Poly[[(1,10-phenanthroline)(μ-l-tartrato)zinc] hexa­hydrate]

Dong, G.-Y.; He, C.-H.; Liu, T.-F.; Cui, G.-H.; Deng, X.-C.

doi:10.1107/S1600536811024780

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Pages m1005-m1006

doi:10.1107/S1600536811024780

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Poly[[(1,10-phenanthroline)(μ-L-tartrato)zinc] hexahydrate]

Gui-Ying Dong,^a Cui-Hong He,^a Tong-Fei Liu,^a Guang-Hua Cui ^a ^* and Xiao-Chen Deng ^b

^aCollege of Chemical Engineering, Hebei United University, Tangshan 063009, People's Republic of China, and ^bQian'an College, Hebei United University, Tangshan 063009, People's Republic of China
^*Correspondence e-mail: tscghua@126.com

(Received 1 June 2011; accepted 23 June 2011; online 30 June 2011)

The title compouand {[Zn(C₄H₄O₆)(C₁₂H₈N₂)]·6H₂O}_n, has a linear chain structure parallel to [100] with Zn(C₄H₄O₆)(C₁₂H₈N₂) repeat units; the asymmetric unit consists of one Zn²⁺ cation, one L-tartrate dianion, one 1,10-phenanthroline and six free water molecules. The Zn atom is in a distorted octahedral ZnN₂O₄ coordination environment. The crystal structure is stabilized by O—H⋯O hydrogen bonds and π–π stacking of the phenanthroline units [centroid–centroid distances in the range 3.552 (2)–3.625 (2)Å] occurs between the chains. The title compound is isotypic with the Cu and Mn analogues.

Related literature

For chiral multifunctional materials constructed from tartrate, see: Liu et al. (2008 , 2010 ); Gelbrich et al. (2006 ); Kitagawa et al. (2004 ); Ma et al. (2007 ); Adama et al. (2007 ); Lin et al. (2009 ); Templeton et al. (1985 ). For the isotypic copper and manganese analogues, see: McCann et al. (1997 ); Zhang et al. (2003 ).

Experimental

Crystal data

[Zn(C₄H₄O₆)(C₁₂H₈N₂)]·6H₂O
M_r = 501.76
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.632 (2) Å
b = 15.301 (4) Å
c = 20.087 (5) Å
V = 2038.4 (10) Å³
Z = 4
Mo Kα radiation
μ = 1.27 mm⁻¹
T = 295 K
0.25 × 0.18 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.754, T_max = 0.844
16280 measured reflections
3541 independent reflections
3251 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.027
wR(F²) = 0.071
S = 0.96
3541 reflections
280 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.29 e Å⁻³
Absolute structure: Flack (1983 ), 1456 Friedel pairs
Flack parameter: 0.025 (12)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1A⋯O5Wⁱ	0.85	1.99	2.787 (3)	157
O2W—H2A⋯O3W	0.85	2.05	2.819 (4)	150
O2W—H2B⋯O6Wⁱⁱ	0.85	1.98	2.822 (4)	172
O3W—H3A⋯O5ⁱⁱⁱ	0.85	2.17	2.802 (3)	131
O3W—H3B⋯O1W^iv	0.85	1.93	2.776 (4)	177
O4W—H4A⋯O5Wⁱ	0.85	2.00	2.789 (4)	154
O4W—H4B⋯O6^v	0.85	1.99	2.718 (3)	143
O5W—H5A⋯O3ⁱⁱⁱ	0.85	2.04	2.880 (3)	168
O5W—H5B⋯O1	0.85	2.10	2.909 (3)	160
O6W—H6A⋯O1W^vi	0.85	2.02	2.816 (4)	155
O6W—H6B⋯O5	0.85	2.04	2.886 (3)	174
O2—H21⋯O2W^vii	0.85	1.82	2.655 (3)	164
O4—H22⋯O4W^viii	0.85	1.75	2.599 (3)	178
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, -y+1, z-{\script{1\over 2}}]$ ; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z]$ ; (v) x, y+1, z; (vi) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (vii) x, y-1, z; (viii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811024780/rk2279sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811024780/rk2279Isup2.hkl

