N,N′-Bis(4-pyridylmethyl)oxalamide, C14H14N4O2, exists as a dimer which is extended into a two-dimensional network with other dimers through pyridine–amide hydrogen bonds. The crystal structure of the title coordination polymer, {[CoCl2(C14H14N4O2)]·0.5H2O}n, features a one-dimensional zigzag chain, in which the cobalt ion sits at a twofold symmetry position and adopts a tetrahedral geometry, and the bridging ligand lies on an inversion center and connects to CoII ions in a bis-monodentate mode. Furthermore, two interwoven chains create a cavity of ca 8.6 × 8.6 Å, which produces a three-dimensional channel. Water molecules are held in the channel by hydrogen bonds.
Supporting information
CCDC references: 649075; 649076
All solvents for syntheses (analytical grade) were used without further
purification, and the metal salt (CoCl2) was commercially available.
N,N'-Bis(4-pyridylmethyl)oxalamide was prepared from
4-(aminomethyl)pyridine and diethyl oxalate according to the method described
by Nguyen et al. (1998), and single crystals were obtained by DMF/ether
diffusion. The metal-organic complex was obtained by mixing CoCl2 (13.0 mg,
0.1 mmol) and 4py-ox (27.0 mg, 0.1 mmol) in methanol (5 ml). The mixture was
placed in a 23 ml Teflon-lined stainless steel autoclave and heated at 423 K
for 48 h. The mixture was then cooled to room temperature at the rate of 5 K h-1. Blue crystals were collected with 68% yield. Analysis calculated for
C14H15Cl2CoN4O2.5: C 41.00, H 3.70, N 13.70%; found: C 41.03, H
3.66, N 13.67%.
In both compounds, H atoms attached to C and N atoms were positioned
geometrically and refined using a riding model [C—H = 0.95–0.99 Å, N—H
= 0.88 Å and Uiso(H) = 1.2Ueq(C,N)]. The site
occupancy factor of the solvent molecule in (II) was refined and its value is
closed to one-quarter; was fixed to 0.25 during the final least-square
refinement. H atoms of the solvent molecule were found in a difference Fourier
map and constrained at an O—H distance of 0.85 Å [Uiso(H) =
1.5Ueq(O)].
For both compounds, data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2000b); software used to prepare material for publication: SHELXTL.
(I)
N,
N'-Bis(4-pyridylmethyl)oxalamide
top
Crystal data top
C14H14N4O2 | F(000) = 1136 |
Mr = 270.29 | Dx = 1.373 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.5188 (4) Å | Cell parameters from 3244 reflections |
b = 15.4474 (7) Å | θ = 2.6–26.7° |
c = 17.8238 (8) Å | µ = 0.10 mm−1 |
β = 93.833 (1)° | T = 150 K |
V = 2615.0 (2) Å3 | Rod, colorless |
Z = 8 | 0.32 × 0.22 × 0.15 mm |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 6006 independent reflections |
Radiation source: fine-focus sealed tube | 4530 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.044 |
ω scans | θmax = 27.5°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000a) | h = −12→12 |
Tmin = 0.970, Tmax = 0.986 | k = −20→19 |
25256 measured reflections | l = −23→23 |
Refinement top
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)] = 0.060 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 1.13 | w = 1/[σ2(Fo2) + (0.0528P)2 + 1.0749P] where P = (Fo2 + 2Fc2)/3 |
6006 reflections | (Δ/σ)max < 0.001 |
361 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.25 e Å−3 |
Crystal data top
C14H14N4O2 | V = 2615.0 (2) Å3 |
Mr = 270.29 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.5188 (4) Å | µ = 0.10 mm−1 |
b = 15.4474 (7) Å | T = 150 K |
c = 17.8238 (8) Å | 0.32 × 0.22 × 0.15 mm |
β = 93.833 (1)° | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 6006 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000a) | 4530 reflections with I > 2σ(I) |
