Tris(2,2′-bi-1H-imidazole-κ2N3,N3′)cobalt(II) hydrogen phosphate

Liang, Z.; Wang, F.; Wu, Q.; Zhi, X.; Pan, Q.

doi:10.1107/S1600536811037299

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 10| October 2011| Page m1399

https://doi.org/10.1107/S1600536811037299

Open

access

Tris(2,2′-bi-1H-imidazole-κ²N³,N^3′)cobalt(II) hydrogen phosphate

Zhiqiang Liang,^a Fuxiang Wang,^b Qihui Wu,^b Xia Zhi ^b and Qinhe Pan ^b ^*

^aState Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130012, Jilin Province, People's Republic of China, and ^bDepartment of Materials and Chemical Engineering, Ministry of Education Key Laboratory of Application Technology of Hainan Superior Resources Chemical Materials, Hainan University, Haikou 570228, Hainan Province, People's Republic of China
^*Correspondence e-mail: panqinhe@163.com

(Received 1 August 2011; accepted 13 September 2011; online 17 September 2011)

The title compound, [Co(C₆H₆N₄)₃]HPO₄, was synthesized under hydrothermal conditions. In the cation, the Co^II atom is octahedrally coordinated by six N atoms from three 2,2′-bi-1H-imidazole ligands [Co—N bond lengths are in the range 2.084 (5)–2.133 (6) Å]. Intermolecular N—H⋯O hydrogen bonds form an extensive hydrogen-bonding network, which links cations and anions into a three-dimensional crystal structure.

Related literature

For related compounds, see Pan et al. (2005 , 2008 , 2010a ,b , 2011 ); Rothammel et al. (1998 ); Stalder & Wilkinson (1997 ); Tong & Pan (2011 ); Wang et al. (2003a ,b ).

Experimental

Crystal data

[Co(C₆H₆N₄)₃]HPO₄
M_r = 557.35
Monoclinic, C c
a = 12.700 (3) Å
b = 21.447 (4) Å
c = 9.1140 (18) Å
β = 95.84 (3)°
V = 2469.6 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.81 mm⁻¹
T = 293 K
0.20 × 0.17 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID-S diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2002 ) T_min = 0.850, T_max = 0.886
12597 measured reflections
5593 independent reflections
3373 reflections with I > 2σ(I)
R_int = 0.098

Refinement

R[F² > 2σ(F²)] = 0.077
wR(F²) = 0.152
S = 1.06
5593 reflections
325 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.32 e Å⁻³
Absolute structure: Flack (1983 ), 2755 Friedel pairs
Flack parameter: −0.02 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O4	0.86	1.82	2.678 (7)	172.1
N4—H4⋯O2	0.86	1.87	2.717 (7)	168.3
N6—H6A⋯O3ⁱ	0.86	1.96	2.725 (8)	148.3
N8—H8⋯O3ⁱ	0.86	1.89	2.669 (8)	149.3
N10—H10⋯O2ⁱⁱ	0.86	2.23	2.887 (7)	133.7
N10—H10⋯O4ⁱⁱⁱ	0.86	2.39	3.034 (9)	132.5
N12—H12A⋯O4ⁱⁱⁱ	0.86	1.93	2.685 (8)	146.0
Symmetry codes: (i) x+1, y, z; (ii) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (iii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); 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 I, global. DOI: https://doi.org/10.1107/S1600536811037299/aa2021sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536811037299/aa2021Isup2.hkl

checkCIF report

Comment top

Recently, more attention has been paid to chiral metal complexes, which could be employed as an interesting template for the synthesis of novel materials, because they are versatile and can be made with a wide of shapes, charges and particularly chirality. Up to now, series of open-frameworks, such as metal phosphates (for example: Stalder & Wilkinson (1997); Wang et al. (2003a,b)) and germanates (for example: Pan et al. (2005, 2008)), have been synthesized with [M(dien)₂]ⁿ⁺ or [M(en)₃]ⁿ⁺ (M = Co, Ni; n = 2, 3; dien = diethylenediamine, en = ethylenediamine) cations. Recently the chiral metal complexes have been introduced into coordination polymers, see Pan et al. (2010a, 2010b, 2011), Tong et al. (2011). In this paper, we present an other metal complex [Co(biim)₃]HPO₄ (biim is 2,2'-biimidazole).

