Poly[bis­(μ₂-4,4′-bipyridine)­bis­(3-nitro­benzoato)nickel(II)]

The crystal structure of the title complex, [Ni(C₇H₄NO₄)₂(C₁₀H₈N₂)₂]_n, exhibits a two-dimensional network, which is built up from slightly distorted NiN₄O₂ polyhedra (2 symmetry), bipyridine ligands, and carboxyl­ate anions. The Ni^II atoms are six-coordinated by two O atoms of two monodentate carboxyl­ate anions and four N atoms from bipyridine ligands and are connected into layers by the 4,4′-bipyridine ligands.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.035
• wR factor = 0.101
• Data-to-parameter ratio = 17.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT220_ALERT_2_C Large Non-Solvent    O     Ueq(max)/Ueq(min) ...       3.64 Ratio
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C12
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for        C13
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N4
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C11
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         34

Alert level G
PLAT794_ALERT_5_G Note: Tentative Bond Valency for Ni1     .......       1.95
PLAT804_ALERT_5_G ARU-Pack Problem in PLATON Analysis ............         12 Times

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

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

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S1. Comment

The synthesis of metal coordination polymers has been a subject of intense research due to their interesting structural chemistry and potential applications in gas storage, separation, catalysis, magnetism, luminescence, and drug delivery (Kitagawa, et al., 2004). Here we report the synthesis of title complex with a two-dimensional structure which was contained nickel and mixed 4,4'-bipyridine and 3-nitrobenzate ligands.

The crystal structure analysis reveals that the title complex possesses similar two-dimensional layer structure. The octahedral metal ions are coordinated by four nitrogen atoms and two oxygen atoms which belonged to the four bpy ligands, and two NB ligands (Fig. 1). The average bond lengths of Ni—O are 2.058 (1) Å and the Ni—N are 2.128 (2) Å which are falling in the expected normal range. Each metal center was linked adjacent metal centers by four bpy ligands, resulting in a two-dimensional neutral rectangular grid in the bc plane with a (4,4)-net (Fig. 2). The neighboring layers interact through π-π interactions between the benzene rings of NB ligands (3.55 Å) and form a mimic three-dimensional framework. In generally, the title complex is an analogous of our precious reported cobalt compound (Chiang, et al., 2009).

Related literature

For background to the hydrothermal synthesis of coordination polymers with organic ligands, see: Kitagawa et al. (2004); Long & Yaghi (2009). For related structures, see: Chiang et al. (2009).

S2. Experimental

Hydrothermal reactions were carried out at 453 K for 3 d in a Teflon-lined acid digestion bomb with an internal volume of 23 ml followed by slow cooling at 6 K/h to room temperature. A single-phase product consisting of blue crystals were obtained from a mixture of 4,4'-bipyridine (C₁₀H₈N₂, 0.0781 g, 0.5 mmol), 3-nitrobenzoic acid (C₇H₅NO₄, 0.0836 g, 0.5 mmol), Ni(NO₃)₂?6H₂O (0.1454 g, 0.5 mmol), and H₂O (12.0 ml), NH₄OH (0.1 ml).

S3. Refinement

H atoms were constrained to ideal geometries, with C—H = 0.93 Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: APEX2 (Bruker, 2010); cell refinement: SAINT (Bruker, 2010); data reduction: SAINT (Bruker, 2010); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures

	Fig. 1. Part of polymeric structure of the title compound, showing 50% probability displacement ellipsoids. [symmetry codes: (i) -x + 1, y, -z + 5/2; (ii) -x + 1/2, -y + 5/2, -z + 2; (iii) x, y - 1, z].
	Fig. 2. Crystal structure of the title compound showing the two-dimensional layers. The H atoms are omitted for clarity.

Poly[bis(µ₂-4,4'-bipyridine)bis(3-nitrobenzoato)nickel(II)]

Crystal data

[Ni(C7H4NO4)2(C10H8N2)2]	F(000) = 1448
Mr = 703.28	Dx = 1.517 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 7469 reflections
a = 18.1237 (10) Å	θ = 2.3–28.4°
b = 11.3663 (6) Å	µ = 0.70 mm^−1
c = 15.0119 (8) Å	T = 295 K
β = 95.439 (2)°	Columnar, blue
V = 3078.5 (3) Å^3	0.45 × 0.30 × 0.10 mm
Z = 4

