Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807051197/bt2549sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807051197/bt2549Isup2.hkl |
CCDC reference: 667195
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (C-C) = 0.003 Å
- Disorder in main residue
- R factor = 0.028
- wR factor = 0.064
- Data-to-parameter ratio = 15.7
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT213_ALERT_2_B Atom O4B has ADP max/min Ratio ............. 4.10 prola PLAT416_ALERT_2_B Short Intra D-H..H-D H4 .. H4B .. 1.86 Ang.
Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 0.25 Ratio PLAT076_ALERT_1_C Occupancy 0.50 less than 1.0 for Sp.pos . O5 PLAT215_ALERT_3_C Disordered O5 has ADP max/min Ratio ....... 3.30 PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.54 Ratio PLAT245_ALERT_2_C U(iso) H2B Smaller than U(eq) O4B by ... 0.04 AngSq PLAT301_ALERT_3_C Main Residue Disorder ......................... 5.00 Perc. PLAT313_ALERT_2_C Oxygen with three covalent bonds (rare) ........ O4A PLAT313_ALERT_2_C Oxygen with three covalent bonds (rare) ........ O4B PLAT416_ALERT_2_C Short Intra D-H..H-D H3 .. H4A .. 1.95 Ang. PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.18 Ratio
Alert level G PLAT793_ALERT_1_G Check the Absolute Configuration of P1 = ... S
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 12 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 5 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 6 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
For background, see: Holtby et al. (2007). For other inorganic networks templated by the same cation, see: Chidambaram et al. (1999); Choudhury et al. (2000); Vaidhyanathan & Natarajan (1999).
Zinc oxide, phosphorus acid and 1,3-diamino-2-propanol were mixed in a 1:2:1:500 molar ratio with 20 ml H2O and shaken. The mixture was placed in a sealted plastic bottle and heated to 353 K for 2 days. Upon cooling and filtration, colourless blocks of (I) were recovered.
The water O5 atom yielded an unreasonably large Uiso value when full fractional occupancy was assumed. Refining the occupancy for O5 led to a value near 1/2, which was fixed for the final cycles of refinement. Reducing the occupancy for O5 also lowered the R factors and led to a more plausible Uiso value, before anisotropic refinement was finally carrued out. The –OH group of the dication is disordered over two positions in a 0.614 (7):0.386 (7) ratio (sum constrained to unity).
Upon anisotropic refinement, O4a, O4b and O5 showed elongated displacement ellipsoids. Attempts to model this situation with split-atom sites or in lower symmetry space groups were not successful. On account of the resulting short H4···H4B distance of 1.86 Å, the positions of the H atoms of the –OH groups should be regarded as less certain. However, it is notable that both H4 and H4b are involved in hydrogen bonds to the same acceptor atom.
The water H atom was located in a difference map and refined as riding in its as-found relative position with Uiso(H) = 1.2Ueq(O). The other H atoms were placed in calculated positions (C—H = 0.99 Å, N—H = 0.91 Å, O—H = 0.90 Å) and refined as riding with Uiso(H) = 1.2Ueq(carrier). The –NH3 group was allowed to rotate, but not to tip, to best fit the electron density.
The title compound, C3H12N2O·Zn(HPO3)2·0.5H2O, (I), (Fig. 1) complements the growing family of templated zincophosphite networks (e.g. Holtby et al., 2007).
The connectivity of the polyhedra in the inorganic zincophosphite component of (I) results in macroanionic chains of 4-rings propagating in [010]. The constituent ZnO4 and HPO3 units have normal geometrical paramters (Table 1), with the Zn atom lying on a crystallographic 2-fold axis. Each Zn atom therefore serves as a node for the chain with O1 and O2 serving as the linking atoms whereas P1—O3 is a terminal bond.
The complete [H3NCH2CHOHCH2NH3]2+ dication in (I) is generated by mirror symmetry, with C2 lying on the reflecting plane. The pendant –OH group attached to C2 is disordered over two positions, with both O atoms also occupying the reflection plane. A water molecule (site symmetry m) with a fractional site occupancy of 0.5 completes the structure of (I).
