Poly[[tris-(μ2-acetato-κ(2) O:O')(4-chloro-benzene-1,2-di-amine-κN)(μ3-hydroxido)dizinc] ethanol monosolvate].

The title compound, {[Zn2(CH3CO2)3(OH)(C6H7ClN2)]·C2H5OH} n , has alternating octa-hedrally and tetra-hedrally coordinated Zn(2+) ions. The octa-hedral coordination sphere is composed of one N atom of the monodentate di-amino-chloro-benzene ligand, three acetate O atoms and two bridging hydroxide ligands. The tetra-hedral coordination sphere consists of three acetate O atoms and the hydroxide ligand. The zinc ions are bridged by acetate and hydroxide ligands. The result is a laddered-chain structure parallel to [100] with ethanol solvent mol-ecules occupying the space between the chains. The di-amine ligand chlorine substitutent is disordered over two equally populated positions as a result of a crystallographically imposed inversion center between adjacent ligands. The ethanol solvent mol-ecule exhibits disorder with the two components having refined occupancies of 0.696 (11) and 0.304 (11). O-H⋯O hydrogen bonds form between the hydroxide ligand and the ethanol solvent mol-ecule. N-H⋯O and N-H⋯N hydrogen bonding between the uncoordinated amine group and the acetate ligands and the coordinated amine group are also observed.

Related literature

A recent review of crystalline metal-organic frameworks has been published by Dey et al. (2014 ▶). For a review of such compounds in chemical sensors, see: Kreno et al. (2012 ▶) and for a review of the synthesis of such compounds, see: Farha & Hupp (2010 ▶). For some other examples of zinc compounds with chain structures and bridging acetate ligands, see: Tan et al. (2011 ▶); Luo et al. (2011 ▶); Liu (2010 ▶); Hou et al. (2007a ▶,b ▶). For examples of zinc complexes with monodentate 1,2-diaminobenzene ligands, see: Geiger (2012 ▶); Ovalle-Marroquín et al. (2002 ▶).

Experimental

Crystal data

[Zn2(C2H3O2)3(OH)(C6H7ClN2)]·C2H6O

M = 513.53

Triclinic,

a = 8.0769 (12) Å

b = 10.8723 (19) Å

c = 12.909 (3) Å

α = 101.511 (6)°

β = 96.399 (6)°

γ = 109.817 (5)°

V = 1025.1 (3) Å3

Z = 2

Mo Kα radiation

μ = 2.51 mm−1

T = 200 K

0.60 × 0.40 × 0.02 mm

Data collection

Bruker SMART X2S benchtop diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2013 ▶) T min = 0.52, T max = 0.95

6443 measured reflections

3329 independent reflections

2403 reflections with I > 2σ(I)

R int = 0.061

Refinement

R[F 2 > 2σ(F 2)] = 0.059

wR(F 2) = 0.181

S = 1.05

3329 reflections

280 parameters

92 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.98 e Å−3

Δρmin = −1.05 e Å−3

Data collection: APEX2 (Bruker, 2013 ▶); cell refinement: SAINT (Bruker, 2013 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814012641/gg2136sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814012641/gg2136Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814012641/gg2136Isup4.mol

CCDC reference: 1006074

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

[Zn2(C2H3O2)3(OH)(C6H7ClN2)]·C2H6O	Z = 2
Mr = 513.53	F(000) = 524
Triclinic, P1	Dx = 1.664 Mg m−3
a = 8.0769 (12) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.8723 (19) Å	Cell parameters from 2325 reflections
c = 12.909 (3) Å	θ = 2.3–24.9°
α = 101.511 (6)°	µ = 2.51 mm−1
β = 96.399 (6)°	T = 200 K
γ = 109.817 (5)°	Plate, clear colourless
V = 1025.1 (3) Å3	0.60 × 0.40 × 0.02 mm

