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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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270107014527/av3082sup1.cif
Contains datablocks global, I, II

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107014527/av3082Isup2.hkl
Contains datablock I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270107014527/av3082IIsup3.hkl
Contains datablock II

CCDC references: 649075; 649076

Comment top

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].

Related literature top

For related literature, see: Barnett & Champness (2003); Burchell et al. (2004); Carlucci et al. (2003); Janiak (2003); Maspoch et al. (2004); Muthu et al. (2002a, 2002b); Nguyen et al. (1998, 2001); Spek (2003); Steiner (1996, 1998); Tzeng et al. (2005).

Experimental top

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%.

Refinement top

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)].

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. Dashed lines represent the hydrogen bonding.
[Figure 2] Fig. 2. The two-dimensional network of (I) formed via hydrogen bonds, viewed along the a axis. Dashed lines represent the hydrogen bonding. Atoms labeled with the suffixes A and B are at the symmetry positions (1/2 - x, 1/2 + y, 1/2 - z) and (1/2 - x, -1/2 + y, 3/2 - z), respectively.
[Figure 3] Fig. 3. The zigzag chain structure of (II), showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 50% probability level. Atoms labeled with the suffixes A and B are at the symmetry position (1/2 - x, 1 - y, z) and (1 - x, 2 - y, 2 - z), respectively.
[Figure 4] Fig. 4. The extended framework of (II), showing the channel structure with dimension of ca 8.6 x 8.6 Å.
(I) N,N'-Bis(4-pyridylmethyl)oxalamide top
Crystal data top
C14H14N4O2F(000) = 1136
Mr = 270.29Dx = 1.373 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 9.5188 (4) ÅCell parameters from 3244 reflections
b = 15.4474 (7) Åθ = 2.6–26.7°
c = 17.8238 (8) ŵ = 0.10 mm1
β = 93.833 (1)°T = 150 K
V = 2615.0 (2) Å3Rod, colorless
Z = 80.32 × 0.22 × 0.15 mm
Data collection top
Bruker SMART APEX CCD area-detector
diffractometer
6006 independent reflections
Radiation source: fine-focus sealed tube4530 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.044
ω scansθmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000a)
h = 1212
Tmin = 0.970, Tmax = 0.986k = 2019
25256 measured reflectionsl = 2323
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)] = 0.060Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143H-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 parametersΔρmax = 0.34 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C14H14N4O2V = 2615.0 (2) Å3
