(Picolinato-κ2N,O)[tris(2-isopropyl-1H-imidazol-4-yl-κN3)phosphane]cobalt(II) nitrate

Reiss, G.J.; Börgardts, M.; Kunz, P.C.

doi:10.1107/S1600536812004485

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 3| March 2012| Pages m265-m266

doi:10.1107/S1600536812004485

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(Picolinato-κ²N,O)[tris(2-isopropyl-1H-imidazol-4-yl-κN³)phosphane]cobalt(II) nitrate

Guido J. Reiss,^a Markus Börgardts ^b and Peter C. Kunz ^c ^*

^aInstitut für Anorganische Chemie und Strukturchemie, Lehrstuhl II: Material- und Strukturforschung, Heinrich-Heine-Universität Düsseldorf, Universitätsstrasse 1, D-40225 Düsseldorf, Germany, ^bInstitut für Anorganische Chemie und Strukturchemie, Lehrstuhl I: Bioanorganische Chemie, Heinrich-Heine-Universität Düsseldorf, Universitätsstrasse 1, D-40225 Düsseldorf, Germany, and ^cInstitut für Pharmazeutische und Medizinische Chemie, Heinrich-Heine-Universität Düsseldorf, Universitätsstrasse 1, D-40225 Düsseldorf, Germany
^*Correspondence e-mail: peter.kunz@uni-duesseldorf.de

(Received 25 January 2012; accepted 2 February 2012; online 10 February 2012)

Single crystals of the title compound, [Co(C₆H₄NO₂)(C₁₈H₂₇N₆P)]NO₃, were obtained from the reaction of nitrato[tris(2-isopropylimidazol-4-yl)phosphane]cobalt(II) nitrate with picolinic acid in the presence of potassium tert-butoxide as base. The coordination polyhedron around the central Co^II ion is about halfway between square-pyramidal and trigonal-bipyramidal geometry. In the structure, the nitrate counter-anion is connected by N—H⋯O hydrogen bonding to the complex cation. Additionally, the complex cations form one-dimensional chains along [010] by hydrogen bonding of the NH group of an imidazole ring to the picolinate group of a neighbouring complex cation.

Related literature

For the synthesis of the title compound, see: Kunz et al. (2011 ). For structures of related complexes, see: Tekeste & Vahrenkamp (2006 ); Kunz et al. (2011). For background to this class of compound, see: Kunz et al. (2003 , 2007 , 2008 , 2009 , 2011); Kunz & Kläui (2007 ). For geometric parameters of hydrogen bonding, see: Steiner (2002 ).

Experimental

Crystal data

[Co(C₆H₄NO₂)(C₁₈H₂₇N₆P)]NO₃
M_r = 601.47
Monoclinic, P 2₁ /c
a = 15.4012 (5) Å
b = 10.7035 (3) Å
c = 17.8548 (5) Å
β = 90.491 (3)°
V = 2943.21 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.68 mm⁻¹
T = 292 K
0.60 × 0.58 × 0.30 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: gaussian (CrysAlis PRO; Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ) T_min = 0.67, T_max = 0.82
12068 measured reflections
5760 independent reflections
4526 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.086
S = 1.01
5760 reflections
370 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Co1—O1	1.9885 (17)
Co1—N5	2.060 (2)
Co1—N3	2.070 (2)
Co1—N1	2.094 (2)
Co1—N7	2.154 (2)

O1—Co1—N5	118.91 (8)
O1—Co1—N3	139.21 (8)
N5—Co1—N3	100.43 (8)
O1—Co1—N1	101.22 (7)
N5—Co1—N1	90.61 (8)
N3—Co1—N1	87.87 (8)
O1—Co1—N7	78.07 (7)
N5—Co1—N7	92.77 (8)
N3—Co1—N7	90.45 (8)
N1—Co1—N7	176.45 (8)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H02⋯O2ⁱ	0.78 (3)	2.01 (3)	2.786 (3)	174 (3)
N4—H04⋯O3	0.82 (3)	1.98 (3)	2.791 (3)	169 (3)
Symmetry code: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England.]$ ); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2010 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812004485/nc2266sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812004485/nc2266Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812004485/nc2266Isup3.mol

