Poly[1,4-bis­(4-pyridylmeth­yl)piperazine­diium [[tetra­aqua­cobaltate(II)]-μ-pyromellitato-κ2O1:O4] dihydrate]

Sposato, L.K.; LaDuca, R.L.

doi:10.1107/S1600536809051101

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 12| December 2009| Page m1709

doi:10.1107/S1600536809051101

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Poly[1,4-bis(4-pyridylmethyl)piperazinediium [[tetraaquacobaltate(II)]-μ-pyromellitato-κ²O¹:O⁴] dihydrate]

Laura K. Sposato ^a and Robert L. LaDuca ^b ^*

^aDepartment of Chemistry and Physics, King's College, Wilkes-Barre, PA 18711, USA, and ^bLyman Briggs College, Department of Chemistry, Michigan State University, East Lansing, MI 48825, USA
^*Correspondence e-mail: laduca@msu.edu

(Received 22 November 2009; accepted 26 November 2009; online 28 November 2009)

In the title compound, {(C₁₆H₂₂N₄)[Co(C₁₀H₂O₈)(H₂O)₄]·2H₂O}_n, the octahedrally coordinated Co^II atom is situated on an inversion center and possesses four aqua ligands. The Co atoms are linked into an anionic coordination polymer chain by bis-monodentate pyromellitate ligands. The chain motifs are connected into a supramolecular layer by hydrogen bonding mediated by uncoordinated water molecules. Charge balance is provided by doubly protonated bis(4-pyridylmethyl)piperazine units, which are anchored to the coordination polymer chain motifs by N—H⋯O hydrogen bonding.

Related literature

For some divalent cobalt pyromellitate coordination polymers containing dipyridyl ligands, see: Majumder et al. (2006 ). For the preparation of bis(4-pyridylmethyl)piperazine, see: Pocic et al. (2005 ).

Experimental

Crystal data

(C₁₆H₂₂N₄)[Co(C₁₀H₂O₈)(H₂O)₄]·2H₂O
M_r = 687.52
Triclinic, $[P \overline 1]$
a = 7.278 (2) Å
b = 9.752 (3) Å
c = 11.257 (3) Å
α = 66.733 (3)°
β = 75.168 (3)°
γ = 83.359 (3)°
V = 709.5 (3) Å³
Z = 1
Mo Kα radiation
μ = 0.69 mm⁻¹
T = 173 K
0.24 × 0.14 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.853, T_max = 0.933
11370 measured reflections
2908 independent reflections
2511 reflections with I > 2σ(I)
R_int = 0.058

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.153
S = 1.05
2908 reflections
226 parameters
10 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.23 e Å⁻³
Δρ_min = −0.91 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1WA⋯O6ⁱ	0.88 (2)	2.38 (3)	2.997 (3)	128 (3)
O1W—H1WB⋯O1ⁱ	0.89 (2)	1.88 (2)	2.764 (3)	174 (3)
O5—H5A⋯N1	0.88 (2)	1.87 (2)	2.739 (3)	177 (3)
O5—H5B⋯O4	0.85 (2)	1.87 (2)	2.697 (3)	163 (3)
O6—H6C⋯O1W	0.86 (2)	1.92 (2)	2.753 (3)	165 (3)
O6—H6D⋯O2ⁱⁱ	0.86 (2)	1.81 (2)	2.624 (3)	158 (3)
N2—H2N⋯O3ⁱⁱⁱ	0.91 (2)	1.73 (2)	2.630 (3)	171 (3)
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+2, -y, -z+1; (iii) -x+1, -y-1, -z+2.

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Palmer, 2007 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809051101/hy2258sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809051101/hy2258Isup2.hkl

checkCIF report

Comment top

The diverse possible binding modes of the pyromellitate ligand (1,2,4,5-benzenetetracarboxylate) has allowed formation of a wide variety of cobalt-containing coordination polymers, especially in the presence of dipyridyl neutral co-ligands (Majumder et al., 2006). This chemistry was further developed by the synthesis of the title compound, which incorporates the long-spanning hydrogen-bonding capable dipyridyl ligand bis(4-pyridylmethyl)piperazine (bpmp).

The asymmetric unit of the title compound consists of a divalent Co^II atom on a crystallographic inversion center, one-half of a pyromellitate tetraanion situated across another crystallographic inversion center, one-half of a (H₂bpmp)²⁺ dication (protonated at each of the two piperazinyl N atoms) sited across another crystallographic inversion center, and one water molecule of crystallization. The local coordination and surrounding supramolecular environment is illustrated in Fig. 1.

