Bis[4-amino-3,5-bis­(pyridin-2-yl)-4H-1,2,4-triazole-κ2N1,N5]diaqua­cobalt(II) bis­(perchlorate)

Feng, M.; Ji, Y.-F.; Liang, S.-L.; Liu, Z.-L.

doi:10.1107/S1600536812038573

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 10| October 2012| Pages m1272-m1273

https://doi.org/10.1107/S1600536812038573

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Bis[4-amino-3,5-bis(pyridin-2-yl)-4H-1,2,4-triazole-κ²N¹,N⁵]diaquacobalt(II) bis(perchlorate)

Mi Feng,^a Yu-Fei Ji,^a Sheng-Li Liang ^a and Zhi-Liang Liu ^a ^*

^aCollege of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot, People's Republic of China
^*Correspondence e-mail: cezlliu@imu.edu.cn

(Received 23 July 2012; accepted 8 September 2012; online 15 September 2012)

In the title structure, [Co(C₁₂H₁₀N₆)₂(H₂O)₂](ClO₄)₂, the Co^II atom lies on an inversion centre and is coordinated in a slightly distorted octahedral geometry by four N atoms from two 4-amino-3,5-bis(pyridin-2-yl)-4H-1,2,4-triazole (adpt) ligands in equatorial positions and two O atoms from two water molecules in axial positions. An intramolecular N—H⋯N interaction stabilizes the molecular conformation. Intermolecular N—H⋯O and O—H⋯O interactions involving the perchlorate counter-anions extend the monomeric compound into a two-dimensional network parallel to the bc plane.

Related literature

For the synthesis of the adpt ligand, see: Geldard & Lions (1965 ). For background to the coordination chemistry of the adpt ligand, see: Meng et al. (2009 ). For intramolecular hydrogen bonds in the adpt ligand, see: Kitchen et al. (2008 ). For other Co(II) coordination compounds with the same ligand, see: Keij et al. (1984 ); Peng et al. (2006 ); García-Couceiro et al. (2009 ); White et al. (2010 ).

Experimental

Crystal data

[Co(C₁₂H₁₀N₆)₂(H₂O)₂](ClO₄)₂
M_r = 770.38
Monoclinic, P 2₁ /c
a = 8.5839 (17) Å
b = 12.950 (3) Å
c = 14.975 (5) Å
β = 114.34 (2)°
V = 1516.7 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.82 mm⁻¹
T = 293 K
0.04 × 0.03 × 0.01 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.971, T_max = 0.992
10155 measured reflections
2681 independent reflections
2336 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.121
S = 1.07
2681 reflections
223 parameters
H-atom parameters constrained
Δρ_max = 0.87 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N6—H6B⋯N5	0.89	2.29	2.897 (4)	125
N6—H6B⋯O3ⁱ	0.89	2.39	2.989 (4)	124
O1—H1A⋯O4	0.85	2.16	2.782 (4)	130
O1—H1B⋯O2ⁱⁱ	0.85	2.22	2.983 (4)	150
O1—H1B⋯O5ⁱⁱ	0.85	2.58	3.284 (5)	141
Symmetry codes: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812038573/wm2664sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812038573/wm2664Isup2.hkl

checkCIF report

Comment top

Recently, 4-amine-3,5-di-2-pyridyl-1,2,4-triazol (adpt) has been used as a potential multidentate ligand to generate novel metal-organic complexes due to containing five N coordination sites and three potentially conjugated aromatic rings (Meng et al., 2009). Such complexes with adpt have interesting properties for potential applications in the fields of magnetic materials (Keij et al., 1984). Several Co(II) compounds containing adpt have been reported previously (Keij et al., 1984; Peng et al., 2006; García-Couceiro et al., 2009; White et al., 2010). Herein, the synthesis and crystal structure of the title complex [Co(C₁₂H₁₀N₆)₂(H₂O)₂](ClO₄)₂, (I), is reported.

