catena-Poly[[[diaqua­cobalt(II)]bis­(μ-1,3-di-4-pyridylpropane-κ2N:N′)] bis­(perchlorate) bis­(1,3-di-4-pyridyl­propane) bis­(2-methyl-4-nitro­aniline)]

Fu, Z.; Chen, Y.; Yi, J.

doi:10.1107/S1600536808026470

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 9| September 2008| Pages m1199-m1200

doi:10.1107/S1600536808026470

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catena-Poly[[[diaquacobalt(II)]bis(μ-1,3-di-4-pyridylpropane-κ²N:N′)] bis(perchlorate) bis(1,3-di-4-pyridylpropane) bis(2-methyl-4-nitroaniline)]

Zhiyong Fu,^a ^* Yuan Chen ^a and Jianglong Yi ^a

^aSchool of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, People's Republic of China
^*Correspondence e-mail: zyfu@scut.edu.cn

(Received 5 August 2008; accepted 17 August 2008; online 23 August 2008)

In the title compound, {[Co(C₁₃H₁₄N₂)₂(H₂O)₂](ClO₄)₂·2C₁₃H₁₄N₂·2C₇H₈N₂O₂}_n, the Co^II ion lies on a crystallographic inversion center and is coordinated by four N atoms from four symmetry-related 1,3-di-4-pyridylpropane ligands and two O atoms from two water ligands in a slightly distorted octahedral coordination environment. The 1,3-di-4-pyridylpropane ligands are doubly bridging and connect the Co^II ions into one-dimensional chains. The asymmetric unit also contains one uncoordinated 1,3-di-4-pyridylpropane molecule, one 2-methyl-4-nitroaniline molecule and one perchlorate anion. In the crystal structure, intermolecular O—H⋯N hydrogen bonds connect the one-dimensional chains into a two-dimensional network.

Related literature

For a related complex with a similar crystal structure, see: Merz et al. (2004 ). For related literature, see: James (2003 ).

Experimental

Crystal data

[Co(C₁₃H₁₄N₂)₂(H₂O)₂](ClO₄)₂·2C₁₃H₁₄N₂·2C₇H₈N₂O₂
M_r = 1391.22
Triclinic, $[P \overline 1]$
a = 10.9310 (3) Å
b = 11.6505 (5) Å
c = 15.2054 (4) Å
α = 71.0112 (7)°
β = 82.4011 (6)°
γ = 68.3933 (7)°
V = 1702.22 (10) Å³
Z = 1
Mo Kα radiation
μ = 0.40 mm⁻¹
T = 298 (2) K
0.30 × 0.22 × 0.1 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.892, T_max = 0.967
8612 measured reflections
5827 independent reflections
3438 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.066
wR(F²) = 0.168
S = 1.02
5827 reflections
438 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Co1—O1	2.090 (3)
Co1—N2ⁱ	2.179 (3)
Co1—N1	2.208 (3)

O1ⁱⁱ—Co1—O1	180
O1ⁱⁱ—Co1—N2ⁱ	92.94 (13)
O1—Co1—N2ⁱ	87.06 (13)
N2ⁱⁱⁱ—Co1—N2ⁱ	180
O1ⁱⁱ—Co1—N1	88.90 (12)
O1—Co1—N1	91.10 (12)
N2ⁱⁱⁱ—Co1—N1	87.20 (11)
N2ⁱⁱⁱ—Co1—N1ⁱⁱ	92.80 (11)
N1—Co1—N1ⁱⁱ	180
Symmetry codes: (i) x, y+1, z; (ii) -x, -y, -z; (iii) -x, -y-1, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯N3ⁱⁱⁱ	0.85 (6)	1.94 (3)	2.744 (5)	173 (4)
O1—H2⋯N4^iv	0.73 (4)	2.07 (2)	2.810 (3)	174 (3)
Symmetry codes: (iii) -x, -y-1, -z; (iv) -x-1, -y, -z.

