Piperidine-1-carboxamidinium ethyl carbonate.

In the title salt, C6H14N3(+)·C3H5O3(-), the C-N bond lengths in the central CN3 unit of the carboxamidinium cation are 1.3262 (18), 1.3359 (18) and 1.3498 (18) Å, indicating partial double-bond character. The central C atom is bonded to the three N atoms in a nearly ideal trigonal-planar geometry and the positive charge is delocalized in the CN3 plane. The piperidine ring is in a chair conformation. The C-O bond lengths in the ethyl carbonate anion are characteristic for a delocalized double bond and a typical single bond. In the crystal, N-H⋯O hydrogen bonds between cations and anions generate a two-dimensional network in the direction of the ab plane, whereas adjacent ion pairs form chains running along the b axis.

Related literature

For the synthesis and crystal structures of guanidinium hydrogencarbonates, see: Tiritiris et al. (2011 ▶). For the crystal structure of piperidine-1-carboximidamide, see: Tiritiris (2012 ▶), and for the crystal structure of sodium methyl carbonate, see: Kunert et al. (1998 ▶).

Experimental

Crystal data

C6H14N3 +·C3H5O3 −

M = 217.27

Monoclinic,

a = 11.8320 (6) Å

b = 7.2407 (4) Å

c = 13.3755 (9) Å

β = 105.292 (3)°

V = 1105.33 (11) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 100 K

0.25 × 0.20 × 0.05 mm

Data collection

Bruker–Nonius KappaCCD diffractometer

4452 measured reflections

2638 independent reflections

1982 reflections with I > 2σ(I)

R int = 0.047

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.106

S = 1.02

2638 reflections

153 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.28 e Å−3

Δρmin = −0.23 e Å−3

Data collection: COLLECT (Hooft, 2004 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: SHELXL97.

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812045497/kp2439sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812045497/kp2439Isup2.hkl

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

C6H14N3+·C3H5O3−	F(000) = 472
Mr = 217.27	Dx = 1.306 Mg m−3
Monoclinic, P21/n	Melting point: 397 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 11.8320 (6) Å	Cell parameters from 2732 reflections
b = 7.2407 (4) Å	θ = 0.4–27.9°
c = 13.3755 (9) Å	µ = 0.10 mm−1
β = 105.292 (3)°	T = 100 K
V = 1105.33 (11) Å3	Plate, colourless
Z = 4	0.25 × 0.20 × 0.05 mm

Bruker–Nonius KappaCCD diffractometer	1982 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.047
Graphite monochromator	θmax = 27.9°, θmin = 2.1°
φ scans, and ω scans	h = −15→15
4452 measured reflections	k = −9→8
2638 independent reflections	l = −17→17

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)] = 0.042	Hydrogen site location: difference Fourier map
wR(F2) = 0.106	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0412P)2 + 0.424P] where P = (Fo2 + 2Fc2)/3
2638 reflections	(Δ/σ)max < 0.001
153 parameters	Δρmax = 0.28 e Å−3
0 restraints	Δρmin = −0.23 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
N1	−0.01610 (11)	0.84504 (19)	0.10282 (10)	0.0182 (3)
H11	0.0373 (17)	0.810 (3)	0.0712 (16)	0.030 (5)*
H12	−0.0527 (16)	0.949 (3)	0.0829 (15)	0.029 (5)*
N2	−0.11973 (10)	0.83590 (18)	0.22402 (10)	0.0162 (3)
H21	−0.1508 (14)	0.936 (3)	0.1994 (14)	0.019 (4)*
H22	−0.1552 (15)	0.779 (3)	0.2649 (15)	0.023 (5)*
N3	0.01511 (10)	0.60093 (16)	0.22039 (9)	0.0140 (2)
C1	−0.04041 (11)	0.75874 (19)	0.18211 (11)	0.0138 (3)
C2	−0.02711 (12)	0.4939 (2)	0.29709 (11)	0.0163 (3)
H2A	−0.0969	0.4214	0.2610	0.020*
H2B	−0.0508	0.5798	0.3455	0.020*
C3	0.06700 (13)	0.3636 (2)	0.35824 (11)	0.0192 (3)
H3A	0.1322	0.4369	0.4019	0.023*
H3B	0.0338	0.2866	0.4046	0.023*
C4	0.11384 (13)	0.2397 (2)	0.28736 (12)	0.0191 (3)
H4A	0.0498	0.1632	0.2446	0.023*
H4B	0.1748	0.1564	0.3288	0.023*
C5	0.16564 (13)	0.3613 (2)	0.21824 (12)	0.0219 (3)
H5A	0.2320	0.4326	0.2617	0.026*
H5B	0.1963	0.2825	0.1709	0.026*
C6	0.07529 (12)	0.4939 (2)	0.15493 (11)	0.0188 (3)
H6A	0.1144	0.5805	0.1175	0.023*
H6B	0.0163	0.4232	0.1027	0.023*
O1	0.25289 (8)	0.31135 (14)	0.63820 (8)	0.0173 (2)
O2	0.36182 (9)	0.34098 (15)	0.52507 (8)	0.0210 (2)
O3	0.26553 (8)	0.08408 (14)	0.52492 (8)	0.0175 (2)
C7	0.29380 (11)	0.2563 (2)	0.56646 (11)	0.0144 (3)
C8	0.18221 (12)	−0.0237 (2)	0.56032 (11)	0.0169 (3)
H8A	0.1079	0.0451	0.5511	0.020*
H8B	0.2132	−0.0548	0.6346	0.020*
C9	0.16276 (14)	−0.1971 (2)	0.49492 (12)	0.0232 (3)
H9A	0.1235	−0.1652	0.4229	0.035*
H9B	0.1137	−0.2832	0.5215	0.035*
H9C	0.2384	−0.2551	0.4980	0.035*

