Bis(μ-3-carb-oxy-2-hy-droxy-propane-1,2-dicarboxyl-ato)bis(diaquazinc)-1,2-bis-(pyridin-4-yl)ethene-water (1/1/2).

The asymmetric unit of the title compound, [Zn(2)(C(6)H(6)O(7))(2)(H(2)O)(4)]·C(12)H(10)N(2)·2H(2)O, comprises half of a centrosymmetric complex dimer, half of a 1,2-bis-(pyridin-4-yl)ethene mol-ecule, which lies across an inversion centre, and one lattice water mol-ecule. Carboxyl-ate groups of two dianionic citrate ligands bridge two Zn(II) ions to give the cyclic dimer, with each Zn(II) ion coordinated by four O atoms from the chelating citrate ligand (one hy-droxy and three carboxyl-ate, with one bridging) and two water O atoms, forming a distorted octa-hedral environment [Zn-O = 2.040 (3)-2.244 (3) Å]. In the crystal, O-H⋯O and O-H⋯N hydrogen bonds involving hy-droxy groups and both coordinating and lattice water mol-ecules link the dimers to give a three-dimensional framework structure.

Related literature

For inter­actions of metal ions with biologically active mol­ecules, see: Daniele et al. (2008 ▶); Parkin (2004 ▶); Tshuva & Lippard (2004 ▶); Stoumpos et al. (2009 ▶). For a manganese citrate complex, see: Hwang et al. (2012 ▶). For related complexes, see: Shin et al. (2009 ▶); Yu et al. (2009 ▶); Kim et al. (2011 ▶).

Experimental

Crystal data

[Zn2(C6H6O7)2(H2O)4]·C12H10N2·2H2O

M = 801.31

Triclinic,

a = 9.4360 (19) Å

b = 9.4540 (19) Å

c = 10.098 (2) Å

α = 66.87 (3)°

β = 70.19 (3)°

γ = 75.91 (3)°

V = 773.0 (3) Å3

Z = 1

Mo Kα radiation

μ = 1.64 mm−1

T = 170 K

0.30 × 0.10 × 0.10 mm

Data collection

Bruker SMART CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1997 ▶) T min = 0.638, T max = 0.853

4216 measured reflections

2924 independent reflections

2382 reflections with I > 2σ(I)

R int = 0.034

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.140

S = 1.09

2924 reflections

239 parameters

7 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.77 e Å−3

Δρmin = −1.36 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) I, global. DOI: 10.1107/S1600536812039761/zs2234sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812039761/zs2234Isup2.hkl

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

[Zn2(C6H6O7)2(H2O)4]·C12H10N2·2H2O	Z = 1
Mr = 801.31	F(000) = 412
Triclinic, P1	Dx = 1.721 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.4360 (19) Å	Cell parameters from 11909 reflections
b = 9.4540 (19) Å	θ = 2.7–27.6°
c = 10.098 (2) Å	µ = 1.64 mm−1
α = 66.87 (3)°	T = 170 K
β = 70.19 (3)°	Block, colourless
γ = 75.91 (3)°	0.30 × 0.10 × 0.10 mm
V = 773.0 (3) Å3

Bruker SMART CCD diffractometer	2924 independent reflections
Radiation source: fine-focus sealed tube	2382 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
φ and ω scans	θmax = 26.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −11→6
Tmin = 0.638, Tmax = 0.853	k = −11→11
4216 measured reflections	l = −12→12

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.140	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ2(Fo2) + (0.0822P)2] where P = (Fo2 + 2Fc2)/3
2924 reflections	(Δ/σ)max < 0.001
239 parameters	Δρmax = 0.77 e Å−3
7 restraints	Δρmin = −1.36 e Å−3

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.

