Poly[[(μ-benzene-1,4-dicarboxyl­ato)bis­[μ-4-(1H-1,3,7,8-tetra­aza­cyclo­penta­[l]phenanthren-2-yl)benzoato]dizinc] tetra­hydrate]

Wang, C.-J.; Wang, Q.-Q.; Xu, X.-J.; Liu, C.-B.; Che, G.-B.

doi:10.1107/S1600536811040062

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Pages m1493-m1494

doi:10.1107/S1600536811040062

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Poly[[(μ-benzene-1,4-dicarboxylato)bis[μ-4-(1H-1,3,7,8-tetraazacyclopenta[l]phenanthren-2-yl)benzoato]dizinc] tetrahydrate]

Chun-Jie Wang,^a Qian-Qian Wang,^a Xiang-Jun Xu,^a Chun-Bo Liu ^a ^* and Guang-Bo Che ^a ^*

^aSchool of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, People's Republic of China
^*Correspondence e-mail: , guangbochejl@yahoo.com

(Received 14 September 2011; accepted 29 September 2011; online 5 October 2011)

In the title complex, [Zn₂(C₈H₄O₄)(C₂₀H₁₁N₄O₂)₂]·4H₂O, the Zn^II atom is six-coordinated by two carboxylate O atoms from one bidentate benzene-1,4-dicarboxylate (1,4-BDC) ligand, two carboxylate O atoms from two different monodentate 4-(1H-1,3,7,8-tetraazacyclopenta[l]phenanthren-2-yl)benzoate (HNCP) ligands and two HNCP N atoms. The Zn^II atoms are bridged by the centrosymmetric 1,4-BDC ligands, forming an extended single-chain structure. Neighbouring single chains are connected by the HNCP ligands from two opposite directions, resulting in a sheet. In addition, there are N—H⋯O hydrogen-bonding interactions between adjacent layers. As a result, the polymeric sheets are further extended into a three-dimensional supramolecular structure.

Related literature

For the preparation of the 4-(1H-1,3,7,8-tetraazacyclopenta[l]phenanthren-2-yl)benzoate (HNCP) ligand, see: Yongqin et al. (2007 ). For coordination polymers with a variety of supramolecular structures, see: Eddaoudi et al. (2001 ); Chen & Liu (2002 ). For HNCP-based complexes, see Yongqin et al. (2007); Hsu et al. (2005 ).

Experimental

Crystal data

[Zn₂(C₈H₄O₄)(C₂₀H₁₁N₄O₂)₂]·4H₂O
M_r = 1037.54
Triclinic, $[P \overline 1]$
a = 9.7477 (16) Å
b = 10.2610 (18) Å
c = 11.0480 (19) Å
α = 88.849 (3)°
β = 72.115 (4)°
γ = 83.121 (3)°
V = 1043.9 (3) Å³
Z = 1
Mo Kα radiation
μ = 1.23 mm⁻¹
T = 293 K
0.2 × 0.2 × 0.2 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ) T_min = 0.782, T_max = 0.782
5406 measured reflections
3783 independent reflections
2797 reflections with I > 2σ(I)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.139
S = 1.02
3783 reflections
316 parameters
H-atom parameters constrained
Δρ_max = 0.94 e Å⁻³
Δρ_min = −0.66 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H4⋯O3ⁱ	0.86	2.10	2.781 (5)	136
Symmetry code: (i) -x+1, -y, -z+1.

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); 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 global, I. DOI: 10.1107/S1600536811040062/bg2420sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811040062/bg2420Isup2.hkl

checkCIF report

Comment top

Coordination polymers with a variety of supramolecular structures have been studied extensively because of their novel topologies and potential applications as functional materials (Eddaoudi et al., 2001). 1,10-Phenanthroline (phen), as a common organic ligand, has been widely used in the construction of metal-organic coordination polymers (Chen & Liu, 2002). The phen derivative 4-(1H-1, 3, 7, 8-Tetraaza-cyclopenta [l]phenanthren-2-yl)-benzoic acid (HNCP) with both phenanthroline ring and carboxylate groups, is a good building block for construction of coordination polymers. Moreover, the long-conjugated system and the carboxylate groups are inclined to form π-π stacking interactions and hydrogen bonding interactions, which are important factors in the formation of supramolecular architectures. However, to date, only a handful of supramolecular architectures based on HNCP molecules have been described (Yongqin et al., 2007; Hsu et al., 2005). We selected benzene-1,4-dicarboxylic acid (1,4-BDC) as a linker and HNCP as a secondary ligand, generating a new coordination polymer, [Zn₂(1,4-BDC)_(NCP)2_(H2_O)4] (I), which is reported here.

