Poly[hemi(hexa-aqua-zinc) [[μ(2)-1,3-bis-(1,2,4-triazol-1-yl)methane](μ(2)-5-sulfonato-benzene-1,3-dicarboxyl-ato)zinc] sesquihydrate].

The title coordination polymer, {[Zn(H(2)O)(6)](0.5)[Zn(C(8)H(3)O(7)S)(C(5)H(6)N(6))]·1.5H(2)O}(n), synthesized under hydro-thermal conditions, possesses a one-dimensional tube-like chain structure along [100], with octahedral [Zn(H(2)O)(6)](2+) groups ([Formula: see text] symmetry) trapped in the pores. The other Zn atom is five-coordinated in a highly distorted trigonal-biyramidal coordin-ation that is defined by two different N atoms from two 1,3-bis-(1,2,4-triazol-1-yl)methane (btrm) ligands and three carboxyl-ate O atoms from 5-sulfonato-benzene-1,3-dicarboxyl-ate ligands. The chains carry negative charges, whereas the free [Zn(H(2)O)(6)](2+) cations are positively charged. The [Zn(H(2)O)(6)](2+) cation is connected with the one-dimensional tubelike chain through weak classical O-H⋯O and O-H⋯N hydrogen-bonding inter-actions as well as through electrostatic inter-actions. One of the two uncoordinated water molecules exhibits half-occupancy.

Related literature

For properties of organic–inorganic hybrid materials, see: Ishikava et al. (2003 ▶). One of the key steps in the preparation of polymeric transition metal complexes is to select multidentate bridging ligands or mixed multidentate ligands, see: Biradha et al. (2006 ▶).

Experimental

Crystal data

[Zn(H2O)6]0.5[Zn(C8H3O7S)(C5H6N6)]·1.5H2O

M = 571.48

Monoclinic,

a = 10.2611 (3) Å

b = 16.9967 (4) Å

c = 11.4808 (3) Å

β = 93.812 (2)°

V = 1997.88 (9) Å3

Z = 4

Mo Kα radiation

μ = 2.00 mm−1

T = 293 K

0.23 × 0.15 × 0.14 mm

Data collection

Bruker SuperNova Eos diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T min = 0.657, T max = 0.767

7740 measured reflections

3524 independent reflections

2763 reflections with I > 2σ(I)

R int = 0.030

Refinement

R[F 2 > 2σ(F 2)] = 0.049

wR(F 2) = 0.155

S = 1.11

3524 reflections

304 parameters

30 restraints

H-atom parameters constrained

Δρmax = 1.67 e Å−3

Δρmin = −0.90 e Å−3

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1997 ▶); 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.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811022835/br2168sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811022835/br2168Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Zn(H2O)6]0.5[Zn(C8H3O7S)(C5H6N6)]·1.5H2O	F(000) = 1160
Mr = 571.48	Dx = 1.900 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4538 reflections
a = 10.2611 (3) Å	θ = 2.4–25.0°
b = 16.9967 (4) Å	µ = 2.00 mm−1
c = 11.4808 (3) Å	T = 293 K
β = 93.812 (2)°	BLOCK, colourless
V = 1997.88 (9) Å3	0.23 × 0.15 × 0.14 mm
Z = 4

Bruker SuperNova Eos diffractometer	3524 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	2763 reflections with I > 2σ(I)
mirror	Rint = 0.030
Detector resolution: 16.2116 pixels mm-1	θmax = 25.0°, θmin = 2.4°
ω scans	h = −12→10
Absorption correction: multi-scan (SADABS; Bruker, 1997)	k = −20→19
Tmin = 0.657, Tmax = 0.767	l = −8→13
7740 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)] = 0.049	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.155	H-atom parameters constrained
S = 1.11	w = 1/[σ2(Fo2) + (0.0939P)2 + 1.3769P] where P = (Fo2 + 2Fc2)/3
3524 reflections	(Δ/σ)max = 0.001
304 parameters	Δρmax = 1.67 e Å−3
30 restraints	Δρmin = −0.90 e Å−3