As shown in Fig. 1, the crystal structure of title compound consists of a discrete [Co(biim)₃]²⁺ cations and HPO₄^2- anions. In [Co(biim)₃]²⁺, the Co^II center is six coorinated and linked by six N atoms from three different biim ligands, resulting in a slightly distorted octahedral geometry. The Co^II—N bond distances are in the range of 2.084 (5)–2.133 (6) Å. The P atom displays a slightly distorted tetrahedal geometry and is bonded to three O atoms and one OH group with the P—O distances of 1.484 (6)–1.564 (5) Å. N—H···O hydrogen bonds connect cations and anions into a three-dimensional network (see Table 1).

Related literature top

For related compounds, see Pan et al. (2005, 2008, 2010a,b, 2011); Rothammel et al. (1998); Stalder & Wilkinson (1997); Tong & Pan (2011); Wang et al. (2003a,b).

Experimental top

In a typical synthesis, a mixture of Co(OAc)₂.2H₂O (0.25 g), biimidazole (0.067 g), H₃PO₄ (0.12 ml) and H₂O (10 ml) were added to a 25 ml Teflon-lined reactor and kept under autogenous pressure at 120 °C for 3 days.

Structure description top

For related compounds, see Pan et al. (2005, 2008, 2010a,b, 2011); Rothammel et al. (1998); Stalder & Wilkinson (1997); Tong & Pan (2011); Wang et al. (2003a,b).

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); 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. A view of the structure of complex. Ellipsoids are drawn at the 30% probability level.

Tris(2,2'-bi-1H-imidazole-κ²N³,N^3')cobalt(II) hydrogen phosphate top

Crystal data top

[Co(C₆H₆N₄)₃]HPO₄	F(000) = 1140
M_r = 557.35	D_x = 1.499 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 12761 reflections
a = 12.700 (3) Å	θ = 3.1–27.5°
b = 21.447 (4) Å	µ = 0.81 mm⁻¹
c = 9.1140 (18) Å	T = 293 K
β = 95.84 (3)°	Block, blue
V = 2469.6 (8) Å³	0.2 × 0.17 × 0.15 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID-S diffractometer	5593 independent reflections
Radiation source: fine-focus sealed tube	3373 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.098
ω scans	θ_max = 27.5°, θ_min = 3.1°
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2002)	h = −16→16
T_min = 0.850, T_max = 0.886	k = −27→27
12597 measured reflections	l = −11→11

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.077	H-atom parameters constrained
wR(F²) = 0.152	w = 1/[σ²(F_o²) + (0.0453P)²] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.042
5593 reflections	Δρ_max = 0.40 e Å⁻³
325 parameters	Δρ_min = −0.32 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 2755 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.02 (2)

Crystal data top

[Co(C₆H₆N₄)₃]HPO₄	V = 2469.6 (8) Å³
M_r = 557.35	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 12.700 (3) Å	µ = 0.81 mm⁻¹
b = 21.447 (4) Å	T = 293 K
c = 9.1140 (18) Å	0.2 × 0.17 × 0.15 mm
β = 95.84 (3)°

Data collection top

Rigaku R-AXIS RAPID-S diffractometer	5593 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2002)	3373 reflections with I > 2σ(I)
T_min = 0.850, T_max = 0.886	R_int = 0.098
12597 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.077	H-atom parameters constrained
wR(F²) = 0.152	Δρ_max = 0.40 e Å⁻³
S = 1.06	Δρ_min = −0.32 e Å⁻³
5593 reflections	Absolute structure: Flack (1983), 2755 Friedel pairs
325 parameters	Absolute structure parameter: −0.02 (2)
2 restraints