Mr = 270.29Z = 8
Monoclinic, P21/nMo Kα radiation
a = 9.5188 (4) ŵ = 0.10 mm1
b = 15.4474 (7) ÅT = 150 K
c = 17.8238 (8) Å0.32 × 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 = 0.986Rint = 0.044
25256 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0600 restraints
wR(F2) = 0.143H-atom parameters constrained
S = 1.13Δρmax = 0.34 e Å3
6006 reflectionsΔρmin = 0.25 e Å3
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
xyzUiso*/Ueq
O10.27862 (14)0.49834 (8)0.40856 (7)0.0241 (3)
O20.02876 (15)0.65640 (9)0.35216 (7)0.0254 (3)
N10.2152 (2)0.33400 (15)0.08532 (12)0.0490 (6)
N20.23215 (16)0.56187 (10)0.29444 (8)0.0194 (3)
H20.17460.59670.26810.023*
N30.07727 (16)0.59737 (10)0.46793 (8)0.0186 (3)
H30.13360.56220.49460.022*
N40.11569 (18)0.80950 (10)0.68638 (9)0.0248 (4)
C10.3346 (3)0.3791 (2)0.08474 (15)0.0573 (8)
H10.39410.36850.04500.069*
C20.3776 (2)0.44002 (17)0.13779 (13)0.0391 (6)
H2A0.46350.47050.13380.047*
C30.2945 (2)0.45641 (12)0.19686 (10)0.0214 (4)
C40.1703 (2)0.41028 (13)0.19821 (11)0.0265 (4)
H40.10920.41950.23750.032*
C50.1352 (2)0.35056 (15)0.14220 (13)0.0356 (5)
H50.04920.31960.14440.043*
C60.3444 (2)0.51944 (13)0.25742 (10)0.0216 (4)
H6A0.40500.48820.29570.026*
H6B0.40290.56420.23490.026*
C70.21346 (19)0.54981 (11)0.36692 (10)0.0173 (4)
C80.09608 (19)0.60771 (11)0.39500 (10)0.0174 (4)
C90.03317 (19)0.64233 (12)0.50485 (10)0.0200 (4)
H9A0.09870.59910.52400.024*
H9B0.08710.67880.46740.024*
C100.0079 (2)0.76838 (13)0.68657 (11)0.0261 (4)
H100.06440.77780.72780.031*
C110.0578 (2)0.71299 (13)0.63022 (10)0.0230 (4)
H110.14620.68510.63320.028*
C120.02241 (19)0.69834 (12)0.56889 (10)0.0180 (4)
C130.1509 (2)0.74020 (12)0.56878 (10)0.0196 (4)
H130.20980.73190.52840.024*
C140.1924 (2)0.79405 (12)0.62786 (11)0.0233 (4)
H140.28120.82190.62680.028*
O30.22234 (14)0.50284 (8)0.59179 (7)0.0235 (3)
O40.46974 (15)0.34272 (9)0.64601 (7)0.0257 (3)
N50.3074 (2)0.66508 (13)0.90842 (11)0.0383 (5)
N60.26497 (16)0.43590 (10)0.70461 (8)0.0184 (3)
H60.32090.39980.73050.022*
N70.41804 (16)0.40165 (10)0.53061 (8)0.0179 (3)
H70.35940.43540.50390.021*
N80.38497 (18)0.17985 (11)0.32010 (9)0.0281 (4)
C150.2681 (2)0.58569 (16)0.92753 (12)0.0355 (5)
H150.27570.57060.97930.043*
C160.2169 (2)0.52399 (13)0.87661 (11)0.0286 (5)
H160.18840.46880.89360.034*
C170.20756 (19)0.54329 (12)0.80063 (10)0.0212 (4)
C180.2486 (2)0.62546 (13)0.78050 (12)0.0282 (5)
H180.24420.64190.72900.034*
C190.2962 (2)0.68374 (14)0.83530 (13)0.0349 (5)
H190.32220.74010.82000.042*
C200.1525 (2)0.47910 (13)0.74215 (10)0.0220 (4)
H20A0.09540.43500.76640.026*
H20B0.09020.50950.70410.026*
C210.28526 (19)0.44946 (11)0.63280 (10)0.0176 (4)
