Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807056280/hk2367sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807056280/hk2367Isup2.hkl |
CCDC reference: 1150427
Crystals of the title compound were synthesized using hydrothermal method in a 23 ml Teflon-lined Parr bomb. Copper sulfate pentahydrate (249.7 mg, 1 mmol), ethylene diamine (120.2 mg, 2 mmol), p-acetaminobenzoic acid (179.1 mg, 1 mmol) and distilled water (6 g) were placed into the bomb and sealed. The bomb was then heated under autogenous pressure up to 443 K over the course of 7 d and allowed to cool at room temperature for 24 h. Upon opening the bomb, a clear colorless solution was decanted from small colorless crystals. These crystals were washed with distilled water followed by ethanol, and allowed to air-dry at room temperature.
H atoms were positioned geometrically, with N—H = 0.89 Å (for NH3) and C—H = 0.97 Å for methylene H atoms, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,N), where x = 1.2 for methylene H, and x = 1.5 for NH3 H atoms.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL (Siemens, 1996).
C2H10N22+·SO42− | F(000) = 336 |
Mr = 158.18 | Dx = 1.583 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 2361 reflections |
a = 7.5092 (16) Å | θ = 2.7–28.1° |
b = 11.754 (2) Å | µ = 0.44 mm−1 |
c = 7.9981 (13) Å | T = 273 K |
β = 109.873 (6)° | Prism, colorless |
V = 663.9 (2) Å3 | 0.23 × 0.16 × 0.15 mm |
Z = 4 |
Bruker SMART CCD area-detector diffractometer | 1292 independent reflections |
Radiation source: fine-focus sealed tube | 1063 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.020 |
ϕ and ω scans | θmax = 26.0°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −9→8 |
Tmin = 0.906, Tmax = 0.935 | k = −14→14 |
4223 measured reflections | l = −9→9 |
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)] = 0.044 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.152 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.1018P)2 + 0.5371P] where P = (Fo2 + 2Fc2)/3 |
1292 reflections | (Δ/σ)max < 0.001 |
84 parameters | Δρmax = 0.74 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
C2H10N22+·SO42− | V = 663.9 (2) Å3 |
Mr = 158.18 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 7.5092 (16) Å | µ = 0.44 mm−1 |
b = 11.754 (2) Å | T = 273 K |
c = 7.9981 (13) Å | 0.23 × 0.16 × 0.15 mm |
β = 109.873 (6)° |
Bruker SMART CCD area-detector diffractometer | 1292 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1063 reflections with I > 2σ(I) |
Tmin = 0.906, Tmax = 0.935 | Rint = 0.020 |
4223 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.152 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.74 e Å−3 |
1292 reflections | Δρmin = −0.48 e Å−3 |
84 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 | ||
S1 | 0.58508 (9) | 0.36383 (5) | 0.24204 (8) | 0.0186 (3) | |
O1 | 0.6651 (3) | 0.25601 (15) | 0.3432 (2) | 0.0257 (5) | |
O2 | 0.3693 (3) | 0.35509 (15) | 0.1524 (2) | 0.0225 (5) | |
O3 | 0.6419 (3) | 0.46893 (15) | 0.3572 (2) | 0.0227 (5) | |
O4 | 0.6766 (3) | 0.38077 (16) | 0.0927 (2) | 0.0265 (5) | |
