Morpholine-4-carboxamidinium ethyl carbonate.

The asymmetric unit of the title salt, C5H12N3O(+)·C3H5O3(-), contains two carboxamidinium and two ethyl carbonate ions. In the crystal, the C-N bond lengths in the central CN3 units of the cations range between 1.324 (2) and 1.352 (2) Å, indicating partial double-bond character. The central C atoms are bonded to the three N atoms in a nearly ideal trigonal-planar geometry and the positive charges are delocalized in the CN3 planes. The morpholine rings are in chair conformations. The C-O bond lengths in both ethyl carbonate ions are characteristic for delocalized double bonds [1.243 (2)-1.251 (2) Å] and typical single bonds [1.368 (2) and 1.375 (2) Å]. In the crystal, N-H⋯O hydrogen bonds between cations and anions generate a two-dimensional network in the ac plane.

Related literature

For the synthesis and crystal structures of guanidinium hydrogen carbonates, see: Tiritiris et al. (2011 ▶). For the crystal structure of 4-morpholine­carboxamidine, see: Tiritiris (2012a ▶). For the crystal structure of piperidine-1-carboxamidinium ethyl carbonate, see: Tiritiris (2012b ▶).

Experimental

Crystal data

C5H12N3O+·C3H5O3 −

M = 219.25

Monoclinic,

a = 10.2163 (5) Å

b = 20.8874 (9) Å

c = 10.4616 (5) Å

β = 109.505 (2)°

V = 2104.31 (17) Å3

Z = 8

Mo Kα radiation

μ = 0.11 mm−1

T = 100 K

0.30 × 0.25 × 0.15 mm

Data collection

Bruker–Nonius KappaCCD diffractometer

9902 measured reflections

5199 independent reflections

2981 reflections with I > 2σ(I)

R int = 0.055

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.112

S = 1.00

5199 reflections

305 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.25 e Å−3

Δρmin = −0.30 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/S1600536812046922/kp2441sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812046922/kp2441Isup2.hkl

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

C5H12N3O+·C3H5O3−	F(000) = 944
Mr = 219.25	Dx = 1.384 Mg m−3
Monoclinic, P21/n	Melting point: 413 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 10.2163 (5) Å	Cell parameters from 5142 reflections
b = 20.8874 (9) Å	θ = 0.4–28.3°
c = 10.4616 (5) Å	µ = 0.11 mm−1
β = 109.505 (2)°	T = 100 K
V = 2104.31 (17) Å3	Block, colourless
Z = 8	0.30 × 0.25 × 0.15 mm

Bruker–Nonius KappaCCD diffractometer	2981 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.055
Graphite monochromator	θmax = 28.3°, θmin = 2.3°
φ scans, and ω scans	h = −13→13
9902 measured reflections	k = −27→27
5199 independent reflections	l = −13→13

