4-Aza-niumyl-2,2,6,6-tetra-methyl-piperidin-1-ium dinitrate.

In the crystal structure of the title salt, C9H22N2 (2+)·2NO3 (-), the piperidine ring of the dication adopts a chair conformation and the orientation of the C-NH3 bond is equatorial. The ions are linked by normal and bifurcated N-H⋯O hydrogen bonds in R 2 (2)(6), two R 4 (2)(8) and R 3 (4)(14) graf-set motifs, generating a three-dimensional network.

Related literature

For related structures, see: Chebbi & Driss (2001 ▶); El Glaoui, Mrad, Jenneau & Ben Nasr (2010 ▶); Mrad et al. (2009 ▶); Huang & Deng (2007 ▶). For hydrogen bonding and graph-set motifs, see: Jeffrey (1997 ▶); Bernstein et al. (1995 ▶); Etter et al. (1990 ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶); Spek (2009 ▶).

Experimental

Crystal data

C9H22N2 2+·2NO3 −

M = 282.31

Monoclinic,

a = 10.367 (2) Å

b = 11.054 (1) Å

c = 13.167 (2) Å

β = 112.45 (2)°

V = 1394.5 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.11 mm−1

T = 298 K

0.45 × 0.30 × 0.25 mm

Data collection

Enraf–Nonius CAD-4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.860, T max = 0.978

2849 measured reflections

2731 independent reflections

1908 reflections with I > 2σ(I)

R int = 0.017

2 standard reflections every 120 min intensity decay: 1.0%

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.121

S = 1.05

2731 reflections

261 parameters

All H-atom parameters refined

Δρmax = 0.24 e Å−3

Δρmin = −0.15 e Å−3

Data collection: CAD-4 EXPRESS (Duisenberg, 1992 ▶; Macíček & Yordanov, 1992 ▶); cell refinement: CAD-4 EXPRESS; data reduction: MolEN (Fair, 1990 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2001 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814009787/nc2324sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814009787/nc2324Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814009787/nc2324Isup3.cml

CCDC reference: 1000438

Additional supporting information: crystallographic information; 3D view; checkCIF report

C9H22N22+·2NO3−	F(000) = 608
Mr = 282.31	Dx = 1.345 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 10.367 (2) Å	θ = 10–15°
b = 11.054 (1) Å	µ = 0.11 mm−1
c = 13.167 (2) Å	T = 298 K
β = 112.45 (2)°	Prism, dark brown
V = 1394.5 (4) Å3	0.45 × 0.30 × 0.25 mm
Z = 4

Enraf–Nonius CAD-4 diffractometer	1908 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
Graphite monochromator	θmax = 26.0°, θmin = 2.5°
ω/2θ scans	h = −11→12
Absorption correction: ψ scan (North et al., 1968)	k = −13→0
Tmin = 0.860, Tmax = 0.978	l = −16→0
2849 measured reflections	2 standard reflections every 120 min
2731 independent reflections	intensity decay: 1.0%

