(Di­methyl­phosphor­yl)methanaminium nitrate

Bianga, C.M.; Eggeling, J.; Reiss, G.J.

doi:10.1107/S1600536813027694

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 11| November 2013| Pages o1639-o1640

doi:10.1107/S1600536813027694

Open

access

(Dimethylphosphoryl)methanaminium nitrate

Claudia M. Bianga,^a Julia Eggeling ^a and Guido J. Reiss ^a ^*

^aInstitut für Anorganische Chemie und Strukturchemie, Lehrstuhl II: Material- und Strukturforschung, Heinrich-Heine-Universität Düsseldorf, Universitätsstrasse 1, D-40225 Düsseldorf, Germany
^*Correspondence e-mail: reissg@hhu.de

(Received 22 September 2013; accepted 9 October 2013; online 16 October 2013)

In the crystal of the title salt, C₃H₁₁NOP⁺·NO₃⁻, dicationic inversion dimers are head-to-tail connected by a pair of strong N—H⋯O hydrogen bonds. The resulting graph-set descriptor of this ring system is R₂²(10). The nitrate counter-anions connect the dicationic dimers via N—H⋯O hydrogen bonds, forming two-dimensional networks in the bc plane.

CCDC reference: 965649

Related literature

For transition metal complexes of the (dimethylphosphoryl)methanamine (dpma) ligand, see: Dodoff et al. (1990 ); Borisov et al. (1994 ); Trendafilova et al. (1997 ); Kochel (2009 ). For transition metal complexes of the protonated dpmaH⁺ ligand, see: Reiss (2013a ,b ). For simple dpmaH⁺ salts, see: Reiss & Jörgens (2012 ); Lambertz et al. (2013 ); Buhl et al. (2013 ); Reiss (2013c ,d ). For a definition of the term tecton, see: Brunet et al. (1997 ). For a definition of the term antitype, see: Lima-de-Faria et al. (1990 ). For graph-set theory, see: Etter et al.(1990 ); Grell et al. (2002 ). For structures showing an analogous topology, see: Holl & Thewalt (1986 ); Reiss (2002 ); Reiss & Helmbrecht (2012 ).

Experimental

Crystal data

C₃H₁₁NOP⁺·NO₃⁻
M_r = 170.11
Monoclinic, P 2₁ /c
a = 8.7718 (3) Å
b = 7.9892 (3) Å
c = 11.2921 (6) Å
β = 96.581 (4)°
V = 786.14 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 290 K
0.63 × 0.38 × 0.19 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.809, T_max = 1.000
82785 measured reflections
3770 independent reflections
3313 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.065
S = 1.01
3770 reflections
106 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H11⋯O2	0.894 (14)	1.966 (15)	2.8555 (11)	173.1 (12)
N1—H12⋯O3ⁱ	0.902 (14)	1.979 (14)	2.8784 (12)	174.5 (13)
N1—H13⋯O1ⁱⁱ	0.874 (14)	1.888 (14)	2.7493 (10)	168.2 (13)
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x, -y+1, -z.

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXL2013 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2013; molecular graphics: DIAMOND (Brandenburg, 2012 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 965649

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536813027694/lh5656sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813027694/lh5656Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813027694/lh5656Isup3.cml

checkCIF report

Comment top

There are several reports which prove the ability of the bidentate dpma ligand (dpma = (dimethylphosphoryl)methanamine) to coordinate a variety of transition metals (Dodoff et al., 1990; Borisov et al., 1994; Trendafilova et al., 1997; Kochel, 2009). Additionally, two metal complexes containing the dpmaH⁺ cation have been structurally characterized so far (Reiss, 2013a,b). For simple dpmaH⁺ salt structures it has been shown that this tecton (Brunet et al., 1997) can be used to construct hydrogen bonded one-dimensional polymers (Reiss & Jörgens, 2012; Lambertz et al., 2013; Buhl et al., 2013; Reiss, 2013c). Only for the double salt (H₃O)dpmaHBr the ions are connected by hydrogen bonds, forming a two-dimensional network (Reiss, 2013d)

