catena-Poly[[triaqua­nickel(II)]-μ-5-carb­oxy­benzene-1,3-dicarboxyl­ato-κ²O¹:O³]

In the title compound, [Ni(C₉H₄O₆)(H₂O)₃]_n, the Ni^II ion has a distorted NiO₅ square-pyramidal geometry, the maximum deviation from the least-squares plane formed by the basal atoms being 0.9351 (13) Å. The basal plane is formed by two O atoms from carboxyl­ate residues of the 5-carb­oxy­benzene-1,3-dicarboxyl­ate ligand and by two O atoms from water mol­ecules. The O atom of the third water mol­ecule is axially positioned, 1.7890 (19) Å perpendicular to the basal plane. The 5-carb­oxy­benzene-1,3-dicarboxyl­ate ligand bridges the metal atoms, forming a polymeric chain along the b axis. O—H...O hydrogen bonds between the water mol­ecules and carboxyl­ate groups stabilize the crystal structure.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.023
• wR factor = 0.102
• Data-to-parameter ratio = 11.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    O4     --  C8      ..        6.0 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    --  O1      ..        7.3 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    --  O1W     ..        5.5 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    --  O3W     ..        6.6 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Ni1    --  O6_b    ..        7.3 su
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Ni1
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.1
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.596         13

Alert level G
PLAT004_ALERT_5_G Info: Polymeric Structure Found with Dimension .          1
PLAT005_ALERT_5_G No _iucr_refine_instructions_details in CIF ....          ?
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          91 Perc.

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   8 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   3 ALERT level G = General information/check it is not something unexpected

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   7 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   2 ALERT type 5 Informative message, check

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S1. Comment

In recent years, the construction of metal complexes based on 1,3,5-benzenetricarboxylic acid ligand has been investigated owing to their potential applications in many fields (Xia et al., 2004; Modec & Brencic, 2005; Wei & Han, 2005; Han & Wei, 2005; Wang et al., 2005; Che et al., 2008; He et al., 2008; Li et al., 2008; Gao et al., 2009). In order to search for new metal complex based on 1,3,5-benzenetricarboxylic acid ligand, the title complex, (I) was synthesized and its crystal determined (Fig. 1). The bond lengths and angles are normal (Allen et al., 1987). In the crystal structure, the HBTC ligands bridge the Ni atoms, forming a chain along the b axis (Fig. 2). O—H···O hydrogen bonds between the water molecules and carboxylate groups stabilize the structure.

Related literature

For the applications and stuctures of related metal complexes of 1,3,5-benzenetricarboxylic acid, see: Xia et al. (2004); Modec & Brencic (2005); Wei & Han (2005); Han & Wei (2005); Wang et al. (2005); Che et al. (2008); He et al. (2008); Li et al. (2008); Gao et al. (2009). For bond-length data, see: Allen et al. (1987).

S2. Experimental

A mixture of NiNO₃^.6H₂O (0.10 mmol), 1,3,5-benzenetricarboxylic acid (H3BTC, 0.10 mmol), Et₃N (0.1 ml), EtOH (2 ml) and H₂O (2 ml) was sealed in a 10 ml Tefon-lined stainless-steel reactor and then heated to 393 K for 48 h under autogenous pressure. The mixture was slowly cooled to room temperature. Green block crystals suitable for X-ray diffraction analysis were collected by filtration..

S3. Refinement

H atoms attached to C atoms were placed in calculated positions (C—H = 0.93 Å) and refined as riding atoms and with U_iso(H) = 1.2 U_eq(C, N),respectively. The carboxy and water H atoms were located in a difference map and refined with O—H bond length from 0.82 to 0.85 Å and U_iso(H) = 1.5 U_eq(O).