Bruker SMART X2S benchtop diffractometer	3329 independent reflections
Radiation source: XOS X-beam microfocus source	2403 reflections with I > 2σ(I)
Doubly curved silicon crystal monochromator	Rint = 0.061
Detector resolution: 8.3330 pixels mm-1	θmax = 25.1°, θmin = 2.7°
ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −12→12
Tmin = 0.52, Tmax = 0.95	l = −15→13
6443 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)] = 0.059	Hydrogen site location: mixed
wR(F2) = 0.181	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0797P)2 + 5.5001P] where P = (Fo2 + 2Fc2)/3
3329 reflections	(Δ/σ)max < 0.001
280 parameters	Δρmax = 0.98 e Å−3
92 restraints	Δρmin = −1.05 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	Occ. (<1)
Zn1	0.51291 (11)	0.64882 (9)	0.49816 (7)	0.0220 (3)
Zn2	0.10138 (11)	0.36887 (9)	0.47758 (7)	0.0235 (3)
O1	0.3290 (7)	0.4519 (5)	0.4368 (4)	0.0206 (12)
H1	0.311 (11)	0.419 (8)	0.370 (2)	0.031*
Cl1	0.1090 (8)	0.5949 (6)	0.0220 (4)	0.0601 (15)	0.5
Cl2	0.4363 (11)	0.9055 (7)	0.0139 (4)	0.087 (2)	0.5
N1	0.6409 (9)	0.9892 (7)	0.4111 (6)	0.0293 (16)
H1A	0.744 (6)	1.047 (7)	0.399 (6)	0.035*
H1B	0.682 (9)	0.964 (8)	0.469 (4)	0.035*
N2	0.3623 (9)	0.7554 (7)	0.4280 (5)	0.0247 (15)
H2A	0.242 (3)	0.719 (7)	0.422 (6)	0.03*
H2B	0.396 (9)	0.822 (6)	0.490 (4)	0.03*
C1	0.5200 (11)	0.8997 (8)	0.3188 (7)	0.0273 (17)
C2	0.3789 (11)	0.7860 (8)	0.3266 (6)	0.0232 (16)
C3	0.2564 (12)	0.6995 (9)	0.2341 (7)	0.0340 (19)
H3	0.1629	0.6209	0.2395	0.041*
C4	0.2699 (14)	0.7271 (11)	0.1347 (8)	0.050 (2)
H4	0.1854	0.6683	0.0721	0.06*	0.5
C5	0.4063 (15)	0.8402 (12)	0.1269 (8)	0.051 (2)
H5	0.4145	0.8598	0.0588	0.062*	0.5
C6	0.5331 (14)	0.9267 (10)	0.2183 (8)	0.045 (2)
H6	0.628	1.0037	0.2117	0.054*
O71	0.0171 (7)	0.1738 (5)	0.3941 (5)	0.0304 (14)
O72	0.7122 (7)	0.8392 (5)	0.5729 (5)	0.0334 (14)
C7	0.1261 (11)	0.1117 (8)	0.3829 (7)	0.030 (2)
C71	0.0524 (14)	−0.0317 (10)	0.3175 (10)	0.062 (4)
H71A	0.073	−0.0348	0.2438	0.093*
H71B	−0.0767	−0.071	0.3161	0.093*
H71C	0.1127	−0.0834	0.3498	0.093*
O81	−0.1322 (7)	0.3856 (5)	0.4406 (4)	0.0243 (12)
O82	0.4119 (7)	0.6770 (6)	0.6442 (4)	0.0260 (13)
C8	−0.2514 (11)	0.3399 (7)	0.3538 (6)	0.0213 (17)
C81	−0.1933 (12)	0.3104 (9)	0.2482 (6)	0.033 (2)
H20A	−0.2959	0.2829	0.189	0.05*
H20B	−0.1474	0.2373	0.2451	0.05*
H20C	−0.0986	0.3917	0.2416	0.05*
O91	0.1070 (7)	0.3617 (6)	0.6295 (4)	0.0265 (13)
O92	0.3883 (8)	0.3702 (6)	0.6454 (5)	0.0360 (15)
C9	0.2520 (12)	0.3665 (8)	0.6821 (7)	0.0277 (19)
C91	0.2600 (14)	0.3703 (10)	0.7993 (7)	0.039 (2)
H91A	0.355	0.3401	0.8245	0.059*
H91B	0.1445	0.3104	0.8094	0.059*
H91C	0.2858	0.4629	0.8406	0.059*
OE1	0.7175 (15)	0.6924 (13)	0.7773 (8)	0.062 (3)	0.7
H1E1	0.6255	0.7008	0.7473	0.093*	0.7
C1E1	0.711 (4)	0.698 (2)	0.8858 (13)	0.103 (9)	0.7
HE1A	0.7271	0.6172	0.9035	0.124*	0.7
HE1B	0.5934	0.6975	0.9	0.124*	0.7
C2E1	0.855 (4)	0.821 (3)	0.954 (2)	0.126 (9)	0.7
HE1C	0.9712	0.8238	0.9361	0.189*	0.7
HE1D	0.8568	0.8222	1.0297	0.189*	0.7
HE1E	0.8339	0.9008	0.94	0.189*	0.7
OE2	0.719 (4)	0.591 (3)	0.7894 (18)	0.062 (3)	0.3
H1E2	0.6074	0.5492	0.7742	0.093*	0.3
C1E2	0.765 (11)	0.688 (4)	0.887 (3)	0.103 (9)	0.3
HE2A	0.8724	0.6864	0.9316	0.124*	0.3
HE2B	0.6656	0.6665	0.9267	0.124*	0.3
C2E2	0.803 (9)	0.821 (4)	0.869 (5)	0.126 (9)	0.3
HE2C	0.9333	0.8675	0.8779	0.189*	0.3
HE2D	0.7577	0.8733	0.9218	0.189*	0.3
HE2E	0.7449	0.813	0.7962	0.189*	0.3