C220.40124 (19)0.39142 (11)0.60343 (10)0.0171 (4)
C230.53094 (19)0.35846 (12)0.49355 (10)0.0197 (4)
H23A0.59070.32620.53160.024*
H23B0.59050.40270.47110.024*
C240.4363 (2)0.25705 (13)0.30350 (11)0.0253 (4)
H240.44090.27210.25210.030*
C250.4831 (2)0.31632 (12)0.35749 (10)0.0233 (4)
H250.51990.37050.34290.028*
C260.47640 (19)0.29659 (12)0.43297 (10)0.0187 (4)
C270.4224 (2)0.21695 (14)0.45048 (11)0.0313 (5)
H270.41500.20050.50140.038*
C280.3791 (3)0.16140 (15)0.39275 (12)0.0369 (6)
H280.34290.10650.40570.044*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0302 (8)0.0242 (7)0.0177 (7)0.0080 (6)0.0000 (6)0.0026 (5)
O20.0320 (8)0.0262 (7)0.0179 (7)0.0098 (6)0.0009 (6)0.0028 (6)
N10.0351 (11)0.0637 (15)0.0489 (13)0.0089 (10)0.0090 (10)0.0339 (11)
N20.0225 (8)0.0211 (8)0.0144 (7)0.0049 (7)0.0002 (6)0.0003 (6)
N30.0220 (8)0.0190 (8)0.0145 (7)0.0041 (6)0.0001 (6)0.0007 (6)
N40.0312 (9)0.0219 (9)0.0215 (8)0.0014 (7)0.0027 (7)0.0040 (7)
C10.0411 (15)0.084 (2)0.0493 (15)0.0176 (14)0.0223 (12)0.0434 (15)
C20.0264 (11)0.0577 (16)0.0346 (12)0.0117 (11)0.0120 (9)0.0229 (11)
C30.0224 (10)0.0228 (10)0.0189 (9)0.0047 (8)0.0016 (7)0.0016 (8)
C40.0261 (10)0.0275 (11)0.0267 (10)0.0002 (8)0.0086 (8)0.0049 (8)
C50.0297 (12)0.0362 (12)0.0414 (13)0.0073 (10)0.0064 (10)0.0128 (10)
C60.0206 (9)0.0254 (10)0.0188 (9)0.0017 (8)0.0020 (7)0.0018 (8)
C70.0199 (9)0.0160 (9)0.0158 (8)0.0004 (7)0.0013 (7)0.0020 (7)
C80.0202 (9)0.0169 (9)0.0147 (8)0.0019 (7)0.0016 (7)0.0026 (7)
C90.0189 (9)0.0234 (10)0.0177 (9)0.0014 (8)0.0011 (7)0.0034 (7)
C100.0295 (11)0.0292 (11)0.0204 (9)0.0017 (9)0.0073 (8)0.0053 (8)
C110.0216 (10)0.0266 (10)0.0214 (9)0.0032 (8)0.0048 (8)0.0036 (8)
C120.0235 (9)0.0162 (9)0.0143 (8)0.0039 (7)0.0011 (7)0.0016 (7)
C130.0228 (9)0.0178 (9)0.0187 (9)0.0023 (8)0.0045 (7)0.0013 (7)
C140.0228 (10)0.0206 (10)0.0268 (10)0.0020 (8)0.0035 (8)0.0025 (8)
O30.0292 (8)0.0238 (7)0.0174 (6)0.0072 (6)0.0007 (6)0.0024 (5)
O40.0303 (8)0.0281 (7)0.0187 (7)0.0106 (6)0.0017 (6)0.0039 (6)
N50.0335 (10)0.0415 (12)0.0403 (11)0.0012 (9)0.0056 (9)0.0173 (9)
N60.0195 (8)0.0209 (8)0.0150 (7)0.0038 (6)0.0019 (6)0.0006 (6)
N70.0206 (8)0.0185 (8)0.0144 (7)0.0036 (6)0.0001 (6)0.0009 (6)
N80.0287 (9)0.0337 (10)0.0224 (8)0.0074 (8)0.0044 (7)0.0089 (7)
C150.0421 (13)0.0448 (14)0.0200 (10)0.0069 (11)0.0046 (9)0.0083 (10)
C160.0383 (12)0.0253 (11)0.0229 (10)0.0041 (9)0.0080 (9)0.0012 (8)
C170.0182 (9)0.0234 (10)0.0225 (9)0.0043 (8)0.0049 (7)0.0036 (8)
C180.0284 (11)0.0276 (11)0.0293 (11)0.0011 (9)0.0071 (9)0.0000 (9)
C190.0337 (12)0.0270 (11)0.0453 (13)0.0037 (9)0.0131 (10)0.0074 (10)
C200.0212 (9)0.0263 (10)0.0189 (9)0.0006 (8)0.0042 (7)0.0018 (8)
C210.0198 (9)0.0168 (9)0.0160 (9)0.0015 (7)0.0006 (7)0.0015 (7)
