cyclo-Tetra-kis{μ-N'-[(8-oxidoquinolin-7-yl)methyl-idene]isonicotino-hydrazidato}tetra-zinc tetra-hydrate.

In the title compound, [Zn(4)(C(16)H(10)N(4)O(2))(4)]·4H(2)O, the N'-[(8-oxidoquinolin-7-yl)methyl-idene]isonicotinohydrazidate (L(2-)) ligand binds to the metal ions, forming stable five- and six-membered chelate rings, leaving the pyridyl groups free. The compound is a tetra-nuclear Zn(II) complex centered about a fourfold roto-inversion axis, with the ligand coordinating in the doubly deprotonated form. The Zn(II) atom has a distorted square-pyramidal geometry being coordinated by one N and two O-atom donors from the doubly deprotonated L(2-) ligand, and by one N atom and one O-atom donor from a symmetry-related L(2-) ligand. In the crystal, four symmetry-related lattice water mol-ecules, centred about a fourfold roto-inversion axis, form a cyclic tetra-mer through O-H⋯O hydrogen bonds. These tetra-mers connect to the complex mol-ecules through O-H⋯N hydrogen bonds, forming a chain propagating along [100]. Neighbouring mol-ecules are linked by π-π inter-actions [centroid-centroid distance = 3.660 (2) Å] involving the quinolidine rings.

Related literature

For heterometallic coordination n class="Chemical">polymers and coordination compounds involving bridging N-donor ligands, see: Palacios et al. (2008 ▶); Tao et al. (2002 ▶); Dong et al. (2005 ▶). For details of bond lengths in similar zinc(II) complexes, see: Kumar et al. (2006 ▶); Woodward et al. (2006 ▶).

Experimental

Crystal data

[Zn4(C16n class="Species">H10N4O2)4]·4H2O

M = 1494.66

Tetragonal,

a = 21.407 (2) Å

c = 13.626 (3) Å

V = 6244.1 (15) Å3

Z = 4

Mo Kα radiation

μ = 1.60 mm−1

T = 298 K

0.13 × 0.11 × 0.07 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T min = 0.819, T max = 0.897

16035 measured reflections

2900 independent reflections

2324 reflections with I > 2σ(I)

R int = 0.054

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.087

S = 1.03

2900 reflections

217 parameters

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.23 e Å−3

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAIn class="Chemical">NT; 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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812018995/su2415sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812018995/su2415Isup2.hkl

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

[Zn4(C16H10N4O2)4]·4H2O	Dx = 1.590 Mg m−3
Mr = 1494.66	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/a	Cell parameters from 2897 reflections
Hall symbol: I 41/a	θ = 2.6–22.7°
a = 21.407 (2) Å	µ = 1.60 mm−1
c = 13.626 (3) Å	T = 298 K
V = 6244.1 (15) Å3	Block, yellow
Z = 4	0.13 × 0.11 × 0.07 mm
F(000) = 3040

Bruker SMART CCD area-detector diffractometer	2900 independent reflections
Radiation source: fine-focus sealed tube	2324 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.054
phi and ω scans	θmax = 25.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −22→25
Tmin = 0.819, Tmax = 0.897	k = −25→25
16035 measured reflections	l = −13→16

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0372P)2 + 5.0654P] where P = (Fo2 + 2Fc2)/3
2900 reflections	(Δ/σ)max = 0.001
217 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.23 e Å−3

