The crystal structure of the title compound, (C
4H
12N
2)[Co(H
2O)
6](SO
4)
2, is built of [Co(H
2O)
6]
2+ cations, diprotonated piperazinium cations (each of the two crystallographically independent piperazinium cations occupies a special position on an inversion centre) and sulfate anions. The Co atom is coordinated by six water molecules in a slightly distorted octahedral geometry. The cations are linked to anions by N—H
O and O—H
O hydrogen bonds, forming an extensive three-dimensional hydrogen-bond network in the crystal structure.
Supporting information
CCDC reference: 214578
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.007 Å
- R factor = 0.043
- wR factor = 0.112
- Data-to-parameter ratio = 11.4
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
PLAT_354 Alert C Short O-H Bond (0.82A) O(3W) - H(32) = 0.70 Ang.
PLAT_354 Alert C Short O-H Bond (0.82A) O(6W) - H(61) = 0.69 Ang.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
The title compound was prepared by hydrothermal synthesis from a mixture of CoSO4·7H2O (0.562 g, 2 mmol), H3BO3 (0.124 g, 2 mmol), piperazine (0.172 g, 2 mmol), 85% H3PO4 (0.27 ml, 4 mmol) and 37% HCl (1 ml) in H2O (5 ml). The mixture was sealed in a Teflon autoclave, heated at 438 K for 5 d and cooled. After filtration, the red filtrate was allowed to stand in air for 2 d, whereupon red crystals were obtained.
The aqua H atoms were located in the difference Fourier maps and their positions and isotropic displacement parameters were refined. H atoms bonded to C and N atoms were positioned geometrically (the C—H and N—H bonds were fixed at 0.97 and 0.90 Å, respectively) and allowed to ride on their parent atoms.
Data collection: SMART (Siemens, 1996); cell refinement: SMART; data reduction: SAINT (Siemens, 1994); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.
Piperazinium hexaaquacobalt disulfate
top
Crystal data top
(C4H12N2)[Co(H2O)6](SO4)2 | F(000) = 932 |
Mr = 447.30 | Dx = 1.775 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 68 reflections |
a = 12.8796 (6) Å | θ = 1.8–25.1° |
b = 10.6984 (6) Å | µ = 1.34 mm−1 |
c = 13.3098 (7) Å | T = 293 K |
β = 114.118 (2)° | Polyhedron, red |
V = 1673.88 (15) Å3 | 0.34 × 0.26 × 0.24 mm |
Z = 4 | |
Data collection top
Siemens SMART CCD diffractometer | 2914 independent reflections |
Radiation source: fine-focus sealed tube | 2163 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
