Di-ethyl-ammonium di-hydrogen orthophosphate.

In the title molecular salt, [NH2(CH2CH3)2][H2PO4], two unique types of cations and anions, which are configurationally very similar, are present in the asymmetric unit. Both ions form sheets approximately parallel to (-1-1) linked by weak hydrogen bonds. The inter-connection within and between the sheets is reinforced by O-H⋯O and N-H⋯O hydrogen bonds involving the tetra-hedral H2PO4 anions and the ammonium groups.

Related literature

For preparative details, see: Hanna et al. (1999 ▶). For related structures, see: Averbuch-Pouchot et al. (1987 ▶); Held (2003 ▶).

Experimental

Crystal data

C4H12N+·H2PO4 −

M = 171.13

Triclinic,

a = 8.3643 (6) Å

b = 8.8308 (15) Å

c = 11.6446 (12) Å

α = 88.219 (10)°

β = 83.649 (7)°

γ = 79.700 (7)°

V = 841.00 (18) Å3

Z = 4

Mo Kα radiation

μ = 0.29 mm−1

T = 295 K

0.30 × 0.28 × 0.26 mm

Data collection

Nonius MACH3 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.858, T max = 0.998

10831 measured reflections

5096 independent reflections

3164 reflections with I > 2σ(I)

R int = 0.037

3 standard reflections every 100 reflections intensity decay: −6.3%

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.119

S = 0.98

5096 reflections

181 parameters

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.39 e Å−3

Data collection: CAD-4 (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4; data reduction: WinGX (Farrugia, 2012 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ATOMS (Dowty, 2002 ▶) and ORTEP-3 for Windows (Farrugia, 2012 ▶)’; software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814000464/wm2794sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814000464/wm2794Isup2.hkl

CCDC reference:

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

C4H12N+·H2PO4−	Z = 4
Mr = 171.13	F(000) = 368
Triclinic, P1	Dx = 1.352 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.3643 (6) Å	Cell parameters from 25 reflections
b = 8.8308 (15) Å	θ = 21.0–26.0°
c = 11.6446 (12) Å	µ = 0.29 mm−1
α = 88.219 (10)°	T = 295 K
β = 83.649 (7)°	Parallelepiped, colourless
γ = 79.700 (7)°	0.30 × 0.28 × 0.26 mm
V = 841.00 (18) Å3

Nonius MACH3 diffractometer	3164 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.037
Graphite monochromator	θmax = 30.4°, θmin = 2.5°
ω/2θ scans	h = −11→11
Absorption correction: ψ scan (North et al., 1968)	k = −12→12
Tmin = 0.858, Tmax = 0.998	l = −16→16
10831 measured reflections	3 standard reflections every 100 reflections
5096 independent reflections	intensity decay: −6.3%

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.119	H-atom parameters constrained
S = 0.98	w = 1/[σ2(Fo2) + (0.0553P)2 + 0.1855P] where P = (Fo2 + 2Fc2)/3
5096 reflections	(Δ/σ)max < 0.001
181 parameters	Δρmax = 0.37 e Å−3
0 restraints	Δρmin = −0.39 e Å−3

Experimental. A suitable single-crystal was carefully selected under a polarizing microscope and mounted in a glass capillary.

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. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. 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.