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
C1	1.10071 (14)	0.45462 (15)	1.1624 (3)	0.0485 (8)
H1	1.1119	0.4530	1.2283	0.058*
C2	1.12416 (16)	0.50312 (16)	1.1052 (3)	0.0611 (10)
H2	1.1506	0.5329	1.1324	0.073*
C3	1.10790 (16)	0.50630 (15)	1.0094 (3)	0.0590 (10)
H3	1.1230	0.5388	0.9707	0.071*
C4	1.06842 (14)	0.46097 (14)	0.9677 (3)	0.0442 (8)
C5	1.04647 (12)	0.41352 (13)	1.0312 (2)	0.0336 (6)
C6	1.00568 (12)	0.36577 (12)	0.9960 (2)	0.0303 (6)
C7	0.98754 (13)	0.36698 (13)	0.8981 (2)	0.0361 (7)
C8	1.01152 (15)	0.41496 (15)	0.8363 (2)	0.0497 (8)
H8	1.0003	0.4149	0.7704	0.060*
C9	1.04951 (15)	0.46024 (16)	0.8689 (3)	0.0538 (9)
H9	1.0633	0.4911	0.8262	0.065*
C10	0.94522 (13)	0.32259 (14)	0.8548 (2)	0.0394 (7)
H10	0.9397	0.3241	0.7871	0.047*
C11	0.84867 (13)	0.20093 (13)	0.9058 (2)	0.0374 (7)
C12	0.80184 (14)	0.15938 (14)	0.8575 (3)	0.0453 (8)
C13	0.77607 (18)	0.17239 (18)	0.7669 (3)	0.0684 (11)
H13	0.7896	0.2065	0.7303	0.082*
C14	0.7291 (2)	0.1330 (2)	0.7317 (4)	0.0865 (15)
H14	0.7106	0.1434	0.6721	0.104*
C15	0.7364 (2)	0.0697 (2)	0.8615 (4)	0.0953 (16)
H15	0.7244	0.0332	0.8935	0.114*
C16	0.78125 (17)	0.10645 (17)	0.9055 (3)	0.0641 (10)
H16	0.7974	0.0958	0.9666	0.077*
N1	1.06328 (10)	0.41084 (10)	1.12773 (18)	0.0352 (6)
N2	0.91453 (11)	0.28117 (11)	0.90248 (18)	0.0356 (6)
N3	0.87505 (12)	0.24302 (11)	0.84775 (18)	0.0418 (6)
N4	0.70908 (18)	0.0828 (2)	0.7760 (3)	0.0948 (13)
O1	0.85836 (9)	0.19375 (9)	0.99696 (16)	0.0407 (5)
O2	0.98781 (8)	0.32250 (8)	1.06007 (13)	0.0321 (4)
O3	0.90970 (15)	0.23053 (16)	0.6420 (2)	0.1038 (11)
H3A	0.9434	0.2098	0.6371	0.125*
H3B	0.8948	0.2309	0.6998	0.125*
Zn1	0.910323 (15)	0.265779 (15)	1.04977 (2)	0.03319 (13)

	U11	U22	U33	U12	U13	U23
C1	0.0442 (18)	0.0485 (19)	0.053 (2)	0.0001 (15)	−0.0103 (16)	−0.0125 (16)
C2	0.055 (2)	0.048 (2)	0.080 (3)	−0.0168 (16)	−0.010 (2)	−0.009 (2)
C3	0.056 (2)	0.0398 (19)	0.081 (3)	−0.0139 (16)	0.004 (2)	0.0075 (19)
C4	0.0402 (17)	0.0385 (17)	0.054 (2)	−0.0054 (14)	0.0016 (15)	0.0072 (15)
C5	0.0317 (15)	0.0319 (15)	0.0371 (17)	0.0010 (11)	0.0006 (13)	0.0033 (13)
C6	0.0312 (14)	0.0295 (14)	0.0301 (16)	0.0012 (11)	0.0024 (12)	0.0056 (12)
C7	0.0407 (16)	0.0377 (16)	0.0299 (16)	−0.0028 (13)	0.0030 (13)	0.0026 (13)
C8	0.056 (2)	0.059 (2)	0.0336 (18)	−0.0082 (17)	−0.0018 (16)	0.0167 (16)
C9	0.058 (2)	0.052 (2)	0.051 (2)	−0.0124 (17)	0.0043 (17)	0.0212 (17)
C10	0.0448 (17)	0.0518 (18)	0.0214 (15)	−0.0025 (14)	−0.0032 (13)	0.0025 (14)
C11	0.0369 (16)	0.0375 (16)	0.0378 (18)	0.0022 (13)	−0.0078 (14)	−0.0077 (14)
C12	0.0392 (17)	0.0460 (18)	0.051 (2)	0.0003 (14)	−0.0057 (15)	−0.0151 (16)
C13	0.077 (3)	0.062 (2)	0.066 (3)	−0.008 (2)	−0.033 (2)	−0.008 (2)
C14	0.089 (3)	0.090 (3)	0.080 (3)	−0.004 (3)	−0.043 (3)	−0.022 (3)
C15	0.103 (4)	0.092 (3)	0.091 (4)	−0.053 (3)	−0.001 (3)	−0.016 (3)
C16	0.069 (2)	0.066 (2)	0.057 (3)	−0.0237 (19)	−0.004 (2)	−0.004 (2)
N1	0.0334 (13)	0.0337 (13)	0.0386 (15)	0.0000 (10)	−0.0030 (11)	−0.0050 (11)
N2	0.0406 (14)	0.0419 (14)	0.0244 (13)	−0.0053 (11)	−0.0040 (11)	−0.0006 (11)
N3	0.0492 (15)	0.0483 (15)	0.0279 (14)	−0.0088 (12)	−0.0102 (12)	−0.0038 (12)
N4	0.082 (3)	0.105 (3)	0.097 (3)	−0.035 (2)	−0.019 (2)	−0.029 (3)
O1	0.0476 (12)	0.0410 (11)	0.0335 (12)	−0.0098 (9)	−0.0072 (10)	−0.0006 (10)
O2	0.0395 (11)	0.0339 (10)	0.0228 (10)	−0.0075 (8)	−0.0038 (8)	0.0046 (8)
O3	0.128 (3)	0.144 (3)	0.0396 (17)	−0.007 (2)	0.0108 (17)	−0.0185 (19)
Zn1	0.0380 (2)	0.0382 (2)	0.02344 (19)	−0.00629 (14)	−0.00228 (14)	0.00205 (14)