The unit-cell packing for (I) (Fig. 2) results in the [010] chains of stoichiometry [Zn(HPO3)2]2- being crosslinked by the water molecule in the [001] direction, with linking O—H···O hydrogen bonds (Table 2) as the key structural feature. The organic cation occupies the space between the pseudo (100) layes and further consolidates the structure through O—H···O and also N—H···O hydrogen bonds.
The [H3NCH2CHOHCH2NH3]2+ cation has been used to template other inorganic networks including zinc phosphates (Chidambaram et al., 1999), tin phosphates (Vaidhyanathan & Natarajan, 1999) and iron oxalato-phosphates (Choudhury et al., 2000). It is notable that in most of these phases, the –OH group of the template shows similar positional disorder to that observed here.
For background, see: Holtby et al. (2007). For other inorganic networks templated by the same cation, see: Chidambaram et al. (1999); Choudhury et al. (2000); Vaidhyanathan & Natarajan (1999).
Data collection: COLLECT (Nonius BV, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997), and SORTAV (Blessing, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).
(C3H12N2O)[Zn(HPO3)2]·0.5H2O | F(000) = 668 |
Mr = 326.48 | Dx = 1.877 Mg m−3 |
Orthorhombic, Pbcm | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2c 2b | Cell parameters from 1544 reflections |
a = 8.8554 (3) Å | θ = 2.9–27.5° |
b = 7.8466 (3) Å | µ = 2.43 mm−1 |
c = 16.6251 (5) Å | T = 120 K |
V = 1155.19 (7) Å3 | Block, colourless |
Z = 4 | 0.28 × 0.20 × 0.10 mm |
Nonius KappaCCD diffractometer | 1370 independent reflections |
Radiation source: fine-focus sealed tube | 1271 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.031 |
ω and φ scans | θmax = 27.5°, θmin = 3.5° |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | h = −9→11 |
Tmin = 0.550, Tmax = 0.793 | k = −10→8 |
10217 measured reflections | l = −21→19 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difmap and geom |
R[F2 > 2σ(F2)] = 0.028 | H-atom parameters constrained |
wR(F2) = 0.064 | w = 1/[σ2(Fo2) + (0.0046P)2 + 2.8213P] where P = (Fo2 + 2Fc2)/3 |
S = 1.12 | (Δ/σ)max = 0.002 |
1370 reflections | Δρmax = 0.45 e Å−3 |
87 parameters | Δρmin = −0.38 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0029 (6) |
(C3H12N2O)[Zn(HPO3)2]·0.5H2O | V = 1155.19 (7) Å3 |
Mr = 326.48 | Z = 4 |
Orthorhombic, Pbcm | Mo Kα radiation |
a = 8.8554 (3) Å | µ = 2.43 mm−1 |
b = 7.8466 (3) Å | T = 120 K |
c = 16.6251 (5) Å | 0.28 × 0.20 × 0.10 mm |
Nonius KappaCCD diffractometer | 1370 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2003) | 1271 reflections with I > 2σ(I) |
Tmin = 0.550, Tmax = 0.793 | Rint = 0.031 |
10217 measured reflections |
R[F2 > 2σ(F2)] = 0.028 | 0 restraints |
wR(F2) = 0.064 | H-atom parameters constrained |