Tmin = 0.970, Tmax = 0.986 | Rint = 0.044 |
25256 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.060 | 0 restraints |
wR(F2) = 0.143 | H-atom parameters constrained |
S = 1.13 | Δρmax = 0.34 e Å−3 |
6006 reflections | Δρmin = −0.25 e Å−3 |
361 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 | x | y | z | Uiso*/Ueq | |
O1 | 0.27862 (14) | 0.49834 (8) | 0.40856 (7) | 0.0241 (3) | |
O2 | 0.02876 (15) | 0.65640 (9) | 0.35216 (7) | 0.0254 (3) | |
N1 | 0.2152 (2) | 0.33400 (15) | 0.08532 (12) | 0.0490 (6) | |
N2 | 0.23215 (16) | 0.56187 (10) | 0.29444 (8) | 0.0194 (3) | |
H2 | 0.1746 | 0.5967 | 0.2681 | 0.023* | |
N3 | 0.07727 (16) | 0.59737 (10) | 0.46793 (8) | 0.0186 (3) | |
H3 | 0.1336 | 0.5622 | 0.4946 | 0.022* | |
N4 | 0.11569 (18) | 0.80950 (10) | 0.68638 (9) | 0.0248 (4) | |
C1 | 0.3346 (3) | 0.3791 (2) | 0.08474 (15) | 0.0573 (8) | |
H1 | 0.3941 | 0.3685 | 0.0450 | 0.069* | |
C2 | 0.3776 (2) | 0.44002 (17) | 0.13779 (13) | 0.0391 (6) | |
H2A | 0.4635 | 0.4705 | 0.1338 | 0.047* | |
C3 | 0.2945 (2) | 0.45641 (12) | 0.19686 (10) | 0.0214 (4) | |
C4 | 0.1703 (2) | 0.41028 (13) | 0.19821 (11) | 0.0265 (4) | |
H4 | 0.1092 | 0.4195 | 0.2375 | 0.032* | |
C5 | 0.1352 (2) | 0.35056 (15) | 0.14220 (13) | 0.0356 (5) | |
H5 | 0.0492 | 0.3196 | 0.1444 | 0.043* | |
C6 | 0.3444 (2) | 0.51944 (13) | 0.25742 (10) | 0.0216 (4) | |
H6A | 0.4050 | 0.4882 | 0.2957 | 0.026* | |
H6B | 0.4029 | 0.5642 | 0.2349 | 0.026* | |
C7 | 0.21346 (19) | 0.54981 (11) | 0.36692 (10) | 0.0173 (4) | |
C8 | 0.09608 (19) | 0.60771 (11) | 0.39500 (10) | 0.0174 (4) | |
C9 | −0.03317 (19) | 0.64233 (12) | 0.50485 (10) | 0.0200 (4) | |
H9A | −0.0987 | 0.5991 | 0.5240 | 0.024* | |
H9B | −0.0871 | 0.6788 | 0.4674 | 0.024* | |
C10 | −0.0079 (2) | 0.76838 (13) | 0.68657 (11) | 0.0261 (4) | |
H10 | −0.0644 | 0.7778 | 0.7278 | 0.031* | |
C11 | −0.0578 (2) | 0.71299 (13) | 0.63022 (10) | 0.0230 (4) | |
H11 | −0.1462 | 0.6851 | 0.6332 | 0.028* | |
C12 | 0.02241 (19) | 0.69834 (12) | 0.56889 (10) | 0.0180 (4) | |
C13 | 0.1509 (2) | 0.74020 (12) | 0.56878 (10) | 0.0196 (4) | |
H13 | 0.2098 | 0.7319 | 0.5284 | 0.024* | |
C14 | 0.1924 (2) | 0.79405 (12) | 0.62786 (11) | 0.0233 (4) | |
H14 | 0.2812 | 0.8219 | 0.6268 | 0.028* | |
O3 | 0.22234 (14) | 0.50284 (8) | 0.59179 (7) | 0.0235 (3) | |
O4 | 0.46974 (15) | 0.34272 (9) | 0.64601 (7) | 0.0257 (3) | |
N5 | 0.3074 (2) | 0.66508 (13) | 0.90842 (11) | 0.0383 (5) | |
N6 | 0.26497 (16) | 0.43590 (10) | 0.70461 (8) | 0.0184 (3) | |
H6 | 0.3209 | 0.3998 | 0.7305 | 0.022* | |
N7 | 0.41804 (16) | 0.40165 (10) | 0.53061 (8) | 0.0179 (3) | |
H7 | 0.3594 | 0.4354 | 0.5039 | 0.021* | |
N8 | 0.38497 (18) | 0.17985 (11) | 0.32010 (9) | 0.0281 (4) | |
C15 | 0.2681 (2) | 0.58569 (16) | 0.92753 (12) | 0.0355 (5) | |
H15 | 0.2757 | 0.5706 | 0.9793 | 0.043* | |
C16 | 0.2169 (2) | 0.52399 (13) | 0.87661 (11) | 0.0286 (5) | |
H16 | 0.1884 | 0.4688 | 0.8936 | 0.034* | |
C17 | 0.20756 (19) | 0.54329 (12) | 0.80063 (10) | 0.0212 (4) | |
C18 | 0.2486 (2) | 0.62546 (13) | 0.78050 (12) | 0.0282 (5) | |
H18 | 0.2442 | 0.6419 | 0.7290 | 0.034* | |
C19 | 0.2962 (2) | 0.68374 (14) | 0.83530 (13) | 0.0349 (5) | |
H19 | 0.3222 | 0.7401 | 0.8200 | 0.042* | |
C20 | 0.1525 (2) | 0.47910 (13) | 0.74215 (10) | 0.0220 (4) | |
H20A | 0.0954 | 0.4350 | 0.7664 | 0.026* | |
H20B | 0.0902 | 0.5095 | 0.7041 | 0.026* | |
C21 | 0.28526 (19) | 0.44946 (11) | 0.63280 (10) | 0.0176 (4) | |
C22 | 0.40124 (19) | 0.39142 (11) | 0.60343 (10) | 0.0171 (4) | |
C23 | 0.53094 (19) | 0.35846 (12) | 0.49355 (10) | 0.0197 (4) | |
H23A | 0.5907 | 0.3262 | 0.5316 | 0.024* | |