C1—N1	1.321 (4)	C11—C12	1.493 (4)
C1—C2	1.392 (5)	C12—C13	1.380 (5)
C1—H1	0.9300	C12—C16	1.381 (5)
C2—C3	1.353 (5)	C13—C14	1.397 (5)
C2—H2	0.9300	C13—H13	0.9300
C3—C4	1.406 (5)	C14—N4	1.305 (6)
C3—H3	0.9300	C14—H14	0.9300
C4—C9	1.406 (5)	C15—N4	1.333 (6)
C4—C5	1.414 (4)	C15—C16	1.379 (5)
C5—N1	1.365 (4)	C15—H15	0.9300
C5—C6	1.427 (4)	C16—H16	0.9300
C6—O2	1.329 (3)	N1—Zn1i	2.081 (2)
C6—C7	1.390 (4)	N2—N3	1.392 (3)
C7—C8	1.423 (4)	N2—Zn1	2.036 (2)
C7—C10	1.439 (4)	O1—Zn1	2.0329 (19)
C8—C9	1.341 (4)	O2—Zn1i	2.0350 (18)
C8—H8	0.9300	O2—Zn1	2.0605 (18)
C9—H9	0.9300	O3—H3A	0.8499
C10—N2	1.281 (3)	O3—H3B	0.8502
C10—H10	0.9300	Zn1—O2ii	2.0350 (18)
C11—O1	1.269 (4)	Zn1—N1ii	2.081 (2)
C11—N3	1.325 (4)
N1—C1—C2	123.2 (3)	C12—C13—C14	118.2 (4)
N1—C1—H1	118.4	C12—C13—H13	120.9
C2—C1—H1	118.4	C14—C13—H13	120.9
C3—C2—C1	119.0 (3)	N4—C14—C13	125.1 (4)
C3—C2—H2	120.5	N4—C14—H14	117.5
C1—C2—H2	120.5	C13—C14—H14	117.5
C2—C3—C4	120.6 (3)	N4—C15—C16	124.4 (4)
C2—C3—H3	119.7	N4—C15—H15	117.8
C4—C3—H3	119.7	C16—C15—H15	117.8
C9—C4—C3	124.5 (3)	C15—C16—C12	119.0 (4)
C9—C4—C5	118.8 (3)	C15—C16—H16	120.5
C3—C4—C5	116.7 (3)	C12—C16—H16	120.5
N1—C5—C4	122.1 (3)	C1—N1—C5	118.4 (3)
N1—C5—C6	117.0 (2)	C1—N1—Zn1i	130.2 (2)
C4—C5—C6	120.8 (3)	C5—N1—Zn1i	111.07 (17)
O2—C6—C7	124.3 (2)	C10—N2—N3	116.5 (2)
O2—C6—C5	117.0 (2)	C10—N2—Zn1	129.4 (2)
C7—C6—C5	118.7 (2)	N3—N2—Zn1	113.97 (17)
C6—C7—C8	118.7 (3)	C11—N3—N2	109.7 (2)
C6—C7—C10	123.9 (3)	C14—N4—C15	115.7 (4)
C8—C7—C10	117.5 (3)	C11—O1—Zn1	110.12 (18)
C9—C8—C7	123.0 (3)	C6—O2—Zn1i	113.95 (16)
C9—C8—H8	118.5	C6—O2—Zn1	126.71 (17)
C7—C8—H8	118.5	Zn1i—O2—Zn1	114.03 (8)
C8—C9—C4	120.0 (3)	H3A—O3—H3B	113.4
C8—C9—H9	120.0	O1—Zn1—O2ii	102.00 (8)
C4—C9—H9	120.0	O1—Zn1—N2	78.35 (9)
N2—C10—C7	124.9 (3)	O2ii—Zn1—N2	164.76 (8)
N2—C10—H10	117.6	O1—Zn1—O2	155.73 (8)
C7—C10—H10	117.6	O2ii—Zn1—O2	87.94 (8)
O1—C11—N3	126.7 (3)	N2—Zn1—O2	86.34 (8)
O1—C11—C12	118.0 (3)	O1—Zn1—N1ii	97.94 (8)
N3—C11—C12	115.3 (3)	O2ii—Zn1—N1ii	80.24 (8)
C13—C12—C16	117.5 (3)	N2—Zn1—N1ii	114.92 (9)
