catena-Poly[piperazindiium [zincate(II)-bis­(μ-pyridine-2,3-dicarboxyl­ato)-κ3N,O2:O3;κ3O3:N,O2] tetra­hydrate]

Aghabozorg, H.; Daneshvar, S.; Motyeian, E.; Ghadermazi, M.; Attar Gharamaleki, J.

doi:10.1107/S1600536807042651

catena-Poly[piperazindiium [zincate(II)-bis(μ-pyridine-2,3-dicarboxylato)-κ³N,O²:O³;κ³O³:N,O²] tetrahydrate]

H. Aghabozorg, S. Daneshvar, E. Motyeian, M. Ghadermazi and J. Attar Gharamaleki

The centrosymmetric title compound, {(C₄H₁₂N₂)[Zn(C₁₄H₆N₂O₈)₂]·4H₂O}_n or {(pipzH₂)[Zn(py-2,3-dc)₂]·4H₂O}_n, where py-2,3-dcH₂ is pyridine-2,3-dicarboxylic acid and pipz is piperazine, was obtained by the reaction of zinc(II) nitrate tetrahydrate with (pipzH₂)(py-2,3-dc) as a proton-transfer compound in aqueous solution. Each Zn^II (site symmetry ${\overline 1}$ ) is coordinated in a distorted octahedral geometry by four O atoms and two N atoms from two bidentate (py-2,3-dc)²⁻ ligands, which also act as bridging ligands between Zn^II atoms. The four donor atoms of the two coplanar (py-2,3-dc)²⁻ anions form a square-planar arrangement around the Zn^II centre. In the crystal structure, extensive O—H

O, N—H

O and C—H

O hydrogen bonds, as well as ion pairing and π–π stacking [with a distance of 3.8693 (8) Å between two aromatic rings] between different fragments, play an important role in the stabilization of the supramolecular structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807042651/om2156sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807042651/om2156Isup2.hkl Contains datablock I

CCDC reference: 663557

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Key indicators

Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.002 Å
R factor = 0.027
wR factor = 0.071
Data-to-parameter ratio = 19.4

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No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        200 Deg.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          8

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Zn1         (2)       1.97

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

Here we report a new polymeric compound obtained from reaction of zinc(II) nitrate tetrahydrate with (pipzH₂)(py-2,3-dc) as proton-transfer compound. The crystal structure of the title polymeric compound is shown in Fig. 1.Some selected bond distances and bond angles are listed in Table 1. The intermolecular hydrogen bond distances are listed in Table 2.

This compound crystallizes in the triclinic system, space group P1, with one formula in the unit cell. In anionic complex, [Zn(py-2,3-dc)₂]^2–, the Zn^II (site symmetry 1) is hexacoordinated by two nitrogen atoms N1, and N1c (c: -x, -y, -z) and four oxygen atoms O1, O1c, O3a and O3d of carboxylate groups (a: x - 1, y, z; d: -x + 1, -y, -z) of two (py-2,3-dc)^2- fragments which also act as bridging ligands between Zn^II. O3a and O3d atoms from two neighbor (py-2,3-dc)^2- fragments occupy the axial positions, while O1, O1c, N1, N1c from two (py-2,3-dc)^2- fragments as bidentate ligands, form the equatorial plane. The N—Zn—N and O—Zn—O bond angles are linear. The four donor atoms of the two coplanar (py-2,3-dc)^2- anions form a square-planar arrangement around the Zn^II center.

The equatorial Zn—N and Zn—O bond lengths for Zn1 are 2.0543 (10) and 2.0605 (9) Å, respectively. The axial Zn—O bond length [2.2985 (9) Å] is significantly longer than equatorial bond lengths which is consistent with the corresponding data reported in literature (Aghabozorg, Sadr-khanlou et al., 2007). According to bond lengths, bond and torsion angles, arrangement of the six donor atoms around Zn^II is a distorted octahedral. The angle between plane passing from pyridine ring (N1/C1—C5) and the plane passing carboxylate group (OCO) is 88.15 (3)°, indicating that these bridging carboxylate groups are almost perpendicular to the aromatic ring.

A considerable feature of the compound (I) is the presence of π–π stacking with distance of 3.8693 (8) Å (1 - x, -1 - y, -z) between two centroids of aromatic rings (Aghabozorg, Zabihi, et al., 2006) (Fig. 2).

