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In the crystal structure of the title compound, [O(CH2CH2)2NH2][C6H7O7]·H2O, the cation interacts with the negatively charged carboxyl­ato group of adjacent anions [N...O 2.847 (3) and 2.942 (3) Å], forming a linear chain running along the b axis of the crystal. Adjacent chains are linked through the carboxyl­ic —CO2H groups and the water mol­ecule into a layer structure.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803013874/cm6050sup1.cif
Contains datablocks I, citmor

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803013874/cm6050Isup2.hkl
Contains datablock I

CCDC reference: 217608

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.055
  • wR factor = 0.143
  • Data-to-parameter ratio = 11.0

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


Yellow Alert Alert Level C:
PLAT_731 Alert C Bond Calc 0.85(3), Rep 0.850(10) ...... 3.00 su-Rat O1W -H1W2 1.555 1.555 PLAT_735 Alert C D-H Calc 0.86(4), Rep 0.850(10) ...... 4.00 su-Rat O3 -H3O 1.555 1.555 PLAT_735 Alert C D-H Calc 0.85(3), Rep 0.850(10) ...... 3.00 su-Rat O1W -H1W2 1.555 1.555 PLAT_736 Alert C H...A Calc 1.76(4), Rep 1.760(10) ...... 4.00 su-Rat H3O -O2 1.555 2.665 PLAT_736 Alert C H...A Calc 1.93(3), Rep 1.930(10) ...... 3.00 su-Rat H1W2 -O7 1.555 8.755
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
5 Alert Level C = Please check

Comment top

A previous report described the dicyclohexylammonium salts of monocarboxylic and dicarboxylic acids (Ng, 2003). For some of the acids, their reaction with dicyclohexylamine afforded ammonium carboxylate as a hydrate (Ng, 1992; Yang et al., 2000). On the other hand, others reacted with an excess of this secondary amine to yield only the mono(ammonium) salt, e.g., dicyclohexylammonium hydrogen oxalate (Ng, 1994). The reaction with the tribasic acid, citric acid, gave a compound that rapidly turned opaque when the crystals were removed from its solution in ethanol; on the other hand, the use of diisopropylamine in place of dicyclohexylamine led to a syrupy material after the solvent had evaported. A check on the sec-ammonium derivatives of carboxylic acids suggested the use of morpholine as this amine furnishes a large number of isolable carboxylates, such as chloronitrobenzoates (Ishida et al., 2001a; 2001b, 2001c) and morpholinoformate (Brown & Gray, 1982). Citric has also been characterized as an N-substituted morpholinium derivative (Peeters et al., 1979). In the present study, the reaction of citric acid with either one or two molar equivalents of morpholine gave the air-stable title compound, (I) (Fig. 1).

In the crystal structure of (I), the cation interacts with the carboxyl O atoms of two citrato anions [N···O 2.847 (3) and 2.942 (3) Å] resulting in the formation of a linear chain running along the b axis of the crystal. Such a hydrogen-bonded motif has previously been noted in dicyclohexylammonium trifluoroacetate (Ng et al., 1999). Adjacent chains are linked through the carboxylic —CO2H groups and water molecule into a layer structure (Fig. 2, Table 2).

Experimental top

Morpholine (0.87 g, 10 mmol) and citric acid monohydrate (0.21 g, 10 mol) were heated in a small volume of ethanol (25 ml); a few drops of water were added to dissolve the acid completely. Slow evaporation of the solvent yielded the mono(morpholinium) dihydrate citrate as a a monohydrate. The use of twice the quantity of the amine gave the identical compound. Elemental analysis. Found/Calc. for C10H19O9N: 40.8 (40.4); H 6.5 (6.4); N 4.5% (4.7%). IR (KBr pellet): νCOOH 1717, νas(COO) 1414, νs(COO) 1414, 1396; νC=N 1107 cm−1.