Data collection

Bruker APEXII CCD diffractometer	3836 independent reflections
Radiation source: fine-focus sealed tube	3470 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
Detector resolution: 8.3333 pixels mm^-1	θmax = 28.4°, θmin = 2.1°
φ and ω scans	h = −24→24
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −10→15
Tmin = 0.745, Tmax = 0.934	l = −20→18
13263 measured reflections

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.101	H-atom parameters constrained
S = 1.03	w = 1/[σ^2(Fo^2) + (0.055P)^2 + 3.5308P] where P = (Fo^2 + 2Fc^2)/3
3836 reflections	(Δ/σ)max = 0.002
224 parameters	Δρmax = 0.71 e Å^−3
0 restraints	Δρmin = −0.53 e Å^−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
Ni1	0.5000	1.19295 (2)	1.2500	0.02130 (10)
O1	0.57303 (7)	1.18647 (10)	1.15316 (8)	0.0311 (3)
N1	0.5000	1.37958 (17)	1.2500	0.0274 (4)
C1	0.58736 (10)	1.20357 (14)	1.07335 (12)	0.0298 (3)
O2	0.54917 (9)	1.25698 (16)	1.01439 (10)	0.0515 (4)
C2	0.66083 (10)	1.15107 (15)	1.05145 (12)	0.0318 (3)
N2	0.5000	2.00284 (16)	1.2500	0.0264 (4)
O3	0.81171 (16)	1.0200 (3)	0.83539 (19)	0.1131 (10)
N3	0.40568 (8)	1.19913 (11)	1.15701 (9)	0.0261 (3)
C3	0.67500 (11)	1.13723 (17)	0.96282 (13)	0.0387 (4)
H3A	0.6403	1.1601	0.9165	0.046*
O4	0.70979 (17)	1.1035 (3)	0.79302 (15)	0.1014 (9)
N4	0.75517 (16)	1.0686 (2)	0.85108 (18)	0.0693 (7)
C4	0.74173 (13)	1.08876 (19)	0.94515 (15)	0.0474 (5)
C5	0.79625 (13)	1.0578 (2)	1.01120 (18)	0.0529 (6)
H5A	0.8413	1.0273	0.9969	0.063*
C6	0.78225 (12)	1.0733 (2)	1.09890 (17)	0.0500 (5)
H6A	0.8184	1.0544	1.1448	0.060*
C7	0.71441 (11)	1.11721 (17)	1.11888 (14)	0.0395 (4)
H7A	0.7046	1.1241	1.1784	0.047*
C8	0.49914 (10)	1.44061 (15)	1.17354 (11)	0.0323 (4)
H8A	0.4989	1.3993	1.1201	0.039*
C9	0.49863 (11)	1.56217 (15)	1.17042 (12)	0.0343 (4)
H9A	0.4974	1.6013	1.1159	0.041*
C10	0.5000	1.6253 (2)	1.2500	0.0289 (5)
C11	0.5000	1.75560 (19)	1.2500	0.0292 (5)
C12	0.53631 (16)	1.94065 (18)	1.19430 (19)	0.0637 (8)
H12A	0.5634	1.9812	1.1546	0.076*
C13	0.53672 (18)	1.81906 (18)	1.1911 (2)	0.0685 (9)
H13A	0.5621	1.7805	1.1486	0.082*
C14	0.40194 (9)	1.15368 (17)	1.07508 (12)	0.0320 (4)
H14A	0.4413	1.1079	1.0595	0.038*
C15	0.34223 (9)	1.17121 (17)	1.01177 (12)	0.0333 (4)
