Propane-1,3-di­ammonium molybdate

Wane, A.; Kama, A.B.; Diop, M.B.; Diop, L.; Plasseraud, L.; Cattey, H.

doi:10.1107/S2414314619005005

metal-organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 4| Part 4| April 2019| x190500

https://doi.org/10.1107/S2414314619005005

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Propane-1,3-diammonium molybdate

Alioune Wane,^a Antoine Blaise Kama,^a Mouhamadou Birame Diop,^a ^* Libasse Diop,^a Laurent Plasseraud ^b and Hélène Cattey ^b

^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: mouhamadoubdiop@gmail.com

Edited by M. Weil, Vienna University of Technology, Austria (Received 25 March 2019; accepted 12 April 2019; online 16 April 2019)

The reaction between equimolar amounts of propane-1,3-diamine and molybdenum trioxide in water led to the formation of single crystals of the title salt, (C₃H₁₂N₂)[MoO₄]. The asymmetric unit is comprised of one propane-1,3-diammonium cation and one molybdate anion. The latter is isolated in the structure and has a slightly distorted tetrahedral configuration. An extensive network of N—H⋯O hydrogen bonds connects anions and cations, giving rise to a compact three-dimensional packing.

Keywords: crystal structure; molybdate salt; propane-1,3-diammonium; hydrogen bonds.

CCDC reference: 1909766

Structure description

In recent decades, oxyanions of metals from groups 5 and 6 in the periodic table (polyoxometalates, POMs) have attracted great interest in many fields (catalysis, medicine, functional materials and photochemistry) and continue to be extensively studied for energy applications (An et al., 2018 ). This is particularly the case for molybdenum compounds which constitute suitable building blocks for the assembly of more complex and unusual structures (Süss-Fink et al., 1997 ; Plasseraud et al., 1999 ).

Numerous crystal structures of hetero- and polyoxidomolybdates are known from the literature (Li & Xu, 2011 ). For mononuclear molybdates with tetrahedral anions, the first crystal structure determination was reported for Na₂[MoO₄]·2H₂O (Lindqvist, 1950 ; Matsumoto et al., 1975 ), followed by the potassium compound K₂[MoO₄] (Gatehouse & Leverett, 1969 ). Ammonium salts of [MoO₄]^2– have also been isolated in the solid state and their crystal structures determined: (CH₆N₃)₂[MoO₄] (Ozeki et al., 1987 ), (C₆H₁₄N)₂[MoO₄] and (C₁₂H₂₆N)₂[MoO₄]·2H₂O (Thiele & Fuchs, 1979 ), (C₂H₁₀N₂)[MoO₄] (Bensch et al., 1987 ), (C₄H₁₂NO)₂[MoO₄] (Sheikhshoaie & Ghazizadeh, 2013 ), (Cy₂NH₂)₂[MoO₄]·2H₂O (Pouye et al., 2014 ) and (ⁱPr₂NH₂)₂[MoO₄] (Sarr et al., 2018 ). In this context and in continuation of our studies of interactions between organic ammonium cations and transition-metal or main-group metal anions (Pouye et al., 2014; Diallo et al., 2014 ), we report here the crystal structure of (C₃H₁₂N₂)[MoO₄], (I).