Data collection: SMART (Bruker, 1996 ); cell refinement: SAINT (Bruker, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808026470/lh2679sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808026470/lh2679Isup2.hkl

checkCIF report

Comment top

Crystal engineering of metal organic frameworks has advanced dramatically over the past decade as a result of the number of interesting structural motifs (James, 2003). As part of our investigation of the use of 4,4,-trimethylenedipyridine as ligand in the construction of new coordination polymers, the title compound was obtained as a salt. The crystal structure of the title compound (I) comprises [Co(4,4,-trimethylenedipyridine)₂(H₂O)₂]_n polymeric chains, solvate 2-methyl-4-nitroaniline molecules, solvate 4,4,-trimethylenedipyridine molecules, and perchlorate anions. The asymmetric unit of (I) plus some symmetry related atoms are shown in Fig. 1. Each Co^II ion is in a slightly distorted octahedral environment. The equatorial plane consists of four nitrogen atoms from 4,4,-trimethylenedipyridine (Co—N 2.177 (4)–2.208 (4) Å) and the axial positions are occupied by two aqua molecules (Co—O 2.109 (3) Å). The Co^II ions, separated by approximately 11.65 Å, are bridged by 4,4,-trimethylenedipyridine ligands forming a polymeric chain. The structure possesses a distorted macrocycle enclosed by 4,4,-trimethylenedipyridine liaginds. The dimensions of the distorted square cavity are approximately 11.65*4.36 Å, measured from opposite phenyl ring to phenyl ring. The distorted macrocyclic structure includes low-symmetry guest molecules. The solvated 2-methyl-4-nitroaniline molecules solvated in the structure interact with the rest of the structure by normal van der Waals forces. There are two types of 4,4,-trimethylenedipyridine ligands located in the crystal structure. One is coordinated to the Co center while the other is a guest molecule. In the crystal structure, O—H···N hydrogen bonds exist between the water molecules and the guest 4,4,-trimethylenedipyridine molecules. Figure 2 shows the packing in (I) the extended two-dimensional network.

Related literature top

For a related complex with a similar crystal structure, see: Merz et al. (2004). For related literature, see: James (2003).

Experimental top

An aqueous mixture (10 ml) containing 4,4,-trimethylenedipyridine (0.1 g, 0.5 mmol), Co(ClO₄)₂(H₂O)₆ (0.365 g, 1 mmol), 2-methyl-4-nitroaniline (0.075 g, 0.5 mmol) was placed in a Parr Teflonlined stainless steel vessel(25 ml), and the vessel was sealed and heated to 388.15 K for 24 h. 0.090 g Orange sheet-like crystals were obtained.

Computing details top

Data collection: SMART (Bruker, 1996); cell refinement: SAINT (Bruker, 1996); data reduction: SAINT (Bruker, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of (I) with some symmetry related atoms. Displacement ellipsoids are drawn at the 50% probability level [Symmetry Codes: (a) -x, -1-y, -z, (b) x, -1+y, z, (c) -x, -y, -z].
	Fig. 2. The packing of (I), viewed approximately along the a axis, showing the O—H···N hydrogen bonds between the guest 4,4,-trimethylenedipyridine molecule and the coordinated water molecules.

catena-Poly[[[diaquacobalt(II)]bis(µ-1,3-di-4-pyridylpropane-κ²N:N')] bis(perchlorate) bis(1,3-di-4-pyridylpropane) bis(2-methyl-4-nitroaniline)] top

Crystal data top

[Co(C₁₃H₁₄N₂)₂(H₂O)₂](ClO₄)₂·2C₁₃H₁₄N₂·2C₇H₈N₂O₂	Z = 1
M_r = 1391.22	F(000) = 729
Triclinic, P1	D_x = 1.357 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 10.9310 (3) Å	Cell parameters from 5827 reflections
b = 11.6505 (5) Å	θ = 2.8–25.0°
c = 15.2054 (4) Å	µ = 0.40 mm⁻¹
α = 71.0112 (7)°	T = 298 K
β = 82.4011 (6)°	Block, orange
γ = 68.3933 (7)°	0.30 × 0.22 × 0.1 mm
V = 1702.22 (10) Å³

Data collection top

Bruker SMART CCD diffractometer	5827 independent reflections
Radiation source: fine-focus sealed tube	3438 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
ω scans	θ_max = 25.0°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→13
T_min = 0.892, T_max = 0.967	k = −13→13
8612 measured reflections	l = −18→18

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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.168	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0705P)²] where P = (F_o² + 2F_c²)/3
5827 reflections	(Δ/σ)_max < 0.001
438 parameters	Δρ_max = 0.53 e Å⁻³
0 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

[Co(C₁₃H₁₄N₂)₂(H₂O)₂](ClO₄)₂·2C₁₃H₁₄N₂·2C₇H₈N₂O₂	γ = 68.3933 (7)°
M_r = 1391.22	V = 1702.22 (10) Å³
Triclinic, P1	Z = 1
a = 10.9310 (3) Å	Mo Kα radiation
b = 11.6505 (5) Å	µ = 0.40 mm⁻¹
c = 15.2054 (4) Å	T = 298 K
α = 71.0112 (7)°	0.30 × 0.22 × 0.1 mm
β = 82.4011 (6)°