C220.0192 (9)0.0154 (9)0.0167 (9)0.0019 (7)0.0008 (7)0.0012 (7)
C230.0196 (9)0.0224 (10)0.0172 (9)0.0005 (7)0.0029 (7)0.0044 (7)
C240.0319 (11)0.0284 (11)0.0158 (9)0.0031 (9)0.0024 (8)0.0016 (8)
C250.0300 (11)0.0194 (10)0.0205 (9)0.0020 (8)0.0025 (8)0.0008 (8)
C260.0158 (9)0.0215 (9)0.0191 (9)0.0019 (7)0.0025 (7)0.0046 (7)
C270.0456 (13)0.0330 (12)0.0162 (9)0.0170 (10)0.0080 (9)0.0014 (8)
C280.0498 (14)0.0327 (12)0.0293 (11)0.0221 (11)0.0115 (10)0.0075 (9)
Geometric parameters (Å, º) top
O1—C71.227 (2)O3—C211.231 (2)
O2—C81.222 (2)O4—C221.225 (2)
N1—C51.333 (3)N5—C191.332 (3)
N1—C11.334 (3)N5—C151.333 (3)
N2—C71.329 (2)N6—C211.324 (2)
N2—C61.449 (2)N6—C201.461 (2)
N2—H20.8800N6—H60.8800
N3—C81.334 (2)N7—C221.328 (2)
N3—C91.454 (2)N7—C231.460 (2)
N3—H30.8800N7—H70.8800
N4—C141.334 (2)N8—C241.329 (3)
N4—C101.337 (3)N8—C281.331 (3)
C1—C21.376 (3)C15—C161.382 (3)
C1—H10.9500C15—H150.9500
C2—C31.382 (3)C16—C171.384 (3)
C2—H2A0.9500C16—H160.9500
C3—C41.382 (3)C17—C181.383 (3)
C3—C61.507 (3)C17—C201.507 (3)
C4—C51.384 (3)C18—C191.382 (3)
C4—H40.9500C18—H180.9500
C5—H50.9500C19—H190.9500
C6—H6A0.9900C20—H20A0.9900
C6—H6B0.9900C20—H20B0.9900
C7—C81.541 (2)C21—C221.541 (2)
C9—C121.500 (2)C23—C261.508 (2)
C9—H9A0.9900C23—H23A0.9900
C9—H9B0.9900C23—H23B0.9900
C10—C111.379 (3)C24—C251.380 (3)
C10—H100.9500C24—H240.9500
C11—C121.393 (2)C25—C261.385 (3)
C11—H110.9500C25—H250.9500
C12—C131.383 (3)C26—C271.377 (3)
C13—C141.379 (3)C27—C281.381 (3)
C13—H130.9500C27—H270.9500
C14—H140.9500C28—H280.9500
C5—N1—C1115.9 (2)C19—N5—C15116.33 (19)
C7—N2—C6122.00 (16)C21—N6—C20121.95 (16)
C7—N2—H2119.0C21—N6—H6119.0
C6—N2—H2119.0C20—N6—H6119.0
C8—N3—C9122.16 (16)C22—N7—C23121.89 (16)
C8—N3—H3118.9C22—N7—H7119.1
C9—N3—H3118.9C23—N7—H7119.1
C14—N4—C10116.39 (17)C24—N8—C28116.65 (17)
N1—C1—C2124.5 (2)N5—C15—C16124.0 (2)
N1—C1—H1117.8N5—C15—H15118.0
C2—C1—H1117.8C16—C15—H15118.0
C1—C2—C3119.3 (2)C15—C16—C17119.4 (2)
C1—C2—H2A120.3C15—C16—H16120.3
C3—C2—H2A120.3C17—C16—H16120.3
C2—C3—C4116.93 (18)C18—C17—C16116.81 (19)
C2—C3—C6119.68 (18)C18—C17—C20121.05 (17)
C4—C3—C6123.34 (17)C16—C17—C20122.13 (18)
C3—C4—C5119.79 (18)C19—C18—C17120.0 (2)
C3—C4—H4120.1C19—C18—H18120.0
C5—C4—H4120.1C17—C18—H18120.0
N1—C5—C4123.6 (2)N5—C19—C18123.5 (2)
N1—C5—H5118.2N5—C19—H19118.3
C4—C5—H5118.2C18—C19—H19118.3
N2—C6—C3114.33 (16)N6—C20—C17112.68 (15)
N2—C6—H6A108.7N6—C20—H20A109.1
C3—C6—H6A108.7C17—C20—H20A109.1
N2—C6—H6B108.7N6—C20—H20B109.1
C3—C6—H6B108.7C17—C20—H20B109.1
H6A—C6—H6B107.6H20A—C20—H20B107.8
O1—C7—N2125.71 (17)O3—C21—N6125.71 (17)
O1—C7—C8121.85 (15)O3—C21—C22121.29 (15)
N2—C7—C8112.43 (15)N6—C21—C22112.99 (15)
O2—C8—N3125.71 (17)O4—C22—N7125.79 (17)