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	0.61255 (7)	0.33459 (3)	0.15859 (9)	0.0466 (3)
P1	0.12445 (13)	0.48617 (7)	0.34051 (17)	0.0397 (4)
O1	0.1291 (4)	0.5348 (2)	0.4686 (5)	0.0560 (13)
H1	0.1900	0.5375	0.5077	0.067*
O2	0.1932 (4)	0.5113 (2)	0.2233 (4)	0.0512 (12)
O3	0.0119 (4)	0.4852 (3)	0.2777 (6)	0.0828 (17)
O4	0.1658 (4)	0.4249 (2)	0.4011 (5)	0.0699 (15)
N1	0.4828 (5)	0.3189 (3)	0.2765 (7)	0.0619 (18)
N2	0.3328 (5)	0.3553 (3)	0.3473 (7)	0.0648 (18)
H2	0.2794	0.3792	0.3565	0.078*
N3	0.5206 (5)	0.4153 (2)	0.0992 (6)	0.0513 (14)
N4	0.3842 (4)	0.4723 (3)	0.1484 (6)	0.0566 (16)
H4	0.3274	0.4838	0.1847	0.068*
N5	0.7019 (4)	0.3812 (2)	0.3368 (6)	0.0513 (15)
N6	0.8457 (5)	0.4352 (3)	0.4042 (7)	0.0584 (16)
H6A	0.9047	0.4544	0.3993	0.070*
N7	0.7434 (4)	0.3656 (3)	0.0530 (6)	0.0477 (14)
N8	0.8950 (4)	0.4176 (2)	0.0763 (7)	0.0482 (14)
H8	0.9473	0.4395	0.1150	0.058*
N9	0.6751 (5)	0.2470 (3)	0.2311 (8)	0.0603 (17)
N10	0.6751 (6)	0.1449 (3)	0.1916 (9)	0.074 (2)
H10	0.6636	0.1093	0.1498	0.089*
N11	0.5563 (4)	0.2775 (3)	−0.0218 (8)	0.0625 (18)
N12	0.5553 (5)	0.1820 (3)	−0.1166 (9)	0.077 (2)
H12A	0.5652	0.1426	−0.1244	0.092*
C1	0.4432 (7)	0.2771 (4)	0.3717 (12)	0.095 (3)
H1A	0.4748	0.2395	0.4015	0.114*
C2	0.3535 (7)	0.2987 (4)	0.4145 (12)	0.097 (3)
H2A	0.3118	0.2790	0.4787	0.116*
C3	0.4129 (5)	0.3662 (3)	0.2641 (8)	0.0511 (18)
C4	0.4347 (5)	0.4180 (3)	0.1736 (8)	0.0449 (17)
C5	0.4392 (7)	0.5059 (4)	0.0548 (10)	0.078 (3)
H5	0.4226	0.5454	0.0177	0.094*
C6	0.5240 (6)	0.4697 (3)	0.0261 (9)	0.063 (2)
H6	0.5756	0.4811	−0.0342	0.076*
C7	0.7044 (7)	0.3963 (3)	0.4839 (9)	0.064 (2)
H7	0.6529	0.3853	0.5447	0.077*
C8	0.7923 (8)	0.4291 (4)	0.5266 (9)	0.071 (2)
H8A	0.8128	0.4446	0.6205	0.086*
C9	0.7899 (5)	0.4063 (3)	0.2959 (8)	0.0446 (16)
C10	0.8109 (5)	0.3975 (3)	0.1443 (8)	0.0415 (16)
C11	0.8805 (6)	0.3960 (3)	−0.0667 (8)	0.0520 (17)
H11	0.9254	0.4018	−0.1400	0.062*
C12	0.7866 (6)	0.3645 (3)	−0.0789 (8)	0.0562 (19)
H12	0.7563	0.3452	−0.1643	0.067*
C13	0.7277 (7)	0.2186 (4)	0.3508 (9)	0.070 (2)
H13	0.7583	0.2388	0.4348	0.083*
C14	0.7284 (8)	0.1565 (4)	0.3283 (12)	0.078 (3)
H14	0.7593	0.1268	0.3933	0.094*
C15	0.6450 (5)	0.2012 (3)	0.1372 (9)	0.057 (2)
C16	0.5860 (6)	0.2179 (3)	0.0014 (10)	0.061 (2)
C17	0.5049 (8)	0.2208 (5)	−0.2230 (12)	0.094 (3)
H17	0.4756	0.2088	−0.3164	0.113*
C18	0.5058 (7)	0.2797 (4)	−0.1671 (12)	0.086 (3)