The title compound dpmaHNO₃ crystallizes in the monoclinic space group, P2₁/c, with one dpmaH⁺ cation and one nitrate anion in the asymmetric unit. The angles and bond lengths of both ions are all in the typical ranges. The dpmaH⁺ cation features the hydrogen bond donor group NH₃⁺ at the one end and the hydrogen bond accepting group –P=O at the other end. Therefore, this tecton in principle is capable to form connections among other dpmaH⁺ cations and to counter anions. In the title structure two dpmaH⁺ cations are connected by two strong, charge supported –NH⁺···O=P– hydrogen bonds (N···O = 2.7493 (10) Å) head to tail forming cyclic dimers (Fig. 1; first level graph-set descriptor: R₂²(10); Etter et al.,1990; Grell et al., 2002). Moreover, each dimer is associated by charge supported, strong –NH⁺···O≐ N– hydrogen bonds (N···O = 2.8555 (11) Å, 2.8784 (12) Å) to four adjacent nitrate counter anions (Fig. 2). Consequently, each nitrate anion forms two hydrogen bonds to two adjacent dicationic dimers constructing a two-dimensional network in the bc plane. The dimers act as a tetradentate hydrogen bond donor. The nitrate anions act as bidentate hydrogen bond acceptors by two of their oxygen atoms.

In three related structures built up by the complex anions [SnCl₆]^2- and [IrCl₆]^2- these anions are tetradentate hydrogen bond acceptors whereas the simple diisopropylammonium (Reiss, 2002; Reiss & Helmbrecht, 2012) and the aminothiodithiazyl ((S₃N₂)NH₂)⁺ (Holl & Thewalt, 1986) counter cations are bidentate hydrogen bond donors. The title structure can be understood as the antitype (Lima-de-Faria et al. 1990) of these hexahalogenometallate salts.

Related literature top

For transition metal complexes of the dpma ligand, see: Dodoff et al. (1990); Borisov et al. (1994); Trendafilova et al. (1997); Kochel (2009). For transition metal complexes of the protonated dpmaH⁺ ligand, see: Reiss (2013a,b). For simple dpmaH⁺ salts, see: Reiss & Jörgens (2012); Lambertz et al. (2013); Buhl et al. (2013); Reiss (2013c,d). For a definition of the term tecton, see: Brunet et al. (1997). For a definition of the term antitype, see: Lima-de-Faria et al. (1990). For graph-set theory, see: Etter et al.(1990); Grell et al. (2002). For structures showing an analogous topology, see: Holl & Thewalt (1986); Reiss (2002); Reiss & Helmbrecht (2012).

Experimental top

The title compound was synthesized by dissolving 1.07 g (10.0 mmol) (dimethylphosphoryl)methanamine in dilute nitric acid (2 ml, 12%) while the mixture was heated. After a few days colourless platelets were obtained by slow evaporation of the solvent at room temperature.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXL2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2012); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. A view of the asymmetric unit of the title structure together with a symmetry related cation and their hydrogen bonds (dashed lines) to adjacent ions. Displacement ellipsoids are drawn at the 45% probability level (' = –x, 1 – y, –z). The green numbers mark the ring size of the first level R₂²(10) graph-set descriptor for the cyclic dimer consisting of two dpmaH⁺ cations.)
	Fig. 2. View along [100] on the two-dimensional network of the title structure. Hydrogen bonds are shown as dashed lines.

