Tris(5-amino-1H-1,2,4-triazol-4-ium) dihydrogenphosphate hydrogen-phosphate trihydrate.

In the crystal structure of the title molecular salt, 3C2H5N4(+)·HPO4(2-)·H2PO4(-)·3H2O, the phosphate-based framework is built upon layers parallel to (010) made up from the H2PO4(-) and HPO4(2-) anions and water mol-ecules, which are inter-connected through O-H⋯O hydrogen bonds. The organic cations are located between the phosphate-water layers and are connected to them via N-H⋯O hydrogen bonds. The bond-length features are consistent with an imino resonance form for the exocyclic amino group, as is commonly found for a C-N single bond involving sp(2)-hybridized C and N atoms.

Related literature

For applications of organic <span class="Chemical">phosphaten> complexes, see: Bringley & Rajeswaran (2006 ▶); Dai et al. (2002 ▶); Masse et al. (1993 ▶). For graph-set motifs and theory, see: Bernstein et al. (1995 ▶). For reference structural data, see: Kaabi et al. (2004 ▶); Shanmuga Sundara Raj et al. (2000 ▶). For P—OH bond lengths, see: Chtioui & Jouini (2005 ▶).

Experimental

Crystal data

3C2<span class="Species">H5n class="Chemical">N4 +·HO4P2−·<spn>an class="Chemical">H2O4P−·3H2O

M = 502.31

Monoclinic,

a = 10.4793 (13) Å

b = 8.7655 (11) Å

c = 11.4536 (14) Å

β = 107.489 (2)°

V = 1003.5 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.30 mm−1

T = 100 K

0.60 × 0.35 × 0.18 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2011 ▶) T min = 0.693, T max = 0.746

13833 measured reflections

6229 independent reflections

6132 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.023

wR(F 2) = 0.059

S = 1.04

6229 reflections

322 parameters

32 restraints

<span class="Disease">H atomsn> treated by a mixture of independent and constrained refinement

Δρmax = 0.33 e Å−3

Δρmin = −0.19 e Å−3

Absolute structure: Flack (1983 ▶), 2950 Friedel pairs

Flack parameter: −0.02 (4)

Data collection: APEX2 (Bruker, 2011 ▶); cell refinement: SAINT (Bruker, 2011 ▶); data reduction: SAIn class="Chemical">NT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXLE (Hübschle et al., 2011 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812044492/ru2044sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812044492/ru2044Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812044492/ru2044Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

3C2H5N4+·HO4P2−·H2O4P−·3H2O	F(000) = 524
Mr = 502.31	Dx = 1.662 Mg m−3
Monoclinic, Pc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P -2yc	Cell parameters from 5573 reflections
a = 10.4793 (13) Å	θ = 3.0–31.8°
b = 8.7655 (11) Å	µ = 0.30 mm−1
c = 11.4536 (14) Å	T = 100 K
β = 107.489 (2)°	Block, colourless
V = 1003.5 (2) Å3	0.60 × 0.35 × 0.18 mm
Z = 2

Bruker SMART APEX CCD diffractometer	6229 independent reflections
Radiation source: fine-focus sealed tube	6132 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.016
ω scans	θmax = 32.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2011)	h = −14→15
Tmin = 0.693, Tmax = 0.746	k = −12→13
13833 measured reflections	l = −16→16

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.059	w = 1/[σ2(Fo2) + (0.0385P)2 + 0.0562P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
6229 reflections	Δρmax = 0.33 e Å−3
322 parameters	Δρmin = −0.19 e Å−3
32 restraints	Absolute structure: Flack (1983), 2950 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.02 (4)