checkCIF report

Comment top

Zinc complexes of tripodal N,N,N ligands are interesting model compounds for the active sites found in many zinc enzymes, e.g. carbonic anhydrase. We developed the tris[imidazolyl-4(5)-yl] phosphane ligands as water-stable and, depending on their substituents, water soluble N,N,N ligands (Kunz et al. 2003). Their zinc complexes display some esterase-like activity (Kunz& Kläui, 2007). Recently we investigated the coordination behavior of zinc(II) and cobalt(II) complexes of these ligands in the presence of different biologically relevant N,O ligands related to the Vahrenkamp-type complexes (Tekeste & Vahrenkamp, 2006). Cobalt(II) resembles in many points the structural coordination chemistry of zinc(II) and often is used to probe the coordination environment in corresponding complexes. UV/Vis data of the title compound indicated the presence of five-and six-coordinate Co(II)-species in solution (Kunz et al. 2011).

The molecular structure of the title compound is shown in Figure 1. The coordination polyhedron around the central cobalt(II) atom is about half way from square-pyramidal to trigonal-bipyramidal geometry. The deviation from the tbp geometry is due to the bite of the ligand which allows only for N—M—N angles of up to about 100°. The above mentioned similarity in the structural coordination behavior is shown here, too, as the title compound is isotopic to the corresponding zinc compound (Kunz et al., 2011). In the crystal structure of the title compound the molecules are connected via N–H···O hydrogen bonding between the N–H atoms of the imidazolyl substituents in the complex cation and the O-atom of the picolinato ligand of a neighboring complex cation (N2H02···O2', d = 2.786 (3) Å) as well as the O-atoms of nitrate ions (N4H04···O3, d = 2.791 (3) Å, Figure 2). According to these geometric parameters these hydrogen bonds may be classified as medium strong (Steiner, 2002).

Related literature top

For the synthesis of the title compound, see: Kunz et al. (2011). For structures of related complexes, see: Tekeste & Vahrenkamp (2006); Kunz et al. (2011). For background to this class of compound, see: Kunz et al. (2003, 2008, 2009, 2011); Kunz & Kläui (2007). For geometric parameters of hydrogen bonding, see: Steiner (2002).

Experimental top

The synthesis of the title compound was performed as previously reported (Kunz et al. 2011). The title compound was crystallized from methanol solution by slow vapor diffusion of diethyl ether to yield purple crystals.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The structure of the asymmetric unit, showing 40% probability displacement ellipsoids. Hydrogen bonding is shown as dashed lines. Hydrogen atoms are shown as spheres of arbitrary radius. Non-acidic hydrogen atoms are omitted for clarity.
	Fig. 2. Part of the hydrogen bonded chain (hydrogen bonding is shown as dashed lines, for clarity the isopropy groups are drawn as wires without hydrogen atoms; ' = 1 - x, 0.5 + y, 0.5 - z).

(Picolinato-κ²N,O)[Tris(2-isopropyl-1H-imidazol- 4-yl-κN³)phosphane]cobalt(II) nitrate top

Crystal data top

[Co(C₆H₄NO₂)(C₁₈H₂₇N₆P)]NO₃	F(000) = 1252
M_r = 601.47	D_x = 1.357 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 15.4012 (5) Å	Cell parameters from 6583 reflections
b = 10.7035 (3) Å	θ = 3.3–27.2°
c = 17.8548 (5) Å	µ = 0.68 mm⁻¹
β = 90.491 (3)°	T = 292 K
V = 2943.21 (15) Å³	Block, purple
Z = 4	0.60 × 0.58 × 0.30 mm

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	5760 independent reflections
Radiation source: fine-focus sealed tube	4526 reflections with I > 2σ(I)
Equatorial mounted graphite monochromator	R_int = 0.022
Detector resolution: 16.2711 pixels mm^-1	θ_max = 26.0°, θ_min = 3.3°
ω scans	h = −17→18
Absorption correction: gaussian (CrysAlis PRO; Oxford Diffraction, 2009)	k = −11→13
T_min = 0.67, T_max = 0.82	l = −22→10
12068 measured reflections

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ²(F_o²) + (0.017P)² + 2.8P] where P = (F_o² + 2F_c²)/3
5760 reflections	(Δ/σ)_max = 0.001
370 parameters	Δρ_max = 0.43 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

