# Ethylammonium hydrogen oxalate-oxalic acid (2/1)

Assane Toure, Cheikh Abdoul Khadir Diop, Libasse Diop, Laurent Plasseraud, Hélène Cattey

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Assane Toure, Cheikh Abdoul Khadir Diop, Libasse Diop, Laurent Plasseraud, Hélène Cattey. Ethylammonium hydrogen oxalate-oxalic acid (2/1). IUCrData, 2019, 4 (5), 10.1107/S2414314619006357. hal-02187663

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IUCrData

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IUCrData

ISSN 2414-3146

Received 30 March 2019

Accepted 4 May 2019

Edited by R. J. Butcher, Howard University, USA

Keywords: crystal structure; ammonium carboxylate salt; hydrogen bonding; hydrogen oxalate; oxalic acid.

CCDC reference: 1914197

Structural data: full structural data are available from iucrdata.iucr.org

# Ethylammonium hydrogen oxalate–oxalic acid (2/1)

Assane Toure,ª Cheikh Abdoul Khadir Diop,ª Libasse Diop,ª\* Laurent Plasseraudᵇ and Hélène Catteyᵇ

The reaction between ethylamine and oxalic acid in water in a 1:1 molar ratio afforded the title salt, C₂H₈N⁺·C₂HO₄⁻·0.5C₂H₂O₄. The hydrogen oxalate anions interact through hydrogen bonding and are organized into a chains propagating along the c-axis direction. The chains are connected to the neighbouring cations and oxalic acid molecules by N–H···O and O–H···O hydrogen bonds and N···O dipole–dipole contacts, leading to a supramolecular three-dimensional network.

3D view

<figure><img src="image_4.png" /></figure>

Chemical scheme

<figure><img src="image_5.png" /></figure>

## Structure description

Ammonium carboxylate networks obtained by mixing dicarboxylic acids with amines is of interest in the field of crystal engineering (Ballabh *et al.* 2002; Haynes & Pietersen, 2008; Dziuk *et al.* 2014a). These compounds exhibit a variety of structures that can lead, through non-covalent interactions (hydrogen bonding, π–π stacking, van der Waals and C–H···π contacts), to a large diversity of architectures and topologies. Dicarboxylic acids can act as polydirectional synths, and amines, *via* the formation of ammonium, greatly increase the possible of linkages and interactions (Ivasenko & Perepichka, 2011; Yuge *et al.*, 2008; Lemmerer, 2011). To date, many examples of such crystalline networks from oxalic acid and hydrogen oxalate have been described, see for example: Dziuk *et al.* (2014b,c); Braga *et al.* (2013); Ejsmont (2006, 2007); Ejsmont & Zaleski (2006a,b); MacDonald *et al.* (2001). Our group has also contributed to this area by reporting recently two new structures of such compounds (Diallo *et al.*, 2015; Diop *et al.*, 2016). In a continuation of this work, we describe herein the synthesis and structure of the title salt I, isolated from an equimolar mixture of oxalic acid and ethylamine.

Compound I crystallizes in the monoclinic C2/c space group with the asymmetric unit comprising of one ethylammonium cation (C₂H₈N⁺), one hydrogen oxalate anion

<footnote>ªLaboratoire de Chimie Minérale et Analytique (LACHIMIA), Département de Chimie, Faculté des Sciences et Techniques, Université Cheikh Anta Diop, Dakar, Senegal, and ᵇICMUB UMR 6302, Université de Bourgogne, Faculté des Sciences, 9 avenue Alain Savary, 21000 DIJON, France. \*Correspondence e-mail: dlibasse@gmail.com</footnote>
<table><caption>**Table 1**
Hydrogen-bond geometry (Å, °).</caption><thead><tr><th>D–H···A</th><th>D–H</th><th>H···A</th><th>D···A</th><th>D–H···A</th></tr></thead><tbody><tr><td>O2–H2···O3<sup>i</sup></td><td>0.84</td><td>1.74</td><td>2.5717 (9)</td><td>173</td></tr><tr><td>N–H··O4</td><td>0.91</td><td>1.94</td><td>2.8472 (11)</td><td>177</td></tr><tr><td>N–H··O1<sup>ii</sup></td><td>0.91</td><td>2.04</td><td>2.9409 (11)</td><td>172</td></tr><tr><td>N–H··O6<sup>iii</sup></td><td>0.91</td><td>2.16</td><td>3.0400 (10)</td><td>163</td></tr><tr><td>O5–H··O4</td><td>0.84</td><td>1.68</td><td>2.5139 (10)</td><td>173</td></tr></tbody></table>