checkCIF report

Comment top

An enormous effort has been devoted to the development of new homochiral coordination polymer duo to their the possibility of applications to enantioselective separation, catalytic processes and magneto-optical processes (Kitagawa et al., 2004; Ma et al., 2007; Liu et al., 2008; Gelbrich et al., 2006)). L-tartaric acid, a simple and inexpensive chiral ligand source, was often used to construct novel chiral multifunctional metal-organic frameworks (McCann et al.,1997; Zhang et al., 2003). However, only four zinc-tartrate compounds have been reported (Adama et al., 2007; Lin et al., 2009; Liu et al., 2010; Templeton et al., 1985) up to now. We report here the synthesis and crystal structure of the first mixed-ligand zinc(II) complex with tartrate and 1,10-phenanthroline, I, which has a linear chain structure.

The asymmetric unit of I consists of one Zn atom, one L-tartrate dianion, one phenanthroline and six free water molecules, (Fig. 1). The Zn atom is hexacoordinated by four O atoms (Zn-O = 2.046 (2)-2.200 (2)Å) and two N atoms (Zn-N = 2.127 (2)Å and 2.132 (2)Å) forming [ZnO₄N₂] distorted octahedral geometry with three trans-angles form 159.21 (10)° to 160.73 (10)°. The Zn-O(hydroxy) and Zn–O(carboxylate) distances are typical for Zn-O bonds. The L-tartrate dianion adopts η₄µ₂-chelating/bridging mode to extend Zn(C₁₂H₈N₂)²⁺ to one-dimensional polymeric chain, which is assembled together to genterate a zipper-like double chain through strong π–π packing interactions between parallel phenanthroline aromatic rings with centroid–centroid distances of 3.552 (2)-3.625 (2)Å. The most noteworthy structural feature of I, is the existence of one-dimensional helical chain water cluster (Fig. 2). In crystal achitecture of I, there are six crystllography independent lattice water molecules, which are interconnected by hydrogen bonds forming a right-handed helical chain. The average Ow···Ow distance of 2.79 (2)Å in I is slightly small than the Ow···Ow distance observed in liquid water (2.85 (3)Å). The hydrogen bonding interactions between the Ow atoms from water cluster chains and the tartrate O atoms from one-dimensional double zipper chains with the average Ow···O distance of 2.77 (2)Å lead to the formation of a three-dimensional supramolecular framework of I.

Related literature top

For chiral multifunctional materials constructed from tartrate, see: Liu et al. (2008, 2010); Gelbrich et al. (2006); Kitagawa et al. (2004); Ma et al. (2007); Adama et al. (2007); Lin et al. (2009); Templeton et al. (1985). For the isotypic copper and manganese analogues, see: McCann et al. (1997); Zhang et al. (2003).

Experimental top

A mixture of Zn(NO₃)₂^.6H₂O (298 mg, 1 mmol), L-(+)-tartaric acid (150 mg, 1 mmol) and 1,10-phenanthroline (180 mg, 1 mmol) in H₂O (12 ml) was placed in a teflon-lined stainless vessel and heated to 413 K for 72 h. Then, the reaction system was cooled to room temperature during 24 h to give rise to colourless crystals, which were collected and washed with water. Yield 0.191 g (38% based on Zn). Analysis calculated for C₁₆H₂₄N₂ZnO₁₂ (501.76): C 38.30, H 4.82, N 5.58%; found: C 38.06, H 4.71 N 5.49%.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. Part of the structure of I, showing the bridging mode of the L-tartrate anion and one of the independent structural units with the atom numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are presented as a small spheres of arbitrary radius. Symmetry codes: (i) x-1, y, z; (ii) x+1, y, z.
	Fig. 2. The one-dimensional helical chain water clusters in I.