N1 | 0.7498 (3) | 0.65774 (18) | 0.2216 (3) | 0.0197 (5) | |
H1AA | 0.7111 | 0.6552 | 0.1035 | 0.030* | |
H1BB | 0.7051 | 0.7204 | 0.2559 | 0.030* | |
H1CC | 0.7071 | 0.5968 | 0.2623 | 0.030* | |
N2 | 1.2438 (3) | 0.55725 (18) | 0.2858 (3) | 0.0198 (5) | |
H2AA | 1.2887 | 0.6207 | 0.2542 | 0.030* | |
H2BB | 1.2833 | 0.4974 | 0.2399 | 0.030* | |
H2CC | 1.2853 | 0.5516 | 0.4038 | 0.030* | |
C1 | 0.9598 (4) | 0.6591 (2) | 0.2939 (4) | 0.0237 (6) | |
H1A | 1.0029 | 0.6537 | 0.4225 | 0.028* | |
H1B | 1.0067 | 0.7299 | 0.2622 | 0.028* | |
C2 | 1.0347 (4) | 0.5606 (2) | 0.2187 (4) | 0.0285 (7) | |
H2A | 0.9862 | 0.4903 | 0.2500 | 0.034* | |
H2B | 0.9899 | 0.5663 | 0.0901 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0197 (4) | 0.0186 (4) | 0.0184 (4) | −0.0005 (2) | 0.0074 (3) | 0.0003 (2) |
O1 | 0.0326 (11) | 0.0209 (10) | 0.0245 (10) | 0.0087 (8) | 0.0110 (8) | 0.0061 (7) |
O2 | 0.0170 (10) | 0.0255 (10) | 0.0228 (10) | −0.0019 (7) | 0.0039 (8) | 0.0014 (7) |
O3 | 0.0301 (10) | 0.0203 (10) | 0.0180 (9) | −0.0041 (7) | 0.0085 (7) | −0.0033 (7) |
O4 | 0.0333 (11) | 0.0276 (10) | 0.0257 (11) | −0.0070 (8) | 0.0191 (9) | −0.0014 (7) |
N1 | 0.0147 (11) | 0.0225 (11) | 0.0212 (11) | 0.0022 (8) | 0.0053 (9) | −0.0003 (8) |
N2 | 0.0176 (11) | 0.0212 (11) | 0.0211 (11) | 0.0019 (8) | 0.0074 (8) | 0.0000 (8) |
C1 | 0.0166 (13) | 0.0264 (14) | 0.0269 (14) | 0.0003 (10) | 0.0056 (10) | −0.0072 (11) |
C2 | 0.0188 (14) | 0.0301 (15) | 0.0333 (15) | 0.0005 (11) | 0.0046 (11) | −0.0127 (11) |
S1—O3 | 1.5133 (18) | N2—H2AA | 0.8900 |
S1—O1 | 1.5137 (18) | N2—H2BB | 0.8900 |
S1—O2 | 1.5366 (19) | N2—H2CC | 0.8900 |
S1—O4 | 1.5803 (19) | C1—C2 | 1.499 (4) |
N1—C1 | 1.484 (3) | C1—H1A | 0.9700 |
N1—H1AA | 0.8900 | C1—H1B | 0.9700 |
N1—H1BB | 0.8900 | C2—H2A | 0.9700 |
N1—H1CC | 0.8900 | C2—H2B | 0.9700 |
N2—C2 | 1.477 (3) | ||
O3—S1—O1 | 112.30 (11) | C2—N2—H2CC | 109.5 |
O3—S1—O2 | 111.91 (10) | H2AA—N2—H2CC | 109.5 |
O1—S1—O2 | 110.94 (10) | H2BB—N2—H2CC | 109.5 |
O3—S1—O4 | 104.61 (10) | N1—C1—C2 | 109.2 (2) |
O1—S1—O4 | 108.32 (11) | N1—C1—H1A | 109.8 |
O2—S1—O4 | 108.45 (11) | C2—C1—H1A | 109.8 |
C1—N1—H1AA | 109.5 | N1—C1—H1B | 109.8 |
C1—N1—H1BB | 109.5 | C2—C1—H1B | 109.8 |
H1AA—N1—H1BB | 109.5 | H1A—C1—H1B | 108.3 |
C1—N1—H1CC | 109.5 | N2—C2—C1 | 111.8 (2) |
H1AA—N1—H1CC | 109.5 | N2—C2—H2A | 109.2 |
H1BB—N1—H1CC | 109.5 | C1—C2—H2A | 109.2 |
C2—N2—H2AA | 109.5 | N2—C2—H2B | 109.2 |
C2—N2—H2BB | 109.5 | C1—C2—H2B | 109.2 |
H2AA—N2—H2BB | 109.5 | H2A—C2—H2B | 107.9 |
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···O4 | 0.97 | 2.58 | 3.297 (3) | 131 |
N1—H1BB···S1i | 0.89 | 2.76 | 3.574 (2) | 153 |
N1—H1BB···O1i | 0.89 | 2.65 | 3.195 (3) | 120 |
N1—H1BB···O2i | 0.89 | 1.91 | 2.794 (3) | 175 |
N1—H1AA···S1ii | 0.89 | 2.91 | 3.715 (2) | 152 |
N1—H1AA···O2ii | 0.89 | 1.93 | 2.820 (3) | 178 |
N1—H1CC···O3 | 0.89 | 1.82 | 2.712 (3) | 175 |
N1—H1CC···S1 | 0.89 | 2.87 | 3.692 (2) | 153 |
N2—H2CC···S1iii | 0.89 | 2.84 | 3.670 (2) | 155 |
N2—H2CC···O3iii | 0.89 | 1.82 | 2.705 (3) | 176 |
N2—H2BB···S1iv | 0.89 | 2.75 | 3.531 (2) | 147 |