Adjacent Co^II ions are linked into [Co(H₂O)₄(pyromellitate)]_n^2n- anionic one-dimensional coordination polymer motifs, via symmetrically related monodentate carboxylate termini of the pyromellitate ligands. These chain motifs are oriented parallel to the [1 1 0] direction; the Co···Co distance along the chain is 11.474 (3) Å. Two of the pyromellitate carboxylate groups do not ligate to Co^II ions. Neighboring chain motifs aggregate into supramolecular layers coincident with the ab planes (Fig. 2), established by hydrogen-bonding patterns between the co-crystallized water molecules, aqua ligands, and ligated pyromellitate carboxylate O atoms (Table 1). In turn, the supramolecular layers stack in an AAA pattern along the c axis, with charge-balancing (H₂bpmp)²⁺ dications situated in the interlamellar regions (Fig. 3), thus forming the three-dimensional crystal structure of the title compound. The closest Co···Co contact distance between neighboring layers is 11.257 (3) Å, which defines the c lattice parameter.

Related literature top

For some divalent cobalt pyromellitate coordination polymers containing dipyridyl ligands, see: Majumder et al. (2006). For the preparation of bis(4-pyridylmethyl)piperazine, see: Pocic et al. (2005).

Experimental top

All starting materials were obtained commercially, except for bpmp, which was prepared by a published procedure (Pocic et al., 2005). A mixture of cobalt nitrate hexahydrate (108 mg, 0.37 mmol), pyromellitic acid (94 mg, 0.37 mmol), bpmp (99 mg, 0.37 mmol) and 10.0 g water (550 mmol) was placed into a 23 ml Teflon-lined Parr Acid Digestion bomb, which was then heated under autogenous pressure at 393 K for 48 h. After cooling to 293 K, orange blocks of the title compound were obtained along with a white powder.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Palmer, 2007); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The coordination environment of the title compound, showing 50% probability ellipsoids. H atom positions are shown as grey sticks. [Color codes: dark blue Co; light blue N; red O; black C; orange O in uncoordinated water molecule. Symmetry code: (i) -x+2, -y, -z+1.]
	Fig. 2. A view of the supramolecular layer in the title compound. Hydrogen bonding contacts are indicated as dashed bars.
	Fig. 3. Stacking diagram for the title compound, viewed down the a axis. Hydrogen bonding contacts are indicated as dashed bars.

Poly[1,4-bis(4-pyridylmethyl)piperazinediium [[tetraaquacobaltate(II)]-µ-pyromellitato-κ²O¹:O⁴] dihydrate] top

Crystal data top

(C₁₆H₂₂N₄)[Co(C₁₀H₂O₈)(H₂O)₄]·2H₂O	Z = 1
M_r = 687.52	F(000) = 359
Triclinic, P1	D_x = 1.609 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.278 (2) Å	Cell parameters from 11370 reflections
b = 9.752 (3) Å	θ = 2.0–26.5°
c = 11.257 (3) Å	µ = 0.69 mm⁻¹
α = 66.733 (3)°	T = 173 K
β = 75.168 (3)°	Block, pink
γ = 83.359 (3)°	0.24 × 0.14 × 0.10 mm
V = 709.5 (3) Å³

Data collection top

Bruker APEXII CCD diffractometer	2908 independent reflections
Radiation source: fine-focus sealed tube	2511 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.058
ϕ and ω scans	θ_max = 26.5°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→9
T_min = 0.853, T_max = 0.933	k = −12→12
11370 measured reflections	l = −14→14

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.1134P)²] where P = (F_o² + 2F_c²)/3
2908 reflections	(Δ/σ)_max < 0.001
226 parameters	Δρ_max = 1.23 e Å⁻³
10 restraints	Δρ_min = −0.91 e Å⁻³

Crystal data top

(C₁₆H₂₂N₄)[Co(C₁₀H₂O₈)(H₂O)₄]·2H₂O	γ = 83.359 (3)°
M_r = 687.52	V = 709.5 (3) Å³
Triclinic, P1	Z = 1
a = 7.278 (2) Å	Mo Kα radiation
b = 9.752 (3) Å	µ = 0.69 mm⁻¹
c = 11.257 (3) Å	T = 173 K
α = 66.733 (3)°	0.24 × 0.14 × 0.10 mm
β = 75.168 (3)°

