Poly­[nickel(II)-μ-4,4′-bi­pyridine-μ-terephthalato]

4,4′-Bi­pyridine­(terephthalato)­nickel(II), [Ni(C₈H₄O₄)(C₁₀H₈N₂)], exists as poly­[μ₂-terephthalato-μ₄-terephthalato-bis­[(μ₂-4,4′-bi­pyridine)­nickel(II)]]. Two independent terephthalato groups both occupy positions of 2/m symmetry; one of these groups acts as a μ₄ bridge and coordinates four different Ni atoms, one with each of its O atoms. The other one acts as a μ₂-bridge and serves as a bidentate chelate for two neighboring metal atoms. The Ni atom lies in a special position of m site symmetry.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.055
• wR factor = 0.135
• Data-to-parameter ratio = 13.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level B:



PLAT_213  Alert B Atom         has ADP max/min Ratio .............       4.20 C6

PLAT_213  Alert B Atom         has ADP max/min Ratio .............       4.40 C7


 Alert Level C:



ABSTM_02  Alert C The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
          Tmin and Tmax reported:      0.696     0.877
          Tmin' and Tmax expected:      0.802     0.877
          RR' =      0.868
          Please check that your absorption correction is appropriate.

CELLV_02  Alert C The supplied cell volume s.u. differs from that
          calculated from the cell parameter s.u.'s by > 2
          Calculated cell volume su =       7.23
          Cell volume su given      =       5.00

PLAT_213  Alert C Atom         has ADP max/min Ratio .............       3.60 C12

PLAT_710  Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle #        13
                   N2  -NI1 -N1  -C8     90.20  0.50   1.556   1.555   1.555   1.555

PLAT_710  Alert C Delete 1-2-3 or 2-3-4 (CIF) Linear Torsion Angle #        18
                   N2  -NI1 -N1  -C8    -90.20  0.50   1.556   1.555   1.555   6.565


 0 Alert Level A = Potentially serious problem

 2 Alert Level B = Potential problem

 5 Alert Level C = Please check

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S1. Comment

4,4'-Bipyridine(terephthalato)nickel(II), [Ni(C₈H₄O₄)(C₁₀H₈N₂)], exists as poly[µ₂-terephthalato-µ₄-terephthalato-bis[(µ₂-4,4'- bipyridine)nickel(II)]]. Two independent terephthalato groups both occupy positions of 2/m symmetry; one of these groups acts as a µ₄ bridge and coordinates four different Ni atoms with each of its O atoms. The other one acts as a µ₂-bridge and serves as a bidentate chelate for two neighboring metal atoms (Fig. 1). Consequently, the terephthalate–nickel framework forms infinite two-dimensional layers parallel to the ab plane of the crystal. The layers are linked into a three-dimensional network through the µ₂-bridging 4,4'-bipyridine ligands occupying a special position across the mirror plane. The compound is isostructural with the published cobalt analog, whose detailed description (Tao et al., 2000) also applies to the title compound.

S2. Experimental

The compound was synthesized hydrothermally from nickel nitrate hexahydrate (0.29 g, 1 mmol), terephthalic acid (0.17 g, 1 mmol), 4,4'-bipyridine dihydrochloride (0.23 g, 1 mmol) and sodium hydroxide (0.16 g, 4 mmol) in water (18 ml). The mixture was placed in a 20 ml Teflon-lined stainless-steel vessel, which was heated at 493 K for 100 h. The vessel was cooled to room temperature at a rate of 6 K h⁻¹. The product was isolated in 25% yield.

S3. Refinement

The aromatic portion of one of the terephthalate groups (at the Wyckoff 2 d site of 2/m symmetry), made up of atoms C5, C6 and C7, showed large displacement parameters for atoms C6 and C7. However, the free refinement of these two atoms by imposing a PART −1 command in SHELXL97 (Sheldrick, 1997) was unstable. H atoms were generated geometrically (C—H = 0.93 Å) and included in the subsequent refinement in the riding motion approximation with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: CAD-4 Software (Enraf-Nonius, 1988); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. ORTEPII (Johnson, 1976) plot of a fragment of the structure of (I), with ellipsoids drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radii. [Symmetry codes: (i) x, 1 − y, z; (ii) x, y, 1 + z.]

