Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270102009629/av1110sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270102009629/av1110Isup2.hkl |
CCDC reference: 183115
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.
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.
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.
C4H14N2O2+·HO4P2−·H2O | Dx = 1.504 Mg m−3 |
Mr = 220.17 | Melting point: not measured K |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 7.0863 (3) Å | Cell parameters from 5486 reflections |
b = 28.4885 (11) Å | θ = 2.9–32.5° |
c = 4.8336 (2) Å | µ = 0.29 mm−1 |
β = 94.874 (1)° | T = 293 K |
V = 972.27 (7) Å3 | Chunk, colourless |
Z = 4 | 0.46 × 0.30 × 0.19 mm |
F(000) = 472 |
Bruker SMART 1000 CCD area-detector diffractometer | 3520 independent reflections |
Radiation source: fine-focus sealed tube | 3051 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.016 |
ω scans | θmax = 32.5°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Bruker, 1999) | h = −10→10 |
Tmin = 0.902, Tmax = 0.947 | k = −43→34 |
9939 measured reflections | l = −6→7 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: none |
R[F2 > 2σ(F2)] = 0.032 | Hydrogen site location: mixed |
wR(F2) = 0.091 | H 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 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
C4H14N2O2+·HO4P2−·H2O | V = 972.27 (7) Å3 |
Mr = 220.17 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.0863 (3) Å | µ = 0.29 mm−1 |
b = 28.4885 (11) Å | T = 293 K |
c = 4.8336 (2) Å | 0.46 × 0.30 × 0.19 mm |
β = 94.874 (1)° |
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 = 0.947 | Rint = 0.016 |
9939 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.091 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.34 e Å−3 |
3520 reflections | Δρmin = −0.25 e Å−3 |
162 parameters |
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 | 0.24386 (3) | 0.066713 (9) | 0.53198 (5) | 0.01795 (7) | |
O1 | 0.29299 (11) | 0.03924 (3) | 0.79651 (15) | 0.02687 (16) | |
O2 | 0.06383 (10) | 0.09652 (3) | 0.54860 (15) | 0.02467 (15) | |
O3 | 0.40488 (10) | 0.09761 (3) | 0.44708 (16) | 0.02603 (16) | |
O4 | 0.19514 (14) | 0.02854 (3) | 0.29789 (17) | 0.0344 (2) | |
H4 | 0.227 (4) | 0.0375 (10) | 0.152 (5) | 0.090 (8)* | |
O5 | 0.32252 (15) | 0.18549 (3) | 0.3287 (2) | 0.0384 (2) | |
H5 | 0.346 (3) | 0.1595 (7) | 0.351 (4) | 0.050 (5)* | |
O1W | 0.67791 (16) | 0.22440 (5) | 0.4570 (2) | 0.0462 (3) | |
H1A | 0.572 (4) | 0.2120 (9) | 0.435 (5) | 0.074 (7)* | |
H1B | 0.667 (3) | 0.2415 (8) | 0.595 (5) | 0.069 (7)* | |
N1 | −0.01794 (12) | 0.13671 (3) | 0.03106 (18) | 0.02173 (16) | |
H111 | 0.022 (2) | 0.1264 (6) | 0.198 (3) | 0.036 (4)* | |
H112 | 0.027 (2) | 0.1211 (6) | −0.094 (4) | 0.038 (4)* | |
N2 | −0.27371 (12) | 0.05690 (4) | 0.27835 (19) | 0.02369 (17) | |
H211 | −0.278 (2) | 0.0247 (6) | 0.264 (3) | 0.038 (4)* | |
H212 | −0.371 (2) | 0.0689 (6) | 0.354 (4) | 0.040 (4)* | |
H213 | −0.167 (2) | 0.0633 (6) | 0.385 (3) | 0.035 (4)* | |
