2,2,6,6-Tetra-methyl-4-oxopiperidin-1-ium 4-chloro-3-nitro-benzoate.

The title salt, C(9)H(18)NO(+)·C(7)H(3)ClNO(4) (-), was obtained as an unexpected product of the reaction of 4-chloro-3-nitro-benzoyl isothio-cyanate with pyrrolidine. The six-membered ring of the 4-oxopiperidinium cation adopts a chair conformation. In the crystal structure, two cations and three anions are linked together by inter-molecular N-H⋯O and C-H⋯O hydrogen bonds and arranged diagonally along the ac face.

Related literature

For related structures, see: Wang et al. (2008 ▶); Jasinski et al. (2009 ▶), Smith & Wermuth (2011 ▶). For bond-length data, see Allen et al. (1987 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C9H18NO+·C7H3ClNO4 −

M = 356.80

Triclinic,

a = 7.9974 (10) Å

b = 10.3267 (13) Å

c = 11.9196 (15) Å

α = 109.101 (3)°

β = 96.785 (3)°

γ = 104.720 (3)°

V = 877.58 (19) Å3

Z = 2

Mo Kα radiation

μ = 0.25 mm−1

T = 298 K

0.40 × 0.14 × 0.09 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.908, T max = 0.978

10082 measured reflections

3431 independent reflections

2268 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.126

S = 1.01

3431 reflections

229 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.25 e Å−3

Δρmin = −0.18 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811025074/ff2016sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811025074/ff2016Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811025074/ff2016Isup3.cml

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

C9H18NO+·C7H3ClNO4−	Z = 2
Mr = 356.80	F(000) = 376
Triclinic, P1	Dx = 1.350 Mg m−3
Hall symbol: -P 1	Melting point = 447.3–448.1 K
a = 7.9974 (10) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.3267 (13) Å	Cell parameters from 1985 reflections
c = 11.9196 (15) Å	θ = 1.8–26.0°
α = 109.101 (3)°	µ = 0.25 mm−1
β = 96.785 (3)°	T = 298 K
γ = 104.720 (3)°	Slab, colourless
V = 877.58 (19) Å3	0.40 × 0.14 × 0.09 mm