H18	0.4781	0.3151	−0.2158	0.103*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0401 (4)	0.0300 (4)	0.0746 (6)	−0.0043 (5)	0.0292 (4)	−0.0064 (5)
P1	0.0473 (10)	0.0415 (9)	0.0323 (8)	−0.0023 (8)	0.0134 (8)	−0.0013 (8)
O1	0.075 (4)	0.048 (3)	0.046 (3)	0.005 (3)	0.012 (3)	−0.004 (2)
O2	0.057 (3)	0.051 (3)	0.048 (3)	−0.002 (2)	0.014 (2)	0.009 (2)
O3	0.058 (3)	0.100 (4)	0.091 (4)	−0.007 (3)	0.011 (3)	−0.023 (3)
O4	0.104 (4)	0.042 (3)	0.068 (3)	0.020 (3)	0.028 (3)	0.011 (2)
N1	0.053 (4)	0.043 (3)	0.098 (5)	−0.005 (3)	0.047 (4)	0.000 (3)
N2	0.055 (4)	0.047 (3)	0.100 (5)	−0.002 (3)	0.043 (4)	−0.002 (4)
N3	0.049 (3)	0.045 (3)	0.063 (4)	0.004 (3)	0.020 (3)	0.001 (3)
N4	0.047 (4)	0.060 (4)	0.064 (4)	0.018 (3)	0.013 (3)	0.009 (3)
N5	0.055 (4)	0.038 (3)	0.065 (4)	−0.004 (3)	0.026 (3)	−0.007 (3)
N6	0.059 (4)	0.054 (4)	0.064 (4)	−0.014 (3)	0.016 (4)	−0.006 (3)
N7	0.040 (3)	0.048 (3)	0.057 (4)	−0.006 (3)	0.016 (3)	−0.004 (3)
N8	0.036 (3)	0.044 (3)	0.066 (4)	−0.005 (2)	0.016 (3)	0.005 (3)
N9	0.057 (4)	0.046 (4)	0.084 (5)	0.002 (3)	0.038 (4)	−0.004 (4)
N10	0.079 (5)	0.034 (3)	0.115 (6)	−0.005 (3)	0.036 (5)	−0.005 (4)
N11	0.040 (3)	0.040 (4)	0.112 (6)	−0.001 (3)	0.026 (4)	−0.015 (4)
N12	0.063 (4)	0.038 (3)	0.129 (6)	−0.006 (3)	0.012 (4)	−0.022 (4)
C1	0.076 (6)	0.051 (5)	0.171 (9)	0.006 (4)	0.075 (7)	0.029 (6)
C2	0.084 (6)	0.053 (5)	0.167 (10)	0.006 (5)	0.082 (7)	0.029 (6)
C3	0.053 (4)	0.035 (4)	0.070 (5)	−0.008 (3)	0.028 (4)	−0.011 (4)
C4	0.030 (4)	0.046 (4)	0.060 (5)	0.002 (3)	0.013 (3)	−0.007 (3)
C5	0.086 (6)	0.070 (6)	0.084 (6)	0.015 (5)	0.037 (6)	0.031 (5)
C6	0.060 (5)	0.058 (5)	0.077 (5)	0.006 (4)	0.033 (4)	0.022 (4)
C7	0.079 (6)	0.056 (5)	0.062 (5)	−0.003 (4)	0.031 (5)	−0.009 (4)
C8	0.089 (6)	0.069 (6)	0.060 (5)	−0.010 (5)	0.025 (5)	−0.010 (4)
C9	0.037 (4)	0.038 (4)	0.060 (5)	−0.001 (3)	0.014 (4)	0.006 (3)
C10	0.043 (4)	0.032 (3)	0.052 (4)	−0.002 (3)	0.019 (4)	0.002 (3)
C11	0.043 (4)	0.063 (5)	0.052 (4)	−0.009 (4)	0.016 (4)	0.000 (4)
C12	0.061 (5)	0.055 (5)	0.053 (5)	−0.007 (4)	0.009 (4)	−0.007 (4)
C13	0.080 (6)	0.058 (5)	0.074 (6)	−0.006 (4)	0.023 (5)	0.004 (4)
C14	0.090 (7)	0.042 (5)	0.107 (8)	0.007 (4)	0.029 (6)	0.005 (5)
C15	0.046 (4)	0.035 (4)	0.094 (6)	−0.003 (3)	0.027 (4)	−0.002 (4)
C16	0.041 (4)	0.035 (4)	0.111 (7)	−0.005 (3)	0.031 (5)	−0.009 (5)
C17	0.081 (7)	0.064 (6)	0.134 (9)	−0.013 (5)	−0.007 (6)	−0.029 (6)
C18	0.059 (6)	0.079 (7)	0.116 (8)	−0.001 (5)	−0.006 (6)	0.003 (6)

