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The title compound, C4H14N2O2+·HPO42-·H2O, contains alternating interleaved layers of hydrogenphosphate and N-(2-hydroxyethyl)ethyl­enedi­ammonium moieties. The water mol­ecules are associated with channel-like voids in the structure and a network of hydrogen bonds stabilizes the crystal packing.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102009629/av1110sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270102009629/av1110Isup2.hkl
Contains datablock I

CCDC reference: 183115

Comment top

During the synthesis of metal phosphates templated by organic amines (Cheetham et al., 1999), amine phosphates may occur as unexpected side products and may also act as intermediates in the formation of open-framework structures (Oliver et al., 1998; Neeraj et al., 1999). Here, we describe the structure of one such amine phosphate, the title compound, (I). \sch

The structure of (I) (Fig. 1) consists of a molecular network. Both amino groups of the N-(2-hydroxyethyl)ethylenediammonium moiety are protonated, to result in a divalent species. The N-(2-hydroxyethyl)ethylenediammonium cation exibits a gauche conformation, and bond distances within the cation are comparable to the neutral molecule coordinated to CuII and CdII ions (Yilmaz et al., 2002). One of the phosphate P—O vertices is protonated, and shows the expected lengthening relative to the other P—O bonds (Oliver et al., 1998).

The crystal packing in (I) is shown in Fig. 2. The structure contains alternating interleaved layers of anions and cations, with the layers propagating in the (101) plane. The water molecules occupy channel-like voids propagating along [001]. All H atoms of the ammonium groups form N—H···O hydrogen bonds to neighboring phosphate O atoms, while the hydroxyl group of the organic species makes hydrogen bonds to O atoms of the phosphate ions and water molecules. Adjacent phosphate anions are also linked by P—OH···O hydrogen bonds in the [001] direction.

Experimental top

H3PO4 (0.814 ml, 12 mmol) (aqueous, 85% w/w) was added dropwise to an aqueous solution of ethylene glycol (20%, 20 ml) with monoethanolethylenediamine (1.012 ml, 10 mmol) and stirred for 2 h at 323 K. The resulting mixture was left to crystallize at room temperature. Colourless chunk-type crystals of (I) were formed, and these were washed with a small amount of water and acetone, and dried in air.

Refinement top

Water, hydroxyl and amine H atoms were found in difference maps and were refined freely. H atoms bonded to C atoms were placed in calculated positions (C—H = 0.97 Å) and treated as riding.