Data collection top

Bruker SMART CCD diffractometer	5827 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3438 reflections with I > 2σ(I)
T_min = 0.892, T_max = 0.967	R_int = 0.039
8612 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.066	0 restraints
wR(F²) = 0.168	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.53 e Å⁻³
5827 reflections	Δρ_min = −0.31 e Å⁻³
438 parameters

Special details top

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	0.0000	0.0000	0.0000	0.0368 (2)
O1	−0.0308 (3)	−0.0246 (3)	0.1425 (2)	0.0450 (8)
H2	−0.095 (4)	0.007 (4)	0.161 (3)	0.035 (14)*
H1	−0.009 (5)	−0.091 (6)	0.190 (4)	0.10 (2)*
O2	0.0102 (8)	−0.3950 (9)	−0.2105 (4)	0.185 (3)
O3	−0.1176 (7)	−0.1911 (10)	−0.2256 (7)	0.218 (5)
O4	0.6660 (4)	−0.3125 (5)	−0.7027 (3)	0.1267 (17)
O5	0.5089 (6)	−0.3630 (6)	−0.7540 (3)	0.146 (2)
O6	0.4479 (6)	−0.1872 (5)	−0.7051 (4)	0.160 (2)
O7	0.5165 (4)	−0.3851 (5)	−0.5995 (3)	0.1177 (16)
N1	−0.1793 (3)	−0.0409 (3)	−0.0082 (2)	0.0380 (8)
N2	−0.1087 (3)	−0.7946 (3)	−0.0213 (2)	0.0412 (8)
N3	−0.0498 (4)	−0.7448 (4)	−0.2812 (3)	0.0679 (11)
N4	−0.7219 (4)	−0.0999 (4)	−0.2125 (3)	0.0621 (10)
N5	0.3025 (6)	−0.1123 (7)	−0.5321 (4)	0.139 (2)
H5A	0.3638	−0.1666	−0.5550	0.167*
H5B	0.2891	−0.0309	−0.5548	0.167*
N6	−0.0249 (11)	−0.2734 (10)	−0.2435 (5)	0.156 (4)
C1	−0.2391 (4)	−0.0147 (3)	−0.0875 (3)	0.0422 (10)
H1A	−0.2139	0.0379	−0.1416	0.051*
C2	−0.3361 (4)	−0.0616 (4)	−0.0933 (3)	0.0464 (10)
H2A	−0.3749	−0.0399	−0.1501	0.056*
C3	−0.2207 (4)	−0.1150 (4)	0.0678 (3)	0.0499 (11)
H3A	−0.1830	−0.1329	0.1243	0.060*
C4	−0.3148 (4)	−0.1659 (4)	0.0676 (3)	0.0507 (11)
H4A	−0.3386	−0.2177	0.1229	0.061*
C5	−0.3749 (4)	−0.1408 (4)	−0.0143 (3)	0.0455 (11)
C6	−0.4719 (4)	−0.2046 (4)	−0.0158 (3)	0.0528 (11)
H6A	−0.5153	−0.1653	−0.0754	0.063*
H6B	−0.5386	−0.1897	0.0321	0.063*
C7	−0.4055 (4)	−0.3506 (4)	0.0001 (3)	0.0521 (11)
H7A	−0.3683	−0.3907	0.0619	0.062*
H7B	−0.4714	−0.3867	−0.0025	0.062*
C8	−0.2983 (4)	−0.3827 (4)	−0.0706 (3)	0.0528 (11)
H8A	−0.3356	−0.3428	−0.1323	0.063*
H8B	−0.2325	−0.3462	−0.0680	0.063*
C9	−0.2331 (4)	−0.5255 (4)	−0.0547 (3)	0.0426 (10)
C10	−0.1315 (4)	−0.5980 (4)	0.0076 (3)	0.0513 (11)
H10A	−0.1023	−0.5576	0.0398	0.062*
C11	−0.0732 (4)	−0.7292 (4)	0.0225 (3)	0.0488 (11)
H11A	−0.0055	−0.7749	0.0652	0.059*
C12	−0.2711 (4)	−0.5940 (4)	−0.0986 (3)	0.0484 (10)
H12A	−0.3400	−0.5508	−0.1405	0.058*
C13	−0.2081 (4)	−0.7249 (4)	−0.0807 (3)	0.0450 (10)
H13A	−0.2360	−0.7676	−0.1117	0.054*
C14	−0.1616 (6)	−0.7095 (5)	−0.3234 (4)	0.0786 (15)