Refinement top

The water, hydroxyl and ammonium H atoms were located and refined. The aliphatic H atoms were positioned geometrically (C—H 0.97 Å), and were included in the refinement in the riding model approximation; the temperature factors were set to 1.5 (methyl) or 1.2 (other H atoms) times Ueq of the parent atom.

The diffraction measurements were performed up to a 2θ angle of 56°; however, as the inclusion of reflections above 50° led to an R factor greater than 7%, these were excluded from the refinement.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. ORTEPII (Johnson, 1976) plot of (I), with displacement ellipsoids drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radii.
[Figure 2] Fig. 2. ORTEPII (Johnson, 1976) plot illustrating the hydrogen-bonded layer structure. H atoms are omitted.
Morpholinium dihydrogen citrate dihydrate top
Crystal data top
C4H10NO·C6H7O7·H2ODx = 1.508 Mg m3
Mr = 297.26Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PbcaCell parameters from 4726 reflections
a = 11.3774 (6) Åθ = 2.4–27.3°
b = 12.4823 (7) ŵ = 0.13 mm1
c = 18.437 (1) ÅT = 298 K
V = 2618.3 (2) Å3Block, colorless
Z = 80.28 × 0.18 × 0.18 mm
F(000) = 1264
Data collection top
Bruker AXS area-detector
diffractometer
2103 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.028
Graphite monochromatorθmax = 25.0°, θmin = 2.2°
ϕ and ω scanh = 1313
12407 measured reflectionsk = 1410
2305 independent reflectionsl = 2021
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.055Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143H atoms treated by a mixture of independent and constrained refinement
S = 1.15 w = 1/[σ2(Fo2) + (0.0711P)2 + 1.4573P]
where P = (Fo2 + 2Fc2)/3
2305 reflections(Δ/σ)max = 0.001
209 parametersΔρmax = 0.29 e Å3
7 restraintsΔρmin = 0.19 e Å3
Crystal data top
C4H10NO·C6H7O7·H2OV = 2618.3 (2) Å3
Mr = 297.26Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 11.3774 (6) ŵ = 0.13 mm1
b = 12.4823 (7) ÅT = 298 K
c = 18.437 (1) Å0.28 × 0.18 × 0.18 mm
Data collection top
Bruker AXS area-detector
diffractometer
2103 reflections with I > 2σ(I)
12407 measured reflectionsRint = 0.028
2305 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0557 restraints
wR(F2) = 0.143H atoms treated by a mixture of independent and constrained refinement
S = 1.15Δρmax = 0.29 e Å3
2305 reflectionsΔρmin = 0.19 e Å3
209 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.7018 (2)0.4461 (2)0.3243 (1)0.0458 (5)
O20.8506 (2)0.5350 (2)0.2768 (1)0.0370 (4)
