Bis(4,4'-bipyrid-yl)bis{2-[4,6-bis-(carboxy-methyl-sulfan-yl)-1,3,5-triazin-2-ylsulfan-yl]acetato}zinc(II).

In the title compound, [Zn(C(9)H(8)N(3)O(6)S(3))(2)(C(10)H(8)N(2))(2)], the central Zn(II) ion, situated on a center of inversion, adopts an octa-hedral geometry coordinated by four O atoms from two carboxyl-ate groups and two carboxylic groups of two symmetry-related TTTA ligands and two N atoms from two bpy mol-ecules {TTTA is 2,2',2''-[1,3,5-triazine-2,4,6-triyltris(sulfanedi-yl)]triacetic acid and bpy is 4,4'-bipyridine}. These mononuclear units are connected through complementary O-H⋯X hydrogen bonds, as well as through weak C-H⋯X (X = O and N) inter-actions, resulting in a three-dimensional supra-molecular architecture.

Related literature

For crystal engineering of carboxyl­ates, see: Moulton & Zaworotko (2001 ▶); Rao et al. (2004 ▶); Ferey et al. (2005 ▶). For inter­actions involved in the self-assembly process, see: Braga & Grepioni (2000 ▶); Roesky & Andruh (2003 ▶); Chen et al. (2009 ▶). For our work on the coordination chemistry of semirigid polycarboxyl­ate ligands with functional groups introduced between the aromatic ring and carboxyl­ate groups, see: Wang et al. (2007 ▶); Hong et al. (2005 ▶); Sun et al. (2007 ▶).

Experimental

Crystal data

[Zn(C9H8N3O6S3)2(C10H8N2)2]

M = 1078.47

Triclinic,

a = 8.6025 (7) Å

b = 8.7606 (7) Å

c = 15.3187 (12) Å

α = 99.518 (1)°

β = 105.802 (2)°

γ = 98.805 (1)°

V = 1071.41 (15) Å3

Z = 1

Mo Kα radiation

μ = 0.94 mm−1

T = 293 K

0.28 × 0.24 × 0.23 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.81, T max = 0.84

5465 measured reflections

3745 independent reflections

3103 reflections with I > 2σ(I)

R int = 0.067

Refinement

R[F 2 > 2σ(F 2)] = 0.041

wR(F 2) = 0.116

S = 1.05

3745 reflections

306 parameters

H-atom parameters constrained

Δρmax = 0.55 e Å−3

Δρmin = −0.63 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681000735X/rn2067sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681000735X/rn2067Isup2.hkl

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

[Zn(C9H8N3O6S3)2(C10H8N2)2]	Z = 1
Mr = 1078.47	F(000) = 552
Triclinic, P1	Dx = 1.671 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.6025 (7) Å	Cell parameters from 2836 reflections
b = 8.7606 (7) Å	θ = 2.5–28.1°
c = 15.3187 (12) Å	µ = 0.94 mm−1
α = 99.518 (1)°	T = 293 K
β = 105.802 (2)°	Block, colorless
γ = 98.805 (1)°	0.28 × 0.24 × 0.23 mm
V = 1071.41 (15) Å3

Bruker SMART APEX CCD diffractometer	3745 independent reflections
Radiation source: fine-focus sealed tube	3103 reflections with I > 2σ(I)
graphite	Rint = 0.067
phi and ω scans	θmax = 25.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→10
Tmin = 0.81, Tmax = 0.84	k = −10→9
5465 measured reflections	l = −18→16