As shown in Figure 1, compound (I) consists of one Co(II) atom located on an inversion centre, two adpt ligands, two water molecules and two isolated perchlorate counter anions. The Co(II) is six-coordinated by four N atoms from two adpt ligands and two O atoms from two water molecules, giving a slightly distorted octahedral coordination environment. The equatorial plane is defined by four N atoms from two adpt ligands with a chelate formation, and the axial positions are occupied by two O atoms of water molecules. The dihedral angle between the non-coordinated pyridine ring and the coordinating pyridine ring is 11.94 (16) ° and that between the coordinating pyridine ring and the triazole ring is 6.76 (6)°. In the mononuclear unit, an intramolecular N—H···N hydrogen-bonding interaction between the NH₂ group attached to the the triazole ring and the non-coordinating N atom of pyridine is observed (Kitchen et al., 2008). Intermolecular N—H···O and O—H···O hydrogen-bonding interactions exist between the amine group and the coordinating water molecules, respectively, with the O atoms of the isolated perchlorate counter anions. In the crystal, the molecular entities are linked by O—H···O hydrogen bonds generating chains along the b axis. These chains in turn aggregate into a two-dimensional network parallel to the bc plane (Fig. 2).

Related literature top

For the synthesis of the adpt ligand, see: Geldard & Lions (1965). For background to the coordination chemistry of the adpt ligand, see: Meng et al. (2009). For intramolecular hydrogen bonds in the adpt ligand, see: Kitchen et al. (2008). For other Co(II) coordination compounds with the same ligand, see: Keij et al. (1984); Peng et al. (2006); García-Couceiro et al. (2009); White et al. (2010).

Experimental top

4-Amino-3,5-bis(pyridin-2-yl)-4H-1,2,4-triazole (abpt, 5mmol) was dissolved in 20 ml mixture solution of water and methanol (1:1, v/v). Then Co(ClO₄)_2`4H₂O (5 mmol) was added to the above solution. The resulting solution was stirred for 3 h at room temperature. Upon slow evaporation of the solvent, dark red block-shaped crystals formed from the filtrate in a few days. The used 4-amine-3,5-di-2-pyridyl-1,2,4-triazol (adpt) was synthesized according to the previously reported procedure (Geldard & Lions, 1965).

Structure description top

For the synthesis of the adpt ligand, see: Geldard & Lions (1965). For background to the coordination chemistry of the adpt ligand, see: Meng et al. (2009). For intramolecular hydrogen bonds in the adpt ligand, see: Kitchen et al. (2008). For other Co(II) coordination compounds with the same ligand, see: Keij et al. (1984); Peng et al. (2006); García-Couceiro et al. (2009); White et al. (2010).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of the title compound, with atom labels and 30% probability displacement ellipsoids for non-H atoms. N—H···N and O—H···O interactions are shown as dashed lines.
	Fig. 2. The crystal packing of the title compound. O—H···O interactions are shown as dashed lines.

Bis[4-amino-3,5-bis(pyridin-2-yl)-4H-1,2,4-triazole- κ²N¹,N⁵]diaquacobalt(II) bis(perchlorate) top

Crystal data top

[Co(C₁₂H₁₀N₆)₂(H₂O)₂](ClO₄)₂	F(000) = 786
M_r = 770.38	D_x = 1.687 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3601 reflections
a = 8.5839 (17) Å	θ = 2.2–27.9°
b = 12.950 (3) Å	µ = 0.82 mm⁻¹
c = 14.975 (5) Å	T = 293 K
β = 114.34 (2)°	Block, dark red
V = 1516.7 (7) Å³	0.04 × 0.03 × 0.01 mm
Z = 2

Data collection top

Bruker SMART APEX CCD diffractometer	2681 independent reflections
Radiation source: fine-focus sealed tube	2336 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.038
ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→10
T_min = 0.971, T_max = 0.992	k = −15→15
10155 measured reflections	l = −17→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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.121	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0587P)² + 2.3812P] where P = (F_o² + 2F_c²)/3
2681 reflections	(Δ/σ)_max < 0.001
223 parameters	Δρ_max = 0.87 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

