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ISSN: 2056-9890

Synthesis, crystal structure and Hirshfeld surface analysis of tert-butyl N-acetyl­carbamate

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aUnité de Chimie Moléculaire et Environnement, Département de Chimie, FST, UNA, Nouakchott, Mauritania, bDépartement des Sciences Exactes, Ecole Normale Supérieure de Nouakchott, Nouakchott, Mauritania, cAgence Nationale de Recherches Géologiques et du Patrimoine Minier (ANARPAM), Nouakchott, Mauritania, dLaboratoire CRM2, CNRS, Institut Jean Barriol, Université de, Lorraine, 54000, Nancy, France, and eDépartement de Chimie, Faculté des Sciences et Techniques, Université Cheik Anta Diop, Dakar, Senegal
*Correspondence e-mail: mlgayeastou@yahoo.fr

Edited by A. S. Batsanov, University of Durham, England (Received 31 March 2022; accepted 26 September 2022; online 30 September 2022)

This article reports a practical synthesis of tert-butyl acetyl­carbamate, C7H13NO3, from N-Boc-thio­acetamide and the study of its crystal structure. The reaction proceeds in the presence of natural phosphate as a catalyst, with excellent yield, simple workup and benign environment. The crystal structure was refined using a transferred multipolar atom model. In the crystal, symmetrical pairs of strong N—H⋯O hydrogen bonds connect the mol­ecules into dimers with an R22(8) ring motif. The inter­actions between neighbouring dimers are mostly van der Waals, between hydro­phobic methyl groups. Hirshfeld surface analysis shows the major contributions to the crystal packing are from H⋯H (42.6%) and O⋯H (26.7%) contacts.

1. Chemical context

Carbamates are widely used as agrochemicals, in the polymer industry, in peptide synthesis (Dibenedetto et al., 2002[Dibenedetto, A., Aresta, M., Fragale, C. & Narracci, M. (2002). Green Chem. 4, 439-443.]) and in medicinal chemistry, where many derivatives are specifically designed to make drug–target inter­actions through their carbamate moiety (Ghosh & Brindisi, 2015[Ghosh, A. K. & Brindisi, M. (2015). J. Med. Chem. 58, 2895-2940.]). Here we report the crystal structure of tert-butyl-acetyl­carbamate, C7H13NO3 (I)[link], which we obtained while attempting to synthesize polyfunctional amidines (which are useful in synthetic fields, especially as templates for the development of various novel heterocycles) using heterogeneous catalysis on natural phosphates (NP) – readily available, stable, easy to handle and regenerate, non-toxic and inexpensive catalysts with both basic and acidic active sites (Sebti et al., 1994[Sebti, S., Saber, A. & Rhihil, A. (1994). Tetrahedron Lett. 35, 9399-9400.], 1996[Sebti, S., Rhihil, A. & Saber, A. (1996). Chem. Lett. 25, 721.]).

[Scheme 1]

We followed the procedure described by Lee et al. (1998[Lee, H. K., Ten, L. N. & Pak, C. S. (1998). Bull. Korean Chem. Soc. 19, 1148-1149.]), but using natural phosphate (NP) as a catalyst instead of Lewis acids such as ZnCl2, Et3O+BF4 and FeCl2. The synthesis was carried out by blending N-(t-Boc)thio­acetamide with various amino­esters, in the presence of NEt3 and NP. The reaction yielded (I)[link] instead of the desired amidine, i.e. the sulfur atom was substituted by oxygen. In the absence of NP, no product was obtained and the starting materials were recovered.

2. Structural commentary

The title compound, C7H13NO3, (Fig. 1[link]) crystallizes in the space group P21/n with one mol­ecule per asymmetric unit. The skeleton of the mol­ecule is nearly planar if the C3 and C4 atoms are excluded, the root-mean-square deviation from the mean plane being 0.070 Å. The C3H3 and C4H3 methyl groups, located on either side of the mean plane, generate two weak intra­molecular hydrogen bonds with the carbonyl O2 atom located in the plane [C3—H3C⋯O2 and C4—H4A⋯O2, d(H⋯O)= 2.49 and 2.48 Å, respectively; Table 1[link]].

