Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807053627/bx2109sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807053627/bx2109Isup2.hkl |
CCDC reference: 672601
Key indicators
- Single-crystal X-ray study
- T = 100 K
- R factor = 0.024
- wR factor = 0.067
- Data-to-parameter ratio = 18.1
checkCIF/PLATON results
No syntax errors found No errors found in this datablock
The proton transfer compound [(pipzH2)(py-2,5-dc)].2H2O, was prepared by the reaction of pyridine-2,5-dicarboxylic acid, py-2,5-dcH2, with piperazine, (pipz). The reaction between Ni(NO3)2.6H2O (145 mg, 0.5 mmol) in water (25 ml) and the proton transfer compound, (pipzH2)(py-2,5-dc) (253 mg, 1.0 mmol) in water (25 ml), in a 1:2 molar ratio was carried by the slow evaporation of the solvent at room temperature.
The hydrogen atoms of OH2 molecules were found in difference Fourier synthesis. The H(C) atom positions were calculated. All hydrogen atoms were refined in isotropic approximation in riding model with the Uiso(H) parameters equal to 1.2 Ueq(Ci), where U(Ci) the equivalent thermal parameters of the carbon atoms to which corresponding H atoms are bonded.
Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2 (Bruker, 2005); data reduction: APEX2 (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL (Sheldrick, 1998); molecular graphics: SHELXTL (Sheldrick, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 1998).
[Ni(C7H3NO4)(H2O)4]·H2O | Z = 2 |
Mr = 313.89 | F(000) = 324 |
Triclinic, P1 | Dx = 1.882 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 6.6633 (3) Å | Cell parameters from 5275 reflections |
b = 8.3996 (3) Å | θ = 2.6–34.8° |
c = 10.7882 (4) Å | µ = 1.80 mm−1 |
α = 84.7541 (9)° | T = 100 K |
β = 83.0010 (8)° | Prism, blue |
γ = 67.6991 (8)° | 0.25 × 0.20 × 0.10 mm |
V = 553.81 (4) Å3 |
Bruker APEX2 CCD area-detector diffractometer | 2950 independent reflections |
Radiation source: fine-focus sealed tube | 2710 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.024 |
ϕ and ω scans | θmax = 29.0°, θmin = 1.9° |
Absorption correction: multi-scan (APEX2; Bruker, 2005) | h = −9→9 |
Tmin = 0.662, Tmax = 0.841 | k = −11→11 |
9105 measured reflections | l = −14→14 |
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)] = 0.024 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.067 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0397P)2 + 0.1995P] where P = (Fo2 + 2Fc2)/3 |
2950 reflections | (Δ/σ)max = 0.001 |
163 parameters | Δρmax = 0.58 e Å−3 |
0 restraints | Δρmin = −0.48 e Å−3 |
[Ni(C7H3NO4)(H2O)4]·H2O | γ = 67.6991 (8)° |