S = 1.12 | Δρmax = 0.45 e Å−3 |
1370 reflections | Δρmin = −0.38 e Å−3 |
87 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 | Occ. (<1) | |
Zn1 | 0.04498 (4) | 0.2500 | 0.0000 | 0.01367 (13) | |
P1 | 0.19574 (7) | 0.55780 (8) | 0.09909 (4) | 0.01743 (16) | |
H1 | 0.1771 | 0.4733 | 0.1670 | 0.021* | |
O1 | 0.06921 (19) | 0.6883 (2) | 0.09460 (10) | 0.0226 (4) | |
O2 | 0.18811 (18) | 0.4268 (2) | 0.03132 (10) | 0.0207 (4) | |
O3 | 0.3492 (2) | 0.6382 (3) | 0.10293 (17) | 0.0458 (7) | |
C1 | 0.6993 (3) | 0.5624 (3) | 0.17508 (14) | 0.0230 (5) | |
H1A | 0.6814 | 0.6869 | 0.1765 | 0.028* | |
H1B | 0.8097 | 0.5431 | 0.1735 | 0.028* | |
C2 | 0.6344 (4) | 0.4814 (6) | 0.2500 | 0.0280 (9) | |
H2A | 0.5234 | 0.4971 | 0.2500 | 0.034* | 0.614 (7) |
H2B | 0.6565 | 0.3578 | 0.2500 | 0.034* | 0.386 (7) |
O4A | 0.4821 (4) | 0.4546 (7) | 0.2500 | 0.0288 (14) | 0.614 (7) |
H4A | 0.4429 | 0.5079 | 0.2067 | 0.035* | 0.307 (4) |
O4B | 0.6225 (16) | 0.3254 (10) | 0.2500 | 0.071 (5) | 0.386 (7) |
H4B | 0.6301 | 0.2665 | 0.2038 | 0.085* | 0.193 (4) |
N1 | 0.6289 (2) | 0.4895 (3) | 0.10193 (12) | 0.0197 (4) | |
H2 | 0.6785 | 0.5282 | 0.0576 | 0.024* | |
H3 | 0.5303 | 0.5217 | 0.0995 | 0.024* | |
H4 | 0.6348 | 0.3738 | 0.1038 | 0.024* | |
O5 | 0.0333 (10) | 0.8202 (10) | 0.2500 | 0.063 (3) | 0.50 |
H5 | 0.0134 | 0.7591 | 0.2956 | 0.075* | 0.50 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zn1 | 0.01189 (19) | 0.0156 (2) | 0.0135 (2) | 0.000 | 0.000 | −0.00179 (14) |
P1 | 0.0180 (3) | 0.0157 (3) | 0.0186 (3) | −0.0003 (2) | −0.0065 (2) | −0.0010 (2) |
O1 | 0.0190 (8) | 0.0317 (10) | 0.0170 (8) | 0.0083 (7) | −0.0034 (7) | −0.0029 (7) |
O2 | 0.0190 (8) | 0.0211 (9) | 0.0219 (8) | −0.0053 (7) | 0.0026 (7) | −0.0059 (7) |
O3 | 0.0162 (9) | 0.0245 (11) | 0.097 (2) | 0.0013 (8) | −0.0156 (11) | −0.0235 (12) |
C1 | 0.0217 (12) | 0.0284 (13) | 0.0189 (12) | −0.0072 (10) | −0.0013 (10) | −0.0016 (10) |
C2 | 0.0234 (18) | 0.043 (2) | 0.0173 (16) | −0.0162 (17) | 0.000 | 0.000 |
O4A | 0.012 (2) | 0.059 (3) | 0.0146 (19) | −0.0111 (19) | 0.000 | 0.000 |
O4B | 0.174 (13) | 0.016 (4) | 0.022 (4) | −0.029 (6) | 0.000 | 0.000 |
N1 | 0.0168 (10) | 0.0230 (11) | 0.0195 (10) | −0.0010 (8) | 0.0024 (8) | −0.0028 (8) |
O5 | 0.113 (7) | 0.062 (5) | 0.013 (3) | −0.052 (5) | 0.000 | 0.000 |
Zn1—O1i | 1.9314 (17) | C2—O4B | 1.229 (9) |
Zn1—O1ii | 1.9314 (17) | C2—O4A | 1.365 (5) |
Zn1—O2 | 1.9501 (16) | C2—C1iv | 1.512 (3) |
Zn1—O2iii | 1.9501 (16) | C2—H2A | 0.9900 |
P1—O3 | 1.4999 (19) | C2—H2B | 0.9900 |
P1—O1 | 1.5197 (17) | O4A—H2A | 0.4951 |
P1—O2 | 1.5264 (17) | O4A—H4A | 0.9023 |
P1—H1 | 1.3200 | O4B—H2B | 0.3939 |
O1—Zn1i | 1.9314 (17) | O4B—H4B | 0.8991 |
C1—N1 | 1.481 (3) | N1—H2 | 0.9100 |
C1—C2 | 1.512 (3) | N1—H3 | 0.9100 |