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)] = 0.050	Hydrogen site location: difference Fourier map
wR(F2) = 0.112	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0468P)2] where P = (Fo2 + 2Fc2)/3
5199 reflections	(Δ/σ)max < 0.001
305 parameters	Δρmax = 0.25 e Å−3
0 restraints	Δρmin = −0.30 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
C1	0.14782 (18)	0.19683 (9)	0.08078 (17)	0.0138 (4)
N1	0.14407 (18)	0.21777 (9)	−0.03987 (16)	0.0186 (4)
H11	0.082 (2)	0.2060 (11)	−0.111 (2)	0.027 (6)*
H12	0.209 (2)	0.2468 (11)	−0.039 (2)	0.028 (6)*
N2	0.24717 (16)	0.21987 (9)	0.18879 (16)	0.0168 (4)
H21	0.2567 (18)	0.2083 (9)	0.269 (2)	0.013 (5)*
H22	0.308 (2)	0.2486 (11)	0.171 (2)	0.032 (6)*
N3	0.05782 (14)	0.15198 (8)	0.09382 (13)	0.0138 (3)
C2	0.04415 (18)	0.14053 (10)	0.22786 (16)	0.0174 (4)
H2A	−0.0106	0.1755	0.2491	0.021*
H2B	0.1374	0.1404	0.2982	0.021*
C3	−0.02671 (19)	0.07728 (10)	0.22976 (17)	0.0239 (5)
H3A	0.0343	0.0421	0.2203	0.029*
H3B	−0.0410	0.0721	0.3182	0.029*
O1	−0.15763 (13)	0.07261 (7)	0.12343 (12)	0.0227 (3)
C4	−0.13597 (19)	0.07748 (10)	−0.00376 (17)	0.0194 (4)
H4A	−0.2261	0.0727	−0.0777	0.023*
H4B	−0.0746	0.0422	−0.0120	0.023*
C5	−0.07145 (18)	0.14066 (9)	−0.01951 (17)	0.0168 (4)
H5A	−0.0515	0.1408	−0.1058	0.020*
H5B	−0.1379	0.1757	−0.0233	0.020*
C6	0.61678 (17)	0.19115 (9)	0.08546 (16)	0.0122 (4)
N4	0.60204 (17)	0.21566 (9)	−0.03589 (15)	0.0161 (4)
H41	0.656 (2)	0.2472 (11)	−0.038 (2)	0.026 (6)*
H42	0.533 (2)	0.2013 (12)	−0.113 (2)	0.041 (7)*
N5	0.71439 (16)	0.21538 (8)	0.19268 (15)	0.0144 (4)
H51	0.773 (2)	0.2459 (11)	0.185 (2)	0.023 (6)*
H52	0.745 (2)	0.1933 (11)	0.271 (2)	0.035 (6)*
N6	0.53305 (14)	0.14360 (7)	0.10007 (13)	0.0134 (3)
C7	0.56842 (19)	0.11205 (10)	0.23299 (16)	0.0176 (4)
H7A	0.5906	0.1449	0.3053	0.021*
H7B	0.6517	0.0850	0.2480	0.021*
C8	0.4493 (2)	0.07110 (10)	0.24096 (17)	0.0189 (4)
H8A	0.4791	0.0472	0.3277	0.023*
H8B	0.3709	0.0991	0.2401	0.023*
O2	0.40359 (13)	0.02701 (6)	0.13163 (11)	0.0198 (3)
C9	0.35206 (18)	0.06230 (10)	0.00799 (17)	0.0182 (4)
H9A	0.2758	0.0907	0.0117	0.022*
H9B	0.3137	0.0321	−0.0684	0.022*
C10	0.46389 (18)	0.10203 (9)	−0.01694 (17)	0.0169 (4)
H10A	0.5335	0.0734	−0.0341	0.020*
H10B	0.4226	0.1288	−0.0986	0.020*
C11	−0.07231 (18)	0.16716 (9)	0.57058 (16)	0.0133 (4)
O3	−0.16622 (12)	0.18499 (7)	0.46539 (11)	0.0196 (3)
O4	−0.04966 (12)	0.18664 (6)	0.68830 (11)	0.0179 (3)
O5	0.01060 (12)	0.11991 (7)	0.54704 (11)	0.0181 (3)
C12	0.12224 (18)	0.09664 (10)	0.66226 (17)	0.0188 (4)
H12A	0.0849	0.0761	0.7281	0.023*
H12B	0.1836	0.1324	0.7081	0.023*
C13	0.20159 (19)	0.04887 (10)	0.60972 (18)	0.0224 (5)
H13A	0.2355	0.0695	0.5427	0.034*
H13B	0.1405	0.0131	0.5671	0.034*
H13C	0.2806	0.0328	0.6851	0.034*
C14	0.40406 (17)	0.17608 (9)	0.57044 (16)	0.0130 (4)
O6	0.31041 (12)	0.19554 (6)	0.46676 (11)	0.0180 (3)
O7	0.42103 (13)	0.19133 (6)	0.69029 (11)	0.0183 (3)
O8	0.49287 (12)	0.13310 (6)	0.54411 (11)	0.0166 (3)
C15	0.60379 (18)	0.10913 (10)	0.65905 (17)	0.0179 (4)
H15A	0.5655	0.0877	0.7232	0.021*
H15B	0.6641	0.1448	0.7070	0.021*
C16	0.68612 (19)	0.06219 (10)	0.60715 (18)	0.0199 (4)
H16A	0.6270	0.0257	0.5651	0.030*
H16B	0.7659	0.0470	0.6828	0.030*
H16C	0.7190	0.0833	0.5398	0.030*