(Dimethylphosphoryl)methanaminium nitrate top

Crystal data top

C₃H₁₁NOP⁺·NO₃⁻	F(000) = 360
M_r = 170.11	D_x = 1.437 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.7718 (3) Å	Cell parameters from 40230 reflections
b = 7.9892 (3) Å	θ = 3.8–36.3°
c = 11.2921 (6) Å	µ = 0.32 mm⁻¹
β = 96.581 (4)°	T = 290 K
V = 786.14 (6) Å³	Block, colourless
Z = 4	0.63 × 0.38 × 0.19 mm

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	3770 independent reflections
Radiation source: fine-focus sealed tube	3313 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
Detector resolution: 16.2711 pixels mm^-1	θ_max = 36.4°, θ_min = 3.8°
ω scans	h = −14→14
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −13→13
T_min = 0.809, T_max = 1.000	l = −18→18
82785 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.030	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.065	w = 1/[σ²(F_o²) + (0.011P)² + 0.3P] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max = 0.001
3770 reflections	Δρ_max = 0.40 e Å⁻³
106 parameters	Δρ_min = −0.34 e Å⁻³
0 restraints	Extinction correction: SHELXL2013 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0296 (13)

Crystal data top

C₃H₁₁NOP⁺·NO₃⁻	V = 786.14 (6) Å³
M_r = 170.11	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.7718 (3) Å	µ = 0.32 mm⁻¹
b = 7.9892 (3) Å	T = 290 K
c = 11.2921 (6) Å	0.63 × 0.38 × 0.19 mm
β = 96.581 (4)°

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	3770 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	3313 reflections with I > 2σ(I)
T_min = 0.809, T_max = 1.000	R_int = 0.032
82785 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.065	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.40 e Å⁻³
3770 reflections	Δρ_min = −0.34 e Å⁻³
106 parameters

Special details top

Experimental. The Raman spectrum was measured using a Bruker MULTIRAM spectrometer (Nd:YAG-Laser at 1064 nm; RT-InGaAs-detector; backscattering geometry); 4000–70 cm^-1: 3112 (w), 2994 (s), 2952 (m), 2916 (s), 2854 (w), 2834 (w), 2804 (w), 2654 (w), 2625 (w), 2588 (w), 1645 (w), 1615 (w), 1549 (w), 1430 (w), 1407 (w), 1373 (w), 1309 (w), 1155 (m), 1126 (w), 1092 (w), 1046 (s), 1029 (w), 947 (w), 918 (w), 895 (w), 858 (w), 787 (w), 759 (w), 726 (m), 662 (s), 456 (w), 369 (w), 314 (m), 295 (w), 268 (w), 238 (w), 137 (w), 121 (m), 95 (s), 73 (s). – IR spectroscopic data were recorded on a Digilab FT3400 spectrometer using a MIRacle ATR unit (Pike Technologies); 4000–560 cm^-1: 3439 (w), 2993 (s), 2946 (s), 2915 (s), 2885 (s), 2830 (s), 2749 (m), 2722 (m), 2651 (m), 2625 (m), 2403 (w), 2066 (w), 1757 (w), 1638 (m), 1551 (m), 1432 (m), 1420 (m), 1405 (m), 1346 (s), 1330 (s), 1306 (s), 1297 (s), 1157 (s), 1119 (m), 1088 (s), 1045 (w), 1029 (w), 944 (s), 914 (m), 889 (s), 855 (m), 826 (m), 784 (m), 756 (m), 723 (w), 714 (w), 657 (w).

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.