C1—H1A | 0.9900 | N1—H4 | 0.9100 |
C1—H1B | 0.9900 | O5—H5 | 0.9142 |
O1i—Zn1—O1ii | 116.86 (10) | O4A—C2—C1iv | 116.1 (2) |
O1i—Zn1—O2 | 112.29 (8) | O4B—C2—C1 | 116.8 (3) |
O1ii—Zn1—O2 | 107.53 (7) | O4A—C2—C1 | 116.1 (2) |
O1i—Zn1—O2iii | 107.53 (7) | C1iv—C2—C1 | 110.9 (3) |
O1ii—Zn1—O2iii | 112.29 (8) | O4B—C2—H2A | 92.2 |
O2—Zn1—O2iii | 98.92 (10) | C1iv—C2—H2A | 109.0 |
O3—P1—O1 | 112.76 (11) | C1—C2—H2A | 109.0 |
O3—P1—O2 | 110.78 (12) | O4A—C2—H2B | 92.5 |
O1—P1—O2 | 112.62 (10) | C1iv—C2—H2B | 109.7 |
O3—P1—H1 | 106.7 | C1—C2—H2B | 109.7 |
O1—P1—H1 | 106.7 | H2A—C2—H2B | 108.5 |
O2—P1—H1 | 106.7 | C2—O4A—H4A | 108.0 |
P1—O1—Zn1i | 126.51 (10) | H2A—O4A—H4A | 88.4 |
P1—O2—Zn1 | 134.82 (10) | C2—O4B—H4B | 120.4 |
N1—C1—C2 | 110.7 (2) | H2B—O4B—H4B | 105.9 |
N1—C1—H1A | 109.5 | C1—N1—H2 | 109.5 |
C2—C1—H1A | 109.5 | C1—N1—H3 | 109.5 |
N1—C1—H1B | 109.5 | H2—N1—H3 | 109.5 |
C2—C1—H1B | 109.5 | C1—N1—H4 | 109.5 |
H1A—C1—H1B | 108.1 | H2—N1—H4 | 109.5 |
O4B—C2—O4A | 76.2 (7) | H3—N1—H4 | 109.5 |
O4B—C2—C1iv | 116.8 (3) | ||
O3—P1—O1—Zn1i | 103.54 (17) | O1ii—Zn1—O2—P1 | −23.26 (18) |
O2—P1—O1—Zn1i | −22.74 (17) | O2iii—Zn1—O2—P1 | −140.15 (19) |
O3—P1—O2—Zn1 | 168.39 (15) | N1—C1—C2—O4B | 45.9 (8) |
O1—P1—O2—Zn1 | −64.28 (18) | N1—C1—C2—O4A | −41.3 (5) |
O1i—Zn1—O2—P1 | 106.65 (16) | N1—C1—C2—C1iv | −176.8 (2) |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x, y−1/2, z; (iii) x, −y+1/2, −z; (iv) x, y, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O4A—H4A···O3 | 0.90 | 2.17 | 3.072 (4) | 179 |
O4B—H4B···O3v | 0.90 | 1.96 | 2.863 (5) | 179 |
N1—H2···O2vi | 0.91 | 1.92 | 2.822 (3) | 168 |
N1—H3···O3 | 0.91 | 1.85 | 2.738 (3) | 166 |
N1—H4···O3v | 0.91 | 1.85 | 2.763 (3) | 177 |
O5—H5···O1iv | 0.91 | 1.97 | 2.801 (4) | 150 |
Symmetry codes: (iv) x, y, −z+1/2; (v) −x+1, y−1/2, z; (vi) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | (C3H12N2O)[Zn(HPO3)2]·0.5H2O |
Mr | 326.48 |
Crystal system, space group | Orthorhombic, Pbcm |
Temperature (K) | 120 |
a, b, c (Å) | 8.8554 (3), 7.8466 (3), 16.6251 (5) |
V (Å3) | 1155.19 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.43 |
Crystal size (mm) | 0.28 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (SADABS; Bruker, 2003) |
Tmin, Tmax | 0.550, 0.793 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10217, 1370, 1271 |
Rint | 0.031 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.028, 0.064, 1.12 |
No. of reflections | 1370 |
No. of parameters | 87 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.45, −0.38 |
Computer programs: COLLECT (Nonius BV, 1998), SCALEPACK (Otwinowski & Minor, 1997), SCALEPACK and DENZO (Otwinowski & Minor, 1997), and SORTAV (Blessing, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997).
