Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807055353/dn2259sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807055353/dn2259Isup2.hkl |
CCDC reference: 672617
Key indicators
- Single-crystal X-ray study
- T = 298 K
- Mean (C-C) = 0.015 Å
- Disorder in main residue
- R factor = 0.054
- wR factor = 0.132
- Data-to-parameter ratio = 13.4
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT241_ALERT_2_B Check High Ueq as Compared to Neighbors for C4
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.99 PLAT213_ALERT_2_C Atom C4 has ADP max/min Ratio ............. 3.90 prola PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.21 Ratio PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O1 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C3 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for Ni1 PLAT242_ALERT_2_C Check Low Ueq as Compared to Neighbors for C6 PLAT301_ALERT_3_C Main Residue Disorder ......................... 3.00 Perc. PLAT341_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 15 PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond C4 - C5 ... 1.38 Ang. PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) . 1.21 Ratio
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 11 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 8 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 2 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
Ni(AC)2(0.036 g, 0.028 mmol), dbp (0.018 g, 0.013 mmol) a mixed solvent of acetonitrile, the mixture was heated for eight hours under reflux. During the process stirring and influx were required. The resultant was then filtered to give a pure solution which was infiltrated by diethyl ether freely in a closed vessel, weeks later some single crystals of the size suitable for X-Ray diffraction analysis.
All H atoms attached to C atoms and N atom were fixed geometrically and treated as riding with C—H = 0.93 Å (aromatic) or 0.96 Å (methyl) and N—H = 0.86 Å with Uiso(H) = 1.2Ueq(Caromatic or N) and Uiso(H) = 1.5Ueq(Cmethyl).
Some of the C atoms of the pyridyl group display very elongated ellipsoids, however no correct disordered models could be defined.
Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Bruker, 1997).
[Ni2(C2H3O2)4(C10H7N3)] | F(000) = 1072 |
Mr = 522.78 | Dx = 1.581 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 1973 reflections |
a = 13.4008 (13) Å | θ = 2.9–25.2° |
b = 8.4880 (9) Å | µ = 1.76 mm−1 |
c = 20.112 (2) Å | T = 298 K |
β = 106.191 (7)° | Block, green |
V = 2196.9 (4) Å3 | 0.27 × 0.21 × 0.16 mm |
Z = 4 |
Bruker APEXII area-detector diffractometer | 1973 independent reflections |
Radiation source: fine-focus sealed tube | 1098 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.095 |
Detector resolution: 0 pixels mm-1 | θmax = 25.2°, θmin = 2.9° |
ϕ and ω scan | h = −14→16 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | k = −10→8 |
Tmin = 0.648, Tmax = 0.766 | l = −24→18 |
5441 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.054 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0465P)2] where P = (Fo2 + 2Fc2)/3 |
1973 reflections | (Δ/σ)max = 0.001 |
147 parameters | Δρmax = 0.57 e Å−3 |
0 restraints | Δρmin = −0.45 e Å−3 |
[Ni2(C2H3O2)4(C10H7N3)] | V = 2196.9 (4) Å3 |
Mr = 522.78 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 13.4008 (13) Å | µ = 1.76 mm−1 |
b = 8.4880 (9) Å | T = 298 K |
c = 20.112 (2) Å | 0.27 × 0.21 × 0.16 mm |
β = 106.191 (7)° |
Bruker APEXII area-detector diffractometer | 1973 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 1098 reflections with I > 2σ(I) |