Poly[[(1,10-phenanthroline)(µ-L-tartrato)zinc] hexahydrate] top

Crystal data top

[Zn(C₄H₄O₆)(C₁₂H₈N₂)]·6H₂O	F(000) = 1040
M_r = 501.76	D_x = 1.635 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3086 reflections
a = 6.632 (2) Å	θ = 4.3–23.8°
b = 15.301 (4) Å	µ = 1.27 mm⁻¹
c = 20.087 (5) Å	T = 295 K
V = 2038.4 (10) Å³	Block, colourless
Z = 4	0.25 × 0.18 × 0.16 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3541 independent reflections
Radiation source: fine-focus sealed tube	3251 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ϕ and ω scans	θ_max = 25.0°, θ_min = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
T_min = 0.754, T_max = 0.844	k = −18→18
16280 measured reflections	l = −23→23

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.071	w = 1/[σ²(F_o²) + (0.0466P)² + 0.136P] where P = (F_o² + 2F_c²)/3
S = 0.96	(Δ/σ)_max = 0.001
3541 reflections	Δρ_max = 0.32 e Å⁻³
280 parameters	Δρ_min = −0.29 e Å⁻³
3 restraints	Absolute structure: Flack (1983), 1456 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.025 (12)

Crystal data top

[Zn(C₄H₄O₆)(C₁₂H₈N₂)]·6H₂O	V = 2038.4 (10) Å³
M_r = 501.76	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.632 (2) Å	µ = 1.27 mm⁻¹
b = 15.301 (4) Å	T = 295 K
c = 20.087 (5) Å	0.25 × 0.18 × 0.16 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3541 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3251 reflections with I > 2σ(I)
T_min = 0.754, T_max = 0.844	R_int = 0.036
16280 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.027	H-atom parameters constrained
wR(F²) = 0.071	Δρ_max = 0.32 e Å⁻³
S = 0.96	Δρ_min = −0.29 e Å⁻³
3541 reflections	Absolute structure: Flack (1983), 1456 Friedel pairs
280 parameters	Absolute structure parameter: 0.025 (12)
3 restraints

Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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
O3	0.1075 (3)	−0.01758 (12)	0.20025 (11)	0.0366 (5)
C16	0.2759 (4)	−0.02548 (17)	0.22862 (14)	0.0298 (6)
O4	0.3195 (3)	0.12657 (10)	0.20244 (9)	0.0284 (4)
C15	0.3940 (4)	0.05857 (18)	0.24324 (14)	0.0250 (6)
H15	0.3646	0.0748	0.2894	0.030*
Zn1	1.00853 (5)	0.102577 (17)	0.169795 (13)	0.02690 (10)
C12	1.0062 (5)	0.22189 (16)	0.05463 (11)	0.0271 (5)
O5W	1.0162 (4)	0.30592 (14)	0.32821 (11)	0.0563 (6)
N2	1.0235 (4)	0.06704 (14)	0.06729 (11)	0.0314 (5)
N1	1.0013 (4)	0.22682 (12)	0.12231 (9)	0.0275 (4)
C4	1.0048 (5)	0.29597 (17)	0.01369 (13)	0.0338 (6)
C11	1.0136 (5)	0.13644 (17)	0.02535 (12)	0.0287 (5)
O1	0.8915 (3)	0.14883 (13)	0.25782 (9)	0.0361 (5)
O2	0.6953 (3)	0.05600 (11)	0.17118 (9)	0.0304 (4)
C5	1.0043 (5)	0.2840 (2)	−0.05749 (13)	0.0422 (7)
H5	1.0039	0.3328	−0.0851	0.051*
C1	0.9968 (5)	0.30549 (16)	0.14973 (13)	0.0353 (6)
H1	0.9926	0.3097	0.1959	0.042*
C3	1.0025 (5)	0.37765 (18)	0.04495 (16)	0.0431 (7)
H3	1.0040	0.4286	0.0197	0.052*
C6	1.0043 (6)	0.2046 (2)	−0.08455 (13)	0.0466 (7)
H6	0.9991	0.1992	−0.1306	0.056*
C14	0.6229 (4)	0.04665 (19)	0.23801 (14)	0.0265 (6)
H14	0.6551	−0.0127	0.2529	0.032*
C2	0.9980 (5)	0.38216 (16)	0.11246 (16)	0.0425 (7)
H2	0.9957	0.4362	0.1337	0.051*
C7	1.0121 (5)	0.12713 (19)	−0.04425 (13)	0.0367 (6)
C8	1.0180 (6)	0.0416 (2)	−0.06949 (15)	0.0472 (8)
H8	1.0127	0.0323	−0.1152	0.057*
O4W	0.6195 (4)	0.77423 (16)	0.23686 (14)	0.0661 (8)
C9	1.0313 (5)	−0.0270 (2)	−0.02751 (17)	0.0488 (9)
H9	1.0393	−0.0836	−0.0443	0.059*
O6	0.3450 (3)	−0.09500 (13)	0.24989 (13)	0.0541 (6)
O6W	0.9593 (4)	0.09008 (17)	0.44919 (13)	0.0668 (8)
O5	0.6820 (3)	0.11830 (13)	0.34059 (9)	0.0421 (5)
C13	0.7393 (4)	0.11022 (17)	0.28205 (13)	0.0284 (6)
O2W	0.5435 (5)	0.93830 (16)	0.08799 (12)	0.0691 (9)
C10	1.0329 (5)	−0.0129 (2)	0.04130 (16)	0.0433 (8)
H10	1.0407	−0.0607	0.0697	0.052*
O3W	0.4092 (5)	0.76383 (18)	0.08031 (13)	0.0717 (9)
O1W	0.8120 (4)	0.74506 (16)	0.05396 (12)	0.0688 (8)
H2A	0.5009	0.8888	0.1012	0.103*
H4A	0.7053	0.7907	0.2081	0.103*
H4B	0.5115	0.8013	0.2270	0.103*
H6B	0.8707	0.0962	0.4190	0.103*
H6A	0.9938	0.1431	0.4439	0.103*
H5A	0.9930	0.3578	0.3153	0.103*
H2B	0.5516	0.9338	0.0459	0.103*
H5B	0.9921	0.2536	0.3163	0.103*
H1A	0.8804	0.7738	0.0823	0.103*
H1B	0.6869	0.7508	0.0620	0.103*
H3B	0.3756	0.7608	0.0396	0.103*
H3A	0.3169	0.7389	0.1028	0.103*
H21	0.6634	0.0119	0.1475	0.103*
H22	0.3426	0.1744	0.2228	0.103*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0324 (12)	0.0319 (10)	0.0456 (12)	−0.0066 (8)	−0.0060 (10)	0.0044 (9)
C16	0.0262 (16)	0.0296 (14)	0.0336 (15)	−0.0017 (11)	0.0054 (12)	0.0052 (12)
O4	0.0266 (10)	0.0255 (9)	0.0330 (10)	0.0005 (8)	−0.0037 (8)	0.0036 (8)
C15	0.0249 (15)	0.0290 (13)	0.0211 (15)	−0.0003 (11)	0.0004 (12)	0.0035 (12)
Zn1	0.02568 (16)	0.03218 (15)	0.02283 (15)	0.00036 (16)	0.00039 (16)	0.00170 (11)
C12	0.0165 (12)	0.0402 (12)	0.0246 (12)	0.0009 (15)	−0.0026 (14)	0.0047 (10)
O5W	0.0625 (16)	0.0543 (12)	0.0520 (13)	0.0103 (13)	−0.0063 (17)	0.0013 (10)
N2	0.0297 (14)	0.0366 (11)	0.0279 (11)	−0.0001 (11)	0.0019 (12)	−0.0022 (9)
N1	0.0238 (11)	0.0356 (10)	0.0230 (10)	0.0007 (12)	0.0002 (12)	0.0012 (8)
C4	0.0178 (13)	0.0480 (14)	0.0355 (14)	0.0030 (16)	−0.0017 (16)	0.0086 (11)
C11	0.0167 (13)	0.0449 (13)	0.0247 (12)	−0.0039 (14)	−0.0001 (13)	−0.0012 (10)
O1	0.0322 (12)	0.0496 (12)	0.0263 (10)	−0.0117 (9)	0.0021 (9)	−0.0066 (9)
O2	0.0253 (10)	0.0444 (10)	0.0215 (10)	−0.0036 (8)	0.0049 (8)	−0.0063 (8)
C5	0.0266 (15)	0.0682 (19)	0.0317 (14)	−0.0002 (19)	−0.0007 (16)	0.0209 (13)
C1	0.0337 (15)	0.0380 (13)	0.0341 (13)	0.0063 (15)	−0.0014 (15)	−0.0038 (11)
C3	0.0305 (15)	0.0443 (15)	0.0545 (18)	0.0027 (17)	0.0012 (18)	0.0182 (13)
C6	0.0348 (17)	0.085 (2)	0.0199 (13)	−0.004 (2)	−0.0027 (17)	0.0078 (14)
C14	0.0231 (16)	0.0336 (14)	0.0229 (14)	0.0021 (11)	0.0023 (12)	0.0053 (12)
C2	0.0375 (16)	0.0327 (13)	0.0572 (19)	0.0038 (17)	−0.0030 (18)	−0.0016 (12)
C7	0.0215 (14)	0.0637 (17)	0.0250 (13)	−0.0066 (16)	−0.0028 (14)	−0.0034 (12)
C8	0.0355 (18)	0.075 (2)	0.0308 (15)	−0.006 (2)	−0.0018 (17)	−0.0196 (14)
O4W	0.0657 (18)	0.0476 (14)	0.0849 (19)	0.0199 (12)	0.0118 (15)	0.0257 (13)
C9	0.040 (2)	0.0525 (17)	0.054 (2)	−0.0013 (16)	−0.0003 (17)	−0.0231 (15)
O6	0.0400 (13)	0.0317 (11)	0.0906 (18)	0.0011 (10)	0.0008 (12)	0.0195 (12)
O6W	0.079 (2)	0.0599 (14)	0.0614 (16)	−0.0124 (15)	−0.0221 (14)	0.0128 (12)
O5	0.0411 (12)	0.0659 (14)	0.0193 (10)	−0.0092 (10)	0.0030 (9)	−0.0049 (9)
C13	0.0284 (15)	0.0348 (13)	0.0220 (14)	0.0016 (12)	−0.0018 (11)	−0.0002 (12)
O2W	0.099 (3)	0.0630 (14)	0.0455 (14)	−0.0279 (15)	0.0035 (15)	−0.0172 (11)
C10	0.042 (2)	0.0426 (15)	0.0450 (17)	−0.0001 (15)	0.0033 (16)	−0.0089 (13)
O3W	0.096 (2)	0.0713 (18)	0.0477 (15)	−0.0241 (15)	0.0004 (14)	0.0072 (13)
O1W	0.0779 (19)	0.0765 (17)	0.0521 (15)	0.0169 (15)	−0.0096 (14)	−0.0161 (13)