O2—C8—C7121.04 (15)O4—C22—C21120.70 (15)
N3—C8—C7113.25 (15)N7—C22—C21113.50 (15)
N3—C9—C12113.02 (15)N7—C23—C26112.65 (15)
N3—C9—H9A109.0N7—C23—H23A109.1
C12—C9—H9A109.0C26—C23—H23A109.1
N3—C9—H9B109.0N7—C23—H23B109.1
C12—C9—H9B109.0C26—C23—H23B109.1
H9A—C9—H9B107.8H23A—C23—H23B107.8
N4—C10—C11123.58 (18)N8—C24—C25123.11 (18)
N4—C10—H10118.2N8—C24—H24118.4
C11—C10—H10118.2C25—C24—H24118.4
C10—C11—C12119.47 (18)C24—C25—C26119.82 (18)
C10—C11—H11120.3C24—C25—H25120.1
C12—C11—H11120.3C26—C25—H25120.1
C13—C12—C11117.13 (17)C27—C26—C25117.32 (17)
C13—C12—C9122.37 (16)C27—C26—C23121.31 (17)
C11—C12—C9120.45 (17)C25—C26—C23121.33 (17)
C14—C13—C12119.28 (17)C26—C27—C28118.89 (19)
C14—C13—H13120.4C26—C27—H27120.6
C12—C13—H13120.4C28—C27—H27120.6
N4—C14—C13124.15 (18)N8—C28—C27124.2 (2)
N4—C14—H14117.9N8—C28—H28117.9
C13—C14—H14117.9C27—C28—H28117.9
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2···N8i0.882.082.903 (2)155
N3—H3···O30.882.092.916 (2)157
N6—H6···N4ii0.882.092.930 (2)158
N7—H7···O10.882.062.888 (2)156
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x+1/2, y1/2, 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)]·0.5H2ODx = 1.360 Mg m3
Mr = 409.13Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PnnaCell parameters from 1450 reflections
a = 7.4566 (2) Åθ = 1.8–26.5°
b = 11.8572 (4) ŵ = 1.14 mm1
c = 22.6024 (7) ÅT = 150 K
V = 1998.38 (11) Å3Rod, blue
Z = 40.30 × 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 tube1627 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.051
ω scansθmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000a)
h = 99
Tmin = 0.681, Tmax = 0.852k = 1315
11410 measured reflectionsl = 2929
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.060H-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 reflectionsΔρmax = 0.82 e Å3
110 parametersΔρmin = 0.31 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.012 (2)
Crystal data top
[CoCl2(C14H14N4O2)]·0.5H2OV = 1998.38 (11) Å3
Mr = 409.13Z = 4
Orthorhombic, PnnaMo Kα radiation
a = 7.4566 (2) ŵ = 1.14 mm1
b = 11.8572 (4) ÅT = 150 K
c = 22.6024 (7) Å0.30 × 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 = 0.852Rint = 0.051
11410 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0600 restraints
wR(F2) = 0.189H-atom parameters constrained
S = 1.19Δρmax = 0.82 e Å3
2297 reflectionsΔρmin = 0.31 e Å3
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
xyzUiso*/UeqOcc. (<1)
Co10.25000.50000.74238 (3)0.0367 (3)
Cl10.02665 (15)0.58555 (9)0.69342 (4)0.0516 (4)
O10.6128 (4)0.8831 (2)1.02790 (12)0.0505 (7)
N10.3819 (4)0.6100 (2)0.79555 (12)0.0349 (7)
N20.5575 (4)0.9321 (3)0.93247 (13)0.0404 (8)
H2A0.49570.97790.90960.048*