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

	x	y	z	U_iso*/U_eq
P1	0.16112 (2)	0.75856 (3)	0.06006 (2)	0.02633 (6)
O1	0.04435 (8)	0.70859 (9)	−0.04036 (6)	0.03792 (15)
N1	0.24474 (9)	0.42711 (10)	0.08323 (7)	0.03066 (14)
H11	0.2939 (15)	0.3482 (18)	0.1290 (12)	0.050 (4)*
H12	0.2989 (15)	0.4449 (17)	0.0211 (13)	0.051 (4)*
H13	0.1553 (16)	0.3832 (18)	0.0591 (12)	0.052 (4)*
C1	0.09272 (13)	0.90021 (14)	0.16403 (10)	0.0431 (2)
H1A	0.0774	1.0085	0.1278	0.065*
H1B	0.1667	0.9085	0.2333	0.065*
H1C	−0.0027	0.8598	0.1869	0.065*
C2	0.32841 (11)	0.84891 (13)	0.00985 (10)	0.0400 (2)
H2A	0.3758	0.7689	−0.0377	0.060*
H2B	0.3994	0.8799	0.0774	0.060*
H2C	0.3000	0.9465	−0.0371	0.060*
C3	0.22309 (10)	0.57989 (11)	0.15315 (7)	0.02919 (15)
H3A	0.3190	0.6073	0.2007	0.035*
H3B	0.1473	0.5578	0.2073	0.035*
O2	0.41973 (10)	0.17393 (12)	0.21553 (7)	0.0511 (2)
O3	0.41189 (9)	0.03797 (10)	0.37965 (7)	0.04730 (19)
O4	0.26575 (11)	0.25210 (12)	0.33988 (9)	0.0596 (2)
N2	0.36518 (9)	0.15533 (10)	0.31187 (7)	0.03293 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
P1	0.02420 (9)	0.02590 (9)	0.02829 (10)	−0.00258 (7)	0.00046 (7)	0.00021 (7)
O1	0.0351 (3)	0.0393 (3)	0.0364 (3)	−0.0046 (3)	−0.0083 (3)	−0.0003 (3)
N1	0.0296 (3)	0.0285 (3)	0.0324 (3)	0.0006 (3)	−0.0028 (3)	0.0034 (3)
C1	0.0432 (5)	0.0381 (5)	0.0488 (5)	0.0000 (4)	0.0091 (4)	−0.0112 (4)
C2	0.0363 (4)	0.0384 (5)	0.0463 (5)	−0.0080 (4)	0.0093 (4)	0.0071 (4)
C3	0.0303 (4)	0.0314 (4)	0.0255 (3)	−0.0033 (3)	0.0015 (3)	0.0026 (3)
O2	0.0497 (4)	0.0641 (5)	0.0410 (4)	0.0132 (4)	0.0115 (3)	0.0187 (4)
O3	0.0484 (4)	0.0474 (4)	0.0467 (4)	0.0145 (3)	0.0078 (3)	0.0202 (3)
O4	0.0608 (5)	0.0584 (5)	0.0621 (5)	0.0296 (4)	0.0177 (4)	0.0120 (4)
N2	0.0290 (3)	0.0338 (4)	0.0346 (3)	0.0006 (3)	−0.0021 (3)	0.0046 (3)

Geometric parameters (Å, º) top

P1—O1	1.4927 (7)	C1—H1C	0.9600
P1—C1	1.7834 (10)	C2—H2A	0.9600
P1—C2	1.7851 (9)	C2—H2B	0.9600
P1—C3	1.8186 (9)	C2—H2C	0.9600
N1—C3	1.4777 (12)	C3—H3A	0.9700
N1—H11	0.894 (14)	C3—H3B	0.9700
N1—H12	0.902 (14)	O2—N2	1.2465 (11)
N1—H13	0.874 (14)	O3—N2	1.2494 (10)
C1—H1A	0.9600	O4—N2	1.2336 (11)
C1—H1B	0.9600

O1—P1—C1	114.62 (5)	H1B—C1—H1C	109.5
O1—P1—C2	112.60 (5)	P1—C2—H2A	109.5
C1—P1—C2	107.66 (5)	P1—C2—H2B	109.5
O1—P1—C3	111.27 (4)	H2A—C2—H2B	109.5
C1—P1—C3	102.61 (5)	P1—C2—H2C	109.5
C2—P1—C3	107.38 (5)	H2A—C2—H2C	109.5
C3—N1—H11	110.9 (9)	H2B—C2—H2C	109.5
C3—N1—H12	113.4 (9)	N1—C3—P1	112.81 (6)
H11—N1—H12	107.4 (12)	N1—C3—H3A	109.0
C3—N1—H13	109.4 (9)	P1—C3—H3A	109.0
H11—N1—H13	104.7 (12)	N1—C3—H3B	109.0
H12—N1—H13	110.7 (12)	P1—C3—H3B	109.0
P1—C1—H1A	109.5	H3A—C3—H3B	107.8
P1—C1—H1B	109.5	O4—N2—O2	120.16 (8)
H1A—C1—H1B	109.5	O4—N2—O3	120.34 (9)
P1—C1—H1C	109.5	O2—N2—O3	119.50 (8)
H1A—C1—H1C	109.5