Geometric parameters (Å, º) top

O3—C16	1.260 (3)	C5—C6	1.331 (4)
O3—Zn1ⁱ	2.046 (2)	C5—H5	0.9300
C16—O6	1.235 (3)	C1—C2	1.392 (4)
C16—C15	1.534 (4)	C1—H1	0.9300
O4—C15	1.414 (3)	C3—C2	1.358 (4)
O4—Zn1ⁱ	2.1952 (19)	C3—H3	0.9300
O4—H22	0.8525	C6—C7	1.437 (4)
C15—C14	1.533 (4)	C6—H6	0.9300
C15—H15	0.9800	C14—C13	1.524 (4)
Zn1—O3ⁱⁱ	2.046 (2)	C14—H14	0.9800
Zn1—O1	2.0567 (19)	C2—H2	0.9300
Zn1—N1	2.1274 (19)	C7—C8	1.403 (4)
Zn1—N2	2.132 (2)	C8—C9	1.350 (5)
Zn1—O4ⁱⁱ	2.1952 (19)	C8—H8	0.9300
Zn1—O2	2.1966 (19)	O4W—H4A	0.8490
C12—N1	1.362 (3)	O4W—H4B	0.8507
C12—C4	1.400 (3)	C9—C10	1.399 (4)
C12—C11	1.434 (4)	C9—H9	0.9300
O5W—H5A	0.8493	O6W—H6B	0.8495
O5W—H5B	0.8502	O6W—H6A	0.8494
N2—C10	1.331 (4)	O5—C13	1.242 (3)
N2—C11	1.357 (3)	O2W—H2A	0.8511
N1—C1	1.324 (3)	O2W—H2B	0.8494
C4—C3	1.399 (4)	C10—H10	0.9300
C4—C5	1.442 (4)	O3W—H3B	0.8496
C11—C7	1.406 (4)	O3W—H3A	0.8513
O1—C13	1.267 (3)	O1W—H1A	0.8500
O2—C14	1.433 (3)	O1W—H1B	0.8500
O2—H21	0.8519

