(Di-methyl-phosphor-yl)methanaminium hydrogen oxalate-oxalic acid (2/1).

The reaction of (di-methyl-phosphor-yl)methanamine (dpma) with oxalic acid in ethanol yielded the title solvated salt, C3H11NOP(+)·C2HO4 (-)·0.5C2H2O4. Its asymmetric unit consists of one dpmaH(+) cation, one hydrogen oxalate anion and a half-mol-ecule of oxalic acid located around a twofold rotation axis. The H atom of the hydrogen oxalate anion is statistically disordered over two positions that are trans to each other. The hydrogen oxalate monoanion is not planar (bend angle ∼16°) whereas the oxalic acid molecule shows a significantly smaller bend angle (∼7°). In the crystal, the components are connected by strong O-H⋯O and much weaker N-H⋯O hydrogen bonds, leading to the formation of layers extending parallel to (001). The structure was refined from a racemically twinned crystal with twin components in an approximate 1:1 ratio.

Related literature

For transition metal complexes of the cationic dpmaH+ ligand, see: Reiss (2013a ▶,c ▶). For simple dpmaH+ salts, see: Reiss & Jörgens (2012 ▶); Bianga et al. (2013 ▶); Buhl et al. (2013 ▶); Lambertz et al. (2013 ▶); Reiss (2013b ▶,d ▶).

Experimental

Crystal data

C3H11NOP+·C2HO4 −·0.5C2H2O4

M = 242.14

Orthorhombic,

a = 11.1482 (6) Å

b = 13.0903 (7) Å

c = 7.0432 (4) Å

V = 1027.84 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.29 mm−1

T = 296 K

0.52 × 0.24 × 0.14 mm

Data collection

Bruker APEXII CCD diffractometer

92924 measured reflections

3002 independent reflections

2990 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.019

wR(F 2) = 0.052

S = 1.05

3002 reflections

192 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.24 e Å−3

Δρmin = −0.16 e Å−3

Absolute structure: refined as an inversion twin

Absolute structure parameter: 0.54 (7)

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2012 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536814002931/wm5001sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814002931/wm5001Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814002931/wm5001Isup3.cml

CCDC reference:

Additional supporting information: crystallographic information; 3D view; checkCIF report

C3H11NOP+·C2HO4−·0.5C2H2O4	Dx = 1.565 Mg m−3
Mr = 242.14	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P21212	Cell parameters from 9422 reflections
a = 11.1482 (6) Å	θ = 2.9–35.9°
b = 13.0903 (7) Å	µ = 0.29 mm−1
c = 7.0432 (4) Å	T = 296 K
V = 1027.84 (10) Å3	Lath, colourless
Z = 4	0.52 × 0.24 × 0.14 mm
F(000) = 508

Bruker APEXII CCD diffractometer	2990 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.020
Graphite monochromator	θmax = 30.0°, θmin = 2.4°
φ and ω scans	h = −15→15
92924 measured reflections	k = −18→18
3002 independent reflections	l = −9→9

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.019	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.052	w = 1/[σ2(Fo2) + (0.030P)2 + 0.150P] where P = (Fo2 + 2Fc2)/3
S = 1.05	(Δ/σ)max = 0.001
3002 reflections	Δρmax = 0.24 e Å−3
192 parameters	Δρmin = −0.16 e Å−3
0 restraints	Absolute structure: refined as an inversion twin
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.54 (7)

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.

Refinement. Refined as a 2-component inversion twin.