Symmetry codes: (i) x, -y, z + ½; (ii) -x + ½, y + ½, -z + ½; (iii) -x + 1, y, -z + ½.

(C₂HO₄⁻) and a half-molecule of oxalic acid (C₂H₂O₄). The three components are linked together by several intermolecular interactions (Table 1 and Fig. 1). The interatomic distances and angles of the ethylammonium cation are in the range of those previously measured for comparable salts (Ejsmont & Zaleski, 2006a; Ejsmont, 2006). Each C₂H₈N⁺ cation is involved in N–H···O hydrogen bonding with two distinct C₂HO₄⁻ anions [N–HA···O4 = 2.8472 (11) and N–HB···O1 = 2.9409 (11) Å] and also with one neutral C₂H₂O₄ molecule [N–HC···O6 = 3.0400 (10) Å]. These interactions are reinforced by van der Waals contacts involving C₂H₈N⁺, and C₂HO₄⁻ and C₂H₂O₄, respectively [N···O3 = 2.8960 (11) and N···O5 = 2.9423 (11) Å]. The hydrogen oxalate anion is twisted with an O3–C2–C1–O2 torsion angle of 168.94 (8)°. The C–C and C–O bond distances [C1–C2 = 1.5570 (13), C1–O1 = 1.2141 (12), C1–O2 = 1.3090 (11), C2–O3 = 1.2415 (11), C2–O4 = 1.2565 (12) Å] are similar to those observed in the literature for other organic salts containing this anion (Barnes, 2003; Essid *et al.*, 2013).

The hydrogen oxalate anions in I⁻ are linked into chains running parallel to the c axis by O2–H2···O3 hydrogen bonds [2.5717 (9) Å]. Adjacent chains are bridged by neutral

<figure><img src="image_6.png" /><figcaption>**Figure 1**
View of the title salt showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dotted lines [symmetry codes: (i) x, -y, ½ + z; (ii) 1 - x, -y, 1 - z; (iii) 1 - x, y, ½ - z; (iv): ½ - x, -½ + y, ½ - z].</figcaption></figure>

<table><caption>**Table 2**
Experimental details.</caption><tbody><tr><td colspan="2"><strong>Crystal data</strong></td></tr><tr><td>Chemical formula</td><td>C₂H₈N⁺·C₂HO₄⁻·0.5C₂H₂O₄</td></tr><tr><td>M<sub>r</sub></td><td>360.28</td></tr><tr><td>Crystal system, space group</td><td>Monoclinic, C2/c</td></tr><tr><td>Temperature (K)</td><td>100</td></tr><tr><td>a, b, c (Å)</td><td>21.1667 (8), 6.6243 (3), 11.3247 (4)</td></tr><tr><td>β (°)</td><td>91.509 (2)</td></tr><tr><td>V (Å³)</td><td>1587.34 (11)</td></tr><tr><td>Z</td><td>4</td></tr><tr><td>Radiation type</td><td>Mo Kα</td></tr><tr><td>μ (mm⁻¹)</td><td>0.14</td></tr><tr><td>Crystal size (mm)</td><td>0.47 × 0.3 × 0.17</td></tr><tr><td colspan="2"><strong>Data collection</strong></td></tr><tr><td>Diffractometer</td><td>Bruker D8 Venture triumph Mo</td></tr><tr><td>Absorption correction</td><td>Multi-scan (SADABS; Bruker, 2014)</td></tr><tr><td>T<sub>min</sub>, T<sub>max</sub></td><td>0.712, 0.746</td></tr><tr><td>No. of measured, independent and observed [I > 2σ(I)] reflections</td><td>14201, 1829, 1624</td></tr><tr><td>R<sub>int</sub></td><td>0.027</td></tr><tr><td>(sin θ/λ)<sub>max</sub> (Å⁻¹)</td><td>0.650</td></tr><tr><td colspan="2"><strong>Refinement</strong></td></tr><tr><td>R[F² > 2σ(F²)], wR(F²), S</td><td>0.028, 0.075, 1.03</td></tr><tr><td>No. of reflections</td><td>1829</td></tr><tr><td>No. of parameters</td><td>113</td></tr><tr><td>H-atom treatment</td><td>H-atom parameters constrained</td></tr><tr><td>Δρ<sub>max</sub>, Δρ<sub>min</sub> (e Å⁻³)</td><td>0.50, -0.20</td></tr></tbody></table>