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)] = 0.044	All H-atom parameters refined
wR(F2) = 0.121	w = 1/[σ2(Fo2) + (0.0508P)2 + 0.3472P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
2731 reflections	Δρmax = 0.24 e Å−3
261 parameters	Δρmin = −0.15 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.022 (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
N1	0.65815 (16)	0.64785 (14)	0.03529 (14)	0.0327 (4)
H1A	0.607 (2)	0.614 (2)	−0.0322 (19)	0.051 (6)*
H1B	0.636 (2)	0.6145 (19)	0.0858 (17)	0.041 (6)*
N2	0.8793 (2)	0.8680 (2)	−0.10476 (17)	0.0459 (5)
H2A	0.972 (3)	0.854 (2)	−0.085 (2)	0.072 (8)*
H2B	0.857 (3)	0.950 (3)	−0.109 (2)	0.076 (9)*
H2C	0.838 (3)	0.834 (2)	−0.170 (2)	0.059 (7)*
C1	0.80955 (19)	0.61008 (17)	0.06283 (15)	0.0356 (5)
C2	0.8620 (2)	0.67784 (19)	−0.01499 (17)	0.0392 (5)
H2D	0.959 (2)	0.666 (2)	0.0075 (17)	0.050 (6)*
H2E	0.820 (2)	0.6457 (19)	−0.0867 (18)	0.047 (6)*
C3	0.8315 (2)	0.81240 (18)	−0.02154 (16)	0.0360 (5)
H3	0.881 (2)	0.8515 (17)	0.0414 (16)	0.034 (5)*
C4	0.6767 (2)	0.8365 (2)	−0.05477 (18)	0.0396 (5)
H4A	0.627 (2)	0.8029 (18)	−0.1287 (18)	0.044 (6)*
H4B	0.660 (2)	0.921 (2)	−0.0601 (17)	0.046 (6)*
C5	0.6175 (2)	0.78055 (17)	0.02436 (16)	0.0366 (5)
C6	0.8059 (3)	0.4739 (2)	0.0425 (3)	0.0533 (6)
H6A	0.759 (3)	0.455 (2)	−0.032 (2)	0.067 (8)*
H6B	0.772 (3)	0.431 (2)	0.091 (2)	0.068 (8)*
H6C	0.899 (3)	0.449 (3)	0.060 (2)	0.082 (9)*
C7	0.8987 (3)	0.6347 (3)	0.18384 (18)	0.0512 (6)
H7A	0.848 (3)	0.609 (3)	0.229 (2)	0.088 (9)*
H7B	0.922 (3)	0.721 (3)	0.201 (2)	0.075 (8)*
H7C	0.983 (3)	0.587 (2)	0.201 (2)	0.072 (8)*
C8	0.6690 (3)	0.8427 (2)	0.1367 (2)	0.0530 (6)
H8A	0.625 (3)	0.921 (3)	0.127 (2)	0.075 (8)*
H8B	0.774 (3)	0.854 (2)	0.1702 (19)	0.062 (7)*
H8C	0.640 (2)	0.798 (2)	0.186 (2)	0.059 (7)*
C9	0.4579 (2)	0.7821 (2)	−0.0251 (2)	0.0513 (6)
H9A	0.430 (3)	0.867 (3)	−0.038 (2)	0.072 (8)*
H9B	0.425 (2)	0.742 (2)	0.0249 (19)	0.052 (6)*
H9C	0.423 (3)	0.732 (2)	−0.099 (2)	0.068 (7)*
N3	0.97658 (17)	1.01245 (16)	0.27175 (13)	0.0414 (4)
O1	0.96306 (16)	0.99288 (15)	0.36111 (11)	0.0581 (5)
O2	0.9133 (2)	1.09726 (19)	0.21402 (16)	0.0806 (6)
O3	1.0499 (2)	0.94507 (17)	0.24364 (15)	0.0735 (6)
N4	1.24475 (18)	0.83006 (17)	0.15347 (14)	0.0452 (4)
O4	1.16626 (17)	0.87793 (16)	0.06514 (12)	0.0578 (5)
O5	1.2237 (2)	0.72440 (15)	0.17517 (14)	0.0692 (5)
O6	1.34062 (19)	0.88941 (19)	0.21907 (14)	0.0779 (6)