C1 | 0.25351 (17) | 0.19171 (5) | 0.0471 (3) | 0.0361 (3) | |
H11 | 0.3124 | 0.1687 | −0.0661 | 0.053 (5)* | |
H12 | 0.2891 | 0.2227 | −0.0138 | 0.045 (5)* | |
C2 | 0.03989 (17) | 0.18656 (4) | 0.0031 (3) | 0.0328 (2) | |
H21 | −0.0190 | 0.2055 | 0.1386 | 0.049 (5)* | |
H22 | −0.0038 | 0.1979 | −0.1804 | 0.050 (5)* | |
C3 | −0.22630 (14) | 0.12816 (4) | −0.0113 (2) | 0.0261 (2) | |
H31 | −0.2751 | 0.1413 | −0.1882 | 0.040 (4)* | |
H32 | −0.2887 | 0.1438 | 0.1339 | 0.052 (5)* | |
C4 | −0.27073 (14) | 0.07612 (4) | −0.0070 (2) | 0.0252 (2) | |
H4A | −0.3932 | 0.0708 | −0.1076 | 0.040 (4)* | |
H4B | −0.1766 | 0.0593 | −0.1026 | 0.038 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
P1 | 0.01798 (11) | 0.02074 (13) | 0.01533 (11) | −0.00010 (8) | 0.00256 (7) | −0.00059 (8) |
O1 | 0.0317 (4) | 0.0298 (4) | 0.0188 (3) | 0.0015 (3) | 0.0009 (3) | 0.0046 (3) |
O2 | 0.0181 (3) | 0.0311 (4) | 0.0249 (3) | 0.0035 (3) | 0.0023 (2) | −0.0001 (3) |
O3 | 0.0202 (3) | 0.0264 (4) | 0.0324 (4) | −0.0010 (3) | 0.0074 (3) | 0.0029 (3) |
O4 | 0.0533 (5) | 0.0300 (4) | 0.0213 (4) | −0.0118 (4) | 0.0108 (3) | −0.0072 (3) |
O5 | 0.0470 (5) | 0.0253 (4) | 0.0400 (5) | −0.0064 (4) | −0.0119 (4) | 0.0015 (3) |
O1W | 0.0382 (5) | 0.0562 (7) | 0.0438 (6) | −0.0040 (5) | 0.0006 (4) | −0.0047 (5) |
N1 | 0.0220 (4) | 0.0214 (4) | 0.0215 (4) | 0.0001 (3) | 0.0009 (3) | −0.0001 (3) |
N2 | 0.0200 (4) | 0.0274 (5) | 0.0238 (4) | −0.0008 (3) | 0.0027 (3) | 0.0011 (3) |
C1 | 0.0363 (6) | 0.0342 (6) | 0.0368 (6) | −0.0120 (5) | −0.0026 (5) | 0.0073 (5) |
C2 | 0.0357 (6) | 0.0215 (5) | 0.0397 (6) | −0.0021 (4) | −0.0048 (5) | 0.0045 (4) |
C3 | 0.0212 (4) | 0.0288 (5) | 0.0279 (5) | 0.0027 (4) | −0.0001 (3) | 0.0035 (4) |
C4 | 0.0247 (4) | 0.0302 (5) | 0.0202 (4) | −0.0049 (4) | −0.0003 (3) | −0.0009 (3) |
P1—O1 | 1.5144 (8) | N2—H211 | 0.920 (18) |
P1—O2 | 1.5402 (7) | N2—H212 | 0.876 (18) |
P1—O3 | 1.5247 (8) | N2—H213 | 0.897 (16) |
P1—O4 | 1.5862 (8) | C1—C2 | 1.5178 (17) |
O4—H4 | 0.80 (3) | C1—H11 | 0.9700 |
O5—C1 | 1.4179 (16) | C1—H12 | 0.9700 |
O5—H5 | 0.77 (2) | C2—H21 | 0.9700 |
O1W—H1A | 0.83 (3) | C2—H22 | 0.9700 |
O1W—H1B | 0.83 (2) | C3—C4 | 1.5162 (16) |
N1—C2 | 1.4875 (15) | C3—H31 | 0.9700 |
N1—C3 | 1.4933 (13) | C3—H32 | 0.9700 |
N1—H111 | 0.881 (16) | C4—H4A | 0.9700 |
N1—H112 | 0.832 (18) | C4—H4B | 0.9700 |
N2—C4 | 1.4857 (13) | ||
O1—P1—O3 | 113.71 (4) | C2—C1—H11 | 109.1 |
O1—P1—O2 | 111.90 (4) | O5—C1—H12 | 109.1 |
O3—P1—O2 | 109.75 (5) | C2—C1—H12 | 109.1 |
O1—P1—O4 | 105.57 (5) | H11—C1—H12 | 107.9 |
O3—P1—O4 | 109.05 (5) | N1—C2—C1 | 111.03 (10) |
O2—P1—O4 | 106.51 (5) | N1—C2—H21 | 109.4 |
P1—O4—H4 | 110 (2) | C1—C2—H21 | 109.4 |
C1—O5—H5 | 108.1 (15) | N1—C2—H22 | 109.4 |
H1A—O1W—H1B | 102 (2) | C1—C2—H22 | 109.4 |
C2—N1—C3 | 114.85 (9) | H21—C2—H22 | 108.0 |
C2—N1—H111 | 109.4 (10) | N1—C3—C4 | 111.21 (9) |
C3—N1—H111 | 107.9 (10) | N1—C3—H31 | 109.4 |
C2—N1—H112 | 108.6 (12) | C4—C3—H31 | 109.4 |
C3—N1—H112 | 104.2 (11) | N1—C3—H32 | 109.4 |
H111—N1—H112 | 111.7 (15) | C4—C3—H32 | 109.4 |