H23B | 0.5905 | 0.4027 | 0.4711 | 0.024* | |
C24 | 0.4363 (2) | 0.25705 (13) | 0.30350 (11) | 0.0253 (4) | |
H24 | 0.4409 | 0.2721 | 0.2521 | 0.030* | |
C25 | 0.4831 (2) | 0.31632 (12) | 0.35749 (10) | 0.0233 (4) | |
H25 | 0.5199 | 0.3705 | 0.3429 | 0.028* | |
C26 | 0.47640 (19) | 0.29659 (12) | 0.43297 (10) | 0.0187 (4) | |
C27 | 0.4224 (2) | 0.21695 (14) | 0.45048 (11) | 0.0313 (5) | |
H27 | 0.4150 | 0.2005 | 0.5014 | 0.038* | |
C28 | 0.3791 (3) | 0.16140 (15) | 0.39275 (12) | 0.0369 (6) | |
H28 | 0.3429 | 0.1065 | 0.4057 | 0.044* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0302 (8) | 0.0242 (7) | 0.0177 (7) | 0.0080 (6) | 0.0000 (6) | 0.0026 (5) |
O2 | 0.0320 (8) | 0.0262 (7) | 0.0179 (7) | 0.0098 (6) | 0.0009 (6) | 0.0028 (6) |
N1 | 0.0351 (11) | 0.0637 (15) | 0.0489 (13) | −0.0089 (10) | 0.0090 (10) | −0.0339 (11) |
N2 | 0.0225 (8) | 0.0211 (8) | 0.0144 (7) | 0.0049 (7) | 0.0002 (6) | −0.0003 (6) |
N3 | 0.0220 (8) | 0.0190 (8) | 0.0145 (7) | 0.0041 (6) | −0.0001 (6) | −0.0007 (6) |
N4 | 0.0312 (9) | 0.0219 (9) | 0.0215 (8) | −0.0014 (7) | 0.0027 (7) | −0.0040 (7) |
C1 | 0.0411 (15) | 0.084 (2) | 0.0493 (15) | −0.0176 (14) | 0.0223 (12) | −0.0434 (15) |
C2 | 0.0264 (11) | 0.0577 (16) | 0.0346 (12) | −0.0117 (11) | 0.0120 (9) | −0.0229 (11) |
C3 | 0.0224 (10) | 0.0228 (10) | 0.0189 (9) | 0.0047 (8) | 0.0016 (7) | −0.0016 (8) |
C4 | 0.0261 (10) | 0.0275 (11) | 0.0267 (10) | 0.0002 (8) | 0.0086 (8) | −0.0049 (8) |
C5 | 0.0297 (12) | 0.0362 (12) | 0.0414 (13) | −0.0073 (10) | 0.0064 (10) | −0.0128 (10) |
C6 | 0.0206 (9) | 0.0254 (10) | 0.0188 (9) | 0.0017 (8) | 0.0020 (7) | −0.0018 (8) |
C7 | 0.0199 (9) | 0.0160 (9) | 0.0158 (8) | 0.0004 (7) | −0.0013 (7) | −0.0020 (7) |
C8 | 0.0202 (9) | 0.0169 (9) | 0.0147 (8) | −0.0019 (7) | −0.0016 (7) | −0.0026 (7) |
C9 | 0.0189 (9) | 0.0234 (10) | 0.0177 (9) | 0.0014 (8) | 0.0011 (7) | −0.0034 (7) |
C10 | 0.0295 (11) | 0.0292 (11) | 0.0204 (9) | −0.0017 (9) | 0.0073 (8) | −0.0053 (8) |
C11 | 0.0216 (10) | 0.0266 (10) | 0.0214 (9) | −0.0032 (8) | 0.0048 (8) | −0.0036 (8) |
C12 | 0.0235 (9) | 0.0162 (9) | 0.0143 (8) | 0.0039 (7) | 0.0011 (7) | 0.0016 (7) |
C13 | 0.0228 (9) | 0.0178 (9) | 0.0187 (9) | 0.0023 (8) | 0.0045 (7) | 0.0013 (7) |
C14 | 0.0228 (10) | 0.0206 (10) | 0.0268 (10) | −0.0020 (8) | 0.0035 (8) | −0.0025 (8) |
O3 | 0.0292 (8) | 0.0238 (7) | 0.0174 (6) | 0.0072 (6) | 0.0007 (6) | 0.0024 (5) |
O4 | 0.0303 (8) | 0.0281 (7) | 0.0187 (7) | 0.0106 (6) | 0.0017 (6) | 0.0039 (6) |
N5 | 0.0335 (10) | 0.0415 (12) | 0.0403 (11) | −0.0012 (9) | 0.0056 (9) | −0.0173 (9) |
N6 | 0.0195 (8) | 0.0209 (8) | 0.0150 (7) | 0.0038 (6) | 0.0019 (6) | 0.0006 (6) |
N7 | 0.0206 (8) | 0.0185 (8) | 0.0144 (7) | 0.0036 (6) | 0.0001 (6) | −0.0009 (6) |
N8 | 0.0287 (9) | 0.0337 (10) | 0.0224 (8) | −0.0074 (8) | 0.0044 (7) | −0.0089 (7) |
C15 | 0.0421 (13) | 0.0448 (14) | 0.0200 (10) | 0.0069 (11) | 0.0046 (9) | −0.0083 (10) |
C16 | 0.0383 (12) | 0.0253 (11) | 0.0229 (10) | 0.0041 (9) | 0.0080 (9) | −0.0012 (8) |
C17 | 0.0182 (9) | 0.0234 (10) | 0.0225 (9) | 0.0043 (8) | 0.0049 (7) | −0.0036 (8) |
C18 | 0.0284 (11) | 0.0276 (11) | 0.0293 (11) | −0.0011 (9) | 0.0071 (9) | 0.0000 (9) |
C19 | 0.0337 (12) | 0.0270 (11) | 0.0453 (13) | −0.0037 (9) | 0.0131 (10) | −0.0074 (10) |
C20 | 0.0212 (9) | 0.0263 (10) | 0.0189 (9) | 0.0006 (8) | 0.0042 (7) | −0.0018 (8) |
C21 | 0.0198 (9) | 0.0168 (9) | 0.0160 (9) | −0.0015 (7) | −0.0006 (7) | −0.0015 (7) |
C22 | 0.0192 (9) | 0.0154 (9) | 0.0167 (9) | −0.0019 (7) | 0.0008 (7) | −0.0012 (7) |
C23 | 0.0196 (9) | 0.0224 (10) | 0.0172 (9) | −0.0005 (7) | 0.0029 (7) | −0.0044 (7) |
