metal-organic compounds
[μ-1,4-Bis(1,2,4-triazol-1-ylmethyl)benzene]bis[aqua(pyridine-2,6-dicarboxylato)copper(II)] monohydrate
aCollege of Chemical Engineering, Hebei United University, Tangshan 063009, People's Republic of China, and bQian'an College, Hebei United University, Tangshan 063009, People's Republic of China
*Correspondence e-mail: tsdgying@126.com
The title compound, [Cu2(C7H3NO4)2(C12H12N6)(H2O)2]·H2O, displays a discrete dinuclear structure, in which the central CuII atom is five-coordinated in a distorted square-based pyramidal coordination geometry and the flexible ligand 1,4-bis(1,2,4-triazol-1-ylmethyl)benzene adopts a bis-monodentate bridging mode linking the CuII atoms. It is further assembled by O—H⋯O hydrogen-bond interactions involving both the coordinated and uncoordinated water molecules. The latter exhibits half-occupancy.
Related literature
For the versatile conformations of the flexible 1,4-bis(1,2,4- triazol-1-yl-methyl)benzene ligand and related complexes, see: Arion et al. (2003); Peng et al. (2004, 2006); Meng et al. (2004); Li et al. (2005); Lin & Dong (2007); Ding et al. (2009).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 1998); cell SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536811022756/jh2295sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811022756/jh2295Isup2.hkl
A mixture of Cu(NO3)2 3H2O(120.5 mg, 0.5 mmol), 2,6-Pyridinedicarboxylic acid (167 mg, 1 mmol),NaOH(80 mg, 2 mm mol), btx (60 mg, 0.5 mmol) and water (12 ml) was sealed in a 25 ml teflon-lined stainless steel reactor and heated to 413 K for 72 h. The reaction was cooled to room temperature over a period of 24 h. Blue prism crystals of 1 suitable for X-ray difraction analysis were obtained with a yield of 37%(based btx)
H atoms were placed in calculated positions, with C—H = 0.93 or 0.97 Å included in the final cycles of
using a riding model, with Uiso(H) = 1.2Ueq(parent atom).Water H atoms were located in Fourier difference maps and isotropically.Data collection: SMART (Bruker, 1998); cell
SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).Fig. 1. Fig. 1. The part molecular structure of (I), showing displacement ellipsoids at the 30% probability level for atoms [symmetry code: (i) -x, -y + 3, -z) |
[Cu2(C7H3NO4)2(C12H12N6)(H2O)2]·H2O | F(000) = 764 |
Mr = 751.63 | Dx = 1.641 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 3568 reflections |
a = 4.9017 (4) Å | θ = 22.3–3.6° |
b = 10.3022 (9) Å | µ = 1.47 mm−1 |
c = 30.178 (3) Å | T = 298 K |
β = 93.541 (1)° | Prism, blue |
V = 1521.0 (2) Å3 | 0.20 × 0.15 × 0.11 mm |
Z = 2 |
Bruker SMART CCD area-detector diffractometer | 2678 independent reflections |
