Tris(2,2'-bi-1H-imidazole-κN,N)cobalt(II) hydrogen phosphate.

The title compound, [Co(C(6)H(6)N(4))(3)]HPO(4), was synthesized under hydro-thermal conditions. In the cation, the Co(II) atom is octa-hedrally 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]. Inter-molecular 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 = 557.35

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.077

wR(F 2) = 0.152

S = 1.06

5593 reflections

325 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.40 e Å−3

Δρmin = −0.32 e Å−3

Absolute structure: Flack (1983 ▶), 2755 Friedel pairs

Flack parameter: −0.02 (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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811037299/aa2021sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037299/aa2021Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Co(C6H6N4)3]HPO4	F(000) = 1140
Mr = 557.35	Dx = 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

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

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(Fo2) + (0.0453P)2] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max = 0.042
5593 reflections	Δρmax = 0.40 e Å−3
325 parameters	Δρmin = −0.32 e Å−3
2 restraints	Absolute structure: Flack (1983), 2755 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.02 (2)

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.

	x	y	z	Uiso*/Ueq
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*

	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)

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

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

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) ; (ii) ; (iii) .