catena-Poly[[tetraaquanickel(II)]-μ3-benzene-1,3,5-tricarboxylato-3′:1:2-κ4O1:O3,O3′:O5-[tetraaquanickel(II)]-μ2-benzene-1,3,5-tricarboxylato-2:3κ2O1:O3-[tetraaquanickel(II)]]

Hsu, S.-C.; Chiang, P.-H.; Chang, C.-H.; Lin, C.-H.

doi:10.1107/S1600536809016729

metal-organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 6| June 2009| Pages m625-m626

doi:10.1107/S1600536809016729

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catena-Poly[[tetraaquanickel(II)]-μ₃-benzene-1,3,5-tricarboxylato-3′:1:2-κ⁴O¹:O³,O^3′:O⁵-[tetraaquanickel(II)]-μ₂-benzene-1,3,5-tricarboxylato-2:3κ²O¹:O³-[tetraaquanickel(II)]]

Shih-Chen Hsu,^a Pei-Hsuan Chiang,^a Chih-Hsien Chang ^a and Chia-Her Lin ^a ^*

^aDepartment of Chemistry, Chung-Yuan Christian University, Chung-Li 320, Taiwan
^*Correspondence e-mail: chiaher@cycu.edu.tw

(Received 14 March 2009; accepted 4 May 2009; online 14 May 2009)

The microwave solvothermal reaction of nickel nitrate with trimesic acid provided the title compound, [Ni₃(BTC)₂(H₂O)₁₂]_n (BTC = benzene-1,3,5-tricarboxylate anion, C₉H₃O₆), which is a metal coordination polymer composed of one-dimensional zigzag chains. The crystal under investigation was ramecically twinned with an approximate twin domain ratio of 1:1. In the asymmetric unit, there are two types of Ni atoms. One of the NiO₆ groups (2 symmetry) is coordinated to only one carboxylate group and thus terminal, the other is bridging, forming the coordination polymer. The extended chains are connected by the organic BTC anions via μ₂-linkages. O—H⋯O hydrogen bonds and π–π interactions between the chains [centroid–centroid distance 3.58 (1) Å] induce the complex to mimic a three-dimensional structure.

Related literature

For background information on the solvothermal synthesis of coordination polymers with organic carboxylate ligands, see: Kitagawa et al. (2004 ).

Experimental

Crystal data

[Ni₃(C₉H₃O₆)₂(H₂O)₁₂]
M_r = 806.49
Monoclinic, C 2
a = 17.3394 (10) Å
b = 12.8724 (7) Å
c = 6.5462 (3) Å
β = 111.609 (2)°
V = 1358.42 (12) Å³
Z = 2
Mo Kα radiation
μ = 2.17 mm⁻¹
T = 295 K
0.25 × 0.18 × 0.15 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.613, T_max = 0.737
6798 measured reflections
3299 independent reflections
3156 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.068
S = 1.07
3299 reflections
208 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.38 e Å⁻³
Absolute structure: Flack (1983 ), 1531 Friedel pairs
Flack parameter: 0.549 (12)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O9—H9B⋯O10ⁱ	0.87	1.90	2.767 (3)	172
O9—H9A⋯O12ⁱⁱ	0.81	2.33	3.102 (3)	160
O6—H6B⋯O1ⁱⁱⁱ	0.97	1.98	2.942 (3)	173
O6—H6A⋯O11^iv	0.85	1.83	2.683 (3)	173
O5—H5B⋯O12^iv	0.92	1.95	2.825 (3)	158
O5—H5A⋯O11	0.81	1.79	2.559 (3)	156
O4—H4C⋯O1ⁱ	0.92	1.97	2.870 (3)	167
O4—H4B⋯O10	0.91	1.77	2.617 (3)	154
O3—H3B⋯O12^v	0.94	1.97	2.907 (3)	171
O3—H3A⋯O4^vi	0.94	2.03	2.917 (3)	156
O2—H2B⋯O5^vii	0.83	1.81	2.638 (3)	173
O2—H2A⋯O12^viii	0.85	2.02	2.861 (4)	171
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+1]$ ; (iii) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z]$ ; (iv) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z]$ ; (v) $[x-{\script{1\over 2}}, y+{\script{3\over 2}}, z]$ ; (vi) $[x-{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (vii) x, y+1, z; (viii) $[-x+{\script{3\over 2}}, y+{\script{3\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); 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/S1600536809016729/zl2190sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809016729/zl2190Isup2.hkl