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
N1A	0.62032 (11)	0.15272 (11)	0.77449 (9)	0.01772 (18)
H1A1	0.6049 (17)	0.2392 (16)	0.7386 (16)	0.021*
H1A2	0.6042 (17)	0.1391 (19)	0.8421 (13)	0.021*
N2A	0.60906 (10)	0.04376 (11)	0.58172 (9)	0.01488 (17)
H2A	0.6141	0.1293	0.5432	0.018*
N3A	0.59896 (10)	−0.09961 (11)	0.52940 (9)	0.01524 (17)
N4A	0.60216 (9)	−0.11435 (11)	0.72352 (9)	0.01336 (16)
H4A	0.6017	−0.1543	0.7939	0.016*
C1A	0.61011 (10)	0.03524 (12)	0.69840 (10)	0.01299 (18)
C2A	0.59494 (11)	−0.19168 (13)	0.61746 (10)	0.01451 (18)
H2AA	0.5879	−0.2995	0.6093	0.017*
N1B	0.95278 (11)	0.16763 (12)	0.67577 (9)	0.01933 (19)
H1B1	0.9835 (17)	0.2502 (16)	0.7144 (15)	0.023*
H1B2	0.9369 (18)	0.0936 (17)	0.7129 (16)	0.023*
N2B	0.92010 (10)	0.02876 (11)	0.48939 (9)	0.01598 (17)
H2B1	0.8958	−0.0591	0.5132	0.019*
N3B	0.93026 (11)	0.05748 (11)	0.37327 (10)	0.01706 (18)
N4B	0.98316 (9)	0.26338 (10)	0.49075 (8)	0.01343 (16)
H4B	1.0082	0.3574	0.5133	0.016*
C1B	0.95240 (10)	0.15303 (12)	0.56033 (10)	0.01362 (18)
C2B	0.96750 (11)	0.19962 (13)	0.37803 (10)	0.01543 (19)
H2B2	0.9821	0.2531	0.3110	0.019*
N1C	0.28072 (10)	0.15370 (11)	0.42295 (9)	0.01621 (17)
H1C1	0.2900 (16)	0.137 (2)	0.4966 (12)	0.019*
H1C2	0.2796 (17)	0.2424 (15)	0.3916 (15)	0.019*
N2C	0.28411 (10)	0.04801 (11)	0.23314 (8)	0.01377 (16)
H2C	0.2843	0.1345	0.1942	0.017*
N3C	0.28565 (10)	−0.09510 (11)	0.18257 (9)	0.01465 (17)
N4C	0.28158 (9)	−0.11349 (11)	0.37482 (8)	0.01238 (16)
H4C	0.2795	−0.1547	0.4443	0.015*
C1C	0.28234 (10)	0.03715 (12)	0.34900 (9)	0.01169 (17)
C2C	0.28461 (10)	−0.18892 (12)	0.27069 (10)	0.01394 (18)
H2CA	0.2858	−0.2969	0.2636	0.017*
P1A	0.23842 (2)	0.41894 (3)	0.11253 (2)	0.00876 (5)
O1A	0.09137 (7)	0.45148 (9)	0.04480 (7)	0.01176 (13)
O2A	0.31520 (8)	0.55501 (9)	0.07195 (7)	0.01273 (14)
H2AB	0.3902 (19)	0.5380 (10)	0.0918 (15)	0.019*
O3A	0.26391 (8)	0.42577 (8)	0.25172 (7)	0.01225 (14)
O4A	0.28676 (8)	0.26682 (9)	0.07706 (7)	0.01314 (14)
P1B	0.59788 (2)	0.42266 (3)	0.46934 (2)	0.00962 (5)
O1B	0.49521 (8)	0.52280 (9)	0.37270 (7)	0.01584 (15)
H1B	0.4300 (18)	0.4769 (15)	0.3450 (15)	0.024*
O2B	0.73507 (8)	0.50517 (10)	0.48323 (7)	0.01466 (14)
H2BA	0.7526 (10)	0.5008 (18)	0.4177 (17)	0.022*
O3B	0.57479 (8)	0.43008 (9)	0.59371 (7)	0.01269 (14)
O4B	0.59985 (9)	0.26114 (9)	0.42328 (7)	0.01614 (15)
O1	0.78679 (8)	0.52112 (11)	0.77991 (8)	0.01834 (16)
H1D	0.8624 (15)	0.502 (2)	0.7733 (18)	0.028*
H1E	0.7308 (17)	0.484 (2)	0.7240 (15)	0.028*
O2	1.04601 (8)	0.44288 (10)	0.79982 (7)	0.01506 (15)
H2D	1.0714 (18)	0.4441 (19)	0.8747 (12)	0.023*
H2E	1.1091 (15)	0.481 (2)	0.7840 (17)	0.023*
O3	0.91292 (8)	0.75025 (9)	0.58426 (8)	0.01633 (15)
H3D	0.8480 (15)	0.699 (2)	0.5712 (17)	0.025*
H3E	0.9680 (16)	0.6944 (19)	0.5732 (17)	0.025*