In compound (I), the Zn atom is coordinated by two N atoms from one HNCP ligand, two O atoms from one 1,4-BDC ligand, and two O atoms from two different HNCP ligands in a distorted octahedral coordination (Fig. 1). The single unique 1,4-BDC species is generated from the atoms of the asymmetric unit by inversion. Two Zn^II centers are bridged by the carboxylate groups of HNCP ligands to furnish a binuclear unit with a Zn^II···Zn^II distance of 3.2224 (9) Å. Neighbouring binuclear units are bridged by 1,4-BDC ligands, forming a single-chain structure. The neighboring single chains constructed by the 1,4-BDC ligand and the Zn^II atoms are connected by the HNCP ligands from two opposite directions and result in a two-dimensional sheet (Fig. 2).

Even though the H atoms pertaining to water molecules could not be confidently found, and accordingly were not included in the model, the short O1···O2Wⁱ 2.891 (9)Å; O1W···O2Wⁱⁱ 2.886 (14)Å; O1W···N4: 2.899 (10)Å distances, (i): x, -1+y, -1+z; (ii): 1-x,-y,1-z might indicate the formation of hydrogen bonds between these atoms.

Besides, there are hydrogen bonding interactions between adjacent layers. The imidazole nitrogen atoms of HNCP ligands act as hydrogen bond donors, while the carboxylate oxygen atoms of 1,4-BDC ligands from the neighboring layer act as hydrogen bond acceptors (N3—H···O3) (Table 1). As a result, these two-dimensional polymeric sheets are further extended into three-dimensional supramolecular structures through these hydrogen-bonding interactions(Fig. 3).

Related literature top

For the preparation of the 4-(1H-1,3,7,8-tetraazacyclopenta[l]phenanthren-2-yl)benzoate (HNCP) ligand, see: Yongqin et al. (2007). For coordination polymers with a variety of supramolecular structures, see: Eddaoudi et al. (2001); Chen & Liu (2002). For HNCP-based complexes, see Yongqin et al. (2007); Hsu et al.(2005).

Experimental top

HNCP was prepared according to the literature method (Yongqin et al., 2007). Other reagents were commercially available and used without further purification. Zn(CH₃COO)2 (0.2 mmol), 1,4-BDC (0.1 mmol), and HNCP (0.1 mmol) were mixed in 10 ml deionized water. And its pH value was controlled in the range of 7–8 with 1 mol/L NaOH solution. Then, the resulting precursor was placed in 25 ml Teflon-lined stainless steel reactor, and heated at 433 K for 3 d. Cooling slowly to room temperature, the yellow block crystals of the title complex suitable for X-ray diffraction analysis were obtained.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); 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. The asymmetric unit of (I), together with further atoms to complete the Zn1 coordination and the 1,4-BDC ligand. Displacement ellipsoids are drawn at the 30% probability level. (arbitrary spheres for the H atoms). Atoms O2A, O2B and C21A/C22A/C23A/C24A/O3A/O4A are generated by the symmetry code (x, -y + 1, -z + 1), (-x + 1, -y, -z) and (-x, -y + 1, -z + 2), respectively.
	Fig. 2. View of the two-dimensional sheet formed by HNCP linked linear chain. H atoms have been omitted.
	Fig. 3. A view of the three-dimensional structure of 1 linked by hydrogen bonds between the adjacent sheets. H atoms have been omitted.