Mr = 313.89 | V = 553.81 (4) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.6633 (3) Å | Mo Kα radiation |
b = 8.3996 (3) Å | µ = 1.80 mm−1 |
c = 10.7882 (4) Å | T = 100 K |
α = 84.7541 (9)° | 0.25 × 0.20 × 0.10 mm |
β = 83.0010 (8)° |
Bruker APEX2 CCD area-detector diffractometer | 2950 independent reflections |
Absorption correction: multi-scan (APEX2; Bruker, 2005) | 2710 reflections with I > 2σ(I) |
Tmin = 0.662, Tmax = 0.841 | Rint = 0.024 |
9105 measured reflections |
R[F2 > 2σ(F2)] = 0.024 | 0 restraints |
wR(F2) = 0.067 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.58 e Å−3 |
2950 reflections | Δρmin = −0.48 e Å−3 |
163 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 | ||
Ni1 | 0.77628 (3) | 0.75902 (2) | 0.630569 (16) | 0.00700 (7) | |
O1W | 0.77995 (19) | 0.68571 (14) | 0.45564 (10) | 0.0126 (2) | |
H1WB | 0.7787 | 0.7443 | 0.3870 | 0.015* | |
H1WA | 0.8033 | 0.5842 | 0.4356 | 0.015* | |
O2W | 0.78206 (18) | 0.52659 (13) | 0.72019 (10) | 0.0098 (2) | |
H2WA | 0.7725 | 0.4447 | 0.6835 | 0.012* | |
H2WB | 0.8982 | 0.4780 | 0.7563 | 0.012* | |
O3W | 1.11699 (17) | 0.65681 (13) | 0.60822 (10) | 0.0103 (2) | |
H3WA | 1.1717 | 0.6918 | 0.5411 | 0.012* | |
H3WB | 1.1825 | 0.6608 | 0.6700 | 0.012* | |
O4W | 0.44345 (18) | 0.83688 (14) | 0.64479 (10) | 0.0105 (2) | |
H4WA | 0.3886 | 0.8822 | 0.5770 | 0.013* | |
H4WB | 0.3777 | 0.9136 | 0.6975 | 0.013* | |
O1 | 0.75524 (18) | 1.00066 (13) | 0.56414 (10) | 0.0098 (2) | |
O2 | 0.73095 (19) | 1.25596 (13) | 0.62085 (10) | 0.0117 (2) | |
N1 | 0.7735 (2) | 0.86760 (16) | 0.79577 (11) | 0.0081 (2) | |
O3 | 0.78193 (19) | 0.87359 (14) | 1.23625 (10) | 0.0132 (2) | |
O4 | 0.88292 (18) | 0.62574 (14) | 1.14249 (10) | 0.0116 (2) | |
C1 | 0.7470 (2) | 1.03522 (18) | 0.77991 (13) | 0.0082 (3) | |
C2 | 0.7297 (2) | 1.13475 (18) | 0.87916 (13) | 0.0088 (3) | |
H2A | 0.7081 | 1.2532 | 0.8654 | 0.011* | |
C3 | 0.7443 (2) | 1.05790 (19) | 0.99975 (14) | 0.0092 (3) | |
H3A | 0.7299 | 1.1236 | 1.0698 | 0.011* | |
C4 | 0.7805 (2) | 0.88336 (18) | 1.01541 (13) | 0.0075 (3) | |
C5 | 0.7925 (2) | 0.79291 (18) | 0.91115 (13) | 0.0082 (3) | |
H5A | 0.8149 | 0.6741 | 0.9222 | 0.010* | |
C6 | 0.7433 (2) | 1.10494 (19) | 0.64500 (14) | 0.0089 (3) | |
C7 | 0.8158 (2) | 0.78780 (19) | 1.14149 (13) | 0.0086 (3) | |
O5W | 0.3102 (2) | 0.61554 (15) | 0.83049 (11) | 0.0174 (2) | |
H5WB | 0.4476 | 0.5843 | 0.8153 | 0.021* | |
H5WA | 0.2859 | 0.5247 | 0.8543 | 0.021* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.00988 (11) | 0.00577 (10) | 0.00542 (10) | −0.00289 (7) | −0.00096 (7) | −0.00040 (6) |
O1W | 0.0224 (6) | 0.0090 (5) | 0.0065 (5) | −0.0058 (4) | −0.0019 (4) | −0.0007 (4) |