	U11	U22	U33	U12	U13	U23
N1	0.0210 (6)	0.0191 (6)	0.0183 (6)	0.0056 (5)	0.0120 (5)	0.0059 (5)
N2	0.0193 (6)	0.0147 (6)	0.0175 (6)	0.0039 (5)	0.0100 (5)	0.0048 (5)
N3	0.0151 (5)	0.0161 (6)	0.0124 (5)	0.0021 (4)	0.0064 (4)	0.0022 (5)
C1	0.0155 (6)	0.0145 (6)	0.0115 (6)	−0.0020 (5)	0.0037 (5)	−0.0012 (5)
C2	0.0177 (6)	0.0194 (7)	0.0141 (7)	0.0018 (6)	0.0086 (5)	0.0035 (6)
C3	0.0228 (7)	0.0207 (7)	0.0154 (7)	0.0043 (6)	0.0072 (6)	0.0048 (6)
C4	0.0243 (7)	0.0145 (7)	0.0207 (7)	0.0026 (6)	0.0098 (6)	0.0027 (6)
C5	0.0232 (7)	0.0229 (8)	0.0240 (8)	0.0081 (6)	0.0137 (6)	0.0062 (6)
C6	0.0229 (7)	0.0206 (7)	0.0168 (7)	0.0060 (6)	0.0122 (6)	0.0028 (6)
O1	0.0201 (5)	0.0178 (5)	0.0171 (5)	−0.0018 (4)	0.0104 (4)	−0.0027 (4)
O2	0.0244 (5)	0.0221 (6)	0.0209 (5)	−0.0078 (4)	0.0139 (4)	−0.0052 (4)
O3	0.0188 (5)	0.0184 (5)	0.0181 (5)	−0.0050 (4)	0.0099 (4)	−0.0041 (4)
C7	0.0123 (6)	0.0181 (7)	0.0131 (7)	0.0006 (5)	0.0037 (5)	−0.0003 (5)
C8	0.0169 (6)	0.0186 (7)	0.0174 (7)	−0.0021 (5)	0.0081 (6)	−0.0004 (6)
C9	0.0250 (7)	0.0238 (8)	0.0241 (8)	−0.0083 (6)	0.0121 (6)	−0.0052 (7)