Data collection top

Bruker APEXII CCD diffractometer	2908 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2511 reflections with I > 2σ(I)
T_min = 0.853, T_max = 0.933	R_int = 0.058
11370 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	10 restraints
wR(F²) = 0.153	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 1.23 e Å⁻³
2908 reflections	Δρ_min = −0.91 e Å⁻³
226 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Co1	1.0000	0.0000	0.5000	0.0155 (2)
O1	0.8311 (2)	0.19744 (19)	0.45730 (18)	0.0192 (4)
O1W	0.4690 (3)	−0.1576 (2)	0.6340 (2)	0.0255 (4)
H1WA	0.437 (4)	−0.070 (3)	0.639 (3)	0.031*
H1WB	0.375 (4)	−0.178 (4)	0.607 (3)	0.031*
O2	0.9191 (3)	0.2866 (2)	0.58976 (19)	0.0235 (4)
O3	0.3143 (3)	0.2159 (2)	0.82962 (18)	0.0236 (4)
O4	0.5304 (3)	0.1042 (2)	0.7189 (2)	0.0332 (5)
O5	0.8431 (3)	−0.0690 (2)	0.69373 (18)	0.0183 (4)
H5A	0.829 (4)	−0.163 (2)	0.748 (3)	0.022*
H5B	0.742 (3)	−0.024 (3)	0.718 (3)	0.022*
O6	0.8063 (3)	−0.0969 (2)	0.44473 (18)	0.0193 (4)
H6C	0.705 (3)	−0.132 (3)	0.504 (3)	0.023*
H6D	0.876 (4)	−0.166 (3)	0.425 (3)	0.023*
N1	0.7991 (3)	−0.3648 (3)	0.8552 (2)	0.0284 (6)
N2	0.8089 (3)	−0.9425 (2)	1.0284 (2)	0.0170 (5)
H2N	0.755 (4)	−1.033 (2)	1.080 (3)	0.020*
C1	0.7611 (4)	−0.4408 (3)	0.9870 (3)	0.0258 (6)
H1	0.7635	−0.3891	1.0426	0.031*
C2	0.7185 (4)	−0.5911 (3)	1.0460 (3)	0.0224 (6)
H2	0.6933	−0.6409	1.1399	0.027*
C3	0.7131 (4)	−0.6683 (3)	0.9661 (3)	0.0187 (5)
C4	0.7549 (4)	−0.5898 (3)	0.8292 (3)	0.0242 (6)
H4	0.7544	−0.6384	0.7709	0.029*
C5	0.7970 (4)	−0.4404 (3)	0.7793 (3)	0.0275 (6)
H5	0.8261	−0.3883	0.6856	0.033*
C6	0.6512 (4)	−0.8286 (3)	1.0280 (3)	0.0204 (6)
H6A	0.5805	−0.8497	1.1210	0.024*
H6B	0.5619	−0.8407	0.9798	0.024*
C7	0.9515 (4)	−0.9366 (3)	1.1004 (3)	0.0192 (5)
H7A	0.8864	−0.9431	1.1912	0.023*
H7B	1.0192	−0.8407	1.0532	0.023*
C8	0.9075 (4)	−0.9347 (3)	0.8919 (3)	0.0196 (5)
H8A	0.9749	−0.8389	0.8415	0.024*
H8B	0.8124	−0.9387	0.8443	0.024*
C11	0.8099 (3)	0.2813 (3)	0.5227 (2)	0.0170 (5)
C12	0.6437 (3)	0.3901 (3)	0.5118 (2)	0.0161 (5)
C13	0.4741 (4)	0.3639 (3)	0.6092 (2)	0.0172 (5)
C14	0.6677 (4)	0.5255 (3)	0.4034 (3)	0.0178 (5)
H14	0.7827	0.5429	0.3367	0.021*
C15	0.4396 (3)	0.2173 (3)	0.7278 (3)	0.0176 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0153 (3)	0.0153 (3)	0.0161 (3)	0.00250 (18)	−0.0074 (2)	−0.0044 (2)
O1	0.0192 (9)	0.0174 (9)	0.0221 (9)	0.0051 (7)	−0.0094 (8)	−0.0073 (8)
O1W	0.0222 (10)	0.0262 (11)	0.0285 (10)	0.0026 (8)	−0.0124 (9)	−0.0074 (9)
O2	0.0238 (10)	0.0250 (10)	0.0270 (10)	0.0084 (8)	−0.0149 (8)	−0.0123 (8)
O3	0.0281 (10)	0.0165 (9)	0.0198 (10)	−0.0002 (8)	−0.0011 (8)	−0.0031 (8)
O4	0.0277 (11)	0.0174 (10)	0.0351 (12)	0.0074 (8)	0.0045 (9)	0.0008 (9)
O5	0.0186 (9)	0.0162 (9)	0.0184 (9)	0.0007 (7)	−0.0045 (8)	−0.0049 (7)
O6	0.0165 (9)	0.0201 (10)	0.0232 (10)	0.0033 (7)	−0.0082 (8)	−0.0090 (8)
N1	0.0265 (13)	0.0193 (12)	0.0329 (14)	0.0013 (9)	−0.0061 (11)	−0.0042 (10)
N2	0.0187 (11)	0.0141 (10)	0.0169 (10)	0.0003 (8)	−0.0062 (9)	−0.0033 (8)
C1	0.0251 (14)	0.0242 (14)	0.0303 (15)	0.0026 (11)	−0.0081 (12)	−0.0125 (12)
C2	0.0236 (14)	0.0207 (14)	0.0211 (13)	0.0019 (11)	−0.0074 (11)	−0.0052 (11)
C3	0.0156 (12)	0.0184 (13)	0.0207 (13)	0.0023 (9)	−0.0067 (10)	−0.0051 (10)
C4	0.0260 (14)	0.0226 (14)	0.0211 (13)	0.0030 (11)	−0.0072 (11)	−0.0049 (11)
C5	0.0297 (15)	0.0211 (14)	0.0216 (14)	0.0035 (11)	−0.0048 (12)	0.0004 (11)
C6	0.0181 (13)	0.0189 (13)	0.0212 (13)	0.0013 (10)	−0.0060 (11)	−0.0040 (10)
C7	0.0216 (13)	0.0195 (13)	0.0175 (12)	0.0017 (10)	−0.0089 (10)	−0.0060 (10)
C8	0.0204 (13)	0.0207 (13)	0.0176 (12)	0.0027 (10)	−0.0080 (10)	−0.0058 (10)
C11	0.0149 (12)	0.0135 (12)	0.0155 (12)	0.0013 (9)	−0.0016 (10)	0.0002 (9)
C12	0.0167 (12)	0.0132 (12)	0.0172 (12)	0.0022 (9)	−0.0070 (10)	−0.0034 (10)
C13	0.0178 (12)	0.0137 (12)	0.0177 (12)	0.0020 (9)	−0.0063 (10)	−0.0026 (10)
C14	0.0163 (12)	0.0160 (12)	0.0179 (12)	0.0013 (9)	−0.0052 (10)	−0.0027 (10)
C15	0.0142 (12)	0.0165 (12)	0.0196 (13)	0.0008 (9)	−0.0063 (10)	−0.0032 (10)