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C4—H4A⋯O2 1.10 2.48 3.0651 (14) 112
C3—H3C⋯O2 1.10 2.49 2.9928 (15) 107
N1—H1⋯O3i 1.01 (1) 1.92 (1) 2.9285 (11) 173 (1)
Symmetry code: (i) [-x+1, -y, -z+1].
[Figure 1]
Figure 1
View of mol­ecule (I)[link], showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

3. Supra­molecular features

In the crystal, a centrosymmetric dimer of mol­ecules is held together by two N—H⋯O=C hydrogen bonds, N1—H1⋯O3 and its symmetry equivalent [d(H⋯O) = 1.92 (1) Å, Table 1[link]], which represent the strongest inter­actions in the packing and create an inversion-symmetric supra­molecular motif of graph-set [R_{2}^{2}](8) (Fig. 2[link]). Fig. 3[link] shows the packing of these dimers. If we consider the Hirshfeld surface around the dimer as a whole, this surface is constituted mainly by hydro­phobic (C and H-c) atoms (81%) and oxygen atoms (13%). The inter­actions between neighbouring dimers are mostly hydro­phobic: H-c⋯H-c between methyl groups (43%) and C⋯H-c between carbonyl and methyl groups (21%). Weak C—H⋯O hydrogen bonds also occur between dimers (23%). The steric hindrance of the methyl groups causes an offset of the mol­ecules of consecutive dimers, so that no strong hydrogen bond is observed between the dimers. Consequently, the crystal appears to be stabilized by strong hydrogen bonding within the dimers and van der Waals forces without.

[Figure 2]
Figure 2
View of the mol­ecular dimer linked by a double hydrogen bond.
[Figure 3]
Figure 3
Mol­ecular packing of (I)[link], viewed along the a axis, showing different orientations of the dimers.

4. Hirshfeld analysis

MoProViewer (Jelsch et al., 2005[Jelsch, C., Guillot, B., Lagoutte, A. & Lecomte, C. (2005). J. Appl. Cryst. 38, 38-54.]) was used to further investigate and visualize the inter­molecular inter­actions in the crystal. The Hirshfeld surface was computed from the model after multipolar refinement but using electron density from the spherical-neutral atom model. The 2D fingerprint plots (Fig. 4[link]) were generated with Crystal Explorer (Spackman et al., 2021[Spackman, P. R., Turner, M. J., McKinnon, J. J., Wolff, S. K., Grimwood, D. J., Jayatilaka, D. & Spackman, M. A. (2021). J. Appl. Cryst. 54, 1006-1011.]). The most significant contributions for the contacts in the crystal packing (Table 2[link]) are from H⋯H (46.2%), O⋯H/H⋯O (26.7%) and C⋯H/H⋯C contacts (18.7%), whereas only 2.8% are from N⋯H/H⋯N contacts. In the fingerprint plots (Fig. 4[link]), the two reciprocal spikes at a short distance correspond to the O⋯H—N/N—H⋯O contacts, i.e. strong hydrogen bonds. The H⋯H contacts show also a small spike on the diagonal line, the shortest distances being 2.447 Å between H2B and H7A(x + 1, y − 1, z) (Fig. 5[link]a). The inter­molecular inter­actions were further evaluated by computing the enrichment ratios (E, see Table 2[link]) in order to highlight which contacts are over-represented and are likely to represent energetically strong inter­actions and be the driving force in crystal formation (Jelsch et al., 2014[Jelsch, C., Ejsmont, K. & Huder, L. (2014). IUCrJ, 1, 119-128.]). The enrichment values are obtained as the ratio between the shares of actual contacts Cxy and the random (equiprobable) contacts Rxy, the latter calculated as if all types of contacts had the same propensity to occur and are obtained by probability products (Rxy = Sx·Sy). The H-c⋯H-c hydro­phobic contacts are the most abundant on the Hirshfeld surface but have a unitary enrichment ratio. The O⋯H-c and C⋯H-c weak hydrogen bonds are the next most abundant inter­actions and are slightly enriched (E = 1.04 and 1.12, respectively). While the strong O⋯H-n hydrogen bonds in the fourth position represent only 5.9% of the contact surface, they are the most enriched at E = 3.41. The H-c⋯N contacts are over-represented with E = 1.46 as the nitro­gen atom inter­acts mostly with methyl groups on both sides of the sp2 plane.