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H-atom parameters constrained
S = 1.05	w = 1/[σ2(Fo2) + (0.0632P)2] where P = (Fo2 + 2Fc2)/3
3745 reflections	(Δ/σ)max = 0.001
306 parameters	Δρmax = 0.55 e Å−3
0 restraints	Δρmin = −0.63 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
Zn1	0.5000	0.0000	0.5000	0.02725 (17)
N1	0.1818 (3)	−0.1424 (3)	0.74960 (17)	0.0324 (6)
N2	0.4260 (3)	−0.1972 (3)	0.71830 (15)	0.0265 (5)
N3	0.4458 (3)	−0.0022 (3)	0.85212 (16)	0.0276 (6)
N4	0.3822 (3)	0.1179 (3)	0.58899 (16)	0.0260 (5)
N5	0.0151 (3)	0.5510 (3)	0.88027 (19)	0.0402 (7)
O1	0.3126 (3)	−0.2111 (2)	0.48345 (15)	0.0365 (5)
O2	0.3316 (3)	−0.4383 (2)	0.40496 (14)	0.0368 (5)
H2	0.3378	−0.5271	0.4142	0.044*
O3	0.6664 (2)	−0.0338 (2)	0.62169 (13)	0.0291 (5)
O4	0.6623 (3)	−0.2886 (2)	0.57706 (14)	0.0352 (5)
O5	0.1025 (3)	0.2799 (3)	1.01154 (16)	0.0456 (6)
H5	0.0713	0.3389	1.0476	0.055*
O6	0.3494 (3)	0.4151 (3)	1.09911 (19)	0.0634 (8)
S1	0.13117 (9)	−0.35869 (9)	0.60274 (5)	0.0338 (2)
S2	0.72472 (9)	−0.03437 (9)	0.82517 (5)	0.0308 (2)
S3	0.17169 (10)	0.05612 (10)	0.89085 (6)	0.0401 (2)
C1	0.2626 (3)	−0.2188 (3)	0.69989 (19)	0.0252 (6)
C2	0.5103 (3)	−0.0856 (3)	0.79407 (19)	0.0247 (6)
C3	0.2811 (4)	−0.0367 (3)	0.8256 (2)	0.0287 (7)
C4	0.2717 (4)	−0.4370 (3)	0.5489 (2)	0.0267 (6)
H4A	0.3749	−0.4300	0.5965	0.032*
H4B	0.2259	−0.5481	0.5205	0.032*
C5	0.3071 (4)	−0.3530 (3)	0.4759 (2)	0.0272 (6)
C6	0.7620 (4)	−0.1775 (3)	0.73879 (19)	0.0282 (7)
H6A	0.8804	−0.1675	0.7521	0.034*
H6B	0.7170	−0.2824	0.7447	0.034*
C7	0.6901 (3)	−0.1647 (3)	0.63890 (19)	0.0250 (6)
C8	0.3335 (4)	0.2042 (4)	0.9770 (2)	0.0325 (7)
H8A	0.4075	0.1532	1.0167	0.039*
H8B	0.3968	0.2662	0.9465	0.039*
C9	0.2604 (4)	0.3118 (4)	1.0352 (2)	0.0346 (7)
C10	0.2189 (4)	0.1151 (4)	0.5617 (2)	0.0334 (7)
H10	0.1555	0.0562	0.5031	0.040*
C11	0.1411 (4)	0.1955 (4)	0.6167 (2)	0.0329 (7)
H11	0.0278	0.1896	0.5950	0.039*
C12	0.2330 (4)	0.2856 (3)	0.7048 (2)	0.0269 (6)
C13	0.4010 (4)	0.2880 (3)	0.7317 (2)	0.0309 (7)
H13	0.4681	0.3470	0.7896	0.037*
C14	0.4687 (4)	0.2032 (3)	0.6729 (2)	0.0297 (7)
H14	0.5815	0.2061	0.6932	0.036*
C15	0.1554 (4)	0.3774 (3)	0.7653 (2)	0.0277 (6)
C16	−0.0110 (4)	0.3372 (4)	0.7560 (2)	0.0388 (8)
H16	−0.0784	0.2503	0.7110	0.047*
C17	−0.0762 (4)	0.4272 (4)	0.8142 (2)	0.0447 (9)
H17	−0.1885	0.3999	0.8068	0.054*
C18	0.1757 (4)	0.5904 (4)	0.8904 (2)	0.0383 (8)
H18	0.2401	0.6770	0.9367	0.046*
C19	0.2497 (4)	0.5074 (4)	0.8345 (2)	0.0352 (7)
H19	0.3622	0.5382	0.8431	0.042*