	U11	U22	U33	U12	U13	U23
Zn1	0.0152 (5)	0.0202 (5)	0.0324 (5)	0.0073 (4)	0.0046 (4)	0.0096 (4)
Zn2	0.0130 (5)	0.0251 (5)	0.0337 (5)	0.0071 (4)	0.0057 (4)	0.0100 (4)
O1	0.016 (3)	0.024 (3)	0.021 (3)	0.008 (2)	0.004 (2)	0.003 (2)
Cl1	0.071 (4)	0.065 (4)	0.030 (2)	0.018 (3)	−0.002 (2)	0.003 (2)
Cl2	0.130 (6)	0.073 (4)	0.033 (3)	0.008 (4)	0.005 (3)	0.020 (3)
N1	0.025 (4)	0.024 (4)	0.041 (4)	0.006 (3)	0.014 (3)	0.015 (3)
N2	0.017 (3)	0.024 (4)	0.031 (4)	0.006 (3)	0.005 (3)	0.007 (3)
C1	0.027 (4)	0.025 (4)	0.040 (4)	0.014 (3)	0.018 (3)	0.017 (3)
C2	0.023 (4)	0.021 (4)	0.035 (4)	0.015 (3)	0.012 (3)	0.012 (3)
C3	0.030 (4)	0.037 (4)	0.038 (4)	0.016 (4)	0.006 (3)	0.011 (3)
C4	0.050 (5)	0.058 (5)	0.039 (4)	0.021 (4)	0.002 (4)	0.009 (4)
C5	0.054 (5)	0.064 (5)	0.045 (4)	0.021 (4)	0.014 (4)	0.032 (4)
C6	0.047 (5)	0.046 (5)	0.048 (4)	0.013 (4)	0.019 (4)	0.026 (4)
O71	0.015 (3)	0.019 (3)	0.055 (4)	0.004 (3)	0.008 (2)	0.009 (3)
O72	0.021 (3)	0.017 (3)	0.057 (4)	0.002 (3)	−0.003 (3)	0.010 (3)
C7	0.020 (5)	0.020 (4)	0.044 (5)	0.002 (4)	0.000 (4)	0.010 (4)
C71	0.033 (6)	0.028 (6)	0.101 (9)	0.010 (5)	−0.014 (6)	−0.019 (6)
O81	0.017 (3)	0.026 (3)	0.026 (3)	0.008 (2)	0.000 (2)	0.003 (2)
O82	0.019 (3)	0.030 (3)	0.028 (3)	0.010 (3)	0.001 (2)	0.004 (2)
C8	0.025 (4)	0.016 (3)	0.029 (3)	0.012 (3)	0.006 (3)	0.011 (3)
C81	0.029 (5)	0.043 (5)	0.032 (4)	0.019 (4)	0.010 (4)	0.010 (4)
O91	0.022 (3)	0.030 (3)	0.033 (3)	0.012 (3)	0.007 (2)	0.014 (2)
O92	0.034 (4)	0.048 (4)	0.044 (3)	0.025 (3)	0.023 (3)	0.023 (3)
C9	0.032 (5)	0.018 (4)	0.040 (5)	0.015 (4)	0.008 (4)	0.010 (4)
C91	0.050 (6)	0.041 (5)	0.034 (5)	0.023 (5)	0.012 (4)	0.012 (4)
OE1	0.057 (6)	0.092 (8)	0.044 (5)	0.044 (6)	−0.001 (4)	0.009 (5)
C1E1	0.103 (11)	0.106 (10)	0.102 (9)	0.048 (6)	0.009 (6)	0.021 (6)
C2E1	0.135 (14)	0.120 (13)	0.110 (13)	0.030 (11)	0.007 (11)	0.041 (11)
OE2	0.057 (6)	0.092 (8)	0.044 (5)	0.044 (6)	−0.001 (4)	0.009 (5)
C1E2	0.103 (11)	0.106 (10)	0.102 (9)	0.048 (6)	0.009 (6)	0.021 (6)
C2E2	0.135 (14)	0.120 (13)	0.110 (13)	0.030 (11)	0.007 (11)	0.041 (11)