H14A	−0.2033	−0.7700	−0.3105	0.094*
C15	−0.2205 (5)	−0.5909 (5)	−0.3846 (4)	0.0716 (14)
H15A	−0.2992	−0.5733	−0.4120	0.086*
C16	0.0060 (5)	−0.6559 (5)	−0.3035 (4)	0.0723 (14)
H16A	0.0856	−0.6768	−0.2760	0.087*
C17	−0.0468 (5)	−0.5330 (5)	−0.3655 (4)	0.0681 (14)
H17A	−0.0019	−0.4751	−0.3792	0.082*
C18	−0.1640 (4)	−0.4972 (4)	−0.4060 (3)	0.0536 (11)
C19	−0.2286 (5)	−0.3641 (5)	−0.4704 (3)	0.0738 (14)
H19A	−0.2426	−0.3711	−0.5298	0.089*
H19B	−0.1699	−0.3154	−0.4809	0.089*
C20	−0.3608 (6)	−0.2899 (5)	−0.4324 (4)	0.0908 (18)
H20A	−0.3999	−0.2071	−0.4786	0.109*
H20B	−0.4196	−0.3383	−0.4226	0.109*
C21	−0.3491 (5)	−0.2670 (5)	−0.3435 (4)	0.0829 (16)
H21A	−0.2998	−0.2092	−0.3551	0.099*
H21B	−0.3000	−0.3485	−0.2997	0.099*
C22	−0.4832 (5)	−0.2082 (5)	−0.2996 (3)	0.0655 (13)
C23	−0.5308 (5)	−0.0799 (5)	−0.3042 (3)	0.0755 (15)
H23A	−0.4834	−0.0265	−0.3359	0.091*
C24	−0.6487 (5)	−0.0307 (5)	−0.2618 (3)	0.0696 (14)
H24A	−0.6797	0.0573	−0.2677	0.084*
C25	−0.5612 (5)	−0.2796 (5)	−0.2533 (4)	0.0686 (14)
H25A	−0.5359	−0.3659	−0.2511	0.082*
C26	−0.6763 (5)	−0.2240 (5)	−0.2102 (3)	0.0642 (13)
H26A	−0.7251	−0.2757	−0.1776	0.077*
C27	0.1226 (7)	0.0718 (7)	−0.4533 (5)	0.120 (2)
H27A	0.0538	0.1196	−0.4192	0.180*
H27B	0.1029	0.1068	−0.5184	0.180*
H27C	0.2046	0.0781	−0.4435	0.180*
C28	0.1332 (6)	−0.0690 (6)	−0.4197 (4)	0.0822 (16)
C29	0.2250 (6)	−0.1562 (7)	−0.4586 (4)	0.0839 (17)
C30	0.2475 (6)	−0.2857 (7)	−0.4235 (5)	0.0873 (17)
H30A	0.3157	−0.3425	−0.4485	0.105*
C31	0.1723 (7)	−0.3344 (6)	−0.3523 (5)	0.0910 (18)
H31A	0.1872	−0.4226	−0.3277	0.109*
C32	0.0689 (6)	−0.2398 (8)	−0.3182 (4)	0.086 (2)
C33	0.0569 (6)	−0.1127 (7)	−0.3516 (4)	0.0845 (17)
H33A	−0.0073	−0.0540	−0.3257	0.101*
Cl1	0.53712 (14)	−0.31378 (14)	−0.69036 (9)	0.0756 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0321 (4)	0.0319 (4)	0.0486 (5)	−0.0089 (3)	0.0030 (4)	−0.0188 (4)
O1	0.0393 (19)	0.0465 (19)	0.0476 (19)	−0.0105 (15)	0.0078 (16)	−0.0203 (17)
O2	0.257 (8)	0.263 (9)	0.105 (4)	−0.181 (8)	0.027 (5)	−0.054 (5)
O3	0.150 (6)	0.336 (12)	0.284 (9)	−0.104 (6)	0.096 (6)	−0.257 (9)
O4	0.084 (3)	0.198 (5)	0.098 (3)	−0.081 (3)	0.011 (3)	−0.014 (3)
O5	0.168 (5)	0.224 (6)	0.110 (4)	−0.110 (5)	0.030 (3)	−0.097 (4)
O6	0.159 (5)	0.099 (4)	0.183 (5)	−0.025 (3)	0.006 (4)	−0.017 (4)
O7	0.121 (3)	0.154 (4)	0.077 (3)	−0.079 (3)	0.013 (3)	−0.001 (3)
N1	0.0388 (19)	0.0339 (18)	0.0442 (19)	−0.0108 (14)	0.0062 (16)	−0.0202 (15)
N2	0.0374 (19)	0.0380 (19)	0.0479 (19)	−0.0095 (15)	0.0041 (16)	−0.0185 (16)
N3	0.057 (3)	0.063 (3)	0.067 (3)	−0.008 (2)	0.009 (2)	−0.016 (2)