Table 2
Statistical analysis of inter­molecular contacts on the Hirshfeld surface

H-c and H-n signify hydrogen atoms bound to C (hydro­phobic) and N (hydro­philic), respectively. Reciprocal contacts (XY and YX) are merged. The most prevalent and enriched contacts are highlighted in bold.

Atom H-n N O H-c C
Sx (%) 5.5 1.5 15.5 64.0 13.5
Cxy (%) (Exy)          
H-n 0.4 (1.39)        
N 0 (0) 0 (0)      
O 5.9 (3.41) 0 (0) 0.4 (0.16)    
H-c 4.2 (0.59) 2.8 (1.46) 20.8 (1.04) 41.6 (0.99)  
C 0.2 (0.13) 0.1 (0.41) 3.4 (0.86) 18.5 (1.12) 1.6 (1.00)
[Figure 4]
Figure 4
Two-dimensional fingerprint plots of the major contacts on the Hirshfeld surface.
[Figure 5]
Figure 5
(a) Hirshfeld and (b) van der Waals surfaces around mol­ecule (I)[link]. The N—H⋯O and C—H⋯O hydrogen bonds as well as a short H⋯H contacts are shown. The surfaces are coloured according to the electrostatic potential.

The Hirshfeld surface was partitioned into (H-c, C) and (H-n, O, N) atoms' shares in order to analyse the contacts in terms of hydro­phobic and hydro­philic inter­actions. Overall, hydro­phobic atoms (C and H-c) comprise 77.5% of the surface, but the hydro­phobic contacts between these atoms (61.8%) are not significantly enriched at E = 1.03. Contacts between hydro­philic atoms (22.5% of the surface), mostly in the form of strong hydrogen bonds, are enriched to 6.7% (E = 1.32) while cross-inter­actions (between hydro­phobic and hydro­philic atoms) are under-represented (31.6%, E = 0.90).

The electrostatic potential was computed on the Hirshfeld and van der Waals surfaces of the mol­ecule (Fig. 5[link]). The two surfaces show similar potential values which are both in the −0.12 to +0.12 e Å−1 range. The regions around the three oxygen atoms are electronegative while the NH group displays positive potential on the surface, followed by the methyl groups which are moderately electropositive.

5. Database survey

The Cambridge Structural Database (Version 5.43, November 2021[Groom, C. R., Bruno, I. J., Lightfoot, M. P. & Ward, S. C. (2016). Acta Cryst. B72, 171-179.]; Groom et al., 2016) was surveyed using ConQuest (version 2020.2.0; Bruno et al., 2002[Bruno, I. J., Cole, J. C., Edgington, P. R., Kessler, M., Macrae, C. F., McCabe, P., Pearson, J. & Taylor, R. (2002). Acta Cryst. B58, 389-397.]). The eight-membered supra­molecular motif, with a double N—H⋯O=C hydrogen bond between two amide groups, is quite common, being encountered in 10,336 crystal structures. The amide-ester fragment, encountered in 35 structures, exists in three different near-planar conformations (Fig. 6[link]). Conformation (a) with the syn disposition of C=O bonds appears in 23 structures, including the nearest reported analogue of (I)[link], 1,1-di­methyl­ethyl-N-propano­ylcarbamate (II) (Brodesser et al., 2003[Brodesser, S., Mikeska, T., Nieger, M. & Kolter, T. (2003). Acta Cryst. E59, o1359-o1361.]). Two different anti conformations, (b) and (c), are adopted by nine and three compounds, respectively. Mol­ecule (I)[link] adopts the anti conformation (b). Compound (I)[link] is the homologue of (II).

[Figure 6]
Figure 6
Conformations of amide-ester derivatives.

6. Synthesis and crystallization

Materials and physical methods. All reagents were purchased from Sigma-Aldrich. Reaction progress was monitored by thin-layer chromatography (TLC) on silica-gel plates (Fluka Kieselgel 60 F254). Flash chromatography purifications were performed on Inter­chim Puriflash (Puriflash columns 50 µ). X-ray fluorescence analysis was performed on a PANalytical AxiosmAX spectrometer.