	U11	U22	U33	U12	U13	U23
C1	0.0137 (9)	0.0140 (11)	0.0127 (9)	0.0045 (8)	0.0031 (7)	0.0005 (7)
N1	0.0180 (9)	0.0236 (10)	0.0114 (8)	−0.0068 (8)	0.0011 (7)	0.0008 (7)
N2	0.0189 (9)	0.0223 (10)	0.0080 (8)	−0.0050 (7)	0.0031 (7)	0.0016 (7)
N3	0.0118 (7)	0.0192 (9)	0.0088 (7)	−0.0017 (7)	0.0012 (6)	−0.0003 (6)
C2	0.0178 (9)	0.0251 (12)	0.0085 (8)	−0.0042 (8)	0.0033 (7)	−0.0007 (8)
C3	0.0261 (11)	0.0301 (13)	0.0102 (9)	−0.0091 (9)	−0.0011 (8)	0.0013 (8)
O1	0.0251 (7)	0.0279 (9)	0.0138 (6)	−0.0121 (6)	0.0048 (5)	−0.0029 (6)
C4	0.0217 (10)	0.0216 (12)	0.0130 (9)	−0.0007 (9)	0.0032 (8)	−0.0024 (8)
C5	0.0148 (9)	0.0201 (11)	0.0115 (8)	−0.0027 (8)	−0.0007 (7)	0.0001 (8)
C6	0.0143 (9)	0.0123 (10)	0.0107 (9)	0.0040 (8)	0.0051 (7)	−0.0004 (7)
N4	0.0166 (8)	0.0182 (10)	0.0107 (8)	−0.0043 (8)	0.0009 (7)	0.0016 (7)
N5	0.0164 (8)	0.0145 (10)	0.0103 (8)	−0.0029 (7)	0.0018 (6)	0.0000 (6)
N6	0.0158 (8)	0.0148 (9)	0.0083 (7)	−0.0017 (7)	0.0023 (6)	−0.0007 (6)
C7	0.0218 (10)	0.0185 (11)	0.0105 (9)	−0.0053 (8)	0.0027 (7)	0.0016 (7)
C8	0.0268 (10)	0.0179 (12)	0.0125 (9)	−0.0045 (9)	0.0074 (8)	−0.0022 (8)
O2	0.0281 (7)	0.0145 (8)	0.0147 (6)	−0.0057 (6)	0.0043 (5)	−0.0011 (5)
C9	0.0187 (10)	0.0187 (12)	0.0137 (9)	−0.0021 (8)	0.0006 (7)	0.0008 (8)
C10	0.0200 (10)	0.0167 (11)	0.0117 (8)	−0.0022 (8)	0.0025 (7)	−0.0013 (7)
C11	0.0130 (9)	0.0173 (11)	0.0095 (9)	−0.0009 (8)	0.0037 (7)	0.0013 (7)
O3	0.0191 (7)	0.0258 (9)	0.0101 (6)	0.0043 (6)	−0.0001 (5)	0.0003 (5)
O4	0.0183 (7)	0.0231 (8)	0.0102 (6)	0.0030 (6)	0.0020 (5)	−0.0016 (5)
O5	0.0175 (7)	0.0238 (8)	0.0108 (6)	0.0056 (6)	0.0016 (5)	−0.0002 (5)
C12	0.0167 (10)	0.0226 (12)	0.0138 (9)	0.0045 (8)	0.0007 (7)	0.0022 (8)
C13	0.0234 (10)	0.0219 (12)	0.0211 (10)	0.0027 (9)	0.0064 (8)	0.0014 (8)
C14	0.0131 (9)	0.0131 (11)	0.0116 (9)	−0.0027 (8)	0.0027 (7)	0.0001 (7)
O6	0.0179 (7)	0.0231 (8)	0.0101 (6)	0.0050 (6)	0.0010 (5)	0.0010 (5)
O7	0.0208 (7)	0.0215 (8)	0.0096 (6)	0.0050 (6)	0.0010 (5)	−0.0021 (5)
O8	0.0163 (7)	0.0211 (8)	0.0103 (6)	0.0056 (6)	0.0014 (5)	0.0005 (5)
C15	0.0177 (9)	0.0214 (12)	0.0113 (9)	0.0057 (8)	0.0005 (7)	0.0012 (8)
C16	0.0171 (10)	0.0218 (12)	0.0198 (10)	0.0037 (8)	0.0047 (8)	0.0023 (8)