ϕ and ω scans | θmax = 25.1°, θmin = 1.8° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = −6→15 |
Tmin = 0.639, Tmax = 0.724 | k = −8→12 |
5044 measured reflections | l = −15→12 |
Refinement top
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)] = 0.043 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.112 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0415P)2 + 3.1275P] where P = (Fo2 + 2Fc2)/3 |
2914 reflections | (Δ/σ)max = 0.001 |
256 parameters | Δρmax = 0.40 e Å−3 |
0 restraints | Δρmin = −0.51 e Å−3 |
Crystal data top
(C4H12N2)[Co(H2O)6](SO4)2 | V = 1673.88 (15) Å3 |
Mr = 447.30 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.8796 (6) Å | µ = 1.34 mm−1 |
b = 10.6984 (6) Å | T = 293 K |
c = 13.3098 (7) Å | 0.34 × 0.26 × 0.24 mm |
β = 114.118 (2)° | |
Data collection top
Siemens SMART CCD diffractometer | 2914 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 2163 reflections with I > 2σ(I) |
Tmin = 0.639, Tmax = 0.724 | Rint = 0.026 |
5044 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.043 | 0 restraints |
wR(F2) = 0.112 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.07 | Δρmax = 0.40 e Å−3 |
2914 reflections | Δρmin = −0.51 e Å−3 |
256 parameters | |
Special details top
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 | x | y | z | Uiso*/Ueq | |
Co | 0.4965 (1) | 0.5071 (1) | 0.2440 (1) | 0.0287 (2) | |
S1 | 0.7925 (1) | 0.3710 (1) | 0.1303 (1) | 0.0280 (3) | |
S2 | 0.2483 (1) | 0.6485 (1) | 0.3966 (1) | 0.0292 (3) | |
O1 | 0.7219 (3) | 0.4818 (3) | 0.0949 (3) | 0.0529 (9) | |
O2 | 0.9131 (3) | 0.4082 (3) | 0.1798 (2) | 0.0489 (9) | |
O3 | 0.7760 (3) | 0.2901 (3) | 0.0360 (2) | 0.0412 (8) | |
O4 | 0.7679 (3) | 0.3038 (3) | 0.2139 (3) | 0.0465 (8) | |
O5 | 0.2532 (3) | 0.5142 (3) | 0.3851 (3) | 0.0580 (9) | |
O6 | 0.2503 (3) | 0.7144 (3) | 0.3005 (2) | 0.0402 (8) | |
O7 | 0.3459 (3) | 0.6916 (4) | 0.4933 (3) | 0.0694 (9) | |
O8 | 0.1440 (3) | 0.6790 (3) | 0.4103 (3) | 0.0482 (9) | |
N1 | 0.4701 (3) | 0.8778 (3) | 0.4530 (3) | 0.0353 (9) | |
H1A | 0.5119 | 0.8715 | 0.4131 | 0.042* | |
H1B | 0.4308 | 0.8062 | 0.4448 | 0.042* | |
N2 | 0.5033 (3) | 0.9896 (4) | 0.1071 (3) | 0.0380 (9) | |
H2A | 0.5317 | 0.9546 | 0.1745 | 0.046* | |
H2B | 0.4508 | 1.0464 | 0.1049 | 0.046* | |
C1 | 0.5959 (4) | 1.0536 (5) | 0.0891 (4) | 0.0454 (12) | |
H1C | 0.6563 | 0.9945 | 0.0984 | 0.055* | |
H1D | 0.6272 | 1.1196 | 0.1430 | 0.055* | |
C2 | 0.4482 (4) | 0.8922 (4) | 0.0242 (4) | 0.0440 (12) | |