[Co(C₁₂H₁₀N₆)₂(H₂O)₂](ClO₄)₂	V = 1516.7 (7) Å³
M_r = 770.38	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.5839 (17) Å	µ = 0.82 mm⁻¹
b = 12.950 (3) Å	T = 293 K
c = 14.975 (5) Å	0.04 × 0.03 × 0.01 mm
β = 114.34 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	2681 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2336 reflections with I > 2σ(I)
T_min = 0.971, T_max = 0.992	R_int = 0.038
10155 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	0 restraints
wR(F²) = 0.121	H-atom parameters constrained
S = 1.07	Δρ_max = 0.87 e Å⁻³
2681 reflections	Δρ_min = −0.50 e Å⁻³
223 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	0.5000	0.5000	0.0181 (2)
Cl1	0.51836 (11)	0.31957 (6)	0.20373 (6)	0.0255 (2)
N1	0.2655 (3)	0.5819 (2)	0.46508 (18)	0.0182 (6)
N2	0.7370 (3)	0.6987 (2)	0.59168 (19)	0.0203 (6)
N3	0.5833 (3)	0.64755 (19)	0.55294 (19)	0.0188 (6)
N4	0.5287 (3)	0.80947 (19)	0.56599 (18)	0.0165 (6)
N5	0.7829 (4)	0.9719 (2)	0.6482 (2)	0.0247 (6)
N6	0.4322 (4)	0.9001 (2)	0.5607 (2)	0.0295 (7)
H6A	0.3984	0.9278	0.5012	0.044*
H6B	0.4971	0.9452	0.6054	0.044*
O1	0.5064 (3)	0.54303 (18)	0.36619 (16)	0.0287 (6)
H1A	0.5952	0.5177	0.3628	0.043*
H1B	0.5093	0.6085	0.3630	0.043*
O2	0.6254 (4)	0.2589 (3)	0.1740 (3)	0.0633 (10)
O3	0.4116 (4)	0.3823 (2)	0.1213 (2)	0.0555 (9)
O4	0.6210 (4)	0.3837 (2)	0.2840 (2)	0.0475 (8)
O5	0.4126 (4)	0.2533 (3)	0.2297 (2)	0.0687 (11)
C1	0.2804 (4)	0.6823 (2)	0.4928 (2)	0.0181 (7)
C2	0.1401 (4)	0.7437 (3)	0.4777 (2)	0.0229 (7)
H2	0.1537	0.8123	0.4977	0.027*
C3	−0.0217 (4)	0.7004 (3)	0.4318 (3)	0.0273 (8)
H3	−0.1184	0.7398	0.4211	0.033*
C4	−0.0381 (4)	0.5988 (3)	0.4024 (2)	0.0261 (8)
H4	−0.1457	0.5692	0.3704	0.031*
C5	0.1082 (4)	0.5415 (3)	0.4210 (2)	0.0228 (7)
H5	0.0969	0.4724	0.4023	0.027*
C6	0.4598 (4)	0.7148 (2)	0.5385 (2)	0.0171 (7)
C7	0.7014 (4)	0.7965 (2)	0.5981 (2)	0.0190 (7)
C8	0.8325 (4)	0.8777 (2)	0.6329 (2)	0.0205 (7)
C9	0.9991 (4)	0.8547 (3)	0.6470 (3)	0.0285 (8)
H9	1.0293	0.7879	0.6378	0.034*
C10	1.1191 (5)	0.9332 (3)	0.6750 (3)	0.0334 (9)
H10	1.2307	0.9207	0.6828	0.040*
C11	1.0696 (5)	1.0310 (3)	0.6914 (3)	0.0313 (8)
H11	1.1477	1.0851	0.7107	0.038*
C12	0.9036 (5)	1.0464 (3)	0.6786 (3)	0.0287 (8)
H12	0.8726	1.1116	0.6915	0.034*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0183 (3)	0.0139 (3)	0.0231 (3)	−0.0002 (2)	0.0096 (3)	−0.0014 (2)
Cl1	0.0309 (5)	0.0211 (4)	0.0282 (5)	−0.0011 (3)	0.0160 (4)	−0.0031 (3)
N1	0.0186 (14)	0.0168 (14)	0.0212 (13)	−0.0010 (11)	0.0103 (11)	0.0001 (11)
N2	0.0157 (14)	0.0183 (14)	0.0245 (14)	−0.0012 (11)	0.0058 (12)	−0.0021 (11)
N3	0.0174 (14)	0.0143 (13)	0.0244 (14)	0.0001 (11)	0.0083 (12)	−0.0013 (11)
N4	0.0191 (14)	0.0131 (13)	0.0185 (13)	0.0010 (10)	0.0091 (11)	−0.0003 (10)
N5	0.0233 (15)	0.0187 (14)	0.0297 (16)	−0.0012 (12)	0.0086 (13)	−0.0012 (12)
N6	0.0262 (16)	0.0185 (15)	0.0424 (18)	0.0023 (12)	0.0128 (14)	−0.0011 (13)
O1	0.0389 (15)	0.0206 (12)	0.0312 (13)	0.0066 (11)	0.0191 (12)	0.0034 (10)
O2	0.0474 (19)	0.070 (2)	0.073 (2)	0.0008 (17)	0.0256 (17)	−0.0440 (19)
O3	0.062 (2)	0.0395 (18)	0.0509 (18)	0.0045 (16)	0.0092 (16)	0.0161 (14)
O4	0.0537 (19)	0.0519 (18)	0.0393 (16)	−0.0126 (15)	0.0217 (14)	−0.0229 (14)
O5	0.060 (2)	0.096 (3)	0.0425 (18)	−0.046 (2)	0.0130 (16)	0.0131 (18)
C1	0.0217 (17)	0.0179 (16)	0.0181 (16)	−0.0007 (13)	0.0116 (14)	0.0017 (12)
C2	0.0237 (18)	0.0196 (17)	0.0283 (18)	0.0016 (14)	0.0138 (15)	−0.0002 (14)
C3	0.0205 (18)	0.0293 (19)	0.035 (2)	0.0053 (15)	0.0145 (16)	0.0059 (15)
C4	0.0165 (17)	0.032 (2)	0.0295 (18)	−0.0049 (15)	0.0090 (15)	−0.0010 (15)
C5	0.0240 (18)	0.0206 (17)	0.0268 (17)	−0.0019 (14)	0.0134 (15)	−0.0012 (14)
C6	0.0212 (17)	0.0156 (16)	0.0175 (15)	−0.0007 (13)	0.0109 (13)	0.0007 (12)
C7	0.0218 (17)	0.0181 (16)	0.0193 (16)	−0.0002 (13)	0.0107 (14)	0.0002 (13)
C8	0.0214 (17)	0.0196 (17)	0.0198 (16)	−0.0013 (13)	0.0077 (14)	−0.0007 (13)
C9	0.0248 (19)	0.0256 (19)	0.0339 (19)	−0.0015 (15)	0.0111 (16)	−0.0073 (15)
C10	0.0230 (19)	0.039 (2)	0.038 (2)	−0.0043 (16)	0.0120 (17)	−0.0086 (17)
C11	0.028 (2)	0.029 (2)	0.031 (2)	−0.0115 (16)	0.0065 (16)	−0.0048 (16)
C12	0.029 (2)	0.0191 (18)	0.0338 (19)	−0.0032 (15)	0.0089 (16)	−0.0063 (15)