[Co(C₆H₄NO₂)(C₁₈H₂₇N₆P)]NO₃	V = 2943.21 (15) Å³
M_r = 601.47	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.4012 (5) Å	µ = 0.68 mm⁻¹
b = 10.7035 (3) Å	T = 292 K
c = 17.8548 (5) Å	0.60 × 0.58 × 0.30 mm
β = 90.491 (3)°

Data collection top

Oxford Diffraction Xcalibur Eos diffractometer	5760 independent reflections
Absorption correction: gaussian (CrysAlis PRO; Oxford Diffraction, 2009)	4526 reflections with I > 2σ(I)
T_min = 0.67, T_max = 0.82	R_int = 0.022
12068 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.43 e Å⁻³
5760 reflections	Δρ_min = −0.30 e Å⁻³
370 parameters

Special details top

Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.34.44. Numerical absorption correction based on gaussian integration over a multifaceted crystal model

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	0.29459 (2)	0.83916 (3)	0.173518 (18)	0.04257 (10)
P1	0.20777 (5)	0.62495 (7)	0.28876 (4)	0.05045 (18)
C1	0.32126 (16)	0.6636 (2)	0.30250 (13)	0.0456 (6)
C2	0.37830 (18)	0.6149 (3)	0.35249 (14)	0.0522 (6)
H2	0.3672	0.5519	0.3870	0.063*
C3	0.44493 (17)	0.7603 (2)	0.28778 (14)	0.0475 (6)
C4	0.21002 (17)	0.5951 (2)	0.18877 (14)	0.0486 (6)
C5	0.1718 (2)	0.5000 (3)	0.15108 (16)	0.0614 (8)
H5	0.1336	0.4413	0.1706	0.074*
C6	0.25358 (18)	0.6041 (2)	0.07286 (14)	0.0499 (6)
C7	0.16572 (16)	0.7822 (3)	0.29169 (14)	0.0473 (6)
C8	0.10861 (17)	0.8315 (3)	0.34061 (15)	0.0586 (7)
H8	0.0803	0.7891	0.3787	0.070*
C9	0.15266 (17)	0.9811 (3)	0.26536 (14)	0.0523 (7)
C10	0.51532 (18)	0.8439 (3)	0.26060 (17)	0.0617 (8)
H10	0.4884	0.9060	0.2275	0.074*
C11	0.5792 (3)	0.7712 (5)	0.2147 (3)	0.154 (2)
H11A	0.6242	0.8261	0.1978	0.230*
H11B	0.5499	0.7352	0.1722	0.230*
H11C	0.6042	0.7059	0.2448	0.230*
C12	0.5591 (3)	0.9134 (5)	0.3234 (2)	0.144 (2)
H12A	0.5165	0.9600	0.3508	0.215*
H12B	0.6014	0.9698	0.3033	0.215*
H12C	0.5873	0.8551	0.3564	0.215*
C13	0.3025 (2)	0.6388 (3)	0.00336 (15)	0.0616 (8)
H13	0.2719	0.7095	−0.0197	0.074*
C14	0.3928 (2)	0.6827 (4)	0.02242 (18)	0.0877 (11)
H14A	0.3897	0.7524	0.0561	0.131*
H14B	0.4218	0.7078	−0.0225	0.131*
H14C	0.4246	0.6160	0.0458	0.131*
C15	0.3043 (3)	0.5351 (4)	−0.05373 (19)	0.1029 (14)
H15A	0.2460	0.5140	−0.0682	0.154*
H15B	0.3323	0.4631	−0.0324	0.154*
H15C	0.3359	0.5622	−0.0969	0.154*
C16	0.1601 (2)	1.1072 (3)	0.23097 (16)	0.0653 (8)