Computer programs: *APEX3* and *SAINT* (Bruker, 2014), *SHELXT* (Sheldrick, 2015a), *SHELXL* (Sheldrick, 2015b) and *OLEX2* (Dolomanov *et al.*, 2009).

oxalic acid molecules whose two OH groups participate in hydrogen-bonding interactions with two distinct hydrogen oxalate anions [O5–H5···O4 = 2.5139 (10) Å], resulting in the formation of sheets. These sheets are stacked along the b axis with the ethylammonium cations intercalated between the sheets, generating a three-dimensional network (Fig. 2).

A search on the online portal of the Cambridge Structural Database (WebCSD; Thomas *et al.*, 2010) yielded 188 hits for ethylammonium salts and 25 hits for the hydrogen oxalate-oxalic acid combination.

<figure><img src="image_7.png" /><figcaption>**Figure 2**
The packing, viewed along the c axis, showing the intermolecular hydrogen-bonding scheme (dashed lines) [colour code: C dark grey, H white, O red, N blue].</figcaption></figure>
## Synthesis and crystallization

All the chemicals were purchased from Aldrich (Germany) and used without further purification. The title compound was obtained by reacting equimolar amounts of oxalic acid (1.26 g, 0.02 mol) and ethylamine (50% in water, 2.6 ml, 0.02 mol), in 25 ml of water at 298 K. The resulting solution was allowed to evaporate at 338 K, leading after few days to colourless prismatic suitable for X-ray analysis.

## Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

## Acknowledgements

The authors gratefully acknowledge the Cheikh Anta Diop University of Dakar (Senegal), the Centre National de la Recherche Scientifique (CNRS, France) and the University of Bourgogne Franche-Comté (Dijon, France) for support.

## References

Ballabh, A., Trivedi, D. D., Dastidar, P. & Suresh, E. (2002). *CrystEngComm*, **4**, 135–142.

Barnes, J. C. (2003). *Acta Cryst.* **E59**, o931–o933.

Braga, D., Chelazzi, L., Ciabatti, I. & Grepionoi, F. (2013). *New J. Chem.* **37**, 97–104.

Bruker (2014). *APEX3*, *SADABS* and *SAINT*. Bruker AXS Inc, Madison, Wisconsin, USA.

Diallo, W., Gueye, N., Crochet, A., Plasseraud, L. & Cattey, H. (2015). *Acta Cryst.* **E71**, 473–475.

Diop, M. B., Diop, L., Plasseraud, L. & Cattey, H. (2016). *Acta Cryst.* **E72**, 1113–1115.

Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). *J. Appl. Cryst.* **42**, 339–341.

Dziuk, B., Ejsmont, K. & Zaleski, J. (2014a). *CHEMIK*, **68*, 391–395.

Dziuk, B., Zarychta, B. & Ejsmont, K. (2014b). *Acta Cryst.* **E70**, o852.

Dziuk, B., Zarychta, B. & Ejsmont, K. (2014c). *Acta Cryst.* **E70**, o917–o918.

Ejsmont, K. (2006). *Acta Cryst.* **E62**, o5852–o5854.