C24 | 0.0319 (11) | 0.0284 (11) | 0.0158 (9) | 0.0031 (9) | 0.0024 (8) | −0.0016 (8) |
C25 | 0.0300 (11) | 0.0194 (10) | 0.0205 (9) | 0.0020 (8) | 0.0025 (8) | 0.0008 (8) |
C26 | 0.0158 (9) | 0.0215 (9) | 0.0191 (9) | 0.0019 (7) | 0.0025 (7) | −0.0046 (7) |
C27 | 0.0456 (13) | 0.0330 (12) | 0.0162 (9) | −0.0170 (10) | 0.0080 (9) | −0.0014 (8) |
C28 | 0.0498 (14) | 0.0327 (12) | 0.0293 (11) | −0.0221 (11) | 0.0115 (10) | −0.0075 (9) |
Geometric parameters (Å, º) top
O1—C7 | 1.227 (2) | O3—C21 | 1.231 (2) |
O2—C8 | 1.222 (2) | O4—C22 | 1.225 (2) |
N1—C5 | 1.333 (3) | N5—C19 | 1.332 (3) |
N1—C1 | 1.334 (3) | N5—C15 | 1.333 (3) |
N2—C7 | 1.329 (2) | N6—C21 | 1.324 (2) |
N2—C6 | 1.449 (2) | N6—C20 | 1.461 (2) |
N2—H2 | 0.8800 | N6—H6 | 0.8800 |
N3—C8 | 1.334 (2) | N7—C22 | 1.328 (2) |
N3—C9 | 1.454 (2) | N7—C23 | 1.460 (2) |
N3—H3 | 0.8800 | N7—H7 | 0.8800 |
N4—C14 | 1.334 (2) | N8—C24 | 1.329 (3) |
N4—C10 | 1.337 (3) | N8—C28 | 1.331 (3) |
C1—C2 | 1.376 (3) | C15—C16 | 1.382 (3) |
C1—H1 | 0.9500 | C15—H15 | 0.9500 |
C2—C3 | 1.382 (3) | C16—C17 | 1.384 (3) |
C2—H2A | 0.9500 | C16—H16 | 0.9500 |
C3—C4 | 1.382 (3) | C17—C18 | 1.383 (3) |
C3—C6 | 1.507 (3) | C17—C20 | 1.507 (3) |
C4—C5 | 1.384 (3) | C18—C19 | 1.382 (3) |
C4—H4 | 0.9500 | C18—H18 | 0.9500 |
C5—H5 | 0.9500 | C19—H19 | 0.9500 |
C6—H6A | 0.9900 | C20—H20A | 0.9900 |
C6—H6B | 0.9900 | C20—H20B | 0.9900 |
C7—C8 | 1.541 (2) | C21—C22 | 1.541 (2) |
C9—C12 | 1.500 (2) | C23—C26 | 1.508 (2) |
C9—H9A | 0.9900 | C23—H23A | 0.9900 |
C9—H9B | 0.9900 | C23—H23B | 0.9900 |
C10—C11 | 1.379 (3) | C24—C25 | 1.380 (3) |
C10—H10 | 0.9500 | C24—H24 | 0.9500 |
C11—C12 | 1.393 (2) | C25—C26 | 1.385 (3) |
C11—H11 | 0.9500 | C25—H25 | 0.9500 |
C12—C13 | 1.383 (3) | C26—C27 | 1.377 (3) |
C13—C14 | 1.379 (3) | C27—C28 | 1.381 (3) |
C13—H13 | 0.9500 | C27—H27 | 0.9500 |
C14—H14 | 0.9500 | C28—H28 | 0.9500 |
| | | |
C5—N1—C1 | 115.9 (2) | C19—N5—C15 | 116.33 (19) |
C7—N2—C6 | 122.00 (16) | C21—N6—C20 | 121.95 (16) |
C7—N2—H2 | 119.0 | C21—N6—H6 | 119.0 |
C6—N2—H2 | 119.0 | C20—N6—H6 | 119.0 |
C8—N3—C9 | 122.16 (16) | C22—N7—C23 | 121.89 (16) |
C8—N3—H3 | 118.9 | C22—N7—H7 | 119.1 |
C9—N3—H3 | 118.9 | C23—N7—H7 | 119.1 |
C14—N4—C10 | 116.39 (17) | C24—N8—C28 | 116.65 (17) |
N1—C1—C2 | 124.5 (2) | N5—C15—C16 | 124.0 (2) |
N1—C1—H1 | 117.8 | N5—C15—H15 | 118.0 |
C2—C1—H1 | 117.8 | C16—C15—H15 | 118.0 |
C1—C2—C3 | 119.3 (2) | C15—C16—C17 | 119.4 (2) |
C1—C2—H2A | 120.3 | C15—C16—H16 | 120.3 |
C3—C2—H2A | 120.3 | C17—C16—H16 | 120.3 |
C2—C3—C4 | 116.93 (18) | C18—C17—C16 | 116.81 (19) |
C2—C3—C6 | 119.68 (18) | C18—C17—C20 | 121.05 (17) |
C4—C3—C6 | 123.34 (17) | C16—C17—C20 | 122.13 (18) |
C3—C4—C5 | 119.79 (18) | C19—C18—C17 | 120.0 (2) |
C3—C4—H4 | 120.1 | C19—C18—H18 | 120.0 |
C5—C4—H4 | 120.1 | C17—C18—H18 | 120.0 |
N1—C5—C4 | 123.6 (2) | N5—C19—C18 | 123.5 (2) |
N1—C5—H5 | 118.2 | N5—C19—H19 | 118.3 |
C4—C5—H5 | 118.2 | C18—C19—H19 | 118.3 |
N2—C6—C3 | 114.33 (16) | N6—C20—C17 | 112.68 (15) |
N2—C6—H6A | 108.7 | N6—C20—H20A | 109.1 |
C3—C6—H6A | 108.7 | C17—C20—H20A | 109.1 |
N2—C6—H6B | 108.7 | N6—C20—H20B | 109.1 |
C3—C6—H6B | 108.7 | C17—C20—H20B | 109.1 |
H6A—C6—H6B | 107.6 | H20A—C20—H20B | 107.8 |
O1—C7—N2 | 125.71 (17) | O3—C21—N6 | 125.71 (17) |
O1—C7—C8 | 121.85 (15) | O3—C21—C22 | 121.29 (15) |
N2—C7—C8 | 112.43 (15) | N6—C21—C22 | 112.99 (15) |
O2—C8—N3 | 125.71 (17) | O4—C22—N7 | 125.79 (17) |
O2—C8—C7 | 121.04 (15) | O4—C22—C21 | 120.70 (15) |
N3—C8—C7 | 113.25 (15) | N7—C22—C21 | 113.50 (15) |
N3—C9—C12 | 113.02 (15) | N7—C23—C26 | 112.65 (15) |