Bruker SMART APEX CCD area-detector diffractometer	3431 independent reflections
Radiation source: fine-focus sealed tube	2268 reflections with I > 2σ(I)
graphite	Rint = 0.030
Detector resolution: 83.66 pixels mm-1	θmax = 26.0°, θmin = 1.8°
ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −12→12
Tmin = 0.908, Tmax = 0.978	l = −14→14
10082 measured 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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.0655P)2 + 0.0942P] where P = (Fo2 + 2Fc2)/3
3431 reflections	(Δ/σ)max < 0.001
229 parameters	Δρmax = 0.25 e Å−3
2 restraints	Δρmin = −0.18 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	0.10661 (8)	0.44819 (7)	0.35541 (6)	0.0712 (2)
O1	0.1974 (3)	0.1497 (2)	0.57035 (16)	0.0823 (6)
O2	0.7048 (2)	0.76828 (18)	0.88016 (14)	0.0742 (5)
O3	0.7880 (2)	0.93410 (17)	0.80065 (14)	0.0624 (5)
O4	0.3749 (3)	0.8614 (2)	0.41307 (17)	0.0802 (6)
O5	0.3627 (3)	0.6544 (2)	0.28559 (16)	0.0862 (6)
N1	0.1289 (2)	0.11990 (18)	0.88732 (15)	0.0386 (4)
H1A	0.0241 (16)	0.0568 (17)	0.8704 (17)	0.042 (6)*
H1B	0.176 (3)	0.151 (2)	0.9662 (10)	0.052 (6)*
N2	0.3733 (2)	0.7373 (2)	0.38805 (18)	0.0578 (5)
C1	0.2358 (3)	0.0336 (2)	0.81718 (18)	0.0452 (5)
C2	0.0998 (3)	0.2474 (2)	0.86054 (19)	0.0460 (5)
C3	0.0313 (3)	0.1960 (3)	0.7231 (2)	0.0561 (6)
H3A	−0.0898	0.1326	0.7014	0.067*
H3B	0.0300	0.2788	0.7019	0.067*
C4	0.1398 (3)	0.1179 (3)	0.6502 (2)	0.0559 (6)
C5	0.1637 (3)	−0.0069 (3)	0.68090 (19)	0.0575 (6)
H5A	0.2447	−0.0452	0.6356	0.069*
H5B	0.0505	−0.0824	0.6552	0.069*
C6	0.2039 (3)	−0.1004 (2)	0.8498 (2)	0.0587 (6)
H6A	0.2490	−0.0723	0.9354	0.088*
H6B	0.2636	−0.1627	0.8047	0.088*
H6C	0.0791	−0.1504	0.8297	0.088*
C7	0.4326 (3)	0.1167 (3)	0.8553 (2)	0.0642 (7)
H7A	0.4688	0.1553	0.9425	0.096*
H7B	0.4550	0.1943	0.8259	0.096*
H7C	0.4984	0.0532	0.8216	0.096*
C8	−0.0406 (3)	0.2880 (3)	0.9280 (2)	0.0639 (7)
H8A	0.0056	0.3221	1.0141	0.096*
H8B	−0.1435	0.2050	0.9045	0.096*
H8C	−0.0723	0.3627	0.9080	0.096*
C9	0.2697 (3)	0.3757 (2)	0.9055 (2)	0.0682 (7)
H9A	0.3208	0.3943	0.9885	0.102*
H9B	0.2425	0.4593	0.9006	0.102*
H9C	0.3525	0.3541	0.8558	0.102*
C10	0.4375 (3)	0.5931 (2)	0.67661 (19)	0.0457 (5)
H10A	0.4547	0.5605	0.7398	0.055*
