Crystal structure of di-μ-acetato-di-acetatobis-(μ-6,6'-dimeth-oxy-2,2'-{[(propane-1,3-diylbis(aza-nylyl-idene)]bis-(methanylyl-idene)}diphenolato)tetra-zinc.

The tetra-nuclear title complex, [Zn4(C19H20N2O4)2(CH3COO)4], is formed from two dinuclear motifs related by an inversion centre. The two crystallographically independent Zn(II) ions in the asymmetric unit are in different coordination environments. One is square-based pyramidal with one O atom of an acetate group occupying the axial position and two N and O atoms of one bmspd [H2bmspd = N,N'-bis-(3-meth-oxy-salicyl-idene)propyl-ene-1,3-di-amine] Schiff base ligand forming the basal plane. The other Zn(II) atom is six-coordinated by four O atoms of the bmspd ligand forming the equatoral plane and two O atoms of different acetate groups located in the axial positions. As a result, the two phenolic planes of the bicompartmental Schiff base ligand are distorted slightly. However, the planes of the two Schiff base ligands are parallel. In addition, the Zn-N and Zn-O bond lengths span the reasonable ranges 2.062 (2)-2.073 (2) and 1.9261 (15)-2.4356 (16) Å, respectively. The Zn⋯Zn distances separated by phenolic O atoms are 3.2466 (4) Å while the Zn⋯Zn distances bridged by acetate groups are 5.9835 (6) Å. The tetra-nuclear moieties are connected by van der Waals interactions, and form a chain along c axis.

Related literature

Metal-organic coordination complexes of N,N′-bis­(salicyl­idene)ethyl­enedi­amine (salen) Schiff-base derivatives have been studied extensively within the fields of homogeneous catalysis (Wezenberg & Kleij, 2008 ▸), non-linear optics (Rigamonti et al., 2006 ▸), magnetics (Yuan et al., 2007 ▸) and biological metalloenzyme mimics (Laskin et al., 2008 ▸).

Experimental

Crystal data

[Zn4(C19H20N2O4)2(C2H3O2)4]

M = 1178.48

Triclinic,

a = 10.4894 (9) Å

b = 10.7917 (9) Å

c = 11.9550 (11) Å

α = 103.425 (2)°

β = 94.323 (1)°

γ = 115.677 (1)°

V = 1162.17 (18) Å3

Z = 1

Mo Kα radiation

μ = 2.12 mm−1

T = 298 K

0.15 × 0.10 × 0.08 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▸) T min = 0.742, T max = 0.849

6281 measured reflections

4497 independent reflections

3969 reflections with I > 2σ(I)

R int = 0.013

Refinement

R[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.071

S = 1.05

4497 reflections

318 parameters

H-atom parameters constrained

Δρmax = 0.26 e Å−3

Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker, 2004 ▸); cell refinement: SAINT-Plus (Bruker, 2001 ▸); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: XP in SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablock(s) 1, I. DOI: 10.1107/S2056989015020551/pj2024sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015020551/pj2024Isup2.hkl

Click here for additional data file.

ORTEP 4 2 4 . DOI: 10.1107/S2056989015020551/pj2024fig1.tif

ORTEP diagram of mol­ecular structure for complex [Zn4(bmspd)2(OAc)4] with atoms drawn as 50% probability ellipsoids.

Click here for additional data file.

4 2 4 ac . DOI: 10.1107/S2056989015020551/pj2024fig2.tif

The perspective drawing of complex [Zn4(bmspd)2(OAc)4] packing in ac plane.

CCDC reference: 724776

Additional supporting information: crystallographic information; 3D view; checkCIF report

[Zn4(C19H20N2O4)2(C2H3O2)4]	Z = 1
Mr = 1178.48	F(000) = 604
Triclinic, P1	Dx = 1.684 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.4894 (9) Å	Cell parameters from 4019 reflections
b = 10.7917 (9) Å	θ = 2.2–27.5°
c = 11.9550 (11) Å	µ = 2.12 mm−1
α = 103.425 (2)°	T = 298 K
β = 94.323 (1)°	Block, yellow
γ = 115.677 (1)°	0.15 × 0.10 × 0.08 mm
V = 1162.17 (18) Å3

Bruker SMART APEX CCD area-detector diffractometer	4497 independent reflections
Radiation source: fine-focus sealed tube	3969 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.013
Detector resolution: 0 pixels mm-1	θmax = 26.0°, θmin = 1.8°
phi and ω scans	h = −6→12
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −13→13
Tmin = 0.742, Tmax = 0.849	l = −13→14
6281 measured reflections