	x	y	z	Uiso*/Ueq
Zn1	0.68767 (6)	0.59099 (5)	0.60957 (5)	0.02122 (19)
O1	0.5132 (3)	0.4257 (3)	0.7203 (3)	0.0209 (6)
H1O	0.466 (4)	0.431 (5)	0.651 (4)	0.031*
O2	0.8003 (4)	0.3981 (3)	0.5435 (3)	0.0260 (7)
O3	0.8228 (4)	0.1376 (3)	0.6320 (4)	0.0341 (8)
O4	0.7490 (4)	0.4656 (3)	0.8125 (3)	0.0282 (7)
O5	0.6894 (4)	0.3353 (3)	1.0577 (3)	0.0310 (7)
H5	0.7402	0.3981	1.0558	0.046*
O6	0.4181 (4)	0.3256 (3)	0.5605 (3)	0.0262 (7)
O7	0.4259 (5)	0.0698 (3)	0.6153 (4)	0.0427 (9)
O8	0.5622 (4)	0.7538 (3)	0.7112 (3)	0.0287 (7)
H8A	0.542 (6)	0.8518 (11)	0.668 (5)	0.034*
H8B	0.480 (3)	0.733 (5)	0.782 (4)	0.034*
O9	0.8800 (4)	0.7008 (3)	0.5133 (4)	0.0333 (7)
H9A	0.9753 (13)	0.675 (6)	0.507 (6)	0.040*
H9B	0.866 (6)	0.8005 (4)	0.482 (5)	0.040*
C1	0.5996 (5)	0.2711 (4)	0.7563 (4)	0.0192 (8)
C2	0.7522 (5)	0.2671 (4)	0.6340 (4)	0.0222 (9)
C3	0.6235 (5)	0.2336 (4)	0.9105 (4)	0.0249 (9)
H3A	0.5242	0.2187	0.9867	0.030*
H3B	0.6906	0.1340	0.9338	0.030*
C4	0.6919 (5)	0.3555 (4)	0.9255 (4)	0.0238 (9)
C5	0.5058 (5)	0.1490 (4)	0.7724 (4)	0.0235 (9)
H5A	0.5694	0.0469	0.7911	0.028*
H5B	0.4176	0.1417	0.8617	0.028*
C6	0.4474 (5)	0.1808 (4)	0.6386 (4)	0.0228 (9)
N11	0.1862 (4)	0.4370 (4)	0.9552 (4)	0.0282 (8)
C11	0.1610 (6)	0.3080 (5)	1.0802 (5)	0.0300 (10)
H11	0.1826	0.3029	1.1674	0.036*
C12	0.1051 (5)	0.1855 (5)	1.0827 (5)	0.0290 (10)
H12	0.0875	0.0967	1.1705	0.035*
C13	0.0741 (5)	0.1939 (5)	0.9522 (5)	0.0271 (9)
C14	0.0990 (5)	0.3284 (5)	0.8255 (5)	0.0280 (10)
H14	0.0771	0.3372	0.7372	0.034*
C15	0.1555 (5)	0.4480 (5)	0.8300 (5)	0.0285 (10)
H15	0.1729	0.5388	0.7441	0.034*
C16	0.0212 (5)	0.0643 (5)	0.9421 (4)	0.0297 (10)
H16	0.0168	0.0727	0.8467	0.036*
O1W	0.8324 (4)	0.0166 (4)	0.4122 (4)	0.0430 (9)
H1WA	0.819 (6)	0.057 (6)	0.490 (4)	0.052*
H1WB	0.736 (3)	0.034 (6)	0.391 (6)	0.052*