Zn1—O1i | 1.9314 (17) | P1—O3 | 1.4999 (19) |
Zn1—O1ii | 1.9314 (17) | P1—O1 | 1.5197 (17) |
Zn1—O2 | 1.9501 (16) | P1—O2 | 1.5264 (17) |
Zn1—O2iii | 1.9501 (16) |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x, y−1/2, z; (iii) x, −y+1/2, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O4A—H4A···O3 | 0.90 | 2.17 | 3.072 (4) | 179 |
O4B—H4B···O3iv | 0.90 | 1.96 | 2.863 (5) | 179 |
N1—H2···O2v | 0.91 | 1.92 | 2.822 (3) | 168 |
N1—H3···O3 | 0.91 | 1.85 | 2.738 (3) | 166 |
N1—H4···O3iv | 0.91 | 1.85 | 2.763 (3) | 177 |
O5—H5···O1vi | 0.91 | 1.97 | 2.801 (4) | 150 |
Symmetry codes: (iv) −x+1, y−1/2, z; (v) −x+1, −y+1, −z; (vi) x, y, −z+1/2. |
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The title compound, C3H12N2O·Zn(HPO3)2·0.5H2O, (I), (Fig. 1) complements the growing family of templated zincophosphite networks (e.g. Holtby et al., 2007).
The connectivity of the polyhedra in the inorganic zincophosphite component of (I) results in macroanionic chains of 4-rings propagating in [010]. The constituent ZnO4 and HPO3 units have normal geometrical paramters (Table 1), with the Zn atom lying on a crystallographic 2-fold axis. Each Zn atom therefore serves as a node for the chain with O1 and O2 serving as the linking atoms whereas P1—O3 is a terminal bond.
The complete [H3NCH2CHOHCH2NH3]2+ dication in (I) is generated by mirror symmetry, with C2 lying on the reflecting plane. The pendant –OH group attached to C2 is disordered over two positions, with both O atoms also occupying the reflection plane. A water molecule (site symmetry m) with a fractional site occupancy of 0.5 completes the structure of (I).
The unit-cell packing for (I) (Fig. 2) results in the [010] chains of stoichiometry [Zn(HPO3)2]2- being crosslinked by the water molecule in the [001] direction, with linking O—H···O hydrogen bonds (Table 2) as the key structural feature. The organic cation occupies the space between the pseudo (100) layes and further consolidates the structure through O—H···O and also N—H···O hydrogen bonds.
The [H3NCH2CHOHCH2NH3]2+ cation has been used to template other inorganic networks including zinc phosphates (Chidambaram et al., 1999), tin phosphates (Vaidhyanathan & Natarajan, 1999) and iron oxalato-phosphates (Choudhury et al., 2000). It is notable that in most of these phases, the –OH group of the template shows similar positional disorder to that observed here.