C16—O3—Zn1ⁱ	120.39 (17)	C14—O2—Zn1	111.16 (15)
O6—C16—O3	124.6 (3)	C14—O2—H21	111.1
O6—C16—C15	117.8 (3)	Zn1—O2—H21	119.0
O3—C16—C15	117.3 (2)	C6—C5—C4	121.4 (2)
C15—O4—Zn1ⁱ	112.24 (15)	C6—C5—H5	119.3
C15—O4—H22	106.9	C4—C5—H5	119.3
Zn1ⁱ—O4—H22	117.1	N1—C1—C2	122.8 (2)
O4—C15—C14	113.2 (2)	N1—C1—H1	118.6
O4—C15—C16	109.1 (2)	C2—C1—H1	118.6
C14—C15—C16	113.1 (2)	C2—C3—C4	119.6 (2)
O4—C15—H15	107.0	C2—C3—H3	120.2
C14—C15—H15	107.0	C4—C3—H3	120.2
C16—C15—H15	107.0	C5—C6—C7	121.5 (2)
O3ⁱⁱ—Zn1—O1	99.98 (9)	C5—C6—H6	119.2
O3ⁱⁱ—Zn1—N1	160.80 (9)	C7—C6—H6	119.2
O1—Zn1—N1	93.98 (8)	O2—C14—C13	108.1 (2)
O3ⁱⁱ—Zn1—N2	92.56 (9)	O2—C14—C15	112.6 (2)
O1—Zn1—N2	159.34 (9)	C13—C14—C15	112.7 (2)
N1—Zn1—N2	78.22 (8)	O2—C14—H14	107.8
O3ⁱⁱ—Zn1—O4ⁱⁱ	76.09 (7)	C13—C14—H14	107.8
O1—Zn1—O4ⁱⁱ	92.31 (8)	C15—C14—H14	107.8
N1—Zn1—O4ⁱⁱ	90.32 (8)	C3—C2—C1	119.6 (2)
N2—Zn1—O4ⁱⁱ	106.70 (9)	C3—C2—H2	120.2
O3ⁱⁱ—Zn1—O2	90.46 (8)	C1—C2—H2	120.2
O1—Zn1—O2	75.15 (7)	C11—C7—C8	117.0 (3)
N1—Zn1—O2	105.92 (9)	C11—C7—C6	118.5 (3)
N2—Zn1—O2	88.49 (8)	C8—C7—C6	124.5 (3)
O4ⁱⁱ—Zn1—O2	159.91 (7)	C9—C8—C7	120.1 (3)
N1—C12—C4	122.8 (2)	C9—C8—H8	119.9
N1—C12—C11	117.4 (2)	C7—C8—H8	119.9
C4—C12—C11	119.8 (2)	H4A—O4W—H4B	105.1
H5A—O5W—H5B	139.5	C8—C9—C10	119.8 (3)
C10—N2—C11	118.5 (2)	C8—C9—H9	120.1
C10—N2—Zn1	128.0 (2)	C10—C9—H9	120.1
C11—N2—Zn1	113.43 (16)	H6B—O6W—H6A	89.5
C1—N1—C12	117.8 (2)	O5—C13—O1	124.1 (2)
C1—N1—Zn1	128.78 (17)	O5—C13—C14	117.3 (2)
C12—N1—Zn1	113.42 (15)	O1—C13—C14	118.6 (2)
C3—C4—C12	117.4 (2)	H2A—O2W—H2B	105.1
C3—C4—C5	124.0 (2)	N2—C10—C9	122.0 (3)
C12—C4—C5	118.7 (2)	N2—C10—H10	119.0
N2—C11—C7	122.6 (2)	C9—C10—H10	119.0
N2—C11—C12	117.4 (2)	H3B—O3W—H3A	107.4
C7—C11—C12	120.0 (2)	H1A—O1W—H1B	109.9
C13—O1—Zn1	118.07 (17)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O5Wⁱⁱⁱ	0.85	1.99	2.787 (3)	157
O2W—H2A···O3W	0.85	2.05	2.819 (4)	150
O2W—H2B···O6W^iv	0.85	1.98	2.822 (4)	172
O3W—H3A···O5^v	0.85	2.17	2.802 (3)	131
O3W—H3B···O1W^vi	0.85	1.93	2.776 (4)	177
O4W—H4A···O5Wⁱⁱⁱ	0.85	2.00	2.789 (4)	154
O4W—H4B···O6^vii	0.85	1.99	2.718 (3)	143
O5W—H5A···O3^v	0.85	2.04	2.880 (3)	168
O5W—H5B···O1	0.85	2.10	2.909 (3)	160
O6W—H6A···O1W^viii	0.85	2.02	2.816 (4)	155
O6W—H6B···O5	0.85	2.04	2.886 (3)	174
O2—H21···O2W^ix	0.85	1.82	2.655 (3)	164
O4—H22···O4W^x	0.85	1.75	2.599 (3)	178