H15A	0.3423	1.1383	0.9551	0.040*
C16	0.28214 (8)	1.23809 (14)	1.03306 (10)	0.0258 (3)
C17	0.28557 (10)	1.28207 (17)	1.11967 (12)	0.0337 (4)
H17A	0.2461	1.3252	1.1381	0.040*
C18	0.34745 (10)	1.26177 (17)	1.17822 (11)	0.0331 (4)
H18A	0.3488	1.2933	1.2355	0.040*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni1	0.02510 (15)	0.01629 (15)	0.02124 (15)	0.000	−0.00447 (10)	0.000
O1	0.0359 (6)	0.0310 (6)	0.0264 (6)	−0.0015 (5)	0.0027 (5)	0.0002 (5)
N1	0.0350 (10)	0.0183 (8)	0.0277 (9)	0.000	−0.0025 (7)	0.000
C1	0.0353 (8)	0.0257 (8)	0.0280 (8)	−0.0033 (6)	0.0005 (6)	0.0002 (6)
O2	0.0540 (9)	0.0647 (10)	0.0352 (7)	0.0153 (8)	0.0006 (6)	0.0132 (7)
C2	0.0397 (9)	0.0245 (8)	0.0318 (8)	−0.0039 (7)	0.0063 (7)	0.0018 (7)
N2	0.0301 (9)	0.0181 (8)	0.0300 (9)	0.000	−0.0026 (7)	0.000
O3	0.116 (2)	0.138 (2)	0.0964 (18)	0.0219 (18)	0.0682 (17)	−0.0171 (17)
N3	0.0267 (6)	0.0246 (7)	0.0255 (6)	0.0016 (5)	−0.0053 (5)	−0.0006 (5)
C3	0.0510 (11)	0.0325 (9)	0.0339 (9)	−0.0080 (8)	0.0110 (8)	0.0009 (7)
O4	0.124 (2)	0.142 (2)	0.0431 (11)	0.0011 (18)	0.0311 (13)	−0.0084 (13)
N4	0.0897 (17)	0.0634 (14)	0.0620 (14)	−0.0163 (13)	0.0458 (14)	−0.0110 (11)
C4	0.0611 (13)	0.0358 (10)	0.0494 (12)	−0.0121 (9)	0.0271 (10)	−0.0027 (9)
C5	0.0479 (11)	0.0395 (11)	0.0751 (16)	0.0005 (9)	0.0260 (11)	0.0024 (11)
C6	0.0432 (11)	0.0449 (12)	0.0619 (14)	0.0054 (9)	0.0052 (10)	0.0076 (10)
C7	0.0441 (10)	0.0355 (9)	0.0390 (10)	0.0014 (8)	0.0054 (8)	0.0047 (8)
C8	0.0471 (9)	0.0209 (8)	0.0282 (8)	0.0022 (7)	−0.0007 (7)	−0.0016 (6)
C9	0.0517 (10)	0.0207 (8)	0.0302 (8)	0.0017 (7)	0.0020 (7)	0.0035 (6)
C10	0.0360 (11)	0.0164 (10)	0.0339 (12)	0.000	0.0009 (9)	0.000
C11	0.0380 (12)	0.0169 (10)	0.0321 (11)	0.000	0.0005 (9)	0.000
C12	0.0924 (19)	0.0214 (9)	0.0867 (19)	0.0000 (10)	0.0572 (17)	0.0040 (10)
C13	0.104 (2)	0.0216 (10)	0.090 (2)	0.0037 (11)	0.0647 (19)	−0.0007 (10)
C14	0.0261 (7)	0.0354 (9)	0.0330 (8)	0.0052 (6)	−0.0053 (6)	−0.0092 (7)
C15	0.0285 (8)	0.0419 (10)	0.0279 (8)	0.0051 (7)	−0.0053 (6)	−0.0105 (7)
C16	0.0253 (7)	0.0260 (8)	0.0250 (7)	−0.0001 (6)	−0.0027 (6)	0.0009 (6)
C17	0.0324 (8)	0.0425 (10)	0.0252 (8)	0.0131 (7)	−0.0027 (6)	−0.0022 (7)
C18	0.0359 (8)	0.0396 (9)	0.0224 (7)	0.0104 (7)	−0.0044 (6)	−0.0036 (7)