The asymmetric unit of (I) consists of a propane 1,3-diammonium cation and a molybdate anion (Fig. 1). Several crystal structures of salts containing the propane-1,3-diammonium dication are reported in the literature (e.g. Ayadi et al., 2017 ; Kamoun et al., 1992 ). Bond lengths and angles of the (C₃H₁₂N₂)²⁺ cation in (I) are in accordance with those reported previously for other oxidometalate salts, such as {(C₃H₁₂N₂)[Mo₃O₁₀]·2H₂O}_n (Ding et al., 2007 ) or (C₃H₁₂N₂)[Cr₂O₇] (Trabelsi et al., 2012 ). A search of the Cambridge Structural Database (WebCSD; Thomas et al., 2010 ) revealed 30 crystal structures of salts involving the propane-1,3-diammonium cation associated with anions containing molybdenum. The [MoO₄]²⁻ anion in (I) exhibits a slightly distorted tetrahedral configuration. Three of the four Mo—O bond lengths (involving O2, O3 and O4; Table 1) are in the range of those reported in the literature (Bensch et al., 1987; Sarr et al., 2018). The fourth (involving O1; Table 1) is considerably longer because it is the acceptor atom of three hydrogen bonds, whereas the other O atoms are involved in only one hydrogen bond each. From a supramolecular point of view, the (C₃H₁₂N₂)²⁺ cations and [MoO₄]²⁻ anions are connected via several N—H⋯O hydrogen bonds, with D⋯A contacts ranging from 2.6808 (19) to 2.8512 (18) Å (Table 2). Each molybdate anion is surrounded by six propane-1,3-diammonium cations, and each of the cations is hydrogen bonded to five neighbouring anions. These interactions lead to a three-dimensional network structure (Fig. 2).

Table 1
Selected geometric parameters (Å, °)

Mo—O1	1.8035 (12)	Mo—O3	1.7548 (12)
Mo—O2	1.7536 (12)	Mo—O4	1.7547 (13)

O2—Mo—O1	108.69 (6)	O3—Mo—O1	109.06 (6)
O2—Mo—O3	108.94 (6)	O4—Mo—O1	111.04 (6)
O2—Mo—O4	109.52 (6)	O4—Mo—O3	109.55 (7)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3ⁱ	0.91	1.85	2.7550 (19)	173
N1—H1B⋯O1	0.91	2.00	2.8512 (18)	156
N1—H1C⋯O2ⁱⁱ	0.91	1.89	2.7670 (19)	163
N2—H2A⋯O1ⁱⁱⁱ	0.91	1.93	2.8048 (18)	162
N2—H2B⋯O1^iv	0.91	1.87	2.7690 (18)	170
N2—H2C⋯O4	0.91	1.80	2.6808 (19)	162
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x-1, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iv) x-1, y, z.

Figure 1
The expanded asymmetric unit of (I). Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds are shown as dotted lines. [Symmetry codes: (i) x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (ii) −x + 2, y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (iii) x − 1, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ ; (iv) x − 1, y, z.]

Figure 2
Partial packing diagram of (I), showing the intermolecular hydrogen-bonding scheme (dashed lines). Colour code: C dark grey, H white, O red, N blue and Mo blue metal.

The crystal structure of the tetrathiomolybdate analog of (I), i.e. (C₃H₁₂N₂)[MoS₄] (Srinivasan et al., 2005 ), is comprised of the same building units [an organic (C₃H₁₂N₂)²⁺ cation and a tetrahedral [MoS₄]²⁻ anion] but is not isotypic. However, the crystal structure of (C₃H₁₂N₂)[MoS₄] likewise is consolidated by hydrogen bonds between the cation and the anion (here of type N—H⋯S).

Synthesis and crystallization

All chemicals were purchased from Sigma–Aldrich (Germany) and used without further purification. The title salt was prepared by mixing equimolar amounts of propane-1,3-diamine (0.50 g, 6.75 mmol) and molybdenum trioxide (0.97 g, 6.75 mmol) in 25 ml of water (75% yield). Colourless prismatic crystals, suitable for X-ray crystallographic analysis, were obtained by slow evaporation (10 d) at 333 K.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 3.