Ejsmont, K. (2007). *Acta Cryst.* **E63**, o107–o109.

Ejsmont, K. & Zaleski, J. (2006a). *Acta Cryst.* **E62**, o3879–o3880.

Ejsmont, K. & Zaleski, J. (2006b). *Acta Cryst.* **E62**, o2512–o2513.

Essid, M., Marouani, H., Al-Deyab, S. S. & Rzaigui, M. (2013). *Acta Cryst.* **E69**, o1279.

Haynes, D. A. & Pietersen, L. K. (2008). *CrystEngComm*, **10**, 518–524.

Ivasenko, O. & Perepichka, D. F. (2011). *Chem. Soc. Rev.* **40**, 191–206.

Lemmerer, A. (2011). *Cryst. Growth Des.* **11**, 583–593.

MacDonald, J. C., Dorrestein, P. C. & Pilley, M. M. (2001). *Cryst. Growth Des.* **1**, 29–38.

Sheldrick, G. M. (2015a). *Acta Cryst.* **A71**, 3–8.

Sheldrick, G. M. (2015b). *Acta Cryst.* **C71**, 3–8.

Thomas, I. R., Bruno, I. J., Cole, J. C., Macrae, C. F., Pidcock, E. & Wood, P. A. (2010). *J. Appl. Cryst.* **43**, 362–366.

Yuge, T., Sakai, T., Kai, N., Hisaki, I., Miyata, M. & Tohnai, N. (2008). *Chem. Eur. J.* **14**, 2984–2993.
full crystallographic data

IUCrData (2019). **4**, x190635 [https://doi.org/10.1107/S2414314619006357]

Ethylammonium hydrogen oxalate-oxalic acid (2/1)

Assane Toure, Cheikh Abdoul Khadir Diop, Libasse Diop, Laurent Plasseraud and Hélène Cattey

Ethylammonium hydrogen oxalate-oxalic acid (2/1)

Crystal data

$C_2H_8N^+·C_2HO_4^−·0.5C_2H_2O_4$

$M_r = 360.28$

Monoclinic, C2/c

$a = 21.1667 (8) Å$

$b = 6.6243 (3) Å$

$c = 11.3247 (4) Å$

$\beta = 91.509 (2)°$

$V = 1587.34 (11) Å^3$

$Z = 4$

$F(000) = 760$

$D_x = 1.508 \text{ Mg m}^{-3}$

Mo Kα radiation, $\lambda = 0.71073$ Å

Cell parameters from 7758 reflections

$\theta = 3.2–27.5°$

$\mu = 0.14 \text{ mm}^{-1}$

$T = 100$ K

Prism, colourless

$0.47 \times 0.3 \times 0.17 \text{ mm}$

Data collection

Bruker D8 Venture triumph Mo
diffractometer

Radiation source: X-ray tube, Siemens KFF Mo
2K-90C

TRIUMPH curved crystal monochromator

Detector resolution: 1024 x 1024 pixels mm$^{-1}$

$\varphi$ and $\omega$ scans

Absorption correction: multi-scan
(SADABS; Bruker, 2014)

$T_{\text{min}} = 0.712, T_{\text{max}} = 0.746$

14201 measured reflections

1829 independent reflections

1624 reflections with $I > 2\sigma(I)$

$R_{\text{int}} = 0.027$

$\theta_{\text{max}} = 27.5°, \theta_{\text{min}} = 3.2°$

$h = -27 \rightarrow 27$

$k = -8 \rightarrow 8$

$l = -14 \rightarrow 13$

Refinement

Refinement on $F^2$

Least-squares matrix: full

$R[F^2 > 2\sigma(F^2)] = 0.028$

$wR(F^2) = 0.075$

$S = 1.03$

1829 reflections

113 parameters

0 restraints

Hydrogen site location: inferred from
neighbouring sites

H-atom parameters constrained

$$w = 1/[\sigma^2(F_o^2) + (0.0383P)^2 + 1.1891P]$$
where $P = (F_o^2 + 2F_c^2)/3$