O30.7367 (2)0.5590 (2)0.6623 (1)0.0451 (5)
O40.6867 (2)0.4115 (2)0.6037 (1)0.0516 (6)
O50.9106 (2)0.3694 (1)0.4891 (1)0.0424 (5)
O60.7354 (2)0.3010 (1)0.4610 (1)0.0379 (5)
O70.6357 (1)0.4984 (1)0.4561 (1)0.0290 (4)
O80.3538 (2)0.2267 (2)0.2404 (1)0.0481 (5)
O1w0.9859 (2)0.1797 (2)0.5015 (1)0.0497 (6)
N10.5971 (2)0.2640 (2)0.2574 (1)0.0371 (5)
C10.7892 (2)0.5054 (2)0.3295 (1)0.0266 (5)
C20.8230 (2)0.5481 (2)0.4041 (1)0.0273 (5)
C30.7591 (2)0.4941 (2)0.4678 (1)0.0244 (5)
C40.7850 (2)0.5521 (2)0.5388 (1)0.0269 (5)
C50.7300 (2)0.4999 (2)0.6041 (1)0.0280 (5)
C60.7983 (2)0.3765 (2)0.4727 (1)0.0258 (5)
C70.5131 (2)0.2781 (2)0.3181 (1)0.0420 (6)
C80.4100 (2)0.2064 (2)0.3076 (2)0.0479 (7)
C90.4334 (2)0.2074 (2)0.1824 (2)0.0464 (7)
C100.5379 (2)0.2798 (2)0.1865 (1)0.0409 (6)
H3o0.708 (3)0.526 (3)0.699 (2)0.09 (1)*
H5o0.930 (3)0.303 (1)0.491 (2)0.06 (1)*
H7o0.626 (3)0.476 (3)0.413 (1)0.06 (1)*
H1w11.059 (1)0.168 (3)0.502 (2)0.06 (1)*
H1w20.950 (3)0.125 (2)0.485 (2)0.08 (1)*
H1n10.628 (3)0.202 (1)0.260 (2)0.06 (1)*
H1n20.653 (2)0.307 (2)0.265 (2)0.06 (1)*
H2a0.80680.62430.40560.033*
H2b0.90700.53880.41070.033*
H4a0.86940.55510.54570.032*
H4b0.75640.62510.53520.032*
H7a0.48710.35210.32000.050*
H7b0.55150.26130.36370.050*
H8a0.43570.13230.30920.058*
H8b0.35440.21730.34680.058*
H9a0.39330.21850.13660.056*
H9b0.45930.13340.18410.056*
H10a0.59200.26360.14740.049*
H10b0.51320.35380.18170.049*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.053 (1)0.056 (1)0.028 (1)0.027 (1)0.002 (1)0.009 (1)
O20.045 (1)0.044 (1)0.022 (1)0.010 (1)0.004 (1)0.001 (1)
O30.071 (1)0.043 (1)0.021 (1)0.016 (1)0.006 (1)0.002 (1)
O40.082 (2)0.042 (1)0.031 (1)0.023 (1)0.007 (1)0.001 (1)
O50.033 (1)0.027 (1)0.067 (1)0.003 (1)0.009 (1)0.001 (9)
O60.039 (1)0.023 (1)0.051 (1)0.003 (1)0.004 (1)0.001 (1)
O70.027 (1)0.032 (1)0.029 (1)0.002 (1)0.001 (1)0.000 (1)
O80.026 (1)0.060 (1)0.059 (1)0.002 (1)0.005 (1)0.002 (1)
O1w0.035 (1)0.035 (1)0.079 (2)0.009 (1)0.014 (1)0.006 (1)
N10.025 (1)0.034 (1)0.053 (1)0.001 (1)0.005 (1)0.003 (1)
C10.033 (1)0.023 (1)0.024 (1)0.000 (1)0.001 (1)0.001 (1)
C20.030 (1)0.025 (1)0.026 (1)0.003 (1)0.001 (1)0.001 (1)
C30.027 (1)0.024 (1)0.022 (1)0.003 (1)0.000 (1)0.001 (1)
C40.032 (1)0.025 (1)0.024 (1)0.001 (1)0.001 (1)0.001 (1)
C50.028 (1)0.031 (1)0.025 (1)0.001 (1)0.001 (1)0.002 (1)
C60.029 (1)0.027 (1)0.022 (1)0.003 (1)0.002 (1)0.001 (1)
C70.039 (2)0.050 (2)0.037 (2)0.004 (1)0.004 (1)0.003 (1)
C80.038 (2)0.054 (2)0.052 (2)0.002 (1)0.006 (1)0.008 (1)
C90.042 (2)0.054 (2)0.044 (2)0.004 (1)0.010 (1)0.005 (1)