N2—H2BB···O3iv | 0.89 | 2.55 | 3.030 (3) | 114 |
N2—H2BB···O2iv | 0.89 | 2.00 | 2.891 (3) | 175 |
N2—H2AA···S1v | 0.89 | 3.01 | 3.858 (2) | 160 |
N2—H2AA···O1v | 0.89 | 1.86 | 2.734 (3) | 169 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z; (iii) −x+2, −y+1, −z+1; (iv) x+1, y, z; (v) −x+2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C2H10N22+·SO42− |
Mr | 158.18 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 273 |
a, b, c (Å) | 7.5092 (16), 11.754 (2), 7.9981 (13) |
β (°) | 109.873 (6) |
V (Å3) | 663.9 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.44 |
Crystal size (mm) | 0.23 × 0.16 × 0.15 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.906, 0.935 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4223, 1292, 1063 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.152, 1.05 |
No. of reflections | 1292 |
No. of parameters | 84 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.74, −0.48 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens, 1996).
D—H···A | D—H | H···A | D···A | D—H···A |
C2—H2A···O4 | 0.97 | 2.58 | 3.297 (3) | 131 |
N1—H1BB···S1i | 0.89 | 2.76 | 3.574 (2) | 153 |
N1—H1BB···O1i | 0.89 | 2.65 | 3.195 (3) | 120 |
N1—H1BB···O2i | 0.89 | 1.91 | 2.794 (3) | 175 |
N1—H1AA···S1ii | 0.89 | 2.91 | 3.715 (2) | 152 |
N1—H1AA···O2ii | 0.89 | 1.93 | 2.820 (3) | 178 |
N1—H1CC···O3 | 0.89 | 1.82 | 2.712 (3) | 175 |
N1—H1CC···S1 | 0.89 | 2.87 | 3.692 (2) | 153 |
N2—H2CC···S1iii | 0.89 | 2.84 | 3.670 (2) | 155 |
N2—H2CC···O3iii | 0.89 | 1.82 | 2.705 (3) | 176 |
N2—H2BB···S1iv | 0.89 | 2.75 | 3.531 (2) | 147 |
N2—H2BB···O3iv | 0.89 | 2.55 | 3.030 (3) | 114 |
N2—H2BB···O2iv | 0.89 | 2.00 | 2.891 (3) | 175 |
N2—H2AA···S1v | 0.89 | 3.01 | 3.858 (2) | 160 |
N2—H2AA···O1v | 0.89 | 1.86 | 2.734 (3) | 169 |
Symmetry codes: (i) −x+1, y+1/2, −z+1/2; (ii) −x+1, −y+1, −z; (iii) −x+2, −y+1, −z+1; (iv) x+1, y, z; (v) −x+2, y+1/2, −z+1/2. |
In the synthesis of crystal structures by design, the assembly of molecular units in predefined arrangements is a key goal (Desiraju, 1995, 1997; Braga et al., 1998). Due to hydrogen-bonding interactions are of critical importance in biological systems, organic materials and coordination chemistry, hydrogen -bonding is currently the best tool in achieving this goal (Zaworotko, 1997; Braga & Grepioni, 2000). Supramolecular architectures are of considerable contemporary interest by virtue of their potential applications in various fields (Moulton & Zaworotko, 2001; Pan et al., 2001; Ma et al., 2001; Prior & Rosseinsky, 2001). We originally attempted to synthesize complexes featuring Cu metal chains by reaction of the copper(II) ion with ethylene diamine and p-acetaminobenzoic acid ligands. Unfortunately, we obtained only the title compound, (I), and we report herein its crystal structure.
In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). It contains one (C2N2H10)2+ cation and one (SO4)2- anion.
In the crystal structure, C—H···O, N—H···O and N—H···S hydrogen bonds (Table 1, Fig. 2) result in the formation of a supramolecular network structure.