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 > 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	−0.05241 (5)	0.44539 (3)	0.65524 (5)	0.0173 (2)
Zn2	0.5000	0.5000	1.0000	0.0242 (3)
C1	−0.1029 (5)	0.5844 (3)	0.8059 (5)	0.0223 (12)
H1	−0.1689	0.5583	0.8420	0.027*
C2	0.0432 (6)	0.6157 (3)	0.6959 (5)	0.0290 (13)
H2	0.1013	0.6129	0.6372	0.035*
C3	−0.0915 (6)	0.7063 (3)	0.9310 (4)	0.0222 (12)
H3A	−0.0726	0.7606	0.9123	0.027*
H3B	−0.1841	0.7020	0.9418	0.027*
C4	−0.0526 (5)	0.6384 (3)	1.1245 (5)	0.0226 (12)
H4	−0.1355	0.6172	1.1301	0.027*
C5	0.1439 (5)	0.6712 (3)	1.1562 (5)	0.0263 (13)
H5	0.2270	0.6761	1.1930	0.032*
C6	0.3270 (5)	0.4047 (3)	0.5589 (4)	0.0164 (11)
C7	0.3175 (5)	0.3543 (3)	0.4624 (4)	0.0177 (11)
H7	0.2362	0.3380	0.4308	0.021*
C8	0.4303 (5)	0.3289 (3)	0.4144 (4)	0.0166 (11)
C9	0.5517 (5)	0.3537 (3)	0.4584 (4)	0.0178 (11)
H9	0.6265	0.3364	0.4247	0.021*
C10	0.5614 (5)	0.4045 (3)	0.5531 (4)	0.0156 (11)
C11	0.4512 (5)	0.4286 (3)	0.6035 (4)	0.0168 (11)
H11	0.4587	0.4614	0.6685	0.020*
C12	0.2081 (5)	0.4314 (3)	0.6171 (5)	0.0191 (11)
C13	0.6940 (5)	0.4296 (3)	0.6051 (4)	0.0173 (11)
N1	−0.0406 (4)	0.5563 (2)	0.7185 (4)	0.0198 (10)
N2	−0.0580 (4)	0.6556 (2)	0.8351 (4)	0.0201 (10)
N3	0.0351 (5)	0.6768 (3)	0.7636 (4)	0.0308 (12)
N4	−0.0173 (4)	0.6839 (2)	1.0379 (4)	0.0199 (9)
N5	0.1097 (5)	0.7049 (3)	1.0573 (4)	0.0285 (11)
N6	0.0471 (4)	0.6278 (2)	1.2015 (4)	0.0210 (10)
O1	0.0957 (3)	0.4135 (2)	0.5658 (3)	0.0265 (9)
O2	0.2190 (3)	0.4662 (2)	0.7126 (3)	0.0258 (9)
O3	0.7036 (3)	0.4664 (2)	0.6994 (3)	0.0263 (9)
O4	0.7944 (3)	0.4118 (2)	0.5511 (3)	0.0245 (9)
O5	0.3252 (4)	0.1997 (2)	0.3349 (4)	0.0410 (11)
O6	0.3664 (4)	0.3024 (2)	0.1958 (4)	0.0401 (11)
O7	0.5457 (4)	0.2277 (2)	0.2870 (4)	0.0391 (11)
O8	0.3948 (5)	0.5718 (3)	1.1028 (5)	0.0574 (14)
H8A	0.3892	0.5761	1.1773	0.028*
H8B	0.3861	0.6192	1.0761	0.028*
O9	0.6329 (5)	0.5931 (3)	0.9813 (5)	0.0526 (13)
H9A	0.6046	0.6261	0.9278	0.028*
H9B	0.6511	0.6216	1.0425	0.028*
O10	0.3976 (5)	0.5446 (3)	0.8539 (5)	0.0565 (14)
H10A	0.3721	0.5071	0.8081	0.028*
H10B	0.3284	0.5688	0.8745	0.028*
O11	0.3350 (5)	0.6924 (3)	0.9006 (4)	0.0494 (12)
H11A	0.3859	0.7322	0.8968	0.028*
H11B	0.2577	0.7116	0.9057	0.028*
O12	0.133 (2)	0.5302 (11)	0.9610 (18)	0.138 (6)	0.50
S1	0.41635 (13)	0.25941 (8)	0.29848 (12)	0.0236 (3)