checkCIF report

Comment top

The synthesis of coordination polymers has been a subject of intense research owing to their interesting structural chemistry and potential applications in gas storage, separation, catalysis, magnetism, and luminescence. A large number of these materials have been synthesized by solvothermal reactions with organic carboxyl acids (Kitagawa et al. 2004). The coordination polymers commonly adopt three-dimensional, two-dimensional, and one-dimensional structures via employed metal ions as connectors and rigid or flexible organic ligands as linkers. As a further study of such a complex, we report here the structure of the title compound, a nickel coordination polymer with one dimensional zigzag chains.

The crystal structure analysis of the title compound reveals the structure to be composed of zigzag chains. The compound has a non-centrosymmetric C2 space group and the crystal under investigation was twinned with a Flack parameter of 0.549 (12). The asymmetric unit contains two types of NiO₆ groups (Fig. 1). The group of Ni1 is terminal and the metal atom is coordinated in a bidentate fashion to one carboxylate ligand and to four water oxygen atoms. The other nickel atom, Ni2, is coordinated in the axial positions by two monodenate carboxylate groups, and by four water molecules in the equatorial positions. All Ni–O bond lengths range from 2.021 (3) to 2.102 (3) Å. The BTC anions also have two types of coordination modes towards the NiO₆ groups. One of the BTC bridges between two Ni2 atoms via two of its carboxylate groups. The third carboxylate is protonated and not metal coordinated. The other BTC ligand bridges via two of its carboxylates between two Ni2 atoms. Its third carboxylate group coordinates to a Ni1 atom. The one-dimensional chains thus formed are further linked with each other by hydrogen bonds and π-π interactions to form a layered structure. Hydrogen bonding interactions between coordination waters are O2–H2B···O5^ix, O3–H3A···O4^viii, O4–H4B···O10, O4–H4C···O1ⁱⁱⁱ, O5–H5A···O11, O6–H6A···O11^vi, O6–H6B···O1^v, and O9–H9B···O10ⁱⁱⁱ (Fig. 2). The uncoordinated carboxylate group is involved in hydrogen bonding via O2–H2A···O12^x, O3–H3B···O12^vii, O5–H5B···O12^vi, and O9–H9A···O12^iv between nearby layers (Fig. 3, see table 1 for numerical values and symmetry operators). π-π stacking interactions are found between aromatic rings made up of C1 to C5, C1ⁱⁱ and C5ⁱⁱ, and the ring defined by C2, C7, C9, C10, C10ⁱ and C9ⁱ (symmetry operators: (i) -x+1, y, -z; (ii) -x+2, y, -z+1). The centroid to centroid distance between Cg1 and Cg2^ix defined by the two rings is 3.58 (1) Å. The rings are slipped against each other, and the approximate interplanar distance is 3.27 Å (as defined by the distance of carbon atom C4 and Cg2^ix (symmetry operator: (ix) 1/2+x, -1/2+y, z). These π-π interactions connect nearby layers with each other (Fig. 4).

Related literature top

For background information on the solvothermal synthesis of coordination polymers with organic carboxylateligands, see: Kitagawa et al. (2004).