Poly[[(µ-benzene-1,4-dicarboxylato)bis[µ-4-(1H-1,3,7,8- tetraazacyclopenta[l]phenanthren-2-yl)benzoato]dizinc] tetrahydrate] top

Crystal data top

[Zn₂(C₈H₄O₄)(C₂₀H₁₁N₄O₂)₂]·4H₂O	Z = 1
M_r = 1037.54	F(000) = 526
Triclinic, P1	D_x = 1.651 Mg m⁻³ D_m = 1.651 Mg m⁻³ D_m measured by not measured
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.7477 (16) Å	Cell parameters from 5729 reflections
b = 10.2610 (18) Å	θ = 2.9–25.3°
c = 11.0480 (19) Å	µ = 1.23 mm⁻¹
α = 88.849 (3)°	T = 293 K
β = 72.115 (4)°	Block, yellow
γ = 83.121 (3)°	0.2 × 0.2 × 0.2 mm
V = 1043.9 (3) Å³

Data collection top

Bruker SMART CCD area-detector diffractometer	3783 independent reflections
Radiation source: fine-focus sealed tube	2797 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.029
ω scans	θ_max = 25.3°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −11→10
T_min = 0.782, T_max = 0.782	k = −12→11
5406 measured reflections	l = −10→13

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.139	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0678P)² + 0.7102P] where P = (F_o² + 2F_c²)/3
3783 reflections	(Δ/σ)_max < 0.001
316 parameters	Δρ_max = 0.94 e Å⁻³
0 restraints	Δρ_min = −0.66 e Å⁻³

Crystal data top

[Zn₂(C₈H₄O₄)(C₂₀H₁₁N₄O₂)₂]·4H₂O	γ = 83.121 (3)°
M_r = 1037.54	V = 1043.9 (3) Å³
Triclinic, P1	Z = 1
a = 9.7477 (16) Å	Mo Kα radiation
b = 10.2610 (18) Å	µ = 1.23 mm⁻¹
c = 11.0480 (19) Å	T = 293 K
α = 88.849 (3)°	0.2 × 0.2 × 0.2 mm
β = 72.115 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3783 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2002)	2797 reflections with I > 2σ(I)
T_min = 0.782, T_max = 0.782	R_int = 0.029
5406 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	0 restraints
wR(F²) = 0.139	H-atom parameters constrained
S = 1.02	Δρ_max = 0.94 e Å⁻³
3783 reflections	Δρ_min = −0.66 e Å⁻³
316 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 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.