Symmetry codes: (iii) −x+2, y+1/2, −z+1/2; (iv) −x+3/2, −y+1, z−1/2; (v) −x+1, y+1/2, −z+1/2; (vi) x−1/2, −y+3/2, −z; (vii) x, y+1, z; (viii) −x+2, y−1/2, −z+1/2; (ix) x, y−1, z; (x) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Zn(C₄H₄O₆)(C₁₂H₈N₂)]·6H₂O
M_r	501.76
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	295
a, b, c (Å)	6.632 (2), 15.301 (4), 20.087 (5)
V (Å³)	2038.4 (10)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.27
Crystal size (mm)	0.25 × 0.18 × 0.16

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.754, 0.844
No. of measured, independent and observed [I > 2σ(I)] reflections	16280, 3541, 3251
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.027, 0.071, 0.96
No. of reflections	3541
No. of parameters	280
No. of restraints	3
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.32, −0.29
Absolute structure	Flack (1983), 1456 Friedel pairs
Absolute structure parameter	0.025 (12)

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O5Wⁱ	0.85	1.99	2.787 (3)	157
O2W—H2A···O3W	0.85	2.05	2.819 (4)	150
O2W—H2B···O6Wⁱⁱ	0.85	1.98	2.822 (4)	172
O3W—H3A···O5ⁱⁱⁱ	0.85	2.17	2.802 (3)	131
O3W—H3B···O1W^iv	0.85	1.93	2.776 (4)	177
O4W—H4A···O5Wⁱ	0.85	2.00	2.789 (4)	154
O4W—H4B···O6^v	0.85	1.99	2.718 (3)	143
O5W—H5A···O3ⁱⁱⁱ	0.85	2.04	2.880 (3)	168
O5W—H5B···O1	0.85	2.10	2.909 (3)	160
O6W—H6A···O1W^vi	0.85	2.02	2.816 (4)	155
O6W—H6B···O5	0.85	2.04	2.886 (3)	174
O2—H21···O2W^vii	0.85	1.82	2.655 (3)	164
O4—H22···O4W^viii	0.85	1.75	2.599 (3)	178

Symmetry codes: (i) −x+2, y+1/2, −z+1/2; (ii) −x+3/2, −y+1, z−1/2; (iii) −x+1, y+1/2, −z+1/2; (iv) x−1/2, −y+3/2, −z; (v) x, y+1, z; (vi) −x+2, y−1/2, −z+1/2; (vii) x, y−1, z; (viii) −x+1, y−1/2, −z+1/2.

Acknowledgements

The authors thank Hebei United University for supporting this work.

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