	U11	U22	U33	U12	U13	U23
Zn1	0.0323 (3)	0.0258 (3)	0.0252 (3)	0.0085 (2)	0.0130 (2)	0.0003 (2)
N1	0.0275 (14)	0.0362 (14)	0.0309 (14)	0.0065 (11)	0.0110 (11)	−0.0026 (11)
N2	0.0244 (13)	0.0290 (13)	0.0244 (13)	0.0052 (11)	0.0077 (10)	0.0012 (11)
N3	0.0256 (13)	0.0322 (13)	0.0241 (13)	0.0078 (11)	0.0089 (10)	−0.0001 (11)
N4	0.0286 (13)	0.0230 (12)	0.0266 (13)	0.0066 (10)	0.0109 (11)	0.0013 (10)
N5	0.0369 (16)	0.0439 (16)	0.0404 (16)	0.0147 (13)	0.0159 (13)	−0.0018 (13)
O1	0.0389 (13)	0.0255 (12)	0.0460 (13)	0.0062 (9)	0.0162 (10)	0.0056 (10)
O2	0.0511 (14)	0.0299 (11)	0.0338 (12)	0.0098 (11)	0.0192 (10)	0.0071 (10)
O3	0.0352 (12)	0.0253 (10)	0.0276 (11)	0.0089 (9)	0.0110 (9)	0.0028 (9)
O4	0.0466 (14)	0.0284 (11)	0.0301 (12)	0.0123 (10)	0.0124 (10)	0.0000 (9)
O5	0.0359 (14)	0.0519 (15)	0.0437 (14)	0.0148 (11)	0.0142 (11)	−0.0129 (11)
O6	0.0462 (16)	0.0648 (17)	0.0614 (18)	0.0071 (14)	0.0157 (13)	−0.0295 (14)
S1	0.0239 (4)	0.0386 (5)	0.0307 (4)	−0.0020 (3)	0.0090 (3)	−0.0085 (3)
S2	0.0220 (4)	0.0406 (5)	0.0236 (4)	0.0047 (3)	0.0050 (3)	−0.0051 (3)
S3	0.0272 (4)	0.0481 (5)	0.0387 (5)	0.0078 (4)	0.0134 (4)	−0.0135 (4)
C1	0.0253 (15)	0.0254 (15)	0.0257 (15)	0.0063 (12)	0.0099 (12)	0.0032 (12)
C2	0.0250 (15)	0.0265 (15)	0.0222 (14)	0.0062 (12)	0.0070 (12)	0.0034 (12)
C3	0.0281 (16)	0.0310 (16)	0.0275 (16)	0.0085 (13)	0.0107 (13)	0.0022 (13)
C4	0.0273 (15)	0.0241 (14)	0.0272 (15)	0.0048 (12)	0.0096 (12)	−0.0005 (12)
C5	0.0266 (16)	0.0238 (16)	0.0294 (16)	0.0050 (12)	0.0085 (12)	0.0013 (12)
C6	0.0248 (15)	0.0309 (16)	0.0289 (16)	0.0088 (13)	0.0090 (12)	0.0023 (13)
C7	0.0232 (15)	0.0267 (15)	0.0259 (15)	0.0057 (12)	0.0113 (12)	0.0013 (12)
C8	0.0281 (16)	0.0381 (17)	0.0300 (16)	0.0106 (14)	0.0094 (13)	−0.0002 (14)
C9	0.0316 (18)	0.0373 (18)	0.0320 (17)	0.0084 (14)	0.0100 (14)	−0.0018 (14)
C10	0.0335 (17)	0.0319 (16)	0.0318 (17)	0.0054 (14)	0.0117 (14)	−0.0030 (13)
C11	0.0290 (16)	0.0347 (17)	0.0329 (17)	0.0068 (13)	0.0112 (13)	−0.0013 (14)
C12	0.0293 (16)	0.0259 (15)	0.0274 (15)	0.0074 (12)	0.0118 (12)	0.0044 (12)
C13	0.0308 (17)	0.0325 (16)	0.0279 (16)	0.0080 (14)	0.0098 (13)	−0.0003 (13)
C14	0.0293 (16)	0.0312 (16)	0.0290 (16)	0.0094 (13)	0.0097 (13)	0.0033 (13)
C15	0.0287 (16)	0.0298 (15)	0.0258 (15)	0.0099 (13)	0.0099 (12)	0.0034 (12)
C16	0.0355 (18)	0.0409 (19)	0.0383 (19)	0.0095 (15)	0.0137 (15)	−0.0015 (15)
C17	0.0361 (19)	0.052 (2)	0.046 (2)	0.0134 (17)	0.0169 (16)	−0.0018 (17)
C18	0.0390 (19)	0.0377 (18)	0.0368 (18)	0.0103 (15)	0.0142 (15)	−0.0026 (15)
C19	0.0319 (17)	0.0356 (17)	0.0378 (18)	0.0089 (14)	0.0148 (14)	−0.0018 (14)

