (7)	0.0009 (7)
C2	0.0306 (8)	0.0285 (8)	0.0382 (10)	−0.0009 (6)	0.0009 (7)	0.0042 (7)
O1	0.0577 (10)	0.0596 (10)	0.0445 (9)	−0.0371 (8)	−0.0041 (7)	0.0103 (7)
C4	0.0265 (7)	0.0258 (7)	0.0442 (10)	−0.0024 (6)	0.0056 (7)	0.0089 (7)
C3	0.0261 (7)	0.0242 (7)	0.0425 (10)	−0.0044 (6)	0.0011 (7)	0.0036 (7)
C1	0.0293 (8)	0.0284 (7)	0.0366 (9)	−0.0038 (6)	0.0041 (7)	0.0083 (7)
C6	0.0282 (8)	0.0305 (8)	0.0409 (10)	−0.0069 (6)	0.0002 (7)	0.0103 (7)
N3	0.0397 (8)	0.0313 (7)	0.0467 (10)	−0.0014 (6)	0.0122 (7)	0.0101 (7)
N1	0.0435 (9)	0.0361 (8)	0.0369 (9)	−0.0018 (7)	0.0037 (7)	0.0020 (7)
O5	0.0504 (9)	0.0417 (8)	0.0711 (12)	−0.0223 (7)	0.0093 (8)	0.0074 (8)
O2	0.0626 (11)	0.0575 (10)	0.0627 (11)	−0.0316 (8)	0.0238 (9)	−0.0016 (8)
O4	0.0494 (9)	0.0505 (9)	0.0590 (11)	−0.0126 (7)	−0.0051 (8)	−0.0080 (8)
O3	0.0639 (11)	0.0647 (11)	0.0439 (9)	−0.0126 (9)	0.0067 (8)	0.0163 (8)
O7	0.0923 (16)	0.1001 (17)	0.0461 (11)	−0.0532 (14)	−0.0013 (10)	−0.0075 (10)
O6	0.0833 (15)	0.142 (2)	0.0462 (11)	−0.0453 (16)	0.0161 (10)	0.0066 (13)

Cl—C7	1.788 (2)	C12—H12A	0.96 (3)
N4—C8	1.497 (2)	C12—H12B	0.99 (3)
N4—C11	1.503 (2)	C5—C4	1.374 (2)
N4—C9	1.504 (2)	C5—C6	1.455 (2)
N4—H4'	0.91 (2)	C5—N1	1.460 (3)
C8—C7	1.500 (3)	N2—O4	1.228 (3)
C8—H8B	0.94 (2)	N2—O5	1.229 (2)
C8—H8A	0.87 (3)	N2—C3	1.449 (2)
C9—C10	1.510 (3)	C2—C3	1.382 (3)
C9—H9B	0.98 (3)	C2—C1	1.386 (2)
C9—H9A	0.97 (2)	C2—H2	0.83 (3)
O8—C12	1.420 (3)	O1—C6	1.250 (2)
O8—C10	1.426 (3)	C4—C3	1.383 (3)
C11—C12	1.517 (3)	C4—H4	0.89 (2)
C11—H11A	0.98 (3)	C1—C6	1.450 (3)
C11—H11B	0.97 (2)	C1—N3	1.456 (2)
C10—H10A	0.98 (3)	N3—O3	1.220 (2)
C10—H10B	0.96 (3)	N3—O2	1.225 (2)
C7—H7B	0.93 (3)	N1—O7	1.206 (3)
C7—H7A	0.94 (3)	N1—O6	1.210 (3)
C8—N4—C11	112.20 (15)	Cl—C7—H7A	105.7 (17)
C8—N4—C9	110.07 (14)	H7B—C7—H7A	103 (3)
C11—N4—C9	108.38 (14)	O8—C12—C11	111.16 (18)
C8—N4—H4'	106.9 (15)	O8—C12—H12A	106.5 (17)
C11—N4—H4'	113.0 (15)	C11—C12—H12A	110.6 (16)
C9—N4—H4'	106.1 (15)	O8—C12—H12B	106.1 (17)
N4—C8—C7	115.12 (16)	C11—C12—H12B	108.8 (16)
N4—C8—H8B	107.4 (14)	H12A—C12—H12B	113 (2)
C7—C8—H8B	108.0 (14)	C4—C5—C6	124.17 (18)
N4—C8—H8A	106.8 (16)	C4—C5—N1	116.02 (16)