Radiation source: fine–focus sealed tube | 2256 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.029 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −5→5 |
Tmin = 0.881, Tmax = 0.901 | k = −12→12 |
7340 measured reflections | l = −35→27 |
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.161 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.1045P)2 + 1.8845P] where P = (Fo2 + 2Fc2)/3 |
2678 reflections | (Δ/σ)max < 0.001 |
217 parameters | Δρmax = 1.40 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
[Cu2(C7H3NO4)2(C12H12N6)(H2O)2]·H2O | V = 1521.0 (2) Å3 |
Mr = 751.63 | Z = 2 |
Monoclinic, P21/c | Mo Kα radiation |
a = 4.9017 (4) Å | µ = 1.47 mm−1 |
b = 10.3022 (9) Å | T = 298 K |
c = 30.178 (3) Å | 0.20 × 0.15 × 0.11 mm |
β = 93.541 (1)° |
Bruker SMART CCD area-detector diffractometer | 2678 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2256 reflections with I > 2σ(I) |
Tmin = 0.881, Tmax = 0.901 | Rint = 0.029 |
7340 measured reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.161 | H-atom parameters constrained |
S = 1.06 | Δρmax = 1.40 e Å−3 |
2678 reflections | Δρmin = −0.40 e Å−3 |
217 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) | |
Cu1 | 0.08344 (10) | 0.98034 (5) | 0.149509 (16) | 0.0318 (2) | |
O3 | −0.1809 (6) | 0.9403 (3) | 0.19769 (10) | 0.0376 (7) | |
O1 | 0.3528 (6) | 0.9508 (3) | 0.10311 (10) | 0.0392 (7) | |
N1 | 0.1905 (7) | 0.8071 (3) | 0.16460 (11) | 0.0300 (8) | |
C7 | −0.1409 (9) | 0.8318 (4) | 0.21771 (14) | 0.0328 (9) | |
O4 | −0.2555 (7) | 0.7960 (3) | 0.25024 (11) | 0.0469 (8) | |
N4 | −0.0779 (7) | 1.1422 (3) | 0.12697 (12) | 0.0346 (8) | |
C2 | 0.3801 (9) | 0.7519 (4) | 0.14164 (14) | 0.0335 (9) | |
C3 | 0.4592 (10) | 0.6261 (4) | 0.15103 (16) | 0.0419 (11) | |
H3 | 0.5917 | 0.5859 | 0.1350 | 0.050* | |
C6 | 0.0697 (8) | 0.7462 (4) | 0.19736 (13) | 0.0309 (9) | |
O2 | 0.6818 (8) | 0.8113 (4) | 0.08671 (12) | 0.0565 (10) | |
C11 | −0.1952 (9) | 1.4310 (5) | 0.02197 (15) | 0.0415 (11) | |
C1 | 0.4833 (9) | 0.8436 (4) | 0.10695 (14) | 0.0358 (10) | |
C5 | 0.1422 (10) | 0.6216 (4) | 0.20832 (16) | 0.0417 (11) | |
H5 | 0.0613 | 0.5787 | 0.2312 | 0.050* | |
C12 | −0.0882 (11) | 1.3819 (5) | −0.01557 (17) | 0.0486 (12) | |
H12 | −0.1473 | 1.3016 | −0.0266 | 0.058* | |
C4 | 0.3384 (10) | 0.5605 (5) | 0.18465 (17) | 0.0453 (11) | |
H4 | 0.3890 | 0.4754 | 0.1914 | 0.054* | |
O1W | 0.3552 (8) | 1.0793 (4) | 0.20033 (14) | 0.0698 (13) | |
N2 | −0.2780 (8) | 1.2853 (4) | 0.08451 (13) | 0.0439 (10) | |
C13 | −0.1072 (11) | 1.5492 (5) | 0.03729 (17) | 0.0492 (12) | |
H13 | −0.1788 | 1.5841 | 0.0625 | 0.059* | |
C10 | −0.4037 (11) | 1.3552 (6) | 0.04620 (19) | 0.0576 (15) | |
H10A | −0.5411 | 1.4144 | 0.0562 | 0.069* | |
H10B | −0.4942 | 1.2936 | 0.0259 | 0.069* | |