poly[µ₂-terephthalato-µ₄-terephthalato-bis[(µ₂-4,4'- bipyridine)nickel(II)]]

Crystal data

[Ni(C8H4O4)(C10H8N2)]	F(000) = 776
Mr = 379.01	Dx = 1.512 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
a = 16.610 (3) Å	Cell parameters from 25 reflections
b = 10.222 (2) Å	θ = 14.0–16.0°
c = 11.237 (2) Å	µ = 1.19 mm^−1
β = 119.22 (3)°	T = 298 K
V = 1665.1 (5) Å^3	Block, green
Z = 4	0.18 × 0.18 × 0.11 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	1312 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.038
Graphite monochromator	θmax = 26.0°, θmin = 2.1°
ω scans	h = 0→20
Absorption correction: ψ scan (North et al., 1968)	k = 0→12
Tmin = 0.696, Tmax = 0.877	l = −13→12
1790 measured reflections	3 standard reflections every 60 min
1728 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.135	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.0649P)^2 + 1.5719P] where P = (Fo^2 + 2Fc^2)/3
1728 reflections	(Δ/σ)max = 0.001
128 parameters	Δρmax = 0.67 e Å^−3
0 restraints	Δρmin = −0.73 e Å^−3

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

	x	y	z	Uiso*/Ueq
Ni1	0.63763 (5)	0.5000	0.15968 (7)	0.0204 (2)
O1	0.5599 (2)	0.3384 (3)	0.1060 (3)	0.030 (1)
O2	0.7648 (2)	0.6073 (3)	0.2635 (3)	0.034 (1)
N1	0.6494 (4)	0.5000	−0.0159 (5)	0.029 (1)
N2	0.6350 (4)	0.5000	−0.6569 (5)	0.028 (1)
C1	0.5000	0.2834 (6)	0.0000	0.023 (1)
C2	0.5000	0.1366 (6)	0.0000	0.026 (1)
C3	0.5728 (3)	0.0668 (4)	0.1012 (5)	0.037 (1)
C4	0.8056 (4)	0.5000	0.3015 (6)	0.031 (2)
C5	0.9073 (4)	0.5000	0.4034 (7)	0.032 (2)
C6	0.9709 (6)	0.5000	0.3714 (9)	0.17 (1)
C7	1.0645 (7)	0.5000	0.468 (1)	0.20 (1)
C8	0.6533 (3)	0.3893 (5)	−0.0760 (5)	0.036 (1)
C9	0.6551 (4)	0.3842 (5)	−0.1963 (5)	0.040 (1)
C10	0.6537 (5)	0.5000	−0.2622 (6)	0.032 (2)
C11	0.6482 (5)	0.5000	−0.3981 (6)	0.032 (2)
C12	0.6469 (6)	0.3881 (5)	−0.4644 (6)	0.080 (3)
C13	0.6392 (5)	0.3915 (6)	−0.5913 (6)	0.071 (2)
H3	0.6224	0.1116	0.1702	0.044*
H6	0.9544	0.5000	0.2795	0.207*
H7	1.1078	0.5000	0.4386	0.245*
H8	0.6548	0.3107	−0.0334	0.044*
H9	0.6573	0.3040	−0.2336	0.048*
H12	0.6514	0.3078	−0.4227	0.096*
H13	0.6368	0.3123	−0.6337	0.085*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.0262 (4)	0.0165 (4)	0.0159 (4)	0.000	0.0082 (3)	0.000
O1	0.041 (2)	0.016 (2)	0.025 (2)	−0.006 (1)	0.010 (1)	−0.002 (1)
O2	0.031 (2)	0.026 (2)	0.036 (2)	−0.001 (1)	0.008 (1)	0.002 (1)
N1	0.036 (3)	0.029 (3)	0.023 (3)	0.000	0.015 (2)	0.000
N2	0.041 (3)	0.018 (3)	0.027 (3)	0.000	0.018 (3)	0.000
C1	0.029 (3)	0.014 (3)	0.026 (3)	0.000	0.014 (3)	0.000
C2	0.032 (3)	0.010 (3)	0.034 (3)	0.000	0.015 (3)	0.000
C3	0.034 (3)	0.018 (2)	0.036 (2)	0.001 (2)	−0.001 (2)	−0.002 (2)
C4	0.033 (4)	0.029 (4)	0.028 (3)	0.000	0.013 (3)	0.000
C5	0.026 (3)	0.031 (4)	0.030 (3)	0.000	0.007 (3)	0.000
C6	0.026 (5)	0.46 (3)	0.033 (5)	0.000	0.011 (4)	0.000
C7	0.027 (5)	0.53 (4)	0.047 (6)	0.000	0.014 (5)	0.000
C8	0.060 (3)	0.024 (3)	0.035 (2)	0.005 (2)	0.032 (2)	0.003 (2)
C9	0.070 (4)	0.026 (3)	0.036 (3)	0.006 (2)	0.035 (3)	0.000 (2)
C10	0.047 (4)	0.024 (3)	0.025 (3)	0.000	0.017 (3)	0.000
C11	0.049 (4)	0.023 (4)	0.031 (3)	0.000	0.024 (3)	0.000
C12	0.198 (8)	0.020 (3)	0.052 (4)	0.002 (4)	0.083 (5)	0.006 (3)
C13	0.153 (7)	0.029 (3)	0.048 (3)	0.001 (4)	0.062 (4)	−0.002 (3)