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

	x	y	z	U_iso*/U_eq
Zn1	0.39808 (6)	0.38395 (5)	0.54113 (5)	0.0246 (2)
C1	0.6671 (5)	0.1755 (5)	0.4727 (5)	0.0305 (12)
H1	0.7021	0.2253	0.5235	0.037*
C2	0.7546 (5)	0.0643 (5)	0.4098 (5)	0.0318 (12)
H2	0.8454	0.0403	0.4200	0.038*
C3	0.7059 (5)	−0.0093 (5)	0.3327 (5)	0.0304 (12)
H3	0.7632	−0.0835	0.2900	0.036*
C4	0.5686 (5)	0.0291 (4)	0.3194 (4)	0.0212 (10)
C5	0.5041 (5)	−0.0321 (4)	0.2395 (4)	0.0237 (11)
C6	0.3733 (5)	0.0143 (4)	0.2210 (5)	0.0252 (11)
C7	0.2859 (5)	0.1260 (5)	0.2933 (5)	0.0253 (11)
C8	0.1468 (5)	0.1777 (5)	0.2890 (5)	0.0333 (12)
H8	0.1048	0.1402	0.2352	0.040*
C9	0.0745 (6)	0.2835 (5)	0.3647 (5)	0.0380 (14)
H9	−0.0181	0.3176	0.3641	0.046*
C10	0.1403 (5)	0.3396 (5)	0.4423 (5)	0.0333 (13)
H10	0.0903	0.4124	0.4924	0.040*
C11	0.3431 (5)	0.1878 (4)	0.3759 (4)	0.0232 (10)
C12	0.4856 (5)	0.1422 (4)	0.3874 (4)	0.0208 (10)
C13	0.4616 (5)	−0.1529 (4)	0.0957 (5)	0.0243 (11)
C14	0.4894 (5)	−0.2566 (4)	−0.0019 (5)	0.0255 (11)
C15	0.6139 (5)	−0.3454 (5)	−0.0274 (5)	0.0299 (12)
H15	0.6767	−0.3415	0.0207	0.036*
C16	0.6468 (5)	−0.4398 (5)	−0.1230 (5)	0.0298 (12)
H16	0.7298	−0.4998	−0.1371	0.036*
C17	0.5563 (5)	−0.4452 (4)	−0.1980 (4)	0.0246 (11)
C18	0.4302 (5)	−0.3563 (4)	−0.1718 (4)	0.0251 (11)
H18	0.3680	−0.3587	−0.2206	0.030*
C19	0.3971 (5)	−0.2648 (5)	−0.0741 (5)	0.0271 (11)
H19	0.3114	−0.2079	−0.0566	0.033*
C20	0.5974 (6)	−0.5445 (5)	−0.3046 (5)	0.0296 (12)
C21	−0.0493 (5)	0.4022 (5)	1.0852 (5)	0.0307 (12)
H23	−0.0820	0.3366	1.1424	0.037*
C22	0.0434 (5)	0.3690 (5)	0.9641 (5)	0.0315 (12)
H22	0.0721	0.2812	0.9401	0.038*
C23	0.0935 (5)	0.4665 (5)	0.8785 (5)	0.0291 (12)
C24	0.1997 (5)	0.4312 (5)	0.7506 (5)	0.0261 (11)
N1	0.5364 (4)	0.2129 (4)	0.4629 (4)	0.0230 (9)
N2	0.2706 (4)	0.2945 (4)	0.4484 (4)	0.0248 (9)
N3	0.5581 (4)	−0.1389 (4)	0.1592 (4)	0.0242 (9)
H4	0.6385	−0.1880	0.1506	0.029*
N4	0.3485 (4)	−0.0610 (4)	0.1302 (4)	0.0256 (9)
O1	0.6824 (5)	−0.6414 (4)	−0.3044 (4)	0.0562 (12)
O2	0.5370 (4)	−0.5184 (3)	−0.3944 (3)	0.0269 (8)
O3	0.2806 (4)	0.3234 (3)	0.7355 (3)	0.0326 (8)
O4	0.2120 (4)	0.5109 (3)	0.6606 (3)	0.0333 (8)
O1W	0.0693 (8)	−0.0278 (10)	0.0842 (10)	0.193 (5)
O2W	0.9457 (7)	0.2012 (9)	0.7044 (9)	0.165 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Zn1	0.0281 (3)	0.0233 (3)	0.0200 (3)	−0.0011 (2)	−0.0043 (2)	−0.0080 (2)
C1	0.030 (3)	0.034 (3)	0.028 (3)	0.000 (2)	−0.011 (2)	−0.012 (2)
C2	0.023 (3)	0.038 (3)	0.038 (3)	0.001 (2)	−0.015 (2)	−0.011 (2)
C3	0.032 (3)	0.026 (3)	0.033 (3)	0.005 (2)	−0.013 (2)	−0.008 (2)
C4	0.027 (2)	0.017 (2)	0.019 (2)	−0.0010 (19)	−0.007 (2)	−0.0037 (19)
C5	0.029 (3)	0.022 (2)	0.019 (3)	0.002 (2)	−0.009 (2)	−0.008 (2)
C6	0.032 (3)	0.025 (3)	0.020 (3)	−0.006 (2)	−0.009 (2)	−0.003 (2)
C7	0.030 (3)	0.025 (2)	0.022 (3)	0.001 (2)	−0.011 (2)	−0.003 (2)
C8	0.032 (3)	0.031 (3)	0.040 (3)	0.002 (2)	−0.018 (3)	−0.009 (2)
C9	0.033 (3)	0.036 (3)	0.046 (4)	0.011 (2)	−0.019 (3)	−0.011 (3)
C10	0.028 (3)	0.030 (3)	0.037 (3)	0.009 (2)	−0.007 (2)	−0.010 (2)
C11	0.024 (2)	0.027 (3)	0.017 (3)	−0.004 (2)	−0.004 (2)	−0.001 (2)
C12	0.024 (2)	0.018 (2)	0.017 (2)	−0.0006 (19)	−0.003 (2)	−0.0024 (19)
C13	0.028 (3)	0.024 (3)	0.023 (3)	−0.001 (2)	−0.011 (2)	−0.001 (2)
C14	0.033 (3)	0.022 (2)	0.021 (3)	−0.004 (2)	−0.007 (2)	−0.003 (2)
C15	0.039 (3)	0.028 (3)	0.027 (3)	0.003 (2)	−0.019 (2)	−0.011 (2)
C16	0.034 (3)	0.025 (3)	0.033 (3)	0.003 (2)	−0.016 (2)	−0.005 (2)
C17	0.039 (3)	0.019 (2)	0.018 (3)	−0.004 (2)	−0.011 (2)	−0.0010 (19)
C18	0.033 (3)	0.025 (3)	0.021 (3)	−0.008 (2)	−0.012 (2)	0.001 (2)
C19	0.028 (3)	0.028 (3)	0.025 (3)	0.001 (2)	−0.008 (2)	−0.004 (2)
C20	0.036 (3)	0.024 (3)	0.029 (3)	0.000 (2)	−0.012 (2)	−0.004 (2)
C21	0.029 (3)	0.032 (3)	0.026 (3)	0.002 (2)	−0.003 (2)	0.001 (2)
C22	0.029 (3)	0.033 (3)	0.027 (3)	0.002 (2)	−0.002 (2)	−0.009 (2)
C23	0.025 (3)	0.038 (3)	0.022 (3)	0.002 (2)	−0.004 (2)	−0.010 (2)
C24	0.022 (2)	0.032 (3)	0.024 (3)	0.000 (2)	−0.008 (2)	−0.009 (2)
N1	0.026 (2)	0.022 (2)	0.022 (2)	−0.0031 (17)	−0.0075 (18)	−0.0031 (17)
N2	0.030 (2)	0.020 (2)	0.023 (2)	0.0034 (17)	−0.0070 (18)	−0.0079 (17)
N3	0.024 (2)	0.025 (2)	0.024 (2)	0.0051 (17)	−0.0101 (18)	−0.0102 (17)
N4	0.029 (2)	0.025 (2)	0.024 (2)	0.0014 (17)	−0.0113 (18)	−0.0052 (17)
O1	0.084 (3)	0.042 (2)	0.048 (3)	0.023 (2)	−0.038 (2)	−0.021 (2)
O2	0.0374 (19)	0.0286 (18)	0.0185 (18)	−0.0098 (15)	−0.0122 (16)	−0.0003 (14)
O3	0.0286 (18)	0.037 (2)	0.026 (2)	0.0072 (16)	−0.0025 (16)	−0.0083 (16)
O4	0.034 (2)	0.038 (2)	0.022 (2)	0.0040 (16)	−0.0042 (16)	−0.0012 (16)
O1W	0.133 (6)	0.237 (10)	0.239 (11)	0.082 (6)	−0.129 (7)	−0.141 (9)
O2W	0.077 (5)	0.214 (9)	0.183 (9)	0.004 (5)	−0.022 (5)	0.052 (7)