H16	0.2069	1.1030	0.1942	0.078*
C17	0.1845 (3)	1.2070 (4)	0.2869 (2)	0.1028 (13)
H17A	0.2001	1.2820	0.2608	0.154*
H17B	0.2329	1.1790	0.3167	0.154*
H17C	0.1360	1.2235	0.3188	0.154*
C18	0.0780 (3)	1.1407 (4)	0.1889 (3)	0.153 (2)
H18A	0.0897	1.2079	0.1548	0.230*
H18B	0.0344	1.1664	0.2238	0.230*
H18C	0.0577	1.0693	0.1614	0.230*
C19	0.35434 (18)	1.0474 (3)	0.08976 (14)	0.0504 (6)
C20	0.26933 (16)	1.0186 (2)	0.05122 (13)	0.0442 (6)
C21	0.23571 (19)	1.0905 (3)	−0.00650 (15)	0.0582 (7)
H21	0.2653	1.1603	−0.0239	0.070*
C22	0.1571 (2)	1.0558 (3)	−0.03758 (16)	0.0654 (8)
H22	0.1327	1.1025	−0.0763	0.078*
C23	0.11511 (19)	0.9523 (3)	−0.01114 (16)	0.0616 (8)
H23	0.0626	0.9270	−0.0323	0.074*
C24	0.15199 (17)	0.8861 (3)	0.04739 (16)	0.0562 (7)
H24	0.1230	0.8166	0.0659	0.067*
N1	0.36426 (13)	0.75589 (19)	0.26150 (11)	0.0447 (5)
N2	0.45508 (17)	0.6754 (2)	0.34284 (13)	0.0542 (6)
H02	0.498 (2)	0.665 (3)	0.3653 (17)	0.072 (11)*
N3	0.26053 (13)	0.6614 (2)	0.13840 (11)	0.0471 (5)
N4	0.19990 (18)	0.5066 (2)	0.07917 (14)	0.0629 (7)
H04	0.180 (2)	0.459 (3)	0.0471 (18)	0.080 (11)*
N5	0.19332 (13)	0.8781 (2)	0.24447 (11)	0.0466 (5)
N6	0.10047 (17)	0.9546 (3)	0.32355 (14)	0.0627 (7)
H06	0.074 (2)	1.005 (3)	0.3463 (17)	0.069 (10)*
N7	0.22815 (13)	0.91894 (19)	0.07825 (11)	0.0462 (5)
O1	0.37455 (11)	0.97651 (17)	0.14465 (10)	0.0547 (5)
O2	0.39853 (14)	1.1354 (2)	0.06762 (11)	0.0740 (6)
N8	0.0460 (2)	0.3434 (3)	−0.03062 (17)	0.0736 (7)
O3	0.12255 (18)	0.3765 (3)	−0.03933 (13)	0.0974 (8)
O4	0.0256 (2)	0.3016 (3)	0.02838 (17)	0.1439 (13)
O5	−0.00042 (18)	0.3488 (4)	−0.08683 (19)	0.1316 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.04483 (19)	0.04102 (19)	0.04190 (19)	−0.00224 (15)	0.00195 (13)	0.00386 (15)
P1	0.0584 (4)	0.0487 (4)	0.0443 (4)	−0.0100 (3)	0.0062 (3)	0.0048 (3)
C1	0.0544 (15)	0.0421 (14)	0.0404 (13)	0.0009 (12)	0.0025 (11)	0.0017 (11)
C2	0.0661 (18)	0.0455 (15)	0.0449 (14)	0.0025 (13)	0.0016 (12)	0.0060 (12)
C3	0.0497 (15)	0.0473 (15)	0.0455 (14)	0.0059 (12)	−0.0001 (11)	0.0019 (12)
C4	0.0579 (16)	0.0415 (14)	0.0466 (14)	−0.0043 (12)	0.0002 (12)	0.0012 (12)
C5	0.077 (2)	0.0508 (17)	0.0564 (17)	−0.0144 (15)	−0.0013 (14)	0.0044 (14)
C6	0.0601 (17)	0.0444 (15)	0.0453 (14)	0.0030 (13)	−0.0022 (12)	0.0005 (12)
C7	0.0413 (14)	0.0550 (16)	0.0456 (14)	−0.0064 (12)	0.0029 (11)	−0.0024 (12)