Experimental top

The title complex was obtained from the reaction of 1,3,5-benzenetricarboxylic acid (C₉H₆O₆, H₃BTC, 0.421 g, 2 mmol), Ni(NO₃)₂.6H₂O (0.8724 g, 3 mmol), ethanol (5.0 ml) and H₂O (5.0 ml) with pH value of 2.15. The reaction mixture was heated to 453 K for 20 minutes using a microwave output power of 400 W. The title compound in the form of green crystals was collected in a yield of 0.0979 g (12.2%, based on carboxylic acid reagent).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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. A view of the title compound, showing 50% probability displacement ellipsoids. [symmetry codes: (i) -x+1, y, -z; (ii) -x+2, y, -z+1].
	Fig. 2. The zigzag chains of the title compound with hydrogen bonding (blue dashed lines, H atoms are omitted).
	Fig. 3. The packing diagram of zigzag chains with hydrogen bonding (blue dashed lines, H atoms are omitted).
	Fig. 4. The side view of the layers with the pi-pi interactions (blue dashed lines, H atoms are omitted).

catena-Poly[[tetraaquanickel(II)]-µ₃-benzene-1,3,5-tricarboxylato- 3':1:2-κ⁴O¹:O³,O^3':O⁵- [tetraaquanickel(II)]-\m₂-benzene-1,3,5-tricarboxylato- 2:3κ²O¹:O³-[tetraaquanickel(II)]] top

Crystal data top

[Ni₃(C₉H₃O₆)₂(H₂O)₁₂]	F(000) = 828
M_r = 806.49	D_x = 1.972 Mg m⁻³
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2y	Cell parameters from 4802 reflections
a = 17.3394 (10) Å	θ = 2.5–28.3°
b = 12.8724 (7) Å	µ = 2.17 mm⁻¹
c = 6.5462 (3) Å	T = 295 K
β = 111.609 (2)°	Columnar, light-blue
V = 1358.42 (12) Å³	0.25 × 0.18 × 0.15 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	3299 independent reflections
Radiation source: fine-focus sealed tube	3156 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
ϕ and ω scans	θ_max = 28.4°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −23→22
T_min = 0.613, T_max = 0.737	k = −16→17
6798 measured reflections	l = −7→8

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)] = 0.028	H-atom parameters constrained
wR(F²) = 0.068	w = 1/[σ^2^(F_o^2^) + (0.0363P)^2^] where P = (F_o^2^ + 2F_c^2^)/3
S = 1.07	(Δ/σ)_max = 0.001
3299 reflections	Δρ_max = 0.48 e Å⁻³
208 parameters	Δρ_min = −0.38 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1531 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.549 (12)

Crystal data top

[Ni₃(C₉H₃O₆)₂(H₂O)₁₂]	V = 1358.42 (12) Å³
M_r = 806.49	Z = 2
Monoclinic, C2	Mo Kα radiation
a = 17.3394 (10) Å	µ = 2.17 mm⁻¹
b = 12.8724 (7) Å	T = 295 K
c = 6.5462 (3) Å	0.25 × 0.18 × 0.15 mm
β = 111.609 (2)°

Data collection top

Bruker APEXII CCD diffractometer	3299 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	3156 reflections with I > 2σ(I)
T_min = 0.613, T_max = 0.737	R_int = 0.046
6798 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	H-atom parameters constrained
wR(F²) = 0.068	Δρ_max = 0.48 e Å⁻³
S = 1.07	Δρ_min = −0.38 e Å⁻³
3299 reflections	Absolute structure: Flack (1983), 1531 Friedel pairs
208 parameters	Absolute structure parameter: 0.549 (12)
1 restraint