N3—C9—H9A | 109.0 | N7—C23—H23A | 109.1 |
C12—C9—H9A | 109.0 | C26—C23—H23A | 109.1 |
N3—C9—H9B | 109.0 | N7—C23—H23B | 109.1 |
C12—C9—H9B | 109.0 | C26—C23—H23B | 109.1 |
H9A—C9—H9B | 107.8 | H23A—C23—H23B | 107.8 |
N4—C10—C11 | 123.58 (18) | N8—C24—C25 | 123.11 (18) |
N4—C10—H10 | 118.2 | N8—C24—H24 | 118.4 |
C11—C10—H10 | 118.2 | C25—C24—H24 | 118.4 |
C10—C11—C12 | 119.47 (18) | C24—C25—C26 | 119.82 (18) |
C10—C11—H11 | 120.3 | C24—C25—H25 | 120.1 |
C12—C11—H11 | 120.3 | C26—C25—H25 | 120.1 |
C13—C12—C11 | 117.13 (17) | C27—C26—C25 | 117.32 (17) |
C13—C12—C9 | 122.37 (16) | C27—C26—C23 | 121.31 (17) |
C11—C12—C9 | 120.45 (17) | C25—C26—C23 | 121.33 (17) |
C14—C13—C12 | 119.28 (17) | C26—C27—C28 | 118.89 (19) |
C14—C13—H13 | 120.4 | C26—C27—H27 | 120.6 |
C12—C13—H13 | 120.4 | C28—C27—H27 | 120.6 |
N4—C14—C13 | 124.15 (18) | N8—C28—C27 | 124.2 (2) |
N4—C14—H14 | 117.9 | N8—C28—H28 | 117.9 |
C13—C14—H14 | 117.9 | C27—C28—H28 | 117.9 |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···N8i | 0.88 | 2.08 | 2.903 (2) | 155 |
N3—H3···O3 | 0.88 | 2.09 | 2.916 (2) | 157 |
N6—H6···N4ii | 0.88 | 2.09 | 2.930 (2) | 158 |
N7—H7···O1 | 0.88 | 2.06 | 2.888 (2) | 156 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+1/2, y−1/2, −z+3/2. |
(II)
catena-poly[[[dichloridocobalt(II)]-µ-
N,
N'-bis(4–4-pyridylmethyl)oxalamide-
κ2N:
N'] hemihydrate]
top
Crystal data top
[CoCl2(C14H14N4O2)]·0.5H2O | Dx = 1.360 Mg m−3 |
Mr = 409.13 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pnna | Cell parameters from 1450 reflections |
a = 7.4566 (2) Å | θ = 1.8–26.5° |
b = 11.8572 (4) Å | µ = 1.14 mm−1 |
c = 22.6024 (7) Å | T = 150 K |
V = 1998.38 (11) Å3 | Rod, blue |
Z = 4 | 0.30 × 0.15 × 0.15 mm |
F(000) = 832 | |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 2297 independent reflections |
Radiation source: fine-focus sealed tube | 1627 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.051 |
ω scans | θmax = 27.5°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000a) | h = −9→9 |
Tmin = 0.681, Tmax = 0.852 | k = −13→15 |
11410 measured reflections | l = −29→29 |
Refinement top
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.060 | H-atom parameters constrained |
wR(F2) = 0.189 | w = 1/[σ2(Fo2) + (0.1048P)2 + 0.3815P] where P = (Fo2 + 2Fc2)/3 |
S = 1.19 | (Δ/σ)max = 0.008 |
2297 reflections | Δρmax = 0.82 e Å−3 |
110 parameters | Δρmin = −0.31 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.012 (2) |
Crystal data top
[CoCl2(C14H14N4O2)]·0.5H2O | V = 1998.38 (11) Å3 |
Mr = 409.13 | Z = 4 |
Orthorhombic, Pnna | Mo Kα radiation |
a = 7.4566 (2) Å | µ = 1.14 mm−1 |
b = 11.8572 (4) Å | T = 150 K |
c = 22.6024 (7) Å | 0.30 × 0.15 × 0.15 mm |
Data collection top
Bruker SMART APEX CCD area-detector diffractometer | 2297 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000a) | 1627 reflections with I > 2σ(I) |
Tmin = 0.681, Tmax = 0.852 | Rint = 0.051 |
11410 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.060 | 0 restraints |
wR(F2) = 0.189 | H-atom parameters constrained |
S = 1.19 | Δρmax = 0.82 e Å−3 |
2297 reflections | Δρmin = −0.31 e Å−3 |
110 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 | x | y | z | Uiso*/Ueq | Occ. (<1) |
Co1 | 0.2500 | 0.5000 | 0.74238 (3) | 0.0367 (3) | |
Cl1 | 0.02665 (15) | 0.58555 (9) | 0.69342 (4) | 0.0516 (4) | |
O1 | 0.6128 (4) | 0.8831 (2) | 1.02790 (12) | 0.0505 (7) | |
N1 | 0.3819 (4) | 0.6100 (2) | 0.79555 (12) | 0.0349 (7) | |
N2 | 0.5575 (4) | 0.9321 (3) | 0.93247 (13) | 0.0404 (8) | |
H2A | 0.4957 | 0.9779 | 0.9096 | 0.048* | |
C1 | 0.2927 (5) | 0.6762 (3) | 0.83343 (18) | 0.0419 (9) | |