Geometric parameters (Å, º)

Ni1—O1	1.999 (3)	C5—C6	1.27 (1)
Ni1—O1^i	1.999 (3)	C5—C7^v	1.28 (1)
Ni1—O2	2.149 (3)	C6—C7	1.40 (1)
Ni1—O2^i	2.149 (3)	C7—C5^v	1.28 (1)
Ni1—N1	2.076 (5)	C8—C9	1.367 (6)
Ni1—N2^ii	2.084 (5)	C9—C10	1.391 (6)
O1—C1	1.252 (4)	C10—C9^i	1.391 (6)
O2—C4	1.250 (4)	C10—C11	1.484 (8)
N1—C8	1.335 (5)	C11—C12^i	1.360 (6)
N1—C8^i	1.335 (5)	C11—C12	1.360 (6)
N2—C13^i	1.314 (6)	C12—C13	1.369 (7)
N2—C13	1.314 (6)	C3—H3	0.93
C1—O1^iii	1.252 (4)	C6—H6	0.93
C1—C2	1.501 (8)	C7—H7	0.93
C2—C3^iii	1.387 (5)	C8—H8	0.93
C2—C3	1.387 (5)	C9—H9	0.93
C3—C3^iv	1.365 (9)	C12—H12	0.93
C4—O2^i	1.250 (4)	C13—H13	0.93
C4—C5	1.508 (9)
O1—Ni1—O1^i	111.4 (2)	O2^i—C4—C5	118.6 (3)
O1—Ni1—O2	154.7 (1)	O2—C4—C5	118.6 (3)
O1—Ni1—O2^i	93.5 (1)	C6—C5—C7^v	114.9 (8)
O1—Ni1—N1	93.4 (1)	C6—C5—C4	124.2 (7)
O1—Ni1—N2^ii	88.6 (1)	C7^v—C5—C4	120.9 (7)
O1^i—Ni1—O2	93.5 (1)	C5—C6—C7	122.8 (9)
O1^i—Ni1—O2^i	154.7 (1)	C5^v—C7—C6	122 (1)
O1^i—Ni1—N1	93.4 (1)	N1—C8—C9	124.2 (4)
O1^i—Ni1—N2^ii	88.6 (1)	C8—C9—C10	119.4 (5)
O2—Ni1—O2^i	61.3 (2)	C9^i—C10—C9	116.7 (6)
O2—Ni1—N1	89.5 (2)	C9^i—C10—C11	121.7 (3)
O2—Ni1—N2^ii	87.3 (2)	C9—C10—C11	121.7 (3)
O2^i—Ni1—N1	89.5 (2)	C12^i—C11—C12	114.5 (6)
O2^i—Ni1—N2^ii	87.3 (2)	C12^i—C11—C10	122.7 (3)
N1—Ni1—N2^ii	176.3 (2)	C12—C11—C10	122.7 (3)
C1—O1—Ni1	138.9 (3)	C11—C12—C13	121.3 (5)
C4—O2—Ni1	87.9 (3)	N2—C13—C12	123.9 (5)
C8—N1—C8^i	115.8 (5)	C3^iv—C3—H3	119.5
C8—N1—Ni1	122.1 (3)	C2—C3—H3	119.5
C8^i—N1—Ni1	122.1 (3)	C5—C6—H6	118.6
C13^i—N2—C13	115.1 (6)	C7—C6—H6	118.6
C13^i—N2—Ni1^vi	122.2 (3)	C5^v—C7—H7	118.8
C13—N2—Ni1^vi	122.2 (3)	C6—C7—H7	118.8