C1—N1	1.324 (2)	C7—H7A	0.9900
C1—N2	1.331 (2)	C7—H7B	0.9900
C1—N3	1.351 (2)	C8—O2	1.420 (2)
N1—H11	0.84 (2)	C8—H8A	0.9900
N1—H12	0.89 (2)	C8—H8B	0.9900
N2—H21	0.85 (2)	O2—C9	1.428 (2)
N2—H22	0.92 (2)	C9—C10	1.504 (3)
N3—C5	1.470 (2)	C9—H9A	0.9900
N3—C2	1.474 (2)	C9—H9B	0.9900
C2—C3	1.510 (3)	C10—H10A	0.9900
C2—H2A	0.9900	C10—H10B	0.9900
C2—H2B	0.9900	C11—O4	1.243 (2)
C3—O1	1.429 (2)	C11—O3	1.251 (2)
C3—H3A	0.9900	C11—O5	1.375 (2)
C3—H3B	0.9900	O5—C12	1.439 (2)
O1—C4	1.424 (2)	C12—C13	1.501 (3)
C4—C5	1.508 (3)	C12—H12A	0.9900
C4—H4A	0.9900	C12—H12B	0.9900
C4—H4B	0.9900	C13—H13A	0.9800
C5—H5A	0.9900	C13—H13B	0.9800
C5—H5B	0.9900	C13—H13C	0.9800
C6—N5	1.327 (2)	C14—O7	1.248 (2)
C6—N4	1.330 (2)	C14—O6	1.2507 (19)
C6—N6	1.352 (2)	C14—O8	1.368 (2)
N4—H41	0.86 (2)	O8—C15	1.4390 (19)
N4—H42	0.93 (2)	C15—C16	1.506 (3)
N5—H51	0.90 (2)	C15—H15A	0.9900
N5—H52	0.90 (2)	C15—H15B	0.9900
N6—C7	1.471 (2)	C16—H16A	0.9800
N6—C10	1.474 (2)	C16—H16B	0.9800
C7—C8	1.512 (3)	C16—H16C	0.9800
N1—C1—N2	117.44 (18)	C8—C7—H7B	109.5
N1—C1—N3	121.41 (16)	H7A—C7—H7B	108.0
N2—C1—N3	121.10 (16)	O2—C8—C7	112.11 (14)
C1—N1—H11	121.6 (14)	O2—C8—H8A	109.2
C1—N1—H12	115.2 (13)	C7—C8—H8A	109.2
H11—N1—H12	123.1 (19)	O2—C8—H8B	109.2
C1—N2—H21	122.7 (13)	C7—C8—H8B	109.2
C1—N2—H22	116.0 (13)	H8A—C8—H8B	107.9
H21—N2—H22	121.3 (17)	C8—O2—C9	108.51 (14)
C1—N3—C5	119.25 (14)	O2—C9—C10	111.74 (14)
C1—N3—C2	119.50 (14)	O2—C9—H9A	109.3
C5—N3—C2	113.33 (13)	C10—C9—H9A	109.3
N3—C2—C3	110.65 (14)	O2—C9—H9B	109.3
N3—C2—H2A	109.5	C10—C9—H9B	109.3
C3—C2—H2A	109.5	H9A—C9—H9B	107.9
N3—C2—H2B	109.5	N6—C10—C9	111.24 (14)
C3—C2—H2B	109.5	N6—C10—H10A	109.4
H2A—C2—H2B	108.1	C9—C10—H10A	109.4
O1—C3—C2	112.19 (15)	N6—C10—H10B	109.4
O1—C3—H3A	109.2	C9—C10—H10B	109.4
C2—C3—H3A	109.2	H10A—C10—H10B	108.0
O1—C3—H3B	109.2	O4—C11—O3	127.48 (17)
C2—C3—H3B	109.2	O4—C11—O5	119.35 (15)
H3A—C3—H3B	107.9	O3—C11—O5	113.17 (14)
C4—O1—C3	109.00 (13)	C11—O5—C12	117.10 (13)
O1—C4—C5	112.00 (15)	O5—C12—C13	106.96 (14)
O1—C4—H4A	109.2	O5—C12—H12A	110.3
C5—C4—H4A	109.2	C13—C12—H12A	110.3
O1—C4—H4B	109.2	O5—C12—H12B	110.3
C5—C4—H4B	109.2	C13—C12—H12B	110.3
H4A—C4—H4B	107.9	H12A—C12—H12B	108.6
N3—C5—C4	111.13 (14)	C12—C13—H13A	109.5
N3—C5—H5A	109.4	C12—C13—H13B	109.5
C4—C5—H5A	109.4	H13A—C13—H13B	109.5
N3—C5—H5B	109.4	C12—C13—H13C	109.5
C4—C5—H5B	109.4	H13A—C13—H13C	109.5