C100.040 (2)0.044 (2)0.039 (1)0.001 (1)0.002 (1)0.003 (1)
Geometric parameters (Å, º) top
O1—C11.243 (3)O5—H5o0.86 (1)
O2—C11.253 (3)O7—H7o0.85 (1)
O3—C51.304 (3)O1w—H1w10.85 (1)
O4—C51.207 (3)O1w—H1w20.85 (1)
O5—C61.316 (3)N1—H1n10.85 (1)
O6—C61.203 (3)N1—H1n20.85 (1)
O7—C31.421 (3)C2—H2a0.97
O8—C81.418 (3)C2—H2b0.97
O8—C91.421 (3)C4—H4a0.97
N1—C71.482 (3)C4—H4b0.97
N1—C101.484 (3)C7—H7a0.97
C1—C21.524 (3)C7—H7b0.97
C2—C31.536 (3)C8—H8a0.97
C3—C41.525 (3)C8—H8b0.97
C3—C61.536 (3)C9—H9a0.97
C4—C51.505 (3)C9—H9b0.97
C7—C81.489 (4)C10—H10a0.97
C9—C101.496 (4)C10—H10b0.97
O3—H3o0.85 (1)
C8—O8—C9109.9 (2)C1—C2—H2a108.6
O1—C1—O2124.2 (2)C3—C2—H2a108.6
O1—C1—C2118.7 (2)C1—C2—H2b108.6
O2—C1—C2117.2 (2)C3—C2—H2b108.6
C1—C2—C3114.6 (2)H2a—C2—H2b107.6
O7—C3—C2109.6 (2)C5—C4—H4a108.8
O7—C3—C4107.7 (2)C3—C4—H4a108.8
C2—C3—C4110.9 (2)C5—C4—H4b108.8
O7—C3—C6109.4 (2)C3—C4—H4b108.8
C2—C3—C6109.0 (2)H4a—C4—H4b107.7
C4—C3—C6110.3 (2)N1—C7—H7a109.7
C3—C4—C5113.6 (2)C8—C7—H7a109.7
O3—C5—O4123.1 (2)N1—C7—H7b109.7
O3—C5—C4112.8 (2)C8—C7—H7b109.7
O4—C5—C4124.1 (2)H7a—C7—H7b108.2
O5—C6—O6124.4 (2)O8—C8—H8a109.4
O5—C6—C3111.1 (2)C7—C8—H8a109.4
O6—C6—C3124.4 (2)O8—C8—H8b109.4
N1—C7—C8109.8 (2)C7—C8—H8b109.4
O8—C8—C7111.1 (2)H8a—C8—H8b108.0
O8—C9—C10111.4 (2)O8—C9—H9a109.3
N1—C10—C9109.0 (2)C10—C9—H9a109.3
C5—O3—H3o110 (3)O8—C9—H9b109.3
C6—O5—H5o109 (2)C10—C9—H9b109.3
C3—O7—H7o105 (2)H9a—C9—H9b108.0
H1w1—O1w—H1w2109 (4)N1—C10—H10a109.9
C7—N1—H1n1109 (2)C9—C10—H10a109.9
C10—N1—H1n1111 (2)N1—C10—H10b109.9
C7—N1—H1n2107 (2)C9—C10—H10b109.9
C10—N1—H1n2113 (2)H10a—C10—H10b108.3
H1n1—N1—H1n2106 (3)
O1—C1—C2—C311.9 (3)C4—C3—C6—O6125.1 (2)
O2—C1—C2—C3169.8 (2)C2—C3—C6—O6113.0 (2)
C1—C2—C3—O753.2 (2)O7—C3—C6—O5175.1 (2)
C1—C2—C3—C4171.9 (2)C4—C3—C6—O556.9 (2)
C1—C2—C3—C666.5 (2)C2—C3—C6—O565.1 (2)
O7—C3—C4—C563.2 (2)C10—N1—C7—C854.3 (3)
C2—C3—C4—C5177.0 (2)C9—O8—C8—C761.1 (3)
C6—C3—C4—C556.1 (3)N1—C7—C8—O857.6 (3)
C3—C4—C5—O412.2 (3)C8—O8—C9—C1061.4 (3)
C3—C4—C5—O3169.6 (2)C7—N1—C10—C954.1 (3)
O7—C3—C6—O66.8 (3)O8—C9—C10—N157.7 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3o···O2i0.85 (1)1.76 (1)2.612 (2)176 (4)
O5—H5o···O1w0.86 (1)1.68 (1)2.529 (3)172 (4)
O7—H7o···O10.85 (1)1.89 (2)2.625 (2)144 (3)
N1—H1n2···O10.85 (1)2.13 (2)2.847 (3)143 (3)
N1—H1n1···O2ii0.85 (1)2.12 (2)2.942 (3)162 (3)
O1w—H1w1···O6iii0.85 (1)2.16 (2)2.932 (3)152 (3)
O1w—H1w2···O7ii0.85 (1)1.93 (1)2.782 (3)175 (4)
Symmetry codes: (i) x+3/2, y+1, z+1/2; (ii) x+3/2, y1/2, z; (iii) x+1/2, y+1/2, z+1.