Geometric parameters (Å, º) top

Zn1—O2ⁱ	2.071 (3)	C13—N4	1.326 (6)
Zn1—O2ⁱⁱ	2.102 (3)	C13—N3	1.356 (6)
Zn1—N1	2.103 (4)	C13—C14	1.472 (6)
Zn1—N2	2.128 (4)	C14—C19	1.384 (7)
Zn1—O4	2.182 (3)	C14—C15	1.385 (6)
Zn1—O3	2.217 (4)	C15—C16	1.384 (7)
Zn1—C24	2.530 (5)	C15—H15	0.9300
C1—N1	1.322 (6)	C16—C17	1.390 (7)
C1—C2	1.396 (7)	C16—H16	0.9300
C1—H1	0.9300	C17—C18	1.396 (6)
C2—C3	1.371 (7)	C17—C20	1.499 (6)
C2—H2	0.9300	C18—C19	1.380 (6)
C3—C4	1.400 (6)	C18—H18	0.9300
C3—H3	0.9300	C19—H19	0.9300
C4—C12	1.415 (6)	C20—O1	1.216 (6)
C4—C5	1.424 (6)	C20—O2	1.310 (6)
C5—N3	1.370 (5)	C21—C22	1.388 (7)
C5—C6	1.379 (6)	C21—C23ⁱⁱⁱ	1.392 (7)
C6—N4	1.374 (6)	C21—H23	0.9300
C6—C7	1.436 (6)	C22—C23	1.388 (7)
C7—C11	1.403 (6)	C22—H22	0.9300
C7—C8	1.410 (6)	C23—C21ⁱⁱⁱ	1.392 (7)
C8—C9	1.366 (7)	C23—C24	1.494 (7)
C8—H8	0.9300	C24—O4	1.260 (6)
C9—C10	1.388 (7)	C24—O3	1.261 (5)
C9—H9	0.9300	N3—H4	0.8600
C10—N2	1.320 (6)	O2—Zn1^iv	2.071 (3)
C10—H10	0.9300	O2—Zn1ⁱⁱ	2.102 (3)
C11—N2	1.358 (6)	O1—O2W^iv	2.891 (9)
C11—C12	1.455 (6)	O1W—O2W^v	2.886 (14)
C12—N1	1.352 (6)	O1W—N4	2.899 (10)