	U11	U22	U33	U12	U13	U23
N1A	0.0286 (5)	0.0117 (4)	0.0144 (4)	−0.0010 (4)	0.0086 (4)	−0.0005 (3)
N2A	0.0231 (4)	0.0110 (4)	0.0115 (4)	−0.0008 (3)	0.0067 (3)	0.0012 (3)
N3A	0.0212 (4)	0.0128 (4)	0.0127 (4)	−0.0002 (3)	0.0067 (3)	−0.0007 (3)
N4A	0.0176 (4)	0.0118 (4)	0.0114 (4)	0.0000 (3)	0.0054 (3)	0.0021 (3)
C1A	0.0142 (4)	0.0125 (5)	0.0123 (5)	−0.0003 (3)	0.0041 (3)	0.0017 (3)
C2A	0.0177 (4)	0.0134 (5)	0.0134 (5)	−0.0004 (4)	0.0061 (4)	0.0002 (3)
N1B	0.0291 (5)	0.0157 (4)	0.0145 (4)	−0.0063 (4)	0.0085 (4)	−0.0010 (3)
N2B	0.0207 (4)	0.0123 (4)	0.0155 (4)	−0.0025 (3)	0.0063 (3)	−0.0011 (3)
N3B	0.0207 (4)	0.0154 (4)	0.0154 (4)	−0.0004 (3)	0.0058 (3)	−0.0014 (3)
N4B	0.0169 (4)	0.0105 (4)	0.0129 (4)	−0.0015 (3)	0.0045 (3)	−0.0001 (3)
C1B	0.0139 (4)	0.0119 (4)	0.0146 (5)	−0.0004 (3)	0.0037 (3)	0.0000 (3)
C2B	0.0172 (4)	0.0154 (5)	0.0139 (5)	−0.0002 (4)	0.0048 (4)	−0.0006 (4)
N1C	0.0248 (4)	0.0124 (4)	0.0129 (4)	−0.0016 (3)	0.0079 (3)	−0.0013 (3)
N2C	0.0222 (4)	0.0099 (4)	0.0106 (4)	0.0010 (3)	0.0070 (3)	0.0005 (3)
N3C	0.0225 (4)	0.0101 (4)	0.0123 (4)	0.0017 (3)	0.0066 (3)	0.0002 (3)
N4C	0.0167 (4)	0.0104 (4)	0.0109 (4)	−0.0008 (3)	0.0054 (3)	0.0008 (3)
C1C	0.0135 (4)	0.0112 (5)	0.0107 (4)	−0.0004 (3)	0.0040 (3)	0.0008 (3)
C2C	0.0186 (5)	0.0113 (4)	0.0126 (4)	0.0005 (4)	0.0056 (4)	0.0006 (3)
P1A	0.01123 (10)	0.00815 (11)	0.00727 (11)	0.00019 (8)	0.00335 (8)	0.00021 (8)
O1A	0.0118 (3)	0.0126 (3)	0.0107 (3)	0.0004 (3)	0.0031 (2)	0.0007 (3)
O2A	0.0126 (3)	0.0103 (3)	0.0161 (4)	0.0001 (3)	0.0057 (3)	0.0030 (3)
O3A	0.0152 (3)	0.0137 (3)	0.0078 (3)	0.0001 (3)	0.0034 (3)	−0.0008 (2)
O4A	0.0200 (3)	0.0094 (3)	0.0113 (3)	0.0015 (3)	0.0067 (3)	−0.0003 (3)
P1B	0.01187 (10)	0.00900 (11)	0.00812 (11)	−0.00035 (8)	0.00319 (8)	−0.00054 (8)
O1B	0.0154 (3)	0.0138 (4)	0.0150 (4)	−0.0008 (3)	−0.0006 (3)	0.0036 (3)
O2B	0.0131 (3)	0.0193 (4)	0.0127 (3)	−0.0036 (3)	0.0057 (3)	−0.0023 (3)
O3B	0.0136 (3)	0.0160 (4)	0.0095 (3)	−0.0003 (3)	0.0051 (3)	−0.0022 (3)
O4B	0.0291 (4)	0.0099 (3)	0.0115 (3)	−0.0003 (3)	0.0093 (3)	−0.0011 (3)
O1	0.0131 (3)	0.0292 (5)	0.0127 (4)	−0.0018 (3)	0.0039 (3)	−0.0045 (3)
O2	0.0152 (3)	0.0208 (4)	0.0099 (3)	−0.0028 (3)	0.0047 (3)	−0.0007 (3)
O3	0.0162 (3)	0.0120 (4)	0.0225 (4)	−0.0001 (3)	0.0083 (3)	−0.0010 (3)