Geometric parameters (Å, º) top

Co1—N1	2.084 (5)	N9—C15	1.332 (9)
Co1—N7	2.110 (5)	N9—C13	1.364 (10)
Co1—N11	2.115 (7)	N10—C15	1.346 (9)
Co1—N9	2.120 (6)	N10—C14	1.379 (11)
Co1—N3	2.127 (6)	N10—H10	0.8600
Co1—N5	2.133 (6)	N11—C16	1.344 (9)
P1—O3	1.485 (6)	N11—C18	1.412 (11)
P1—O4	1.500 (4)	N12—C16	1.348 (10)
P1—O2	1.544 (4)	N12—C17	1.384 (11)
P1—O1	1.563 (5)	N12—H12A	0.8600
O1—H1	0.8200	C1—C2	1.325 (10)
N1—C3	1.344 (9)	C1—H1A	0.9300
N1—C1	1.378 (9)	C2—H2A	0.9300
N2—C3	1.350 (8)	C3—C4	1.429 (9)
N2—C2	1.373 (9)	C5—C6	1.373 (10)
N2—H2	0.8600	C5—H5	0.9300
N3—C4	1.343 (8)	C6—H6	0.9300
N3—C6	1.347 (8)	C7—C8	1.343 (11)
N4—C4	1.337 (8)	C7—H7	0.9300
N4—C5	1.363 (9)	C8—H8A	0.9300
N4—H4	0.8600	C9—C10	1.446 (9)
N5—C9	1.327 (8)	C11—C12	1.365 (9)
N5—C7	1.376 (8)	C11—H11	0.9300
N6—C9	1.311 (8)	C12—H12	0.9300
N6—C8	1.370 (9)	C13—C14	1.347 (10)
N6—H6A	0.8600	C13—H13	0.9300
N7—C10	1.323 (8)	C14—H14	0.9300
N7—C12	1.372 (8)	C15—C16	1.426 (11)
N8—C10	1.358 (8)	C17—C18	1.361 (11)
N8—C11	1.377 (9)	C17—H17	0.9300
N8—H8	0.8600	C18—H18	0.9300