In the crystal structure, the spaces between two layers of [Zn(py-2,3-dc)₂]^2–fragments are filled with layers of (pipzH₂)²⁺ cations and uncoordinated water molecules (Fig. 3). The most important features of the crystal structure of (I) is the presence of a large number of O—H···O, N—H···O and C—H···O hydrogen bonds between (pipzH₂)²⁺ and [Zn(py-2,3-dc)₂]^2–fragments and uncoordinated water molecules with D···A distances ranging from 2.746 (2) Å to 3.420 (2) Å (Table 2). Ion pairing and π–π stacking are also effective in the stabilization of the crystal structure. These interactions result in the formation of a supramolecular structure (Fig. 4).

Related literature top

We have reported cases in which proton transfer from pyridine-2,6-dicarboxylic acid (pydcH₂) and benzene-1,2,4,5-tetracarboxylic acid (btcH₄) to piperazine (pipz) and 1,10-phenanthroline (phen) resulted in the formation of novel self- assembled (pipzH₂)(pydc) (Aghabozorg, Ghadermazi, Manteghi & Nakhjavan, 2006) and (phenH)₄(btcH₃)₂(btcH₂) (Aghabozorg, Ghadermazi & Attar Gharamaleki, 2006) systems, respectively. The resulting compounds, with some remaining sites as electron donors, can coordinate to metallic ions (Aghabozorg, Ghasemikhah, Ghadermazi et al., 2006; Aghabozorg, Ghasemikhah, Soleimannejad et al., 2006; Aghabozorg, Sadr-khanlou et al., 2007; Aghabozorg, Zabihi et al., 2006; Aghabozorg, Bahrami et al., 2007).

Experimental top

The proton-transfer ion pair was prepared by a reaction between piperazine and pyridine-2,3-dicarboxylic acid. Starting with a 1:1 molar ratio of the reactants in THF, a puffy white precipitate was obtained. By recrystallization in an aqueous solution, pale-yellow crystals were obtained. A solution of Zn(NO₃)₂.4H₂O (130 mg, 0.5 mmol) in water (20 ml) was added to an aqueous solution of (pipzH₂)(py-2,3-dc)(253 mg, 1.0 mmol) in water (20 ml) in a 1:2 molar ratio. Colorless crystals of (I) suitable for X-ray characterization were obtained after a few days at room temperature.

Structure description top

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXTL (Sheldrick, 1998); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL a.

Figures top

	Fig. 1. The structure of (I), showing the atom-numbering scheme and displacement. Ellipsoids are at the 50% probability level. Water molecules are omitted for clarity.Atoms marked with a, c, d and e suffixes are related by the symmetry codes: (a: x - 1, y, z; b: x + 1, y, z; c: -x, -y, -z; d: -x + 1, -y, -z; e: -x, -y, -z+1).
	Fig. 2. π-π Stacking interactions between two aromatic rings of (I), The average distance between the planes is 3.8693 (8) Å (1 - x, -1 - y, -z).
	Fig. 3. A layered packing diagram of (I). The space between the two layers of [Zn(py-2,3-dc)₂]^2– fragments is filled with a layer of (pipzH₂)²⁺ cations and water molecules.
	Fig. 4. The crystal packing of (I), hydrogen bonds are shown as dashed lines.

catena-Poly[piperazindiium [zincate(II)-bis(µ-pyridine-2,3-dicarboxylato)- κ³N,O²:O³;κ³O³:N,O²] tetrahydrate] top

Crystal data top

(C₄H₁₂N₂)[Zn(C₁₄H₆N₂O₈)₂]·4H₂O	Z = 1
M_r = 555.80	F(000) = 288
Triclinic, P1	D_x = 1.731 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6535 (6) Å	Cell parameters from 3747 reflections
b = 8.4170 (8) Å	θ = 2.6–30.1°
c = 10.3399 (9) Å	µ = 1.23 mm⁻¹
α = 78.493 (2)°	T = 100 K
β = 79.524 (2)°	Plate, colourless
γ = 71.284 (2)°	0.35 × 0.31 × 0.20 mm
V = 533.07 (8) Å³