	U11	U22	U33	U12	U13	U23
N1	0.0349 (9)	0.0339 (9)	0.0300 (8)	−0.0027 (7)	0.0131 (7)	0.0000 (7)
N2	0.0492 (12)	0.0511 (13)	0.0432 (11)	−0.0107 (10)	0.0242 (9)	0.0002 (9)
C1	0.0318 (10)	0.0372 (11)	0.0366 (10)	0.0014 (8)	0.0115 (8)	0.0010 (8)
C2	0.0348 (11)	0.0467 (12)	0.0383 (11)	0.0011 (9)	0.0165 (9)	−0.0018 (9)
C3	0.0367 (10)	0.0423 (11)	0.0298 (10)	−0.0076 (9)	0.0136 (8)	−0.0026 (9)
C4	0.0411 (11)	0.0366 (12)	0.0404 (11)	0.0002 (9)	0.0149 (9)	0.0060 (9)
C5	0.0392 (11)	0.0316 (10)	0.0409 (11)	0.0008 (8)	0.0176 (9)	0.0004 (8)
C6	0.0536 (15)	0.0400 (13)	0.0697 (17)	0.0061 (11)	0.0273 (14)	0.0030 (12)
C7	0.0458 (13)	0.0594 (16)	0.0384 (12)	0.0019 (12)	0.0049 (10)	0.0069 (11)
C8	0.0714 (17)	0.0443 (14)	0.0518 (14)	−0.0047 (12)	0.0332 (13)	−0.0113 (11)
C9	0.0405 (12)	0.0452 (14)	0.0740 (17)	0.0067 (11)	0.0284 (12)	0.0114 (13)
N3	0.0442 (10)	0.0464 (10)	0.0364 (9)	−0.0044 (8)	0.0184 (8)	−0.0020 (8)
O1	0.0696 (11)	0.0758 (12)	0.0380 (8)	0.0214 (9)	0.0308 (8)	0.0116 (8)
O2	0.0791 (13)	0.0862 (14)	0.0787 (13)	0.0209 (11)	0.0326 (10)	0.0404 (11)
O3	0.0933 (13)	0.0714 (12)	0.0814 (13)	0.0112 (10)	0.0620 (11)	−0.0097 (10)
N4	0.0438 (10)	0.0528 (12)	0.0404 (10)	0.0018 (9)	0.0178 (8)	0.0005 (9)
O4	0.0591 (10)	0.0670 (11)	0.0409 (8)	0.0074 (8)	0.0121 (7)	0.0089 (8)
O5	0.0950 (14)	0.0465 (10)	0.0616 (11)	−0.0037 (9)	0.0247 (10)	0.0053 (8)
O6	0.0676 (12)	0.0939 (15)	0.0564 (10)	−0.0306 (11)	0.0061 (9)	−0.0065 (10)