O2ⁱ—Zn1—O2ⁱⁱ	78.91 (13)	C4—C12—C11	120.6 (4)
O2ⁱ—Zn1—N1	100.31 (14)	N4—C13—N3	111.6 (4)
O2ⁱⁱ—Zn1—N1	101.54 (14)	N4—C13—C14	127.0 (4)
O2ⁱ—Zn1—N2	171.64 (14)	N3—C13—C14	121.4 (4)
O2ⁱⁱ—Zn1—N2	93.17 (14)	C19—C14—C15	118.3 (4)
N1—Zn1—N2	78.50 (14)	C19—C14—C13	121.7 (4)
O2ⁱ—Zn1—O4	90.24 (13)	C15—C14—C13	120.0 (4)
O2ⁱⁱ—Zn1—O4	96.74 (13)	C16—C15—C14	121.4 (5)
N1—Zn1—O4	160.32 (14)	C16—C15—H15	119.3
N2—Zn1—O4	93.37 (14)	C14—C15—H15	119.3
O2ⁱ—Zn1—O3	92.56 (13)	C15—C16—C17	120.2 (5)
O2ⁱⁱ—Zn1—O3	155.21 (12)	C15—C16—H16	119.9
N1—Zn1—O3	102.89 (14)	C17—C16—H16	119.9
N2—Zn1—O3	95.77 (14)	C16—C17—C18	118.4 (4)
O4—Zn1—O3	59.73 (13)	C16—C17—C20	119.3 (4)
O2ⁱ—Zn1—C24	90.48 (14)	C18—C17—C20	122.3 (4)
O2ⁱⁱ—Zn1—C24	126.02 (15)	C19—C18—C17	120.6 (4)
N1—Zn1—C24	132.44 (16)	C19—C18—H18	119.7
N2—Zn1—C24	96.40 (15)	C17—C18—H18	119.7
O4—Zn1—C24	29.87 (14)	C18—C19—C14	121.0 (4)
O3—Zn1—C24	29.89 (14)	C18—C19—H19	119.5
N1—C1—C2	122.6 (4)	C14—C19—H19	119.5
N1—C1—H1	118.7	O1—C20—O2	124.2 (5)
C2—C1—H1	118.7	O1—C20—C17	120.2 (5)
C3—C2—C1	119.6 (4)	O2—C20—C17	115.6 (4)
C3—C2—H2	120.2	C22—C21—C23ⁱⁱⁱ	120.2 (5)
C1—C2—H2	120.2	C22—C21—H23	119.9
C2—C3—C4	118.9 (4)	C23ⁱⁱⁱ—C21—H23	119.9
C2—C3—H3	120.5	C21—C22—C23	120.3 (5)
C4—C3—H3	120.5	C21—C22—H22	119.9
C3—C4—C12	118.2 (4)	C23—C22—H22	119.9
C3—C4—C5	126.3 (4)	C22—C23—C21ⁱⁱⁱ	119.5 (5)
C12—C4—C5	115.5 (4)	C22—C23—C24	120.4 (4)
N3—C5—C6	105.5 (4)	C21ⁱⁱⁱ—C23—C24	120.0 (5)
N3—C5—C4	129.5 (4)	O4—C24—O3	120.6 (4)
C6—C5—C4	124.8 (4)	O4—C24—C23	120.1 (4)
N4—C6—C5	110.1 (4)	O3—C24—C23	119.2 (5)
N4—C6—C7	129.9 (4)	O4—C24—Zn1	59.6 (2)
C5—C6—C7	120.0 (4)	O3—C24—Zn1	61.2 (2)
C11—C7—C8	117.4 (4)	C23—C24—Zn1	174.0 (3)
C11—C7—C6	117.2 (4)	C1—N1—C12	119.0 (4)
C8—C7—C6	125.4 (4)	C1—N1—Zn1	127.1 (3)
C9—C8—C7	119.3 (5)	C12—N1—Zn1	113.7 (3)
C9—C8—H8	120.4	C10—N2—C11	118.4 (4)
C7—C8—H8	120.4	C10—N2—Zn1	127.5 (3)
C8—C9—C10	119.4 (5)	C11—N2—Zn1	113.5 (3)
C8—C9—H9	120.3	C13—N3—C5	107.5 (4)
C10—C9—H9	120.3	C13—N3—H4	126.2
N2—C10—C9	123.1 (5)	C5—N3—H4	126.2
N2—C10—H10	118.5	C13—N4—C6	105.3 (4)
C9—C10—H10	118.5	C20—O2—Zn1^iv	132.2 (3)
N2—C11—C7	122.4 (4)	C20—O2—Zn1ⁱⁱ	125.3 (3)
N2—C11—C12	115.9 (4)	Zn1^iv—O2—Zn1ⁱⁱ	101.09 (13)
C7—C11—C12	121.8 (4)	C24—O3—Zn1	88.9 (3)
N1—C12—C4	121.7 (4)	C24—O4—Zn1	90.6 (3)
N1—C12—C11	117.7 (4)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H4···O3^v	0.86	2.10	2.781 (5)	136