	U11	U22	U33	U12	U13	U23
Zn1	0.0120 (3)	0.0235 (3)	0.0165 (4)	−0.0001 (2)	0.0004 (2)	−0.0058 (2)
Zn2	0.0253 (5)	0.0277 (5)	0.0200 (5)	−0.0025 (4)	0.0037 (4)	−0.0067 (4)
C1	0.021 (3)	0.020 (3)	0.026 (3)	−0.003 (2)	0.005 (2)	−0.003 (2)
C2	0.034 (3)	0.031 (3)	0.024 (3)	−0.010 (3)	0.012 (3)	0.000 (3)
C3	0.031 (3)	0.020 (3)	0.016 (3)	0.003 (2)	0.002 (2)	−0.004 (2)
C4	0.020 (3)	0.025 (3)	0.023 (3)	0.000 (2)	0.000 (2)	−0.003 (2)
C5	0.019 (3)	0.031 (3)	0.029 (3)	−0.005 (2)	0.002 (2)	−0.002 (3)
C6	0.013 (3)	0.018 (2)	0.018 (3)	0.002 (2)	0.002 (2)	0.004 (2)
C7	0.010 (3)	0.022 (3)	0.020 (3)	−0.004 (2)	−0.003 (2)	0.002 (2)
C8	0.018 (3)	0.016 (2)	0.016 (3)	−0.002 (2)	0.000 (2)	−0.001 (2)
C9	0.015 (3)	0.019 (2)	0.020 (3)	−0.002 (2)	0.004 (2)	−0.002 (2)
C10	0.012 (3)	0.021 (2)	0.013 (3)	0.000 (2)	−0.001 (2)	0.004 (2)
C11	0.016 (3)	0.019 (2)	0.014 (3)	0.000 (2)	−0.002 (2)	−0.002 (2)
C12	0.013 (3)	0.023 (3)	0.022 (3)	0.000 (2)	0.003 (2)	0.004 (2)
C13	0.015 (3)	0.022 (2)	0.015 (3)	−0.002 (2)	0.002 (2)	0.007 (2)
N1	0.018 (2)	0.023 (2)	0.019 (2)	0.0011 (18)	0.0012 (18)	−0.0030 (18)
N2	0.023 (2)	0.020 (2)	0.018 (2)	0.0012 (18)	0.0054 (19)	−0.0008 (18)
N3	0.044 (3)	0.027 (2)	0.023 (3)	−0.014 (2)	0.012 (2)	−0.004 (2)
N4	0.018 (2)	0.022 (2)	0.020 (2)	0.0000 (18)	0.0022 (18)	−0.0052 (19)
N5	0.025 (3)	0.030 (2)	0.031 (3)	−0.004 (2)	0.004 (2)	−0.001 (2)
N6	0.019 (2)	0.024 (2)	0.020 (2)	0.0025 (19)	0.0004 (18)	−0.0021 (19)
O1	0.0118 (19)	0.042 (2)	0.025 (2)	0.0029 (16)	0.0014 (16)	−0.0110 (18)
O2	0.017 (2)	0.037 (2)	0.024 (2)	0.0014 (17)	0.0025 (16)	−0.0123 (18)
O3	0.016 (2)	0.043 (2)	0.020 (2)	−0.0070 (17)	0.0008 (15)	−0.0093 (18)
O4	0.0080 (18)	0.041 (2)	0.025 (2)	0.0024 (16)	0.0027 (15)	−0.0077 (17)
O5	0.041 (3)	0.032 (2)	0.051 (3)	−0.019 (2)	0.009 (2)	−0.009 (2)
O6	0.044 (3)	0.052 (3)	0.023 (2)	−0.001 (2)	−0.0047 (19)	−0.008 (2)
O7	0.026 (2)	0.050 (2)	0.042 (3)	0.0041 (19)	0.0052 (19)	−0.022 (2)
O8	0.063 (2)	0.0562 (19)	0.054 (2)	0.0053 (17)	0.0110 (17)	−0.0018 (16)
O9	0.052 (2)	0.0526 (19)	0.053 (2)	−0.0027 (16)	−0.0012 (16)	−0.0009 (16)
O10	0.059 (2)	0.0541 (19)	0.055 (2)	0.0054 (16)	−0.0057 (17)	−0.0066 (16)
O11	0.0467 (19)	0.0461 (17)	0.057 (2)	−0.0014 (16)	0.0128 (16)	−0.0003 (16)
O12	0.138 (6)	0.138 (6)	0.138 (6)	0.000 (2)	0.009 (2)	0.000 (2)
S1	0.0189 (7)	0.0269 (7)	0.0250 (8)	−0.0024 (6)	0.0008 (6)	−0.0094 (6)