N1—C5	1.518 (2)	C5—C8	1.530 (3)
N1—C1	1.528 (2)	C6—H6A	0.94 (3)
N1—H1A	0.93 (2)	C6—H6B	0.97 (3)
N1—H1B	0.87 (2)	C6—H6C	0.95 (3)
N2—C3	1.496 (2)	C7—H7A	0.97 (3)
N2—H2A	0.90 (3)	C7—H7B	0.99 (3)
N2—H2B	0.93 (3)	C7—H7C	0.97 (3)
N2—H2C	0.88 (3)	C8—H8A	0.97 (3)
C1—C2	1.527 (3)	C8—H8B	1.01 (2)
C1—C6	1.527 (3)	C8—H8C	0.95 (3)
C1—C7	1.530 (3)	C9—H9A	0.98 (3)
C2—C3	1.516 (3)	C9—H9B	0.95 (2)
C2—H2D	0.94 (2)	C9—H9C	1.05 (3)
C2—H2E	0.95 (2)	N3—O3	1.219 (2)
C3—C4	1.517 (3)	N3—O2	1.227 (2)
C3—H3	0.90 (2)	N3—O1	1.256 (2)
C4—C5	1.527 (3)	N4—O6	1.228 (2)
C4—H4A	0.98 (2)	N4—O5	1.241 (2)
C4—H4B	0.95 (2)	N4—O4	1.254 (2)
C5—C9	1.530 (3)
C5—N1—C1	120.63 (14)	N1—C5—C4	106.67 (15)
C5—N1—H1A	105.5 (14)	N1—C5—C9	105.52 (16)
C1—N1—H1A	106.3 (14)	C4—C5—C9	110.84 (17)
C5—N1—H1B	109.7 (14)	N1—C5—C8	111.14 (17)
C1—N1—H1B	104.7 (14)	C4—C5—C8	113.24 (18)
H1A—N1—H1B	109.7 (19)	C9—C5—C8	109.1 (2)
C3—N2—H2A	109.4 (16)	C1—C6—H6A	111.5 (16)
C3—N2—H2B	107.5 (17)	C1—C6—H6B	111.3 (15)
H2A—N2—H2B	113 (2)	H6A—C6—H6B	114 (2)
C3—N2—H2C	111.5 (16)	C1—C6—H6C	107.1 (17)
H2A—N2—H2C	106 (2)	H6A—C6—H6C	105 (2)
H2B—N2—H2C	109 (2)	H6B—C6—H6C	107 (2)
C2—C1—C6	110.92 (18)	C1—C7—H7A	109.7 (17)
C2—C1—N1	107.66 (15)	C1—C7—H7B	113.9 (15)
C6—C1—N1	105.86 (17)	H7A—C7—H7B	106 (2)
C2—C1—C7	112.54 (18)	C1—C7—H7C	106.3 (15)
C6—C1—C7	108.8 (2)	H7A—C7—H7C	110 (2)
N1—C1—C7	110.82 (17)	H7B—C7—H7C	111 (2)
C3—C2—C1	113.53 (16)	C5—C8—H8A	107.8 (15)
C3—C2—H2D	109.4 (14)	C5—C8—H8B	113.4 (13)
C1—C2—H2D	109.2 (13)	H8A—C8—H8B	109 (2)
C3—C2—H2E	107.8 (13)	C5—C8—H8C	110.5 (14)
C1—C2—H2E	109.8 (13)	H8A—C8—H8C	107 (2)
H2D—C2—H2E	107.0 (18)	H8B—C8—H8C	109 (2)
N2—C3—C2	108.91 (17)	C5—C9—H9A	106.6 (15)
N2—C3—C4	109.06 (17)	C5—C9—H9B	108.1 (14)
C2—C3—C4	111.33 (17)	H9A—C9—H9B	114 (2)
N2—C3—H3	104.1 (12)	C5—C9—H9C	108.5 (14)
C2—C3—H3	112.6 (12)	H9A—C9—H9C	112 (2)
C4—C3—H3	110.5 (12)	H9B—C9—H9C	107.9 (19)
C3—C4—C5	112.84 (16)	O3—N3—O2	121.79 (19)
C3—C4—H4A	108.2 (12)	O3—N3—O1	119.03 (18)
C5—C4—H4A	109.2 (12)	O2—N3—O1	119.16 (18)
C3—C4—H4B	110.0 (13)	O6—N4—O5	120.45 (19)
C5—C4—H4B	109.7 (13)	O6—N4—O4	119.4 (2)
H4A—C4—H4B	106.7 (17)	O5—N4—O4	120.12 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1i	0.93 (2)	1.99 (2)	2.868 (2)	156.9 (19)
N1—H1B···O1ii	0.87 (2)	1.97 (2)	2.772 (2)	152.9 (19)
N2—H2A···O4	0.90 (3)	2.24 (3)	2.964 (3)	137 (2)
N2—H2A···O2iii	0.90 (3)	2.48 (3)	3.034 (3)	120 (2)
N2—H2B···O4iii	0.93 (3)	2.03 (3)	2.928 (3)	161 (2)
N2—H2B···O3iii	0.93 (3)	2.59 (3)	3.030 (3)	109 (2)
N2—H2C···O5i	0.88 (3)	2.03 (3)	2.910 (3)	172 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1i	0.93 (2)	1.99 (2)	2.868 (2)	156.9 (19)
N1—H1B⋯O1ii	0.87 (2)	1.97 (2)	2.772 (2)	152.9 (19)
N2—H2A⋯O4	0.90 (3)	2.24 (3)	2.964 (3)	137 (2)
N2—H2A⋯O2iii	0.90 (3)	2.48 (3)	3.034 (3)	120 (2)
N2—H2B⋯O4iii	0.93 (3)	2.03 (3)	2.928 (3)	161 (2)
N2—H2B⋯O3iii	0.93 (3)	2.59 (3)	3.030 (3)	109 (2)
N2—H2C⋯O5i	0.88 (3)	2.03 (3)	2.910 (3)	172 (2)

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