N4	0.041 (2)	0.073 (3)	0.068 (3)	−0.005 (2)	−0.001 (2)	−0.033 (2)
N5	0.126 (5)	0.208 (7)	0.109 (4)	−0.096 (5)	0.034 (4)	−0.051 (4)
N6	0.242 (10)	0.174 (8)	0.120 (6)	−0.154 (9)	−0.045 (7)	−0.020 (6)
C1	0.043 (2)	0.034 (2)	0.051 (3)	−0.0155 (18)	0.001 (2)	−0.0131 (19)
C2	0.043 (2)	0.034 (2)	0.065 (3)	−0.0071 (19)	−0.007 (2)	−0.023 (2)
C3	0.054 (3)	0.055 (3)	0.049 (3)	−0.026 (2)	0.002 (2)	−0.019 (2)
C4	0.049 (3)	0.059 (3)	0.057 (3)	−0.032 (2)	0.011 (2)	−0.024 (2)
C5	0.028 (2)	0.032 (2)	0.081 (3)	−0.0046 (17)	0.004 (2)	−0.030 (2)
C6	0.029 (2)	0.049 (3)	0.088 (3)	−0.0095 (19)	0.005 (2)	−0.037 (2)
C7	0.043 (2)	0.037 (2)	0.084 (3)	−0.0168 (19)	0.009 (2)	−0.029 (2)
C8	0.062 (3)	0.032 (2)	0.062 (3)	−0.013 (2)	0.011 (2)	−0.019 (2)
C9	0.039 (2)	0.033 (2)	0.053 (2)	−0.0119 (18)	0.012 (2)	−0.0160 (19)
C10	0.049 (3)	0.044 (3)	0.068 (3)	−0.014 (2)	0.003 (2)	−0.031 (2)
C11	0.046 (3)	0.041 (2)	0.060 (3)	−0.0072 (19)	−0.009 (2)	−0.023 (2)
C12	0.044 (2)	0.036 (2)	0.062 (3)	−0.0081 (19)	−0.004 (2)	−0.015 (2)
C13	0.043 (2)	0.041 (2)	0.058 (3)	−0.0158 (19)	0.004 (2)	−0.024 (2)
C14	0.074 (4)	0.072 (4)	0.095 (4)	−0.030 (3)	0.005 (3)	−0.028 (3)
C15	0.058 (3)	0.081 (4)	0.077 (4)	−0.015 (3)	−0.010 (3)	−0.030 (3)
C16	0.047 (3)	0.084 (4)	0.078 (4)	−0.018 (3)	−0.005 (3)	−0.017 (3)
C17	0.055 (3)	0.066 (3)	0.082 (4)	−0.025 (3)	0.004 (3)	−0.018 (3)
C18	0.044 (3)	0.058 (3)	0.050 (3)	−0.003 (2)	0.008 (2)	−0.025 (2)
C19	0.066 (3)	0.072 (3)	0.058 (3)	−0.002 (3)	0.011 (3)	−0.018 (3)
C20	0.090 (4)	0.081 (4)	0.061 (3)	0.015 (3)	−0.004 (3)	−0.019 (3)
C21	0.066 (4)	0.084 (4)	0.085 (4)	−0.003 (3)	−0.004 (3)	−0.033 (3)
C22	0.052 (3)	0.075 (4)	0.061 (3)	−0.006 (3)	0.005 (2)	−0.029 (3)
C23	0.074 (4)	0.073 (4)	0.069 (3)	−0.018 (3)	0.017 (3)	−0.024 (3)
C24	0.067 (3)	0.063 (3)	0.070 (3)	−0.005 (3)	0.009 (3)	−0.032 (3)
C25	0.057 (3)	0.060 (3)	0.083 (4)	−0.001 (3)	−0.007 (3)	−0.035 (3)
C26	0.051 (3)	0.075 (4)	0.065 (3)	−0.017 (3)	−0.005 (3)	−0.023 (3)
C27	0.131 (6)	0.113 (6)	0.127 (6)	−0.042 (5)	−0.030 (5)	−0.038 (5)
C28	0.073 (4)	0.100 (5)	0.078 (4)	−0.024 (4)	−0.012 (4)	−0.036 (4)
C29	0.073 (4)	0.120 (6)	0.078 (4)	−0.045 (4)	0.000 (3)	−0.041 (4)
C30	0.074 (4)	0.104 (5)	0.096 (5)	−0.027 (4)	0.004 (4)	−0.052 (4)
C31	0.099 (5)	0.094 (5)	0.101 (5)	−0.041 (4)	−0.019 (4)	−0.040 (4)
C32	0.089 (5)	0.156 (7)	0.051 (3)	−0.083 (5)	0.005 (3)	−0.034 (4)
C33	0.065 (4)	0.119 (5)	0.091 (4)	−0.032 (4)	0.003 (3)	−0.061 (4)
Cl1	0.0767 (10)	0.0836 (10)	0.0635 (8)	−0.0338 (8)	0.0127 (7)	−0.0164 (7)