	U11	U22	U33	U12	U13	U23
Zn1	0.0271 (3)	0.0171 (3)	0.0208 (3)	−0.00588 (19)	−0.0053 (2)	−0.00706 (19)
O1	0.0261 (16)	0.0154 (12)	0.0223 (14)	−0.0028 (12)	−0.0067 (13)	−0.0072 (11)
O2	0.0314 (17)	0.0210 (14)	0.0240 (14)	−0.0041 (13)	−0.0066 (13)	−0.0064 (12)
O3	0.0333 (19)	0.0196 (14)	0.0436 (18)	0.0001 (13)	−0.0025 (15)	−0.0135 (13)
O4	0.0400 (19)	0.0243 (15)	0.0248 (15)	−0.0135 (14)	−0.0144 (14)	−0.0028 (12)
O5	0.047 (2)	0.0309 (15)	0.0236 (14)	−0.0232 (15)	−0.0075 (15)	−0.0089 (13)
O6	0.0399 (19)	0.0193 (13)	0.0234 (14)	−0.0032 (13)	−0.0146 (14)	−0.0066 (11)
O7	0.076 (3)	0.0190 (15)	0.0502 (19)	−0.0098 (16)	−0.037 (2)	−0.0102 (14)
O8	0.040 (2)	0.0188 (14)	0.0242 (15)	−0.0045 (14)	−0.0040 (14)	−0.0081 (12)
O9	0.0251 (17)	0.0230 (15)	0.0490 (19)	−0.0057 (14)	−0.0071 (16)	−0.0103 (14)
C1	0.025 (2)	0.0144 (17)	0.0204 (19)	−0.0048 (16)	−0.0068 (17)	−0.0062 (15)
C2	0.025 (2)	0.0218 (19)	0.023 (2)	−0.0038 (18)	−0.0084 (18)	−0.0098 (16)
C3	0.032 (3)	0.0210 (19)	0.022 (2)	−0.0100 (18)	−0.0042 (19)	−0.0062 (16)
C4	0.024 (2)	0.024 (2)	0.025 (2)	−0.0020 (18)	−0.0075 (18)	−0.0095 (17)
C5	0.028 (2)	0.0186 (18)	0.024 (2)	−0.0050 (17)	−0.0079 (18)	−0.0052 (16)
C6	0.027 (2)	0.0221 (19)	0.0231 (19)	−0.0049 (17)	−0.0074 (18)	−0.0098 (16)
N11	0.031 (2)	0.0290 (18)	0.0293 (18)	−0.0035 (17)	−0.0072 (17)	−0.0162 (16)
C11	0.039 (3)	0.029 (2)	0.028 (2)	−0.006 (2)	−0.009 (2)	−0.0143 (18)
C12	0.036 (3)	0.025 (2)	0.029 (2)	−0.0079 (19)	−0.010 (2)	−0.0094 (18)
C13	0.026 (2)	0.026 (2)	0.031 (2)	−0.0023 (19)	−0.0034 (19)	−0.0156 (18)
C14	0.031 (3)	0.031 (2)	0.028 (2)	−0.0002 (19)	−0.011 (2)	−0.0169 (18)
C15	0.028 (3)	0.030 (2)	0.028 (2)	−0.0052 (19)	−0.0042 (19)	−0.0118 (18)
C16	0.037 (3)	0.029 (2)	0.027 (2)	0.000 (2)	−0.009 (2)	−0.0172 (18)
O1W	0.042 (2)	0.0371 (18)	0.057 (2)	−0.0027 (17)	−0.0159 (19)	−0.0224 (17)