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 > 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
Ni1	0.5000	0.68238 (4)	0.0000	0.02554 (13)
Ni2	0.757745 (18)	−0.02765 (2)	0.22999 (5)	0.01825 (9)
O1	0.56460 (12)	0.54287 (15)	0.1157 (3)	0.0269 (4)
O2	0.58008 (19)	0.7828 (2)	0.1959 (5)	0.0659 (10)
H2A	0.5729	0.8177	0.2978	0.079*
H2B	0.6113	0.8141	0.1460	0.079*
O3	0.44433 (15)	0.68727 (18)	0.2333 (4)	0.0396 (5)
H3A	0.4101	0.6382	0.2657	0.047*
H3B	0.4382	0.7546	0.2822	0.047*
O4	0.83989 (12)	0.08047 (16)	0.4286 (3)	0.0259 (4)
H4B	0.8029	0.1274	0.4439	0.031*
H4C	0.8708	0.0577	0.5683	0.031*
O5	0.67707 (12)	−0.13068 (15)	0.0142 (3)	0.0229 (4)
H5A	0.7035	−0.1838	0.0246	0.028*
H5B	0.6543	−0.1191	−0.1354	0.028*
O6	0.77890 (12)	0.03467 (16)	−0.0377 (3)	0.0316 (5)
H6A	0.7595	0.0949	−0.0829	0.038*
H6B	0.8290	0.0322	−0.0698	0.038*
O7	0.85264 (11)	−0.12996 (14)	0.3010 (3)	0.0223 (4)
O8	0.65774 (12)	0.06587 (15)	0.1685 (3)	0.0237 (4)
O9	0.73419 (13)	−0.09194 (17)	0.4944 (3)	0.0299 (5)
H9A	0.6945	−0.0832	0.5292	0.036*
H9B	0.7453	−0.1563	0.5346	0.036*
O10	0.71601 (12)	0.21051 (15)	0.3445 (3)	0.0271 (4)
O11	0.78560 (12)	−0.27492 (14)	0.1508 (3)	0.0253 (4)
O12	0.93126 (13)	−0.61400 (16)	0.4291 (4)	0.0333 (5)
C1	0.92709 (16)	−0.3961 (2)	0.3927 (4)	0.0156 (5)
H1A	0.8781	−0.4324	0.3216	0.019*
C2	0.5000	0.1625 (3)	0.0000	0.0159 (7)
H2C	0.5000	0.0903	0.0000	0.019*
C3	1.0000	−0.4499 (3)	0.5000	0.0157 (7)
C4	1.0000	−0.2341 (3)	0.5000	0.0158 (6)
H4A	1.0000	−0.1618	0.5000	0.019*
C5	0.92667 (15)	−0.28782 (19)	0.3907 (4)	0.0149 (5)
C6	0.65536 (16)	0.1604 (2)	0.2156 (4)	0.0178 (5)
C7	0.5000	0.3778 (3)	0.0000	0.0163 (7)
C8	0.84852 (15)	−0.2270 (2)	0.2722 (4)	0.0159 (5)
C9	0.57403 (16)	0.2158 (2)	0.1077 (4)	0.0159 (5)
C10	0.57306 (15)	0.3237 (2)	0.1084 (4)	0.0167 (5)
H10A	0.6218	0.3601	0.1821	0.020*
C11	0.5000	0.4925 (3)	0.0000	0.0204 (8)
C12	1.0000	−0.5673 (3)	0.5000	0.0211 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Ni1	0.0250 (3)	0.0154 (2)	0.0335 (3)	0.000	0.0076 (2)	0.000
Ni2	0.01496 (14)	0.01230 (14)	0.02472 (16)	0.00137 (13)	0.00407 (11)	0.00049 (13)
O1	0.0201 (10)	0.0127 (9)	0.0360 (11)	−0.0018 (8)	−0.0037 (9)	−0.0020 (8)
O2	0.081 (2)	0.065 (2)	0.0751 (18)	−0.0546 (18)	0.0557 (17)	−0.0443 (17)
O3	0.0483 (14)	0.0264 (11)	0.0539 (13)	−0.0045 (11)	0.0305 (11)	−0.0004 (11)
O4	0.0207 (10)	0.0182 (10)	0.0317 (11)	0.0019 (8)	0.0013 (9)	−0.0023 (9)
O5	0.0204 (9)	0.0168 (10)	0.0260 (9)	0.0023 (7)	0.0019 (8)	−0.0001 (8)
O6	0.0284 (11)	0.0259 (11)	0.0450 (12)	0.0085 (9)	0.0187 (10)	0.0130 (9)
O7	0.0154 (9)	0.0131 (9)	0.0353 (11)	0.0028 (7)	0.0057 (8)	0.0000 (8)
O8	0.0203 (9)	0.0134 (9)	0.0345 (11)	0.0048 (7)	0.0068 (9)	−0.0024 (8)
O9	0.0294 (11)	0.0268 (11)	0.0337 (10)	0.0060 (9)	0.0120 (9)	0.0091 (8)
O10	0.0203 (10)	0.0203 (10)	0.0335 (10)	0.0044 (8)	0.0013 (9)	−0.0056 (8)
O11	0.0179 (9)	0.0163 (9)	0.0327 (10)	0.0029 (7)	−0.0014 (8)	−0.0047 (8)
O12	0.0333 (12)	0.0145 (10)	0.0376 (12)	−0.0044 (9)	−0.0040 (10)	0.0022 (9)
C1	0.0168 (12)	0.0127 (12)	0.0161 (12)	−0.0027 (10)	0.0045 (10)	−0.0025 (9)
C2	0.0224 (17)	0.0081 (16)	0.0183 (16)	0.000	0.0089 (14)	0.000
C3	0.0200 (17)	0.0096 (16)	0.0155 (16)	0.000	0.0039 (14)	0.000
C4	0.0202 (16)	0.0100 (15)	0.0184 (15)	0.000	0.0085 (13)	0.000
C5	0.0142 (11)	0.0137 (11)	0.0157 (11)	0.0025 (8)	0.0042 (9)	0.0000 (8)
C6	0.0193 (12)	0.0174 (13)	0.0171 (11)	0.0021 (10)	0.0073 (10)	0.0016 (9)
C7	0.0194 (17)	0.0130 (16)	0.0167 (16)	0.000	0.0068 (14)	0.000
C8	0.0159 (11)	0.0145 (12)	0.0187 (11)	0.0010 (9)	0.0081 (9)	−0.0004 (9)
C9	0.0183 (12)	0.0134 (11)	0.0178 (12)	0.0025 (9)	0.0087 (10)	0.0006 (9)
C10	0.0144 (11)	0.0156 (12)	0.0194 (12)	−0.0013 (9)	0.0052 (10)	0.0002 (9)
C11	0.0188 (16)	0.016 (2)	0.0235 (17)	0.000	0.0036 (14)	0.000
C12	0.029 (2)	0.0099 (17)	0.0175 (17)	0.000	0.0009 (15)	0.000