Zn1—O3i	2.1145 (19)	S3—C3	1.739 (3)
Zn1—O3	2.1145 (19)	S3—C8	1.800 (3)
Zn1—N4i	2.135 (2)	C4—C5	1.507 (4)
Zn1—N4	2.135 (2)	C4—H4A	0.9700
Zn1—O1	2.189 (2)	C4—H4B	0.9700
Zn1—O1i	2.189 (2)	C6—C7	1.516 (4)
N1—C1	1.331 (4)	C6—H6A	0.9700
N1—C3	1.342 (4)	C6—H6B	0.9700
N2—C1	1.333 (4)	C8—C9	1.513 (4)
N2—C2	1.334 (3)	C8—H8A	0.9700
N3—C3	1.334 (4)	C8—H8B	0.9700
N3—C2	1.346 (4)	C10—C11	1.382 (4)
N4—C14	1.325 (4)	C10—H10	0.9300
N4—C10	1.347 (4)	C11—C12	1.394 (4)
N5—C17	1.327 (4)	C11—H11	0.9300
N5—C18	1.331 (4)	C12—C13	1.386 (4)
O1—C5	1.222 (3)	C12—C15	1.486 (4)
O2—C5	1.299 (3)	C13—C14	1.379 (4)
O2—H2	0.8200	C13—H13	0.9300
O3—C7	1.252 (3)	C14—H14	0.9300
O4—C7	1.261 (3)	C15—C16	1.383 (4)
O5—C9	1.279 (4)	C15—C19	1.388 (4)
O5—H5	0.8200	C16—C17	1.380 (4)
O6—C9	1.204 (4)	C16—H16	0.9300
S1—C1	1.747 (3)	C17—H17	0.9300
S1—C4	1.795 (3)	C18—C19	1.379 (4)
S2—C2	1.740 (3)	C18—H18	0.9300
S2—C6	1.797 (3)	C19—H19	0.9300
O3i—Zn1—O3	180.00 (7)	C7—C6—H6A	108.4
O3i—Zn1—N4i	86.91 (8)	S2—C6—H6A	108.4
O3—Zn1—N4i	93.09 (8)	C7—C6—H6B	108.4
O3i—Zn1—N4	93.09 (8)	S2—C6—H6B	108.4
O3—Zn1—N4	86.91 (8)	H6A—C6—H6B	107.4
N4i—Zn1—N4	180.00 (9)	O3—C7—O4	123.7 (3)
O3i—Zn1—O1	84.73 (8)	O3—C7—C6	119.5 (2)
O3—Zn1—O1	95.27 (8)	O4—C7—C6	116.8 (2)
N4i—Zn1—O1	94.10 (8)	C9—C8—S3	110.2 (2)
N4—Zn1—O1	85.90 (8)	C9—C8—H8A	109.6
O3i—Zn1—O1i	95.27 (8)	S3—C8—H8A	109.6
O3—Zn1—O1i	84.73 (8)	C9—C8—H8B	109.6
N4i—Zn1—O1i	85.90 (8)	S3—C8—H8B	109.6
N4—Zn1—O1i	94.10 (8)	H8A—C8—H8B	108.1
O1—Zn1—O1i	180.00 (7)	O6—C9—O5	125.3 (3)
C1—N1—C3	113.8 (3)	O6—C9—C8	120.2 (3)
C1—N2—C2	113.8 (2)	O5—C9—C8	114.4 (3)
C3—N3—C2	113.4 (2)	N4—C10—C11	123.2 (3)
C14—N4—C10	116.8 (3)	N4—C10—H10	118.4
C14—N4—Zn1	121.0 (2)	C11—C10—H10	118.4