N1—Co1—N7	170.6 (2)	C16—N12—H12A	126.5
N1—Co1—N11	94.9 (2)	C17—N12—H12A	126.5
N7—Co1—N11	92.7 (2)	C2—C1—N1	109.8 (7)
N1—Co1—N9	89.3 (2)	C2—C1—H1A	125.1
N7—Co1—N9	97.7 (2)	N1—C1—H1A	125.1
N11—Co1—N9	79.4 (3)	C1—C2—N2	108.0 (7)
N1—Co1—N3	79.6 (2)	C1—C2—H2A	126.0
N7—Co1—N3	93.7 (2)	N2—C2—H2A	126.0
N11—Co1—N3	98.0 (2)	N1—C3—N2	110.6 (6)
N9—Co1—N3	168.4 (2)	N1—C3—C4	118.0 (6)
N1—Co1—N5	94.0 (2)	N2—C3—C4	131.3 (7)
N7—Co1—N5	79.5 (2)	N4—C4—N3	110.6 (6)
N11—Co1—N5	167.1 (2)	N4—C4—C3	131.2 (6)
N9—Co1—N5	91.4 (2)	N3—C4—C3	118.2 (6)
N3—Co1—N5	92.8 (2)	N4—C5—C6	106.4 (6)
O3—P1—O4	114.6 (4)	N4—C5—H5	126.8
O3—P1—O2	109.2 (3)	C6—C5—H5	126.8
O4—P1—O2	111.0 (3)	N3—C6—C5	109.3 (6)
O3—P1—O1	105.1 (3)	N3—C6—H6	125.4
O4—P1—O1	109.0 (3)	C5—C6—H6	125.4
O2—P1—O1	107.6 (3)	C8—C7—N5	110.0 (7)
P1—O1—H1	109.5	C8—C7—H7	125.0
C3—N1—C1	105.3 (6)	N5—C7—H7	125.0
C3—N1—Co1	112.7 (5)	C7—C8—N6	106.3 (7)
C1—N1—Co1	142.0 (5)	C7—C8—H8A	126.9
C3—N2—C2	106.4 (6)	N6—C8—H8A	126.9
C3—N2—H2	126.8	N6—C9—N5	112.7 (6)
C2—N2—H2	126.8	N6—C9—C10	130.0 (6)
C4—N3—C6	106.3 (6)	N5—C9—C10	117.3 (6)
C4—N3—Co1	111.1 (4)	N7—C10—N8	111.5 (6)
C6—N3—Co1	141.9 (5)	N7—C10—C9	119.8 (6)
C4—N4—C5	107.4 (6)	N8—C10—C9	128.7 (7)
C4—N4—H4	126.3	C12—C11—N8	106.0 (6)
C5—N4—H4	126.3	C12—C11—H11	127.0
C9—N5—C7	104.0 (6)	N8—C11—H11	127.0
C9—N5—Co1	112.0 (5)	C11—C12—N7	110.2 (6)
C7—N5—Co1	144.1 (5)	C11—C12—H12	124.9
C9—N6—C8	107.0 (6)	N7—C12—H12	124.9
C9—N6—H6A	126.5	C14—C13—N9	109.3 (8)
C8—N6—H6A	126.5	C14—C13—H13	125.4
C10—N7—C12	105.5 (5)	N9—C13—H13	125.4
C10—N7—Co1	111.5 (4)	C13—C14—N10	107.8 (8)
C12—N7—Co1	143.0 (5)	C13—C14—H14	126.1
C10—N8—C11	106.8 (6)	N10—C14—H14	126.1
C10—N8—H8	126.6	N9—C15—N10	111.8 (8)
C11—N8—H8	126.6	N9—C15—C16	117.7 (7)
C15—N9—C13	105.7 (6)	N10—C15—C16	130.5 (7)
C15—N9—Co1	112.2 (6)	N11—C16—N12	111.3 (8)
C13—N9—Co1	141.6 (6)	N11—C16—C15	119.3 (7)
C15—N10—C14	105.5 (7)	N12—C16—C15	129.3 (7)
C15—N10—H10	127.3	C18—C17—N12	108.0 (9)
C14—N10—H10	127.3	C18—C17—H17	126.0
C16—N11—C18	105.8 (7)	N12—C17—H17	126.0
C16—N11—Co1	111.2 (6)	C17—C18—N11	107.9 (8)
C18—N11—Co1	142.7 (6)	C17—C18—H18	126.1
C16—N12—C17	107.0 (7)	N11—C18—H18	126.1