Zn1—O1	1.967 (4)	C6—C11	1.402 (7)
Zn1—O4i	1.994 (4)	C6—C12	1.500 (7)
Zn1—N1	2.020 (4)	C7—C8	1.384 (7)
Zn1—N6ii	2.059 (4)	C7—H7	0.9300
Zn1—O3i	2.611 (4)	C8—C9	1.378 (7)
Zn2—O8iii	2.053 (5)	C8—S1	1.778 (5)
Zn2—O8	2.053 (5)	C9—C10	1.388 (7)
Zn2—O10iii	2.063 (5)	C9—H9	0.9300
Zn2—O10	2.063 (5)	C10—C11	1.367 (7)
Zn2—O9	2.109 (5)	C10—C13	1.510 (7)
Zn2—O9iii	2.109 (5)	C11—H11	0.9300
C1—N1	1.315 (7)	C12—O2	1.244 (6)
C1—N2	1.331 (6)	C12—O1	1.296 (6)
C1—H1	0.9300	C13—O3	1.248 (6)
C2—N3	1.304 (7)	C13—O4	1.274 (6)
C2—N1	1.363 (7)	N2—N3	1.348 (6)
C2—H2	0.9300	N4—N5	1.355 (6)
C3—N4	1.451 (7)	O5—S1	1.459 (4)
C3—N2	1.457 (6)	O6—S1	1.452 (4)
C3—H3A	0.9700	O7—S1	1.446 (4)
C3—H3B	0.9700	O8—H8A	0.8647
C4—N6	1.319 (7)	O8—H8B	0.8647
C4—N4	1.329 (7)	O9—H9A	0.8672
C4—H4	0.9300	O9—H9B	0.8636
C5—N5	1.299 (7)	O10—H10A	0.8566
C5—N6	1.367 (7)	O10—H10B	0.8672
C5—H5	0.9300	O11—H11A	0.8576
C6—C7	1.398 (7)	O11—H11B	0.8636
O1—Zn1—O4i	102.35 (15)	C8—C9—H9	120.2
O1—Zn1—N1	114.53 (17)	C10—C9—H9	120.2
O4i—Zn1—N1	120.59 (16)	C11—C10—C9	120.0 (5)
O1—Zn1—N6ii	105.67 (16)	C11—C10—C13	119.8 (4)
O4i—Zn1—N6ii	106.46 (16)	C9—C10—C13	120.1 (4)
N1—Zn1—N6ii	106.17 (17)	C10—C11—C6	121.1 (5)
O1—Zn1—O3i	157.39 (13)	C10—C11—H11	119.5
O4i—Zn1—O3i	55.08 (13)	C6—C11—H11	119.5
N1—Zn1—O3i	80.70 (15)	O2—C12—O1	122.5 (5)
N6ii—Zn1—O3i	84.39 (15)	O2—C12—C6	120.6 (5)
O8iii—Zn2—O10iii	89.4 (2)	O1—C12—C6	116.9 (5)
O8—Zn2—O10iii	90.6 (2)	O3—C13—O4	121.4 (5)
O8iii—Zn2—O9	91.1 (2)	O3—C13—C10	120.1 (5)
O8—Zn2—O9	88.9 (2)	O4—C13—C10	118.5 (4)
O10iii—Zn2—O9	93.5 (2)	C1—N1—C2	102.7 (4)
O10—Zn2—O9	86.5 (2)	C1—N1—Zn1	126.3 (4)
O8iii—Zn2—O9iii	88.9 (2)	C2—N1—Zn1	130.3 (4)
O8—Zn2—O9iii	91.1 (2)	C1—N2—N3	109.7 (4)
O10iii—Zn2—O9iii	86.5 (2)	C1—N2—C3	129.3 (5)
O10—Zn2—O9iii	93.5 (2)	N3—N2—C3	120.9 (4)
N1—C1—N2	110.2 (5)	C2—N3—N2	103.0 (4)
N1—C1—H1	124.9	C4—N4—N5	109.7 (4)
N2—C1—H1	124.9	C4—N4—C3	129.2 (5)
N3—C2—N1	114.3 (5)	N5—N4—C3	121.0 (4)
N3—C2—H2	122.9	C5—N5—N4	103.2 (4)
N1—C2—H2	122.9	C4—N6—C5	102.8 (5)
N4—C3—N2	110.3 (4)	C4—N6—Zn1ii	126.6 (4)
N4—C3—H3A	109.6	C5—N6—Zn1ii	130.4 (4)
N2—C3—H3A	109.6	C12—O1—Zn1	113.1 (3)
N4—C3—H3B	109.6	C13—O3—Zn1iv	77.6 (3)
N2—C3—H3B	109.6	C13—O4—Zn1iv	105.7 (3)
H3A—C3—H3B	108.1	Zn2—O8—H8A	133.7
N6—C4—N4	110.1 (5)	Zn2—O8—H8B	113.3
N6—C4—H4	125.0	H8A—O8—H8B	105.1
N4—C4—H4	125.0	Zn2—O9—H9A	111.6
N5—C5—N6	114.2 (5)	Zn2—O9—H9B	116.4
N5—C5—H5	122.9	H9A—O9—H9B	104.9
N6—C5—H5	122.9	Zn2—O10—H10A	110.1
C7—C6—C11	118.7 (5)	Zn2—O10—H10B	109.5
C7—C6—C12	121.5 (4)	H10A—O10—H10B	107.3
C11—C6—C12	119.7 (4)	H11A—O11—H11B	105.8
C8—C7—C6	119.4 (4)	O7—S1—O6	113.0 (3)
C8—C7—H7	120.3	O7—S1—O5	112.1 (3)
C6—C7—H7	120.3	O6—S1—O5	112.6 (3)
C9—C8—C7	121.2 (5)	O7—S1—C8	106.7 (2)
C9—C8—S1	120.2 (4)	O6—S1—C8	106.3 (2)
C7—C8—S1	118.6 (4)	O5—S1—C8	105.6 (2)
C8—C9—C10	119.6 (5)