Computing details

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level [symmetry codes: (A) -x, 1/2 + y, 1/2 - z]
	Fig. 2. View of the chain structure in the title compound.

catena-Poly[[triaquanickel(II)]-µ-5-carboxybenzene-1,3-dicarboxylato- κ²O¹:O³]

Crystal data

[Ni(C9H4O6)(H2O)3]	F(000) = 656
Mr = 320.88	Dx = 1.936 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6807 reflections
a = 6.838 (2) Å	θ = 2.6–27.8°
b = 18.809 (5) Å	µ = 1.81 mm^−1
c = 10.705 (3) Å	T = 296 K
β = 126.901 (14)°	Block, green
V = 1101.0 (5) Å^3	0.30 × 0.25 × 0.20 mm
Z = 4

Data collection

Bruker SMART APEXII CCD area-detector diffractometer	1938 independent reflections
Radiation source: fine-focus sealed tube	1864 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
φ and ω scans	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→8
Tmin = 0.613, Tmax = 0.714	k = −22→21
7973 measured reflections	l = −10→12

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.023	H-atom parameters constrained
wR(F^2) = 0.102	w = 1/[σ^2(Fo^2) + (0.0942P)^2 + 0.090P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.002
1938 reflections	Δρmax = 0.32 e Å^−3
173 parameters	Δρmin = −0.38 e Å^−3
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.036 (3)

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.1199 (3)	0.63000 (10)	0.3748 (2)	0.0228 (4)
C2	0.2227 (3)	0.56454 (10)	0.4747 (2)	0.0203 (4)
C3	0.3935 (3)	0.57173 (10)	0.6364 (2)	0.0213 (4)
H3	0.4431	0.6168	0.6806	0.026*
C4	0.4892 (3)	0.51227 (11)	0.7312 (2)	0.0220 (4)
C5	0.4154 (3)	0.44487 (11)	0.6640 (2)	0.0231 (4)
H5	0.4805	0.4047	0.7273	0.028*
C6	0.2465 (3)	0.43711 (10)	0.5040 (2)	0.0196 (4)
C7	0.1480 (3)	0.49745 (10)	0.4085 (2)	0.0209 (4)
H7	0.0327	0.4925	0.3010	0.025*
C8	0.6645 (4)	0.51904 (11)	0.9031 (2)	0.0281 (5)
C9	0.1625 (3)	0.36441 (10)	0.4346 (2)	0.0214 (4)
Ni1	0.11091 (4)	0.773616 (12)	0.32089 (3)	0.01894 (19)
O1	0.2116 (3)	0.68864 (7)	0.44634 (16)	0.0274 (4)
O2	−0.0451 (3)	0.62603 (8)	0.23299 (18)	0.0408 (4)
