Diaqua­bis­{5-(pyridin-2-yl-κN)-3-[4-(pyri­din-4-yl)phenyl]-1H-1,2,4-triazol-1-ido-κN ¹}zinc

Abstract

The asymmetric unit of the title compound, [Zn(C₁₈H₁₂N₅)₂(H₂O)₂], consists a Zn^II ion, located on an inversion center, a deprotonated 5-pyridin-2-yl-3-[4-(pyridin-4-yl)phen­yl]-1H-1,2,4-triazol-1-ido ligand and a water mol­ecule. The whole mol­ecule is generated by inversion symmetry. The Zn^II ion has a distorted octa­hedral coordination geometry, defined by four N atoms from the two deprotonated organic ligands and two water O atoms. In the crystal, O—H⋯N hydrogen bonds link the mol­ecules, forming a three-dimensional network.

Related literature  

For background to coordination complexes, see: Zhang et al. (2012a ▶,b ▶); Fan et al. (2013 ▶).

Experimental  

Crystal data  

• [Zn(C₁₈H₁₂N₅)₂(H₂O)₂]

• M _r = 698.05

• Monoclinic,

• a = 13.214 (5) Å

• b = 12.049 (5) Å

• c = 9.825 (4) Å

• β = 100.709 (3)°

• V = 1537.0 (10) ų

• Z = 2

• Mo Kα radiation

• μ = 0.85 mm⁻¹

• T = 296 K

• 0.12 × 0.10 × 0.08 mm

Data collection  

• Bruker APEXII CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.905, T _max = 0.935

• 7962 measured reflections

• 2718 independent reflections

• 1731 reflections with I > 2σ(I)

• R _int = 0.070

Refinement  

• R[F ² > 2σ(F ²)] = 0.057

• wR(F ²) = 0.151

• S = 1.00

• 2718 reflections

• 229 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.65 e Å⁻³

• Δρ_min = −0.32 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1W⋯N3i	0.75 (6)	2.07 (6)	2.812 (5)	169 (6)
O1—H2W⋯N5ii	0.85 (6)	2.38 (6)	3.165 (7)	155 (6)

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

The design and synthesis of coordination complexes has attracted upsurging research interest not only because of their appealing structural and topological novelty but also owing to their potential applications in gas storage, microelectronics, ion exchange, chemical separations, nonlinear optics and heterogeneous catalysis. Here, we report on the complex formed by a solvothermal reaction of 2-(3-(4-(pyridin-4- yl)phenyl)-1H-1,2,4-triazol-5-yl)pyridine with zinc(II) acetate.

The title compound, Fig. 1, possesses inversion symmetry, and consists of a zinc atom (located on the inversion center) coordinated to two symmetry related deprotonated 2-(3-(4-(pyridin-4- yl)phenyl)-1H-1,2,4-triazol-5-yl)pyridine ligands and two water molecules. The zinc atom, Zn1, has a distorted ZnN4O2 octahedral coordination geometry; completed by four N atoms of the ligand and two O atoms from the two water molecules. The Zn1—O1 distance is 2.301 (4) Å, and the Zn—N distances varying from 2.048 (3) - 2.134 (3) Å.

In the crystal, O-H···N hydrogen bonds link the molecules forming a three-dimensional network (Fig. 2 and Table 1).

Experimental

A mixture of 2-(3-(4-(pyridin-4- yl)phenyl)-1H-1,2,4-triazol-5-yl)pyridine (0.20 mmol, 0.060 g), zinc acetate dihydrate (0.20 mmol, 0.044 g) and NaOH (0.20 mmol, 0.008 g) in 12 mL H₂O was placed in a Teflon-lined stainless steel vessel and heated to 443 K for 3 days, followed by slow cooling (a descent rate of 10 K/h) to room temperature. Colourless block-like crystals suitable for X-ray diffraction analysis were obtained. Anal. Calc. for C₃₆H₂₈ZnN₁₀O₂: C 61.94, H 4.04, N 20.06%; Found: C 61.89, H 4.01, N 19.97%.

Refinement

The C-bound H atoms were included in calculated positions refined using a riding model: C—H = 0.93 Å with U_iso = 1.2U_eq(C). The water H atoms were located in difference electron density maps and refined with distance restraints: O—H = 0.83 (2) Å and U_iso(H) fixed at 0.80 Ų.

Figures

Fig. 1.

The molecular structure of the title compound, with the atom-labelling. Displacement ellipsoids are drawn at the 30% probability level.