Preparation of the catalyst. The NP used in this work comes from the Bofal phosphate deposit in Mauritania. Before being used in catalysis, it underwent quartering treatment, particle-size separation, aqueous dissolution, filtration and evaporation of water, calcination at 1173 K for 1h and grinding. The fraction of 60–100 µm grain size was used. The nominal chemical compositions of this phosphate were given by X-ray fluorescence (XRF) analysis. The total amount of the natural inorganic components was 90.86% (Table 3[link]). The rest was mainly organic matter, as indicated by the weight loss on combustion, which amounted to 10.43%.

Table 3
X-ray fluorescence (XRF) analysis (%) of natural phosphate

SiO2 TiO2 Al2O3 Fe2O3 MgO CaO Na2O K2O MnO P2O5 SO3
14.17 0.058 17.51 0.530 0.245 31.66 0.319 0.113 0.016 26.18 0.060

Preparation of tert-butyl acetyl­carbamate (I). It should be noted that compound (I)[link] was prepared in our attempt to synthesize polyfunctional amidines, which are useful in synthetic fields, especially as a template for the development of various new heterocycles. In the preparation, we used the same operating conditions as Lee et al. (1998[Lee, H. K., Ten, L. N. & Pak, C. S. (1998). Bull. Korean Chem. Soc. 19, 1148-1149.]), substituting NP as the catalyst for a Lewis acid. To a solution of N-(t-Boc)thio­acetamide (87.6 mg; 0.5 mmol), the hydro­chloride salt of an amino ester (0.5 mmol) and tri­ethyl­amine (1.65 mmol) in a dry solvent (10 mL), NP (87.6 mg) was added with stirring. The reaction was stirred for 30 min at room temperature. The mixture was filtered through a pad of celite. The residue was purified by Inter­chim Puriflash (Puriflash columns 50 µ) using a cyclo­hexa­ne/ethyl acetate eluent system, to yield crystalline (I)[link] in a very high yield (≥ 95%). We have tested this reaction with various solvents (THF, CH3CN and DMF) and hydro­chlorides of different amino esters, viz. glycine ethyl ester, L-valine methyl ester, L-alanine ethyl ester and L-phenyl­alanine methyl ester. N-(Boc)thio­acetamide was prepared as described in the literature (Lee et al., 1998[Lee, H. K., Ten, L. N. & Pak, C. S. (1998). Bull. Korean Chem. Soc. 19, 1148-1149.]).

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 4[link]. A least-squares refinement, based on |F|2 of all reflections, was carried out with the program MoPro (Jelsch et al., 2005[Jelsch, C., Guillot, B., Lagoutte, A. & Lecomte, C. (2005). J. Appl. Cryst. 38, 38-54.]) using the ELMAM2 electron-density database (Domagała et al., 2012[Domagała, S., Fournier, B., Liebschner, D., Guillot, B. & Jelsch, C. (2012). Acta Cryst. A68, 337-351.]). In this approach, scale factors, atomic positions and displacement parameters for all atoms were varied, but a multipolar charged-atom model was applied until convergence. The H—X distances were constrained to the standard values in neutron diffraction studies (Allen & Bruno, 2010[Allen, F. H. & Bruno, I. J. (2010). Acta Cryst. B66, 380-386.]). The anisotropic displacement parameters of hydrogen atoms were constrained to the values obtained from the SHADE3 server (Madsen & Hoser, 2014[Madsen, A. Ø. & Hoser, A. A. (2014). J. Appl. Cryst. 47, 2100-2104.]). Two subsets of the mol­ecule (O-t-butyl moiety and the rest of the mol­ecule) were used as input to the SHADE3 program to obtain better estimations of the Uani(H) displacement parameters. The use of a transferred multipolar atom model allowed the reduction of R(F) to 4.6% and wR2(F2) to 7.2%, compared to 6.1% and 11.8%, respectively, for the neutral-spherical atom model, as refined in MoPro. The r.m.s. residual electron density was likewise reduced from 0.042 to 0.034 e Å−3.