Tmin = 0.648, Tmax = 0.766 | Rint = 0.095 |
5441 measured reflections |
R[F2 > 2σ(F2)] = 0.054 | 0 restraints |
wR(F2) = 0.132 | H-atom parameters constrained |
S = 1.00 | Δρmax = 0.57 e Å−3 |
1973 reflections | Δρmin = −0.45 e Å−3 |
147 parameters |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Ni1 | 0.95385 (5) | 0.92235 (8) | 0.94293 (4) | 0.0423 (3) | |
N1 | 0.8818 (4) | 0.7990 (6) | 0.8453 (3) | 0.0577 (14) | |
N2 | 1.0307 (9) | 0.7655 (13) | 0.8155 (5) | 0.061 (3) | 0.50 |
H2 | 1.0613 | 0.7845 | 0.8584 | 0.074* | 0.50 |
O1 | 1.0991 (3) | 0.8984 (5) | 0.9401 (2) | 0.0644 (12) | |
O2 | 1.1772 (3) | 1.0270 (5) | 1.0372 (3) | 0.0688 (13) | |
O3 | 0.9695 (3) | 0.7416 (5) | 1.0053 (2) | 0.0603 (12) | |
O4 | 1.0480 (3) | 0.8712 (5) | 1.1020 (2) | 0.0654 (13) | |
C1 | 0.7828 (6) | 0.7539 (8) | 0.8293 (4) | 0.077 (2) | |
H1 | 0.7445 | 0.7658 | 0.8611 | 0.092* | |
C2 | 0.7364 (8) | 0.6873 (11) | 0.7633 (6) | 0.121 (4) | |
H21 | 0.6677 | 0.6535 | 0.7516 | 0.145* | |
C3 | 0.7940 (15) | 0.6729 (14) | 0.7163 (7) | 0.165 (8) | |
H3 | 0.7632 | 0.6323 | 0.6724 | 0.198* | |
C4 | 0.8911 (11) | 0.7158 (18) | 0.7332 (5) | 0.170 (8) | |
C5 | 0.9334 (7) | 0.7787 (12) | 0.7980 (4) | 0.098 (3) | |
C6 | 1.1793 (5) | 0.9576 (7) | 0.9823 (4) | 0.0533 (17) | |
C7 | 1.2802 (5) | 0.9406 (8) | 0.9663 (4) | 0.079 (2) | |
H7A | 1.3101 | 1.0428 | 0.9647 | 0.118* | |
H7B | 1.2695 | 0.8897 | 0.9222 | 0.118* | |
H7C | 1.3265 | 0.8782 | 1.0015 | 0.118* | |
C8 | 1.0076 (5) | 0.7494 (8) | 1.0691 (4) | 0.0573 (17) | |
C9 | 1.0085 (6) | 0.6030 (8) | 1.1110 (4) | 0.074 (2) | |
H9A | 0.9487 | 0.6024 | 1.1284 | 0.111* | |
H9B | 1.0704 | 0.6009 | 1.1491 | 0.111* | |
H9C | 1.0069 | 0.5120 | 1.0824 | 0.111* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.0396 (5) | 0.0408 (5) | 0.0436 (5) | −0.0011 (4) | 0.0069 (3) | −0.0036 (4) |
N1 | 0.054 (4) | 0.054 (4) | 0.062 (4) | 0.002 (3) | 0.011 (3) | −0.003 (3) |
N2 | 0.074 (9) | 0.085 (8) | 0.022 (5) | −0.016 (7) | 0.008 (5) | 0.004 (5) |
O1 | 0.051 (3) | 0.068 (3) | 0.072 (3) | 0.003 (2) | 0.014 (2) | −0.009 (2) |
O2 | 0.050 (3) | 0.077 (3) | 0.078 (3) | −0.003 (2) | 0.015 (2) | −0.019 (3) |
O3 | 0.074 (3) | 0.049 (3) | 0.053 (3) | −0.008 (2) | 0.011 (2) | −0.003 (2) |
O4 | 0.082 (3) | 0.043 (3) | 0.062 (3) | −0.003 (2) | 0.006 (2) | 0.005 (2) |
C1 | 0.057 (5) | 0.064 (5) | 0.098 (6) | −0.007 (4) | 0.001 (4) | 0.016 (4) |
C2 | 0.090 (8) | 0.082 (7) | 0.138 (10) | −0.040 (6) | −0.053 (7) | 0.006 (7) |
C3 | 0.25 (2) | 0.111 (9) | 0.082 (9) | 0.083 (11) | −0.048 (10) | −0.036 (7) |
C4 | 0.167 (12) | 0.259 (16) | 0.044 (6) | 0.143 (12) | −0.038 (7) | −0.032 (8) |
C5 | 0.067 (6) | 0.163 (9) | 0.053 (5) | 0.029 (6) | −0.002 (4) | 0.005 (5) |
C6 | 0.042 (4) | 0.050 (4) | 0.070 (5) | 0.003 (3) | 0.019 (4) | 0.006 (4) |
C7 | 0.063 (5) | 0.072 (5) | 0.112 (6) | −0.006 (4) | 0.041 (4) | −0.003 (4) |
C8 | 0.050 (4) | 0.053 (5) | 0.072 (5) | 0.009 (3) | 0.022 (4) | 0.001 (4) |
C9 | 0.095 (6) | 0.056 (5) | 0.072 (5) | −0.005 (4) | 0.027 (4) | 0.013 (4) |
Ni1—O2i | 1.955 (5) | C1—C2 | 1.418 (12) |
Ni1—O3 | 1.956 (4) | C1—H1 | 0.9300 |
Ni1—O4i | 1.968 (4) | C2—C3 | 1.381 (16) |
Ni1—O1 | 1.974 (4) | C2—H21 | 0.9300 |
Ni1—N1 | 2.197 (5) | C3—C4 | 1.30 (2) |
Ni1—Ni1i | 2.6371 (14) | C3—H3 | 0.9300 |
N1—C1 | 1.332 (8) | C4—C5 | 1.376 (13) |
N1—C5 | 1.333 (10) | C4—N2ii | 1.675 (18) |
N2—C5 | 1.258 (12) | C6—C7 | 1.482 (9) |
N2—C4ii | 1.675 (18) | C7—H7A | 0.9600 |
N2—H2 | 0.8600 | C7—H7B | 0.9600 |
O1—C6 | 1.273 (7) | C7—H7C | 0.9600 |
O2—C6 | 1.258 (7) | C8—C9 | 1.501 (9) |
O2—Ni1i | 1.955 (5) | C9—H9A | 0.9600 |
O3—C8 | 1.242 (7) | C9—H9B | 0.9600 |