Geometric parameters (Å, º) top

Co1—O1ⁱ	2.090 (3)	C9—C12	1.385 (5)
Co1—O1	2.090 (3)	C10—C11	1.374 (5)
Co1—N2ⁱⁱ	2.179 (3)	C10—H10A	0.9300
Co1—N2ⁱⁱⁱ	2.179 (3)	C11—H11A	0.9300
Co1—N1	2.208 (3)	C12—C13	1.371 (5)
Co1—N1ⁱ	2.208 (3)	C12—H12A	0.9300
O1—H2	0.73 (4)	C13—H13A	0.9300
O1—H1	0.85 (6)	C14—C15	1.362 (7)
O2—N6	1.263 (10)	C14—H14A	0.9300
O3—N6	1.183 (12)	C15—C18	1.375 (6)
O4—Cl1	1.402 (4)	C15—H15A	0.9300
O5—Cl1	1.390 (4)	C16—C17	1.389 (6)
O6—Cl1	1.400 (5)	C16—H16A	0.9300
O7—Cl1	1.400 (4)	C17—C18	1.358 (6)
N1—C3	1.336 (5)	C17—H17A	0.9300
N1—C1	1.340 (4)	C18—C19	1.500 (6)
N2—C11	1.337 (5)	C19—C20	1.534 (7)
N2—C13	1.338 (5)	C19—H19A	0.9700
N2—Co1^iv	2.179 (3)	C19—H19B	0.9700
N3—C14	1.319 (6)	C20—C21	1.490 (7)
N3—C16	1.320 (6)	C20—H20A	0.9700
N4—C24	1.333 (6)	C20—H20B	0.9700
N4—C26	1.334 (6)	C21—C22	1.537 (7)
N5—C29	1.387 (7)	C21—H21A	0.9700
N5—H5A	0.8600	C21—H21B	0.9700
N5—H5B	0.8600	C22—C23	1.371 (7)
N6—C32	1.481 (10)	C22—C25	1.377 (7)
C1—C2	1.383 (5)	C23—C24	1.372 (7)
C1—H1A	0.9300	C23—H23A	0.9300
C2—C5	1.382 (5)	C24—H24A	0.9300
C2—H2A	0.9300	C25—C26	1.375 (6)
C3—C4	1.365 (5)	C25—H25A	0.9300
C3—H3A	0.9300	C26—H26A	0.9300
C4—C5	1.381 (6)	C27—C28	1.516 (8)
C4—H4A	0.9300	C27—H27A	0.9600
C5—C6	1.508 (5)	C27—H27B	0.9600
C6—C7	1.531 (5)	C27—H27C	0.9600
C6—H6A	0.9700	C28—C33	1.329 (8)
C6—H6B	0.9700	C28—C29	1.368 (8)
C7—C8	1.508 (6)	C29—C30	1.363 (8)
C7—H7A	0.9700	C30—C31	1.370 (8)
C7—H7B	0.9700	C30—H30A	0.9300
C8—C9	1.498 (5)	C31—C32	1.436 (8)
C8—H8A	0.9700	C31—H31A	0.9300
C8—H8B	0.9700	C32—C33	1.361 (8)
C9—C10	1.383 (5)	C33—H33A	0.9300