H5A—C5—H5B	108.0	H13B—C13—H13C	109.5
N5—C6—N4	118.27 (17)	O7—C14—O6	126.70 (17)
N5—C6—N6	120.64 (15)	O7—C14—O8	119.38 (14)
N4—C6—N6	121.08 (16)	O6—C14—O8	113.91 (14)
C6—N4—H41	116.3 (13)	C14—O8—C15	116.75 (12)
C6—N4—H42	121.0 (14)	O8—C15—C16	107.70 (14)
H41—N4—H42	122.5 (19)	O8—C15—H15A	110.2
C6—N5—H51	121.8 (13)	C16—C15—H15A	110.2
C6—N5—H52	120.7 (14)	O8—C15—H15B	110.2
H51—N5—H52	114.0 (18)	C16—C15—H15B	110.2
C6—N6—C7	118.09 (13)	H15A—C15—H15B	108.5
C6—N6—C10	118.98 (14)	C15—C16—H16A	109.5
C7—N6—C10	114.80 (15)	C15—C16—H16B	109.5
N6—C7—C8	110.93 (14)	H16A—C16—H16B	109.5
N6—C7—H7A	109.5	C15—C16—H16C	109.5
C8—C7—H7A	109.5	H16A—C16—H16C	109.5
N6—C7—H7B	109.5	H16B—C16—H16C	109.5
N1—C1—N3—C5	−19.3 (3)	N4—C6—N6—C10	23.7 (2)
N2—C1—N3—C5	163.26 (16)	C6—N6—C7—C8	167.46 (16)
N1—C1—N3—C2	−166.30 (17)	C10—N6—C7—C8	−44.1 (2)
N2—C1—N3—C2	16.3 (3)	N6—C7—C8—O2	53.4 (2)
C1—N3—C2—C3	−163.24 (16)	C7—C8—O2—C9	−62.83 (19)
C5—N3—C2—C3	47.9 (2)	C8—O2—C9—C10	62.98 (19)
N3—C2—C3—O1	−54.7 (2)	C6—N6—C10—C9	−167.27 (15)
C2—C3—O1—C4	61.1 (2)	C7—N6—C10—C9	44.6 (2)
C3—O1—C4—C5	−60.9 (2)	O2—C9—C10—N6	−53.8 (2)
C1—N3—C5—C4	163.03 (16)	O4—C11—O5—C12	−1.3 (2)
C2—N3—C5—C4	−48.1 (2)	O3—C11—O5—C12	179.62 (15)
O1—C4—C5—N3	54.7 (2)	C11—O5—C12—C13	−176.69 (15)
N5—C6—N6—C7	−10.5 (2)	O7—C14—O8—C15	−1.3 (2)
N4—C6—N6—C7	170.74 (16)	O6—C14—O8—C15	179.56 (15)
N5—C6—N6—C10	−157.57 (16)	C14—O8—C15—C16	179.01 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O4i	0.84 (2)	2.12 (2)	2.944 (1)	168 (1)
N1—H12···O3ii	0.89 (2)	1.91 (2)	2.795 (1)	174 (1)
N2—H21···O6	0.85 (2)	1.97 (2)	2.807 (1)	168 (1)
N2—H22···O4ii	0.92 (2)	1.95 (2)	2.851 (1)	164 (1)
N4—H41···O6ii	0.86 (2)	1.97 (2)	2.817 (1)	167 (1)
N4—H42···O7i	0.93 (2)	2.00 (2)	2.889 (1)	159 (1)
N5—H51···O7ii	0.90 (2)	1.99 (2)	2.879 (1)	172 (1)
N5—H52···O3iii	0.90 (2)	1.94 (2)	2.776 (1)	154 (1)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11⋯O4i	0.84 (2)	2.12 (2)	2.944 (1)	168 (1)
N1—H12⋯O3ii	0.89 (2)	1.91 (2)	2.795 (1)	174 (1)
N2—H21⋯O6	0.85 (2)	1.97 (2)	2.807 (1)	168 (1)
N2—H22⋯O4ii	0.92 (2)	1.95 (2)	2.851 (1)	164 (1)
N4—H41⋯O6ii	0.86 (2)	1.97 (2)	2.817 (1)	167 (1)
N4—H42⋯O7i	0.93 (2)	2.00 (2)	2.889 (1)	159 (1)
N5—H51⋯O7ii	0.90 (2)	1.99 (2)	2.879 (1)	172 (1)
N5—H52⋯O3iii	0.90 (2)	1.94 (2)	2.776 (1)	154 (1)

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