N1A—C1A	1.3325 (14)	N2C—C1C	1.3361 (13)
N1A—H1A1	0.854 (13)	N2C—N3C	1.3838 (13)
N1A—H1A2	0.849 (13)	N2C—H2C	0.8800
N2A—C1A	1.3353 (14)	N3C—C2C	1.3044 (14)
N2A—N3A	1.3826 (13)	N4C—C1C	1.3537 (14)
N2A—H2A	0.8800	N4C—C2C	1.3724 (14)
N3A—C2A	1.3022 (14)	N4C—H4C	0.8800
N4A—C1A	1.3504 (15)	C2C—H2CA	0.9500
N4A—C2A	1.3732 (14)	P1A—O4A	1.5243 (8)
N4A—H4A	0.8800	P1A—O1A	1.5294 (8)
C2A—H2AA	0.9500	P1A—O3A	1.5364 (8)
N1B—C1B	1.3272 (15)	P1A—O2A	1.5845 (8)
N1B—H1B1	0.859 (13)	O2A—H2AB	0.7639
N1B—H1B2	0.820 (13)	P1B—O4B	1.5132 (8)
N2B—C1B	1.3401 (14)	P1B—O3B	1.5163 (8)
N2B—N3B	1.3888 (14)	P1B—O1B	1.5612 (8)
N2B—H2B1	0.8800	P1B—O2B	1.5741 (8)
N3B—C2B	1.3018 (15)	O1B—H1B	0.7742
N4B—C1B	1.3524 (14)	O2B—H2BA	0.8262
N4B—C2B	1.3706 (14)	O1—H1D	0.835 (14)
N4B—H4B	0.8800	O1—H1E	0.796 (14)
C2B—H2B2	0.9500	O2—H2D	0.819 (13)
N1C—C1C	1.3304 (14)	O2—H2E	0.808 (13)
N1C—H1C1	0.833 (13)	O3—H3D	0.790 (13)
N1C—H1C2	0.855 (13)	O3—H3E	0.795 (13)
C1A—N1A—H1A1	113.9 (12)	C1C—N1C—H1C2	115.6 (11)
C1A—N1A—H1A2	119.3 (12)	H1C1—N1C—H1C2	124.9 (16)
H1A1—N1A—H1A2	120.2 (17)	C1C—N2C—N3C	110.88 (9)
C1A—N2A—N3A	111.07 (9)	C1C—N2C—H2C	124.6
C1A—N2A—H2A	124.5	N3C—N2C—H2C	124.6
N3A—N2A—H2A	124.5	C2C—N3C—N2C	104.11 (9)
C2A—N3A—N2A	104.11 (9)	C1C—N4C—C2C	106.08 (9)
C1A—N4A—C2A	106.34 (9)	C1C—N4C—H4C	127.0
C1A—N4A—H4A	126.8	C2C—N4C—H4C	127.0
C2A—N4A—H4A	126.8	N1C—C1C—N2C	125.74 (10)
N1A—C1A—N2A	125.90 (10)	N1C—C1C—N4C	127.44 (10)
N1A—C1A—N4A	127.52 (10)	N2C—C1C—N4C	106.81 (9)
N2A—C1A—N4A	106.56 (9)	N3C—C2C—N4C	112.11 (10)
N3A—C2A—N4A	111.92 (10)	N3C—C2C—H2CA	123.9
N3A—C2A—H2AA	124.0	N4C—C2C—H2CA	123.9
N4A—C2A—H2AA	124.0	O4A—P1A—O1A	113.13 (4)
C1B—N1B—H1B1	118.9 (12)	O4A—P1A—O3A	110.03 (4)
C1B—N1B—H1B2	120.0 (13)	O1A—P1A—O3A	110.70 (4)
H1B1—N1B—H1B2	120.2 (18)	O4A—P1A—O2A	109.97 (5)
C1B—N2B—N3B	110.80 (9)	O1A—P1A—O2A	103.52 (4)
C1B—N2B—H2B1	124.6	O3A—P1A—O2A	109.26 (4)
N3B—N2B—H2B1	124.6	P1A—O2A—H2AB	109.5
C2B—N3B—N2B	103.98 (9)	O4B—P1B—O3B	112.98 (5)
C1B—N4B—C2B	106.33 (9)	O4B—P1B—O1B	110.95 (5)
C1B—N4B—H4B	126.8	O3B—P1B—O1B	111.80 (5)
C2B—N4B—H4B	126.8	O4B—P1B—O2B	110.94 (5)
N1B—C1B—N2B	127.37 (10)	O3B—P1B—O2B	106.50 (4)
N1B—C1B—N4B	126.03 (10)	O1B—P1B—O2B	103.13 (5)
N2B—C1B—N4B	106.60 (10)	P1B—O1B—H1B	109.5
N3B—C2B—N4B	112.29 (10)	P1B—O2B—H2BA	109.5