Symmetry code: (v) −x+1, −y, −z+1.

Experimental details

Crystal data
Chemical formula	[Zn₂(C₈H₄O₄)(C₂₀H₁₁N₄O₂)₂]·4H₂O
M_r	1037.54
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	9.7477 (16), 10.2610 (18), 11.0480 (19)
α, β, γ (°)	88.849 (3), 72.115 (4), 83.121 (3)
V (Å³)	1043.9 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.23
Crystal size (mm)	0.2 × 0.2 × 0.2

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2002)
T_min, T_max	0.782, 0.782
No. of measured, independent and observed [I > 2σ(I)] reflections	5406, 3783, 2797
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.139, 1.02
No. of reflections	3783
No. of parameters	316
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.94, −0.66

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), 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
N3—H4···O3ⁱ	0.86	2.10	2.781 (5)	135.7

Symmetry code: (i) −x+1, −y, −z+1.

Acknowledgements

The authors thank Jiangsu University for supporting this work.

References

Bruker (2002). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Chen, X.-M. & Liu, G.-F. (2002). Chem. Eur. J. 8, 4811–4817. CrossRef PubMed CAS Google Scholar
Eddaoudi, M., Moler, D. B., Li, H., Chen, B., Reineke, T. M., O'Keeffe, M. & Yaghi, O. M. (2001). Acc. Chem. Res. 34, 319–330. Web of Science CrossRef PubMed CAS Google Scholar
Hsu, Y.-C., Zheng, H., Lin, J. T. & Ho, K.-C. (2005). Solar Energy Mater. Solar Cells, 87, 357–367. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yongqin, W., Yunfang, Y. & Kechen, W. (2007). Cryst. Growth Des. 7, 2262—2264. Google Scholar

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ISSN: 2056-9890

Volume 67| Part 11| November 2011| Pages m1493-m1494

doi:10.1107/S1600536811040062

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

Poly[[(μ-benzene-1,4-di­carboxyl­ato)bis­­[μ-4-(1H-1,3,7,8-tetra­aza­cyclo­penta­[l]phenanthren-2-yl)benzoato]dizinc] tetra­hydrate]

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Poly[[(μ-benzene-1,4-dicarboxylato)bis[μ-4-(1H-1,3,7,8-tetraazacyclopenta[l]phenanthren-2-yl)benzoato]dizinc] tetrahydrate]