Geometric parameters (Å, º)

Ni1—O1	2.0580 (12)	C5—H5A	0.9300
Ni1—O1^i	2.0580 (12)	C6—C7	1.386 (3)
Ni1—N3	2.1031 (13)	C6—H6A	0.9300
Ni1—N3^i	2.1031 (13)	C7—H7A	0.9300
Ni1—N1	2.1212 (19)	C8—C9	1.382 (2)
Ni1—N2^ii	2.1609 (19)	C8—H8A	0.9300
O1—C1	1.265 (2)	C9—C10	1.391 (2)
N1—C8	1.340 (2)	C9—H9A	0.9300
N1—C8^i	1.340 (2)	C10—C9^i	1.391 (2)
C1—O2	1.231 (2)	C10—C11	1.482 (3)
C1—C2	1.523 (2)	C11—C13	1.363 (3)
C2—C7	1.389 (3)	C11—C13^i	1.363 (3)
C2—C3	1.388 (2)	C12—C13	1.383 (3)
N2—C12	1.318 (2)	C12—H12A	0.9300
N2—C12^i	1.318 (2)	C13—H13A	0.9300
N2—Ni1^iii	2.1610 (19)	C14—C15	1.385 (2)
O3—N4	1.207 (3)	C14—H14A	0.9300
N3—C14	1.330 (2)	C15—C16	1.390 (2)
N3—C18	1.336 (2)	C15—H15A	0.9300
C3—C4	1.377 (3)	C16—C17	1.389 (2)
C3—H3A	0.9300	C16—C16^iv	1.482 (3)
O4—N4	1.207 (4)	C17—C18	1.377 (2)
N4—C4	1.474 (3)	C17—H17A	0.9300
C4—C5	1.377 (4)	C18—H18A	0.9300
C5—C6	1.375 (4)
O1—Ni1—O1^i	175.90 (7)	C6—C5—H5A	120.9
O1—Ni1—N3	93.96 (5)	C4—C5—H5A	120.9
O1^i—Ni1—N3	86.18 (5)	C5—C6—C7	120.1 (2)
O1—Ni1—N3^i	86.18 (5)	C5—C6—H6A	120.0
O1^i—Ni1—N3^i	93.96 (5)	C7—C6—H6A	120.0
N3—Ni1—N3^i	176.17 (7)	C6—C7—C2	121.0 (2)
O1—Ni1—N1	92.05 (3)	C6—C7—H7A	119.5
O1^i—Ni1—N1	92.05 (3)	C2—C7—H7A	119.5
N3—Ni1—N1	88.09 (4)	N1—C8—C9	123.09 (16)
N3^i—Ni1—N1	88.09 (4)	N1—C8—H8A	118.5
O1—Ni1—N2^ii	87.95 (3)	C9—C8—H8A	118.5
O1^i—Ni1—N2^ii	87.95 (3)	C8—C9—C10	119.10 (16)
N3—Ni1—N2^ii	91.91 (4)	C8—C9—H9A	120.4
N3^i—Ni1—N2^ii	91.91 (4)	C10—C9—H9A	120.4
N1—Ni1—N2^ii	180.000 (1)	C9—C10—C9^i	118.0 (2)
C1—O1—Ni1	150.13 (12)	C9—C10—C11	121.02 (10)
C8—N1—C8^i	117.6 (2)	C9^i—C10—C11	121.01 (10)
C8—N1—Ni1	121.18 (10)	C13—C11—C13^i	116.1 (2)
C8^i—N1—Ni1	121.18 (10)	C13—C11—C10	121.95 (12)
O2—C1—O1	127.24 (18)	C13^i—C11—C10	121.96 (12)
O2—C1—C2	118.78 (16)	N2—C12—C13	124.3 (2)
O1—C1—C2	113.98 (15)	N2—C12—H12A	117.9
C7—C2—C3	119.16 (18)	C13—C12—H12A	117.9
C7—C2—C1	121.09 (16)	C11—C13—C12	120.1 (2)
C3—C2—C1	119.76 (17)	C11—C13—H13A	119.9
C12—N2—C12^i	115.1 (2)	C12—C13—H13A	119.9
C12—N2—Ni1^iii	122.44 (11)	N3—C14—C15	123.14 (16)
C12^i—N2—Ni1^iii	122.44 (11)	N3—C14—H14A	118.4
C14—N3—C18	117.08 (14)	C15—C14—H14A	118.4
C14—N3—Ni1	124.60 (11)	C14—C15—C16	119.94 (16)
C18—N3—Ni1	118.05 (11)	C14—C15—H15A	120.0
C4—C3—C2	118.4 (2)	C16—C15—H15A	120.0
C4—C3—H3A	120.8	C17—C16—C15	116.46 (14)
C2—C3—H3A	120.8	C17—C16—C16^iv	121.59 (18)
O3—N4—O4	122.9 (3)	C15—C16—C16^iv	121.95 (18)
O3—N4—C4	118.6 (3)	C18—C17—C16	119.91 (16)
O4—N4—C4	118.5 (2)	C18—C17—H17A	120.0
C3—C4—C5	123.1 (2)	C16—C17—H17A	120.0
C3—C4—N4	118.3 (2)	N3—C18—C17	123.43 (16)
C5—C4—N4	118.5 (2)	N3—C18—H18A	118.3
C6—C5—C4	118.1 (2)	C17—C18—H18A	118.3

Symmetry codes: (i) −x+1, y, −z+5/2; (ii) x, y−1, z; (iii) x, y+1, z; (iv) −x+1/2, −y+5/2, −z+2.