H2C | 0.3859 | 0.8555 | 0.0370 | 0.053* | |
H2D | 0.5027 | 0.8267 | 0.0308 | 0.053* | |
C3 | 0.5472 (4) | 0.8944 (4) | 0.5709 (3) | 0.0394 (11) | |
H3A | 0.6012 | 0.8260 | 0.5945 | 0.047* | |
H3B | 0.5030 | 0.8926 | 0.6150 | 0.047* | |
C4 | 0.3894 (4) | 0.9833 (4) | 0.4108 (4) | 0.0385 (11) | |
H4A | 0.3387 | 0.9849 | 0.4483 | 0.046* | |
H4B | 0.3436 | 0.9718 | 0.3328 | 0.046* | |
O1W | 0.4295 (3) | 0.4177 (4) | 0.0941 (3) | 0.0471 (10) | |
O2W | 0.6073 (3) | 0.3549 (4) | 0.2940 (3) | 0.0515 (10) | |
O3W | 0.5676 (3) | 0.5918 (4) | 0.4021 (3) | 0.0424 (9) | |
O4W | 0.5988 (3) | 0.6047 (4) | 0.1871 (3) | 0.0463 (9) | |
O5W | 0.3791 (3) | 0.6551 (3) | 0.1879 (3) | 0.0420 (8) | |
O6W | 0.3955 (3) | 0.4077 (4) | 0.3049 (3) | 0.0384 (8) | |
H11 | 0.378 (5) | 0.452 (6) | 0.040 (5) | 0.08 (2)* | |
H12 | 0.401 (4) | 0.358 (5) | 0.085 (4) | 0.040 (17)* | |
H21 | 0.662 (5) | 0.350 (6) | 0.279 (5) | 0.08 (2)* | |
H22 | 0.628 (4) | 0.333 (5) | 0.359 (5) | 0.053 (16)* | |
H31 | 0.623 (8) | 0.648 (10) | 0.424 (8) | 0.19 (5)* | |
H32 | 0.595 (5) | 0.548 (6) | 0.444 (5) | 0.06 (2)* | |
H41 | 0.637 (5) | 0.661 (6) | 0.213 (5) | 0.06 (2)* | |
H42 | 0.633 (4) | 0.566 (5) | 0.163 (4) | 0.049 (18)* | |
H51 | 0.338 (5) | 0.664 (6) | 0.125 (5) | 0.08 (2)* | |
H52 | 0.345 (4) | 0.666 (5) | 0.223 (4) | 0.047 (18)* | |
H61 | 0.363 (5) | 0.359 (6) | 0.274 (5) | 0.05 (2)* | |
H62 | 0.352 (4) | 0.444 (5) | 0.326 (4) | 0.047 (17)* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co | 0.0282 (3) | 0.0302 (3) | 0.0269 (3) | 0.0004 (2) | 0.0106 (2) | 0.0004 (2) |
S1 | 0.0298 (5) | 0.0297 (6) | 0.0250 (5) | 0.0032 (4) | 0.0116 (4) | 0.0019 (4) |
S2 | 0.0306 (5) | 0.0280 (6) | 0.0305 (5) | −0.0001 (5) | 0.0140 (4) | 0.0029 (4) |
O1 | 0.075 (2) | 0.046 (2) | 0.0423 (19) | 0.0315 (9) | 0.0293 (9) | 0.0158 (9) |
O2 | 0.0368 (9) | 0.078 (3) | 0.0336 (9) | −0.0151 (9) | 0.0161 (9) | −0.0164 (9) |
O3 | 0.0444 (9) | 0.0426 (9) | 0.0331 (9) | 0.0003 (9) | 0.0122 (9) | −0.0101 (9) |
O4 | 0.055 (2) | 0.047 (2) | 0.054 (2) | 0.0148 (16) | 0.0383 (17) | 0.0203 (17) |
O5 | 0.082 (3) | 0.0298 (19) | 0.091 (3) | 0.0125 (18) | 0.065 (2) | 0.0119 (18) |
O6 | 0.0505 (19) | 0.0409 (19) | 0.0321 (16) | 0.0090 (15) | 0.0200 (15) | 0.0117 (14) |
O7 | 0.054 (2) | 0.113 (4) | 0.0288 (18) | −0.040 (2) | 0.0040 (16) | 0.009 (2) |
O8 | 0.047 (2) | 0.0312 (18) | 0.082 (2) | −0.0010 (15) | 0.0419 (19) | 0.0015 (17) |
N1 | 0.0337 (19) | 0.035 (2) | 0.040 (2) | −0.0070 (17) | 0.0177 (17) | −0.0056 (17) |