Zn1—O1	2.079 (5)	C7—C71	1.494 (12)
Zn1—O92i	2.098 (6)	C71—H71A	0.98
Zn1—O72	2.098 (5)	C71—H71B	0.98
Zn1—O82	2.143 (5)	C71—H71C	0.98
Zn1—O1i	2.147 (5)	O81—C8	1.281 (9)
Zn1—N2	2.185 (7)	O82—C8iv	1.251 (9)
Zn2—O1	1.937 (5)	C8—O82iv	1.251 (9)
Zn2—O81	1.971 (5)	C8—C81	1.500 (11)
Zn2—O91	1.974 (5)	C81—H20A	0.98
Zn2—O71	2.017 (5)	C81—H20B	0.98
O1—Zn1i	2.147 (5)	C81—H20C	0.98
O1—H1	0.84 (2)	O91—C9	1.266 (10)
Cl1—C4	1.830 (11)	O92—C9	1.237 (10)
Cl1—Cl1ii	2.128 (12)	O92—Zn1i	2.098 (6)
Cl2—C5	1.752 (11)	C9—C91	1.499 (12)
Cl2—Cl2iii	2.086 (14)	C91—H91A	0.98
N1—C1	1.398 (11)	C91—H91B	0.98
N1—H1A	0.91 (2)	C91—H91C	0.98
N1—H1B	0.91 (2)	OE1—C1E1	1.398 (15)
N2—C2	1.423 (10)	OE1—H1E1	0.84
N2—H2A	0.90 (2)	C1E1—C2E1	1.474 (17)
N2—H2B	0.90 (2)	C1E1—HE1A	0.99
C1—C6	1.394 (12)	C1E1—HE1B	0.99
C1—C2	1.400 (11)	C2E1—HE1C	0.98
C2—C3	1.395 (11)	C2E1—HE1D	0.98
C3—C4	1.383 (13)	C2E1—HE1E	0.98
C3—H3	0.95	OE2—C1E2	1.39 (2)
C4—C5	1.375 (15)	OE2—H1E2	0.84
C4—H4	0.95	C1E2—C2E2	1.45 (3)
C5—C6	1.399 (14)	C1E2—HE2A	0.99
C5—H5	0.95	C1E2—HE2B	0.99
C6—H6	0.95	C2E2—HE2C	0.98
O71—C7	1.282 (10)	C2E2—HE2D	0.98
O72—C7i	1.248 (10)	C2E2—HE2E	0.98
C7—O72i	1.248 (10)
O1—Zn1—O92i	88.2 (2)	C7—O71—Zn2	121.6 (5)
O1—Zn1—O72	173.5 (2)	C7i—O72—Zn1	138.8 (6)
O92i—Zn1—O72	94.2 (3)	O72i—C7—O71	124.4 (8)
O1—Zn1—O82	93.6 (2)	O72i—C7—C71	117.7 (8)
O92i—Zn1—O82	177.4 (2)	O71—C7—C71	117.8 (7)
O72—Zn1—O82	84.2 (2)	C7—C71—H71A	109.5
O1—Zn1—O1i	82.3 (2)	C7—C71—H71B	109.5
O92i—Zn1—O1i	91.3 (2)	H71A—C71—H71B	109.5
O72—Zn1—O1i	91.6 (2)	C7—C71—H71C	109.5
O82—Zn1—O1i	90.8 (2)	H71A—C71—H71C	109.5
O1—Zn1—N2	99.1 (2)	H71B—C71—H71C	109.5
O92i—Zn1—N2	86.4 (2)	C8—O81—Zn2	132.6 (5)
O72—Zn1—N2	87.1 (2)	C8iv—O82—Zn1	123.4 (5)
O82—Zn1—N2	91.5 (2)	O82iv—C8—O81	121.4 (7)
O1i—Zn1—N2	177.3 (2)	O82iv—C8—C81	120.2 (7)
O1—Zn2—O81	130.8 (2)	O81—C8—C81	118.4 (7)
O1—Zn2—O91	117.1 (2)	C8—C81—H20A	109.5
O81—Zn2—O91	101.1 (2)	C8—C81—H20B	109.5
O1—Zn2—O71	103.6 (2)	H20A—C81—H20B	109.5
O81—Zn2—O71	94.7 (2)	C8—C81—H20C	109.5
O91—Zn2—O71	104.5 (2)	H20A—C81—H20C	109.5
Zn2—O1—Zn1	127.8 (2)	H20B—C81—H20C	109.5
Zn2—O1—Zn1i	101.7 (2)	C9—O91—Zn2	117.2 (5)
Zn1—O1—Zn1i	97.7 (2)	C9—O92—Zn1i	143.2 (6)
Zn2—O1—H1	105 (6)	O92—C9—O91	125.6 (8)
Zn1—O1—H1	117 (6)	O92—C9—C91	117.3 (8)
Zn1i—O1—H1	103 (6)	O91—C9—C91	117.1 (8)
C4—Cl1—Cl1ii	144.8 (6)	C9—C91—H91A	109.5
C5—Cl2—Cl2iii	136.3 (6)	C9—C91—H91B	109.5
C1—N1—H1A	115 (5)	H91A—C91—H91B	109.5
C1—N1—H1B	125 (5)	C9—C91—H91C	109.5
H1A—N1—H1B	102 (4)	H91A—C91—H91C	109.5
C2—N2—Zn1	122.9 (5)	H91B—C91—H91C	109.5
C2—N2—H2A	102 (5)	C1E1—OE1—H1E1	109.5
Zn1—N2—H2A	115 (6)	OE1—C1E1—C2E1	109.4 (18)
C2—N2—H2B	121 (6)	OE1—C1E1—HE1A	109.8
Zn1—N2—H2B	92 (5)	C2E1—C1E1—HE1A	109.8
H2A—N2—H2B	102 (4)	OE1—C1E1—HE1B	109.8
C6—C1—N1	120.2 (8)	C2E1—C1E1—HE1B	109.8
C6—C1—C2	119.1 (8)	HE1A—C1E1—HE1B	108.2
N1—C1—C2	120.6 (7)	C1E1—C2E1—HE1C	109.5
C3—C2—C1	120.0 (8)	C1E1—C2E1—HE1D	109.5
C3—C2—N2	119.5 (7)	HE1C—C2E1—HE1D	109.5
C1—C2—N2	120.5 (7)	C1E1—C2E1—HE1E	109.5
C4—C3—C2	120.6 (9)	HE1C—C2E1—HE1E	109.5
C4—C3—H3	119.7	HE1D—C2E1—HE1E	109.5
C2—C3—H3	119.7	C1E2—OE2—H1E2	109.5
C5—C4—C3	119.7 (9)	OE2—C1E2—C2E2	111 (3)
C5—C4—Cl1	126.1 (8)	OE2—C1E2—HE2A	109.5
C3—C4—Cl1	114.0 (8)	C2E2—C1E2—HE2A	109.5
C5—C4—H4	120.2	OE2—C1E2—HE2B	109.5
C3—C4—H4	120.2	C2E2—C1E2—HE2B	109.5
C4—C5—C6	120.8 (9)	HE2A—C1E2—HE2B	108.1
C4—C5—Cl2	127.8 (9)	C1E2—C2E2—HE2C	109.5
C6—C5—Cl2	111.2 (8)	C1E2—C2E2—HE2D	109.5
C4—C5—H5	119.6	HE2C—C2E2—HE2D	109.5
C6—C5—H5	119.6	C1E2—C2E2—HE2E	109.5
C1—C6—C5	119.9 (9)	HE2C—C2E2—HE2E	109.5
C1—C6—H6	120.1	HE2D—C2E2—HE2E	109.5
C5—C6—H6	120.1