($\Delta/\sigma)_{\text{max}} = 0.001$

$\Delta\rho_{\text{max}} = 0.50 \text{ e Å}^{-3}$

$\Delta\rho_{\text{min}} = -0.20 \text{ e Å}^{-3}$

Special details

**Geometry.** All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

**Refinement.** H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.99 Å (ethyl group) with $U_{\text{iso}}(H) = 1.2U_{\text{eq}}(C)$ or O—H = 0.84 Å (hydroxyl), N—H = 0.91 Å (ammonium) and C—H = 0.98 Å (methyl group) with $U_{\text{iso}}(H) = 1.5U_{\text{eq}}(O)$ or N or C).
<table><caption>Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²)</caption><thead><tr><th></th><th>x</th><th>y</th><th>z</th><th>U<sub>iso</sub>*/U<sub>eq</sub></th></tr></thead><tbody><tr><td>C1</td><td>0.75227 (4)</td><td>-0.01386 (14)</td><td>0.48767 (8)</td><td>0.01041 (19)</td></tr><tr><td>O1</td><td>0.80530 (3)</td><td>-0.07888 (11)</td><td>0.50554 (6)</td><td>0.01374 (16)</td></tr><tr><td>C2</td><td>0.72301 (4)</td><td>-0.00320 (14)</td><td>0.36024 (8)</td><td>0.01042 (19)</td></tr><tr><td>O2</td><td>0.71415 (3)</td><td>0.05216 (11)</td><td>0.56824 (6)</td><td>0.01410 (17)</td></tr><tr><td>H2</td><td>0.731311</td><td>0.037617</td><td>0.635430</td><td>0.021*</td></tr><tr><td>O3</td><td>0.76073 (3)</td><td>-0.03334 (11)</td><td>0.28000 (6)</td><td>0.01506 (17)</td></tr><tr><td>O4</td><td>0.66506 (3)</td><td>0.03493 (11)</td><td>0.34790 (6)</td><td>0.01416 (17)</td></tr><tr><td>N</td><td>0.61063 (4)</td><td>0.32342 (12)</td><td>0.18905 (7)</td><td>0.01222 (18)</td></tr><tr><td>HA</td><td>0.626827</td><td>0.230748</td><td>0.240865</td><td>0.018*</td></tr><tr><td>HB</td><td>0.639850</td><td>0.352637</td><td>0.134066</td><td>0.018*</td></tr><tr><td>HC</td><td>0.575304</td><td>0.272353</td><td>0.152545</td><td>0.018*</td></tr><tr><td>C4</td><td>0.59405 (5)</td><td>0.51142 (15)</td><td>0.25420 (9)</td><td>0.0146 (2)</td></tr><tr><td>H4A</td><td>0.630646</td><td>0.555335</td><td>0.304026</td><td>0.018*</td></tr><tr><td>H4B</td><td>0.558307</td><td>0.484025</td><td>0.306532</td><td>0.018*</td></tr><tr><td>C5</td><td>0.57599 (5)</td><td>0.67710 (16)</td><td>0.16787 (10)</td><td>0.0199 (2)</td></tr><tr><td>H5A</td><td>0.612135</td><td>0.708562</td><td>0.118768</td><td>0.030*</td></tr><tr><td>H5B</td><td>0.563719</td><td>0.798067</td><td>0.211491</td><td>0.030*</td></tr><tr><td>H5C</td><td>0.540406</td><td>0.632035</td><td>0.117391</td><td>0.030*</td></tr><tr><td>C3</td><td>0.52681 (4)</td><td>0.03067 (14)</td><td>0.45853 (8)</td><td>0.0111 (2)</td></tr><tr><td>O5</td><td>0.57859 (3)</td><td>-0.06835 (11)</td><td>0.48337 (6)</td><td>0.01553 (17)</td></tr><tr><td>H5</td><td>0.607761</td><td>-0.025239</td><td>0.441275</td><td>0.023*</td></tr><tr><td>O6</td><td>0.51865 (3)</td><td>0.15638 (11)</td><td>0.38186 (6)</td><td>0.01596 (17)</td></tr></tbody></table>