	x	y	z	Uiso*/Ueq	Occ. (<1)
P1	0.59355 (2)	0.16995 (2)	0.76357 (4)	0.02120 (7)
O1	0.66126 (9)	0.07493 (7)	0.71183 (16)	0.0320 (2)
C1	0.45282 (14)	0.14728 (13)	0.8751 (3)	0.0401 (3)
H1A	0.402 (3)	0.101 (2)	0.800 (4)	0.077 (8)*
H1B	0.415 (2)	0.216 (2)	0.902 (4)	0.066 (7)*
H1C	0.467 (3)	0.120 (2)	0.997 (4)	0.069 (8)*
C2	0.67941 (16)	0.25082 (12)	0.9144 (2)	0.0362 (3)
H2A	0.696 (3)	0.208 (2)	1.021 (4)	0.066 (8)*
H2B	0.637 (2)	0.3147 (18)	0.947 (3)	0.048 (6)*
H2C	0.754 (2)	0.268 (2)	0.851 (4)	0.069 (8)*
C3	0.55056 (10)	0.24000 (9)	0.55333 (18)	0.0226 (2)
H3A	0.5027 (19)	0.1946 (16)	0.482 (3)	0.039 (5)*
H3B	0.5075 (19)	0.3008 (15)	0.593 (3)	0.038 (5)*
N1	0.65260 (10)	0.27530 (8)	0.43508 (17)	0.0253 (2)
H1N	0.6245 (19)	0.3065 (17)	0.341 (3)	0.043 (5)*
H2N	0.694 (2)	0.2243 (17)	0.397 (3)	0.040 (5)*
H3N	0.6989 (19)	0.3213 (16)	0.497 (3)	0.037 (5)*
O2	0.60038 (7)	0.04219 (7)	0.26969 (15)	0.02816 (18)
O3	0.67262 (8)	−0.10318 (7)	0.38932 (17)	0.0314 (2)
O4	0.89578 (8)	−0.03192 (7)	0.33626 (19)	0.0354 (2)
O5	0.82187 (8)	0.12549 (7)	0.30304 (17)	0.0312 (2)
H2	0.539 (3)	0.014 (3)	0.272 (5)	0.035 (7)*	0.5
H4	0.962 (3)	−0.007 (3)	0.328 (5)	0.035 (7)*	0.5
C4	0.68433 (9)	−0.01553 (8)	0.33008 (17)	0.0212 (2)
C5	0.81095 (9)	0.03311 (9)	0.32141 (17)	0.0212 (2)
H6	0.283 (2)	0.476 (2)	0.220 (4)	0.070 (8)*
O6	0.34552 (9)	0.51669 (8)	0.19359 (19)	0.0380 (3)
O7	0.45436 (10)	0.37300 (8)	0.2131 (2)	0.0404 (3)
C6	0.44455 (11)	0.46465 (10)	0.20114 (19)	0.0271 (2)

	U11	U22	U33	U12	U13	U23
P1	0.01823 (12)	0.01867 (12)	0.02670 (13)	0.00132 (9)	0.00031 (11)	−0.00042 (10)
O1	0.0279 (4)	0.0260 (4)	0.0421 (5)	0.0105 (3)	−0.0041 (4)	−0.0037 (4)
C1	0.0283 (6)	0.0398 (8)	0.0521 (9)	0.0016 (6)	0.0134 (7)	0.0109 (7)
C2	0.0451 (8)	0.0336 (7)	0.0299 (6)	−0.0056 (6)	−0.0105 (6)	−0.0022 (5)
C3	0.0179 (5)	0.0198 (5)	0.0300 (5)	0.0019 (4)	−0.0031 (4)	−0.0012 (4)
N1	0.0271 (5)	0.0211 (4)	0.0275 (5)	0.0033 (4)	0.0014 (4)	0.0007 (4)
O2	0.0134 (3)	0.0272 (4)	0.0439 (5)	−0.0003 (3)	−0.0022 (4)	0.0045 (4)
O3	0.0184 (4)	0.0201 (4)	0.0557 (6)	−0.0023 (3)	0.0030 (4)	0.0049 (4)
O4	0.0126 (3)	0.0220 (4)	0.0715 (7)	0.0001 (3)	−0.0009 (4)	0.0047 (4)
O5	0.0194 (4)	0.0187 (4)	0.0556 (6)	−0.0024 (3)	0.0005 (4)	0.0019 (4)
C4	0.0131 (4)	0.0197 (5)	0.0307 (5)	−0.0016 (4)	0.0017 (4)	−0.0027 (4)
C5	0.0129 (4)	0.0203 (4)	0.0305 (5)	−0.0011 (4)	0.0010 (4)	0.0004 (4)
O6	0.0199 (4)	0.0279 (5)	0.0661 (8)	−0.0022 (3)	0.0020 (4)	0.0074 (5)
O7	0.0291 (5)	0.0237 (4)	0.0685 (8)	−0.0027 (4)	−0.0058 (5)	0.0032 (5)
C6	0.0224 (5)	0.0237 (5)	0.0351 (6)	−0.0033 (4)	−0.0017 (4)	0.0014 (4)