N3B—C2B—H2B2	123.9	H1D—O1—H1E	109.7 (19)
N4B—C2B—H2B2	123.9	H2D—O2—H2E	101.5 (17)
C1C—N1C—H1C1	119.1 (12)	H3D—O3—H3E	104.3 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1A1···O3B	0.85 (1)	2.31 (1)	3.1356 (13)	162 (2)
N1A—H1A2···N3Ai	0.85 (1)	2.19 (1)	3.0305 (15)	170 (2)
N2A—H2A···O4B	0.88	1.77	2.6130 (13)	161
N4A—H4A···O4Bi	0.88	1.76	2.6314 (13)	171
N1B—H1B1···O2	0.86 (1)	1.96 (1)	2.8214 (13)	178 (2)
N1B—H1B2···N3Bi	0.82 (1)	2.28 (1)	3.0639 (15)	160 (2)
N2B—H2B1···O3ii	0.88	1.84	2.6824 (13)	159
N4B—H4B···O1Aiii	0.88	1.87	2.7376 (12)	167
N1C—H1C1···N3Ci	0.83 (1)	2.18 (1)	3.0028 (14)	172 (2)
N1C—H1C2···O3A	0.86 (1)	2.24 (1)	3.0589 (13)	160 (2)
N2C—H2C···O4A	0.88	1.78	2.6278 (12)	161
N4C—H4C···O4Ai	0.88	1.79	2.6645 (12)	170
O2A—H2AB···O3Biv	0.76	1.95	2.6593 (11)	155
O1B—H1B···O3A	0.77	1.80	2.5495 (12)	161
O2B—H2BA···O1iv	0.83	1.73	2.5552 (12)	176
O1—H1D···O2	0.84 (1)	1.93 (1)	2.7439 (12)	166 (2)
O1—H1E···O3B	0.80 (1)	1.91 (1)	2.6968 (12)	168 (2)
O2—H2D···O1Av	0.82 (1)	1.90 (1)	2.7024 (11)	168 (2)
O2—H2E···O3Aiii	0.81 (1)	1.95 (1)	2.7566 (12)	178 (2)
O3—H3D···O2B	0.79 (1)	2.14 (2)	2.8515 (12)	149 (2)
O3—H3E···O1Aiii	0.80 (1)	1.92 (1)	2.7085 (11)	176 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1A1⋯O3B	0.85 (1)	2.31 (1)	3.1356 (13)	162 (2)
N1A—H1A2⋯N3A i	0.85 (1)	2.19 (1)	3.0305 (15)	170 (2)
N2A—H2A⋯O4B	0.88	1.77	2.6130 (13)	161
N4A—H4A⋯O4B i	0.88	1.76	2.6314 (13)	171
N1B—H1B1⋯O2	0.86 (1)	1.96 (1)	2.8214 (13)	178 (2)
N1B—H1B2⋯N3B i	0.82 (1)	2.28 (1)	3.0639 (15)	160 (2)
N2B—H2B1⋯O3ii	0.88	1.84	2.6824 (13)	159
N4B—H4B⋯O1A iii	0.88	1.87	2.7376 (12)	167
N1C—H1C1⋯N3C i	0.83 (1)	2.18 (1)	3.0028 (14)	172 (2)
N1C—H1C2⋯O3A	0.86 (1)	2.24 (1)	3.0589 (13)	160 (2)
N2C—H2C⋯O4A	0.88	1.78	2.6278 (12)	161
N4C—H4C⋯O4A i	0.88	1.79	2.6645 (12)	170
O2A—H2AB⋯O3B iv	0.76	1.95	2.6593 (11)	155
O1B—H1B⋯O3A	0.77	1.80	2.5495 (12)	161
O2B—H2BA⋯O1iv	0.83	1.73	2.5552 (12)	176
O1—H1D⋯O2	0.84 (1)	1.93 (1)	2.7439 (12)	166 (2)
O1—H1E⋯O3B	0.80 (1)	1.91 (1)	2.6968 (12)	168 (2)
O2—H2D⋯O1A v	0.82 (1)	1.90 (1)	2.7024 (11)	168 (2)
O2—H2E⋯O3A iii	0.81 (1)	1.95 (1)	2.7566 (12)	178 (2)
O3—H3D⋯O2B	0.79 (1)	2.14 (2)	2.8515 (12)	149 (2)
O3—H3E⋯O1A iii	0.80 (1)	1.92 (1)	2.7085 (11)	176 (2)

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