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O4	0.86	1.82	2.678 (7)	172.1
N4—H4···O2	0.86	1.87	2.717 (7)	168.3
N6—H6A···O3ⁱ	0.86	1.96	2.725 (8)	148.3
N8—H8···O3ⁱ	0.86	1.89	2.669 (8)	149.3
N10—H10···O2ⁱⁱ	0.86	2.23	2.887 (7)	133.7
N10—H10···O4ⁱⁱⁱ	0.86	2.39	3.034 (9)	132.5
N12—H12A···O4ⁱⁱⁱ	0.86	1.93	2.685 (8)	146.0

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

Experimental details

Crystal data
Chemical formula	[Co(C₆H₆N₄)₃]HPO₄
M_r	557.35
Crystal system, space group	Monoclinic, Cc
Temperature (K)	293
a, b, c (Å)	12.700 (3), 21.447 (4), 9.1140 (18)
β (°)	95.84 (3)
V (Å³)	2469.6 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.81
Crystal size (mm)	0.2 × 0.17 × 0.15

Data collection
Diffractometer	Rigaku R-AXIS RAPID-S
Absorption correction	Multi-scan (CrystalClear; Rigaku/MSC, 2002)
T_min, T_max	0.850, 0.886
No. of measured, independent and observed [I > 2σ(I)] reflections	12597, 5593, 3373
R_int	0.098
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.077, 0.152, 1.06
No. of reflections	5593
No. of parameters	325
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.40, −0.32
Absolute structure	Flack (1983), 2755 Friedel pairs
Absolute structure parameter	−0.02 (2)

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O4	0.86	1.82	2.678 (7)	172.1
N4—H4···O2	0.86	1.87	2.717 (7)	168.3
N6—H6A···O3ⁱ	0.86	1.96	2.725 (8)	148.3
N8—H8···O3ⁱ	0.86	1.89	2.669 (8)	149.3
N10—H10···O2ⁱⁱ	0.86	2.23	2.887 (7)	133.7
N10—H10···O4ⁱⁱⁱ	0.86	2.39	3.034 (9)	132.5
N12—H12A···O4ⁱⁱⁱ	0.86	1.93	2.685 (8)	146.0

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

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 21001052 and 21101047), the Natural Science Foundation of Hainan Province (No. 211010) and the Priming Scientific Research Foundation of Hainan University (No. kyqd1051).

References

Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Pan, Q. H., Cheng, Q. & Bu, X.-H. (2010b). CrystEngComm, 12, 4198–4204. Web of Science CSD CrossRef CAS Google Scholar
Pan, Q. H., Cheng, Q. & Bu, X.-H. (2011). Chem. J. Chin. Univ. 32, 527–531. CAS Google Scholar
Pan, Q. H., Li, J. Y. & Bu, X.-H. (2010a). Micropor. Mesopor. Mater. 132, 453–457. Web of Science CSD CrossRef CAS Google Scholar
Pan, Q. H., Yu, J. H. & Xu, R. R. (2005). Chem. J. Chin. Univ. 26, 2199–2202. CAS Google Scholar
Pan, Q. H., Yu, J. H. & Xu, R. R. (2008). Chem. Mater. 20, 370–372. Web of Science CSD CrossRef CAS Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructureand CrystalClear. Rigaku/MSC Inc., USA. Google Scholar
Rothammel, W., Spengler, R., Burzlaff, H., Jarraya, S. & Ben Salah, A. (1998). Acta Cryst. C54, IUC9800059. CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stalder, S. M. & Wilkinson, A. P. (1997). Chem. Mater. 9, 2168–2173. CSD CrossRef CAS Web of Science Google Scholar
Tong, J. & Pan, Q. (2011). Acta Cryst. E67, m579–m580. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Wang, Y., Yu, J. H. & Xu, R. R. (2003a). Angew. Chem. Int. Ed. 42, 4089–4092. Web of Science CSD CrossRef CAS Google Scholar
Wang, Y., Yu, J. H. & Xu, R. R. (2003b). Chem. Eur. J. 9, 5048–5055. Web of Science CSD CrossRef PubMed CAS Google Scholar