C10.2927 (5)0.6762 (3)0.83343 (18)0.0419 (9)
H10.16580.67000.83540.050*
C20.3781 (5)0.7540 (3)0.87003 (16)0.0405 (9)
H2B0.31000.79930.89640.049*
C30.5594 (5)0.7645 (3)0.86774 (16)0.0411 (9)
C40.6507 (6)0.6983 (4)0.8278 (2)0.0645 (14)
H40.77730.70450.82440.077*
C50.5582 (5)0.6229 (4)0.7926 (2)0.0569 (12)
H50.62370.57830.76520.068*
C60.6640 (6)0.8450 (4)0.9055 (2)0.0615 (13)
H6A0.72500.80170.93720.074*
H6B0.75790.88080.88090.074*
C70.5492 (4)0.9459 (3)0.99131 (15)0.0327 (8)
O20.489 (3)0.6409 (18)1.0507 (9)0.124 (7)*0.25
H2C0.54440.69061.03060.186*0.25
H2D0.42620.58471.04030.186*0.25
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Co10.0391 (5)0.0403 (5)0.0307 (4)0.0103 (3)0.0000.000
Cl10.0555 (7)0.0546 (7)0.0446 (6)0.0122 (5)0.0133 (5)0.0135 (4)
O10.0569 (17)0.0474 (16)0.0473 (15)0.0061 (14)0.0130 (14)0.0004 (13)
N10.0361 (17)0.0358 (15)0.0328 (14)0.0059 (13)0.0012 (13)0.0039 (12)
N20.0352 (17)0.0517 (19)0.0342 (16)0.0049 (14)0.0001 (14)0.0122 (14)
C10.0261 (17)0.048 (2)0.052 (2)0.0010 (16)0.0036 (17)0.0079 (19)
C20.0312 (19)0.047 (2)0.043 (2)0.0014 (16)0.0054 (17)0.0114 (17)
C30.037 (2)0.047 (2)0.0396 (19)0.0047 (16)0.0014 (17)0.0097 (17)
C40.034 (2)0.083 (3)0.077 (3)0.011 (2)0.013 (2)0.045 (3)
C50.034 (2)0.075 (3)0.061 (3)0.007 (2)0.016 (2)0.035 (2)
C60.033 (2)0.083 (3)0.068 (3)0.005 (2)0.004 (2)0.043 (3)
C70.0244 (16)0.0373 (19)0.0364 (18)0.0092 (15)0.0009 (15)0.0065 (16)
Geometric parameters (Å, º) top
Co1—N12.028 (3)C2—C31.359 (5)
Co1—N1i2.028 (3)C2—H2B0.9500
Co1—Cl12.2422 (11)C3—C41.377 (6)
Co1—Cl1i2.2422 (11)C3—C61.500 (5)
O1—C71.210 (4)C4—C51.380 (6)
N1—C51.325 (5)C4—H40.9500
N1—C11.339 (5)C5—H50.9500
N2—C71.341 (4)C6—H6A0.9900
N2—C61.438 (5)C6—H6B0.9900
N2—H2A0.8800C7—C7ii1.529 (7)
C1—C21.392 (5)O2—H2C0.8520
C1—H10.9500O2—H2D0.8473
N1—Co1—N1i107.33 (16)C2—C3—C6123.6 (3)
N1—Co1—Cl1111.20 (9)C4—C3—C6118.7 (4)
N1i—Co1—Cl1102.90 (9)C3—C4—C5120.0 (4)
N1—Co1—Cl1i102.90 (9)C3—C4—H4120.0
N1i—Co1—Cl1i111.20 (9)C5—C4—H4120.0
Cl1—Co1—Cl1i120.85 (6)N1—C5—C4122.8 (4)
C5—N1—C1117.2 (3)N1—C5—H5118.6
C5—N1—Co1121.7 (2)C4—C5—H5118.6
C1—N1—Co1121.0 (2)N2—C6—C3114.3 (3)
C7—N2—C6122.2 (4)N2—C6—H6A108.7
C7—N2—H2A118.9C3—C6—H6A108.7
C6—N2—H2A118.9N2—C6—H6B108.7
N1—C1—C2122.7 (3)C3—C6—H6B108.7
N1—C1—H1118.6H6A—C6—H6B107.6
C2—C1—H1118.6O1—C7—N2125.8 (3)
C3—C2—C1119.5 (3)O1—C7—C7ii121.9 (4)
C3—C2—H2B120.2N2—C7—C7ii112.3 (4)
C1—C2—H2B120.2H2C—O2—H2D131.4
C2—C3—C4117.7 (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···AD—HH···AD···AD—H···A
O2—H2C···O10.852.343.06 (2)143
N2—H2A···Cl1iii0.882.663.435 (3)147
C2—H2B···O1iv0.952.463.403 (5)169
C6—H6B···Cl1v0.992.643.605 (4)163
Symmetry codes: (iii) x+1/2, y+1/2, z+3/2; (iv) x1/2, y, z+2; (v) x+1, y+3/2, z+3/2.