C9 | −0.1903 (11) | 1.1643 (5) | 0.08746 (16) | 0.0465 (12) | |
H9 | −0.2064 | 1.1037 | 0.0646 | 0.056* | |
N3 | −0.2233 (16) | 1.3460 (5) | 0.12323 (17) | 0.092 (2) | |
C8 | −0.1028 (17) | 1.2542 (6) | 0.14744 (19) | 0.080 (2) | |
H8 | −0.0398 | 1.2672 | 0.1768 | 0.096* | |
O2W | 0.746 (3) | 0.9295 (7) | 0.0049 (2) | 0.092 (4) | 0.50 |
H2WA | 0.9152 | 0.9472 | 0.0077 | 0.137* | 0.50 |
H2WB | 0.5966 | 0.9714 | 0.0018 | 0.137* | 0.50 |
H1WA | 0.3201 | 1.1370 | 0.2183 | 0.137* | |
H1WB | 0.5177 | 1.0475 | 0.2023 | 0.137* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cu1 | 0.0373 (4) | 0.0240 (3) | 0.0348 (4) | 0.0079 (2) | 0.0068 (2) | 0.00618 (19) |
O3 | 0.0425 (17) | 0.0334 (16) | 0.0376 (16) | 0.0129 (14) | 0.0083 (13) | 0.0073 (14) |
O1 | 0.0469 (18) | 0.0330 (16) | 0.0390 (17) | 0.0053 (14) | 0.0130 (14) | 0.0077 (13) |
N1 | 0.0351 (19) | 0.0255 (17) | 0.0296 (18) | 0.0040 (14) | 0.0026 (14) | 0.0005 (14) |
C7 | 0.037 (2) | 0.030 (2) | 0.033 (2) | 0.0001 (18) | 0.0042 (18) | 0.0012 (17) |
O4 | 0.063 (2) | 0.0381 (18) | 0.0418 (18) | 0.0049 (16) | 0.0205 (16) | 0.0073 (15) |
N4 | 0.042 (2) | 0.0274 (18) | 0.035 (2) | 0.0085 (15) | 0.0039 (15) | 0.0055 (15) |
C2 | 0.038 (2) | 0.030 (2) | 0.032 (2) | 0.0025 (18) | 0.0025 (17) | −0.0045 (17) |
C3 | 0.047 (3) | 0.031 (2) | 0.048 (3) | 0.013 (2) | 0.009 (2) | −0.003 (2) |
C6 | 0.036 (2) | 0.026 (2) | 0.030 (2) | 0.0017 (17) | −0.0005 (17) | 0.0018 (17) |
O2 | 0.063 (2) | 0.054 (2) | 0.056 (2) | 0.0176 (18) | 0.0296 (18) | 0.0073 (17) |
C11 | 0.043 (3) | 0.038 (3) | 0.043 (3) | 0.010 (2) | −0.006 (2) | 0.015 (2) |
C1 | 0.044 (3) | 0.031 (2) | 0.033 (2) | 0.0020 (19) | 0.0056 (19) | −0.0015 (17) |
C5 | 0.051 (3) | 0.030 (2) | 0.044 (3) | 0.004 (2) | 0.008 (2) | 0.008 (2) |
C12 | 0.062 (3) | 0.031 (2) | 0.051 (3) | 0.004 (2) | −0.003 (2) | −0.003 (2) |
C4 | 0.056 (3) | 0.024 (2) | 0.056 (3) | 0.010 (2) | 0.008 (2) | 0.006 (2) |
O1W | 0.049 (2) | 0.074 (3) | 0.083 (3) | 0.026 (2) | −0.0229 (19) | −0.046 (2) |
N2 | 0.046 (2) | 0.041 (2) | 0.045 (2) | 0.0095 (18) | −0.0008 (17) | 0.0148 (18) |
C13 | 0.066 (3) | 0.045 (3) | 0.037 (3) | 0.013 (3) | 0.007 (2) | −0.003 (2) |
C10 | 0.049 (3) | 0.060 (3) | 0.063 (3) | 0.010 (3) | −0.004 (2) | 0.034 (3) |
C9 | 0.068 (3) | 0.031 (2) | 0.040 (3) | 0.005 (2) | −0.005 (2) | 0.006 (2) |
N3 | 0.173 (6) | 0.051 (3) | 0.049 (3) | 0.057 (4) | −0.007 (3) | 0.000 (2) |
C8 | 0.155 (7) | 0.043 (3) | 0.039 (3) | 0.042 (4) | −0.015 (3) | −0.001 (2) |
O2W | 0.235 (12) | 0.026 (4) | 0.017 (3) | 0.038 (5) | 0.034 (5) | 0.010 (3) |
Cu1—N1 | 1.908 (3) | C11—C10 | 1.510 (7) |
Cu1—N4 | 1.950 (3) | C5—C4 | 1.384 (7) |
Cu1—O1 | 2.006 (3) | C5—H5 | 0.9300 |
Cu1—O3 | 2.048 (3) | C12—C13i | 1.389 (7) |
Cu1—O1W | 2.217 (4) | C12—H12 | 0.9300 |