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: inferred from neighbouring sites
wR(F2) = 0.071	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0367P)2 + 0.3975P] where P = (Fo2 + 2Fc2)/3
4497 reflections	(Δ/σ)max = 0.006
318 parameters	Δρmax = 0.26 e Å−3
0 restraints	Δρmin = −0.27 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	0.5747 (2)	0.1717 (3)	0.1390 (2)	0.0479 (6)
H1A	0.5651	0.0938	0.1692	0.072*
H1B	0.5348	0.1350	0.0563	0.072*
H1C	0.5239	0.2186	0.1783	0.072*
C2	0.7601 (2)	0.3909 (2)	0.12186 (18)	0.0334 (4)
C3	0.6657 (2)	0.4234 (3)	0.0636 (2)	0.0431 (5)
H3	0.5666	0.3642	0.0497	0.052*
C4	0.7206 (3)	0.5459 (3)	0.0258 (2)	0.0540 (7)
H4	0.6577	0.5680	−0.0144	0.065*
C5	0.8656 (3)	0.6339 (3)	0.0473 (2)	0.0485 (6)
H5	0.9005	0.7136	0.0193	0.058*
C6	0.9640 (2)	0.6057 (2)	0.11148 (18)	0.0344 (5)
C7	0.9110 (2)	0.4824 (2)	0.14919 (17)	0.0288 (4)
C8	1.1149 (2)	0.7072 (2)	0.13321 (19)	0.0374 (5)
H8	1.1384	0.7791	0.0964	0.045*
C9	1.3647 (2)	0.8311 (2)	0.2054 (2)	0.0428 (5)
H9A	1.3563	0.9191	0.2172	0.051*
H9B	1.3959	0.8132	0.1316	0.051*
C10	1.4783 (2)	0.8521 (2)	0.3040 (2)	0.0438 (5)
H10A	1.4411	0.8567	0.3759	0.053*
H10B	1.5627	0.9436	0.3152	0.053*
C11	1.5238 (3)	0.7346 (3)	0.2830 (2)	0.0503 (6)
H11A	1.5415	0.7156	0.2039	0.060*
H11B	1.6138	0.7683	0.3370	0.060*
C12	1.4643 (2)	0.5208 (3)	0.33241 (19)	0.0396 (5)
H12	1.5642	0.5583	0.3466	0.048*
C13	1.3848 (2)	0.3817 (2)	0.35174 (18)	0.0362 (5)
C14	1.4677 (3)	0.3186 (3)	0.3880 (2)	0.0446 (6)
H14	1.5679	0.3689	0.4015	0.053*
C15	1.4038 (3)	0.1858 (3)	0.4035 (2)	0.0499 (6)
H15	1.4602	0.1465	0.4280	0.060*
C16	1.2532 (3)	0.1083 (3)	0.3828 (2)	0.0435 (5)
H16	1.2093	0.0169	0.3925	0.052*
C17	1.1699 (2)	0.1679 (2)	0.34775 (18)	0.0354 (5)
C18	1.2338 (2)	0.3069 (2)	0.33311 (17)	0.0310 (4)
C19	0.9443 (3)	−0.0457 (3)	0.3169 (3)	0.0661 (8)
H19A	0.8425	−0.0761	0.2991	0.099*
H19B	0.9686	−0.0585	0.3910	0.099*
H19C	0.9691	−0.1021	0.2566	0.099*
C20	0.7933 (2)	−0.0082 (2)	0.06099 (19)	0.0343 (4)
C21	0.7849 (2)	−0.1000 (3)	−0.0585 (2)	0.0422 (5)
H21A	0.7129	−0.1974	−0.0704	0.063*
H21B	0.8769	−0.0973	−0.0633	0.063*
H21C	0.7594	−0.0635	−0.1179	0.063*
C22	0.8649 (2)	0.3057 (2)	0.48569 (18)	0.0314 (4)
C23	1.0099 (3)	0.3370 (3)	0.5482 (2)	0.0493 (6)
H23A	1.0778	0.4354	0.5584	0.074*
H23B	1.0424	0.2747	0.5026	0.074*
H23C	1.0022	0.3208	0.6236	0.074*
N1	1.22093 (19)	0.71044 (18)	0.19729 (15)	0.0340 (4)
N2	1.41504 (19)	0.59888 (19)	0.29835 (16)	0.0359 (4)
O1	0.99395 (15)	0.44590 (15)	0.20882 (13)	0.0329 (3)
O2	1.14934 (15)	0.35966 (15)	0.30055 (13)	0.0343 (3)
O3	0.72225 (16)	0.27149 (18)	0.15849 (17)	0.0488 (4)
O4	1.02202 (17)	0.10166 (16)	0.32310 (15)	0.0437 (4)
O5	0.89752 (18)	0.11959 (17)	0.09127 (14)	0.0436 (4)
O6	0.7050 (2)	−0.0567 (2)	0.12112 (17)	0.0590 (5)
O7	0.82953 (16)	0.25334 (17)	0.37574 (13)	0.0409 (4)
O8	0.77997 (17)	0.33076 (18)	0.54407 (13)	0.0423 (4)
Zn1	1.20447 (2)	0.56385 (2)	0.28798 (2)	0.02906 (8)
Zn2	0.92824 (2)	0.25063 (2)	0.24271 (2)	0.02988 (8)