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A view of the molecule of (I) with 50% displacement ellipsoids. H atoms are drawn as small spheres of arbitrary radii and hydrogen bonds are indicated by dashed lines.
[Figure 2] Fig. 2. A projection of the structure of (I) along [001].
N-(2-hydroxyethyl)ethylenediammonium hydrogenphosphate monohydrate top
Crystal data top
C4H14N2O2+·HO4P2·H2ODx = 1.504 Mg m3
Mr = 220.17Melting point: not measured K
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
a = 7.0863 (3) ÅCell parameters from 5486 reflections
b = 28.4885 (11) Åθ = 2.9–32.5°
c = 4.8336 (2) ŵ = 0.29 mm1
β = 94.874 (1)°T = 293 K
V = 972.27 (7) Å3Chunk, colourless
Z = 40.46 × 0.30 × 0.19 mm
F(000) = 472
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
3520 independent reflections
Radiation source: fine-focus sealed tube3051 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.016
ω scansθmax = 32.5°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
h = 1010
Tmin = 0.902, Tmax = 0.947k = 4334
9939 measured reflectionsl = 67
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: none
R[F2 > 2σ(F2)] = 0.032Hydrogen site location: mixed
wR(F2) = 0.091H atoms treated by a mixture of independent and constrained refinement
S = 1.10 w = 1/[σ2(Fo2) + (0.0512P)2 + 0.0694P]
where P = (Fo2 + 2Fc2)/3
3520 reflections(Δ/σ)max < 0.001
162 parametersΔρmax = 0.34 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C4H14N2O2+·HO4P2·H2OV = 972.27 (7) Å3
Mr = 220.17Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.0863 (3) ŵ = 0.29 mm1
b = 28.4885 (11) ÅT = 293 K
c = 4.8336 (2) Å0.46 × 0.30 × 0.19 mm
β = 94.874 (1)°
Data collection top
Bruker SMART 1000 CCD area-detector
diffractometer
3520 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1999)
3051 reflections with I > 2σ(I)
Tmin = 0.902, Tmax = 0.947Rint = 0.016
9939 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.091H atoms treated by a mixture of independent and constrained refinement
S = 1.10Δρmax = 0.34 e Å3
3520 reflectionsΔρmin = 0.25 e Å3
162 parameters
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
P10.24386 (3)0.066713 (9)0.53198 (5)0.01795 (7)
O10.29299 (11)0.03924 (3)0.79651 (15)0.02687 (16)
O20.06383 (10)0.09652 (3)0.54860 (15)0.02467 (15)
O30.40488 (10)0.09761 (3)0.44708 (16)0.02603 (16)
O40.19514 (14)0.02854 (3)0.29789 (17)0.0344 (2)
H40.227 (4)0.0375 (10)0.152 (5)0.090 (8)*
O50.32252 (15)0.18549 (3)0.3287 (2)0.0384 (2)
H50.346 (3)0.1595 (7)0.351 (4)0.050 (5)*
O1W0.67791 (16)0.22440 (5)0.4570 (2)0.0462 (3)
H1A0.572 (4)0.2120 (9)0.435 (5)0.074 (7)*
H1B0.667 (3)0.2415 (8)0.595 (5)0.069 (7)*
N10.01794 (12)0.13671 (3)0.03106 (18)0.02173 (16)
H1110.022 (2)0.1264 (6)0.198 (3)0.036 (4)*
H1120.027 (2)0.1211 (6)0.094 (4)0.038 (4)*
N20.27371 (12)0.05690 (4)0.27835 (19)0.02369 (17)
H2110.278 (2)0.0247 (6)0.264 (3)0.038 (4)*
H2120.371 (2)0.0689 (6)0.354 (4)0.040 (4)*
H2130.167 (2)0.0633 (6)0.385 (3)0.035 (4)*
C10.25351 (17)0.19171 (5)0.0471 (3)0.0361 (3)
H110.31240.16870.06610.053 (5)*
H120.28910.22270.01380.045 (5)*
C20.03989 (17)0.18656 (4)0.0031 (3)0.0328 (2)
H210.01900.20550.13860.049 (5)*
H220.00380.19790.18040.050 (5)*
C30.22630 (14)0.12816 (4)0.0113 (2)0.0261 (2)
H310.27510.14130.18820.040 (4)*
H320.28870.14380.13390.052 (5)*
C40.27073 (14)0.07612 (4)0.0070 (2)0.0252 (2)
H4A0.39320.07080.10760.040 (4)*
H4B0.17660.05930.10260.038 (4)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
P10.01798 (11)0.02074 (13)0.01533 (11)0.00010 (8)0.00256 (7)0.00059 (8)
O10.0317 (4)0.0298 (4)0.0188 (3)0.0015 (3)0.0009 (3)0.0046 (3)
O20.0181 (3)0.0311 (4)0.0249 (3)0.0035 (3)0.0023 (2)0.0001 (3)
O30.0202 (3)0.0264 (4)0.0324 (4)0.0010 (3)0.0074 (3)0.0029 (3)
O40.0533 (5)0.0300 (4)0.0213 (4)0.0118 (4)0.0108 (3)0.0072 (3)
O50.0470 (5)0.0253 (4)0.0400 (5)0.0064 (4)0.0119 (4)0.0015 (3)
O1W0.0382 (5)0.0562 (7)0.0438 (6)0.0040 (5)0.0006 (4)0.0047 (5)
N10.0220 (4)0.0214 (4)0.0215 (4)0.0001 (3)0.0009 (3)0.0001 (3)
N20.0200 (4)0.0274 (5)0.0238 (4)0.0008 (3)0.0027 (3)0.0011 (3)
C10.0363 (6)0.0342 (6)0.0368 (6)0.0120 (5)0.0026 (5)0.0073 (5)
C20.0357 (6)0.0215 (5)0.0397 (6)0.0021 (4)0.0048 (5)0.0045 (4)
C30.0212 (4)0.0288 (5)0.0279 (5)0.0027 (4)0.0001 (3)0.0035 (4)
C40.0247 (4)0.0302 (5)0.0202 (4)0.0049 (4)0.0003 (3)0.0009 (3)
Geometric parameters (Å, º) top
P1—O11.5144 (8)N2—H2110.920 (18)
P1—O21.5402 (7)N2—H2120.876 (18)
P1—O31.5247 (8)N2—H2130.897 (16)
P1—O41.5862 (8)C1—C21.5178 (17)
O4—H40.80 (3)C1—H110.9700
O5—C11.4179 (16)C1—H120.9700
O5—H50.77 (2)C2—H210.9700
O1W—H1A0.83 (3)C2—H220.9700
O1W—H1B0.83 (2)C3—C41.5162 (16)
N1—C21.4875 (15)C3—H310.9700
N1—C31.4933 (13)C3—H320.9700
N1—H1110.881 (16)C4—H4A0.9700
N1—H1120.832 (18)C4—H4B0.9700
N2—C41.4857 (13)
O1—P1—O3113.71 (4)C2—C1—H11109.1
O1—P1—O2111.90 (4)O5—C1—H12109.1
O3—P1—O2109.75 (5)C2—C1—H12109.1
O1—P1—O4105.57 (5)H11—C1—H12107.9
O3—P1—O4109.05 (5)N1—C2—C1111.03 (10)
O2—P1—O4106.51 (5)N1—C2—H21109.4
P1—O4—H4110 (2)C1—C2—H21109.4
C1—O5—H5108.1 (15)N1—C2—H22109.4
H1A—O1W—H1B102 (2)C1—C2—H22109.4
C2—N1—C3114.85 (9)H21—C2—H22108.0
C2—N1—H111109.4 (10)N1—C3—C4111.21 (9)
C3—N1—H111107.9 (10)N1—C3—H31109.4
C2—N1—H112108.6 (12)C4—C3—H31109.4
C3—N1—H112104.2 (11)N1—C3—H32109.4
H111—N1—H112111.7 (15)C4—C3—H32109.4
C4—N2—H211107.4 (10)H31—C3—H32108.0
C4—N2—H212108.4 (11)N2—C4—C3113.12 (9)
H211—N2—H212113.6 (14)N2—C4—H4A109.0
C4—N2—H213112.2 (10)C3—C4—H4A109.0
H211—N2—H213105.6 (14)N2—C4—H4B109.0
H212—N2—H213109.7 (16)C3—C4—H4B109.0
O5—C1—C2112.40 (11)H4A—C4—H4B107.8
O5—C1—H11109.1
C3—N1—C2—C1179.52 (10)C2—N1—C3—C4174.46 (9)
O5—C1—C2—N171.91 (14)N1—C3—C4—N282.13 (11)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4···O1i0.80 (3)1.82 (3)2.5947 (11)163 (3)
O5—H5···O30.77 (2)1.86 (2)2.6228 (13)174 (2)
O1W—H1A···O50.83 (3)1.95 (3)2.7731 (15)172 (2)
O1W—H1B···O1Wii0.83 (2)2.00 (2)2.8227 (14)170 (2)
N1—H111···O20.881 (16)1.898 (17)2.7674 (12)169 (2)
N1—H112···O2i0.832 (18)1.905 (18)2.7046 (12)161 (2)
N2—H211···O1iii0.920 (18)1.846 (18)2.7643 (13)175 (2)
N2—H212···O3iv0.876 (18)1.875 (18)2.7412 (12)169 (2)
N2—H213···O20.897 (16)1.994 (17)2.8584 (12)162 (2)
Symmetry codes: (i) x, y, z1; (ii) x, y+1/2, z+1/2; (iii) x, y, z+1; (iv) x1, y, z.