N2 | 0.039 (2) | 0.049 (2) | 0.0288 (18) | 0.0177 (19) | 0.0160 (16) | 0.0115 (18) |
C1 | 0.035 (3) | 0.056 (3) | 0.038 (3) | −0.008 (2) | 0.007 (2) | −0.007 (2) |
C2 | 0.043 (3) | 0.034 (3) | 0.058 (3) | −0.005 (2) | 0.024 (2) | 0.006 (2) |
C3 | 0.041 (3) | 0.042 (3) | 0.033 (2) | 0.004 (2) | 0.013 (2) | 0.009 (2) |
C4 | 0.027 (2) | 0.049 (3) | 0.032 (2) | 0.001 (2) | 0.0047 (18) | −0.001 (2) |
O1W | 0.063 (3) | 0.033 (2) | 0.0332 (19) | −0.009 (2) | 0.0072 (18) | −0.0008 (17) |
O2W | 0.049 (2) | 0.075 (3) | 0.037 (2) | 0.0259 (19) | 0.0239 (18) | 0.0188 (19) |
O3W | 0.052 (2) | 0.040 (2) | 0.0298 (18) | −0.0039 (19) | 0.0110 (17) | 0.0010 (17) |
O4W | 0.053 (2) | 0.044 (2) | 0.056 (2) | −0.016 (2) | 0.037 (2) | −0.0201 (19) |
O5W | 0.042 (2) | 0.047 (2) | 0.038 (2) | 0.0124 (16) | 0.0168 (19) | 0.0093 (17) |
O6W | 0.038 (2) | 0.035 (2) | 0.047 (2) | −0.0077 (18) | 0.0219 (18) | −0.0076 (17) |
Geometric parameters (Å, º) top
Co—O1W | 2.057 (4) | N1—H1B | 0.9000 |
Co—O2W | 2.087 (4) | N2—H2A | 0.9000 |
Co—O3W | 2.124 (3) | N2—H2B | 0.9000 |
Co—O4W | 2.052 (4) | C1—H1C | 0.9700 |
Co—O5W | 2.105 (4) | C1—H1D | 0.9700 |
Co—O6W | 2.085 (3) | C2—H2C | 0.9700 |
S1—O1 | 1.451 (3) | C2—H2D | 0.9700 |
S1—O2 | 1.473 (3) | C3—H3A | 0.9700 |
S1—O3 | 1.467 (3) | C3—H3B | 0.9700 |
S1—O4 | 1.463 (3) | C4—H4A | 0.9700 |
S2—O5 | 1.449 (3) | C4—H4B | 0.9700 |
S2—O6 | 1.472 (3) | O1W—H11 | 0.83 (6) |
S2—O7 | 1.458 (3) | O1W—H12 | 0.73 (5) |
S2—O8 | 1.463 (3) | O2W—H21 | 0.81 (6) |
N1—C3 | 1.486 (5) | O2W—H22 | 0.83 (5) |
N1—C4 | 1.481 (6) | O3W—H31 | 0.88 (6) |
N2—C1 | 1.477 (6) | O3W—H32 | 0.70 (6) |
N2—C2 | 1.472 (6) | O4W—H41 | 0.76 (6) |
C1—C2i | 1.494 (6) | O4W—H42 | 0.77 (6) |
C2—C1i | 1.494 (6) | O5W—H51 | 0.79 (6) |
C3—C4ii | 1.509 (6) | O5W—H52 | 0.77 (6) |
C4—C3ii | 1.509 (6) | O6W—H61 | 0.69 (6) |
N1—H1A | 0.9000 | O6W—H62 | 0.81 (6) |
| | | |
O1W—Co—O2W | 84.7 (2) | N2—C1—H1D | 109.6 |
O1W—Co—O3W | 177.5 (2) | C2i—C1—H1C | 109.6 |
O1W—Co—O5W | 92.9 (2) | C2i—C1—H1D | 109.6 |
O1W—Co—O6W | 93.4 (2) | H1C—C1—H1D | 108.2 |
O2W—Co—O3W | 93.2 (2) | N2—C2—C1i | 110.5 (4) |
O2W—Co—O5W | 177.3 (2) | N2—C2—H2C | 109.6 |
O4W—Co—O1W | 87.6 (2) | N2—C2—H2D | 109.6 |
O4W—Co—O2W | 93.2 (2) | C1i—C2—H2C | 109.6 |
O4W—Co—O3W | 93.8 (2) | C1i—C2—H2D | 109.6 |
O4W—Co—O5W | 87.9 (2) | H2C—C2—H2D | 108.1 |
O4W—Co—O6W | 178.8 (2) | N1—C3—C4ii | 111.0 (4) |
O5W—Co—O3W | 89.3 (2) | N1—C3—H3A | 109.4 |
O6W—Co—O2W | 86.1 (2) | N1—C3—H3B | 109.4 |