Experimental details

(I)(II)
Crystal data
Chemical formulaC14H14N4O2[CoCl2(C14H14N4O2)]·0.5H2O
Mr270.29409.13
Crystal system, space groupMonoclinic, P21/nOrthorhombic, Pnna
Temperature (K)150150
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), 9090, 90, 90
V3)2615.0 (2)1998.38 (11)
Z84
Radiation typeMo KαMo Kα
µ (mm1)0.101.14
Crystal size (mm)0.32 × 0.22 × 0.150.30 × 0.15 × 0.15
Data collection
DiffractometerBruker SMART APEX CCD area-detector
diffractometer
Bruker SMART APEX CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2000a)
Multi-scan
(SADABS; Sheldrick, 2000a)
Tmin, Tmax0.970, 0.9860.681, 0.852
No. of measured, independent and
observed [I > 2σ(I)] reflections
25256, 6006, 4530 11410, 2297, 1627
Rint0.0440.051
(sin θ/λ)max1)0.6500.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.060, 0.143, 1.13 0.060, 0.189, 1.19
No. of reflections60062297
No. of parameters361110
H-atom treatmentH-atom parameters constrainedH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.34, 0.250.82, 0.31

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 2000b), SHELXTL.

Selected geometric parameters (Å, º) for (I) top
O1—C71.227 (2)O3—C211.231 (2)
O2—C81.222 (2)O4—C221.225 (2)
N2—C71.329 (2)N6—C211.324 (2)
N2—C61.449 (2)N6—C201.461 (2)
N3—C81.334 (2)N7—C221.328 (2)
N3—C91.454 (2)N7—C231.460 (2)
C7—C81.541 (2)C21—C221.541 (2)
C7—N2—C6122.00 (16)C21—N6—C20121.95 (16)
C8—N3—C9122.16 (16)C22—N7—C23121.89 (16)
O1—C7—N2125.71 (17)O3—C21—N6125.71 (17)
O1—C7—C8121.85 (15)O3—C21—C22121.29 (15)
N2—C7—C8112.43 (15)N6—C21—C22112.99 (15)
O2—C8—N3125.71 (17)O4—C22—N7125.79 (17)
O2—C8—C7121.04 (15)O4—C22—C21120.70 (15)
N3—C8—C7113.25 (15)N7—C22—C21113.50 (15)
Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—H···A
N2—H2···N8i0.882.082.903 (2)155
N3—H3···O30.882.092.916 (2)157
N6—H6···N4ii0.882.092.930 (2)158
N7—H7···O10.882.062.888 (2)156
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x+1/2, y1/2, z+3/2.
Selected geometric parameters (Å, º) for (II) top
Co1—N12.028 (3)O1—C71.210 (4)
Co1—N1i2.028 (3)N2—C71.341 (4)
Co1—Cl12.2422 (11)N2—C61.438 (5)
Co1—Cl1i2.2422 (11)C7—C7ii1.529 (7)
N1—Co1—N1i107.33 (16)Cl1—Co1—Cl1i120.85 (6)
N1—Co1—Cl1111.20 (9)C7—N2—C6122.2 (4)
N1i—Co1—Cl1102.90 (9)O1—C7—N2125.8 (3)
N1—Co1—Cl1i102.90 (9)O1—C7—C7ii121.9 (4)
N1i—Co1—Cl1i111.20 (9)N2—C7—C7ii112.3 (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···AD—HH···AD···AD—H···A
O2—H2C···O10.852.343.06 (2)143
N2—H2A···Cl1iii0.882.663.435 (3)147
C2—H2B···O1iv0.952.463.403 (5)169
C6—H6B···Cl1v0.992.643.605 (4)163
Symmetry codes: (iii) x+1/2, y+1/2, z+3/2; (iv) x1/2, y, z+2; (v) x+1, y+3/2, z+3/2.
 

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