O3—C7 | 1.280 (5) | C4—H4 | 0.9300 |
O1—C1 | 1.278 (5) | O1W—H1WA | 0.8301 |
N1—C2 | 1.322 (5) | O1W—H1WB | 0.8599 |
N1—C6 | 1.339 (5) | N2—C9 | 1.319 (6) |
C7—O4 | 1.218 (5) | N2—N3 | 1.338 (6) |
C7—C6 | 1.517 (6) | N2—C10 | 1.466 (6) |
N4—C9 | 1.302 (6) | C13—C12i | 1.389 (7) |
N4—C8 | 1.318 (7) | C13—H13 | 0.9300 |
C2—C3 | 1.377 (6) | C10—H10A | 0.9700 |
C2—C1 | 1.520 (6) | C10—H10B | 0.9700 |
C3—C4 | 1.382 (7) | C9—H9 | 0.9300 |
C3—H3 | 0.9300 | N3—C8 | 1.313 (7) |
C6—C5 | 1.367 (6) | C8—H8 | 0.9300 |
O2—C1 | 1.226 (5) | O2W—H2WA | 0.8500 |
C11—C13 | 1.364 (8) | O2W—H2WB | 0.8482 |
C11—C12 | 1.374 (7) | ||
N1—Cu1—N4 | 169.43 (16) | O2—C1—C2 | 118.8 (4) |
N1—Cu1—O1 | 80.88 (13) | O1—C1—C2 | 114.4 (4) |
N4—Cu1—O1 | 99.00 (14) | C6—C5—C4 | 118.7 (4) |
N1—Cu1—O3 | 79.57 (13) | C6—C5—H5 | 120.6 |
N4—Cu1—O3 | 99.15 (13) | C4—C5—H5 | 120.6 |
O1—Cu1—O3 | 159.60 (14) | C11—C12—C13i | 120.7 (5) |
N1—Cu1—O1W | 96.92 (16) | C11—C12—H12 | 119.7 |
N4—Cu1—O1W | 93.53 (15) | C13i—C12—H12 | 119.7 |
O1—Cu1—O1W | 99.18 (15) | C3—C4—C5 | 120.0 (4) |
O3—Cu1—O1W | 88.91 (16) | C3—C4—H4 | 120.0 |
C7—O3—Cu1 | 115.2 (3) | C5—C4—H4 | 120.0 |
C1—O1—Cu1 | 114.5 (3) | Cu1—O1W—H1WA | 129.9 |
C2—N1—C6 | 122.9 (4) | Cu1—O1W—H1WB | 112.7 |
C2—N1—Cu1 | 118.0 (3) | H1WA—O1W—H1WB | 117.2 |
C6—N1—Cu1 | 119.1 (3) | C9—N2—N3 | 109.6 (4) |
O4—C7—O3 | 125.5 (4) | C9—N2—C10 | 129.6 (5) |
O4—C7—C6 | 120.6 (4) | N3—N2—C10 | 120.7 (4) |
O3—C7—C6 | 113.9 (3) | C11—C13—C12i | 120.6 (5) |
C9—N4—C8 | 103.3 (4) | C11—C13—H13 | 119.7 |
C9—N4—Cu1 | 127.5 (3) | C12i—C13—H13 | 119.7 |
C8—N4—Cu1 | 129.2 (3) | N2—C10—C11 | 111.8 (4) |
N1—C2—C3 | 119.7 (4) | N2—C10—H10A | 109.2 |
N1—C2—C1 | 111.6 (4) | C11—C10—H10A | 109.2 |
C3—C2—C1 | 128.7 (4) | N2—C10—H10B | 109.2 |
C2—C3—C4 | 118.9 (4) | C11—C10—H10B | 109.2 |
C2—C3—H3 | 120.6 | H10A—C10—H10B | 107.9 |
C4—C3—H3 | 120.6 | N4—C9—N2 | 110.2 (4) |
N1—C6—C5 | 119.9 (4) | N4—C9—H9 | 124.9 |
N1—C6—C7 | 111.7 (3) | N2—C9—H9 | 124.9 |
C5—C6—C7 | 128.5 (4) | C8—N3—N2 | 102.0 (5) |
C13—C11—C12 | 118.7 (5) | N3—C8—N4 | 114.9 (5) |
C13—C11—C10 | 120.4 (5) | N3—C8—H8 | 122.5 |
C12—C11—C10 | 120.9 (5) | N4—C8—H8 | 122.5 |
O2—C1—O1 | 126.7 (4) | H2WA—O2W—H2WB | 137.0 |
Symmetry code: (i) −x, −y+3, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2W—H2WA···O2Wii | 0.85 | 2.15 | 2.920 (5) | 151 |
O2W—H2WB···O2Wiii | 0.85 | 1.96 | 2.807 (5) | 179 |
O1W—H1WA···O4iv | 0.83 | 1.93 | 2.746 (5) | 168 |
O1W—H1WB···O3v | 0.86 | 1.86 | 2.692 (5) | 164 |
Symmetry codes: (ii) −x+2, −y+2, −z; (iii) −x+1, −y+2, −z; (iv) −x, y+1/2, −z+1/2; (v) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | [Cu2(C7H3NO4)2(C12H12N6)(H2O)2]·H2O |
Mr | 751.63 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 4.9017 (4), 10.3022 (9), 30.178 (3) |