H1 | 0.1658 | 0.6700 | 0.8354 | 0.050* | |
C2 | 0.3781 (5) | 0.7540 (3) | 0.87003 (16) | 0.0405 (9) | |
H2B | 0.3100 | 0.7993 | 0.8964 | 0.049* | |
C3 | 0.5594 (5) | 0.7645 (3) | 0.86774 (16) | 0.0411 (9) | |
C4 | 0.6507 (6) | 0.6983 (4) | 0.8278 (2) | 0.0645 (14) | |
H4 | 0.7773 | 0.7045 | 0.8244 | 0.077* | |
C5 | 0.5582 (5) | 0.6229 (4) | 0.7926 (2) | 0.0569 (12) | |
H5 | 0.6237 | 0.5783 | 0.7652 | 0.068* | |
C6 | 0.6640 (6) | 0.8450 (4) | 0.9055 (2) | 0.0615 (13) | |
H6A | 0.7250 | 0.8017 | 0.9372 | 0.074* | |
H6B | 0.7579 | 0.8808 | 0.8809 | 0.074* | |
C7 | 0.5492 (4) | 0.9459 (3) | 0.99131 (15) | 0.0327 (8) | |
O2 | 0.489 (3) | 0.6409 (18) | 1.0507 (9) | 0.124 (7)* | 0.25 |
H2C | 0.5444 | 0.6906 | 1.0306 | 0.186* | 0.25 |
H2D | 0.4262 | 0.5847 | 1.0403 | 0.186* | 0.25 |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Co1 | 0.0391 (5) | 0.0403 (5) | 0.0307 (4) | −0.0103 (3) | 0.000 | 0.000 |
Cl1 | 0.0555 (7) | 0.0546 (7) | 0.0446 (6) | −0.0122 (5) | −0.0133 (5) | 0.0135 (4) |
O1 | 0.0569 (17) | 0.0474 (16) | 0.0473 (15) | 0.0061 (14) | −0.0130 (14) | −0.0004 (13) |
N1 | 0.0361 (17) | 0.0358 (15) | 0.0328 (14) | −0.0059 (13) | −0.0012 (13) | −0.0039 (12) |
N2 | 0.0352 (17) | 0.0517 (19) | 0.0342 (16) | −0.0049 (14) | 0.0001 (14) | −0.0122 (14) |
C1 | 0.0261 (17) | 0.048 (2) | 0.052 (2) | −0.0010 (16) | 0.0036 (17) | −0.0079 (19) |
C2 | 0.0312 (19) | 0.047 (2) | 0.043 (2) | 0.0014 (16) | 0.0054 (17) | −0.0114 (17) |
C3 | 0.037 (2) | 0.047 (2) | 0.0396 (19) | −0.0047 (16) | −0.0014 (17) | −0.0097 (17) |
C4 | 0.034 (2) | 0.083 (3) | 0.077 (3) | −0.011 (2) | 0.013 (2) | −0.045 (3) |
C5 | 0.034 (2) | 0.075 (3) | 0.061 (3) | −0.007 (2) | 0.016 (2) | −0.035 (2) |
C6 | 0.033 (2) | 0.083 (3) | 0.068 (3) | −0.005 (2) | 0.004 (2) | −0.043 (3) |
C7 | 0.0244 (16) | 0.0373 (19) | 0.0364 (18) | −0.0092 (15) | −0.0009 (15) | −0.0065 (16) |
Geometric parameters (Å, º) top
Co1—N1 | 2.028 (3) | C2—C3 | 1.359 (5) |
Co1—N1i | 2.028 (3) | C2—H2B | 0.9500 |
Co1—Cl1 | 2.2422 (11) | C3—C4 | 1.377 (6) |
Co1—Cl1i | 2.2422 (11) | C3—C6 | 1.500 (5) |
O1—C7 | 1.210 (4) | C4—C5 | 1.380 (6) |
N1—C5 | 1.325 (5) | C4—H4 | 0.9500 |
N1—C1 | 1.339 (5) | C5—H5 | 0.9500 |
N2—C7 | 1.341 (4) | C6—H6A | 0.9900 |
N2—C6 | 1.438 (5) | C6—H6B | 0.9900 |
N2—H2A | 0.8800 | C7—C7ii | 1.529 (7) |
C1—C2 | 1.392 (5) | O2—H2C | 0.8520 |
C1—H1 | 0.9500 | O2—H2D | 0.8473 |
| | | |
N1—Co1—N1i | 107.33 (16) | C2—C3—C6 | 123.6 (3) |
N1—Co1—Cl1 | 111.20 (9) | C4—C3—C6 | 118.7 (4) |
N1i—Co1—Cl1 | 102.90 (9) | C3—C4—C5 | 120.0 (4) |
N1—Co1—Cl1i | 102.90 (9) | C3—C4—H4 | 120.0 |
N1i—Co1—Cl1i | 111.20 (9) | C5—C4—H4 | 120.0 |
Cl1—Co1—Cl1i | 120.85 (6) | N1—C5—C4 | 122.8 (4) |
C5—N1—C1 | 117.2 (3) | N1—C5—H5 | 118.6 |
C5—N1—Co1 | 121.7 (2) | C4—C5—H5 | 118.6 |
C1—N1—Co1 | 121.0 (2) | N2—C6—C3 | 114.3 (3) |
C7—N2—C6 | 122.2 (4) | N2—C6—H6A | 108.7 |
C7—N2—H2A | 118.9 | C3—C6—H6A | 108.7 |
C6—N2—H2A | 118.9 | N2—C6—H6B | 108.7 |
N1—C1—C2 | 122.7 (3) | C3—C6—H6B | 108.7 |
N1—C1—H1 | 118.6 | H6A—C6—H6B | 107.6 |
C2—C1—H1 | 118.6 | O1—C7—N2 | 125.8 (3) |
C3—C2—C1 | 119.5 (3) | O1—C7—C7ii | 121.9 (4) |
C3—C2—H2B | 120.2 | N2—C7—C7ii | 112.3 (4) |
C1—C2—H2B | 120.2 | H2C—O2—H2D | 131.4 |
C2—C3—C4 | 117.7 (3) | | |
Symmetry codes: (i) −x+1/2, −y+1, z; (ii) −x+1, −y+2, −z+2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2C···O1 | 0.85 | 2.34 | 3.06 (2) | 143 |
N2—H2A···Cl1iii | 0.88 | 2.66 | 3.435 (3) | 147 |
C2—H2B···O1iv | 0.95 | 2.46 | 3.403 (5) | 169 |
C6—H6B···Cl1v | 0.99 | 2.64 | 3.605 (4) | 163 |
Symmetry codes: (iii) −x+1/2, y+1/2, −z+3/2; (iv) x−1/2, y, −z+2; (v) x+1, −y+3/2, −z+3/2. |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C14H14N4O2 | [CoCl2(C14H14N4O2)]·0.5H2O |