Fig. 2.

The crystal packing of the title compound viewed along the b axis. Hydrogen bonds are shown as dashed cyan lines (see Table 1 for details; C-bound H atoms have been omitted for clarity).

Crystal data

[Zn(C18H12N5)2(H2O)2]	F(000) = 720
Mr = 698.05	Dx = 1.508 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 985 reflections
a = 13.214 (5) Å	θ = 2.3–20.2°
b = 12.049 (5) Å	µ = 0.85 mm−1
c = 9.825 (4) Å	T = 296 K
β = 100.709 (3)°	Block, colorless
V = 1537.0 (10) Å3	0.12 × 0.10 × 0.08 mm
Z = 2

Data collection

Bruker APEXII CCD area-detector diffractometer	2718 independent reflections
Radiation source: fine-focus sealed tube	1731 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.070
phi and ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −15→14
Tmin = 0.905, Tmax = 0.935	k = −14→14
7962 measured reflections	l = −11→9

Refinement

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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.151	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.035P)2 + 1.3183P] where P = (Fo2 + 2Fc2)/3
2718 reflections	(Δ/σ)max = 0.001
229 parameters	Δρmax = 0.65 e Å−3
0 restraints	Δρmin = −0.32 e Å−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.3744 (3)	0.7926 (3)	−0.1269 (4)	0.0397 (11)
H1	0.3415	0.8410	−0.1946	0.048*
C2	0.3495 (4)	0.6829 (4)	−0.1378 (5)	0.0444 (12)
H2	0.3016	0.6568	−0.2124	0.053*
C3	0.3963 (4)	0.6118 (4)	−0.0371 (5)	0.0474 (13)
H3	0.3800	0.5366	−0.0424	0.057*
C4	0.4679 (4)	0.6519 (3)	0.0729 (5)	0.0412 (11)
H4	0.5001	0.6047	0.1426	0.049*
C5	0.4902 (3)	0.7630 (3)	0.0761 (4)	0.0317 (10)
C6	0.5671 (3)	0.8172 (3)	0.1839 (4)	0.0308 (10)
C7	0.6829 (3)	0.8610 (3)	0.3510 (4)	0.0360 (10)
C8	0.7641 (3)	0.8613 (4)	0.4753 (4)	0.0373 (11)
C9	0.8225 (4)	0.9560 (4)	0.5076 (5)	0.0619 (16)
H9	0.8083	1.0183	0.4514	0.074*
C10	0.9010 (4)	0.9603 (4)	0.6208 (6)	0.0636 (16)
H10	0.9395	1.0250	0.6386	0.076*
C11	0.9241 (4)	0.8705 (4)	0.7089 (5)	0.0459 (12)
C12	0.8626 (4)	0.7784 (4)	0.6780 (5)	0.0540 (14)
H12	0.8747	0.7172	0.7364	0.065*
C13	0.7839 (4)	0.7727 (4)	0.5648 (5)	0.0468 (12)
H13	0.7440	0.7088	0.5487	0.056*
C14	1.0114 (4)	0.8769 (4)	0.8265 (5)	0.0523 (13)
C15	1.0930 (5)	0.9456 (6)	0.8211 (7)	0.091 (2)
H15	1.0946	0.9868	0.7415	0.109*
C16	1.1734 (5)	0.9543 (6)	0.9339 (8)	0.091 (2)
H16	1.2270	1.0026	0.9262	0.109*