Table 4
Experimental details

Crystal data
Chemical formula C7H13NO3
Mr 159.18
Crystal system, space group Monoclinic, P21/n
Temperature (K) 293
a, b, c (Å) 6.0404 (6), 8.6114 (7), 17.6110 (17)
β (°) 98.771 (9)
V3) 905.35 (15)
Z 4
Radiation type Mo Kα
μ (mm−1) 0.09
Crystal size (mm) 0.15 × 0.1 × 0.08
 
Data collection
Diffractometer Bruker Kappa CCD
Absorption correction
No. of measured, independent and observed [I > 2 σ(I)] reflections 2405, 2059, 1627
Rint 0.035
(sin θ/λ)max−1) 0.650
 
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.034, 0.072, 1.00
No. of reflections 2059
No. of parameters 139
No. of restraints 31
H-atom treatment Only H-atom coordinates refined
Δρmax, Δρmin (e Å−3) 0.16, −0.17
Computer programs: APEX3 and SAINT (Bruker, 2016[Bruker (2016). APEX3 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]) and MoPro (Jelsch et al., 2005[Jelsch, C., Guillot, B., Lagoutte, A. & Lecomte, C. (2005). J. Appl. Cryst. 38, 38-54.]).

Supporting information


Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: MoPro (Jelsch et al., 2005); molecular graphics: MoPro (Jelsch et al., 2005); software used to prepare material for publication: MoPro (Jelsch et al., 2005).

tert-Butyl N-acetylcarbamate top
Crystal data top
C7H13NO3F(000) = 344
Mr = 159.18Dx = 1.168 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4200 reflections
a = 6.0404 (6) Åθ = 2.4–28.6°
b = 8.6114 (7) ŵ = 0.09 mm1
c = 17.6110 (17) ÅT = 293 K
β = 98.771 (9)°Block, colorless
V = 905.35 (15) Å30.15 × 0.1 × 0.08 mm
Z = 4
Data collection top
Bruker Kappa CCD
diffractometer
1627 reflections with I > 2 σ(I)
Radiation source: fine-focus sealed tubeRint = 0.035
Graphite monochromatorθmax = 27.5°, θmin = 2.6°
CCD scansh = 77
2405 measured reflectionsk = 011
2059 independent reflectionsl = 022
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.034Only H-atom coordinates refined
wR(F2) = 0.072 w = 1/[4.4*σ2(Fo2)]
S = 1.00(Δ/σ)max = 0.002
2059 reflectionsΔρmax = 0.16 e Å3
139 parametersΔρmin = 0.17 e Å3
31 restraintsExtinction correction: Isotropic Gaussian
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.51132
Special details top