Geometric parameters (Å, º) top

Co1—N3	2.079 (3)	N6—H6B	0.8901
Co1—N3ⁱ	2.079 (3)	O1—H1A	0.8500
Co1—O1ⁱ	2.102 (2)	O1—H1B	0.8500
Co1—O1	2.102 (2)	C1—C2	1.381 (4)
Co1—N1	2.141 (3)	C1—C6	1.466 (4)
Co1—N1ⁱ	2.141 (3)	C2—C3	1.389 (5)
Cl1—O2	1.413 (3)	C2—H2	0.9300
Cl1—O5	1.416 (3)	C3—C4	1.376 (5)
Cl1—O4	1.428 (3)	C3—H3	0.9300
Cl1—O3	1.446 (3)	C4—C5	1.385 (5)
N1—C5	1.341 (4)	C4—H4	0.9300
N1—C1	1.355 (4)	C5—H5	0.9300
N2—C7	1.316 (4)	C7—C8	1.470 (4)
N2—N3	1.372 (4)	C8—C9	1.389 (5)
N3—C6	1.319 (4)	C9—C10	1.384 (5)
N4—C6	1.350 (4)	C9—H9	0.9300
N4—C7	1.367 (4)	C10—C11	1.390 (5)
N4—N6	1.420 (4)	C10—H10	0.9300
N5—C8	1.342 (4)	C11—C12	1.372 (5)
N5—C12	1.350 (5)	C11—H11	0.9300
N6—H6A	0.8901	C12—H12	0.9300