Geometric parameters (Å, º) top

Co1—O5	2.0631 (18)	C2—H2	0.9500
Co1—O1	2.1150 (17)	C3—C4	1.392 (4)
Co1—O6	2.1184 (18)	C3—C6	1.507 (4)
O1—C11	1.274 (3)	C4—C5	1.379 (4)
O1W—H1WA	0.881 (18)	C4—H4	0.9500
O1W—H1WB	0.885 (17)	C5—H5	0.9500
O2—C11	1.246 (3)	C6—H6A	0.9900
O3—C15	1.266 (3)	C6—H6B	0.9900
O4—C15	1.244 (3)	C7—C8ⁱ	1.517 (4)
O5—H5A	0.875 (17)	C7—H7A	0.9900
O5—H5B	0.852 (17)	C7—H7B	0.9900
O6—H6C	0.857 (17)	C8—C7ⁱ	1.517 (4)
O6—H6D	0.863 (17)	C8—H8A	0.9900
N1—C5	1.334 (4)	C8—H8B	0.9900
N1—C1	1.340 (4)	C11—C12	1.510 (3)
N2—C7	1.490 (3)	C12—C14	1.391 (3)
N2—C8	1.495 (3)	C12—C13	1.397 (3)
N2—C6	1.502 (3)	C13—C14ⁱⁱ	1.395 (3)
N2—H2N	0.906 (18)	C13—C15	1.514 (3)
C1—C2	1.384 (4)	C14—C13ⁱⁱ	1.394 (3)
C1—H1	0.9500	C14—H14	0.9500
C2—C3	1.393 (4)

O5—Co1—O5ⁱⁱⁱ	180.0	C5—C4—C3	119.0 (3)
O5—Co1—O1	88.13 (7)	C5—C4—H4	120.5
O5ⁱⁱⁱ—Co1—O1	91.87 (7)	C3—C4—H4	120.5
O5—Co1—O1ⁱⁱⁱ	91.87 (7)	N1—C5—C4	123.7 (3)
O5ⁱⁱⁱ—Co1—O1ⁱⁱⁱ	88.13 (7)	N1—C5—H5	118.2
O1—Co1—O1ⁱⁱⁱ	180.000 (1)	C4—C5—H5	118.2
O5—Co1—O6	91.72 (7)	N2—C6—C3	115.3 (2)
O5ⁱⁱⁱ—Co1—O6	88.28 (7)	N2—C6—H6A	108.4
O1—Co1—O6	88.61 (7)	C3—C6—H6A	108.4
O1ⁱⁱⁱ—Co1—O6	91.39 (7)	N2—C6—H6B	108.4
O5—Co1—O6ⁱⁱⁱ	88.28 (7)	C3—C6—H6B	108.4
O5ⁱⁱⁱ—Co1—O6ⁱⁱⁱ	91.72 (7)	H6A—C6—H6B	107.5
O1—Co1—O6ⁱⁱⁱ	91.39 (7)	N2—C7—C8ⁱ	109.5 (2)
O1ⁱⁱⁱ—Co1—O6ⁱⁱⁱ	88.61 (7)	N2—C7—H7A	109.8
O6—Co1—O6ⁱⁱⁱ	180.000 (1)	C8ⁱ—C7—H7A	109.8
C11—O1—Co1	122.61 (16)	N2—C7—H7B	109.8
H1WA—O1W—H1WB	104 (3)	C8ⁱ—C7—H7B	109.8
Co1—O5—H5A	123.9 (19)	H7A—C7—H7B	108.2
Co1—O5—H5B	123 (2)	N2—C8—C7ⁱ	110.4 (2)
H5A—O5—H5B	105 (2)	N2—C8—H8A	109.6
Co1—O6—H6C	116 (2)	C7ⁱ—C8—H8A	109.6
Co1—O6—H6D	102 (2)	N2—C8—H8B	109.6
H6C—O6—H6D	112 (3)	C7ⁱ—C8—H8B	109.6
C5—N1—C1	117.3 (2)	H8A—C8—H8B	108.1
C7—N2—C8	109.8 (2)	O2—C11—O1	125.8 (2)
C7—N2—C6	113.4 (2)	O2—C11—C12	117.0 (2)
C8—N2—C6	112.9 (2)	O1—C11—C12	117.1 (2)
C7—N2—H2N	102 (2)	C14—C12—C13	119.4 (2)
C8—N2—H2N	111.8 (19)	C14—C12—C11	117.6 (2)
C6—N2—H2N	106.2 (19)	C13—C12—C11	122.9 (2)
N1—C1—C2	123.1 (3)	C14ⁱⁱ—C13—C12	119.4 (2)
N1—C1—H1	118.5	C14ⁱⁱ—C13—C15	119.1 (2)
C2—C1—H1	118.5	C12—C13—C15	121.4 (2)
C1—C2—C3	119.2 (3)	C12—C14—C13ⁱⁱ	121.1 (2)
C1—C2—H2	120.4	C12—C14—H14	119.4
C3—C2—H2	120.4	C13ⁱⁱ—C14—H14	119.4
C4—C3—C2	117.7 (2)	O4—C15—O3	123.5 (2)
C4—C3—C6	121.9 (2)	O4—C15—C13	118.8 (2)
C2—C3—C6	120.3 (2)	O3—C15—C13	117.7 (2)

O5—Co1—O1—C11	54.13 (19)	C7—N2—C8—C7ⁱ	59.2 (3)
O5ⁱⁱⁱ—Co1—O1—C11	−125.86 (19)	C6—N2—C8—C7ⁱ	−173.3 (2)
O6—Co1—O1—C11	145.90 (19)	Co1—O1—C11—O2	21.7 (3)
O6ⁱⁱⁱ—Co1—O1—C11	−34.10 (19)	Co1—O1—C11—C12	−161.93 (16)
C5—N1—C1—C2	−0.8 (4)	O2—C11—C12—C14	93.1 (3)
N1—C1—C2—C3	−0.4 (4)	O1—C11—C12—C14	−83.6 (3)
C1—C2—C3—C4	1.2 (4)	O2—C11—C12—C13	−82.8 (3)
C1—C2—C3—C6	−174.9 (2)	O1—C11—C12—C13	100.5 (3)
C2—C3—C4—C5	−0.8 (4)	C14—C12—C13—C14ⁱⁱ	−0.5 (4)
C6—C3—C4—C5	175.2 (2)	C11—C12—C13—C14ⁱⁱ	175.3 (2)
C1—N1—C5—C4	1.2 (4)	C14—C12—C13—C15	178.9 (2)
C3—C4—C5—N1	−0.4 (4)	C11—C12—C13—C15	−5.3 (4)
C7—N2—C6—C3	59.1 (3)	C13—C12—C14—C13ⁱⁱ	0.5 (4)
C8—N2—C6—C3	−66.5 (3)	C11—C12—C14—C13ⁱⁱ	−175.6 (2)
C4—C3—C6—N2	81.0 (3)	C14ⁱⁱ—C13—C15—O4	156.2 (3)
C2—C3—C6—N2	−103.2 (3)	C12—C13—C15—O4	−23.2 (4)
C8—N2—C7—C8ⁱ	−58.7 (3)	C14ⁱⁱ—C13—C15—O3	−21.5 (4)
C6—N2—C7—C8ⁱ	174.0 (2)	C12—C13—C15—O3	159.2 (2)

Symmetry codes: (i) −x+2, −y−2, −z+2; (ii) −x+1, −y+1, −z+1; (iii) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O6^iv	0.88 (2)	2.38 (3)	2.997 (3)	128 (3)
O1W—H1WB···O1^iv	0.89 (2)	1.88 (2)	2.764 (3)	174 (3)
O5—H5A···N1	0.88 (2)	1.87 (2)	2.739 (3)	177 (3)
O5—H5B···O4	0.85 (2)	1.87 (2)	2.697 (3)	163 (3)
O6—H6C···O1W	0.86 (2)	1.92 (2)	2.753 (3)	165 (3)
O6—H6D···O2ⁱⁱⁱ	0.86 (2)	1.81 (2)	2.624 (3)	158 (3)
N2—H2N···O3^v	0.91 (2)	1.73 (2)	2.630 (3)	171 (3)

Symmetry codes: (iii) −x+2, −y, −z+1; (iv) −x+1, −y, −z+1; (v) −x+1, −y−1, −z+2.

Experimental details

Crystal data
Chemical formula	(C₁₆H₂₂N₄)[Co(C₁₀H₂O₈)(H₂O)₄]·2H₂O
M_r	687.52
Crystal system, space group	Triclinic, P1
Temperature (K)	173
a, b, c (Å)	7.278 (2), 9.752 (3), 11.257 (3)
α, β, γ (°)	66.733 (3), 75.168 (3), 83.359 (3)
V (Å³)	709.5 (3)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.69
Crystal size (mm)	0.24 × 0.14 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.853, 0.933
No. of measured, independent and observed [I > 2σ(I)] reflections	11370, 2908, 2511
R_int	0.058
(sin θ/λ)_max (Å⁻¹)	0.628

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.153, 1.05
No. of reflections	2908
No. of parameters	226
No. of restraints	10
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	1.23, −0.91

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), CrystalMaker (Palmer, 2007).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1WA···O6ⁱ	0.88 (2)	2.38 (3)	2.997 (3)	128 (3)
O1W—H1WB···O1ⁱ	0.89 (2)	1.88 (2)	2.764 (3)	174 (3)
O5—H5A···N1	0.88 (2)	1.87 (2)	2.739 (3)	177 (3)
O5—H5B···O4	0.85 (2)	1.87 (2)	2.697 (3)	163 (3)
O6—H6C···O1W	0.86 (2)	1.92 (2)	2.753 (3)	165 (3)
O6—H6D···O2ⁱⁱ	0.86 (2)	1.81 (2)	2.624 (3)	158 (3)
N2—H2N···O3ⁱⁱⁱ	0.91 (2)	1.73 (2)	2.630 (3)	171 (3)

Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, −y, −z+1; (iii) −x+1, −y−1, −z+2.

Acknowledgements

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

References

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