Refinement. Refinement of F2 against reflections. The threshold expression of F2 > 2sigma(F2) is used for calculating R-factors(gt) 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
O10.38211 (11)0.355396 (15)0.40123 (4)0.05484 (14)
O20.63464 (12)0.29985 (8)0.32233 (4)0.06801 (17)
O30.73388 (12)0.08048 (8)0.46784 (4)0.06574 (16)
N10.57479 (13)0.14069 (8)0.42246 (5)0.05046 (16)
H10.474 (2)0.1271 (16)0.4629 (7)0.08754
C50.54053 (15)0.27070 (10)0.37571 (5)0.04754 (17)
C60.73373 (15)0.02549 (11)0.42216 (6)0.05121 (18)
C10.30097 (15)0.50254 (10)0.36327 (6)0.05446 (18)
C70.89889 (19)0.03248 (14)0.36770 (7)0.0716 (3)
H7A1.0210 (16)0.0607 (14)0.3829 (8)0.10454
H7B0.9899 (18)0.1427 (14)0.3755 (9)0.11089
H7C0.818 (2)0.0353 (17)0.3076 (6)0.11503
C40.18467 (19)0.46831 (14)0.28329 (7)0.0740 (3)
H4A0.3039 (17)0.4270 (16)0.2468 (6)0.10880
H4B0.106 (2)0.5761 (14)0.2597 (8)0.11611
H4C0.0505 (16)0.3836 (15)0.2852 (8)0.11411
C30.4904 (2)0.61607 (13)0.36559 (8)0.0758 (2)
H3A0.578 (2)0.6274 (16)0.4245 (8)0.11708
H3B0.419 (2)0.7310 (12)0.3505 (9)0.12094
H3C0.6142 (17)0.5881 (15)0.3283 (7)0.10779
C20.1345 (2)0.55587 (15)0.41419 (8)0.0822 (3)
H2A0.0073 (16)0.4648 (14)0.4127 (9)0.11714
H2B0.054 (2)0.6620 (14)0.3891 (8)0.12347
H2C0.232 (2)0.5828 (17)0.4703 (7)0.12492
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0660 (4)0.0489 (4)0.0515 (4)0.0085 (3)0.0150 (3)0.0127 (3)
O20.0786 (5)0.0669 (5)0.0644 (5)0.0061 (4)0.0300 (4)0.0184 (3)
O30.0745 (5)0.0484 (4)0.0771 (5)0.0077 (3)0.0204 (4)0.0162 (3)
N10.0599 (5)0.0439 (4)0.0495 (5)0.0021 (3)0.0144 (3)0.0091 (3)
H10.098720.083440.091800.027410.050870.03885
C50.0539 (5)0.0441 (5)0.0456 (5)0.0003 (4)0.0107 (4)0.0056 (4)
C60.0573 (5)0.0430 (5)0.0533 (5)0.0001 (4)0.0083 (4)0.0024 (4)
C10.0592 (5)0.0460 (5)0.0551 (5)0.0050 (4)0.0011 (4)0.0103 (4)
C70.0720 (7)0.0747 (7)0.0731 (7)0.0168 (6)0.0274 (6)0.0133 (6)
H7A0.098870.104120.117970.041000.040010.02395
H7B0.088220.094680.160180.000280.052290.03275
H7C0.144230.136210.069530.049030.031930.00590
C40.0757 (7)0.0794 (8)0.0597 (7)0.0079 (6)0.0129 (5)0.0126 (6)
H4A0.127760.133820.062630.002850.007470.00354
H4B0.119330.112720.101740.012870.029730.03707
H4C0.098930.116740.115380.034900.019840.00269
C30.0723 (7)0.0514 (6)0.0968 (9)0.0083 (5)0.0096 (6)0.0110 (6)
H3A0.114670.095110.123960.016590.037800.00724
H3B0.117020.056110.179400.003320.010310.02819
H3C0.087550.094300.143620.015230.024330.02842
C20.0844 (8)0.0751 (8)0.0889 (9)0.0249 (6)0.0193 (6)0.0046 (7)
H2A0.097350.113230.151600.015620.053420.02003
H2B0.125610.094160.151810.053400.024950.01964
H2C0.153920.132170.088980.049220.019500.01800
Geometric parameters (Å, º) top
O1—C51.3344 (11)C7—H7A1.0950
O1—C11.4808 (9)C7—H7B1.0950
O2—C51.1970 (11)C4—H4C1.0950
O3—C61.2164 (11)C4—H4A1.0950
N1—C51.3864 (12)C4—H4B1.0950
N1—C61.3811 (12)C3—H3C1.0950
N1—H11.013 (8)C3—H3B1.0950
C6—C71.4868 (15)C3—H3A1.0950
C1—C31.5009 (14)C2—H2C1.0950
C1—C41.5042 (15)C2—H2B1.0950