Data collection top

Bruker APEXII CCD area-detector diffractometer	3105 independent reflections
Radiation source: fine-focus sealed tube	2876 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.020
φ and ω scans	θ_max = 30.1°, θ_min = 2.0°
Absorption correction: multi-scan (APEX2; Bruker, 2005)	h = −9→9
T_min = 0.673, T_max = 0.791	k = −11→11
6813 measured reflections	l = −14→14

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)] = 0.027	Hydrogen site location: mixed
wR(F²) = 0.071	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0412P)² + 0.2057P] where P = (F_o² + 2F_c²)/3
3105 reflections	(Δ/σ)_max < 0.001
160 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.46 e Å⁻³

Crystal data top

(C₄H₁₂N₂)[Zn(C₁₄H₆N₂O₈)₂]·4H₂O	γ = 71.284 (2)°
M_r = 555.80	V = 533.07 (8) Å³
Triclinic, P1	Z = 1
a = 6.6535 (6) Å	Mo Kα radiation
b = 8.4170 (8) Å	µ = 1.23 mm⁻¹
c = 10.3399 (9) Å	T = 100 K
α = 78.493 (2)°	0.35 × 0.31 × 0.20 mm
β = 79.524 (2)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	3105 independent reflections
Absorption correction: multi-scan (APEX2; Bruker, 2005)	2876 reflections with I > 2σ(I)
T_min = 0.673, T_max = 0.791	R_int = 0.020
6813 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	0 restraints
wR(F²) = 0.071	H-atom parameters constrained
S = 1.01	Δρ_max = 0.45 e Å⁻³
3105 reflections	Δρ_min = −0.46 e Å⁻³
160 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq
Zn1	0.0000	0.0000	0.0000	0.01300 (7)
O1	0.19351 (14)	0.09480 (11)	−0.15435 (9)	0.01152 (17)
O2	0.52743 (14)	0.02875 (12)	−0.25947 (9)	0.01283 (18)
O3	0.96403 (14)	−0.15685 (12)	−0.14797 (9)	0.01339 (18)
O4	0.87264 (15)	−0.31878 (12)	−0.25892 (9)	0.01359 (18)
N1	0.28879 (16)	−0.17768 (13)	0.03105 (10)	0.00907 (18)
C1	0.45027 (19)	−0.15066 (15)	−0.06130 (11)	0.0087 (2)
C2	0.65942 (19)	−0.25589 (15)	−0.05727 (12)	0.0084 (2)
C3	0.6983 (2)	−0.38953 (16)	0.04854 (12)	0.0124 (2)
H3A	0.8366	−0.4613	0.0549	0.015*
C4	0.5320 (2)	−0.41542 (16)	0.14380 (12)	0.0128 (2)
H4A	0.5570	−0.5034	0.2149	0.015*
C5	0.32724 (19)	−0.30735 (16)	0.13094 (12)	0.0105 (2)
H5A	0.2139	−0.3254	0.1933	0.013*
C6	0.38876 (19)	0.00268 (15)	−0.16781 (12)	0.0089 (2)
C7	0.84343 (19)	−0.23815 (15)	−0.16344 (12)	0.0099 (2)
N1S	−0.16806 (17)	0.12631 (13)	−0.56677 (10)	0.0114 (2)
H2S	−0.3041	0.1894	−0.5687	0.014*
H1S	−0.1003	0.1518	−0.6465	0.014*
C1S	−0.0706 (2)	0.16761 (16)	−0.46338 (13)	0.0136 (2)
H1SA	−0.1517	0.1488	−0.3768	0.016*
H1SB	−0.0750	0.2862	−0.4828	0.016*
C2S	0.1594 (2)	0.05685 (16)	−0.46129 (13)	0.0124 (2)
H2SA	0.2420	0.0797	−0.5466	0.015*
H2SB	0.2215	0.0831	−0.3933	0.015*
O1W	−0.42260 (15)	0.66016 (12)	−0.41719 (10)	0.01514 (18)
H1W1	−0.3478	0.6809	−0.3678	0.018*
H2W1	−0.3500	0.6226	−0.4871	0.018*
O2W	0.14990 (16)	0.39242 (12)	−0.35148 (9)	0.01651 (19)
H1W2	0.0730	0.4798	−0.3174	0.020*
H2W2	0.1794	0.3169	−0.2840	0.020*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.00588 (10)	0.01412 (11)	0.01298 (11)	0.00031 (7)	0.00178 (7)	0.00357 (7)
O1	0.0074 (4)	0.0114 (4)	0.0122 (4)	−0.0002 (3)	0.0000 (3)	0.0010 (3)
O2	0.0097 (4)	0.0146 (4)	0.0111 (4)	−0.0027 (3)	0.0012 (3)	0.0012 (3)
O3	0.0091 (4)	0.0167 (4)	0.0141 (4)	−0.0053 (3)	0.0007 (3)	−0.0013 (3)
O4	0.0125 (4)	0.0149 (4)	0.0104 (4)	−0.0006 (3)	0.0010 (3)	−0.0032 (3)
N1	0.0072 (4)	0.0103 (4)	0.0093 (4)	−0.0026 (4)	0.0000 (3)	−0.0015 (3)
C1	0.0082 (5)	0.0088 (5)	0.0085 (5)	−0.0020 (4)	−0.0004 (4)	−0.0018 (4)
C2	0.0076 (5)	0.0091 (5)	0.0085 (5)	−0.0025 (4)	−0.0001 (4)	−0.0017 (4)
C3	0.0093 (5)	0.0124 (5)	0.0125 (5)	−0.0010 (4)	−0.0013 (4)	0.0014 (4)
C4	0.0127 (5)	0.0126 (5)	0.0110 (5)	−0.0030 (4)	−0.0012 (4)	0.0018 (4)
C5	0.0099 (5)	0.0119 (5)	0.0093 (5)	−0.0043 (4)	0.0009 (4)	−0.0006 (4)
C6	0.0091 (5)	0.0086 (5)	0.0092 (5)	−0.0027 (4)	−0.0017 (4)	−0.0013 (4)
C7	0.0064 (5)	0.0101 (5)	0.0090 (5)	0.0010 (4)	−0.0004 (4)	0.0017 (4)
N1S	0.0100 (5)	0.0129 (5)	0.0099 (4)	−0.0031 (4)	−0.0012 (4)	0.0011 (4)
C1S	0.0132 (6)	0.0128 (5)	0.0160 (6)	−0.0044 (4)	−0.0015 (4)	−0.0044 (4)
C2S	0.0123 (5)	0.0131 (5)	0.0131 (5)	−0.0052 (4)	−0.0025 (4)	−0.0017 (4)
O1W	0.0122 (4)	0.0181 (5)	0.0138 (4)	−0.0042 (4)	−0.0004 (3)	−0.0009 (3)
O2W	0.0215 (5)	0.0121 (4)	0.0123 (4)	−0.0005 (4)	−0.0012 (4)	−0.0017 (3)