C10—N4—Zn1	122.14 (19)	C10—C11—C12	119.7 (3)
C17—N5—C18	118.6 (3)	C10—C11—H11	120.1
C5—O1—Zn1	136.6 (2)	C12—C11—H11	120.1
C5—O2—H2	109.5	C13—C12—C11	116.5 (3)
C7—O3—Zn1	125.67 (18)	C13—C12—C15	121.9 (3)
C9—O5—H5	109.5	C11—C12—C15	121.7 (3)
C1—S1—C4	103.09 (14)	C14—C13—C12	120.1 (3)
C2—S2—C6	100.14 (13)	C14—C13—H13	119.9
C3—S3—C8	101.90 (14)	C12—C13—H13	119.9
N1—C1—N2	126.4 (3)	N4—C14—C13	123.7 (3)
N1—C1—S1	113.1 (2)	N4—C14—H14	118.1
N2—C1—S1	120.6 (2)	C13—C14—H14	118.1
N2—C2—N3	126.3 (3)	C16—C15—C19	117.5 (3)
N2—C2—S2	120.1 (2)	C16—C15—C12	122.0 (3)
N3—C2—S2	113.6 (2)	C19—C15—C12	120.5 (3)
N3—C3—N1	126.3 (3)	C17—C16—C15	119.4 (3)
N3—C3—S3	121.1 (2)	C17—C16—H16	120.3
N1—C3—S3	112.6 (2)	C15—C16—H16	120.3
C5—C4—S1	113.8 (2)	N5—C17—C16	122.6 (3)
C5—C4—H4A	108.8	N5—C17—H17	118.7
S1—C4—H4A	108.8	C16—C17—H17	118.7
C5—C4—H4B	108.8	N5—C18—C19	122.3 (3)
S1—C4—H4B	108.8	N5—C18—H18	118.9
H4A—C4—H4B	107.7	C19—C18—H18	118.9
O1—C5—O2	121.7 (3)	C18—C19—C15	119.6 (3)
O1—C5—C4	121.3 (3)	C18—C19—H19	120.2
O2—C5—C4	116.9 (2)	C15—C19—H19	120.2
C7—C6—S2	115.7 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O4ii	0.82	1.64	2.460 (3)	175
O5—H5···N5iii	0.82	1.74	2.554 (3)	174
C13—H13···O6iv	0.93	2.47	3.335 (4)	156
C19—H19···O6iv	0.93	2.34	3.245 (4)	164
C6—H6A···N1v	0.97	2.58	3.533 (4)	168

Table 1

Selected bond lengths (Å)

Zn1—O3	2.1145 (19)
Zn1—N4	2.135 (2)
Zn1—O1	2.189 (2)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O4i	0.82	1.64	2.460 (3)	175
O5—H5⋯N5ii	0.82	1.74	2.554 (3)	174
C13—H13⋯O6iii	0.93	2.47	3.335 (4)	156
C19—H19⋯O6iii	0.93	2.34	3.245 (4)	164
C6—H6A⋯N1iv	0.97	2.58	3.533 (4)	168

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