C7—C8—H8A	110.2 (15)	C6—C5—N1	119.80 (15)
H8B—C8—H8A	109 (2)	O4—N2—O5	123.60 (17)
N4—C9—C10	110.06 (17)	O4—N2—C3	118.95 (17)
N4—C9—H9B	105.2 (15)	O5—N2—C3	117.44 (18)
C10—C9—H9B	108.9 (15)	C3—C2—C1	118.96 (18)
N4—C9—H9A	105.1 (14)	C3—C2—H2	120.0 (18)
C10—C9—H9A	111.6 (14)	C1—C2—H2	121.0 (18)
H9B—C9—H9A	116 (2)	C5—C4—C3	119.30 (16)
C12—O8—C10	109.70 (17)	C5—C4—H4	118.7 (15)
N4—C11—C12	109.86 (17)	C3—C4—H4	122.0 (15)
N4—C11—H11A	109.0 (14)	C2—C3—C4	121.53 (16)
C12—C11—H11A	111.4 (14)	C2—C3—N2	119.26 (17)
N4—C11—H11B	102.7 (14)	C4—C3—N2	119.18 (16)
C12—C11—H11B	116.2 (14)	C2—C1—C6	124.15 (16)
H11A—C11—H11B	107 (2)	C2—C1—N3	114.57 (17)
O8—C10—C9	111.16 (18)	C6—C1—N3	121.27 (15)
O8—C10—H10A	113.2 (15)	O1—C6—C1	125.59 (17)
C9—C10—H10A	109.7 (14)	O1—C6—C5	122.46 (18)
O8—C10—H10B	105.5 (17)	C1—C6—C5	111.90 (15)
C9—C10—H10B	111.4 (17)	O3—N3—O2	121.69 (18)
H10A—C10—H10B	106 (2)	O3—N3—C1	118.95 (17)
C8—C7—Cl	113.24 (15)	O2—N3—C1	119.35 (18)
C8—C7—H7B	113.2 (19)	O7—N1—O6	121.2 (2)
Cl—C7—H7B	107.2 (18)	O7—N1—C5	119.83 (18)
C8—C7—H7A	114.0 (18)	O6—N1—C5	118.78 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4'···O1	0.91 (3)	1.89 (3)	2.718 (2)	151.2 (19)
N4—H4'···O2	0.91 (3)	2.25 (2)	2.896 (2)	127.6 (17)
C2—H2···O3	0.83 (3)	2.34 (3)	2.637 (3)	102 (2)
C2—H2···O4	0.83 (2)	2.45 (2)	2.723 (3)	101 (2)
C4—H4···O6	0.90 (3)	2.34 (3)	2.667 (3)	101.7 (15)
C7—H7A···O7i	0.93 (3)	2.54 (3)	3.026 (3)	113 (2)
C8—H8B···O5ii	0.94 (3)	2.47 (2)	3.290 (2)	146 (2)
C9—H9A···O5ii	0.97 (3)	2.45 (3)	3.341 (2)	154 (2)
C9—H9B···O2	0.97 (3)	2.34 (3)	2.985 (3)	123 (2)
C12—H12A···O1	0.96 (3)	2.57 (2)	3.254 (3)	129 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4′⋯O1	0.91 (3)	1.89 (3)	2.718 (2)	151.2 (19)
N4—H4′⋯O2	0.91 (3)	2.25 (2)	2.896 (2)	127.6 (17)
C2—H2⋯O3	0.83 (3)	2.34 (3)	2.637 (3)	102 (2)
C2—H2⋯O4	0.83 (2)	2.45 (2)	2.723 (3)	101 (2)
C4—H4⋯O6	0.90 (3)	2.34 (3)	2.667 (3)	101.7 (15)
C7—H7A⋯O7i	0.93 (3)	2.54 (3)	3.026 (3)	113 (2)
C8—H8B⋯O5ii	0.94 (3)	2.47 (2)	3.290 (2)	146 (2)
C9—H9A⋯O5ii	0.97 (3)	2.45 (3)	3.341 (2)	154 (2)
C9—H9B⋯O2	0.97 (3)	2.34 (3)	2.985 (3)	123 (2)
C12—H12A⋯O1	0.96 (3)	2.57 (2)	3.254 (3)	129 (2)

Symmetry codes: (i) ; (ii) .