O2W | 0.0135 (5) | 0.0069 (5) | 0.0098 (5) | −0.0041 (4) | −0.0031 (4) | 0.0007 (4) |
O3W | 0.0119 (5) | 0.0114 (5) | 0.0081 (5) | −0.0052 (4) | −0.0008 (4) | 0.0004 (4) |
O4W | 0.0117 (5) | 0.0104 (5) | 0.0083 (5) | −0.0026 (4) | −0.0014 (4) | −0.0012 (4) |
O1 | 0.0151 (5) | 0.0085 (5) | 0.0069 (5) | −0.0054 (4) | −0.0020 (4) | −0.0006 (4) |
O2 | 0.0186 (6) | 0.0090 (5) | 0.0089 (5) | −0.0068 (4) | −0.0019 (4) | 0.0004 (4) |
N1 | 0.0095 (6) | 0.0078 (5) | 0.0074 (5) | −0.0036 (5) | −0.0007 (4) | −0.0006 (4) |
O3 | 0.0201 (6) | 0.0107 (5) | 0.0067 (5) | −0.0031 (4) | −0.0015 (4) | −0.0014 (4) |
O4 | 0.0161 (5) | 0.0086 (5) | 0.0104 (5) | −0.0045 (4) | −0.0034 (4) | 0.0012 (4) |
C1 | 0.0085 (6) | 0.0088 (6) | 0.0074 (6) | −0.0035 (5) | −0.0013 (5) | 0.0010 (5) |
C2 | 0.0096 (7) | 0.0072 (6) | 0.0096 (6) | −0.0030 (5) | −0.0014 (5) | −0.0004 (5) |
C3 | 0.0089 (6) | 0.0108 (7) | 0.0084 (6) | −0.0040 (5) | −0.0006 (5) | −0.0020 (5) |
C4 | 0.0062 (6) | 0.0091 (6) | 0.0064 (6) | −0.0018 (5) | −0.0006 (5) | 0.0000 (5) |
C5 | 0.0093 (6) | 0.0076 (6) | 0.0076 (6) | −0.0031 (5) | −0.0011 (5) | 0.0001 (5) |
C6 | 0.0092 (7) | 0.0094 (6) | 0.0081 (6) | −0.0035 (5) | −0.0018 (5) | 0.0012 (5) |
C7 | 0.0070 (6) | 0.0106 (6) | 0.0080 (6) | −0.0034 (5) | −0.0003 (5) | 0.0002 (5) |
O5W | 0.0168 (6) | 0.0141 (5) | 0.0223 (6) | −0.0078 (5) | 0.0001 (5) | −0.0007 (5) |
Ni1—O1W | 2.0325 (11) | N1—C5 | 1.3395 (18) |
Ni1—O1 | 2.0483 (10) | N1—C1 | 1.3481 (18) |
Ni1—O4W | 2.0505 (11) | O3—C7 | 1.2532 (18) |
Ni1—N1 | 2.0700 (12) | O4—C7 | 1.2608 (18) |
Ni1—O2W | 2.0867 (10) | C1—C2 | 1.385 (2) |
Ni1—O3W | 2.0915 (11) | C1—C6 | 1.518 (2) |
O1W—H1WB | 0.8501 | C2—C3 | 1.396 (2) |
O1W—H1WA | 0.8500 | C2—H2A | 0.9500 |
O2W—H2WA | 0.8500 | C3—C4 | 1.390 (2) |
O2W—H2WB | 0.8500 | C3—H3A | 0.9500 |
O3W—H3WA | 0.8500 | C4—C5 | 1.3917 (19) |
O3W—H3WB | 0.8500 | C4—C7 | 1.5116 (19) |
O4W—H4WA | 0.8500 | C5—H5A | 0.9500 |
O4W—H4WB | 0.8500 | O5W—H5WB | 0.8500 |
O1—C6 | 1.2668 (18) | O5W—H5WA | 0.8501 |
O2—C6 | 1.2446 (18) | ||
O1W—Ni1—O1 | 91.77 (4) | C6—O1—Ni1 | 116.37 (9) |
O1W—Ni1—O4W | 87.70 (4) | C5—N1—C1 | 118.74 (12) |
O1—Ni1—O4W | 90.52 (4) | C5—N1—Ni1 | 128.30 (10) |
O1W—Ni1—N1 | 171.48 (5) | C1—N1—Ni1 | 112.96 (9) |
O1—Ni1—N1 | 79.73 (4) | N1—C1—C2 | 122.40 (13) |
O4W—Ni1—N1 | 93.03 (5) | N1—C1—C6 | 114.88 (12) |
O1W—Ni1—O2W | 95.03 (4) | C2—C1—C6 | 122.70 (13) |
O1—Ni1—O2W | 172.73 (4) | C1—C2—C3 | 118.82 (13) |
O4W—Ni1—O2W | 87.21 (4) | C1—C2—H2A | 120.6 |
N1—Ni1—O2W | 93.48 (4) | C3—C2—H2A | 120.6 |
O1W—Ni1—O3W | 88.12 (4) | C4—C3—C2 | 118.71 (13) |