	x	y	z	Uiso*/Ueq
P1	0.16567 (5)	0.37327 (5)	0.60452 (4)	0.02736 (12)
O11	0.33132 (15)	0.27994 (16)	0.61779 (12)	0.0362 (3)
O12	0.16402 (16)	0.53915 (15)	0.56977 (12)	0.0365 (3)
O13	0.05039 (16)	0.36883 (18)	0.71998 (12)	0.0426 (4)
H13	0.0986	0.3119	0.7669	0.064*
O14	0.08747 (18)	0.29249 (16)	0.51243 (13)	0.0418 (3)
H14	−0.0034	0.3416	0.5037	0.063*
P2	0.67897 (6)	−0.09624 (6)	0.11311 (4)	0.03332 (13)
O21	0.83801 (17)	−0.20760 (18)	0.10779 (12)	0.0431 (4)
O22	0.68455 (18)	0.04631 (17)	0.03943 (13)	0.0454 (4)
O23	0.6256 (2)	−0.04343 (17)	0.24046 (13)	0.0502 (4)
H23	0.6138	−0.1185	0.2816	0.075*
O24	0.54703 (19)	−0.18437 (17)	0.07620 (15)	0.0540 (4)
H24	0.4588	−0.1259	0.0784	0.081*
C11	0.2499 (4)	0.5728 (3)	−0.0009 (3)	0.0663 (7)
H11A	0.3010	0.4677	−0.0143	0.100*
H11B	0.1790	0.5792	0.0702	0.100*
H11C	0.3322	0.6346	0.0040	0.100*
C12	0.1521 (3)	0.6303 (3)	−0.0985 (2)	0.0551 (6)
H12A	0.2234	0.6223	−0.1705	0.066*
H12B	0.0700	0.5668	−0.1043	0.066*
N1	0.0712 (2)	0.7927 (2)	−0.08051 (14)	0.0389 (4)
H1A	0.1462	0.8472	−0.0629	0.047*
H1B	−0.0049	0.7962	−0.0192	0.047*
C13	−0.0092 (4)	0.8696 (3)	−0.1815 (2)	0.0633 (7)
H13A	−0.0518	0.9767	−0.1634	0.076*
H13B	0.0719	0.8668	−0.2481	0.076*
C14	−0.1460 (4)	0.7938 (4)	−0.2114 (2)	0.0674 (8)
H14A	−0.1939	0.8467	−0.2759	0.101*
H14B	−0.2275	0.7978	−0.1461	0.101*
H14C	−0.1040	0.6884	−0.2311	0.101*
C21	0.2697 (4)	0.9059 (3)	0.4832 (3)	0.0767 (9)
H21A	0.2125	1.0088	0.4722	0.115*
H21B	0.3793	0.9091	0.4988	0.115*
H21C	0.2144	0.8581	0.5472	0.115*
C22	0.2739 (3)	0.8160 (3)	0.3772 (2)	0.0530 (6)
H22A	0.3283	0.8650	0.3122	0.064*
H22B	0.1632	0.8138	0.3608	0.064*
N2	0.36206 (19)	0.65586 (19)	0.39194 (14)	0.0387 (4)
H2A	0.4643	0.6596	0.4076	0.046*
H2B	0.3118	0.6126	0.4535	0.046*
C23	0.3717 (3)	0.5556 (3)	0.2904 (2)	0.0524 (6)
H23A	0.4293	0.5993	0.2242	0.063*
H23B	0.2622	0.5520	0.2721	0.063*
C24	0.4584 (3)	0.3952 (3)	0.3128 (2)	0.0599 (7)
H24A	0.4627	0.3337	0.2456	0.090*
H24B	0.4005	0.3509	0.3773	0.090*
H24C	0.5675	0.3983	0.3297	0.090*