N1—C1	1.3262 (18)	C4—H4B	0.9900
N1—H11	0.88 (2)	C5—C6	1.518 (2)
N1—H12	0.88 (2)	C5—H5A	0.9900
N2—C1	1.3359 (18)	C5—H5B	0.9900
N2—H21	0.84 (2)	C6—H6A	0.9900
N2—H22	0.87 (2)	C6—H6B	0.9900
N3—C1	1.3498 (18)	O1—C7	1.2485 (16)
N3—C2	1.4742 (17)	O2—C7	1.2509 (17)
N3—C6	1.4842 (17)	O3—C7	1.3706 (18)
C2—C3	1.5227 (19)	O3—C8	1.4323 (16)
C2—H2A	0.9900	C8—C9	1.512 (2)
C2—H2B	0.9900	C8—H8A	0.9900
C3—C4	1.512 (2)	C8—H8B	0.9900
C3—H3A	0.9900	C9—H9A	0.9800
C3—H3B	0.9900	C9—H9B	0.9800
C4—C5	1.518 (2)	C9—H9C	0.9800
C4—H4A	0.9900
C1—N1—H11	125.4 (13)	H4A—C4—H4B	108.4
C1—N1—H12	117.1 (12)	C6—C5—C4	111.62 (12)
H11—N1—H12	117.4 (18)	C6—C5—H5A	109.3
C1—N2—H21	118.6 (11)	C4—C5—H5A	109.3
C1—N2—H22	125.0 (12)	C6—C5—H5B	109.3
H21—N2—H22	114.7 (16)	C4—C5—H5B	109.3
C1—N3—C2	119.25 (11)	H5A—C5—H5B	108.0
C1—N3—C6	118.65 (11)	N3—C6—C5	112.21 (11)
C2—N3—C6	116.07 (11)	N3—C6—H6A	109.2
N1—C1—N2	117.59 (13)	C5—C6—H6A	109.2
N1—C1—N3	121.04 (12)	N3—C6—H6B	109.2
N2—C1—N3	121.36 (12)	C5—C6—H6B	109.2
N3—C2—C3	111.43 (10)	H6A—C6—H6B	107.9
N3—C2—H2A	109.3	C7—O3—C8	118.52 (10)
C3—C2—H2A	109.3	O1—C7—O2	127.52 (13)
N3—C2—H2B	109.3	O1—C7—O3	119.95 (12)
C3—C2—H2B	109.3	O2—C7—O3	112.53 (12)
H2A—C2—H2B	108.0	O3—C8—C9	105.90 (11)
C4—C3—C2	111.57 (12)	O3—C8—H8A	110.6
C4—C3—H3A	109.3	C9—C8—H8A	110.6
C2—C3—H3A	109.3	O3—C8—H8B	110.6
C4—C3—H3B	109.3	C9—C8—H8B	110.6
C2—C3—H3B	109.3	H8A—C8—H8B	108.7
H3A—C3—H3B	108.0	C8—C9—H9A	109.5
C3—C4—C5	108.14 (12)	C8—C9—H9B	109.5
C3—C4—H4A	110.1	H9A—C9—H9B	109.5
C5—C4—H4A	110.1	C8—C9—H9C	109.5
C3—C4—H4B	110.1	H9A—C9—H9C	109.5
C5—C4—H4B	110.1	H9B—C9—H9C	109.5
C2—N3—C1—N1	−170.39 (13)	C3—C4—C5—C6	−58.57 (17)
C6—N3—C1—N1	−18.76 (19)	C1—N3—C6—C5	160.64 (12)
C2—N3—C1—N2	11.15 (19)	C2—N3—C6—C5	−46.85 (16)
C6—N3—C1—N2	162.78 (13)	C4—C5—C6—N3	52.04 (17)
C1—N3—C2—C3	−160.06 (12)	C8—O3—C7—O1	4.51 (19)
C6—N3—C2—C3	47.59 (16)	C8—O3—C7—O2	−175.98 (12)
N3—C2—C3—C4	−54.20 (16)	C7—O3—C8—C9	175.66 (12)
C2—C3—C4—C5	59.74 (16)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O2i	0.88 (2)	1.99 (2)	2.812 (1)	155 (1)
N1—H12···O2ii	0.88 (2)	1.88 (2)	2.747 (1)	173 (1)
N2—H21···O1ii	0.84 (2)	2.19 (2)	3.033 (1)	175 (1)
N2—H22···O1iii	0.87 (2)	2.06 (2)	2.923 (1)	170 (1)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11⋯O2i	0.88 (2)	1.99 (2)	2.812 (1)	155 (1)
N1—H12⋯O2ii	0.88 (2)	1.88 (2)	2.747 (1)	173 (1)
N2—H21⋯O1ii	0.84 (2)	2.19 (2)	3.033 (1)	175 (1)
N2—H22⋯O1iii	0.87 (2)	2.06 (2)	2.923 (1)	170 (1)

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