O6W—Co—O3W | 85.2 (2) | C4ii—C3—H3A | 109.4 |
O6W—Co—O5W | 92.8 (2) | C4ii—C3—H3B | 109.4 |
O1—S1—O2 | 109.3 (2) | H3A—C3—H3B | 108.0 |
O1—S1—O3 | 110.6 (2) | N1—C4—C3ii | 110.4 (3) |
O1—S1—O4 | 110.3 (2) | N1—C4—H4A | 109.6 |
O3—S1—O2 | 107.4 (2) | N1—C4—H4B | 109.6 |
O4—S1—O2 | 108.0 (2) | C3ii—C4—H4A | 109.6 |
O4—S1—O3 | 111.1 (2) | C3ii—C4—H4B | 109.6 |
O5—S2—O6 | 111.4 (2) | H4A—C4—H4B | 108.1 |
O5—S2—O7 | 110.4 (3) | Co—O1W—H11 | 120 (5) |
O5—S2—O8 | 108.5 (2) | Co—O1W—H12 | 124 (4) |
O7—S2—O6 | 107.4 (2) | H11—O1W—H12 | 94 (6) |
O7—S2—O8 | 109.0 (2) | Co—O2W—H21 | 122 (5) |
O8—S2—O6 | 110.1 (2) | Co—O2W—H22 | 116 (4) |
C4—N1—C3 | 111.8 (3) | H21—O2W—H22 | 107 (5) |
C3—N1—H1A | 109.2 | Co—O3W—H31 | 126 (7) |
C3—N1—H1B | 109.2 | Co—O3W—H32 | 112 (5) |
C4—N1—H1A | 109.2 | H31—O3W—H32 | 96 (7) |
C4—N1—H1B | 109.2 | Co—O4W—H41 | 129 (4) |
H1A—N1—H1B | 107.9 | Co—O4W—H42 | 116 (4) |
C2—N2—C1 | 112.3 (4) | H41—O4W—H42 | 104 (6) |
C1—N2—H2A | 109.1 | Co—O5W—H51 | 123 (5) |
C1—N2—H2B | 109.1 | Co—O5W—H52 | 114 (4) |
C2—N2—H2A | 109.1 | H51—O5W—H52 | 108 (6) |
C2—N2—H2B | 109.1 | Co—O6W—H61 | 118 (5) |
H2A—N2—H2B | 107.9 | Co—O6W—H62 | 121 (4) |
N2—C1—C2i | 110.1 (4) | H61—O6W—H62 | 103 (6) |
N2—C1—H1C | 109.6 | | |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2iii | 0.90 | 1.89 | 2.768 (5) | 163 |
N1—H1B···O6 | 0.90 | 2.53 | 3.239 (5) | 136 |
N1—H1B···O7 | 0.90 | 1.92 | 2.741 (5) | 151 |
N2—H2A···O2iii | 0.90 | 1.84 | 2.733 (4) | 171 |
N2—H2B···O8iv | 0.90 | 1.83 | 2.720 (5) | 170 |
O1W—H11···O1v | 0.83 (6) | 1.87 (7) | 2.698 (5) | 169 (6) |
O1W—H12···O8vi | 0.73 (5) | 2.01 (5) | 2.716 (5) | 166 (6) |
O2W—H21···O4 | 0.81 (6) | 1.95 (7) | 2.742 (5) | 164 (6) |
O2W—H22···O7vii | 0.83 (5) | 1.87 (6) | 2.689 (5) | 168 (5) |
O3W—H31···O3iii | 0.88 (8) | 1.94 (9) | 2.808 (5) | 171 (7) |
O3W—H32···O5vii | 0.70 (6) | 2.41 (6) | 3.049 (6) | 152 (6) |
O4W—H41···O4iii | 0.76 (6) | 1.95 (6) | 2.715 (5) | 176 (6) |
O4W—H42···O1 | 0.77 (6) | 1.95 (6) | 2.710 (5) | 174 (6) |
O5W—H51···O3v | 0.79 (6) | 2.11 (6) | 2.888 (5) | 173 (7) |
O5W—H52···O6 | 0.77 (6) | 1.96 (6) | 2.726 (5) | 172 (6) |
O6W—H61···O6vi | 0.69 (6) | 2.08 (6) | 2.760 (5) | 170 (6) |
O6W—H62···O5 | 0.81 (6) | 1.91 (6) | 2.719 (5) | 174 (5) |
Symmetry codes: (iii) −x+3/2, y+1/2, −z+1/2; (iv) −x+1/2, y+1/2, −z+1/2; (v) −x+1, −y+1, −z; (vi) −x+1/2, y−1/2, −z+1/2; (vii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data |
Chemical formula | (C4H12N2)[Co(H2O)6](SO4)2 |