O4—C8 | 1.265 (8) | C9—H9C | 0.9600 |
O4—Ni1i | 1.968 (4) | ||
O2i—Ni1—O3 | 89.00 (19) | C3—C2—H21 | 120.2 |
O2i—Ni1—O4i | 90.07 (19) | C1—C2—H21 | 120.2 |
O3—Ni1—O4i | 167.99 (17) | C4—C3—C2 | 120.3 (12) |
O2i—Ni1—O1 | 168.00 (18) | C4—C3—H3 | 119.9 |
O3—Ni1—O1 | 90.45 (18) | C2—C3—H3 | 119.8 |
O4i—Ni1—O1 | 87.97 (19) | C3—C4—C5 | 118.2 (14) |
O2i—Ni1—N1 | 95.3 (2) | C3—C4—N2ii | 131.3 (11) |
O3—Ni1—N1 | 98.13 (18) | C5—C4—N2ii | 107.3 (13) |
O4i—Ni1—N1 | 93.87 (18) | N2—C5—N1 | 121.0 (8) |
O1—Ni1—N1 | 96.7 (2) | N2—C5—C4 | 110.5 (10) |
O2i—Ni1—Ni1i | 86.66 (14) | N1—C5—C4 | 124.6 (11) |
O3—Ni1—Ni1i | 83.87 (13) | O2—C6—O1 | 123.3 (6) |
O4i—Ni1—Ni1i | 84.13 (13) | O2—C6—C7 | 118.8 (6) |
O1—Ni1—Ni1i | 81.36 (13) | O1—C6—C7 | 118.0 (7) |
N1—Ni1—Ni1i | 177.22 (17) | C6—C7—H7A | 109.5 |
C1—N1—C5 | 118.1 (7) | C6—C7—H7B | 109.5 |
C1—N1—Ni1 | 120.8 (5) | H7A—C7—H7B | 109.5 |
C5—N1—Ni1 | 120.9 (5) | C6—C7—H7C | 109.5 |
C5—N2—C4ii | 128.9 (9) | H7A—C7—H7C | 109.5 |
C5—N2—H2 | 115.6 | H7B—C7—H7C | 109.5 |
C4ii—N2—H2 | 115.6 | O3—C8—O4 | 125.2 (6) |
C6—O1—Ni1 | 126.6 (4) | O3—C8—C9 | 118.2 (6) |
C6—O2—Ni1i | 121.6 (4) | O4—C8—C9 | 116.6 (6) |
C8—O3—Ni1 | 124.0 (4) | C8—C9—H9A | 109.5 |
C8—O4—Ni1i | 122.5 (4) | C8—C9—H9B | 109.5 |
N1—C1—C2 | 119.1 (8) | H9A—C9—H9B | 109.5 |
N1—C1—H1 | 120.4 | C8—C9—H9C | 109.5 |
C2—C1—H1 | 120.4 | H9A—C9—H9C | 109.5 |
C3—C2—C1 | 119.6 (10) | H9B—C9—H9C | 109.5 |
Symmetry codes: (i) −x+2, −y+2, −z+2; (ii) −x+2, y, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Ni2(C2H3O2)4(C10H7N3)] |
Mr | 522.78 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 298 |
a, b, c (Å) | 13.4008 (13), 8.4880 (9), 20.112 (2) |
β (°) | 106.191 (7) |
V (Å3) | 2196.9 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.76 |
Crystal size (mm) | 0.27 × 0.21 × 0.16 |
Data collection | |
Diffractometer | Bruker APEXII area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.648, 0.766 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5441, 1973, 1098 |
Rint | 0.095 |
(sin θ/λ)max (Å−1) | 0.599 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.054, 0.132, 1.00 |
No. of reflections | 1973 |
No. of parameters | 147 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.57, −0.45 |
Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXTL (Bruker, 1997).
The chemical structure of the organic ligands including the molecular angle, length, and relative orientation of the donor groups plays an extremely important role in dictating polymer topology. So far, much of the research has been concentrated on the exploitation of angular ligands with a molecular angle, such as ligands with a Tshape,V-shape etc, in the construction of versatile coordination polymer architectures (Su et al., 2003; Gudbjartson et al., 1999). In this paper, we report the synthesis and crystal structure of the title complex,(I).
The structure of (I) consists of one-dimensional polymeric [Ni2(dbp)2(Ac)4]n chains built up from dinuclear Ni(II) subunit of the paddle-wheel type. The two nickel atoms are related by symmetry through inversion center (Fig. 1). Each nickel atom has a square pyramid coordination environment, with four oxygen atoms from four acetyl groups, forming the equatorial plane, and the pyridyl nitrogen atom, occupying the apex. This big paddle-wheel type arrangement prevents further torsion of the two pyridine rings of the bridging ligand, and then results in the formation of a neutral one-dimensional linear chain rather than a helical chain. The occurrence of intramolecular (N—H···O) hydrogen bond stabilize the architecture(Table 1).