C13—C12—C11	122.9 (3)	O2—Zn1—N1ii	105.61 (8)
C16—C12—C11	119.6 (3)
N1—C1—C2—C3	0.4 (5)	C4—C5—N1—Zn1i	174.9 (2)
C1—C2—C3—C4	−0.7 (5)	C6—C5—N1—Zn1i	−5.5 (3)
C2—C3—C4—C9	−179.5 (3)	C7—C10—N2—N3	179.0 (3)
C2—C3—C4—C5	1.0 (5)	C7—C10—N2—Zn1	3.4 (4)
C9—C4—C5—N1	179.4 (3)	O1—C11—N3—N2	−2.2 (4)
C3—C4—C5—N1	−1.0 (4)	C12—C11—N3—N2	176.2 (2)
C9—C4—C5—C6	−0.2 (4)	C10—N2—N3—C11	177.3 (3)
C3—C4—C5—C6	179.4 (3)	Zn1—N2—N3—C11	−6.4 (3)
N1—C5—C6—O2	−0.4 (4)	C13—C14—N4—C15	0.4 (8)
C4—C5—C6—O2	179.2 (2)	C16—C15—N4—C14	2.6 (8)
N1—C5—C6—C7	180.0 (2)	N3—C11—O1—Zn1	9.4 (4)
C4—C5—C6—C7	−0.4 (4)	C12—C11—O1—Zn1	−169.0 (2)
O2—C6—C7—C8	−178.2 (3)	C7—C6—O2—Zn1i	−174.1 (2)
C5—C6—C7—C8	1.4 (4)	C5—C6—O2—Zn1i	6.3 (3)
O2—C6—C7—C10	2.3 (4)	C7—C6—O2—Zn1	−21.6 (4)
C5—C6—C7—C10	−178.1 (3)	C5—C6—O2—Zn1	158.79 (18)
C6—C7—C8—C9	−2.0 (5)	C11—O1—Zn1—O2ii	−173.51 (18)
C10—C7—C8—C9	177.6 (3)	C11—O1—Zn1—N2	−9.08 (19)
C7—C8—C9—C4	1.3 (5)	C11—O1—Zn1—O2	−61.1 (3)
C3—C4—C9—C8	−179.8 (3)	C11—O1—Zn1—N1ii	104.85 (19)
C5—C4—C9—C8	−0.2 (5)	C10—N2—Zn1—O1	−175.7 (3)
C6—C7—C10—N2	7.5 (5)	N3—N2—Zn1—O1	8.59 (18)
C8—C7—C10—N2	−172.0 (3)	C10—N2—Zn1—O2ii	−82.8 (4)
O1—C11—C12—C13	163.3 (3)	N3—N2—Zn1—O2ii	101.5 (3)
N3—C11—C12—C13	−15.3 (5)	C10—N2—Zn1—O2	−14.7 (3)
O1—C11—C12—C16	−14.5 (4)	N3—N2—Zn1—O2	169.66 (19)
N3—C11—C12—C16	166.9 (3)	C10—N2—Zn1—N1ii	90.9 (3)
C16—C12—C13—C14	2.8 (6)	N3—N2—Zn1—N1ii	−84.83 (19)
C11—C12—C13—C14	−175.1 (3)	C6—O2—Zn1—O1	73.9 (3)
C12—C13—C14—N4	−3.1 (7)	Zn1i—O2—Zn1—O1	−133.61 (16)
N4—C15—C16—C12	−2.7 (7)	C6—O2—Zn1—O2ii	−170.8 (2)
C13—C12—C16—C15	−0.2 (6)	Zn1i—O2—Zn1—O2ii	−18.38 (9)
C11—C12—C16—C15	177.8 (4)	C6—O2—Zn1—N2	23.3 (2)
C2—C1—N1—C5	−0.4 (4)	Zn1i—O2—Zn1—N2	175.75 (10)
C2—C1—N1—Zn1i	−173.3 (2)	C6—O2—Zn1—N1ii	−91.6 (2)
C4—C5—N1—C1	0.8 (4)	Zn1i—O2—Zn1—N1ii	60.89 (11)
C6—C5—N1—C1	−179.6 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3B···N3	0.85	2.08	2.912 (4)	168
O3—H3A···O3iii	0.85	1.99	2.835 (5)	173

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O3—H3B⋯N3	0.85	2.08	2.912 (4)	168
O3—H3A⋯O3i	0.85	1.99	2.835 (5)	173

Symmetry code: (i) .