O1ⁱ—Co1—O1	180	C12—C13—H13A	118.2
O1ⁱ—Co1—N2ⁱⁱ	87.06 (13)	N3—C14—C15	124.7 (5)
O1—Co1—N2ⁱⁱ	92.94 (13)	N3—C14—H14A	117.6
O1ⁱ—Co1—N2ⁱⁱⁱ	92.94 (13)	C15—C14—H14A	117.6
O1—Co1—N2ⁱⁱⁱ	87.06 (13)	C14—C15—C18	120.3 (5)
N2ⁱⁱ—Co1—N2ⁱⁱⁱ	180	C14—C15—H15A	119.8
O1ⁱ—Co1—N1	88.90 (12)	C18—C15—H15A	119.8
O1—Co1—N1	91.10 (12)	N3—C16—C17	124.1 (5)
N2ⁱⁱ—Co1—N1	87.20 (11)	N3—C16—H16A	118.0
N2ⁱⁱⁱ—Co1—N1	92.80 (11)	C17—C16—H16A	118.0
O1ⁱ—Co1—N1ⁱ	91.10 (12)	C18—C17—C16	120.0 (5)
O1—Co1—N1ⁱ	88.90 (12)	C18—C17—H17A	120.0
N2ⁱⁱ—Co1—N1ⁱ	92.80 (11)	C16—C17—H17A	120.0
N2ⁱⁱⁱ—Co1—N1ⁱ	87.20 (11)	C17—C18—C15	115.8 (4)
N1—Co1—N1ⁱ	180	C17—C18—C19	122.4 (5)
Co1—O1—H2	121 (3)	C15—C18—C19	121.7 (4)
Co1—O1—H1	132 (4)	C18—C19—C20	112.9 (4)
H2—O1—H1	95 (5)	C18—C19—H19A	109.0
C3—N1—C1	115.8 (3)	C20—C19—H19A	109.0
C3—N1—Co1	118.7 (3)	C18—C19—H19B	109.0
C1—N1—Co1	124.6 (3)	C20—C19—H19B	109.0
C11—N2—C13	116.0 (3)	H19A—C19—H19B	107.8
C11—N2—Co1^iv	120.4 (3)	C21—C20—C19	113.4 (4)
C13—N2—Co1^iv	123.6 (2)	C21—C20—H20A	108.9
C14—N3—C16	115.0 (4)	C19—C20—H20A	108.9
C24—N4—C26	115.2 (4)	C21—C20—H20B	108.9
C29—N5—H5A	120.0	C19—C20—H20B	108.9
C29—N5—H5B	120.0	H20A—C20—H20B	107.7
H5A—N5—H5B	120.0	C20—C21—C22	113.0 (4)
O3—N6—O2	130.4 (11)	C20—C21—H21A	109.0
O3—N6—C32	120.4 (10)	C22—C21—H21A	109.0
O2—N6—C32	109.2 (10)	C20—C21—H21B	109.0
N1—C1—C2	123.7 (4)	C22—C21—H21B	109.0
N1—C1—H1A	118.2	H21A—C21—H21B	107.8
C2—C1—H1A	118.2	C23—C22—C25	116.3 (5)
C5—C2—C1	119.6 (4)	C23—C22—C21	120.8 (5)
C5—C2—H2A	120.2	C25—C22—C21	122.9 (5)
C1—C2—H2A	120.2	C24—C23—C22	119.7 (5)
N1—C3—C4	124.0 (4)	C24—C23—H23A	120.1
N1—C3—H3A	118.0	C22—C23—H23A	120.1
C4—C3—H3A	118.0	N4—C24—C23	124.7 (5)
C3—C4—C5	120.2 (4)	N4—C24—H24A	117.7
C3—C4—H4A	119.9	C23—C24—H24A	117.7
C5—C4—H4A	119.9	C26—C25—C22	120.4 (5)
C4—C5—C2	116.7 (3)	C26—C25—H25A	119.8
C4—C5—C6	120.3 (4)	C22—C25—H25A	119.8
C2—C5—C6	123.0 (4)	N4—C26—C25	123.6 (5)
C5—C6—C7	112.2 (3)	N4—C26—H26A	118.2
C5—C6—H6A	109.2	C25—C26—H26A	118.2
C7—C6—H6A	109.2	C28—C27—H27A	109.5
C5—C6—H6B	109.2	C28—C27—H27B	109.5
C7—C6—H6B	109.2	H27A—C27—H27B	109.5
H6A—C6—H6B	107.9	C28—C27—H27C	109.5
C8—C7—C6	112.7 (3)	H27A—C27—H27C	109.5
C8—C7—H7A	109.1	H27B—C27—H27C	109.5
C6—C7—H7A	109.1	C33—C28—C29	117.9 (6)
C8—C7—H7B	109.1	C33—C28—C27	122.1 (7)
C6—C7—H7B	109.1	C29—C28—C27	120.0 (7)
H7A—C7—H7B	107.8	C30—C29—C28	121.7 (6)
C9—C8—C7	112.7 (3)	C30—C29—N5	119.2 (7)
C9—C8—H8A	109.1	C28—C29—N5	119.0 (7)
C7—C8—H8A	109.1	C29—C30—C31	121.8 (6)
C9—C8—H8B	109.1	C29—C30—H30A	119.1
C7—C8—H8B	109.1	C31—C30—H30A	119.1
H8A—C8—H8B	107.8	C30—C31—C32	115.3 (6)
C10—C9—C12	115.6 (3)	C30—C31—H31A	122.3
C10—C9—C8	121.1 (4)	C32—C31—H31A	122.3
C12—C9—C8	123.3 (4)	C33—C32—C31	120.2 (5)
C11—C10—C9	120.7 (4)	C33—C32—N6	116.6 (8)
C11—C10—H10A	119.7	C31—C32—N6	123.2 (8)
C9—C10—H10A	119.7	C28—C33—C32	122.8 (6)
N2—C11—C10	123.5 (4)	C28—C33—H33A	118.6
N2—C11—H11A	118.3	C32—C33—H33A	118.6
C10—C11—H11A	118.3	O5—Cl1—O6	107.3 (4)
C13—C12—C9	120.6 (4)	O5—Cl1—O7	110.2 (3)
C13—C12—H12A	119.7	O6—Cl1—O7	107.4 (3)
C9—C12—H12A	119.7	O5—Cl1—O4	111.1 (3)
N2—C13—C12	123.6 (4)	O6—Cl1—O4	109.6 (3)
N2—C13—H13A	118.2	O7—Cl1—O4	111.0 (3)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N3ⁱⁱ	0.85 (6)	1.94 (3)	2.744 (5)	173 (4)
O1—H2···N4^v	0.73 (4)	2.07 (2)	2.810 (3)	174 (3)