	U11	U22	U33	U12	U13	U23
P1	0.0192 (2)	0.0322 (2)	0.0307 (2)	−0.00441 (17)	−0.00520 (17)	0.00718 (18)
O11	0.0191 (6)	0.0458 (8)	0.0417 (8)	−0.0025 (5)	−0.0037 (5)	0.0122 (6)
O12	0.0325 (7)	0.0347 (7)	0.0448 (8)	−0.0102 (6)	−0.0119 (6)	0.0110 (6)
O13	0.0254 (7)	0.0588 (9)	0.0371 (7)	0.0040 (6)	0.0011 (6)	0.0160 (7)
O14	0.0397 (8)	0.0365 (7)	0.0507 (9)	−0.0017 (6)	−0.0193 (7)	−0.0035 (6)
P2	0.0281 (2)	0.0350 (3)	0.0388 (3)	−0.00980 (19)	−0.0092 (2)	0.0130 (2)
O21	0.0312 (7)	0.0590 (9)	0.0344 (7)	0.0011 (6)	−0.0025 (6)	0.0143 (7)
O22	0.0428 (8)	0.0464 (8)	0.0549 (9)	−0.0229 (7)	−0.0227 (7)	0.0253 (7)
O23	0.0586 (10)	0.0409 (8)	0.0447 (9)	0.0048 (7)	−0.0021 (7)	0.0069 (7)
O24	0.0470 (9)	0.0392 (8)	0.0850 (12)	−0.0202 (7)	−0.0334 (8)	0.0228 (8)
C11	0.0626 (17)	0.0470 (14)	0.092 (2)	−0.0091 (12)	−0.0194 (16)	−0.0012 (14)
C12	0.0502 (14)	0.0593 (15)	0.0571 (15)	−0.0138 (11)	0.0012 (11)	−0.0197 (12)
N1	0.0366 (9)	0.0481 (10)	0.0361 (9)	−0.0195 (8)	−0.0036 (7)	0.0022 (7)
C13	0.0762 (19)	0.0782 (18)	0.0452 (14)	−0.0365 (15)	−0.0179 (13)	0.0191 (13)
C14	0.0759 (19)	0.081 (2)	0.0537 (15)	−0.0226 (15)	−0.0304 (14)	0.0031 (14)
C21	0.074 (2)	0.0466 (15)	0.103 (2)	0.0002 (14)	0.0004 (18)	0.0028 (16)
C22	0.0306 (10)	0.0525 (13)	0.0738 (17)	−0.0069 (9)	−0.0045 (10)	0.0280 (12)
N2	0.0265 (8)	0.0485 (10)	0.0427 (9)	−0.0117 (7)	−0.0050 (7)	0.0104 (8)
C23	0.0418 (12)	0.0802 (18)	0.0401 (12)	−0.0225 (12)	−0.0078 (10)	0.0027 (12)
C24	0.0503 (14)	0.0718 (18)	0.0595 (16)	−0.0205 (13)	0.0058 (12)	−0.0170 (13)