O3	0.7481 (3)	0.58432 (8)	0.95119 (18)	0.0371 (4)
H3A	0.8391	0.5853	1.0470	0.056*
O4	0.7292 (4)	0.47053 (9)	0.99436 (19)	0.0532 (6)
O5	0.2577 (3)	0.31100 (8)	0.51934 (18)	0.0314 (4)
O6	−0.0066 (3)	0.36214 (7)	0.28913 (17)	0.0304 (4)
O1W	−0.1375 (4)	0.78863 (9)	0.3587 (2)	0.0448 (5)
H1W	−0.0823	0.8266	0.4123	0.067*
H2W	−0.1097	0.7563	0.4230	0.067*
O2W	0.3070 (3)	0.74742 (11)	0.2478 (2)	0.0430 (4)
H4W	0.4388	0.7241	0.3076	0.065*
H3W	0.3268	0.7712	0.1886	0.065*
O3W	0.4158 (3)	0.82950 (8)	0.53994 (18)	0.0394 (4)
H5W	0.4312	0.8744	0.5432	0.059*
H6W	0.5507	0.8132	0.5647	0.059*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0263 (9)	0.0193 (10)	0.0166 (9)	0.0008 (7)	0.0096 (7)	−0.0008 (8)
C2	0.0241 (9)	0.0153 (10)	0.0193 (9)	−0.0015 (7)	0.0119 (8)	0.0002 (7)
C3	0.0246 (9)	0.0140 (10)	0.0209 (9)	−0.0032 (7)	0.0113 (8)	−0.0021 (8)
C4	0.0240 (10)	0.0193 (9)	0.0181 (10)	−0.0005 (8)	0.0103 (8)	−0.0008 (8)
C5	0.0285 (9)	0.0155 (10)	0.0227 (10)	0.0014 (7)	0.0141 (8)	0.0032 (7)
C6	0.0238 (9)	0.0163 (10)	0.0192 (9)	−0.0016 (7)	0.0132 (8)	−0.0018 (7)
C7	0.0239 (9)	0.0194 (10)	0.0181 (9)	−0.0020 (8)	0.0119 (8)	−0.0025 (8)
C8	0.0316 (10)	0.0233 (11)	0.0215 (10)	−0.0010 (8)	0.0117 (9)	−0.0021 (8)
C9	0.0246 (9)	0.0170 (10)	0.0243 (10)	−0.0003 (7)	0.0157 (8)	−0.0014 (8)
Ni1	0.0249 (2)	0.0112 (3)	0.0160 (3)	0.00245 (7)	0.00978 (19)	0.00329 (7)
O1	0.0346 (8)	0.0141 (7)	0.0212 (7)	−0.0010 (5)	0.0102 (6)	0.0009 (6)
O2	0.0520 (10)	0.0239 (9)	0.0193 (8)	0.0012 (7)	0.0070 (7)	0.0010 (7)
O3	0.0508 (10)	0.0231 (8)	0.0189 (8)	−0.0080 (7)	0.0111 (7)	−0.0034 (6)
O4	0.0761 (13)	0.0245 (9)	0.0189 (8)	−0.0031 (8)	0.0072 (8)	0.0062 (7)
O5	0.0348 (8)	0.0179 (8)	0.0331 (8)	−0.0015 (6)	0.0159 (7)	0.0024 (6)
O6	0.0358 (8)	0.0196 (7)	0.0222 (7)	−0.0037 (6)	0.0102 (6)	−0.0057 (6)
O1W	0.0583 (11)	0.0283 (8)	0.0682 (13)	0.0123 (9)	0.0489 (11)	0.0156 (9)
O2W	0.0453 (10)	0.0524 (11)	0.0384 (9)	0.0201 (9)	0.0289 (9)	0.0161 (9)
O3W	0.0399 (8)	0.0279 (9)	0.0331 (8)	−0.0027 (7)	0.0126 (7)	−0.0066 (7)