O1—Ni1—O3W | 93.70 (4) | C4—C3—H3A | 120.6 |
O4W—Ni1—O3W | 174.15 (4) | C2—C3—H3A | 120.6 |
N1—Ni1—O3W | 91.71 (5) | C3—C4—C5 | 118.96 (13) |
O2W—Ni1—O3W | 89.09 (4) | C3—C4—C7 | 121.86 (13) |
Ni1—O1W—H1WB | 127.7 | C5—C4—C7 | 119.14 (12) |
Ni1—O1W—H1WA | 126.0 | N1—C5—C4 | 122.29 (13) |
H1WB—O1W—H1WA | 105.7 | N1—C5—H5A | 118.9 |
Ni1—O2W—H2WA | 124.1 | C4—C5—H5A | 118.9 |
Ni1—O2W—H2WB | 110.2 | O2—C6—O1 | 124.76 (13) |
H2WA—O2W—H2WB | 103.2 | O2—C6—C1 | 119.37 (13) |
Ni1—O3W—H3WA | 114.0 | O1—C6—C1 | 115.87 (12) |
Ni1—O3W—H3WB | 117.0 | O3—C7—O4 | 124.86 (13) |
H3WA—O3W—H3WB | 110.6 | O3—C7—C4 | 118.32 (13) |
Ni1—O4W—H4WA | 113.3 | O4—C7—C4 | 116.80 (13) |
Ni1—O4W—H4WB | 114.0 | H5WB—O5W—H5WA | 106.3 |
H4WA—O4W—H4WB | 103.8 | ||
O1W—Ni1—O1—C6 | 178.63 (11) | C1—C2—C3—C4 | 1.4 (2) |
O4W—Ni1—O1—C6 | 90.91 (11) | C2—C3—C4—C5 | −2.4 (2) |
N1—Ni1—O1—C6 | −2.07 (10) | C2—C3—C4—C7 | 175.16 (13) |
O3W—Ni1—O1—C6 | −93.15 (11) | C1—N1—C5—C4 | 1.6 (2) |
O1—Ni1—N1—C5 | −176.85 (13) | Ni1—N1—C5—C4 | −177.79 (10) |
O4W—Ni1—N1—C5 | 93.17 (13) | C3—C4—C5—N1 | 1.0 (2) |
O2W—Ni1—N1—C5 | 5.79 (13) | C7—C4—C5—N1 | −176.67 (13) |
O3W—Ni1—N1—C5 | −83.40 (13) | Ni1—O1—C6—O2 | 179.57 (12) |
O1—Ni1—N1—C1 | 3.74 (10) | Ni1—O1—C6—C1 | 0.15 (16) |
O4W—Ni1—N1—C1 | −86.23 (10) | N1—C1—C6—O2 | −176.29 (13) |
O2W—Ni1—N1—C1 | −173.62 (10) | C2—C1—C6—O2 | 2.2 (2) |
O3W—Ni1—N1—C1 | 97.19 (10) | N1—C1—C6—O1 | 3.17 (19) |
C5—N1—C1—C2 | −2.7 (2) | C2—C1—C6—O1 | −178.29 (13) |
Ni1—N1—C1—C2 | 176.73 (11) | C3—C4—C7—O3 | 9.8 (2) |
C5—N1—C1—C6 | 175.80 (13) | C5—C4—C7—O3 | −172.58 (14) |
Ni1—N1—C1—C6 | −4.73 (16) | C3—C4—C7—O4 | −168.48 (14) |
N1—C1—C2—C3 | 1.3 (2) | C5—C4—C7—O4 | 9.1 (2) |
C6—C1—C2—C3 | −177.16 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WB···O3i | 0.85 | 1.87 | 2.7235 (15) | 179 |
O1W—H1WA···O3Wii | 0.85 | 1.98 | 2.8233 (15) | 175 |
O2W—H2WA···O2iii | 0.85 | 1.90 | 2.7484 (16) | 173 |
O2W—H2WB···O4iv | 0.85 | 1.82 | 2.6658 (17) | 170 |
O3W—H3WA···O2v | 0.85 | 1.86 | 2.7005 (16) | 169 |
O3W—H3WB···O5Wvi | 0.85 | 1.96 | 2.7909 (17) | 164 |
O4W—H4WA···O1vii | 0.85 | 1.89 | 2.7366 (16) | 174 |
O4W—H4WB···O3viii | 0.85 | 1.86 | 2.6732 (15) | 161 |
O5W—H5WB···O2W | 0.85 | 2.23 | 3.0541 (19) | 164 |
O5W—H5WA···O4ix | 0.85 | 1.98 | 2.7619 (18) | 152 |
C3—H3A···O5Wx | 0.95 | 2.44 | 3.3182 (19) | 154 |
Symmetry codes: (i) x, y, z−1; (ii) −x+2, −y+1, −z+1; (iii) x, y−1, z; (iv) −x+2, −y+1, −z+2; (v) −x+2, −y+2, −z+1; (vi) x+1, y, z; (vii) −x+1, −y+2, −z+1; (viii) −x+1, −y+2, −z+2; (ix) −x+1, −y+1, −z+2; (x) −x+2, −y+2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Ni(C7H3NO4)(H2O)4]·H2O |