C17	1.1083 (6)	0.8258 (8)	1.0459 (7)	0.123 (3)
H17	1.1144	0.7771	1.1204	0.148*
C18	1.0230 (5)	0.8124 (7)	0.9395 (7)	0.112 (3)
H18	0.9739	0.7586	0.9472	0.134*
N1	0.4441 (3)	0.8336 (3)	−0.0228 (3)	0.0349 (9)
N2	0.5866 (3)	0.9241 (3)	0.1689 (4)	0.0390 (9)
N3	0.6254 (3)	0.7724 (3)	0.2965 (3)	0.0336 (9)
N4	0.6623 (3)	0.9535 (3)	0.2762 (4)	0.0406 (10)
N5	1.1795 (4)	0.8996 (5)	1.0499 (5)	0.0778 (15)
O1	0.3799 (3)	1.0467 (3)	0.1325 (4)	0.0501 (10)
Zn1	0.5000	1.0000	0.0000	0.0435 (3)
H1W	0.376 (5)	1.109 (5)	0.141 (6)	0.080*
H2W	0.328 (5)	1.006 (5)	0.139 (6)	0.080*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.037 (3)	0.039 (2)	0.035 (3)	0.004 (2)	−0.014 (2)	0.003 (2)
C2	0.051 (3)	0.040 (3)	0.035 (3)	−0.009 (2)	−0.011 (2)	−0.006 (2)
C3	0.056 (3)	0.035 (2)	0.045 (3)	−0.007 (2)	−0.007 (3)	0.002 (2)
C4	0.048 (3)	0.033 (2)	0.036 (3)	0.001 (2)	−0.008 (2)	0.005 (2)
C5	0.035 (2)	0.032 (2)	0.026 (2)	0.0006 (18)	−0.001 (2)	−0.0002 (18)
C6	0.030 (2)	0.029 (2)	0.031 (2)	0.0004 (17)	−0.001 (2)	0.0008 (18)
C7	0.036 (3)	0.036 (2)	0.032 (3)	0.0013 (19)	−0.003 (2)	−0.002 (2)
C8	0.033 (3)	0.044 (3)	0.031 (2)	−0.002 (2)	−0.005 (2)	0.000 (2)
C9	0.068 (4)	0.041 (3)	0.060 (4)	−0.009 (3)	−0.031 (3)	0.010 (3)
C10	0.065 (4)	0.053 (3)	0.058 (4)	−0.016 (3)	−0.027 (3)	0.000 (3)
C11	0.039 (3)	0.061 (3)	0.032 (3)	−0.005 (2)	−0.009 (2)	0.005 (2)
C12	0.049 (3)	0.064 (3)	0.041 (3)	−0.006 (3)	−0.011 (3)	0.019 (3)
C13	0.046 (3)	0.048 (3)	0.040 (3)	−0.011 (2)	−0.008 (2)	0.009 (2)
C14	0.038 (3)	0.074 (4)	0.039 (3)	−0.009 (3)	−0.007 (3)	0.005 (3)
C15	0.076 (5)	0.097 (5)	0.081 (5)	−0.032 (4)	−0.033 (4)	0.014 (4)
C16	0.073 (5)	0.102 (5)	0.083 (5)	−0.026 (4)	−0.026 (4)	0.006 (4)
C17	0.092 (6)	0.197 (9)	0.059 (4)	−0.042 (6)	−0.039 (4)	0.053 (5)
C18	0.070 (5)	0.191 (8)	0.058 (4)	−0.042 (5)	−0.030 (4)	0.049 (5)
N1	0.039 (2)	0.0279 (18)	0.032 (2)	0.0037 (16)	−0.0103 (17)	0.0011 (15)
N2	0.041 (2)	0.034 (2)	0.034 (2)	−0.0006 (17)	−0.0135 (18)	−0.0007 (16)
N3	0.033 (2)	0.0334 (19)	0.029 (2)	0.0020 (15)	−0.0094 (17)	0.0007 (16)
N4	0.041 (2)	0.0330 (19)	0.038 (2)	0.0003 (17)	−0.0174 (19)	0.0022 (17)
N5	0.047 (3)	0.131 (5)	0.047 (3)	−0.003 (3)	−0.015 (2)	−0.003 (3)
O1	0.052 (2)	0.0376 (18)	0.054 (2)	−0.0033 (17)	−0.0082 (18)	−0.0060 (18)
Zn1	0.0506 (5)	0.0289 (4)	0.0399 (5)	−0.0042 (4)	−0.0204 (4)	0.0043 (3)

Geometric parameters (Å, º)