	U11	U22	U33	U12	U13	U23
C1	0.0285 (12)	0.0518 (14)	0.0543 (15)	0.0087 (11)	0.0080 (10)	0.0197 (12)
C2	0.0322 (11)	0.0350 (11)	0.0342 (11)	0.0155 (9)	0.0064 (9)	0.0125 (9)
C3	0.0314 (12)	0.0494 (13)	0.0485 (13)	0.0184 (11)	0.0017 (10)	0.0174 (11)
C4	0.0471 (15)	0.0605 (16)	0.0624 (17)	0.0293 (13)	−0.0030 (12)	0.0281 (14)
C5	0.0517 (15)	0.0470 (14)	0.0532 (15)	0.0243 (12)	0.0024 (12)	0.0258 (12)
C6	0.0383 (12)	0.0344 (11)	0.0332 (11)	0.0177 (9)	0.0062 (9)	0.0136 (9)
C7	0.0311 (10)	0.0288 (10)	0.0270 (10)	0.0145 (8)	0.0052 (8)	0.0081 (8)
C8	0.0461 (13)	0.0308 (11)	0.0363 (11)	0.0151 (10)	0.0110 (10)	0.0164 (9)
C9	0.0401 (13)	0.0356 (12)	0.0433 (13)	0.0061 (10)	0.0100 (10)	0.0178 (10)
C10	0.0331 (12)	0.0387 (12)	0.0445 (13)	0.0024 (10)	0.0072 (10)	0.0141 (10)
C11	0.0302 (12)	0.0540 (15)	0.0619 (16)	0.0099 (11)	0.0159 (11)	0.0262 (13)
C12	0.0259 (11)	0.0473 (13)	0.0384 (12)	0.0149 (10)	0.0045 (9)	0.0046 (10)
C13	0.0352 (12)	0.0427 (12)	0.0292 (10)	0.0220 (10)	0.0001 (8)	0.0019 (9)
C14	0.0394 (13)	0.0543 (14)	0.0402 (12)	0.0284 (12)	−0.0019 (10)	0.0041 (11)
C15	0.0579 (16)	0.0616 (16)	0.0421 (13)	0.0432 (14)	−0.0025 (11)	0.0093 (11)
C16	0.0597 (16)	0.0434 (13)	0.0363 (12)	0.0326 (12)	0.0053 (11)	0.0113 (10)
C17	0.0424 (12)	0.0379 (11)	0.0291 (10)	0.0226 (10)	0.0064 (9)	0.0077 (9)
C18	0.0332 (11)	0.0353 (11)	0.0254 (10)	0.0193 (9)	0.0029 (8)	0.0048 (8)
C19	0.0645 (19)	0.0417 (15)	0.085 (2)	0.0146 (14)	0.0019 (16)	0.0313 (15)
C20	0.0313 (11)	0.0406 (12)	0.0349 (11)	0.0190 (10)	0.0052 (9)	0.0134 (9)
C21	0.0367 (12)	0.0430 (12)	0.0406 (12)	0.0185 (10)	0.0017 (10)	0.0035 (10)
C22	0.0355 (11)	0.0279 (10)	0.0316 (10)	0.0131 (9)	0.0107 (9)	0.0121 (8)
C23	0.0518 (15)	0.0672 (16)	0.0374 (12)	0.0374 (13)	0.0075 (11)	0.0111 (12)
N1	0.0332 (10)	0.0307 (9)	0.0325 (9)	0.0083 (8)	0.0084 (7)	0.0119 (7)
N2	0.0279 (9)	0.0393 (10)	0.0364 (10)	0.0125 (8)	0.0083 (7)	0.0100 (8)
O1	0.0255 (7)	0.0312 (7)	0.0399 (8)	0.0094 (6)	0.0001 (6)	0.0163 (6)
O2	0.0269 (7)	0.0315 (7)	0.0460 (9)	0.0138 (6)	0.0035 (6)	0.0149 (6)
O3	0.0254 (8)	0.0468 (9)	0.0741 (12)	0.0089 (7)	0.0038 (8)	0.0355 (9)
O4	0.0397 (9)	0.0345 (8)	0.0589 (10)	0.0168 (7)	0.0095 (8)	0.0182 (7)
O5	0.0423 (9)	0.0382 (9)	0.0384 (9)	0.0129 (7)	0.0064 (7)	0.0024 (7)
O6	0.0571 (11)	0.0699 (12)	0.0544 (11)	0.0260 (10)	0.0266 (9)	0.0283 (10)
O7	0.0369 (8)	0.0534 (9)	0.0281 (8)	0.0185 (7)	0.0093 (6)	0.0086 (7)
O8	0.0365 (9)	0.0551 (10)	0.0323 (8)	0.0206 (8)	0.0113 (7)	0.0077 (7)
Zn1	0.02476 (13)	0.02968 (13)	0.03096 (13)	0.00999 (10)	0.00664 (9)	0.01083 (10)
Zn2	0.02869 (14)	0.02835 (13)	0.02989 (13)	0.01035 (10)	0.00723 (10)	0.00921 (10)