Geometric parameters (Å, º)

C1—O2	1.236 (3)	C9—O5	1.244 (2)
C1—O1	1.273 (2)	C9—O6	1.266 (3)
C1—C2	1.500 (3)	Ni1—O6^i	1.9129 (15)
C2—C7	1.386 (3)	Ni1—O1	1.9292 (14)
C2—C3	1.397 (3)	Ni1—O2W	1.9781 (17)
C3—C4	1.383 (3)	Ni1—O1W	1.9884 (18)
C3—H3	0.9300	Ni1—O3W	2.2536 (16)
C4—C5	1.394 (3)	O3—H3A	0.8200
C4—C8	1.480 (3)	O6—Ni1^ii	1.9129 (15)
C5—C6	1.383 (3)	O1W—H1W	0.8501
C5—H5	0.9300	O1W—H2W	0.8500
C6—C7	1.400 (3)	O2W—H4W	0.8501
C6—C9	1.496 (3)	O2W—H3W	0.8500
C7—H7	0.9300	O3W—H5W	0.8501
C8—O4	1.210 (3)	O3W—H6W	0.8500
C8—O3	1.321 (3)
O2—C1—O1	123.25 (18)	O5—C9—C6	119.96 (17)
O2—C1—C2	121.17 (17)	O6—C9—C6	115.87 (16)
O1—C1—C2	115.58 (16)	O6^i—Ni1—O1	174.25 (7)
C7—C2—C3	119.92 (18)	O6^i—Ni1—O2W	93.67 (7)
C7—C2—C1	120.79 (17)	O1—Ni1—O2W	91.48 (7)
C3—C2—C1	119.28 (17)	O6^i—Ni1—O1W	87.32 (7)
C4—C3—C2	120.44 (18)	O1—Ni1—O1W	88.13 (7)
C4—C3—H3	119.8	O2W—Ni1—O1W	168.69 (8)
C2—C3—H3	119.8	O6^i—Ni1—O3W	90.27 (6)
C3—C4—C5	119.43 (18)	O1—Ni1—O3W	86.65 (6)
C3—C4—C8	121.08 (18)	O2W—Ni1—O3W	96.01 (8)
C5—C4—C8	119.48 (17)	O1W—Ni1—O3W	95.25 (8)
C6—C5—C4	120.64 (18)	C1—O1—Ni1	117.27 (12)
C6—C5—H5	119.7	C8—O3—H3A	109.5
C4—C5—H5	119.7	C9—O6—Ni1^ii	120.96 (13)
C5—C6—C7	119.76 (18)	Ni1—O1W—H1W	99.8
C5—C6—C9	119.82 (18)	Ni1—O1W—H2W	105.1
C7—C6—C9	120.37 (16)	H1W—O1W—H2W	105.1
C2—C7—C6	119.80 (17)	Ni1—O2W—H4W	119.7
C2—C7—H7	120.1	Ni1—O2W—H3W	127.8
C6—C7—H7	120.1	H4W—O2W—H3W	105.1
O4—C8—O3	121.55 (19)	Ni1—O3W—H5W	121.4
O4—C8—C4	124.72 (19)	Ni1—O3W—H6W	108.0
O3—C8—C4	113.73 (18)	H5W—O3W—H6W	105.1
O5—C9—O6	124.16 (18)
O2—C1—C2—C7	4.9 (3)	C3—C4—C8—O4	169.1 (2)
O1—C1—C2—C7	−176.04 (17)	C5—C4—C8—O4	−9.6 (3)
O2—C1—C2—C3	−174.3 (2)	C3—C4—C8—O3	−10.9 (3)
O1—C1—C2—C3	4.8 (3)	C5—C4—C8—O3	170.43 (19)
C7—C2—C3—C4	0.2 (3)	C5—C6—C9—O5	−5.2 (3)
C1—C2—C3—C4	179.35 (17)	C7—C6—C9—O5	177.22 (18)
C2—C3—C4—C5	0.6 (3)	C5—C6—C9—O6	174.46 (18)
C2—C3—C4—C8	−178.15 (18)	C7—C6—C9—O6	−3.1 (3)
C3—C4—C5—C6	−0.6 (3)	O2—C1—O1—Ni1	−7.3 (3)
C8—C4—C5—C6	178.15 (19)	C2—C1—O1—Ni1	173.69 (13)
C4—C5—C6—C7	−0.1 (3)	O2W—Ni1—O1—C1	−72.99 (16)
C4—C5—C6—C9	−177.68 (17)	O1W—Ni1—O1—C1	95.70 (16)
C3—C2—C7—C6	−0.8 (3)	O3W—Ni1—O1—C1	−168.93 (15)
C1—C2—C7—C6	179.97 (17)	O5—C9—O6—Ni1^ii	−6.8 (3)
C5—C6—C7—C2	0.8 (3)	C6—C9—O6—Ni1^ii	173.52 (12)
C9—C6—C7—C2	178.38 (17)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O3—H3A···O2^iii	0.82	1.81	2.568 (2)	152
O1W—H1W···O3^iv	0.85	2.21	2.869 (3)	134
O1W—H2W···O5^v	0.85	1.94	2.680 (2)	145
O2W—H4W···O5^vi	0.85	1.89	2.715 (2)	165
O3W—H5W···O4^vii	0.85	2.03	2.778 (2)	147
O3W—H6W···O2^viii	0.85	2.49	3.068 (3)	126
O2W—H3W···O1^ix	0.85	2.34	3.123 (2)	154

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