Geometric parameters (Å, º) top

Zn1—N1ⁱ	2.0543 (10)	C3—H3A	0.9300
Zn1—N1	2.0543 (10)	C4—C5	1.3869 (17)
Zn1—O1	2.0605 (9)	C4—H4A	0.9300
Zn1—O1ⁱ	2.0605 (9)	C5—H5A	0.9300
Zn1—O3ⁱⁱ	2.2984 (9)	N1S—C1S	1.4931 (16)
Zn1—O3ⁱⁱⁱ	2.2985 (9)	N1S—C2S^v	1.4948 (16)
O1—C6	1.2803 (14)	N1S—H2S	0.8919
O2—C6	1.2355 (15)	N1S—H1S	0.8863
O3—C7	1.2572 (15)	C1S—C2S	1.5160 (18)
O3—Zn1^iv	2.2985 (9)	C1S—H1SA	0.9700
O4—C7	1.2594 (15)	C1S—H1SB	0.9700
N1—C5	1.3381 (16)	C2S—N1S^v	1.4948 (16)
N1—C1	1.3472 (15)	C2S—H2SA	0.9700
C1—C2	1.3921 (16)	C2S—H2SB	0.9700
C1—C6	1.5179 (16)	O1W—H1W1	0.8500
C2—C3	1.3980 (16)	O1W—H2W1	0.8500
C2—C7	1.5131 (16)	O2W—H1W2	0.8501
C3—C4	1.3839 (17)	O2W—H2W2	0.8500