C11	0.5459 (2)	0.7263 (2)	0.68617 (17)	0.0379 (5)
C12	0.5203 (2)	0.7728 (2)	0.59146 (17)	0.0410 (5)
H12A	0.5910	0.8622	0.5968	0.049*
C13	0.3893 (3)	0.6860 (2)	0.48870 (18)	0.0419 (5)
C14	0.2792 (3)	0.5541 (2)	0.47945 (18)	0.0442 (5)
C15	0.3041 (3)	0.5083 (2)	0.5742 (2)	0.0501 (5)
H15A	0.2311	0.4200	0.5696	0.060*
C16	0.6921 (3)	0.8182 (2)	0.79869 (18)	0.0444 (5)

	U11	U22	U33	U12	U13	U23
Cl1	0.0475 (4)	0.0709 (4)	0.0599 (4)	0.0018 (3)	−0.0096 (3)	−0.0004 (3)
O1	0.0921 (14)	0.1105 (15)	0.0579 (11)	0.0264 (11)	0.0259 (10)	0.0492 (11)
O2	0.0933 (13)	0.0718 (11)	0.0368 (9)	0.0035 (10)	−0.0101 (8)	0.0193 (8)
O3	0.0499 (9)	0.0538 (10)	0.0625 (10)	−0.0038 (8)	−0.0101 (8)	0.0179 (8)
O4	0.0923 (14)	0.0673 (12)	0.0808 (13)	0.0234 (10)	−0.0083 (10)	0.0380 (10)
O5	0.1131 (16)	0.0961 (14)	0.0418 (10)	0.0258 (12)	0.0073 (10)	0.0245 (10)
N1	0.0376 (10)	0.0401 (10)	0.0317 (9)	0.0051 (8)	0.0009 (8)	0.0127 (8)
N2	0.0518 (12)	0.0640 (14)	0.0517 (13)	0.0125 (10)	−0.0058 (9)	0.0241 (11)
C1	0.0452 (12)	0.0525 (13)	0.0394 (11)	0.0177 (10)	0.0074 (9)	0.0178 (10)
C2	0.0479 (12)	0.0425 (12)	0.0479 (12)	0.0111 (9)	0.0079 (10)	0.0203 (10)
C3	0.0547 (14)	0.0666 (15)	0.0555 (14)	0.0179 (12)	0.0054 (11)	0.0369 (12)
C4	0.0526 (13)	0.0719 (16)	0.0384 (12)	0.0106 (12)	0.0014 (10)	0.0240 (11)
C5	0.0676 (16)	0.0656 (15)	0.0383 (12)	0.0252 (12)	0.0132 (11)	0.0142 (11)
C6	0.0660 (15)	0.0537 (14)	0.0607 (15)	0.0240 (12)	0.0115 (12)	0.0234 (12)
C7	0.0469 (14)	0.0842 (18)	0.0701 (16)	0.0235 (13)	0.0146 (12)	0.0365 (14)
C8	0.0691 (16)	0.0586 (15)	0.0727 (17)	0.0284 (13)	0.0236 (13)	0.0263 (13)
C9	0.0698 (17)	0.0487 (14)	0.0756 (18)	0.0016 (12)	0.0062 (13)	0.0262 (13)
C10	0.0469 (12)	0.0481 (12)	0.0415 (12)	0.0116 (10)	0.0106 (9)	0.0178 (10)
C11	0.0354 (10)	0.0399 (11)	0.0344 (10)	0.0119 (9)	0.0068 (8)	0.0092 (9)
C12	0.0361 (11)	0.0389 (11)	0.0426 (12)	0.0084 (9)	0.0056 (9)	0.0120 (9)
C13	0.0387 (11)	0.0469 (12)	0.0385 (11)	0.0148 (9)	0.0058 (9)	0.0136 (9)
C14	0.0341 (11)	0.0445 (12)	0.0416 (12)	0.0106 (9)	0.0043 (9)	0.0030 (9)
C15	0.0436 (12)	0.0403 (12)	0.0575 (14)	0.0029 (9)	0.0120 (10)	0.0146 (10)
C16	0.0414 (12)	0.0472 (13)	0.0357 (11)	0.0133 (10)	0.0015 (9)	0.0068 (10)