C1—C21.5170 (16)C2—H2A1.0950
C7—H7C1.0950
C5—O1—C1121.38 (6)H7C—C7—H7B104 (1)
C5—N1—C6128.22 (7)H7A—C7—H7B107.3 (8)
C5—N1—H1117.3 (7)C1—C4—H4C110.1 (7)
C6—N1—H1114.4 (7)C1—C4—H4A111.0 (6)
O1—C5—O2126.91 (8)C1—C4—H4B107.6 (6)
O1—C5—N1106.93 (7)H4C—C4—H4A111 (1)
O2—C5—N1126.15 (7)H4C—C4—H4B107.3 (10)
O3—C6—N1117.82 (7)H4A—C4—H4B110 (1)
O3—C6—C7121.61 (8)C1—C3—H3C115.4 (7)
N1—C6—C7120.57 (8)C1—C3—H3B108.2 (6)
O1—C1—C3110.28 (7)C1—C3—H3A109.8 (7)
O1—C1—C4109.28 (7)H3C—C3—H3B109 (1)
O1—C1—C2101.29 (7)H3C—C3—H3A108.3 (10)
C3—C1—C4113.48 (8)H3B—C3—H3A105 (1)
C3—C1—C2110.99 (9)C1—C2—H2C106.5 (7)
C4—C1—C2110.85 (9)C1—C2—H2B107.8 (8)
C6—C7—H7C112.4 (7)C1—C2—H2A107.1 (7)
C6—C7—H7A107.8 (6)H2C—C2—H2B109.3 (10)
C6—C7—H7B109.1 (7)H2C—C2—H2A117 (1)
H7C—C7—H7A115.8 (9)H2B—C2—H2A108.8 (10)
O1—C5—N1—C6174.66 (12)H1—N1—C6—C7178 (1)
O1—C5—N1—H14 (1)C5—O1—C1—C360.18 (11)
O1—C1—C3—H3C71.1 (8)C5—O1—C1—C465.21 (11)
O1—C1—C3—H3B166.1 (9)C5—O1—C1—C2177.77 (12)
O1—C1—C3—H3A51.6 (9)C5—N1—C6—C71.01 (14)
O1—C1—C4—H4C55.5 (7)C4—C1—C3—H3C51.9 (7)
O1—C1—C4—H4A67.8 (7)C4—C1—C3—H3B70.9 (7)
O1—C1—C4—H4B172.1 (9)C4—C1—C3—H3A174.6 (9)
O1—C1—C2—H2C66.4 (7)C4—C1—C2—H2C177.8 (9)
O1—C1—C2—H2B176.4 (7)C4—C1—C2—H2B60.5 (7)
O1—C1—C2—H2A59.4 (7)C4—C1—C2—H2A56.4 (8)
O2—C5—O1—C10.45 (12)H4A—C4—C1—C356 (1)
O2—C5—N1—C65.90 (14)H4A—C4—C1—C2179 (1)
O2—C5—N1—H1175 (1)H4B—C4—C1—C364 (1)
O3—C6—N1—C5179.23 (13)H4B—C4—C1—C261 (1)
O3—C6—N1—H12 (1)H4C—C4—C1—C3179 (1)
O3—C6—C7—H7C121.4 (9)H4C—C4—C1—C255 (1)
O3—C6—C7—H7A7.4 (8)C3—C1—C2—H2C50.7 (7)
O3—C6—C7—H7B123.6 (8)C3—C1—C2—H2B66.5 (8)
N1—C5—O1—C1178.99 (12)C3—C1—C2—H2A176.5 (8)
N1—C6—C7—H7C58.8 (8)H3A—C3—C1—C260 (1)
N1—C6—C7—H7A172.4 (8)H3B—C3—C1—C255 (1)
N1—C6—C7—H7B56.1 (8)H3C—C3—C1—C2177 (1)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C4—H4A···O21.102.483.0651 (14)112
C3—H3C···O21.102.492.9928 (15)107
N1—H1···O3i1.01 (1)1.92 (1)2.9285 (11)173 (1)
Symmetry code: (i) x+1, y, z+1.
Statistical analysis of intermolecular contacts on the Hirshfeld surface top
H-c and H-n signify hydrogen atoms bound to C (hydrophobic) and N (hydrophilic), respectively. Reciprocal contacts (X···Y and Y···X) are merged. The most prevalent and enriched contacts are highlighted in bold.
AtomH-nNOH-cC
Sx (%)5.51.515.564.013.5
Cxy (%) (Exy)
H-n0.4 (1.39)
N0 (0)0 (0)
O5.9 (3.41)0 (0)0.4 (0.16)
H-c4.2 (0.59)2.8 (1.46)20.8 (1.04)41.6 (0.99)
C0.2 (0.13)0.1 (0.41)3.4 (0.86)18.5 (1.12)1.6 (1.00)
X-ray fluorescence (XRF) analysis (%) of natural phosphate top
SiO2TiO2Al2O3Fe2O3MgOCaONa2OK2OMnOP2O5SO3
14.170.05817.510.5300.24531.660.3190.1130.01626.180.060
 

Funding information

The authors are grateful to Ministère de l'Enseignement Supéreur et de la Recherche Scientifique de la République Islamique de Mauritanie and the Service de Coopération et d'Action Culturelle (SCAC) de l'Ambassade de France en Mauritanie for financial support.

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