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···OE1i	0.84 (2)	1.99 (3)	2.807 (11)	166 (8)
O1—H1···OE2i	0.84 (2)	2.03 (4)	2.83 (2)	160 (8)
N2—H2A···O81iv	0.90 (2)	2.38 (7)	2.914 (9)	118 (6)
N2—H2B···N1v	0.91 (6)	2.32 (5)	3.128 (10)	148 (7)
N1—H1A···O71vi	0.91 (7)	2.19 (3)	3.082 (9)	169 (6)
N1—H1B···O72	0.91 (6)	2.14 (7)	3.013 (9)	160 (7)
OE1—H1E1···O82	0.84	1.97	2.780 (11)	163
OE2—H1E2···O92	0.84	2.32	3.02 (3)	140

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯OE1i	0.84 (2)	1.99 (3)	2.807 (11)	166 (8)
O1—H1⋯OE2i	0.84 (2)	2.03 (4)	2.83 (2)	160 (8)
N2—H2A⋯O81ii	0.90 (2)	2.38 (7)	2.914 (9)	118 (6)
N2—H2B⋯N1iii	0.91 (6)	2.32 (5)	3.128 (10)	148 (7)
N1—H1A⋯O71iv	0.91 (7)	2.19 (3)	3.082 (9)	169 (6)
OE1—H1E1⋯O82	0.84	1.97	2.780 (11)	163
OE2—H1E2⋯O92	0.84	2.32	3.02 (3)	140

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .