catena-Poly[[[tetra­aqua­cobalt(II)]-μ-4,4′-bipyridine-κ2N:N′] bis­(perchlorate) 4,4′-bipyridine disolvate dihydrate]

Nettleman, J.H.; LaDuca, R.L.

doi:10.1107/S1600536808035125

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page m1485

doi:10.1107/S1600536808035125

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catena-Poly[[[tetraaquacobalt(II)]-μ-4,4′-bipyridine-κ²N:N′] bis(perchlorate) 4,4′-bipyridine disolvate dihydrate]

Joseph H. Nettleman ^a and Robert L. LaDuca ^a ^*

^aLyman Briggs College, Department of Chemistry, Michigan State University, East Lansing, MI 48825, USA
^*Correspondence e-mail: laduca@msu.edu

(Received 23 October 2008; accepted 28 October 2008; online 31 October 2008)

In the title compound, {[Co(C₁₀H₈N₂)(H₂O)₄](ClO₄)₂·2C₁₀H₈N₂·2H₂O}_n, slightly distorted octahedrally coordinated Co^II ions situated on inversion centers are linked into polycationic chains through 4,4′-bipyridine tethering ligands. These are connected into supramolecular layers by hydrogen bonding involving aqua ligands, perchlorate anions and uncoordinated water molecules. A twofold interpenetrated primitive cubic supramolecular network is formed by the interaction of pseudo-layers by hydrogen bonding between aqua ligands and unligated 4,4′-bipyridine molecules.

Related literature

For a review of coordination polymers containing 4,4′-bipyridine, see: Yaghi et al. (1998 ).

Experimental

Crystal data

[Co(C₁₀H₈N₂)(H₂O)₄](ClO₄)₂·2C₁₀H₈N₂·2H₂O
M_r = 834.48
Triclinic, $[P \overline 1]$
a = 8.9590 (17) Å
b = 10.846 (2) Å
c = 11.433 (2) Å
α = 64.290 (2)°
β = 71.747 (2)°
γ = 66.848 (2)°
V = 906.6 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.70 mm⁻¹
T = 173 (2) K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker SMART 1K diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.793, T_max = 0.845
10254 measured reflections
4087 independent reflections
3754 reflections with I > 2σ(I)
R_int = 0.018

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.085
S = 1.06
4087 reflections
259 parameters
9 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1A⋯O1W	0.856 (15)	1.886 (16)	2.7406 (19)	176 (2)
O1—H1B⋯N7ⁱ	0.852 (15)	1.943 (16)	2.7744 (18)	165 (2)
O1W—H1WA⋯O3ⁱⁱ	0.868 (16)	2.079 (17)	2.924 (2)	164 (2)
O1W—H1WB⋯O6	0.881 (16)	2.192 (16)	3.070 (3)	174 (2)
O2—H2A⋯N6ⁱⁱⁱ	0.883 (15)	1.826 (15)	2.7058 (19)	174.1 (19)
O2—H2B⋯O3^iv	0.849 (15)	2.212 (17)	2.957 (2)	146.5 (18)
Symmetry codes: (i) -x+1, -y+1, -z; (ii) -x, -y+1, -z+1; (iii) x+1, y, z; (iv) x+1, y-1, z.

Data collection: SMART (Bruker, 2003 ); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Crystal Maker (Palmer, 2007 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808035125/ng2505sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808035125/ng2505Isup2.hkl

checkCIF report

Comment top

The dipodal tethering ligand 4,4'-bipyridine has proven extremely advantageous for the construction of coordination polymer solids (Yaghi et al., 1998). In an attempt to prepare a divalent cobalt coordination polymer incorporating both 2-methylglutarate and 4,4'-bipyridine, yellow block crystals of the title compound were obtained.

The asymmetric unit of the title compound contains a cobalt atom on a crystallographic inversion center, two aqua ligands, one-half of a 4,4'-bipyridine ligand, one uncoordinated perchlorate anion, one unligated 4,4'-bipyridine molecule and one water molecule of crystallization (Figure 1).

Tethering 4,4'-bipyridine ligands connect the Co^II ions into one-dimensional cationic {[Co(H₂O)₄(C₁₀H₈N₂)]_n²ⁿ⁺ chain motifs that are oriented parallel to the c crystal direction. The Co···Co through-ligand contact distance is 11.433 (2) Å. These chains are connected into pseudolayer patterns by hydrogen-bonding mechanisms involving the aqua ligands, perchlorate anions, and water molecules of crystallization (Figure 2), which lie parallel to the (1 1 0) crystal planes. Unligated 4,4'-bipyridine molecules project axially into and out of the apertures in each pseudolayer.

In turn, the pseudolayers stack in an AB arrangement, and interact with their next nearest neighbors by hydrogen-bonding donation from aqua ligands to the uncoordinated 4,4'-bipyridine molecules to form the three-dimensional structure of the title compound (Figure 3). As a result a twofold interpenetrated primitive cubic supramolecular network can be invoked (Figure 4).

Related literature top

For a review of coordination polymers containing 4,4'-bipyridine, see: Yaghi et al. (1998).

Experimental top

All chemicals were obtained commercially. Cobalt perchlorate hexahydrate (135 mg, 0.37 mmol), 2-methylglutaric acid (59 mg, 0.37 mmol) and 4,4'-bipyridine (116 mg, 0.74 mmol) were placed into 10 ml H₂O in a 23 ml Teflon-lined Parr acid digestion bomb. The bomb was heated at 120° C for 48 h and was then allowed to cool to 25° C. Yellow-orange crystals of the title compound were obtained along with a reddish amorphous solid.

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT-Plus (Bruker, 2003); data reduction: SAINT-Plus (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: Crystal Maker (Palmer, 2007); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. Asymmetric unit of the title compound, showing 50% probability ellipsoids and atom numbering scheme. Hydrogen atom positions are shown as gray sticks. Color codes: dark blue Co, light blue N, red O, orange O within unligated water molecule, black C, green Cl.
	Fig. 2. A single supramolecular layer in the title compound, featuring one-dimensional [Co(H₂O)₄(4,4-bipyridine)]_n chains. Hydrogen bonding is indicated as dashed lines.
	Fig. 3. Packing diagram illustrating the ABAB layer stacking pattern, which forms the 3-D crystal structure of the title compound through hydrogen bonding between ligated water molecules and uncoordinated 4,4'-bipyridine molecules.
	Fig. 4. Schematic perspective of the twofold interpenetrated primitive cubic supramolecular network of the title compound.

catena-Poly[[[tetraaquacobalt(II)]-µ-4,4'-bipyridine-κ²N:N'] perchlorate 4,4'-bipyridine disolvate dihydrate] top

Crystal data top

[Co(C₁₀H₈N₂)(H₂O)₄](ClO₄)₂·2C₁₀H₈N₂·2H₂O	Z = 1
M_r = 834.48	F(000) = 431
Triclinic, P1	D_x = 1.528 Mg m⁻³
a = 8.9590 (17) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.846 (2) Å	Cell parameters from 10254 reflections
c = 11.433 (2) Å	θ = 2.0–28.2°
α = 64.290 (2)°	µ = 0.70 mm⁻¹
β = 71.747 (2)°	T = 173 K
γ = 66.848 (2)°	Block, yellow
V = 906.6 (3) Å³	0.35 × 0.30 × 0.25 mm

Data collection top

Bruker SMART 1K diffractometer	4087 independent reflections
Radiation source: fine-focus sealed tube	3754 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.018
ω scans	θ_max = 28.2°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.793, T_max = 0.845	k = −14→14
10254 measured reflections	l = −15→15

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ²(F_o²) + (0.0438P)² + 0.4101P] where P = (F_o² + 2F_c²)/3
4087 reflections	(Δ/σ)_max < 0.001
259 parameters	Δρ_max = 0.35 e Å⁻³
9 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

[Co(C₁₀H₈N₂)(H₂O)₄](ClO₄)₂·2C₁₀H₈N₂·2H₂O	γ = 66.848 (2)°
M_r = 834.48	V = 906.6 (3) Å³
Triclinic, P1	Z = 1
a = 8.9590 (17) Å	Mo Kα radiation
b = 10.846 (2) Å	µ = 0.70 mm⁻¹
c = 11.433 (2) Å	T = 173 K
α = 64.290 (2)°	0.35 × 0.30 × 0.25 mm
β = 71.747 (2)°

Data collection top

Bruker SMART 1K diffractometer	4087 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3754 reflections with I > 2σ(I)
T_min = 0.793, T_max = 0.845	R_int = 0.018
10254 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	9 restraints
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	Δρ_max = 0.35 e Å⁻³
4087 reflections	Δρ_min = −0.32 e Å⁻³
259 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	U_iso*/U_eq
Co1	0.5000	0.0000	0.5000	0.02019 (9)
Cl1	0.08313 (6)	0.68822 (5)	0.28417 (4)	0.03844 (12)
O1	0.49177 (16)	0.21628 (12)	0.41627 (11)	0.0331 (3)
H1A	0.432 (2)	0.272 (2)	0.4590 (19)	0.040*
H1B	0.527 (2)	0.269 (2)	0.3396 (16)	0.040*
O1W	0.31208 (19)	0.40133 (17)	0.54939 (15)	0.0471 (3)
H1WA	0.233 (3)	0.366 (2)	0.602 (2)	0.057*
H1WB	0.258 (3)	0.4859 (19)	0.499 (2)	0.057*
O2	0.75905 (14)	−0.06554 (13)	0.46036 (11)	0.0291 (2)
H2A	0.818 (2)	−0.0077 (19)	0.4057 (18)	0.035*
H2B	0.809 (2)	−0.1404 (17)	0.4406 (19)	0.035*
O3	−0.0888 (2)	0.76945 (18)	0.28167 (18)	0.0592 (4)
O4	0.1008 (2)	0.53921 (16)	0.32135 (15)	0.0576 (4)
O5	0.1756 (2)	0.73950 (19)	0.15629 (15)	0.0586 (4)
O6	0.1383 (3)	0.7065 (2)	0.37918 (17)	0.0661 (5)
N1	0.49875 (15)	−0.00436 (13)	0.31409 (11)	0.0222 (2)
N6	−0.05017 (19)	0.09941 (17)	0.28287 (17)	0.0413 (4)
N7	0.3813 (2)	0.59027 (15)	−0.19049 (14)	0.0368 (3)
C1	0.5839 (2)	0.06703 (17)	0.20323 (14)	0.0269 (3)
H1	0.6438	0.1163	0.2098	0.032*
C2	0.5878 (2)	0.07151 (17)	0.07951 (14)	0.0263 (3)
H2	0.6488	0.1230	0.0057	0.032*
C3	0.49982 (17)	−0.00143 (15)	0.06583 (13)	0.0195 (3)
C4	0.41216 (18)	−0.07678 (16)	0.18123 (14)	0.0240 (3)
H4	0.3528	−0.1284	0.1777	0.029*
C5	0.41367 (19)	−0.07458 (16)	0.30132 (14)	0.0246 (3)
H5	0.3527	−0.1242	0.3767	0.030*
C11	−0.0014 (3)	0.1789 (2)	0.3167 (2)	0.0486 (5)
H11	−0.0296	0.1723	0.4043	0.058*
C12	0.0890 (3)	0.2709 (2)	0.22857 (18)	0.0462 (5)
H12	0.1211	0.3231	0.2576	0.055*
C13	0.13149 (19)	0.28494 (16)	0.09666 (16)	0.0292 (3)
C14	0.0826 (2)	0.20049 (19)	0.06118 (19)	0.0358 (4)
H14	0.1089	0.2049	−0.0257	0.043*
C15	−0.0056 (2)	0.1098 (2)	0.1566 (2)	0.0413 (4)
H15	−0.0355	0.0530	0.1315	0.050*
C16	0.3327 (3)	0.5801 (2)	−0.06572 (18)	0.0414 (4)
H16	0.3518	0.6430	−0.0410	0.050*
C17	0.2551 (3)	0.4816 (2)	0.03043 (17)	0.0404 (4)
H17	0.2253	0.4787	0.1170	0.048*
C18	0.22204 (19)	0.38758 (16)	−0.00284 (15)	0.0279 (3)
C19	0.2767 (3)	0.3953 (2)	−0.13273 (19)	0.0515 (5)
H19	0.2608	0.3330	−0.1603	0.062*
C20	0.3555 (3)	0.4965 (2)	−0.22154 (19)	0.0544 (6)
H20	0.3924	0.4988	−0.3079	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.02731 (15)	0.02675 (15)	0.01189 (13)	−0.01560 (11)	−0.00041 (10)	−0.00699 (10)
Cl1	0.0476 (3)	0.0431 (2)	0.0316 (2)	−0.0248 (2)	0.00596 (17)	−0.01835 (18)
O1	0.0526 (7)	0.0292 (6)	0.0185 (5)	−0.0218 (5)	0.0047 (5)	−0.0082 (4)
O1W	0.0497 (8)	0.0490 (8)	0.0415 (8)	−0.0157 (7)	0.0008 (6)	−0.0204 (6)
O2	0.0291 (6)	0.0366 (6)	0.0254 (5)	−0.0162 (5)	0.0013 (4)	−0.0126 (5)
O3	0.0490 (9)	0.0616 (10)	0.0690 (11)	−0.0162 (7)	−0.0001 (8)	−0.0324 (8)
O4	0.0855 (12)	0.0422 (8)	0.0454 (8)	−0.0285 (8)	0.0030 (8)	−0.0176 (6)
O5	0.0724 (10)	0.0718 (10)	0.0419 (8)	−0.0498 (9)	0.0185 (7)	−0.0240 (7)
O6	0.0940 (13)	0.0762 (11)	0.0512 (10)	−0.0387 (10)	−0.0143 (9)	−0.0300 (9)
N1	0.0272 (6)	0.0290 (6)	0.0148 (5)	−0.0139 (5)	−0.0012 (4)	−0.0084 (5)
N6	0.0317 (7)	0.0383 (8)	0.0466 (9)	−0.0179 (6)	−0.0048 (6)	−0.0035 (7)
N7	0.0455 (8)	0.0305 (7)	0.0288 (7)	−0.0171 (6)	0.0015 (6)	−0.0062 (6)
C1	0.0365 (8)	0.0369 (8)	0.0179 (7)	−0.0237 (7)	−0.0007 (6)	−0.0104 (6)
C2	0.0355 (8)	0.0357 (8)	0.0150 (6)	−0.0230 (7)	0.0013 (5)	−0.0083 (6)
C3	0.0222 (6)	0.0232 (6)	0.0149 (6)	−0.0080 (5)	−0.0027 (5)	−0.0077 (5)
C4	0.0295 (7)	0.0316 (7)	0.0175 (7)	−0.0175 (6)	−0.0021 (5)	−0.0086 (5)
C5	0.0311 (7)	0.0325 (7)	0.0152 (6)	−0.0188 (6)	−0.0002 (5)	−0.0073 (5)
C11	0.0590 (12)	0.0563 (12)	0.0314 (9)	−0.0358 (10)	−0.0022 (8)	−0.0037 (8)
C12	0.0651 (13)	0.0516 (11)	0.0308 (9)	−0.0385 (10)	−0.0033 (8)	−0.0073 (8)
C13	0.0276 (7)	0.0241 (7)	0.0303 (8)	−0.0082 (6)	−0.0051 (6)	−0.0044 (6)
C14	0.0310 (8)	0.0381 (9)	0.0398 (9)	−0.0132 (7)	−0.0030 (7)	−0.0147 (7)
C15	0.0327 (9)	0.0415 (10)	0.0537 (11)	−0.0185 (8)	−0.0027 (8)	−0.0170 (8)
C16	0.0592 (12)	0.0392 (9)	0.0326 (9)	−0.0292 (9)	0.0017 (8)	−0.0125 (7)
C17	0.0576 (11)	0.0425 (10)	0.0258 (8)	−0.0297 (9)	0.0053 (7)	−0.0119 (7)
C18	0.0285 (7)	0.0231 (7)	0.0271 (8)	−0.0075 (6)	−0.0041 (6)	−0.0053 (6)
C19	0.0893 (16)	0.0470 (11)	0.0311 (9)	−0.0427 (11)	0.0009 (10)	−0.0131 (8)
C20	0.0916 (17)	0.0531 (12)	0.0263 (9)	−0.0436 (12)	0.0055 (10)	−0.0123 (8)

Geometric parameters (Å, º) top

Co1—O1ⁱ	2.0938 (12)	C2—C3	1.3950 (19)
Co1—O1	2.0938 (12)	C2—H2	0.9300
Co1—O2ⁱ	2.1024 (12)	C3—C4	1.3948 (19)
Co1—O2	2.1024 (12)	C3—C3ⁱⁱ	1.491 (3)
Co1—N1	2.1500 (12)	C4—C5	1.3878 (19)
Co1—N1ⁱ	2.1500 (12)	C4—H4	0.9300
Cl1—O5	1.4251 (15)	C5—H5	0.9300
Cl1—O4	1.4361 (15)	C11—C12	1.385 (3)
Cl1—O6	1.4365 (16)	C11—H11	0.9300
Cl1—O3	1.4450 (17)	C12—C13	1.389 (3)
O1—H1A	0.856 (15)	C12—H12	0.9300
O1—H1B	0.852 (15)	C13—C14	1.395 (2)
O1W—H1WA	0.868 (16)	C13—C18	1.492 (2)
O1W—H1WB	0.881 (16)	C14—C15	1.387 (3)
O2—H2A	0.883 (15)	C14—H14	0.9300
O2—H2B	0.849 (15)	C15—H15	0.9300
N1—C1	1.3399 (18)	C16—C17	1.385 (2)
N1—C5	1.3435 (18)	C16—H16	0.9300
N6—C11	1.333 (3)	C17—C18	1.384 (2)
N6—C15	1.337 (3)	C17—H17	0.9300
N7—C16	1.322 (2)	C18—C19	1.386 (3)
N7—C20	1.328 (3)	C19—C20	1.388 (3)
C1—C2	1.384 (2)	C19—H19	0.9300
C1—H1	0.9300	C20—H20	0.9300

O1ⁱ—Co1—O1	180.000 (1)	C4—C3—C2	116.62 (12)
O1ⁱ—Co1—O2ⁱ	91.24 (5)	C4—C3—C3ⁱⁱ	121.98 (15)
O1—Co1—O2ⁱ	88.76 (5)	C2—C3—C3ⁱⁱ	121.39 (15)
O1ⁱ—Co1—O2	88.76 (5)	C5—C4—C3	119.88 (13)
O1—Co1—O2	91.24 (5)	C5—C4—H4	120.1
O2ⁱ—Co1—O2	180.0	C3—C4—H4	120.1
O1ⁱ—Co1—N1	87.77 (5)	N1—C5—C4	123.30 (13)
O1—Co1—N1	92.23 (5)	N1—C5—H5	118.3
O2ⁱ—Co1—N1	90.66 (4)	C4—C5—H5	118.3
O2—Co1—N1	89.34 (4)	N6—C11—C12	123.61 (19)
O1ⁱ—Co1—N1ⁱ	92.23 (5)	N6—C11—H11	118.2
O1—Co1—N1ⁱ	87.77 (5)	C12—C11—H11	118.2
O2ⁱ—Co1—N1ⁱ	89.34 (4)	C11—C12—C13	119.77 (18)
O2—Co1—N1ⁱ	90.66 (4)	C11—C12—H12	120.1
N1—Co1—N1ⁱ	180.0	C13—C12—H12	120.1
O5—Cl1—O4	110.45 (9)	C12—C13—C14	116.80 (16)
O5—Cl1—O6	110.12 (11)	C12—C13—C18	121.64 (16)
O4—Cl1—O6	109.46 (11)	C14—C13—C18	121.55 (15)
O5—Cl1—O3	108.74 (11)	C15—C14—C13	119.38 (17)
O4—Cl1—O3	108.86 (11)	C15—C14—H14	120.3
O6—Cl1—O3	109.19 (11)	C13—C14—H14	120.3
Co1—O1—H1A	119.4 (14)	N6—C15—C14	123.67 (18)
Co1—O1—H1B	133.1 (14)	N6—C15—H15	118.2
H1A—O1—H1B	106.9 (18)	C14—C15—H15	118.2
H1WA—O1W—H1WB	102 (2)	N7—C16—C17	124.13 (17)
Co1—O2—H2A	123.8 (13)	N7—C16—H16	117.9
Co1—O2—H2B	118.8 (13)	C17—C16—H16	117.9
H2A—O2—H2B	101.8 (18)	C18—C17—C16	119.71 (16)
C1—N1—C5	116.71 (12)	C18—C17—H17	120.1
C1—N1—Co1	119.99 (9)	C16—C17—H17	120.1
C5—N1—Co1	123.29 (9)	C17—C18—C19	116.31 (15)
C11—N6—C15	116.74 (16)	C17—C18—C13	121.17 (15)
C16—N7—C20	116.24 (15)	C19—C18—C13	122.51 (16)
N1—C1—C2	123.68 (13)	C18—C19—C20	119.67 (18)
N1—C1—H1	118.2	C18—C19—H19	120.2
C2—C1—H1	118.2	C20—C19—H19	120.2
C1—C2—C3	119.79 (13)	N7—C20—C19	123.85 (18)
C1—C2—H2	120.1	N7—C20—H20	118.1
C3—C2—H2	120.1	C19—C20—H20	118.1

O1ⁱ—Co1—N1—C1	−141.42 (12)	N6—C11—C12—C13	0.8 (4)
O1—Co1—N1—C1	38.58 (12)	C11—C12—C13—C14	−1.6 (3)
O2ⁱ—Co1—N1—C1	127.37 (12)	C11—C12—C13—C18	177.17 (18)
O2—Co1—N1—C1	−52.63 (12)	C12—C13—C14—C15	0.7 (3)
O1ⁱ—Co1—N1—C5	39.55 (12)	C18—C13—C14—C15	−178.08 (16)
O1—Co1—N1—C5	−140.45 (12)	C11—N6—C15—C14	−1.9 (3)
O2ⁱ—Co1—N1—C5	−51.66 (12)	C13—C14—C15—N6	1.1 (3)
O2—Co1—N1—C5	128.34 (12)	C20—N7—C16—C17	−1.5 (3)
C5—N1—C1—C2	0.1 (2)	N7—C16—C17—C18	−1.0 (3)
Co1—N1—C1—C2	−179.04 (13)	C16—C17—C18—C19	2.6 (3)
N1—C1—C2—C3	−0.2 (3)	C16—C17—C18—C13	−177.01 (17)
C1—C2—C3—C4	−0.4 (2)	C12—C13—C18—C17	−5.5 (3)
C1—C2—C3—C3ⁱⁱ	179.68 (16)	C14—C13—C18—C17	173.20 (17)
C2—C3—C4—C5	1.0 (2)	C12—C13—C18—C19	174.9 (2)
C3ⁱⁱ—C3—C4—C5	−179.08 (16)	C14—C13—C18—C19	−6.4 (3)
C1—N1—C5—C4	0.6 (2)	C17—C18—C19—C20	−1.8 (3)
Co1—N1—C5—C4	179.65 (11)	C13—C18—C19—C20	177.9 (2)
C3—C4—C5—N1	−1.1 (2)	C16—N7—C20—C19	2.5 (4)
C15—N6—C11—C12	0.9 (3)	C18—C19—C20—N7	−0.8 (4)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O1W	0.86 (2)	1.89 (2)	2.7406 (19)	176 (2)
O1—H1B···N7ⁱⁱⁱ	0.85 (2)	1.94 (2)	2.7744 (18)	165 (2)
O1W—H1WA···O3^iv	0.87 (2)	2.08 (2)	2.924 (2)	164 (2)
O1W—H1WB···O6	0.88 (2)	2.19 (2)	3.070 (3)	174 (2)
O2—H2A···N6^v	0.88 (2)	1.83 (2)	2.7058 (19)	174 (2)
O2—H2B···O3^vi	0.85 (2)	2.21 (2)	2.957 (2)	147 (2)

Symmetry codes: (iii) −x+1, −y+1, −z; (iv) −x, −y+1, −z+1; (v) x+1, y, z; (vi) x+1, y−1, z.

Experimental details

Crystal data
Chemical formula	[Co(C₁₀H₈N₂)(H₂O)₄](ClO₄)₂·2C₁₀H₈N₂·2H₂O
M_r	834.48
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	8.9590 (17), 10.846 (2), 11.433 (2)
α, β, γ (°)	64.290 (2), 71.747 (2), 66.848 (2)
V (Å³)	906.6 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.70
Crystal size (mm)	0.35 × 0.30 × 0.25

Data collection
Diffractometer	Bruker SMART 1K diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.793, 0.845
No. of measured, independent and observed [I > 2σ(I)] reflections	10254, 4087, 3754
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.666

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.085, 1.06
No. of reflections	4087
No. of parameters	259
No. of restraints	9
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.32

Computer programs: SMART (Bruker, 2003), SAINT-Plus (Bruker, 2003), SAINT-Plus (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), Crystal Maker (Palmer, 2007).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1A···O1W	0.856 (15)	1.886 (16)	2.7406 (19)	176 (2)
O1—H1B···N7ⁱ	0.852 (15)	1.943 (16)	2.7744 (18)	165 (2)
O1W—H1WA···O3ⁱⁱ	0.868 (16)	2.079 (17)	2.924 (2)	164 (2)
O1W—H1WB···O6	0.881 (16)	2.192 (16)	3.070 (3)	174 (2)
O2—H2A···N6ⁱⁱⁱ	0.883 (15)	1.826 (15)	2.7058 (19)	174.1 (19)
O2—H2B···O3^iv	0.849 (15)	2.212 (17)	2.957 (2)	146.5 (18)

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

Acknowledgements

We gratefully acknowledge the donors of the American Chemical Society Petroleum Research Fund and Michigan State University for funding this work.

References

Bruker (2003). SMART and SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Palmer, D. (2007). Crystal Maker. Bicester, England. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yaghi, O. M., Li, H., Davis, C., Richardson, D. & Groy, T. L. (1998). Acc. Chem. Res. 31, 474–484. Web of Science CrossRef CAS Google Scholar

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