N1ⁱ—Zn1—N1	180.00 (10)	C5—C4—H4A	120.7
N1ⁱ—Zn1—O1	99.34 (4)	N1—C5—C4	121.61 (11)
N1—Zn1—O1	80.66 (4)	N1—C5—H5A	119.2
N1ⁱ—Zn1—O1ⁱ	80.66 (4)	C4—C5—H5A	119.2
N1—Zn1—O1ⁱ	99.34 (4)	O2—C6—O1	125.37 (11)
O1—Zn1—O1ⁱ	180.00 (7)	O2—C6—C1	118.55 (11)
N1ⁱ—Zn1—O3ⁱⁱ	88.21 (4)	O1—C6—C1	116.08 (10)
N1—Zn1—O3ⁱⁱ	91.79 (4)	O3—C7—O4	124.35 (11)
O1—Zn1—O3ⁱⁱ	94.38 (3)	O3—C7—C2	119.85 (11)
O1ⁱ—Zn1—O3ⁱⁱ	85.62 (3)	O4—C7—C2	115.61 (11)
N1ⁱ—Zn1—O3ⁱⁱⁱ	91.79 (4)	C1S—N1S—C2S^v	110.07 (10)
N1—Zn1—O3ⁱⁱⁱ	88.21 (4)	C1S—N1S—H2S	111.2
O1—Zn1—O3ⁱⁱⁱ	85.62 (3)	C2S^v—N1S—H2S	108.8
O1ⁱ—Zn1—O3ⁱⁱⁱ	94.38 (3)	C1S—N1S—H1S	109.5
O3ⁱⁱ—Zn1—O3ⁱⁱⁱ	180.00 (3)	C2S^v—N1S—H1S	111.3
C6—O1—Zn1	114.73 (8)	H2S—N1S—H1S	105.9
C7—O3—Zn1^iv	140.01 (8)	N1S—C1S—C2S	109.90 (10)
C5—N1—C1	120.13 (11)	N1S—C1S—H1SA	109.7
C5—N1—Zn1	127.08 (8)	C2S—C1S—H1SA	109.7
C1—N1—Zn1	112.76 (8)	N1S—C1S—H1SB	109.7
N1—C1—C2	121.76 (11)	C2S—C1S—H1SB	109.7
N1—C1—C6	115.51 (10)	H1SA—C1S—H1SB	108.2
C2—C1—C6	122.72 (10)	N1S^v—C2S—C1S	110.09 (10)
C1—C2—C3	117.62 (11)	N1S^v—C2S—H2SA	109.6
C1—C2—C7	123.78 (11)	C1S—C2S—H2SA	109.6
C3—C2—C7	118.54 (10)	N1S^v—C2S—H2SB	109.6
C4—C3—C2	120.27 (11)	C1S—C2S—H2SB	109.6
C4—C3—H3A	119.9	H2SA—C2S—H2SB	108.2
C2—C3—H3A	119.9	H1W1—O1W—H2W1	113.2
C3—C4—C5	118.57 (11)	H1W2—O2W—H2W2	103.3
C3—C4—H4A	120.7