Experimental details

Crystal data
Chemical formulaC4H14N2O2+·HO4P2·H2O
Mr220.17
Crystal system, space groupMonoclinic, P21/c
Temperature (K)293
a, b, c (Å)7.0863 (3), 28.4885 (11), 4.8336 (2)
β (°) 94.874 (1)
V3)972.27 (7)
Z4
Radiation typeMo Kα
µ (mm1)0.29
Crystal size (mm)0.46 × 0.30 × 0.19
Data collection
DiffractometerBruker SMART 1000 CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1999)
Tmin, Tmax0.902, 0.947
No. of measured, independent and
observed [I > 2σ(I)] reflections
9939, 3520, 3051
Rint0.016
(sin θ/λ)max1)0.756
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.091, 1.10
No. of reflections3520
No. of parameters162
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.34, 0.25

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
P1—O11.5144 (8)N1—C21.4875 (15)
P1—O21.5402 (7)N1—C31.4933 (13)
P1—O31.5247 (8)N2—C41.4857 (13)
P1—O41.5862 (8)C1—C21.5178 (17)
O4—H40.80 (3)C3—C41.5162 (16)
O5—C11.4179 (16)
C3—N1—C2—C1179.52 (10)C2—N1—C3—C4174.46 (9)
O5—C1—C2—N171.91 (14)N1—C3—C4—N282.13 (11)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O4—H4···O1i0.80 (3)1.82 (3)2.5947 (11)163 (3)
O5—H5···O30.77 (2)1.86 (2)2.6228 (13)174 (2)
O1W—H1A···O50.83 (3)1.95 (3)2.7731 (15)172 (2)
O1W—H1B···O1Wii0.83 (2)2.00 (2)2.8227 (14)170 (2)
N1—H111···O20.881 (16)1.898 (17)2.7674 (12)169 (2)
N1—H112···O2i0.832 (18)1.905 (18)2.7046 (12)161 (2)
N2—H211···O1iii0.920 (18)1.846 (18)2.7643 (13)175 (2)
N2—H212···O3iv0.876 (18)1.875 (18)2.7412 (12)169 (2)
N2—H213···O20.897 (16)1.994 (17)2.8584 (12)162 (2)
Symmetry codes: (i) x, y, z1; (ii) x, y+1/2, z+1/2; (iii) x, y, z+1; (iv) x1, y, z.
 

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