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

Experimental details

Crystal data
Chemical formula	[Co(C₁₃H₁₄N₂)₂(H₂O)₂](ClO₄)₂·2C₁₃H₁₄N₂·2C₇H₈N₂O₂
M_r	1391.22
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	10.9310 (3), 11.6505 (5), 15.2054 (4)
α, β, γ (°)	71.0112 (7), 82.4011 (6), 68.3933 (7)
V (Å³)	1702.22 (10)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.40
Crystal size (mm)	0.30 × 0.22 × 0.1

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.892, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	8612, 5827, 3438
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.066, 0.168, 1.02
No. of reflections	5827
No. of parameters	438
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.53, −0.31

Computer programs: SMART (Bruker, 1996), SAINT (Bruker, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Co1—O1	2.090 (3)	Co1—N1	2.208 (3)
Co1—N2ⁱ	2.179 (3)

O1ⁱⁱ—Co1—O1	180	O1—Co1—N1	91.10 (12)
O1ⁱⁱ—Co1—N2ⁱ	92.94 (13)	N2ⁱⁱⁱ—Co1—N1	87.20 (11)
O1—Co1—N2ⁱ	87.06 (13)	N2ⁱⁱⁱ—Co1—N1ⁱⁱ	92.80 (11)
N2ⁱⁱⁱ—Co1—N2ⁱ	180	N1—Co1—N1ⁱⁱ	180
O1ⁱⁱ—Co1—N1	88.90 (12)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N3ⁱⁱⁱ	0.85 (6)	1.94 (3)	2.744 (5)	173 (4)
O1—H2···N4^iv	0.73 (4)	2.07 (2)	2.810 (3)	174 (3)

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

Acknowledgements

The authors thank the NNSFC (No. 20701014) and the NSFFPC (No. 2003 F006) for financial support.

References

Bruker (1996). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
James, S. L. (2003). Chem. Soc. Rev. 32, 276–288. Web of Science CrossRef PubMed CAS Google Scholar
Merz, C., Desciak, M., O'Brien, C., LaDuca, R. L., Finn, R. C., Rarig, R. S. & Zubieta, J. A. (2004). Inorg. Chim. Acta. 357, 3331–3335. Web of Science CSD CrossRef CAS 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

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