Experimental details

Crystal data
Chemical formulaC4H10NO·C6H7O7·H2O
Mr297.26
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)298
a, b, c (Å)11.3774 (6), 12.4823 (7), 18.437 (1)
V3)2618.3 (2)
Z8
Radiation typeMo Kα
µ (mm1)0.13
Crystal size (mm)0.28 × 0.18 × 0.18
Data collection
DiffractometerBruker AXS area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
12407, 2305, 2103
Rint0.028
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.055, 0.143, 1.15
No. of reflections2305
No. of parameters209
No. of restraints7
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.29, 0.19

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.

Selected geometric parameters (Å, º) top
O1—C11.243 (3)N1—C71.482 (3)
O2—C11.253 (3)N1—C101.484 (3)
O3—C51.304 (3)C1—C21.524 (3)
O4—C51.207 (3)C2—C31.536 (3)
O5—C61.316 (3)C3—C41.525 (3)
O6—C61.203 (3)C3—C61.536 (3)
O7—C31.421 (3)C4—C51.505 (3)
O8—C81.418 (3)C7—C81.489 (4)
O8—C91.421 (3)C9—C101.496 (4)
C8—O8—C9109.9 (2)C3—C4—C5113.6 (2)
O1—C1—O2124.2 (2)O3—C5—O4123.1 (2)
O1—C1—C2118.7 (2)O3—C5—C4112.8 (2)
O2—C1—C2117.2 (2)O4—C5—C4124.1 (2)
C1—C2—C3114.6 (2)O5—C6—O6124.4 (2)
O7—C3—C2109.6 (2)O5—C6—C3111.1 (2)
O7—C3—C4107.7 (2)O6—C6—C3124.4 (2)
C2—C3—C4110.9 (2)N1—C7—C8109.8 (2)
O7—C3—C6109.4 (2)O8—C8—C7111.1 (2)
C2—C3—C6109.0 (2)O8—C9—C10111.4 (2)
C4—C3—C6110.3 (2)N1—C10—C9109.0 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3o···O2i0.85 (1)1.76 (1)2.612 (2)176 (4)
O5—H5o···O1w0.86 (1)1.68 (1)2.529 (3)172 (4)
O7—H7o···O10.85 (1)1.89 (2)2.625 (2)144 (3)
N1—H1n2···O10.85 (1)2.13 (2)2.847 (3)143 (3)
N1—H1n1···O2ii0.85 (1)2.12 (2)2.942 (3)162 (3)
O1w—H1w1···O6iii0.85 (1)2.16 (2)2.932 (3)152 (3)
O1w—H1w2···O7ii0.85 (1)1.93 (1)2.782 (3)175 (4)
Symmetry codes: (i) x+3/2, y+1, z+1/2; (ii) x+3/2, y1/2, z; (iii) x+1/2, y+1/2, z+1.
 

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