Geometric parameters (Å, º) top

Ni1—O2ⁱ	1.983 (3)	O9—H9A	0.8087
Ni1—O2	1.983 (3)	O9—H9B	0.8686
Ni1—O3ⁱ	2.087 (2)	O10—C6	1.257 (3)
Ni1—O3	2.087 (2)	O11—C8	1.250 (3)
Ni1—O1ⁱ	2.1043 (19)	O12—C12	1.261 (3)
Ni1—O1	2.1043 (19)	C1—C3	1.385 (3)
Ni1—C11	2.445 (4)	C1—C5	1.393 (4)
Ni2—O7	2.0235 (18)	C1—H1A	0.9300
Ni2—O8	2.026 (2)	C2—C9	1.396 (3)
Ni2—O5	2.0630 (19)	C2—C9ⁱ	1.396 (3)
Ni2—O4	2.0716 (19)	C2—H2C	0.9300
Ni2—O6	2.0787 (19)	C3—C1ⁱⁱ	1.385 (3)
Ni2—O9	2.090 (2)	C3—C12	1.512 (5)
O1—C11	1.275 (3)	C4—C5	1.392 (3)
O2—H2A	0.8508	C4—C5ⁱⁱ	1.392 (3)
O2—H2B	0.8329	C4—H4A	0.9300
O3—H3A	0.9431	C5—C8	1.509 (3)
O3—H3B	0.9439	C6—C9	1.504 (3)
O4—H4B	0.9132	C7—C10	1.390 (3)
O4—H4C	0.9216	C7—C10ⁱ	1.390 (3)
O5—H5A	0.8116	C7—C11	1.476 (5)
O5—H5B	0.9233	C9—C10	1.390 (3)
O6—H6A	0.8533	C10—H10A	0.9300
O6—H6B	0.9664	C11—O1ⁱ	1.275 (3)
O7—C8	1.261 (3)	C12—O12ⁱⁱ	1.261 (3)
O8—C6	1.260 (3)