C4—N2—H211 | 107.4 (10) | H31—C3—H32 | 108.0 |
C4—N2—H212 | 108.4 (11) | N2—C4—C3 | 113.12 (9) |
H211—N2—H212 | 113.6 (14) | N2—C4—H4A | 109.0 |
C4—N2—H213 | 112.2 (10) | C3—C4—H4A | 109.0 |
H211—N2—H213 | 105.6 (14) | N2—C4—H4B | 109.0 |
H212—N2—H213 | 109.7 (16) | C3—C4—H4B | 109.0 |
O5—C1—C2 | 112.40 (11) | H4A—C4—H4B | 107.8 |
O5—C1—H11 | 109.1 | ||
C3—N1—C2—C1 | −179.52 (10) | C2—N1—C3—C4 | 174.46 (9) |
O5—C1—C2—N1 | −71.91 (14) | N1—C3—C4—N2 | 82.13 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O1i | 0.80 (3) | 1.82 (3) | 2.5947 (11) | 163 (3) |
O5—H5···O3 | 0.77 (2) | 1.86 (2) | 2.6228 (13) | 174 (2) |
O1W—H1A···O5 | 0.83 (3) | 1.95 (3) | 2.7731 (15) | 172 (2) |
O1W—H1B···O1Wii | 0.83 (2) | 2.00 (2) | 2.8227 (14) | 170 (2) |
N1—H111···O2 | 0.881 (16) | 1.898 (17) | 2.7674 (12) | 169 (2) |
N1—H112···O2i | 0.832 (18) | 1.905 (18) | 2.7046 (12) | 161 (2) |
N2—H211···O1iii | 0.920 (18) | 1.846 (18) | 2.7643 (13) | 175 (2) |
N2—H212···O3iv | 0.876 (18) | 1.875 (18) | 2.7412 (12) | 169 (2) |
N2—H213···O2 | 0.897 (16) | 1.994 (17) | 2.8584 (12) | 162 (2) |
Symmetry codes: (i) x, y, z−1; (ii) x, −y+1/2, z+1/2; (iii) −x, −y, −z+1; (iv) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C4H14N2O2+·HO4P2−·H2O |
Mr | 220.17 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 7.0863 (3), 28.4885 (11), 4.8336 (2) |
β (°) | 94.874 (1) |
V (Å3) | 972.27 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.29 |
Crystal size (mm) | 0.46 × 0.30 × 0.19 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1999) |
Tmin, Tmax | 0.902, 0.947 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9939, 3520, 3051 |
Rint | 0.016 |
(sin θ/λ)max (Å−1) | 0.756 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.091, 1.10 |
No. of reflections | 3520 |
No. of parameters | 162 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 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.
P1—O1 | 1.5144 (8) | N1—C2 | 1.4875 (15) |
P1—O2 | 1.5402 (7) | N1—C3 | 1.4933 (13) |
P1—O3 | 1.5247 (8) | N2—C4 | 1.4857 (13) |
P1—O4 | 1.5862 (8) | C1—C2 | 1.5178 (17) |
O4—H4 | 0.80 (3) | C3—C4 | 1.5162 (16) |
O5—C1 | 1.4179 (16) | ||
C3—N1—C2—C1 | −179.52 (10) | C2—N1—C3—C4 | 174.46 (9) |
O5—C1—C2—N1 | −71.91 (14) | N1—C3—C4—N2 | 82.13 (11) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O1i | 0.80 (3) | 1.82 (3) | 2.5947 (11) | 163 (3) |
O5—H5···O3 | 0.77 (2) | 1.86 (2) | 2.6228 (13) | 174 (2) |
O1W—H1A···O5 | 0.83 (3) | 1.95 (3) | 2.7731 (15) | 172 (2) |
O1W—H1B···O1Wii | 0.83 (2) | 2.00 (2) | 2.8227 (14) | 170 (2) |
N1—H111···O2 | 0.881 (16) | 1.898 (17) | 2.7674 (12) | 169 (2) |
N1—H112···O2i | 0.832 (18) | 1.905 (18) | 2.7046 (12) | 161 (2) |
N2—H211···O1iii | 0.920 (18) | 1.846 (18) | 2.7643 (13) | 175 (2) |
N2—H212···O3iv | 0.876 (18) | 1.875 (18) | 2.7412 (12) | 169 (2) |
N2—H213···O2 | 0.897 (16) | 1.994 (17) | 2.8584 (12) | 162 (2) |
Symmetry codes: (i) x, y, z−1; (ii) x, −y+1/2, z+1/2; (iii) −x, −y, −z+1; (iv) x−1, y, z. |
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.