Mr | 270.29 | 409.13 |
Crystal system, space group | Monoclinic, P21/n | Orthorhombic, Pnna |
Temperature (K) | 150 | 150 |
a, b, c (Å) | 9.5188 (4), 15.4474 (7), 17.8238 (8) | 7.4566 (2), 11.8572 (4), 22.6024 (7) |
α, β, γ (°) | 90, 93.833 (1), 90 | 90, 90, 90 |
V (Å3) | 2615.0 (2) | 1998.38 (11) |
Z | 8 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.10 | 1.14 |
Crystal size (mm) | 0.32 × 0.22 × 0.15 | 0.30 × 0.15 × 0.15 |
|
Data collection |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2000a) | Multi-scan (SADABS; Sheldrick, 2000a) |
Tmin, Tmax | 0.970, 0.986 | 0.681, 0.852 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25256, 6006, 4530 | 11410, 2297, 1627 |
Rint | 0.044 | 0.051 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.060, 0.143, 1.13 | 0.060, 0.189, 1.19 |
No. of reflections | 6006 | 2297 |
No. of parameters | 361 | 110 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.34, −0.25 | 0.82, −0.31 |
Selected geometric parameters (Å, º) for (I) topO1—C7 | 1.227 (2) | O3—C21 | 1.231 (2) |
O2—C8 | 1.222 (2) | O4—C22 | 1.225 (2) |
N2—C7 | 1.329 (2) | N6—C21 | 1.324 (2) |
N2—C6 | 1.449 (2) | N6—C20 | 1.461 (2) |
N3—C8 | 1.334 (2) | N7—C22 | 1.328 (2) |
N3—C9 | 1.454 (2) | N7—C23 | 1.460 (2) |
C7—C8 | 1.541 (2) | C21—C22 | 1.541 (2) |
| | | |
C7—N2—C6 | 122.00 (16) | C21—N6—C20 | 121.95 (16) |
C8—N3—C9 | 122.16 (16) | C22—N7—C23 | 121.89 (16) |
O1—C7—N2 | 125.71 (17) | O3—C21—N6 | 125.71 (17) |
O1—C7—C8 | 121.85 (15) | O3—C21—C22 | 121.29 (15) |
N2—C7—C8 | 112.43 (15) | N6—C21—C22 | 112.99 (15) |
O2—C8—N3 | 125.71 (17) | O4—C22—N7 | 125.79 (17) |
O2—C8—C7 | 121.04 (15) | O4—C22—C21 | 120.70 (15) |
N3—C8—C7 | 113.25 (15) | N7—C22—C21 | 113.50 (15) |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···N8i | 0.88 | 2.08 | 2.903 (2) | 155 |
N3—H3···O3 | 0.88 | 2.09 | 2.916 (2) | 157 |
N6—H6···N4ii | 0.88 | 2.09 | 2.930 (2) | 158 |
N7—H7···O1 | 0.88 | 2.06 | 2.888 (2) | 156 |
Symmetry codes: (i) −x+1/2, y+1/2, −z+1/2; (ii) −x+1/2, y−1/2, −z+3/2. |
Selected geometric parameters (Å, º) for (II) topCo1—N1 | 2.028 (3) | O1—C7 | 1.210 (4) |
Co1—N1i | 2.028 (3) | N2—C7 | 1.341 (4) |
Co1—Cl1 | 2.2422 (11) | N2—C6 | 1.438 (5) |
Co1—Cl1i | 2.2422 (11) | C7—C7ii | 1.529 (7) |
| | | |
N1—Co1—N1i | 107.33 (16) | Cl1—Co1—Cl1i | 120.85 (6) |
N1—Co1—Cl1 | 111.20 (9) | C7—N2—C6 | 122.2 (4) |
N1i—Co1—Cl1 | 102.90 (9) | O1—C7—N2 | 125.8 (3) |
N1—Co1—Cl1i | 102.90 (9) | O1—C7—C7ii | 121.9 (4) |
N1i—Co1—Cl1i | 111.20 (9) | N2—C7—C7ii | 112.3 (4) |
Symmetry codes: (i) −x+1/2, −y+1, z; (ii) −x+1, −y+2, −z+2. |
Hydrogen-bond geometry (Å, º) for (II) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2C···O1 | 0.85 | 2.34 | 3.06 (2) | 143 |
N2—H2A···Cl1iii | 0.88 | 2.66 | 3.435 (3) | 147 |
C2—H2B···O1iv | 0.95 | 2.46 | 3.403 (5) | 169 |
C6—H6B···Cl1v | 0.99 | 2.64 | 3.605 (4) | 163 |
Symmetry codes: (iii) −x+1/2, y+1/2, −z+3/2; (iv) x−1/2, y, −z+2; (v) x+1, −y+3/2, −z+3/2. |
The coordination-bond and hydrogen-bond approaches have recently been recognized as very powerful and versatile strategies in supramolecular design and material synthesis (Janiak, 2003; Nguyen et al., 2001). The pyridyl groups, with effective sites for coordination to transition metal ions, were used for construction of supramolecular coordination compounds (Maspoch et al., 2004; Barnett & Champness, 2003; Carlucci et al., 2003). In addition, organic amides have been proved to be very useful in self-assembly through hydrogen bonding, and the assembled products have relevance to biological systems. Thus, dipyridyl amide ligands have been recently designed and synthesized in crystal engineering, in which the amide-amide hydrogen bonding has been demonstrated to increase supramolecular versatility (Burchell et al., 2004; Muthu et al., 2002a,b; Nguyen et al., 1998). In the present paper, the N,N'-bis(4-pyridylmethyl)oxalamide (4py-ox) ligand has been chosen to construct a supramolecular coordination compound, and the single-crystal X-ray structures of 4py-ox, (I), and its Co complex (II) are reported.