Table 3
Experimental details

Crystal data
Chemical formula	(C₃H₁₂N₂)[MoO₄]
M_r	236.09
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	100
a, b, c (Å)	6.4849 (3), 14.7539 (7), 8.3224 (4)
β (°)	97.2950 (13)
V (Å³)	789.82 (6)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	1.63
Crystal size (mm)	0.55 × 0.45 × 0.30

Data collection
Diffractometer	Bruker D8 Venture Cu
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.613, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	11859, 1813, 1780
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.016, 0.041, 1.11
No. of reflections	1813
No. of parameters	93
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.69, −0.48
Computer programs: APEX3 (Bruker, 2016), SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL2018 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1909766

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314619005005/wm4103sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314619005005/wm4103Isup2.hkl

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Propane-1,3-diammonium molybdate top

Crystal data top

(C₃H₁₂N₂)[MoO₄]	F(000) = 472
M_r = 236.09	D_x = 1.985 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 6.4849 (3) Å	Cell parameters from 9941 reflections
b = 14.7539 (7) Å	θ = 2.8–27.6°
c = 8.3224 (4) Å	µ = 1.63 mm⁻¹
β = 97.2950 (13)°	T = 100 K
V = 789.82 (6) Å³	Prism, colourless
Z = 4	0.55 × 0.45 × 0.30 mm

Data collection top

Bruker D8 Venture Cu diffractometer	1813 independent reflections
Radiation source: sealed X-ray tube, high brilliance microfocus sealed tube, Cu	1780 reflections with I > 2σ(I)
QUAZAR MX multilayer optics monochromator	R_int = 0.024
Detector resolution: 1024 x 1024 pixels mm^-1	θ_max = 27.6°, θ_min = 2.8°
φ and ω scans'	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −19→19
T_min = 0.613, T_max = 0.746	l = −10→10
11859 measured reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.016	H-atom parameters constrained
wR(F²) = 0.041	w = 1/[σ²(F_o²) + (0.0135P)² + 1.0699P] where P = (F_o² + 2F_c²)/3
S = 1.11	(Δ/σ)_max = 0.001
1813 reflections	Δρ_max = 0.69 e Å⁻³
93 parameters	Δρ_min = −0.48 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.8168 (2)	0.43213 (10)	0.26436 (16)	0.0097 (3)
H1A	0.810512	0.429665	0.154588	0.012*
H1B	0.855824	0.377091	0.307292	0.012*
H1C	0.911423	0.474723	0.303924	0.012*
N2	0.2514 (2)	0.27700 (9)	0.08732 (17)	0.0100 (3)
H2A	0.183145	0.271475	−0.014722	0.012*
H2B	0.157872	0.275641	0.160109	0.012*
H2C	0.342784	0.230364	0.107595	0.012*
C1	0.6079 (3)	0.45664 (11)	0.3092 (2)	0.0123 (3)
H1D	0.554783	0.510294	0.245464	0.015*
H1E	0.622845	0.473537	0.425179	0.015*
C2	0.4506 (3)	0.38039 (12)	0.2796 (2)	0.0114 (3)
H2D	0.332328	0.393725	0.340245	0.014*
H2E	0.516258	0.323603	0.324156	0.014*
C3	0.3666 (3)	0.36483 (11)	0.1021 (2)	0.0109 (3)
H3A	0.272418	0.415035	0.062280	0.013*
H3B	0.482908	0.363095	0.035692	0.013*
Mo	0.83296 (2)	0.14663 (2)	0.25817 (2)	0.00677 (6)
O1	0.96985 (18)	0.25143 (8)	0.30707 (14)	0.0106 (2)
O2	0.9652 (2)	0.08535 (8)	0.12245 (15)	0.0143 (2)
O3	0.8303 (2)	0.08287 (9)	0.43589 (15)	0.0170 (3)
O4	0.5768 (2)	0.16715 (9)	0.17004 (17)	0.0179 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0096 (6)	0.0081 (6)	0.0110 (7)	0.0003 (5)	0.0000 (5)	−0.0004 (5)
N2	0.0087 (6)	0.0110 (6)	0.0097 (6)	0.0004 (5)	−0.0009 (5)	0.0004 (5)
C1	0.0108 (7)	0.0118 (7)	0.0143 (8)	0.0019 (6)	0.0014 (6)	−0.0042 (6)
C2	0.0114 (7)	0.0135 (8)	0.0091 (7)	−0.0010 (6)	0.0005 (6)	−0.0010 (6)
C3	0.0108 (7)	0.0112 (7)	0.0104 (8)	−0.0013 (6)	−0.0005 (6)	0.0009 (6)
Mo	0.00632 (8)	0.00583 (8)	0.00786 (8)	0.00055 (4)	−0.00030 (5)	0.00027 (4)
O1	0.0102 (5)	0.0090 (5)	0.0122 (5)	−0.0007 (4)	−0.0005 (4)	0.0001 (4)
O2	0.0168 (6)	0.0135 (6)	0.0126 (6)	0.0037 (5)	0.0017 (5)	−0.0017 (5)
O3	0.0243 (7)	0.0140 (6)	0.0131 (6)	−0.0004 (5)	0.0044 (5)	0.0040 (5)
O4	0.0104 (6)	0.0145 (6)	0.0270 (7)	0.0021 (5)	−0.0051 (5)	−0.0014 (5)