O2ⁱ—Ni1—O2	98.7 (2)	H5A—O5—H5B	103.5
O2ⁱ—Ni1—O3ⁱ	84.80 (10)	Ni2—O6—H6A	118.3
O2—Ni1—O3ⁱ	92.94 (10)	Ni2—O6—H6B	128.5
O2ⁱ—Ni1—O3	92.94 (10)	H6A—O6—H6B	103.1
O2—Ni1—O3	84.80 (10)	C8—O7—Ni2	127.85 (17)
O3ⁱ—Ni1—O3	176.54 (13)	C6—O8—Ni2	128.92 (18)
O2ⁱ—Ni1—O1ⁱ	99.80 (12)	Ni2—O9—H9A	128.6
O2—Ni1—O1ⁱ	160.42 (11)	Ni2—O9—H9B	122.6
O3ⁱ—Ni1—O1ⁱ	95.20 (9)	H9A—O9—H9B	99.5
O3—Ni1—O1ⁱ	87.75 (9)	C3—C1—C5	120.4 (2)
O2ⁱ—Ni1—O1	160.42 (11)	C3—C1—H1A	119.8
O2—Ni1—O1	99.80 (12)	C5—C1—H1A	119.8
O3ⁱ—Ni1—O1	87.75 (9)	C9—C2—C9ⁱ	121.2 (3)
O3—Ni1—O1	95.20 (9)	C9—C2—H2C	119.4
O1ⁱ—Ni1—O1	62.84 (10)	C9ⁱ—C2—H2C	119.4
O2ⁱ—Ni1—C11	130.67 (11)	C1ⁱⁱ—C3—C1	119.9 (3)
O2—Ni1—C11	130.67 (11)	C1ⁱⁱ—C3—C12	120.03 (16)
O3ⁱ—Ni1—C11	91.73 (7)	C1—C3—C12	120.03 (16)
O3—Ni1—C11	91.73 (7)	C5—C4—C5ⁱⁱ	120.4 (3)
O1ⁱ—Ni1—C11	31.42 (5)	C5—C4—H4A	119.8
O1—Ni1—C11	31.42 (5)	C5ⁱⁱ—C4—H4A	119.8
O7—Ni2—O8	175.21 (9)	C4—C5—C1	119.4 (2)
O7—Ni2—O5	91.60 (7)	C4—C5—C8	118.9 (2)
O8—Ni2—O5	86.05 (8)	C1—C5—C8	121.6 (2)
O7—Ni2—O4	88.86 (8)	O10—C6—O8	124.4 (2)
O8—Ni2—O4	93.77 (8)	O10—C6—C9	118.7 (2)
O5—Ni2—O4	176.11 (9)	O8—C6—C9	116.9 (2)
O7—Ni2—O6	93.66 (8)	C10—C7—C10ⁱ	119.9 (3)
O8—Ni2—O6	90.41 (8)	C10—C7—C11	120.07 (17)
O5—Ni2—O6	87.51 (8)	C10ⁱ—C7—C11	120.07 (17)
O4—Ni2—O6	88.61 (8)	O11—C8—O7	124.9 (2)
O7—Ni2—O9	86.70 (8)	O11—C8—C5	118.6 (2)
O8—Ni2—O9	89.18 (8)	O7—C8—C5	116.5 (2)
O5—Ni2—O9	91.29 (8)	C10—C9—C2	118.9 (2)
O4—Ni2—O9	92.59 (8)	C10—C9—C6	118.9 (2)
O6—Ni2—O9	178.76 (9)	C2—C9—C6	122.2 (2)
C11—O1—Ni1	89.19 (17)	C9—C10—C7	120.6 (3)
Ni1—O2—H2A	125.6	C9—C10—H10A	119.7
Ni1—O2—H2B	117.6	C7—C10—H10A	119.7
H2A—O2—H2B	110.8	O1—C11—O1ⁱ	118.8 (3)
Ni1—O3—H3A	130.1	O1—C11—C7	120.61 (16)
Ni1—O3—H3B	114.6	O1ⁱ—C11—C7	120.61 (16)
H3A—O3—H3B	112.3	O1—C11—Ni1	59.39 (16)
Ni2—O4—H4B	99.5	O1ⁱ—C11—Ni1	59.39 (16)
Ni2—O4—H4C	115.0	C7—C11—Ni1	180.0
H4B—O4—H4C	106.1	O12ⁱⁱ—C12—O12	123.1 (4)
Ni2—O5—H5A	105.4	O12ⁱⁱ—C12—C3	118.45 (18)
Ni2—O5—H5B	122.7	O12—C12—C3	118.45 (18)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9B···O10ⁱⁱⁱ	0.87	1.90	2.767 (3)	172
O9—H9A···O12^iv	0.81	2.33	3.102 (3)	160
O6—H6B···O1^v	0.97	1.98	2.942 (3)	173
O6—H6A···O11^vi	0.85	1.83	2.683 (3)	173
O5—H5B···O12^vi	0.92	1.95	2.825 (3)	158
O5—H5A···O11	0.81	1.79	2.559 (3)	156
O4—H4C···O1ⁱⁱⁱ	0.92	1.97	2.870 (3)	167
O4—H4B···O10	0.91	1.77	2.617 (3)	154
O3—H3B···O12^vii	0.94	1.97	2.907 (3)	171
O3—H3A···O4^viii	0.94	2.03	2.917 (3)	156
O2—H2B···O5^ix	0.83	1.81	2.638 (3)	173
O2—H2A···O12^x	0.85	2.02	2.861 (4)	171