<table><caption>Atomic displacement parameters (Å²)</caption><thead><tr><th></th><th>U<sup>11</sup></th><th>U<sup>22</sup></th><th>U<sup>33</sup></th><th>U<sup>12</sup></th><th>U<sup>13</sup></th><th>U<sup>23</sup></th></tr></thead><tbody><tr><td>C1</td><td>0.0115 (4)</td><td>0.0107 (4)</td><td>0.0091 (4)</td><td>-0.0012 (3)</td><td>0.0008 (3)</td><td>0.0006 (3)</td></tr><tr><td>O1</td><td>0.0110 (3)</td><td>0.0190 (4)</td><td>0.0111 (3)</td><td>0.0022 (3)</td><td>-0.0007 (2)</td><td>0.0001 (3)</td></tr><tr><td>C2</td><td>0.0111 (4)</td><td>0.0109 (4)</td><td>0.0092 (4)</td><td>0.0000 (3)</td><td>-0.0002 (3)</td><td>0.0009 (3)</td></tr><tr><td>O2</td><td>0.0135 (3)</td><td>0.0212 (4)</td><td>0.0076 (3)</td><td>0.0033 (3)</td><td>0.0003 (3)</td><td>-0.0010 (3)</td></tr><tr><td>O3</td><td>0.0112 (3)</td><td>0.0251 (4)</td><td>0.0090 (3)</td><td>0.0026 (3)</td><td>0.0014 (2)</td><td>-0.0004 (3)</td></tr><tr><td>O4</td><td>0.0094 (3)</td><td>0.0218 (4)</td><td>0.0113 (3)</td><td>0.0026 (3)</td><td>0.0007 (2)</td><td>0.0037 (3)</td></tr><tr><td>N</td><td>0.0109 (4)</td><td>0.0143 (4)</td><td>0.0114 (4)</td><td>-0.0009 (3)</td><td>-0.0008 (3)</td><td>0.0014 (3)</td></tr><tr><td>C4</td><td>0.0131 (5)</td><td>0.0162 (5)</td><td>0.0145 (5)</td><td>0.0005 (4)</td><td>0.0012 (4)</td><td>-0.0009 (4)</td></tr><tr><td>C5</td><td>0.0187 (5)</td><td>0.0164 (5)</td><td>0.0247 (5)</td><td>0.0010 (4)</td><td>0.0022 (4)</td><td>0.0048 (4)</td></tr><tr><td>C3</td><td>0.0102 (4)</td><td>0.0130 (4)</td><td>0.0100 (4)</td><td>-0.0011 (3)</td><td>0.0003 (3)</td><td>-0.0016 (3)</td></tr><tr><td>O5</td><td>0.0095 (3)</td><td>0.0216 (4)</td><td>0.0157 (4)</td><td>0.0027 (3)</td><td>0.0040 (3)</td><td>0.0060 (3)</td></tr><tr><td>O6</td><td>0.0126 (3)</td><td>0.0202 (4)</td><td>0.0152 (4)</td><td>0.0001 (3)</td><td>0.0012 (3)</td><td>0.0064 (3)</td></tr></tbody></table>