Geometric parameters (Å, º) top

N1—H1A	0.9100	C1—C2	1.518 (2)
N1—H1B	0.9100	C2—H2D	0.9900
N1—H1C	0.9100	C2—H2E	0.9900
N1—C1	1.494 (2)	C2—C3	1.526 (2)
N2—H2A	0.9100	C3—H3A	0.9900
N2—H2B	0.9100	C3—H3B	0.9900
N2—H2C	0.9100	Mo—O1	1.8035 (12)
N2—C3	1.493 (2)	Mo—O2	1.7536 (12)
C1—H1D	0.9900	Mo—O3	1.7548 (12)
C1—H1E	0.9900	Mo—O4	1.7547 (13)

H1A—N1—H1B	109.5	C1—C2—H2D	108.6
H1A—N1—H1C	109.5	C1—C2—H2E	108.6
H1B—N1—H1C	109.5	C1—C2—C3	114.72 (14)
C1—N1—H1A	109.5	H2D—C2—H2E	107.6
C1—N1—H1B	109.5	C3—C2—H2D	108.6
C1—N1—H1C	109.5	C3—C2—H2E	108.6
H2A—N2—H2B	109.5	N2—C3—C2	108.87 (13)
H2A—N2—H2C	109.5	N2—C3—H3A	109.9
H2B—N2—H2C	109.5	N2—C3—H3B	109.9
C3—N2—H2A	109.5	C2—C3—H3A	109.9
C3—N2—H2B	109.5	C2—C3—H3B	109.9
C3—N2—H2C	109.5	H3A—C3—H3B	108.3
N1—C1—H1D	109.0	O2—Mo—O1	108.69 (6)
N1—C1—H1E	109.0	O2—Mo—O3	108.94 (6)
N1—C1—C2	113.10 (13)	O2—Mo—O4	109.52 (6)
H1D—C1—H1E	107.8	O3—Mo—O1	109.06 (6)
C2—C1—H1D	109.0	O4—Mo—O1	111.04 (6)
C2—C1—H1E	109.0	O4—Mo—O3	109.55 (7)

N1—C1—C2—C3	−74.84 (18)	C1—C2—C3—N2	167.95 (13)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱ	0.91	1.85	2.7550 (19)	173
N1—H1B···O1	0.91	2.00	2.8512 (18)	156
N1—H1C···O2ⁱⁱ	0.91	1.89	2.7670 (19)	163
N2—H2A···O1ⁱⁱⁱ	0.91	1.93	2.8048 (18)	162
N2—H2B···O1^iv	0.91	1.87	2.7690 (18)	170
N2—H2C···O4	0.91	1.80	2.6808 (19)	162

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+2, y+1/2, −z+1/2; (iii) x−1, −y+1/2, z−1/2; (iv) x−1, y, z.

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).

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