P1—O11	1.5013 (13)	C13—C14	1.501 (4)
P1—O12	1.5056 (14)	C13—H13A	0.9700
P1—O14	1.5673 (14)	C13—H13B	0.9700
P1—O13	1.5691 (14)	C14—H14A	0.9600
O13—H13	0.8200	C14—H14B	0.9600
O14—H14	0.8200	C14—H14C	0.9600
P2—O21	1.5027 (14)	C21—C22	1.482 (4)
P2—O22	1.5060 (14)	C21—H21A	0.9600
P2—O23	1.5613 (16)	C21—H21B	0.9600
P2—O24	1.5624 (15)	C21—H21C	0.9600
O23—H23	0.8200	C22—N2	1.487 (3)
O24—H24	0.8200	C22—H22A	0.9700
C11—C12	1.497 (4)	C22—H22B	0.9700
C11—H11A	0.9600	N2—C23	1.485 (3)
C11—H11B	0.9600	N2—H2A	0.9000
C11—H11C	0.9600	N2—H2B	0.9000
C12—N1	1.483 (3)	C23—C24	1.501 (4)
C12—H12A	0.9700	C23—H23A	0.9700
C12—H12B	0.9700	C23—H23B	0.9700
N1—C13	1.503 (3)	C24—H24A	0.9600
N1—H1A	0.9000	C24—H24B	0.9600
N1—H1B	0.9000	C24—H24C	0.9600
O11—P1—O12	115.38 (8)	N1—C13—H13B	109.1
O11—P1—O14	107.71 (8)	H13A—C13—H13B	107.9
O12—P1—O14	109.31 (8)	C13—C14—H14A	109.5
O11—P1—O13	110.08 (7)	C13—C14—H14B	109.5
O12—P1—O13	108.20 (8)	H14A—C14—H14B	109.5
O14—P1—O13	105.74 (9)	C13—C14—H14C	109.5
P1—O13—H13	109.5	H14A—C14—H14C	109.5
P1—O14—H14	109.5	H14B—C14—H14C	109.5
O21—P2—O22	114.38 (9)	C22—C21—H21A	109.5
O21—P2—O23	109.41 (8)	C22—C21—H21B	109.5
O22—P2—O23	107.50 (9)	H21A—C21—H21B	109.5
O21—P2—O24	107.55 (9)	C22—C21—H21C	109.5
O22—P2—O24	110.16 (8)	H21A—C21—H21C	109.5
O23—P2—O24	107.65 (10)	H21B—C21—H21C	109.5
P2—O23—H23	109.5	C21—C22—N2	110.6 (2)
P2—O24—H24	109.5	C21—C22—H22A	109.5
C12—C11—H11A	109.5	N2—C22—H22A	109.5
C12—C11—H11B	109.5	C21—C22—H22B	109.5
H11A—C11—H11B	109.5	N2—C22—H22B	109.5
C12—C11—H11C	109.5	H22A—C22—H22B	108.1
H11A—C11—H11C	109.5	C23—N2—C22	114.70 (18)
H11B—C11—H11C	109.5	C23—N2—H2A	108.6
N1—C12—C11	110.87 (19)	C22—N2—H2A	108.6
N1—C12—H12A	109.5	C23—N2—H2B	108.6
C11—C12—H12A	109.5	C22—N2—H2B	108.6
N1—C12—H12B	109.5	H2A—N2—H2B	107.6
C11—C12—H12B	109.5	N2—C23—C24	111.64 (19)
H12A—C12—H12B	108.1	N2—C23—H23A	109.3
C12—N1—C13	115.31 (19)	C24—C23—H23A	109.3
C12—N1—H1A	108.4	N2—C23—H23B	109.3
C13—N1—H1A	108.4	C24—C23—H23B	109.3
C12—N1—H1B	108.4	H23A—C23—H23B	108.0
C13—N1—H1B	108.4	C23—C24—H24A	109.5
H1A—N1—H1B	107.5	C23—C24—H24B	109.5
C14—C13—N1	112.3 (2)	H24A—C24—H24B	109.5
C14—C13—H13A	109.1	C23—C24—H24C	109.5
N1—C13—H13A	109.1	H24A—C24—H24C	109.5
C14—C13—H13B	109.1	H24B—C24—H24C	109.5

D—H···A	D—H	H···A	D···A	D—H···A
O13—H13···O21i	0.82	1.78	2.5851 (19)	166
O14—H14···O12ii	0.82	1.83	2.6058 (19)	158
O24—H24···O22iii	0.82	1.95	2.585 (2)	133
O23—H23···O11i	0.82	1.84	2.620 (2)	158
N1—H1A···O22iv	0.90	1.88	2.779 (2)	174
N1—H1B···O21v	0.90	1.87	2.769 (2)	177
N2—H2A···O11vi	0.90	1.87	2.714 (2)	155
N2—H2B···O12	0.90	1.91	2.795 (2)	168

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O13—H13⋯O21i	0.82	1.78	2.5851 (19)	166
O14—H14⋯O12ii	0.82	1.83	2.6058 (19)	158
O24—H24⋯O22iii	0.82	1.95	2.585 (2)	133
O23—H23⋯O11i	0.82	1.84	2.620 (2)	158
N1—H1A⋯O22iv	0.90	1.88	2.779 (2)	174
N1—H1B⋯O21v	0.90	1.87	2.769 (2)	177
N2—H2A⋯O11vi	0.90	1.87	2.714 (2)	155
N2—H2B⋯O12	0.90	1.91	2.795 (2)	168

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