The crystal structure of 4py-ox is presented in Fig. 1, and selected bond lengths and angles are listed in Table 1. There are two crystallographically independent molecules, which form a dimer through amide–amide hydrogen bonds, with Z = 8 in the unit cell. In the crystal structure of 4py-ox, the two pyridine rings in each molecule are separated by an oxalamide linkage, and the terminal (pyridyl) N···N separations are 13.075 (2) and 12.951 (2) Å. The two pyridine rings in a molecule are almost parallel to each other, with dihedral angles of 4.93 and 6.63°, respectively. The central oxalamide group is planar and nearly perpendicular to the pyridine rings.
The two-dimensional structure of 4py-ox is shown in Fig. 2 and the related hydrogen-bonding geometries are tabulated in Table 2. Besides two amide–amide hydrogen bonds (N3···O3 and N7···O1) binding the two independent molecules into a dimer, two intermolecular hydrogen bonds exist between the oxalamide part of the dimer and pyridyl nitrogen atom of the neighboring dimer (Table 2). Dimers are further linked to form a two-dimensional supramolecular structure.
The one-dimensional zigzag chain structure of compound (II), {[Co{µ2-(4py-ox)}Cl2]·0.5H2O}n, is shown in Fig. 3. The structure consists of a distorted tetrahedral CoII center coordinating to two Cl atoms and two pyridyl N atoms of two 4py-ox ligands [Co1—Cl1 = 2.2420 (11) Å; Co1—N1 = 2.028 (3) Å]. The CoII atom sits on a twofold symmetry position, and has an occupancy of 0.5. The symmetry operation (1/2 - x, 1 - y, z) was used to generate another anion Cl- and 4py-ox ligand. Each 4py-ox ligand has an inversion center in the middle of the C7—C7ii bond, where the symmetry operation (1 - x, 2 - y, 2 - z) was applied to generate the other half of the ligand. By using one C1 atom and half of the ligand in the asymmetric unit, we obtain (II) with four Co atoms, eight C1 atoms and four complete ligands in the unit cell. The selected bond lengths and angles are listed in Table 3.
Interestingly, a square cavity with a cross section dimension of ca 8.6 x 8.6 Å is created from two interwoven chains, and a channel along the a axis is produced (Fig. 4). The void is 23.1% of the volume, as calculated by PLATON (Spek, 2003) upon removal of the hydrate. Both the cavity dimension and the void volume are slightly higher than those in the complex [ZnCl2(4py-ox)2] (8.5 × 8.5 Å and 22.1%; Tzeng et al., 2005). Each repeating unit of the complex contains the half solvent water molecule as a guest molecule. The guest molecules are intercalated into these channels and one of the H atoms is bonded to the carbonyl O of the neighboring oxalamide unit (O2···O1), as shown in Table 4.
The crystal structure of (II) also reveals three sets of intermolecular hydrogen bonds (symmetry codes and geometric parameters are given in Table 4). The C2/H2B···O1ii distance falls in the middle of the range of published values [2.22 (3)–2.62 (2) Å; Steiner, 1996] and the C6/H6B···Cl1iii distance is equal to the published value [2.64 (1) Å; Steiner, 1998].