Mr | 447.30 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 12.8796 (6), 10.6984 (6), 13.3098 (7) |
β (°) | 114.118 (2) |
V (Å3) | 1673.88 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.34 |
Crystal size (mm) | 0.34 × 0.26 × 0.24 |
|
Data collection |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.639, 0.724 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5044, 2914, 2163 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.597 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.112, 1.07 |
No. of reflections | 2914 |
No. of parameters | 256 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.40, −0.51 |
Selected geometric parameters (Å, º) topCo—O1W | 2.057 (4) | S2—O5 | 1.449 (3) |
Co—O2W | 2.087 (4) | S2—O6 | 1.472 (3) |
Co—O3W | 2.124 (3) | S2—O7 | 1.458 (3) |
Co—O4W | 2.052 (4) | S2—O8 | 1.463 (3) |
Co—O5W | 2.105 (4) | N1—C3 | 1.486 (5) |
Co—O6W | 2.085 (3) | N1—C4 | 1.481 (6) |
S1—O1 | 1.451 (3) | N2—C1 | 1.477 (6) |
S1—O2 | 1.473 (3) | N2—C2 | 1.472 (6) |
S1—O3 | 1.467 (3) | C1—C2i | 1.494 (6) |
S1—O4 | 1.463 (3) | C3—C4ii | 1.509 (6) |
| | | |
O1W—Co—O2W | 84.7 (2) | O1—S1—O4 | 110.3 (2) |
O1W—Co—O3W | 177.5 (2) | O3—S1—O2 | 107.4 (2) |
O1W—Co—O5W | 92.9 (2) | O4—S1—O2 | 108.0 (2) |
O1W—Co—O6W | 93.4 (2) | O4—S1—O3 | 111.1 (2) |
O2W—Co—O3W | 93.2 (2) | O5—S2—O6 | 111.4 (2) |
O2W—Co—O5W | 177.3 (2) | O5—S2—O7 | 110.4 (3) |
O4W—Co—O1W | 87.6 (2) | O5—S2—O8 | 108.5 (2) |
O4W—Co—O2W | 93.2 (2) | O7—S2—O6 | 107.4 (2) |
O4W—Co—O3W | 93.8 (2) | O7—S2—O8 | 109.0 (2) |
O4W—Co—O5W | 87.9 (2) | O8—S2—O6 | 110.1 (2) |
O4W—Co—O6W | 178.8 (2) | C4—N1—C3 | 111.8 (3) |
O5W—Co—O3W | 89.3 (2) | C2—N2—C1 | 112.3 (4) |
O6W—Co—O2W | 86.1 (2) | N2—C1—C2i | 110.1 (4) |
O6W—Co—O3W | 85.2 (2) | N2—C2—C1i | 110.5 (4) |
O6W—Co—O5W | 92.8 (2) | N1—C3—C4ii | 111.0 (4) |
O1—S1—O2 | 109.3 (2) | N1—C4—C3ii | 110.4 (3) |
O1—S1—O3 | 110.6 (2) | | |
Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, −y+2, −z+1. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O2iii | 0.90 | 1.89 | 2.768 (5) | 163 |
N1—H1B···O6 | 0.90 | 2.53 | 3.239 (5) | 136 |
N1—H1B···O7 | 0.90 | 1.92 | 2.741 (5) | 151 |
N2—H2A···O2iii | 0.90 | 1.84 | 2.733 (4) | 171 |
N2—H2B···O8iv | 0.90 | 1.83 | 2.720 (5) | 170 |
O1W—H11···O1v | 0.83 (6) | 1.87 (7) | 2.698 (5) | 169 (6) |
O1W—H12···O8vi | 0.73 (5) | 2.01 (5) | 2.716 (5) | 166 (6) |
O2W—H21···O4 | 0.81 (6) | 1.95 (7) | 2.742 (5) | 164 (6) |