O1—P1—C3—N1	40.98 (7)	C2—P1—C3—N1	−82.67 (7)
C1—P1—C3—N1	164.01 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O2	0.894 (14)	1.966 (15)	2.8555 (11)	173.1 (12)
N1—H12···O3ⁱ	0.902 (14)	1.979 (14)	2.8784 (12)	174.5 (13)
N1—H13···O1ⁱⁱ	0.874 (14)	1.888 (14)	2.7493 (10)	168.2 (13)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H11···O2	0.894 (14)	1.966 (15)	2.8555 (11)	173.1 (12)
N1—H12···O3ⁱ	0.902 (14)	1.979 (14)	2.8784 (12)	174.5 (13)
N1—H13···O1ⁱⁱ	0.874 (14)	1.888 (14)	2.7493 (10)	168.2 (13)

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

Acknowledgements

We thank E. Hammes for technical support. Furthermore, the funding by the 'Lehrförderfond' of the Heinrich-Heine-Universität Düsseldorf is gratefully acknowledged.

References

Borisov, G., Varbanov, S. G., Venanzi, L. M., Albinati, A. & Demartin, F. (1994). Inorg. Chem. 33, 5430–5437. CSD CrossRef CAS Web of Science Google Scholar
Brandenburg, K. (2012). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Brunet, P., Simard, M. & Wuest, J. D. (1997). J. Am. Chem. Soc. 119, 2737–2738. CSD CrossRef CAS Web of Science Google Scholar
Buhl, D., Gün, H., Jablonka, A. & Reiss, G. J. (2013). Crystals, 3, 350–362. CSD CrossRef CAS Google Scholar
Dodoff, N., Macicek, J., Angelova, O., Varbanov, S. G. & Spassovska, N. (1990). J. Coord. Chem. 22, 219–228. CrossRef CAS Google Scholar
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262. CrossRef CAS Web of Science IUCr Journals Google Scholar
Grell, J., Bernstein, J. & Tinhofer, G. (2002). Crystallogr. Rev. 8, 1–56. CrossRef CAS Google Scholar
Holl, K. & Thewalt, U. (1986). Z. Naturforsch. Teil B, 41, 581–586. Google Scholar
Kochel, A. (2009). Inorg. Chim. Acta, 362, 1379–1382. Web of Science CSD CrossRef CAS Google Scholar
Lambertz, C., Luppa, A. & Reiss, G. J. (2013). Z. Kristallogr. New Cryst. Struct. 228, 227–228. CAS Google Scholar
Lima-de-Faria, J., Hellner, E., Liebau, F., Makovicky, E. & Parthé, E. (1990). Acta Cryst. A46, 1–11. CrossRef CAS IUCr Journals Google Scholar
Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Reiß, G. J. (2002). Acta Cryst. E58, m47–m50. Web of Science CSD CrossRef IUCr Journals Google Scholar
Reiss, G. J. (2013a). Acta Cryst. E69, m248–m249. CSD CrossRef CAS IUCr Journals Google Scholar
Reiss, G. J. (2013b). Acta Cryst. E69, m250–m251. CSD CrossRef CAS IUCr Journals Google Scholar
Reiss, G. J. (2013c). Acta Cryst. E69, o1253–o1254. CSD CrossRef CAS IUCr Journals Google Scholar
Reiss, G. J. (2013d). Z. Kristallogr. New Cryst. Struct. 228, 431–433. CAS Google Scholar
Reiss, G. J. & Helmbrecht, C. (2012). Acta Cryst. E68, m1402–m1403. CSD CrossRef CAS IUCr Journals Google Scholar
Reiss, G. J. & Jörgens, S. (2012). Acta Cryst. E68, o2899–o2900. CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Trendafilova, N., Georgieva, I., Bauer, G., Varbanov, S. G. & Dodoff, N. (1997). Spectrochim. Acta Part A, 53, 819–828. CrossRef Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar