Diaqua­bis(2,4-dichloro-6-formyl­phenolato)zinc(II)–bis­(μ-2,4-dichloro-6-formyl­phenolato)bis­[aqua­(2,4-dichloro-6-formyl­phenolato)zinc(II)] (2/1)

Watanabe, Y.; Aritake, Y.; Akitsu, T.

doi:10.1107/S160053680904896X

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Pages m1640-m1641

doi:10.1107/S160053680904896X

Open

access

Diaquabis(2,4-dichloro-6-formylphenolato)zinc(II)–bis(μ-2,4-dichloro-6-formylphenolato)bis[aqua(2,4-dichloro-6-formylphenolato)zinc(II)] (2/1)

Yoshimasa Watanabe,^a Yoshikazu Aritake ^a and Takashiro Akitsu ^a ^*

^aDepartment of Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan
^*Correspondence e-mail: akitsu@rs.kagu.tus.ac.jp

(Received 17 October 2009; accepted 17 November 2009; online 21 November 2009)

The crystal of the title compound, [Zn(C₇H₃Cl₂O₂)₂(H₂O)₂]₂·[Zn₂(C₇H₃Cl₂O₂)₄(H₂O)₂], consists of monomeric and dimeric Zn^II complexes. Both complexes afford a six-coordinated coordination environment about the Zn atoms with cis-configuration ligands. The deprotonated hydroxy groups of the 3,5-dichlorosalicylaldehyde ligands bridge two metal cations, forming a centrosymmetric dimeric complex. Intermolecular O—H⋯O hydrogen bonding occurs between the coordinated water molecules and deprotonated hydroxy groups in the crystal structure.

Related literature

For applications of the 3,5-dichlorosalicylaldehydate ligand in the preparation of Schiff base–metal complexes, see: Akitsu et al. (2009 ); Akitsu & Einaga (2005a ,b ); Akitsu (2007 ). For trans and cis forms of complexes, see: Akitsu & Einaga (2004a ,b ); Akitsu et al. (2005 ). For related complexes, see: Chen (2006 ); Chen et al. (2007 ); Xiong & Liu (2005 ).

Experimental

Crystal data

[Zn(C₇H₃Cl₂O₂)₂(H₂O)₂]₂·[Zn₂(C₇H₃Cl₂O₂)₄(H₂O)₂]
M_r = 1889.61
Triclinic, $[P \overline 1]$
a = 8.7532 (9) Å
b = 13.6973 (15) Å
c = 14.2833 (15) Å
α = 96.244 (2)°
β = 91.700 (1)°
γ = 106.096 (1)°
V = 1632.4 (3) Å³
Z = 1
Mo Kα radiation
μ = 2.19 mm⁻¹
T = 100 K
0.15 × 0.15 × 0.08 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.735, T_max = 0.845
9504 measured reflections
7275 independent reflections
5671 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.118
S = 0.75
7275 reflections
445 parameters
H-atom parameters constrained
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Selected bond lengths (Å)

Zn1—O1	2.040 (2)
Zn1—O2	2.096 (2)
Zn1—O3	2.049 (2)
Zn1—O4	2.084 (2)
Zn1—O9	2.112 (2)
Zn1—O10	2.130 (2)
Zn2—O5	2.011 (2)
Zn2—O6	2.114 (2)
Zn2—O7	2.081 (2)
Zn2—O7ⁱ	2.176 (2)
Zn2—O8	2.069 (2)
Zn2—O11	2.134 (2)
Symmetry code: (i) -x+2, -y+1, -z+2.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9A⋯O3ⁱⁱ	0.84	2.02	2.790 (3)	153
O9—H9B⋯O1ⁱⁱ	0.74	2.45	3.015 (3)	134
O10—H10A⋯O7ⁱ	0.84	2.24	2.998 (3)	150
O10—H10B⋯O5ⁱ	0.82	1.95	2.741 (3)	161
O11—H11A⋯O3ⁱ	0.84	2.17	2.931 (3)	151
O11—H11B⋯O1ⁱ	0.84	1.93	2.751 (3)	169
Symmetry codes: (i) -x+2, -y+1, -z+2; (ii) -x+2, -y+2, -z+2.

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680904896X/xu2645sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680904896X/xu2645Isup2.hkl

checkCIF report

Comment top

3,5-Dichlorosalcylaldehydato plays an important role in preparation of Schiff base metal complexes because of electronic properties due to Cl-groups for example supramolecular interactions between metallodendrimers (Akitsu et al., 2009) or photochromic compounds (Akitsu & Einaga, 2005a & 2005b; Akitsu, 2007). Depending on amine reagents and their steric requirement, trans (Akitsu & Einaga, 2004a & 2004b) or cis (Akitsu et al., 2005) forms of complexes can be formed. However, we focused on only 3,5-dichloroaldehyde moiety to elucidate structural features without amine moiety.

The title compound (I) is composed of a co-crystal of monomeric [Zn(C₇H₃Cl₂O₂)₂(H₂O)₂] and dimeric [Zn(C₇H₃Cl₂O₂)₂(H₂O)]. Both complexes afford a six-coordinated coordination environment exhibiting significant distortion. In contrast to known zinc(II) complexes incorporating saldehyde-derivertive ligands (Chen, 2006; Chen et al., 2007; Xiong & Liu, 2005), both ligands bind to Zn(II) ions in a cis-configuration for (I).

Related literature top

For applications of the 3,5-dichlorosalcylaldehydate ligand in the preparation of Schiff base–metal complexes, see: Akitsu et al. (2009); Akitsu & Einaga (2005a,b); Akitsu (2007). For trans and cis forms of complexes, see: Akitsu & Einaga (2004a,b); Akitsu et al. (2005). For related complexes, see: Chen (2006); Chen et al. (2007); Xiong & Liu (2005).

Experimental top

Crystals were obtained accidentally as a byproduct of the treatment of 3,5-dichlorosalcylaldehyde (0.95 g, 5.00 mmol) in methanol (30 ml), L-alanine (0.44 g, 5.00 mmol) in water (5 ml), zinc(II) acetate dihydrate (0.55 g, 2.50 mmol) and several drops of triethylamine at c.a. 350 K for 2 hr.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008.

Figures top

Fig. 1. The molecular structure of (I), showing the atom labeling scheme [symmetry code: (i) 2 - x, 1 - y, 2 - z]. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level.

Diaquabis(2,4-dichloro-6-formylphenolato)zinc(II)–bis(µ-2,4-dichloro- 6-formylphenolato)bis[aqua(2,4-dichloro-6-formylphenolato)zinc(II)] (2/1) top

Crystal data top

[Zn(C₇H₃Cl₂O₂)₂(H₂O)₂]₂·[Zn₂(C₇H₃Cl₂O₂)₄(H₂O)₂]	Z = 1
M_r = 1889.61	F(000) = 940.0
Triclinic, P1	D_x = 1.922 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.7532 (9) Å	Cell parameters from 2792 reflections
b = 13.6973 (15) Å	θ = 2.4–27.8°
c = 14.2833 (15) Å	µ = 2.19 mm⁻¹
α = 96.244 (2)°	T = 100 K
β = 91.700 (1)°	Prismatic, yellow
γ = 106.096 (1)°	0.15 × 0.15 × 0.08 mm
V = 1632.4 (3) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	7275 independent reflections
Radiation source: fine-focus sealed tube	5671 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
Detector resolution: 8.333 pixels mm^-1	θ_max = 27.9°, θ_min = 1.4°
ϕ and ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −16→17
T_min = 0.735, T_max = 0.845	l = −12→18
9504 measured reflections

Refinement top

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 0.75	w = 1/[σ²(F_o²) + (0.1P)² + 1.2111P] where P = (F_o² + 2F_c²)/3
7275 reflections	(Δ/σ)_max = 0.001
445 parameters	Δρ_max = 0.59 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

[Zn(C₇H₃Cl₂O₂)₂(H₂O)₂]₂·[Zn₂(C₇H₃Cl₂O₂)₄(H₂O)₂]	γ = 106.096 (1)°
M_r = 1889.61	V = 1632.4 (3) Å³
Triclinic, P1	Z = 1
a = 8.7532 (9) Å	Mo Kα radiation
b = 13.6973 (15) Å	µ = 2.19 mm⁻¹
c = 14.2833 (15) Å	T = 100 K
α = 96.244 (2)°	0.15 × 0.15 × 0.08 mm
β = 91.700 (1)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	7275 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	5671 reflections with I > 2σ(I)
T_min = 0.735, T_max = 0.845	R_int = 0.021
9504 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 0.75	Δρ_max = 0.59 e Å⁻³
7275 reflections	Δρ_min = −0.46 e Å⁻³
445 parameters

Special details top

Experimental. 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. The water-H atoms wre located in a D-map and refined in riding mode with U_iso(H) = 1.2U_eq(O)."

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Zn1	0.80461 (4)	0.83299 (3)	0.96067 (3)	0.00981 (11)
Zn2	0.92258 (4)	0.39423 (3)	0.93218 (3)	0.00861 (10)
C1	1.0506 (4)	0.8558 (2)	0.8153 (2)	0.0115 (7)
C2	1.2112 (4)	0.8851 (2)	0.7897 (2)	0.0106 (7)
C3	1.2547 (4)	0.8968 (2)	0.6987 (2)	0.0114 (7)
H3	1.3640	0.9165	0.6855	0.014*
C4	1.1363 (4)	0.8794 (3)	0.6263 (2)	0.0123 (7)
C5	0.9784 (4)	0.8516 (3)	0.6459 (2)	0.0144 (7)
H5	0.8984	0.8400	0.5963	0.017*
C6	0.9340 (4)	0.8400 (2)	0.7388 (2)	0.0109 (7)
C7	0.7636 (4)	0.8084 (2)	0.7507 (2)	0.0122 (7)
H7	0.6966	0.7972	0.6946	0.015*
C8	0.8264 (4)	0.8649 (2)	1.1745 (2)	0.0089 (6)
C9	0.9119 (4)	0.8798 (2)	1.2634 (2)	0.0111 (7)
C10	0.8403 (4)	0.8716 (3)	1.3478 (2)	0.0152 (7)
H10C	0.9029	0.8815	1.4053	0.018*
C11	0.6749 (4)	0.8485 (3)	1.3479 (2)	0.0140 (7)
C12	0.5844 (4)	0.8358 (3)	1.2644 (2)	0.0134 (7)
H12	0.4719	0.8215	1.2653	0.016*
C13	0.6573 (4)	0.8437 (2)	1.1784 (2)	0.0105 (6)
C14	0.5495 (4)	0.8274 (2)	1.0955 (2)	0.0130 (7)
H14	0.4403	0.8178	1.1070	0.016*
C15	1.1453 (4)	0.3785 (2)	0.7795 (2)	0.0105 (6)
C16	1.3048 (4)	0.3981 (2)	0.7511 (2)	0.0107 (7)
C17	1.3436 (4)	0.4026 (2)	0.6585 (2)	0.0119 (7)
H17	1.4517	0.4171	0.6429	0.014*
C18	1.2213 (4)	0.3855 (3)	0.5875 (2)	0.0127 (7)
C19	1.0649 (4)	0.3623 (3)	0.6098 (2)	0.0133 (7)
H19	0.9827	0.3478	0.5611	0.016*
C20	1.0254 (4)	0.3598 (2)	0.7050 (2)	0.0109 (6)
C21	0.8572 (4)	0.3365 (3)	0.7224 (2)	0.0130 (7)
H21	0.7847	0.3167	0.6683	0.016*
C22	0.9237 (4)	0.4081 (2)	1.1431 (2)	0.0089 (6)
C23	0.9985 (4)	0.4002 (2)	1.2300 (2)	0.0103 (6)
C24	0.9167 (4)	0.3743 (2)	1.3089 (2)	0.0125 (7)
H24	0.9724	0.3710	1.3660	0.015*
C25	0.7501 (4)	0.3529 (3)	1.3036 (2)	0.0120 (7)
C26	0.6708 (4)	0.3553 (2)	1.2201 (2)	0.0125 (7)
H26	0.5578	0.3389	1.2166	0.015*
C27	0.7539 (4)	0.3816 (2)	1.1396 (2)	0.0097 (6)
C28	0.6570 (4)	0.3854 (2)	1.0564 (2)	0.0100 (6)
H28	0.5461	0.3742	1.0636	0.012*
O1	1.0177 (3)	0.84419 (18)	0.90218 (16)	0.0114 (5)
O2	0.6955 (3)	0.79453 (18)	0.82386 (17)	0.0129 (5)
O3	0.9021 (3)	0.87169 (18)	1.09647 (16)	0.0120 (5)
O4	0.5816 (3)	0.82436 (18)	1.01226 (16)	0.0128 (5)
O5	1.1173 (3)	0.37770 (17)	0.86854 (16)	0.0107 (5)
O6	0.7986 (3)	0.33961 (18)	0.79914 (16)	0.0118 (5)
O7	1.0093 (3)	0.44105 (17)	1.07188 (16)	0.0090 (5)
O8	0.7034 (3)	0.40163 (17)	0.97769 (16)	0.0116 (5)
Cl1	1.36080 (9)	0.90539 (6)	0.87857 (6)	0.01455 (18)
Cl2	1.19192 (11)	0.89319 (7)	0.51136 (6)	0.0199 (2)
Cl3	1.11849 (9)	0.90686 (6)	1.26347 (6)	0.01406 (18)
Cl4	0.58270 (11)	0.83281 (7)	1.45386 (6)	0.0221 (2)
Cl5	1.45564 (9)	0.41888 (6)	0.83825 (6)	0.01241 (17)
Cl6	1.27119 (11)	0.39485 (7)	0.47120 (6)	0.0197 (2)
Cl7	1.20508 (9)	0.43012 (6)	1.23861 (6)	0.01256 (17)
Cl8	0.64683 (11)	0.32313 (7)	1.40347 (6)	0.0193 (2)
O9	0.8187 (3)	0.98658 (18)	0.94441 (17)	0.0133 (5)
H9A	0.9028	1.0128	0.9186	0.016*
H9B	0.8160	1.0363	0.9696	0.016*
O10	0.7513 (3)	0.67389 (17)	0.97417 (17)	0.0118 (5)
H10A	0.8109	0.6479	0.9410	0.014*
H10B	0.7730	0.6619	1.0275	0.014*
O11	0.8612 (3)	0.23683 (17)	0.95443 (17)	0.0120 (5)
H11A	0.9147	0.2065	0.9205	0.014*
H11B	0.8921	0.2170	1.0031	0.014*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.00838 (19)	0.0114 (2)	0.0092 (2)	0.00159 (15)	−0.00065 (14)	0.00263 (14)
Zn2	0.00720 (19)	0.0103 (2)	0.00819 (19)	0.00178 (14)	−0.00008 (14)	0.00230 (14)
C1	0.0112 (16)	0.0069 (15)	0.0166 (17)	0.0020 (12)	0.0003 (13)	0.0044 (12)
C2	0.0133 (16)	0.0074 (15)	0.0109 (16)	0.0028 (12)	−0.0022 (13)	0.0019 (12)
C3	0.0106 (15)	0.0103 (16)	0.0142 (17)	0.0030 (13)	0.0036 (13)	0.0046 (12)
C4	0.0169 (17)	0.0127 (16)	0.0072 (15)	0.0031 (13)	0.0053 (13)	0.0025 (12)
C5	0.0153 (17)	0.0101 (16)	0.0164 (18)	0.0016 (13)	−0.0022 (14)	0.0021 (13)
C6	0.0109 (16)	0.0094 (16)	0.0104 (16)	−0.0005 (13)	0.0010 (12)	0.0019 (12)
C7	0.0117 (16)	0.0118 (16)	0.0123 (16)	0.0022 (13)	−0.0021 (13)	0.0021 (12)
C8	0.0136 (16)	0.0064 (15)	0.0076 (15)	0.0044 (12)	0.0010 (12)	0.0007 (11)
C9	0.0113 (16)	0.0074 (15)	0.0152 (17)	0.0033 (12)	0.0016 (13)	0.0029 (12)
C10	0.0176 (18)	0.0165 (18)	0.0106 (17)	0.0037 (14)	−0.0013 (13)	0.0011 (13)
C11	0.0158 (17)	0.0128 (17)	0.0137 (17)	0.0034 (14)	0.0057 (13)	0.0027 (13)
C12	0.0098 (16)	0.0130 (17)	0.0156 (17)	−0.0006 (13)	0.0025 (13)	0.0039 (13)
C13	0.0110 (16)	0.0089 (15)	0.0120 (16)	0.0029 (12)	−0.0001 (13)	0.0024 (12)
C14	0.0080 (15)	0.0112 (16)	0.0184 (18)	0.0001 (13)	−0.0010 (13)	0.0029 (13)
C15	0.0124 (16)	0.0087 (15)	0.0097 (16)	0.0018 (13)	−0.0003 (13)	0.0012 (12)
C16	0.0103 (15)	0.0084 (15)	0.0108 (16)	−0.0012 (12)	−0.0027 (12)	0.0009 (12)
C17	0.0084 (15)	0.0118 (16)	0.0134 (17)	0.0006 (13)	0.0002 (13)	−0.0007 (12)
C18	0.0176 (17)	0.0127 (16)	0.0075 (15)	0.0033 (13)	0.0047 (13)	0.0013 (12)
C19	0.0111 (16)	0.0173 (18)	0.0113 (16)	0.0044 (14)	−0.0025 (13)	0.0017 (13)
C20	0.0104 (15)	0.0113 (16)	0.0128 (16)	0.0051 (13)	0.0028 (13)	0.0025 (12)
C21	0.0097 (16)	0.0137 (17)	0.0138 (17)	0.0009 (13)	−0.0028 (13)	0.0015 (13)
C22	0.0107 (15)	0.0043 (14)	0.0090 (15)	−0.0026 (12)	0.0003 (12)	0.0017 (11)
C23	0.0091 (15)	0.0090 (15)	0.0111 (16)	−0.0005 (12)	−0.0031 (12)	0.0023 (12)
C24	0.0157 (17)	0.0088 (16)	0.0130 (17)	0.0030 (13)	−0.0010 (13)	0.0031 (12)
C25	0.0136 (16)	0.0101 (16)	0.0118 (16)	0.0007 (13)	0.0044 (13)	0.0052 (12)
C26	0.0092 (15)	0.0098 (16)	0.0174 (17)	0.0014 (13)	0.0033 (13)	−0.0003 (13)
C27	0.0103 (15)	0.0061 (15)	0.0103 (16)	−0.0009 (12)	−0.0013 (12)	−0.0006 (12)
C28	0.0057 (14)	0.0124 (16)	0.0100 (16)	0.0006 (12)	0.0007 (12)	−0.0014 (12)
O1	0.0089 (11)	0.0191 (13)	0.0080 (11)	0.0054 (9)	0.0018 (9)	0.0048 (9)
O2	0.0097 (11)	0.0143 (12)	0.0140 (12)	0.0018 (9)	0.0000 (9)	0.0032 (9)
O3	0.0105 (11)	0.0133 (12)	0.0108 (12)	0.0006 (9)	0.0001 (9)	0.0030 (9)
O4	0.0106 (11)	0.0154 (12)	0.0124 (12)	0.0039 (10)	−0.0012 (9)	0.0015 (9)
O5	0.0103 (11)	0.0127 (12)	0.0103 (11)	0.0039 (9)	0.0001 (9)	0.0045 (9)
O6	0.0068 (11)	0.0156 (12)	0.0123 (12)	0.0012 (9)	−0.0003 (9)	0.0036 (9)
O7	0.0069 (10)	0.0107 (11)	0.0083 (11)	0.0006 (9)	0.0000 (9)	0.0023 (9)
O8	0.0091 (11)	0.0133 (12)	0.0129 (12)	0.0038 (9)	−0.0004 (9)	0.0018 (9)
Cl1	0.0096 (4)	0.0199 (4)	0.0140 (4)	0.0040 (3)	−0.0021 (3)	0.0026 (3)
Cl2	0.0194 (4)	0.0286 (5)	0.0104 (4)	0.0033 (4)	0.0041 (3)	0.0053 (3)
Cl3	0.0105 (4)	0.0191 (4)	0.0124 (4)	0.0037 (3)	−0.0011 (3)	0.0028 (3)
Cl4	0.0225 (5)	0.0287 (5)	0.0146 (4)	0.0045 (4)	0.0097 (3)	0.0060 (4)
Cl5	0.0082 (4)	0.0159 (4)	0.0121 (4)	0.0018 (3)	−0.0015 (3)	0.0022 (3)
Cl6	0.0197 (4)	0.0279 (5)	0.0089 (4)	0.0024 (4)	0.0032 (3)	0.0020 (3)
Cl7	0.0089 (4)	0.0177 (4)	0.0105 (4)	0.0020 (3)	−0.0008 (3)	0.0043 (3)
Cl8	0.0196 (4)	0.0249 (5)	0.0147 (4)	0.0052 (4)	0.0092 (3)	0.0084 (3)
O9	0.0118 (11)	0.0118 (12)	0.0164 (13)	0.0028 (10)	0.0007 (9)	0.0038 (9)
O10	0.0104 (11)	0.0145 (12)	0.0112 (12)	0.0046 (9)	−0.0006 (9)	0.0026 (9)
O11	0.0118 (11)	0.0128 (12)	0.0133 (12)	0.0057 (9)	0.0012 (9)	0.0042 (9)

Geometric parameters (Å, º) top

Zn1—O1	2.040 (2)	C14—O4	1.229 (4)
Zn1—O2	2.096 (2)	C14—H14	0.9500
Zn1—O3	2.049 (2)	C15—O5	1.303 (4)
Zn1—O4	2.084 (2)	C15—C20	1.422 (4)
Zn1—O9	2.112 (2)	C15—C16	1.426 (5)
Zn1—O10	2.130 (2)	C16—C17	1.379 (5)
Zn2—O5	2.011 (2)	C16—Cl5	1.730 (3)
Zn2—O6	2.114 (2)	C17—C18	1.405 (4)
Zn2—O7	2.081 (2)	C17—H17	0.9500
Zn2—O7ⁱ	2.176 (2)	C18—C19	1.373 (5)
Zn2—O8	2.069 (2)	C18—Cl6	1.739 (3)
Zn2—O11	2.134 (2)	C19—C20	1.415 (5)
C1—O1	1.298 (4)	C19—H19	0.9500
C1—C2	1.422 (5)	C20—C21	1.452 (5)
C1—C6	1.429 (4)	C21—O6	1.226 (4)
C2—C3	1.378 (5)	C21—H21	0.9500
C2—Cl1	1.739 (3)	C22—O7	1.327 (4)
C3—C4	1.395 (5)	C22—C23	1.415 (4)
C3—H3	0.9500	C22—C27	1.427 (4)
C4—C5	1.374 (5)	C23—C24	1.378 (5)
C4—Cl2	1.741 (3)	C23—Cl7	1.737 (3)
C5—C6	1.407 (5)	C24—C25	1.404 (5)
C5—H5	0.9500	C24—H24	0.9500
C6—C7	1.454 (5)	C25—C26	1.370 (5)
C7—O2	1.225 (4)	C25—Cl8	1.736 (3)
C7—H7	0.9500	C26—C27	1.406 (5)
C8—O3	1.313 (4)	C26—H26	0.9500
C8—C9	1.419 (4)	C27—C28	1.453 (4)
C8—C13	1.431 (4)	C28—O8	1.228 (4)
C9—C10	1.376 (5)	C28—H28	0.9500
C9—Cl3	1.743 (3)	O7—Zn2ⁱ	2.176 (2)
C10—C11	1.393 (5)	O9—H9A	0.8400
C10—H10C	0.9500	O9—H9B	0.7416
C11—C12	1.379 (5)	O10—H10A	0.8400
C11—Cl4	1.743 (4)	O10—H10B	0.8234
C12—C13	1.403 (5)	O11—H11A	0.8400
C12—H12	0.9500	O11—H11B	0.8371
C13—C14	1.449 (4)

O1—Zn1—O3	94.50 (9)	C12—C13—C14	115.3 (3)
O1—Zn1—O4	176.22 (8)	C8—C13—C14	123.4 (3)
O3—Zn1—O4	88.77 (9)	O4—C14—C13	128.2 (3)
O1—Zn1—O2	87.95 (9)	O4—C14—H14	115.9
O3—Zn1—O2	177.47 (10)	C13—C14—H14	115.9
O4—Zn1—O2	88.76 (9)	O5—C15—C20	124.4 (3)
O1—Zn1—O9	91.79 (10)	O5—C15—C16	120.1 (3)
O3—Zn1—O9	92.35 (9)	C20—C15—C16	115.5 (3)
O4—Zn1—O9	86.17 (9)	C17—C16—C15	123.2 (3)
O2—Zn1—O9	86.93 (9)	C17—C16—Cl5	119.1 (3)
O1—Zn1—O10	95.85 (9)	C15—C16—Cl5	117.7 (2)
O3—Zn1—O10	91.64 (9)	C16—C17—C18	119.2 (3)
O4—Zn1—O10	85.94 (9)	C16—C17—H17	120.4
O2—Zn1—O10	88.74 (9)	C18—C17—H17	120.4
O9—Zn1—O10	171.08 (9)	C19—C18—C17	120.4 (3)
O5—Zn2—O8	171.11 (9)	C19—C18—Cl6	120.6 (3)
O5—Zn2—O7	102.25 (9)	C17—C18—Cl6	119.0 (3)
O8—Zn2—O7	86.59 (9)	C18—C19—C20	120.3 (3)
O5—Zn2—O6	86.25 (9)	C18—C19—H19	119.8
O8—Zn2—O6	84.87 (9)	C20—C19—H19	119.8
O7—Zn2—O6	170.91 (9)	C19—C20—C15	121.2 (3)
O5—Zn2—O11	89.56 (9)	C19—C20—C21	116.7 (3)
O8—Zn2—O11	89.17 (9)	C15—C20—C21	122.1 (3)
O7—Zn2—O11	91.76 (9)	O6—C21—C20	127.1 (3)
O6—Zn2—O11	85.01 (9)	O6—C21—H21	116.4
O5—Zn2—O7ⁱ	93.02 (9)	C20—C21—H21	116.4
O8—Zn2—O7ⁱ	89.27 (9)	O7—C22—C23	120.8 (3)
O7—Zn2—O7ⁱ	81.32 (9)	O7—C22—C27	123.6 (3)
O6—Zn2—O7ⁱ	101.65 (8)	C23—C22—C27	115.6 (3)
O11—Zn2—O7ⁱ	172.99 (9)	C24—C23—C22	123.5 (3)
O1—C1—C2	120.8 (3)	C24—C23—Cl7	118.6 (2)
O1—C1—C6	124.5 (3)	C22—C23—Cl7	117.9 (3)
C2—C1—C6	114.7 (3)	C23—C24—C25	119.2 (3)
C3—C2—C1	123.8 (3)	C23—C24—H24	120.4
C3—C2—Cl1	118.4 (3)	C25—C24—H24	120.4
C1—C2—Cl1	117.7 (2)	C26—C25—C24	119.9 (3)
C2—C3—C4	119.3 (3)	C26—C25—Cl8	120.8 (3)
C2—C3—H3	120.4	C24—C25—Cl8	119.4 (3)
C4—C3—H3	120.4	C25—C26—C27	121.1 (3)
C5—C4—C3	120.1 (3)	C25—C26—H26	119.4
C5—C4—Cl2	120.9 (3)	C27—C26—H26	119.4
C3—C4—Cl2	119.0 (3)	C26—C27—C22	120.7 (3)
C4—C5—C6	120.7 (3)	C26—C27—C28	115.9 (3)
C4—C5—H5	119.7	C22—C27—C28	123.3 (3)
C6—C5—H5	119.7	O8—C28—C27	126.8 (3)
C5—C6—C1	121.4 (3)	O8—C28—H28	116.6
C5—C6—C7	115.7 (3)	C27—C28—H28	116.6
C1—C6—C7	122.9 (3)	C1—O1—Zn1	127.5 (2)
O2—C7—C6	128.1 (3)	C7—O2—Zn1	125.6 (2)
O2—C7—H7	116.0	C8—O3—Zn1	127.4 (2)
C6—C7—H7	116.0	C14—O4—Zn1	126.4 (2)
O3—C8—C9	120.5 (3)	C15—O5—Zn2	128.2 (2)
O3—C8—C13	124.5 (3)	C21—O6—Zn2	126.7 (2)
C9—C8—C13	115.0 (3)	C22—O7—Zn2	121.66 (19)
C10—C9—C8	123.7 (3)	C22—O7—Zn2ⁱ	115.7 (2)
C10—C9—Cl3	119.1 (3)	Zn2—O7—Zn2ⁱ	98.68 (9)
C8—C9—Cl3	117.2 (3)	C28—O8—Zn2	124.9 (2)
C9—C10—C11	119.2 (3)	Zn1—O9—H9A	109.5
C9—C10—H10C	120.4	Zn1—O9—H9B	144.2
C11—C10—H10C	120.4	H9A—O9—H9B	93.4
C12—C11—C10	120.3 (3)	Zn1—O10—H10A	109.5
C12—C11—Cl4	120.1 (3)	Zn1—O10—H10B	113.6
C10—C11—Cl4	119.6 (3)	H10A—O10—H10B	102.5
C11—C12—C13	120.4 (3)	Zn2—O11—H11A	109.5
C11—C12—H12	119.8	Zn2—O11—H11B	122.7
C13—C12—H12	119.8	H11A—O11—H11B	91.6
C12—C13—C8	121.3 (3)

O1—C1—C2—C3	178.7 (3)	C23—C24—C25—Cl8	−178.5 (3)
C6—C1—C2—C3	−0.8 (5)	C24—C25—C26—C27	−1.7 (5)
O1—C1—C2—Cl1	−0.3 (4)	Cl8—C25—C26—C27	178.5 (3)
C6—C1—C2—Cl1	−179.8 (2)	C25—C26—C27—C22	−1.0 (5)
C1—C2—C3—C4	0.1 (5)	C25—C26—C27—C28	−177.6 (3)
Cl1—C2—C3—C4	179.0 (3)	O7—C22—C27—C26	−174.7 (3)
C2—C3—C4—C5	0.4 (5)	C23—C22—C27—C26	3.4 (5)
C2—C3—C4—Cl2	−179.4 (3)	O7—C22—C27—C28	1.7 (5)
C3—C4—C5—C6	−0.2 (5)	C23—C22—C27—C28	179.8 (3)
Cl2—C4—C5—C6	179.7 (3)	C26—C27—C28—O8	−176.2 (3)
C4—C5—C6—C1	−0.6 (5)	C22—C27—C28—O8	7.3 (5)
C4—C5—C6—C7	−178.9 (3)	C2—C1—O1—Zn1	165.8 (2)
O1—C1—C6—C5	−178.4 (3)	C6—C1—O1—Zn1	−14.8 (5)
C2—C1—C6—C5	1.0 (5)	O3—Zn1—O1—C1	−160.0 (3)
O1—C1—C6—C7	−0.3 (5)	O2—Zn1—O1—C1	19.3 (3)
C2—C1—C6—C7	179.2 (3)	O9—Zn1—O1—C1	−67.5 (3)
C5—C6—C7—O2	−179.0 (3)	O10—Zn1—O1—C1	107.9 (3)
C1—C6—C7—O2	2.7 (6)	C6—C7—O2—Zn1	9.7 (5)
O3—C8—C9—C10	−178.5 (3)	O1—Zn1—O2—C7	−16.7 (3)
C13—C8—C9—C10	2.1 (5)	O4—Zn1—O2—C7	161.5 (3)
O3—C8—C9—Cl3	−0.1 (4)	O9—Zn1—O2—C7	75.2 (3)
C13—C8—C9—Cl3	−179.5 (2)	O10—Zn1—O2—C7	−112.6 (3)
C8—C9—C10—C11	−0.7 (5)	C9—C8—O3—Zn1	170.2 (2)
Cl3—C9—C10—C11	−179.1 (3)	C13—C8—O3—Zn1	−10.4 (4)
C9—C10—C11—C12	−1.1 (5)	O1—Zn1—O3—C8	−169.0 (3)
C9—C10—C11—Cl4	177.4 (3)	O4—Zn1—O3—C8	12.9 (3)
C10—C11—C12—C13	1.4 (5)	O9—Zn1—O3—C8	99.0 (3)
Cl4—C11—C12—C13	−177.1 (3)	O10—Zn1—O3—C8	−73.0 (3)
C11—C12—C13—C8	0.2 (5)	C13—C14—O4—Zn1	4.1 (5)
C11—C12—C13—C14	179.1 (3)	O3—Zn1—O4—C14	−9.8 (3)
O3—C8—C13—C12	178.8 (3)	O2—Zn1—O4—C14	170.7 (3)
C9—C8—C13—C12	−1.8 (4)	O9—Zn1—O4—C14	−102.2 (3)
O3—C8—C13—C14	−0.1 (5)	O10—Zn1—O4—C14	81.9 (3)
C9—C8—C13—C14	179.3 (3)	C20—C15—O5—Zn2	−20.6 (5)
C12—C13—C14—O4	−175.5 (3)	C16—C15—O5—Zn2	160.1 (2)
C8—C13—C14—O4	3.4 (5)	O7—Zn2—O5—C15	−158.3 (3)
O5—C15—C16—C17	−178.4 (3)	O6—Zn2—O5—C15	24.9 (3)
C20—C15—C16—C17	2.2 (5)	O11—Zn2—O5—C15	110.0 (3)
O5—C15—C16—Cl5	0.7 (4)	O7ⁱ—Zn2—O5—C15	−76.5 (3)
C20—C15—C16—Cl5	−178.7 (2)	C20—C21—O6—Zn2	6.7 (5)
C15—C16—C17—C18	−1.1 (5)	O5—Zn2—O6—C21	−18.1 (3)
Cl5—C16—C17—C18	179.8 (3)	O8—Zn2—O6—C21	162.4 (3)
C16—C17—C18—C19	−1.5 (5)	O11—Zn2—O6—C21	−108.0 (3)
C16—C17—C18—Cl6	178.2 (3)	O7ⁱ—Zn2—O6—C21	74.2 (3)
C17—C18—C19—C20	2.8 (5)	C23—C22—O7—Zn2	151.4 (2)
Cl6—C18—C19—C20	−176.8 (3)	C27—C22—O7—Zn2	−30.6 (4)
C18—C19—C20—C15	−1.6 (5)	C23—C22—O7—Zn2ⁱ	−89.0 (3)
C18—C19—C20—C21	178.8 (3)	C27—C22—O7—Zn2ⁱ	89.0 (3)
O5—C15—C20—C19	179.8 (3)	O5—Zn2—O7—C22	−141.2 (2)
C16—C15—C20—C19	−0.8 (5)	O8—Zn2—O7—C22	37.8 (2)
O5—C15—C20—C21	−0.7 (5)	O11—Zn2—O7—C22	−51.2 (2)
C16—C15—C20—C21	178.7 (3)	O7ⁱ—Zn2—O7—C22	127.6 (3)
C19—C20—C21—O6	−172.9 (3)	O5—Zn2—O7—Zn2ⁱ	91.22 (10)
C15—C20—C21—O6	7.6 (5)	O8—Zn2—O7—Zn2ⁱ	−89.78 (9)
O7—C22—C23—C24	174.7 (3)	O11—Zn2—O7—Zn2ⁱ	−178.85 (9)
C27—C22—C23—C24	−3.4 (5)	O7ⁱ—Zn2—O7—Zn2ⁱ	0.0
O7—C22—C23—Cl7	−2.5 (4)	C27—C28—O8—Zn2	15.4 (5)
C27—C22—C23—Cl7	179.4 (2)	O7—Zn2—O8—C28	−31.0 (3)
C22—C23—C24—C25	1.0 (5)	O6—Zn2—O8—C28	145.8 (3)
Cl7—C23—C24—C25	178.1 (3)	O11—Zn2—O8—C28	60.8 (3)
C23—C24—C25—C26	1.7 (5)	O7ⁱ—Zn2—O8—C28	−112.4 (3)

Symmetry code: (i) −x+2, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9A···O3ⁱⁱ	0.84	2.02	2.790 (3)	153
O9—H9B···O1ⁱⁱ	0.74	2.45	3.015 (3)	134
O10—H10A···O7ⁱ	0.84	2.24	2.998 (3)	150
O10—H10B···O5ⁱ	0.82	1.95	2.741 (3)	161
O11—H11A···O3ⁱ	0.84	2.17	2.931 (3)	151
O11—H11B···O1ⁱ	0.84	1.93	2.751 (3)	169

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

Experimental details

Crystal data
Chemical formula	[Zn(C₇H₃Cl₂O₂)₂(H₂O)₂]₂·[Zn₂(C₇H₃Cl₂O₂)₄(H₂O)₂]
M_r	1889.61
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	8.7532 (9), 13.6973 (15), 14.2833 (15)
α, β, γ (°)	96.244 (2), 91.700 (1), 106.096 (1)
V (Å³)	1632.4 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	2.19
Crystal size (mm)	0.15 × 0.15 × 0.08

Data collection
Diffractometer	Bruker APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.735, 0.845
No. of measured, independent and observed [I > 2σ(I)] reflections	9504, 7275, 5671
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.658

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.118, 0.75
No. of reflections	7275
No. of parameters	445
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.59, −0.46

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97 (Sheldrick, 2008.

Selected bond lengths (Å) top

Zn1—O1	2.040 (2)	Zn2—O5	2.011 (2)
Zn1—O2	2.096 (2)	Zn2—O6	2.114 (2)
Zn1—O3	2.049 (2)	Zn2—O7	2.081 (2)
Zn1—O4	2.084 (2)	Zn2—O7ⁱ	2.176 (2)
Zn1—O9	2.112 (2)	Zn2—O8	2.069 (2)
Zn1—O10	2.130 (2)	Zn2—O11	2.134 (2)

Symmetry code: (i) −x+2, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9A···O3ⁱⁱ	0.84	2.02	2.790 (3)	153
O9—H9B···O1ⁱⁱ	0.74	2.45	3.015 (3)	134
O10—H10A···O7ⁱ	0.84	2.24	2.998 (3)	150
O10—H10B···O5ⁱ	0.82	1.95	2.741 (3)	161
O11—H11A···O3ⁱ	0.84	2.17	2.931 (3)	151
O11—H11B···O1ⁱ	0.84	1.93	2.751 (3)	169

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

Acknowledgements

This work was supported by the Kato Foundation for the Promotion of Science.

References

Akitsu, T. (2007). Polyhedron, 26, 2527–2535. Web of Science CSD CrossRef CAS Google Scholar
Akitsu, T. & Einaga, Y. (2004a). Acta Cryst. C60, m640–m642. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Akitsu, T. & Einaga, Y. (2004b). Acta Cryst. E60, m1605–m1607. Web of Science CSD CrossRef IUCr Journals Google Scholar
Akitsu, T. & Einaga, Y. (2005a). Polyhedron, 24, 1869–1877. Web of Science CSD CrossRef CAS Google Scholar
Akitsu, T. & Einaga, Y. (2005b). Polyhedron, 24, 2933–2943. Web of Science CSD CrossRef CAS Google Scholar
Akitsu, T., Takeuchi, Y. & Einaga, Y. (2005). Acta Cryst. E61, m772–m774. Web of Science CrossRef IUCr Journals Google Scholar
Akitsu, T., Yamaguchi, J., Uchida, N. & Aritake, Y. (2009). Res. Lett. Mater. Sci. 484172. Google Scholar
Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chen, Q. (2006). Acta Cryst. E62, m56–m57. CrossRef IUCr Journals Google Scholar
Chen, X.-M., Zhang, S.-H., Jin, L.-X., Liu, Z. & Yan, Y. (2007). Acta Cryst. E63, m1321. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Xiong, Z.-Y. & Liu, L.-J. (2005). Acta Cryst. E61, m863–m864. Web of Science CrossRef IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 12| December 2009| Pages m1640-m1641

doi:10.1107/S160053680904896X

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Di­aqua­bis­(2,4-di­chloro-6-formyl­phenolato)zinc(II)–bis­­(μ-2,4-di­chloro-6-formyl­phenolato)bis­­[aqua­(2,4-di­chloro-6-formyl­phenolato)zinc(II)] (2/1)

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Diaquabis(2,4-dichloro-6-formylphenolato)zinc(II)–bis(μ-2,4-dichloro-6-formylphenolato)bis[aqua(2,4-dichloro-6-formylphenolato)zinc(II)] (2/1)