Cl1—C14	1.726 (2)	C6—H6A	0.9600
O1—C4	1.207 (3)	C6—H6B	0.9600
O2—C16	1.245 (3)	C6—H6C	0.9600
O3—C16	1.238 (3)	C7—H7A	0.9600
O4—N2	1.213 (2)	C7—H7B	0.9600
O5—N2	1.219 (2)	C7—H7C	0.9600
N1—C1	1.514 (3)	C8—H8A	0.9600
N1—C2	1.517 (3)	C8—H8B	0.9600
N1—H1A	0.874 (9)	C8—H8C	0.9600
N1—H1B	0.888 (9)	C9—H9A	0.9600
N2—C13	1.467 (3)	C9—H9B	0.9600
C1—C7	1.520 (3)	C9—H9C	0.9600
C1—C6	1.524 (3)	C10—C15	1.383 (3)
C1—C5	1.536 (3)	C10—C11	1.387 (3)
C2—C8	1.521 (3)	C10—H10A	0.9300
C2—C3	1.529 (3)	C11—C12	1.377 (3)
C2—C9	1.529 (3)	C11—C16	1.516 (3)
C3—C4	1.494 (3)	C12—C13	1.379 (3)
C3—H3A	0.9700	C12—H12A	0.9300
C3—H3B	0.9700	C13—C14	1.383 (3)
C4—C5	1.499 (3)	C14—C15	1.372 (3)
C5—H5A	0.9700	C15—H15A	0.9300
C5—H5B	0.9700
C1—N1—C2	120.56 (16)	H6B—C6—H6C	109.5
C1—N1—H1A	103.8 (13)	C1—C7—H7A	109.5
C2—N1—H1A	106.4 (13)	C1—C7—H7B	109.5
C1—N1—H1B	108.5 (14)	H7A—C7—H7B	109.5
C2—N1—H1B	107.7 (13)	C1—C7—H7C	109.5
H1A—N1—H1B	109.6 (19)	H7A—C7—H7C	109.5
O4—N2—O5	124.2 (2)	H7B—C7—H7C	109.5
O4—N2—C13	117.4 (2)	C2—C8—H8A	109.5
O5—N2—C13	118.4 (2)	C2—C8—H8B	109.5
N1—C1—C7	111.61 (17)	H8A—C8—H8B	109.5
N1—C1—C6	105.17 (17)	C2—C8—H8C	109.5
C7—C1—C6	109.29 (17)	H8A—C8—H8C	109.5
N1—C1—C5	107.97 (16)	H8B—C8—H8C	109.5
C7—C1—C5	111.59 (19)	C2—C9—H9A	109.5
C6—C1—C5	111.04 (18)	C2—C9—H9B	109.5
N1—C2—C8	105.96 (17)	H9A—C9—H9B	109.5
N1—C2—C3	107.28 (17)	C2—C9—H9C	109.5
C8—C2—C3	110.62 (19)	H9A—C9—H9C	109.5
N1—C2—C9	111.61 (17)	H9B—C9—H9C	109.5
C8—C2—C9	109.71 (19)	C15—C10—C11	120.8 (2)
C3—C2—C9	111.51 (19)	C15—C10—H10A	119.6
C4—C3—C2	113.43 (18)	C11—C10—H10A	119.6
C4—C3—H3A	108.9	C12—C11—C10	119.08 (18)
C2—C3—H3A	108.9	C12—C11—C16	120.59 (18)
C4—C3—H3B	108.9	C10—C11—C16	120.33 (18)
C2—C3—H3B	108.9	C11—C12—C13	119.65 (19)
H3A—C3—H3B	107.7	C11—C12—H12A	120.2
O1—C4—C3	122.5 (2)	C13—C12—H12A	120.2
O1—C4—C5	123.1 (2)	C12—C13—C14	121.47 (19)
C3—C4—C5	114.4 (2)	C12—C13—N2	117.49 (18)
C4—C5—C1	113.22 (18)	C14—C13—N2	121.03 (18)
C4—C5—H5A	108.9	C15—C14—C13	118.79 (19)
C1—C5—H5A	108.9	C15—C14—Cl1	118.87 (17)
C4—C5—H5B	108.9	C13—C14—Cl1	122.29 (17)
C1—C5—H5B	108.9	C14—C15—C10	120.2 (2)
H5A—C5—H5B	107.7	C14—C15—H15A	119.9
C1—C6—H6A	109.5	C10—C15—H15A	119.9
C1—C6—H6B	109.5	O3—C16—O2	126.28 (19)
H6A—C6—H6B	109.5	O3—C16—C11	117.47 (19)
C1—C6—H6C	109.5	O2—C16—C11	116.24 (19)
H6A—C6—H6C	109.5
C2—N1—C1—C7	73.0 (2)	C16—C11—C12—C13	178.44 (17)
C2—N1—C1—C6	−168.64 (17)	C11—C12—C13—C14	1.6 (3)
C2—N1—C1—C5	−50.0 (2)	C11—C12—C13—N2	−177.04 (18)
C1—N1—C2—C8	168.99 (17)	O4—N2—C13—C12	−47.1 (3)
C1—N1—C2—C3	50.8 (2)	O5—N2—C13—C12	131.6 (2)
C1—N1—C2—C9	−71.6 (2)	O4—N2—C13—C14	134.3 (2)
N1—C2—C3—C4	−49.4 (2)	O5—N2—C13—C14	−47.1 (3)
C8—C2—C3—C4	−164.50 (19)	C12—C13—C14—C15	−1.2 (3)
C9—C2—C3—C4	73.1 (3)	N2—C13—C14—C15	177.42 (19)
C2—C3—C4—O1	−128.3 (2)	C12—C13—C14—Cl1	176.34 (15)
C2—C3—C4—C5	54.4 (3)	N2—C13—C14—Cl1	−5.0 (3)
O1—C4—C5—C1	129.6 (2)	C13—C14—C15—C10	−0.2 (3)
C3—C4—C5—C1	−53.1 (3)	Cl1—C14—C15—C10	−177.79 (16)
N1—C1—C5—C4	47.4 (2)	C11—C10—C15—C14	1.1 (3)
C7—C1—C5—C4	−75.6 (2)	C12—C11—C16—O3	−1.2 (3)
C6—C1—C5—C4	162.25 (19)	C10—C11—C16—O3	177.94 (19)
C15—C10—C11—C12	−0.7 (3)	C12—C11—C16—O2	179.46 (19)
C15—C10—C11—C16	−179.79 (18)	C10—C11—C16—O2	−1.4 (3)
C10—C11—C12—C13	−0.7 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3i	0.87 (2)	1.89 (2)	2.750 (2)	165
N1—H1B···O2ii	0.89 (1)	1.77 (1)	2.653 (2)	171
C3—H3A···O4iii	0.97	2.54	3.269 (3)	132
C8—H8B···O3i	0.96	2.54	3.297 (3)	136

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3i	0.87 (2)	1.89 (2)	2.750 (2)	165
N1—H1B⋯O2ii	0.89 (1)	1.77 (1)	2.653 (2)	171
C3—H3A⋯O4iii	0.97	2.54	3.269 (3)	132
C8—H8B⋯O3i	0.96	2.54	3.297 (3)	136

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