N1ⁱ—Zn1—O1—C6	−175.52 (8)	C1—C2—C3—C4	0.88 (18)
N1—Zn1—O1—C6	4.48 (8)	C7—C2—C3—C4	−176.55 (11)
O3ⁱⁱ—Zn1—O1—C6	95.58 (8)	C2—C3—C4—C5	0.63 (19)
O3ⁱⁱⁱ—Zn1—O1—C6	−84.42 (8)	C1—N1—C5—C4	0.91 (18)
O1—Zn1—N1—C5	176.22 (11)	Zn1—N1—C5—C4	−177.46 (9)
O1ⁱ—Zn1—N1—C5	−3.78 (11)	C3—C4—C5—N1	−1.56 (19)
O3ⁱⁱ—Zn1—N1—C5	82.07 (10)	Zn1—O1—C6—O2	174.12 (10)
O3ⁱⁱⁱ—Zn1—N1—C5	−97.93 (10)	Zn1—O1—C6—C1	−5.63 (13)
O1—Zn1—N1—C1	−2.26 (8)	N1—C1—C6—O2	−176.02 (10)
O1ⁱ—Zn1—N1—C1	177.74 (8)	C2—C1—C6—O2	4.81 (17)
O3ⁱⁱ—Zn1—N1—C1	−96.40 (8)	N1—C1—C6—O1	3.75 (15)
O3ⁱⁱⁱ—Zn1—N1—C1	83.60 (8)	C2—C1—C6—O1	−175.42 (11)
C5—N1—C1—C2	0.71 (17)	Zn1^iv—O3—C7—O4	−177.67 (8)
Zn1—N1—C1—C2	179.30 (9)	Zn1^iv—O3—C7—C2	−2.98 (19)
C5—N1—C1—C6	−178.48 (10)	C1—C2—C7—O3	96.11 (14)
Zn1—N1—C1—C6	0.12 (12)	C3—C2—C7—O3	−86.63 (15)
N1—C1—C2—C3	−1.58 (18)	C1—C2—C7—O4	−88.75 (14)
C6—C1—C2—C3	177.55 (11)	C3—C2—C7—O4	88.51 (14)
N1—C1—C2—C7	175.70 (11)	C2S^v—N1S—C1S—C2S	58.59 (14)
C6—C1—C2—C7	−5.17 (18)	N1S—C1S—C2S—N1S^v	−58.60 (14)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1S—H2S···O1W^vi	0.89	1.87	2.753 (2)	174
N1S—H1S···O3^vii	0.89	2.15	3.012 (1)	164
N1S—H1S···O4^vii	0.89	2.35	3.054 (1)	137
O1W—H1W1···O4^viii	0.85	2.01	2.842 (2)	168
O1W—H2W1···O2W^ix	0.85	1.93	2.746 (2)	159
O2W—H1W2···O4^viii	0.85	1.92	2.763 (1)	172
O2W—H2W2···O1	0.85	2.06	2.868 (1)	159
C2S—H2SA···O2^vii	0.97	2.43	3.298 (2)	148
C2S—H2SA···O4^vii	0.97	2.58	3.264 (2)	128
C2S—H2SB···O1	0.97	2.46	3.307 (2)	145
C2S—H2SB···O2	0.97	2.54	3.420 (2)	151
C4—H4A···O1Wⁱ	0.93	2.43	3.264 (2)	150

Symmetry codes: (i) −x, −y, −z; (vi) −x−1, −y+1, −z−1; (vii) −x+1, −y, −z−1; (viii) x−1, y+1, z; (ix) −x, −y+1, −z−1.

Experimental details

Crystal data
Chemical formula	(C₄H₁₂N₂)[Zn(C₁₄H₆N₂O₈)₂]·4H₂O
M_r	555.80
Crystal system, space group	Triclinic, P1
Temperature (K)	100
a, b, c (Å)	6.6535 (6), 8.4170 (8), 10.3399 (9)
α, β, γ (°)	78.493 (2), 79.524 (2), 71.284 (2)
V (Å³)	533.07 (8)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.23
Crystal size (mm)	0.35 × 0.31 × 0.20

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (APEX2; Bruker, 2005)
T_min, T_max	0.673, 0.791
No. of measured, independent and observed [I > 2σ(I)] reflections	6813, 3105, 2876
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.071, 1.01
No. of reflections	3105
No. of parameters	160
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.46

Computer programs: APEX2 (Bruker, 2005), APEX2, SHELXTL (Sheldrick, 1998), SHELXTL a.

Selected geometric parameters (Å, º) top

Zn1—N1	2.0543 (10)	Zn1—O3ⁱ	2.2985 (9)
Zn1—O1	2.0605 (9)

N1ⁱⁱ—Zn1—O1	99.34 (4)	N1—Zn1—O3ⁱ	88.21 (4)
N1—Zn1—O1	80.66 (4)	O1—Zn1—O3ⁱ	85.62 (3)
N1ⁱⁱ—Zn1—O3ⁱ	91.79 (4)	O1ⁱⁱ—Zn1—O3ⁱ	94.38 (3)

C2—C1—C6—O2	4.81 (17)	C1—C2—C7—O3	96.11 (14)
C2—C1—C6—O1	−175.42 (11)	C1—C2—C7—O4	−88.75 (14)

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