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

Experimental details

Crystal data
Chemical formula	[Ni₃(C₉H₃O₆)₂(H₂O)₁₂]
M_r	806.49
Crystal system, space group	Monoclinic, C2
Temperature (K)	295
a, b, c (Å)	17.3394 (10), 12.8724 (7), 6.5462 (3)
β (°)	111.609 (2)
V (Å³)	1358.42 (12)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.17
Crystal size (mm)	0.25 × 0.18 × 0.15

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.613, 0.737
No. of measured, independent and observed [I > 2σ(I)] reflections	6798, 3299, 3156
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.068, 1.07
No. of reflections	3299
No. of parameters	208
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.38
Absolute structure	Flack (1983), 1531 Friedel pairs
Absolute structure parameter	0.549 (12)

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXTL (Sheldrick, 2008.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9B···O10ⁱ	0.87	1.90	2.767 (3)	171.5
O9—H9A···O12ⁱⁱ	0.81	2.33	3.102 (3)	160.0
O6—H6B···O1ⁱⁱⁱ	0.97	1.98	2.942 (3)	173.1
O6—H6A···O11^iv	0.85	1.83	2.683 (3)	173.1
O5—H5B···O12^iv	0.92	1.95	2.825 (3)	157.6
O5—H5A···O11	0.81	1.79	2.559 (3)	156.4
O4—H4C···O1ⁱ	0.92	1.97	2.870 (3)	166.7
O4—H4B···O10	0.91	1.77	2.617 (3)	154.0
O3—H3B···O12^v	0.94	1.97	2.907 (3)	171.3
O3—H3A···O4^vi	0.94	2.03	2.917 (3)	155.8
O2—H2B···O5^vii	0.83	1.81	2.638 (3)	173.0
O2—H2A···O12^viii	0.85	2.02	2.861 (4)	171.3

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

Acknowledgements

This research project was supported by the National Science Council of Taiwan (NSC97–2113-M-033–003-MY2) and by the project of the specific research fields of Chung Yuan Christian University, Taiwan, under grant No. CYCU-97-CR—CH.

References

Bruker (2008). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Kitagawa, S., Kitaura, R. & Noro, S. (2004). Angew. Chem. Int. Ed. 43, 2334–2375. 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

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