metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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catena-Poly[[nickel(II)-μ-1,3-di­methyl-2,6-dioxo-7H-purinato-κ2N7:N9] hydroxide]

aCollege of Environment and Planning, Henan University, Kaifeng 475001, People's Republic of China
*Correspondence e-mail: linhengw@henu.edu.cn

(Received 11 March 2008; accepted 18 March 2008; online 29 March 2008)

The title complex, {[Ni(C7H7N4O2)]OH}n, has been prepared through hydro­thermal synthesis. The asymmetric unit contains one [Ni(TH)]+ cation (TH is the theophylline anion) and one hydroxide anion. The Ni2+ ion is coordinated by two N atoms from two neighboring theophylline anions. The alternating linkage of the Ni2+ cation and theophylline anion results in a one-dimensional chain along the [010] direction. Intermolec­ular O—H⋯O hydrogen bonds are present n the crystal structure.

Related literature

For related literature, see: Horikoshi & Mochida (2006[Horikoshi, R. & Mochida, T. (2006). Coord. Chem. Rev. 250, 2595-2609.]); Robin & Fromm (2003[Robin, A. Y. & Fromm, K. M. (2003). Coord. Chem. Rev. 250, 2127-2157.]).

[Scheme 1]

Experimental

Crystal data
  • [Ni(C7H7N4O2)]OH

  • Mr = 254.88

  • Monoclinic, P 21 /c

  • a = 11.399 (3) Å

  • b = 11.533 (2) Å

  • c = 6.9807 (15) Å

  • β = 101.993 (3)°

  • V = 897.7 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 2.15 mm−1

  • T = 298 (2) K

  • 0.48 × 0.24 × 0.08 mm

Data collection
  • Bruker SMART APEX CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2001[Sheldrick, G. M. (2001). SADABS. Version 2.10. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.425, Tmax = 0.847

  • 4701 measured reflections

  • 1753 independent reflections

  • 1592 reflections with I > 2σ(I)

  • Rint = 0.024

Refinement
  • R[F2 > 2σ(F2)] = 0.028

  • wR(F2) = 0.078

  • S = 1.07

  • 1753 reflections

  • 142 parameters

  • 7 restraints

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.36 e Å−3

  • Δρmin = −0.43 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
O3—H3⋯O1i 0.832 (11) 2.023 (12) 2.851 (3) 173 (5)
Symmetry code: (i) x, y+1, z+1.

Data collection: SMART (Bruker, 2001[Bruker (2001). SAINT-Plus (Version 6.45) and SMART (Version 5.628). Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT-Plus (Bruker, 2001[Bruker (2001). SAINT-Plus (Version 6.45) and SMART (Version 5.628). Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: PLATON (Spek, 2003[Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.]); software used to prepare material for publication: PLATON.

Supporting information


Comment top

The rational design, synthesis and characterization of coordination polymers construct from transition metal ions, especially the first-row transition metal, and various organic ligands linked with covalent bonds have still been actively researched as one of highly topical research areas aiming to obtain fascinating structures as well as special properties such as magnetism, catalysis, molecular recognition, ion exchange, nonlinear optical behavior and electrical conductivity (Robin & Fromm, 2003; Horikoshi & Mochida, 2006). Herein we present a one-dimensional,linear transition metal complexes, namely {[Ni(TH)]OH}n(TH = theophylline anion), (I).

Each asymmetry unit of the title compound (I) consists of one [Ni(TH)]+ cation and one isolated hydroxyl anion (Fig.1). Ni2+ adopts a two-coordinate coordination mode and coordinated by two nitrogen atoms from two neighboring theophylline anions with average Ni—N length 1.861° and N—Ni—N angle 177.25° (Table 1), respectively. The short Ni—N distances in the compound are caused by the low coordination numbers and highly positive charges. The alternate linkers of Ni2+ ion and theophylline anion within which two adjacent anions are in the trans-position finally give rise to a one-dimensional chain (Fig.2). To best of our knowledge, the title complex is firstly reported. We found 3,5-dinitrobenzoic acid takes an key role in controlling the formation of the title compound. If 3,5-Ddinitrobenzoic acid was not added into the reaction system, the compound can't be obtained. Moreover, we also found basic medium NaOH must be added into the reaction system. Otherwise these compounds can't be prepared. We think that 3,5-dinitrobenzoic acid here acts as a reaction template. Additionally, the effect of the basic medium (NaOH) made NH group of theophylline deprotonate leading to the formation of a monoanionic bidentate ligand.

Related literature top

For related literature, see: Horikoshi & Mochida (2006); Robin & Fromm (2003).

Experimental top

A mixture of NiCl2.6H2O (0.50 mmol, 0.12 g), 3,5-dinitrobenzoic acid (0.50 mmol, 0.110 g), theophylline monohydrate (0.50 mmol, 0.09 g), NaOH (0.5 mmol, 0.02 g) and H2O (20 ml) in the mole ratio 1:1:1:1:2 were heated in a Teflon-lined steel autoclave inside a programmable electric furnace at 1433 K for 72 h. After cooling the autoclave to room temperature for 36 h, brown crystals suitable for single-crystal X-ray diffraction were obtained.