Zn1—O9	2.060 (3)	C1—C2	1.551 (6)
Zn1—O6i	2.069 (3)	C3—C4	1.527 (5)
Zn1—O8	2.086 (3)	C3—H3A	0.9900
Zn1—O2	2.105 (3)	C3—H3B	0.9900
Zn1—O4	2.122 (3)	C5—C6	1.525 (5)
Zn1—O1	2.244 (3)	C5—H5A	0.9900
O1—C1	1.461 (4)	C5—H5B	0.9900
O1—H1O	0.930 (2)	N11—C15	1.351 (5)
O2—C2	1.296 (5)	N11—C11	1.366 (5)
O3—C2	1.248 (5)	C11—C12	1.374 (6)
O4—C4	1.264 (5)	C11—H11	0.9500
O5—C4	1.265 (5)	C12—C13	1.412 (6)
O5—H5	0.8400	C12—H12	0.9500
O6—C6	1.299 (5)	C13—C14	1.404 (6)
O6—Zn1i	2.069 (3)	C13—C16	1.481 (6)
O7—C6	1.236 (5)	C14—C15	1.384 (6)
O8—H8A	0.860 (2)	C14—H14	0.9500
O8—H8B	0.860 (2)	C15—H15	0.9500
O9—H9A	0.860 (2)	C16—C16ii	1.345 (8)
O9—H9B	0.860 (2)	C16—H16	0.9500
C1—C3	1.539 (5)	O1W—H1WA	0.960 (2)
C1—C5	1.547 (5)	O1W—H1WB	0.960 (2)
O9—Zn1—O6i	102.94 (13)	C4—C3—H3A	108.4
O9—Zn1—O8	94.22 (13)	C1—C3—H3A	108.4
O6i—Zn1—O8	94.62 (12)	C4—C3—H3B	108.4
O9—Zn1—O2	92.48 (13)	C1—C3—H3B	108.4
O6i—Zn1—O2	90.97 (11)	H3A—C3—H3B	107.4
O8—Zn1—O2	170.11 (11)	O4—C4—O5	123.4 (4)
O9—Zn1—O4	92.53 (13)	O4—C4—C3	121.6 (3)
O6i—Zn1—O4	164.39 (12)	O5—C4—C3	114.9 (3)
O8—Zn1—O4	86.23 (12)	C6—C5—C1	115.6 (3)
O2—Zn1—O4	86.21 (11)	C6—C5—H5A	108.4
O9—Zn1—O1	167.91 (11)	C1—C5—H5A	108.4
O6i—Zn1—O1	83.38 (11)	C6—C5—H5B	108.4
O8—Zn1—O1	95.54 (12)	C1—C5—H5B	108.4
O2—Zn1—O1	76.98 (11)	H5A—C5—H5B	107.5
O4—Zn1—O1	81.02 (11)	O7—C6—O6	124.9 (4)
C1—O1—Zn1	105.3 (2)	O7—C6—C5	118.7 (3)
C1—O1—H1O	106 (3)	O6—C6—C5	116.3 (3)
Zn1—O1—H1O	109 (3)	C15—N11—C11	120.6 (4)
C2—O2—Zn1	114.9 (2)	N11—C11—C12	121.5 (4)
C4—O4—Zn1	130.7 (3)	N11—C11—H11	119.3
C4—O5—H5	109.5	C12—C11—H11	119.3
C6—O6—Zn1i	126.1 (3)	C11—C12—C13	118.8 (4)
Zn1—O8—H8A	127 (3)	C11—C12—H12	120.6
Zn1—O8—H8B	121 (3)	C13—C12—H12	120.6
H8A—O8—H8B	101 (5)	C14—C13—C12	118.9 (4)
Zn1—O9—H9A	137 (3)	C14—C13—C16	118.6 (4)
Zn1—O9—H9B	117 (4)	C12—C13—C16	122.5 (4)
H9A—O9—H9B	106 (5)	C15—C14—C13	119.6 (4)
O1—C1—C3	106.3 (3)	C15—C14—H14	120.2
O1—C1—C5	110.4 (3)	C13—C14—H14	120.2
C3—C1—C5	107.3 (3)	N11—C15—C14	120.7 (4)
O1—C1—C2	110.7 (3)	N11—C15—H15	119.7
C3—C1—C2	112.1 (3)	C14—C15—H15	119.7
C5—C1—C2	110.0 (3)	C16ii—C16—C13	124.9 (5)
O3—C2—O2	124.3 (4)	C16ii—C16—H16	117.5
O3—C2—C1	117.7 (3)	C13—C16—H16	117.5
O2—C2—C1	118.0 (3)	H1WA—O1W—H1WB	108 (5)
C4—C3—C1	115.6 (3)
O9—Zn1—O1—C1	2.9 (6)	O1—C1—C3—C4	−52.5 (5)