β (°) | 93.541 (1) |
V (Å3) | 1521.0 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 1.47 |
Crystal size (mm) | 0.20 × 0.15 × 0.11 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.881, 0.901 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7340, 2678, 2256 |
Rint | 0.029 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.161, 1.06 |
No. of reflections | 2678 |
No. of parameters | 217 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.40, −0.40 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O2W—H2WA···O2Wi | 0.85 | 2.147 | 2.920 (5) | 151.00 |
O2W—H2WB···O2Wii | 0.85 | 1.959 | 2.807 (5) | 179.11 |
O1W—H1WA···O4iii | 0.83 | 1.928 | 2.746 (5) | 167.54 |
O1W—H1WB···O3iv | 0.86 | 1.859 | 2.692 (5) | 163.64 |
Symmetry codes: (i) −x+2, −y+2, −z; (ii) −x+1, −y+2, −z; (iii) −x, y+1/2, −z+1/2; (iv) x+1, y, z. |
Acknowledgements
The authors thank Hebei United University for supporting this work.
References
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1,4-bis(1,2,4-triazol-1-ylmethyl)benzene (btx=1,4-bis(1,2,4-triazol-1-ylmethyl)benzene) is a ditriazole-containing bridge ligand, in which the flexible nature of spacers allows the ligands to bend and rotate when coordinating to metal centers so as to conform the coordination geometries of metal ions.(Arion, et al., 2003; Peng, et al., 2004, 2006; Meng, et al., 2004; Li et al., 2005;Lin et al. 2007; Ding, et al. 2009) To further understand the coordination behavior of this ligand, we report herein the crystal structure of the title compound,(I).
The asymmetric unit of (I) contains one copperII,one 2,6-pyridinedicarboxylato, one half btx ligand, one coordination water molecule and one half free water molecule. The copper center is five-coordinated in distorted square-based pyramidal coordination geometry. As show in Fig.1, selected geometric parameters see table 1.Each copperII is coordinated by one tridentate dipicolinato ligands via their carboxylate and nitrogen donors.(Cu1—N1= 1.908 (3); Cu1—O1=2.007 (3); Cu(1)—O(3)= 2.048 (3) Å) another one (Cu1—N4=1.951 (3) Å) from btx ligand together with one water molecule (Cu1—O1W = 2.217 (4) Å).Two carboxylate oxygen atoms and two nitrogen atoms define a quadrangle equatorial plane, and the water oxygen atom occupies the apical position. Each btx ligand bridges two copper atoms related by a twofold axis into dinuclear structure. The dihedral angle between the imidazole and phenyl rings is 70.0 (4)° in same btx ligang. It is noteworthy that there exist strong hydrogen-bonding interaction(table 2) involving the carboxy group oxygen atoms of dipicolinato ligands as well as coordinated and free water molecules,this may further stabilize the crytal structure.