Refinement top

H atoms bonded to O atom were located from the difference maps and refined with distance restraints O—H = 0.82 (1) Å. All the remaining H atoms were positioned geometrically, with C—H = 0.93–0.96 Å, and refined as riding, with Uiso(H) = 1.2Ueq(aromatic C) or 1.5Ueq(methyl C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. Asymmetry structural unit of (I). Displacement ellipsoids for non-H atoms are drawn at the 30% probability level.
[Figure 2] Fig. 2. One-dimensional chain structure of the cations {[Ni(TH)]+}n. Hydrogen atoms are omitted for clarity.
catena-Poly[[nickel(II)-µ-1,3-dimethyl-2,6-dioxo-7H-purinato-κ2N7:N9] hydroxide] top
Crystal data top
[Ni(C7H7N4O2)]OHF(000) = 520
Mr = 254.88Dx = 1.886 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1720 reflections
a = 11.399 (3) Åθ = 2.2–28.0°
b = 11.533 (2) ŵ = 2.15 mm1
c = 6.9807 (15) ÅT = 298 K
β = 101.993 (3)°Block, brown
V = 897.7 (3) Å30.48 × 0.24 × 0.08 mm
Z = 4
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
1753 independent reflections
Radiation source: fine-focus sealed tube1592 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.024
ω scansθmax = 26.0°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)
h = 145
Tmin = 0.425, Tmax = 0.847k = 1314
4701 measured reflectionsl = 88
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.028Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.048P)2 + 0.1385P]
where P = (Fo2 + 2Fc2)/3
1753 reflections(Δ/σ)max = 0.001
142 parametersΔρmax = 0.36 e Å3
7 restraintsΔρmin = 0.43 e Å3
Crystal data top
[Ni(C7H7N4O2)]OHV = 897.7 (3) Å3
Mr = 254.88Z = 4
Monoclinic, P21/cMo Kα radiation
a = 11.399 (3) ŵ = 2.15 mm1
b = 11.533 (2) ÅT = 298 K
c = 6.9807 (15) Å0.48 × 0.24 × 0.08 mm
β = 101.993 (3)°
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
1753 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2001)
1592 reflections with I > 2σ(I)
Tmin = 0.425, Tmax = 0.847Rint = 0.024
4701 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0287 restraints
wR(F2) = 0.078H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.36 e Å3
1753 reflectionsΔρmin = 0.43 e Å3
142 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
Ni10.48633 (3)0.53369 (2)0.24668 (4)0.03643 (14)
O10.2600 (2)0.03105 (12)0.0185 (3)0.0546 (5)
O20.04285 (16)0.36076 (15)0.1653 (3)0.0568 (4)
O30.2120 (4)0.7950 (3)0.9081 (7)0.1392 (14)
H30.227 (5)0.8648 (16)0.931 (7)0.135 (6)*
N10.44301 (17)0.37995 (14)0.1875 (3)0.0365 (4)
N20.46418 (17)0.18588 (15)0.1998 (3)0.0367 (4)
N30.15129 (17)0.19704 (15)0.0707 (3)0.0399 (4)
N40.23455 (17)0.38436 (14)0.0017 (2)0.0381 (4)
C10.51491 (19)0.28771 (17)0.2480 (3)0.0368 (5)
H10.59350.29550.31770.044*
C20.35017 (19)0.21287 (15)0.0998 (3)0.0329 (4)
C30.2555 (2)0.13741 (16)0.0164 (3)0.0377 (5)
C40.1381 (2)0.31716 (19)0.0830 (3)0.0393 (5)
C50.33876 (18)0.33133 (15)0.0931 (3)0.0318 (4)
C60.0440 (2)0.1291 (2)0.1542 (4)0.0554 (6)
H6A0.01740.14420.08190.083*
H6B0.06350.04810.14660.083*
H6C0.01570.15070.28870.083*
C70.2229 (3)0.5112 (2)0.0110 (4)0.0520 (6)
H7A0.26960.54560.10540.078*
H7B0.14020.53230.02360.078*
H7C0.25130.53840.12320.078*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni10.0411 (2)0.01831 (18)0.0477 (2)0.00491 (9)0.00408 (13)0.00290 (8)
O10.0644 (13)0.0267 (8)0.0696 (11)0.0096 (7)0.0068 (10)0.0035 (6)
O20.0416 (9)0.0613 (11)0.0608 (10)0.0094 (8)0.0050 (8)0.0053 (8)
O30.118 (3)0.0735 (17)0.203 (4)0.0072 (19)0.019 (3)0.001 (2)