O6i—Zn1—O1—C1	125.2 (2)	C5—C1—C3—C4	−170.6 (3)
O8—Zn1—O1—C1	−140.8 (2)	C2—C1—C3—C4	68.5 (4)
O2—Zn1—O1—C1	32.6 (2)	Zn1—O4—C4—O5	−147.6 (3)
O4—Zn1—O1—C1	−55.5 (2)	Zn1—O4—C4—C3	33.9 (6)
O9—Zn1—O2—C2	148.1 (3)	C1—C3—C4—O4	−11.8 (6)
O6i—Zn1—O2—C2	−108.9 (3)	C1—C3—C4—O5	169.6 (4)
O4—Zn1—O2—C2	55.8 (3)	O1—C1—C5—C6	55.0 (5)
O1—Zn1—O2—C2	−25.9 (3)	C3—C1—C5—C6	170.4 (4)
O9—Zn1—O4—C4	−170.7 (4)	C2—C1—C5—C6	−67.4 (4)
O6i—Zn1—O4—C4	1.6 (7)	Zn1i—O6—C6—O7	5.5 (7)
O8—Zn1—O4—C4	95.3 (4)	Zn1i—O6—C6—C5	−171.6 (3)
O2—Zn1—O4—C4	−78.3 (4)	C1—C5—C6—O7	152.2 (4)
O1—Zn1—O4—C4	−0.9 (3)	C1—C5—C6—O6	−30.6 (5)
Zn1—O1—C1—C3	86.9 (3)	C15—N11—C11—C12	0.5 (7)
Zn1—O1—C1—C5	−157.0 (2)	N11—C11—C12—C13	0.4 (7)
Zn1—O1—C1—C2	−35.0 (3)	C11—C12—C13—C14	−1.2 (7)
Zn1—O2—C2—O3	−164.3 (3)	C11—C12—C13—C16	176.8 (4)
Zn1—O2—C2—C1	13.4 (4)	C12—C13—C14—C15	1.2 (7)
O1—C1—C2—O3	−165.1 (3)	C16—C13—C14—C15	−176.9 (4)
C3—C1—C2—O3	76.4 (4)	C11—N11—C15—C14	−0.5 (7)
C5—C1—C2—O3	−42.9 (5)	C13—C14—C15—N11	−0.4 (7)
O1—C1—C2—O2	17.0 (5)	C14—C13—C16—C16ii	−173.2 (6)
C3—C1—C2—O2	−101.5 (4)	C12—C13—C16—C16ii	8.8 (9)
C5—C1—C2—O2	139.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1O···O6	0.93 (1)	1.80 (2)	2.626 (4)	146 (4)
O5—H5···N11iii	0.84	1.81	2.633 (5)	168
O8—H8B···O5iii	0.86 (1)	1.88 (1)	2.733 (5)	173 (5)
O8—H8A···O7i	0.86 (1)	2.58 (4)	3.031 (4)	114 (4)
O8—H8A···O7iv	0.86 (1)	2.04 (2)	2.866 (4)	161 (5)
O9—H9B···O1Wiv	0.86 (1)	1.87 (1)	2.725 (5)	179 (5)
O9—H9A···O3v	0.86 (1)	2.57 (4)	3.145 (5)	125 (4)
O9—H9A···O2v	0.86 (1)	2.01 (1)	2.860 (5)	168 (5)
O1W—H1WA···O3	0.96 (1)	1.88 (1)	2.838 (5)	172 (5)
O1W—H1WB···O7vi	0.96 (1)	2.04 (3)	2.880 (5)	145 (4)
C14—H14···O9i	0.95	2.58	3.474 (5)	158
C12—H12···O3vii	0.95	2.52	3.390 (5)	152
C11—H11···O4iii	0.95	2.52	3.132 (5)	122

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯O6	0.93 (1)	1.80 (2)	2.626 (4)	146 (4)
O5—H5⋯N11i	0.84	1.81	2.633 (5)	168
O8—H8B⋯O5i	0.86 (1)	1.88 (1)	2.733 (5)	173 (5)
O8—H8A⋯O7ii	0.86 (1)	2.04 (2)	2.866 (4)	161 (5)
O9—H9B⋯O1W ii	0.86 (1)	1.87 (1)	2.725 (5)	179 (5)
O9—H9A⋯O3iii	0.86 (1)	2.57 (4)	3.145 (5)	125 (4)
O9—H9A⋯O2iii	0.86 (1)	2.01 (1)	2.860 (5)	168 (5)
O1W—H1WA⋯O3	0.96 (1)	1.88 (1)	2.838 (5)	172 (5)
O1W—H1WB⋯O7iv	0.96 (1)	2.04 (3)	2.880 (5)	145 (4)

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