P1—O1	1.5000 (9)	N1—H2N	0.86 (2)
P1—C2	1.7791 (15)	N1—H3N	0.91 (2)
P1—C1	1.7796 (15)	O2—C4	1.2759 (14)
P1—C3	1.8064 (12)	O2—H2	0.77 (3)
C1—H1A	0.99 (3)	O3—C4	1.2278 (15)
C1—H1B	1.01 (3)	O4—C5	1.2767 (14)
C1—H1C	0.95 (3)	O4—H4	0.81 (4)
C2—H2A	0.96 (3)	O5—C5	1.2223 (14)
C2—H2B	0.99 (2)	C4—C5	1.5497 (15)
C2—H2C	0.97 (3)	O6—C6	1.2984 (15)
C3—N1	1.4836 (16)	O6—H6	0.89 (3)
C3—H3A	0.94 (2)	O7—C6	1.2076 (15)
C3—H3B	0.97 (2)	C6—C6i	1.544 (2)
N1—H1N	0.84 (2)
O1—P1—C2	111.58 (7)	N1—C3—H3B	106.5 (12)
O1—P1—C1	114.37 (7)	P1—C3—H3B	108.3 (12)
C2—P1—C1	108.05 (9)	H3A—C3—H3B	112.9 (17)
O1—P1—C3	110.81 (6)	C3—N1—H1N	107.9 (15)
C2—P1—C3	109.28 (7)	C3—N1—H2N	110.4 (15)
C1—P1—C3	102.28 (7)	H1N—N1—H2N	109 (2)
P1—C1—H1A	112.1 (17)	C3—N1—H3N	112.0 (13)
P1—C1—H1B	107.9 (15)	H1N—N1—H3N	105.7 (19)
H1A—C1—H1B	114 (2)	H2N—N1—H3N	111.2 (19)
P1—C1—H1C	108.4 (18)	C4—O2—H2	111 (3)
H1A—C1—H1C	110 (2)	C5—O4—H4	113 (3)
H1B—C1—H1C	104 (2)	O3—C4—O2	126.07 (10)
P1—C2—H2A	103.0 (16)	O3—C4—C5	119.62 (10)
P1—C2—H2B	112.4 (13)	O2—C4—C5	114.31 (10)
H2A—C2—H2B	114 (2)	O5—C5—O4	126.48 (10)
P1—C2—H2C	109.1 (17)	O5—C5—C4	120.09 (10)
H2A—C2—H2C	110 (2)	O4—C5—C4	113.42 (9)
H2B—C2—H2C	109 (2)	C6—O6—H6	110.0 (18)
N1—C3—P1	114.51 (8)	O7—C6—O6	126.95 (12)
N1—C3—H3A	109.3 (12)	O7—C6—C6i	121.53 (15)
P1—C3—H3A	105.6 (12)	O6—C6—C6i	111.48 (13)
O1—P1—C3—N1	−61.08 (10)	O2—C4—C5—O5	16.86 (17)
C2—P1—C3—N1	62.27 (11)	O3—C4—C5—O4	15.53 (18)
C1—P1—C3—N1	176.61 (10)	O2—C4—C5—O4	−163.53 (12)
O3—C4—C5—O5	−164.08 (13)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O2ii	0.77 (3)	1.73 (4)	2.4959 (17)	177 (4)
O4—H4···O4iii	0.81 (4)	1.67 (4)	2.4694 (18)	171 (4)
N1—H1N···O6i	0.84 (2)	2.56 (2)	3.2106 (16)	135.4 (19)
N1—H1N···O7	0.84 (2)	2.27 (2)	2.9939 (17)	144 (2)
N1—H2N···O5	0.86 (2)	2.03 (2)	2.8760 (14)	168 (2)
N1—H3N···O3iv	0.91 (2)	1.92 (2)	2.8030 (15)	166.2 (19)
N1—H3N···O4iv	0.91 (2)	2.49 (2)	3.0419 (16)	120.0 (16)
O6—H6···O1v	0.89 (3)	1.59 (3)	2.4701 (14)	168 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O2i	0.77 (3)	1.73 (4)	2.4959 (17)	177 (4)
O4—H4⋯O4ii	0.81 (4)	1.67 (4)	2.4694 (18)	171 (4)
N1—H1N⋯O6iii	0.84 (2)	2.56 (2)	3.2106 (16)	135.4 (19)
N1—H1N⋯O7	0.84 (2)	2.27 (2)	2.9939 (17)	144 (2)
N1—H2N⋯O5	0.86 (2)	2.03 (2)	2.8760 (14)	168 (2)
N1—H3N⋯O3iv	0.91 (2)	1.92 (2)	2.8030 (15)	166.2 (19)
N1—H3N⋯O4iv	0.91 (2)	2.49 (2)	3.0419 (16)	120.0 (16)
O6—H6⋯O1v	0.89 (3)	1.59 (3)	2.4701 (14)	168 (3)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) .