C1—N1	1.338 (5)	C11—C14	1.475 (6)
C1—C2	1.361 (6)	C12—C13	1.375 (6)
C1—H1	0.9300	C12—H12	0.9300
C2—C3	1.366 (6)	C13—H13	0.9300
C2—H2	0.9300	C14—C18	1.341 (7)
C3—C4	1.385 (6)	C14—C15	1.368 (8)
C3—H3	0.9300	C15—C16	1.389 (8)
C4—C5	1.370 (6)	C15—H15	0.9300
C4—H4	0.9300	C16—N5	1.306 (8)
C5—N1	1.348 (5)	C16—H16	0.9300
C5—C6	1.477 (5)	C17—N5	1.289 (8)
C6—N2	1.327 (5)	C17—C18	1.397 (8)
C6—N3	1.338 (5)	C17—H17	0.9300
C7—N4	1.335 (5)	C18—H18	0.9300
C7—N3	1.361 (5)	N1—Zn1	2.134 (3)
C7—C8	1.469 (6)	N2—N4	1.358 (5)
C8—C13	1.378 (6)	N2—Zn1	2.048 (3)
C8—C9	1.381 (6)	O1—Zn1	2.301 (4)
C9—C10	1.374 (7)	O1—H1W	0.75 (6)
C9—H9	0.9300	O1—H2W	0.85 (6)
C10—C11	1.384 (7)	Zn1—N2i	2.048 (3)
C10—H10	0.9300	Zn1—N1i	2.134 (3)
C11—C12	1.376 (6)	Zn1—O1i	2.301 (4)
N1—C1—C2	122.7 (4)	C15—C14—C11	120.6 (5)
N1—C1—H1	118.6	C16—C15—C14	120.5 (6)
C2—C1—H1	118.6	C16—C15—H15	119.8
C3—C2—C1	118.8 (4)	C14—C15—H15	119.8
C3—C2—H2	120.6	N5—C16—C15	124.9 (7)
C1—C2—H2	120.6	N5—C16—H16	117.6
C2—C3—C4	119.9 (4)	C15—C16—H16	117.6
C2—C3—H3	120.1	N5—C17—C18	125.8 (7)
C4—C3—H3	120.1	N5—C17—H17	117.1
C5—C4—C3	118.2 (4)	C18—C17—H17	117.1
C5—C4—H4	120.9	C14—C18—C17	120.3 (7)
C3—C4—H4	120.9	C14—C18—H18	119.9
N1—C5—C4	122.2 (4)	C17—C18—H18	119.8
N1—C5—C6	113.4 (3)	C1—N1—C5	118.2 (4)
C4—C5—C6	124.4 (4)	C1—N1—Zn1	127.1 (3)
N2—C6—N3	112.9 (3)	C5—N1—Zn1	114.6 (3)
N2—C6—C5	118.1 (3)	C6—N2—N4	107.3 (3)
N3—C6—C5	128.9 (4)	C6—N2—Zn1	115.6 (3)
N4—C7—N3	113.3 (4)	N4—N2—Zn1	137.1 (3)
N4—C7—C8	119.9 (4)	C6—N3—C7	101.7 (3)
N3—C7—C8	126.7 (4)	C7—N4—N2	104.8 (3)
C13—C8—C9	117.6 (4)	C17—N5—C16	113.3 (6)
C13—C8—C7	123.5 (4)	Zn1—O1—H1W	112 (5)
C9—C8—C7	119.0 (4)	Zn1—O1—H2W	123 (4)
C10—C9—C8	121.5 (5)	H1W—O1—H2W	119 (6)
C10—C9—H9	119.3	N2i—Zn1—N2	180.0
C8—C9—H9	119.3	N2i—Zn1—N1	101.80 (13)
C9—C10—C11	121.6 (5)	N2—Zn1—N1	78.20 (13)
C9—C10—H10	119.2	N2i—Zn1—N1i	78.20 (13)
C11—C10—H10	119.2	N2—Zn1—N1i	101.80 (13)
C12—C11—C10	116.1 (4)	N1—Zn1—N1i	180.000 (1)
C12—C11—C14	124.0 (4)	N2i—Zn1—O1i	89.48 (14)
C10—C11—C14	119.9 (5)	N2—Zn1—O1i	90.52 (14)
C13—C12—C11	123.1 (4)	N1—Zn1—O1i	88.42 (13)
C13—C12—H12	118.5	N1i—Zn1—O1i	91.58 (13)
C11—C12—H12	118.5	N2i—Zn1—O1	90.52 (14)
C12—C13—C8	120.2 (4)	N2—Zn1—O1	89.48 (14)
C12—C13—H13	119.9	N1—Zn1—O1	91.58 (13)
C8—C13—H13	119.9	N1i—Zn1—O1	88.42 (13)
C18—C14—C15	114.4 (5)	O1i—Zn1—O1	180.000 (1)
C18—C14—C11	124.8 (5)

Symmetry code: (i) −x+1, −y+2, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1W···N3ii	0.75 (6)	2.07 (6)	2.812 (5)	169 (6)
O1—H2W···N5iii	0.85 (6)	2.38 (6)	3.165 (7)	155 (6)

Symmetry codes: (ii) −x+1, y+1/2, −z+1/2; (iii) x−1, y, z−1.