C1—O3	1.412 (3)	C15—C16	1.398 (4)
C1—H1A	0.9600	C15—H15	0.9300
C1—H1B	0.9600	C16—C17	1.382 (3)
C1—H1C	0.9600	C16—H16	0.9300
C2—O3	1.362 (3)	C17—O4	1.370 (3)
C2—C3	1.378 (3)	C17—C18	1.414 (3)
C2—C7	1.416 (3)	C18—O2	1.322 (2)
C3—C4	1.394 (3)	C19—O4	1.418 (3)
C3—H3	0.9300	C19—H19A	0.9600
C4—C5	1.363 (4)	C19—H19B	0.9600
C4—H4	0.9300	C19—H19C	0.9600
C5—C6	1.417 (3)	C20—O6	1.226 (3)
C5—H5	0.9300	C20—O5	1.277 (3)
C6—C7	1.399 (3)	C20—C21	1.509 (3)
C6—C8	1.441 (3)	C21—H21A	0.9600
C7—O1	1.325 (2)	C21—H21B	0.9600
C8—N1	1.285 (3)	C21—H21C	0.9600
C8—H8	0.9300	C22—O8	1.253 (2)
C9—N1	1.482 (3)	C22—O7	1.259 (2)
C9—C10	1.514 (3)	C22—C23	1.501 (3)
C9—H9A	0.9700	C23—H23A	0.9600
C9—H9B	0.9700	C23—H23B	0.9600
C10—C11	1.515 (4)	C23—H23C	0.9600
C10—H10A	0.9700	N1—Zn1	2.0727 (17)
C10—H10B	0.9700	N2—Zn1	2.0616 (18)
C11—N2	1.479 (3)	O1—Zn1	2.0203 (14)
C11—H11A	0.9700	O1—Zn2	2.0639 (14)
C11—H11B	0.9700	O2—Zn2	2.0632 (14)
C12—N2	1.284 (3)	O2—Zn1	2.0676 (14)
C12—C13	1.452 (3)	O3—Zn2	2.4356 (16)
C12—H12	0.9300	O5—Zn2	1.9261 (15)
C13—C18	1.402 (3)	O7—Zn2	1.9635 (14)
C13—C14	1.415 (3)	O8—Zn1i	2.0201 (15)
C14—C15	1.359 (4)	Zn1—O8i	2.0201 (15)
C14—H14	0.9300
O3—C1—H1A	109.5	C13—C18—C17	118.12 (19)
O3—C1—H1B	109.5	O4—C19—H19A	109.5
H1A—C1—H1B	109.5	O4—C19—H19B	109.5
O3—C1—H1C	109.5	H19A—C19—H19B	109.5
H1A—C1—H1C	109.5	O4—C19—H19C	109.5
H1B—C1—H1C	109.5	H19A—C19—H19C	109.5
O3—C2—C3	125.4 (2)	H19B—C19—H19C	109.5
O3—C2—C7	112.88 (18)	O6—C20—O5	124.8 (2)
C3—C2—C7	121.7 (2)	O6—C20—C21	120.8 (2)
C2—C3—C4	119.1 (2)	O5—C20—C21	114.42 (19)
C2—C3—H3	120.4	C20—C21—H21A	109.5
C4—C3—H3	120.4	C20—C21—H21B	109.5
C5—C4—C3	120.6 (2)	H21A—C21—H21B	109.5
C5—C4—H4	119.7	C20—C21—H21C	109.5
C3—C4—H4	119.7	H21A—C21—H21C	109.5
C4—C5—C6	121.0 (2)	H21B—C21—H21C	109.5
C4—C5—H5	119.5	O8—C22—O7	120.8 (2)
C6—C5—H5	119.5	O8—C22—C23	119.36 (19)
C7—C6—C5	119.1 (2)	O7—C22—C23	119.80 (19)