D—H···A	D—H	H···A	D···A	D—H···A
O8—H8A···O3iii	0.86	1.90	2.628 (7)	141
O8—H8B···O11	0.86	2.40	3.126 (7)	143
O8—H8B···O7v	0.86	2.49	2.983 (7)	117
O9—H9A···O6vi	0.86	1.91	2.700 (7)	151
O9—H9B···O5v	0.86	1.94	2.794 (7)	170
O10—H10A···O2	0.86	1.98	2.716 (7)	143
O10—H10B···O11	0.86	2.12	2.656 (7)	119
O10—H10B···O12	0.86	2.39	3.068 (7)	135
O11—H11A···O7vi	0.86	2.37	2.887 (7)	119
O11—H11B···N5	0.86	2.39	3.029 (7)	131

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O8—H8A⋯O3i	0.86	1.90	2.628 (7)	141
O8—H8B⋯O11	0.86	2.40	3.126 (7)	143
O8—H8B⋯O7ii	0.86	2.49	2.983 (7)	117
O9—H9A⋯O6iii	0.86	1.91	2.700 (7)	151
O9—H9B⋯O5ii	0.86	1.94	2.794 (7)	170
O10—H10A⋯O2	0.86	1.98	2.716 (7)	143
O10—H10B⋯O11	0.86	2.12	2.656 (7)	119
O10—H10B⋯O12	0.86	2.39	3.068 (7)	135
O11—H11A⋯O7iii	0.86	2.37	2.887 (7)	119
O11—H11B⋯N5	0.86	2.39	3.029 (7)	131

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