N3—Co1—N3ⁱ	180.0	H1A—O1—H1B	109.5
N3—Co1—O1ⁱ	91.15 (10)	N1—C1—C2	122.4 (3)
N3ⁱ—Co1—O1ⁱ	88.85 (10)	N1—C1—C6	111.5 (3)
N3—Co1—O1	88.85 (10)	C2—C1—C6	126.1 (3)
N3ⁱ—Co1—O1	91.15 (10)	C1—C2—C3	118.4 (3)
O1ⁱ—Co1—O1	180.000 (1)	C1—C2—H2	120.8
N3—Co1—N1	77.24 (10)	C3—C2—H2	120.8
N3ⁱ—Co1—N1	102.76 (10)	C4—C3—C2	119.6 (3)
O1ⁱ—Co1—N1	88.45 (9)	C4—C3—H3	120.2
O1—Co1—N1	91.55 (9)	C2—C3—H3	120.2
N3—Co1—N1ⁱ	102.76 (10)	C3—C4—C5	119.0 (3)
N3ⁱ—Co1—N1ⁱ	77.24 (10)	C3—C4—H4	120.5
O1ⁱ—Co1—N1ⁱ	91.55 (9)	C5—C4—H4	120.5
O1—Co1—N1ⁱ	88.45 (9)	N1—C5—C4	122.3 (3)
N1—Co1—N1ⁱ	180.000 (1)	N1—C5—H5	118.8
O2—Cl1—O5	108.9 (3)	C4—C5—H5	118.8
O2—Cl1—O4	109.47 (19)	N3—C6—N4	109.2 (3)
O5—Cl1—O4	111.4 (2)	N3—C6—C1	120.4 (3)
O2—Cl1—O3	108.0 (2)	N4—C6—C1	130.3 (3)
O5—Cl1—O3	108.8 (2)	N2—C7—N4	110.1 (3)
O4—Cl1—O3	110.2 (2)	N2—C7—C8	123.2 (3)
C5—N1—C1	118.3 (3)	N4—C7—C8	126.7 (3)
C5—N1—Co1	125.6 (2)	N5—C8—C9	123.3 (3)
C1—N1—Co1	116.1 (2)	N5—C8—C7	117.4 (3)
C7—N2—N3	106.5 (3)	C9—C8—C7	119.3 (3)
C6—N3—N2	108.6 (2)	C10—C9—C8	118.7 (3)
C6—N3—Co1	114.6 (2)	C10—C9—H9	120.7
N2—N3—Co1	136.4 (2)	C8—C9—H9	120.7
C6—N4—C7	105.7 (3)	C9—C10—C11	118.7 (3)
C6—N4—N6	124.2 (3)	C9—C10—H10	120.7
C7—N4—N6	130.1 (3)	C11—C10—H10	120.7
C8—N5—C12	117.0 (3)	C12—C11—C10	118.9 (3)
N4—N6—H6A	109.3	C12—C11—H11	120.6
N4—N6—H6B	109.2	C10—C11—H11	120.6
H6A—N6—H6B	109.5	N5—C12—C11	123.5 (3)
Co1—O1—H1A	109.3	N5—C12—H12	118.2
Co1—O1—H1B	109.3	C11—C12—H12	118.2