Mr | 313.89 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 100 |
a, b, c (Å) | 6.6633 (3), 8.3996 (3), 10.7882 (4) |
α, β, γ (°) | 84.7541 (9), 83.0010 (8), 67.6991 (8) |
V (Å3) | 553.81 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.80 |
Crystal size (mm) | 0.25 × 0.20 × 0.10 |
Data collection | |
Diffractometer | Bruker APEX2 CCD area-detector diffractometer |
Absorption correction | Multi-scan (APEX2; Bruker, 2005) |
Tmin, Tmax | 0.662, 0.841 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9105, 2950, 2710 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.682 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.024, 0.067, 1.05 |
No. of reflections | 2950 |
No. of parameters | 163 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.58, −0.48 |
Computer programs: APEX2 (Bruker, 2005), SHELXTL (Sheldrick, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
O1W—H1WB···O3i | 0.85 | 1.87 | 2.7235 (15) | 179 |
O1W—H1WA···O3Wii | 0.85 | 1.98 | 2.8233 (15) | 175 |
O2W—H2WA···O2iii | 0.85 | 1.90 | 2.7484 (16) | 173 |
O2W—H2WB···O4iv | 0.85 | 1.82 | 2.6658 (17) | 170 |
O3W—H3WA···O2v | 0.85 | 1.86 | 2.7005 (16) | 169 |
O3W—H3WB···O5Wvi | 0.85 | 1.96 | 2.7909 (17) | 164 |
O4W—H4WA···O1vii | 0.85 | 1.89 | 2.7366 (16) | 174 |
O4W—H4WB···O3viii | 0.85 | 1.86 | 2.6732 (15) | 161 |
O5W—H5WB···O2W | 0.85 | 2.23 | 3.0541 (19) | 164 |
O5W—H5WA···O4ix | 0.85 | 1.98 | 2.7619 (18) | 152 |
C3—H3A···O5Wx | 0.95 | 2.44 | 3.3182 (19) | 154 |
Symmetry codes: (i) x, y, z−1; (ii) −x+2, −y+1, −z+1; (iii) x, y−1, z; (iv) −x+2, −y+1, −z+2; (v) −x+2, −y+2, −z+1; (vi) x+1, y, z; (vii) −x+1, −y+2, −z+1; (viii) −x+1, −y+2, −z+2; (ix) −x+1, −y+1, −z+2; (x) −x+2, −y+2, −z+2. |
The data collection temperature in our work was 100 (2) K, whereas, the previous work was conducted at the room temperature.
The N1 and O1 atoms of the (py-2,5-dc)2– group, O1W and O2W occupy the equatorial positions, while O3W and O4W atoms accupy axial positions. The O3W—Ni1—O4W, O1—Ni1—O2W and N1- Ni1—O1W angles which equal to 174.15 (4)°, 172.73 (4)° and 171.48 (5)°, respectively, deviate from linearity. Bond distances and bond angles show the coordination around NiII is distorted octahedral. There are a large number of O—H···O and C—H···O hydrogen bonds with distances ranging from 2.6658 (17) Å to 2.8233 (15) Å between [Ni(py-2,5-dc)(H2O)4] and water molecules Considerable π–π staking 3.76 Å (1 - x, 2 - y, 2 - z) and C—H···π 3.247 Å interactions between two aromatic rings of py-2,5-dc are observed. Hydrogen bonds and π–π stacking and van der Waals forces result in the formation of a supramolecular structure.