<table><caption>Geometric parameters (Å, °)</caption><tr><td>C1—O1</td><td>1.2141 (12)</td><td>C4—H4A</td><td>0.9900</td></tr><tr><td>C1—C2</td><td>1.5570 (13)</td><td>C4—H4B</td><td>0.9900</td></tr><tr><td>C1—O2</td><td>1.3090 (11)</td><td>C4—C5</td><td>1.5122 (14)</td></tr><tr><td>C2—O3</td><td>1.2415 (11)</td><td>C5—H5A</td><td>0.9800</td></tr></table>
<table><tbody><tr><td>C2—O4</td><td>1.2565 (12)</td><td>C5—H5B</td><td>0.9800</td></tr><tr><td>O2—H2</td><td>0.8400</td><td>C5—H5C</td><td>0.9800</td></tr><tr><td>N—HA</td><td>0.9100</td><td>C3—C3<sup>i</sup></td><td>1.5467 (18)</td></tr><tr><td>N—HB</td><td>0.9100</td><td>C3—O5</td><td>1.3016 (12)</td></tr><tr><td>N—HC</td><td>0.9100</td><td>C3—O6</td><td>1.2121 (12)</td></tr><tr><td>N—C4</td><td>1.4940 (12)</td><td>O5—H5</td><td>0.8400</td></tr><tr><td>O1—C1—C2</td><td>120.93 (8)</td><td>N—C4—C5</td><td>110.14 (8)</td></tr><tr><td>O1—C1—O2</td><td>125.90 (9)</td><td>H4A—C4—H4B</td><td>108.1</td></tr><tr><td>O2—C1—C2</td><td>113.17 (8)</td><td>C5—C4—H4A</td><td>109.6</td></tr><tr><td>O3—C2—C1</td><td>115.04 (8)</td><td>C5—C4—H4B</td><td>109.6</td></tr><tr><td>O3—C2—O4</td><td>126.56 (9)</td><td>C4—C5—H5A</td><td>109.5</td></tr><tr><td>O4—C2—C1</td><td>118.40 (8)</td><td>C4—C5—H5B</td><td>109.5</td></tr><tr><td>C1—O2—H2</td><td>109.5</td><td>C4—C5—H5C</td><td>109.5</td></tr><tr><td>HA—N—HB</td><td>109.5</td><td>H5A—C5—H5B</td><td>109.5</td></tr><tr><td>HA—N—HC</td><td>109.5</td><td>H5A—C5—H5C</td><td>109.5</td></tr><tr><td>HB—N—HC</td><td>109.5</td><td>H5B—C5—H5C</td><td>109.5</td></tr><tr><td>C4—N—HA</td><td>109.5</td><td>O5—C3—C3<sup>i</sup></td><td>111.32 (10)</td></tr><tr><td>C4—N—HB</td><td>109.5</td><td>O6—C3—C3<sup>i</sup></td><td>121.50 (11)</td></tr><tr><td>C4—N—HC</td><td>109.5</td><td>O6—C3—O5</td><td>127.18 (9)</td></tr><tr><td>N—C4—H4A</td><td>109.6</td><td>C3—O5—H5</td><td>109.5</td></tr><tr><td>N—C4—H4B</td><td>109.6</td><td></td><td></td></tr><tr><td>O1—C1—C2—O3</td><td>-11.28 (13)</td><td>O2—C1—C2—O3</td><td>168.94 (8)</td></tr><tr><td>O1—C1—C2—O4</td><td>169.03 (9)</td><td>O2—C1—C2—O4</td><td>-10.75 (12)</td></tr></tbody></table>

Symmetry code: (i) $-x+1, -y, -z+1$.

<table><caption>Hydrogen-bond geometry (Å, °)</caption><thead><tr><th>D—H···A</th><th>D—H</th><th>H···A</th><th>D···A</th><th>D—H···A</th></tr></thead><tbody><tr><td>O2—H2···O3<sup>ii</sup></td><td>0.84</td><td>1.74</td><td>2.5717 (9)</td><td>173</td></tr><tr><td>N—H4···O4</td><td>0.91</td><td>1.94</td><td>2.8472 (11)</td><td>177</td></tr><tr><td>N—HB···O1<sup>iii</sup></td><td>0.91</td><td>2.04</td><td>2.9409 (11)</td><td>172</td></tr><tr><td>N—HC···O6<sup>iv</sup></td><td>0.91</td><td>2.16</td><td>3.0400 (10)</td><td>163</td></tr><tr><td>O5—H5···O4</td><td>0.84</td><td>1.68</td><td>2.5139 (10)</td><td>173</td></tr></tbody></table>

Symmetry codes: (ii) $x, -y, z+1/2$; (iii) $-x+3/2, y+1/2, -z+1/2$; (iv) $-x+1, y, -z+1/2$.