N3—Co1—N1—C5	−179.1 (3)	Co1—N3—C6—N4	−173.37 (18)
N3ⁱ—Co1—N1—C5	0.9 (3)	N2—N3—C6—C1	176.9 (3)
O1ⁱ—Co1—N1—C5	−87.5 (3)	Co1—N3—C6—C1	3.0 (4)
O1—Co1—N1—C5	92.5 (3)	C7—N4—C6—N3	0.0 (3)
N3—Co1—N1—C1	−0.9 (2)	N6—N4—C6—N3	−179.7 (3)
N3ⁱ—Co1—N1—C1	179.1 (2)	C7—N4—C6—C1	−175.8 (3)
O1ⁱ—Co1—N1—C1	90.7 (2)	N6—N4—C6—C1	4.4 (5)
O1—Co1—N1—C1	−89.3 (2)	N1—C1—C6—N3	−3.6 (4)
C7—N2—N3—C6	−1.0 (3)	C2—C1—C6—N3	176.9 (3)
C7—N2—N3—Co1	171.1 (2)	N1—C1—C6—N4	171.8 (3)
O1ⁱ—Co1—N3—C6	−89.3 (2)	C2—C1—C6—N4	−7.7 (5)
O1—Co1—N3—C6	90.7 (2)	N3—N2—C7—N4	1.0 (3)
N1—Co1—N3—C6	−1.1 (2)	N3—N2—C7—C8	−177.6 (3)
N1ⁱ—Co1—N3—C6	178.9 (2)	C6—N4—C7—N2	−0.6 (3)
O1ⁱ—Co1—N3—N2	99.0 (3)	N6—N4—C7—N2	179.1 (3)
O1—Co1—N3—N2	−81.0 (3)	C6—N4—C7—C8	177.8 (3)
N1—Co1—N3—N2	−172.8 (3)	N6—N4—C7—C8	−2.4 (5)
N1ⁱ—Co1—N3—N2	7.2 (3)	C12—N5—C8—C9	0.2 (5)
C5—N1—C1—C2	0.3 (4)	C12—N5—C8—C7	−178.9 (3)
Co1—N1—C1—C2	−178.0 (2)	N2—C7—C8—N5	−171.5 (3)
C5—N1—C1—C6	−179.2 (3)	N4—C7—C8—N5	10.2 (5)
Co1—N1—C1—C6	2.5 (3)	N2—C7—C8—C9	9.4 (5)
N1—C1—C2—C3	−0.4 (5)	N4—C7—C8—C9	−169.0 (3)
C6—C1—C2—C3	179.1 (3)	N5—C8—C9—C10	−2.3 (5)
C1—C2—C3—C4	−0.4 (5)	C7—C8—C9—C10	176.8 (3)
C2—C3—C4—C5	1.3 (5)	C8—C9—C10—C11	2.3 (5)
C1—N1—C5—C4	0.6 (5)	C9—C10—C11—C12	−0.4 (5)
Co1—N1—C5—C4	178.8 (2)	C8—N5—C12—C11	1.9 (5)
C3—C4—C5—N1	−1.4 (5)	C10—C11—C12—N5	−1.8 (6)
N2—N3—C6—N4	0.6 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6B···N5	0.89	2.29	2.897 (4)	125
N6—H6B···O3ⁱⁱ	0.89	2.39	2.989 (4)	124
O1—H1A···O4	0.85	2.16	2.782 (4)	130
O1—H1B···O2ⁱⁱⁱ	0.85	2.22	2.983 (4)	150
O1—H1B···O5ⁱⁱⁱ	0.85	2.58	3.284 (5)	141

Symmetry codes: (ii) x, −y+3/2, z+1/2; (iii) −x+1, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Co(C₁₂H₁₀N₆)₂(H₂O)₂](ClO₄)₂
M_r	770.38
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	8.5839 (17), 12.950 (3), 14.975 (5)
β (°)	114.34 (2)
V (Å³)	1516.7 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.82
Crystal size (mm)	0.04 × 0.03 × 0.01

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.971, 0.992
No. of measured, independent and observed [I > 2σ(I)] reflections	10155, 2681, 2336
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.121, 1.07
No. of reflections	2681
No. of parameters	223
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.87, −0.50

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N6—H6B···N5	0.89	2.29	2.897 (4)	125.2
N6—H6B···O3ⁱ	0.89	2.39	2.989 (4)	124.3
O1—H1A···O4	0.85	2.16	2.782 (4)	129.7
O1—H1B···O2ⁱⁱ	0.85	2.22	2.983 (4)	150.1
O1—H1B···O5ⁱⁱ	0.85	2.58	3.284 (5)	140.8

Symmetry codes: (i) x, −y+3/2, z+1/2; (ii) −x+1, y+1/2, −z+1/2.

Acknowledgements

We thank the NSFC (21061009) and the National Students of Innovation and Entrepreneurship Training Programs (111012608) for their financial support.

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