N10.0405 (10)0.0246 (7)0.0428 (9)0.0015 (7)0.0052 (8)0.0014 (7)
N20.0397 (10)0.0244 (8)0.0437 (9)0.0021 (7)0.0036 (8)0.0010 (7)
N30.0380 (10)0.0387 (9)0.0406 (9)0.0066 (8)0.0027 (8)0.0010 (7)
N40.0413 (10)0.0291 (8)0.0419 (9)0.0054 (7)0.0040 (8)0.0035 (7)
C10.0370 (12)0.0269 (12)0.0438 (12)0.0005 (8)0.0022 (10)0.0003 (7)
C20.0375 (11)0.0240 (9)0.0363 (10)0.0006 (8)0.0055 (8)0.0002 (7)
C30.0473 (13)0.0286 (10)0.0381 (10)0.0049 (8)0.0107 (9)0.0007 (7)
C40.0409 (12)0.0409 (11)0.0358 (10)0.0024 (9)0.0067 (9)0.0003 (9)
C50.0383 (11)0.0230 (8)0.0339 (9)0.0022 (8)0.0072 (8)0.0006 (7)
C60.0480 (14)0.0587 (15)0.0562 (14)0.0190 (12)0.0033 (12)0.0054 (11)
C70.0574 (16)0.0295 (10)0.0639 (15)0.0110 (11)0.0008 (12)0.0038 (10)
Geometric parameters (Å, º) top
Ni1—N2i1.8577 (17)N4—C51.370 (3)
Ni1—N11.8636 (17)N4—C41.374 (3)
O1—C31.228 (2)N4—C71.469 (3)
O2—C41.226 (3)C1—H10.9300
O3—H30.832 (11)C2—C51.372 (3)
N1—C51.355 (3)C2—C31.414 (3)
N1—C11.356 (3)C6—H6A0.9600
N2—C11.321 (3)C6—H6B0.9600
N2—C21.377 (3)C6—H6C0.9600
N2—Ni1ii1.8577 (17)C7—H7A0.9600
N3—C41.394 (3)C7—H7B0.9600
N3—C31.398 (3)C7—H7C0.9600
N3—C61.467 (3)
N2i—Ni1—N1177.25 (8)O1—C3—C2125.7 (2)
C5—N1—C1103.84 (16)N3—C3—C2112.53 (17)
C5—N1—Ni1131.82 (14)O2—C4—N4121.4 (2)
C1—N1—Ni1124.22 (14)O2—C4—N3120.7 (2)
C1—N2—C2104.20 (15)N4—C4—N3117.9 (2)
C1—N2—Ni1ii133.63 (15)N1—C5—N4129.03 (17)
C2—N2—Ni1ii122.05 (14)N1—C5—C2109.16 (18)
C4—N3—C3125.93 (19)N4—C5—C2121.81 (19)
C4—N3—C6115.8 (2)N3—C6—H6A109.5
C3—N3—C6118.24 (19)N3—C6—H6B109.5
C5—N4—C4119.16 (17)H6A—C6—H6B109.5
C5—N4—C7122.08 (19)N3—C6—H6C109.5
C4—N4—C7118.75 (19)H6A—C6—H6C109.5
N2—C1—N1114.44 (18)H6B—C6—H6C109.5
N2—C1—H1122.8N4—C7—H7A109.5
N1—C1—H1122.8N4—C7—H7B109.5
C5—C2—N2108.36 (18)H7A—C7—H7B109.5
C5—C2—C3122.7 (2)N4—C7—H7C109.5
N2—C2—C3128.95 (17)H7A—C7—H7C109.5
O1—C3—N3121.7 (2)H7B—C7—H7C109.5
Symmetry codes: (i) x+1, y+1/2, z+1/2; (ii) x+1, y1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O1iii0.83 (1)2.02 (1)2.851 (3)173 (5)
Symmetry code: (iii) x, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Ni(C7H7N4O2)]OH
Mr254.88
Crystal system, space groupMonoclinic, P21/c
Temperature (K)298
a, b, c (Å)11.399 (3), 11.533 (2), 6.9807 (15)
β (°) 101.993 (3)
V3)897.7 (3)
Z4
Radiation typeMo Kα
µ (mm1)2.15
Crystal size (mm)0.48 × 0.24 × 0.08
Data collection
DiffractometerBruker SMART APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2001)
Tmin, Tmax0.425, 0.847
No. of measured, independent and
observed [I > 2σ(I)] reflections
4701, 1753, 1592
Rint0.024
(sin θ/λ)max1)0.617
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.028, 0.078, 1.07
No. of reflections1753
No. of parameters142
No. of restraints7
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.36, 0.43

Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O3—H3···O1i0.832 (11)2.023 (12)2.851 (3)173 (5)
Symmetry code: (i) x, y+1, z+1.
 

References

First citationBruker (2001). SAINT-Plus (Version 6.45) and SMART (Version 5.628). Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationHorikoshi, R. & Mochida, T. (2006). Coord. Chem. Rev. 250, 2595–2609.  Web of Science CrossRef CAS Google Scholar
First citationRobin, A. Y. & Fromm, K. M. (2003). Coord. Chem. Rev. 250, 2127–2157.  CrossRef Google Scholar
First citationSheldrick, G. M. (2001). SADABS. Version 2.10. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2003). J. Appl. Cryst. 36, 7–13.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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