O2W—H22···O7vii | 0.83 (5) | 1.87 (6) | 2.689 (5) | 168 (5) |
O3W—H31···O3iii | 0.88 (8) | 1.94 (9) | 2.808 (5) | 171 (7) |
O3W—H32···O5vii | 0.70 (6) | 2.41 (6) | 3.049 (6) | 152 (6) |
O4W—H41···O4iii | 0.76 (6) | 1.95 (6) | 2.715 (5) | 176 (6) |
O4W—H42···O1 | 0.77 (6) | 1.95 (6) | 2.710 (5) | 174 (6) |
O5W—H51···O3v | 0.79 (6) | 2.11 (6) | 2.888 (5) | 173 (7) |
O5W—H52···O6 | 0.77 (6) | 1.96 (6) | 2.726 (5) | 172 (6) |
O6W—H61···O6vi | 0.69 (6) | 2.08 (6) | 2.760 (5) | 170 (6) |
O6W—H62···O5 | 0.81 (6) | 1.91 (6) | 2.719 (5) | 174 (5) |
Symmetry codes: (iii) −x+3/2, y+1/2, −z+1/2; (iv) −x+1/2, y+1/2, −z+1/2; (v) −x+1, −y+1, −z; (vi) −x+1/2, y−1/2, −z+1/2; (vii) −x+1, −y+1, −z+1. |
Intermolecular interactions, such as hydrogen bonds or aromatic π–π stacking, play a dominant role in molecular recognition in nature, and in designing molecular aggregates (Juan et al., 2002). One of the important aspects of cobalt sulfate hydrate structures is the existence of extensive hydrogen-bonding interactions. Up until now, a series of such compounds have been reported in the literature, e.g. CoSO4·7D2O (Olovsson et al., 1991), CoSO4·four-dimensional2O (Kellersohn, 1992) and CoSO4·six-dimensional2O (Olovsson et al., 1993). In the course of our studies of transition metal borophosphates, we tried to prepare a novel cobalt borophosphate containing piperazine as a template. Unfortunately, borophosphate salt was not isolated; instead, single crystals of the title double salt, (I), were obtained.
The crystal structure of (I) consists of discrete [Co(H2O)6]2+ cations, diprotonated piperazinium cations and sulfate anions. All crystallographically independent chemical residues in the crystal of the title compound are shown in Fig. 1. Within the [Co(H2O)6]2+ cation, the Co atom is coordinated by six water molecules in the vertices of a slightly distorted octahedron. The Co—O bond lengths range from 2.052 (4) to 2.124 (3) Å and the O—Co—O bond angles span the intervals of 84.7–93.8 and 177.3–178.8°.
The anions and cations in the crystal are linked via N—H···O and O—H···O hydrogen bonds into an extensive three-dimensional infinite framework. Each cation acts as a donor of hydrogen bonds and each anion acts as an acceptor. The packing diagram of the title compound showing the hydrogen-bonding framework is presented in Fig. 2. Intermolecular N—H···O and O—H···O hydrogen bonds lengths are in the ranges 2.720 (5)–3.239 (5) and 2.689 (5)–3.049 (6) Å, respectively.