O1—C1—O1^iii	126.7 (5)	N1—C8—H8	117.9
O1—C1—C2	116.7 (3)	C9—C8—H8	117.9
O1^iii—C1—C2	116.7 (3)	C8—C9—H9	120.3
C3^iii—C2—C3	118.0 (6)	C10—C9—H9	120.3
C3^iii—C2—C1	121.0 (3)	C11—C12—H12	119.4
C3—C2—C1	121.0 (3)	C13—C12—H12	119.4
C3^iv—C3—C2	121.0 (3)	N2—C13—H13	118.1
O2^i—C4—O2	122.6 (6)	C12—C13—H13	118.1
O1^i—Ni1—O1—C1	62.0 (5)	C3^iii—C2—C3—C3^iv	0.0
N1—Ni1—O1—C1	−33.1 (4)	C1—C2—C3—C3^iv	180.0
N2^ii—Ni1—O1—C1	150.0 (4)	Ni1—O2—C4—O2^i	4.4 (7)
O2—Ni1—O1—C1	−129.3 (4)	Ni1—O2—C4—C5	−172.2 (6)
O2^i—Ni1—O1—C1	−122.8 (4)	O2^i—C4—C5—C6	91.6 (6)
O1—Ni1—O2—C4	4.9 (5)	O2—C4—C5—C6	−91.6 (6)
O1^i—Ni1—O2—C4	174.4 (4)	O2^i—C4—C5—C7^v	−88.4 (6)
N1—Ni1—O2—C4	−92.2 (4)	O2—C4—C5—C7^v	88.4 (6)
N2^ii—Ni1—O2—C4	86.0 (4)	C7^v—C5—C6—C7	0.000 (3)
O2^i—Ni1—O2—C4	−2.5 (4)	C4—C5—C6—C7	180.000 (2)
O1—Ni1—N1—C8	−34.0 (5)	C5—C6—C7—C5^v	0.000 (2)
O1^i—Ni1—N1—C8	−145.7 (5)	C8^i—N1—C8—C9	−4 (1)
N2^ii—Ni1—N1—C8	90.2 (5)	Ni1—N1—C8—C9	175.6 (4)
O2—Ni1—N1—C8	120.8 (5)	N1—C8—C9—C10	0.5 (9)
O2^i—Ni1—N1—C8	59.5 (5)	C8—C9—C10—C9^i	3 (1)
O1—Ni1—N1—C8^i	145.7 (5)	C8—C9—C10—C11	−175.1 (6)
O1^i—Ni1—N1—C8^i	34.0 (5)	C9^i—C10—C11—C12^i	2 (1)
N2^ii—Ni1—N1—C8^i	−90.2 (5)	C9—C10—C11—C12^i	−179.8 (7)
O2—Ni1—N1—C8^i	−59.5 (5)	C9^i—C10—C11—C12	179.8 (7)
O2^i—Ni1—N1—C8^i	−120.8 (5)	C9—C10—C11—C12	−2 (1)
Ni1—O1—C1—O1^iii	−33.8 (3)	C12^i—C11—C12—C13	−4 (2)
Ni1—O1—C1—C2	146.2 (3)	C10—C11—C12—C13	178.2 (7)
O1—C1—C2—C3^iii	168.3 (3)	C13^i—N2—C13—C12	0 (1)
O1^iii—C1—C2—C3^iii	−11.7 (3)	Ni1^vi—N2—C13—C12	173.2 (6)
O1—C1—C2—C3	−11.7 (3)	C11—C12—C13—N2	2 (1)
O1^iii—C1—C2—C3	168.3 (3)

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