C7—C6—C8	123.83 (19)	C22—C23—H23A	109.5
C5—C6—C8	117.1 (2)	C22—C23—H23B	109.5
O1—C7—C6	123.77 (18)	H23A—C23—H23B	109.5
O1—C7—C2	117.92 (17)	C22—C23—H23C	109.5
C6—C7—C2	118.31 (18)	H23A—C23—H23C	109.5
N1—C8—C6	127.81 (19)	H23B—C23—H23C	109.5
N1—C8—H8	116.1	C8—N1—C9	115.46 (18)
C6—C8—H8	116.1	C8—N1—Zn1	125.35 (15)
N1—C9—C10	113.12 (18)	C9—N1—Zn1	119.19 (14)
N1—C9—H9A	109.0	C12—N2—C11	116.01 (19)
C10—C9—H9A	109.0	C12—N2—Zn1	124.81 (15)
N1—C9—H9B	109.0	C11—N2—Zn1	118.53 (15)
C10—C9—H9B	109.0	C7—O1—Zn1	129.06 (12)
H9A—C9—H9B	107.8	C7—O1—Zn2	125.64 (12)
C9—C10—C11	114.1 (2)	Zn1—O1—Zn2	105.29 (6)
C9—C10—H10A	108.7	C18—O2—Zn2	127.10 (13)
C11—C10—H10A	108.7	C18—O2—Zn1	129.24 (13)
C9—C10—H10B	108.7	Zn2—O2—Zn1	103.62 (6)
C11—C10—H10B	108.7	C2—O3—C1	119.07 (18)
H10A—C10—H10B	107.6	C2—O3—Zn2	113.52 (12)
N2—C11—C10	113.20 (19)	C1—O3—Zn2	127.31 (14)
N2—C11—H11A	108.9	C17—O4—C19	119.41 (19)
C10—C11—H11A	108.9	C20—O5—Zn2	120.25 (14)
N2—C11—H11B	108.9	C22—O7—Zn2	137.14 (14)
C10—C11—H11B	108.9	C22—O8—Zn1i	135.32 (15)
H11A—C11—H11B	107.8	O1—Zn1—O8i	109.18 (6)
N2—C12—C13	128.7 (2)	O1—Zn1—N2	149.75 (7)
N2—C12—H12	115.7	O8i—Zn1—N2	98.57 (7)
C13—C12—H12	115.7	O1—Zn1—O2	75.35 (5)
C18—C13—C14	119.5 (2)	O8i—Zn1—O2	100.83 (6)
C18—C13—C12	123.98 (19)	N2—Zn1—O2	88.08 (6)
C14—C13—C12	116.5 (2)	O1—Zn1—N1	88.64 (6)
C15—C14—C13	121.3 (2)	O8i—Zn1—N1	103.96 (7)
C15—C14—H14	119.3	N2—Zn1—N1	96.30 (7)
C13—C14—H14	119.3	O2—Zn1—N1	153.84 (7)
C14—C15—C16	120.0 (2)	O5—Zn2—O7	137.44 (7)
C14—C15—H15	120.0	O5—Zn2—O2	104.92 (7)
C16—C15—H15	120.0	O7—Zn2—O2	110.70 (6)
C17—C16—C15	119.8 (2)	O5—Zn2—O1	103.31 (7)
C17—C16—H16	120.1	O7—Zn2—O1	107.96 (6)
C15—C16—H16	120.1	O2—Zn2—O1	74.53 (5)
O4—C17—C16	125.1 (2)	O5—Zn2—O3	85.68 (7)
O4—C17—C18	113.64 (18)	O7—Zn2—O3	79.46 (6)
C16—C17—C18	121.3 (2)	O2—Zn2—O3	143.50 (5)
O2—C18—C13	122.92 (19)	O1—Zn2—O3	69.03 (5)
O2—C18—C17	118.95 (19)