C8	0.0525 (16)	0.071 (2)	0.0529 (16)	−0.0092 (15)	0.0122 (12)	−0.0059 (15)
C9	0.0507 (16)	0.0590 (18)	0.0472 (15)	0.0075 (13)	−0.0010 (12)	−0.0064 (13)
C10	0.0478 (16)	0.0689 (19)	0.0683 (18)	−0.0029 (15)	−0.0041 (13)	0.0156 (16)
C11	0.116 (4)	0.130 (4)	0.217 (6)	0.008 (3)	0.101 (4)	0.014 (4)
C12	0.167 (5)	0.162 (5)	0.102 (3)	−0.110 (4)	−0.026 (3)	0.020 (3)
C13	0.076 (2)	0.067 (2)	0.0425 (15)	0.0097 (16)	0.0039 (13)	0.0017 (14)
C14	0.095 (3)	0.106 (3)	0.063 (2)	−0.028 (2)	0.0185 (18)	0.003 (2)
C15	0.107 (3)	0.132 (4)	0.070 (2)	−0.022 (3)	0.023 (2)	−0.040 (2)
C16	0.081 (2)	0.0563 (18)	0.0585 (18)	0.0226 (16)	0.0032 (15)	0.0005 (15)
C17	0.145 (4)	0.075 (3)	0.088 (3)	−0.029 (3)	−0.002 (2)	0.002 (2)
C18	0.163 (5)	0.091 (3)	0.204 (6)	0.019 (3)	−0.103 (4)	0.029 (3)
C19	0.0590 (16)	0.0451 (15)	0.0471 (15)	−0.0083 (13)	−0.0044 (12)	0.0039 (12)
C20	0.0513 (15)	0.0415 (14)	0.0399 (13)	0.0001 (12)	−0.0026 (11)	−0.0012 (11)
C21	0.075 (2)	0.0512 (17)	0.0484 (15)	0.0011 (15)	−0.0081 (14)	0.0057 (13)
C22	0.080 (2)	0.064 (2)	0.0523 (17)	0.0168 (17)	−0.0187 (15)	−0.0038 (15)
C23	0.0559 (17)	0.0644 (19)	0.0642 (18)	0.0105 (15)	−0.0167 (14)	−0.0114 (16)
C24	0.0455 (15)	0.0574 (17)	0.0656 (18)	−0.0025 (13)	−0.0040 (13)	−0.0028 (14)
N1	0.0453 (12)	0.0437 (12)	0.0452 (12)	0.0005 (10)	0.0020 (9)	0.0035 (9)
N2	0.0565 (15)	0.0550 (15)	0.0509 (14)	0.0094 (12)	−0.0065 (11)	0.0029 (11)
N3	0.0567 (13)	0.0439 (12)	0.0407 (11)	−0.0043 (10)	0.0020 (9)	0.0015 (10)
N4	0.0872 (19)	0.0533 (15)	0.0480 (14)	−0.0117 (14)	−0.0090 (13)	−0.0062 (12)
N5	0.0450 (12)	0.0492 (13)	0.0454 (12)	0.0043 (10)	0.0003 (9)	0.0000 (10)
N6	0.0578 (15)	0.0702 (19)	0.0603 (16)	0.0101 (14)	0.0102 (12)	−0.0150 (14)
N7	0.0450 (12)	0.0448 (12)	0.0486 (12)	−0.0025 (10)	−0.0024 (9)	−0.0005 (10)
O1	0.0531 (11)	0.0569 (12)	0.0539 (11)	−0.0116 (9)	−0.0122 (8)	0.0139 (9)
O2	0.0810 (14)	0.0689 (14)	0.0719 (13)	−0.0335 (12)	−0.0195 (11)	0.0266 (11)
N8	0.083 (2)	0.0668 (18)	0.0713 (19)	−0.0104 (16)	0.0193 (16)	−0.0039 (15)
O3	0.112 (2)	0.114 (2)	0.0667 (15)	−0.0531 (17)	0.0027 (13)	−0.0108 (14)
O4	0.174 (3)	0.155 (3)	0.104 (2)	−0.012 (2)	0.077 (2)	0.032 (2)
O5	0.0838 (19)	0.191 (4)	0.120 (2)	−0.025 (2)	−0.0192 (18)	0.016 (2)

Geometric parameters (Å, º) top

Co1—O1	1.9885 (17)	C13—C14	1.505 (4)
Co1—N5	2.060 (2)	C13—C15	1.508 (4)
Co1—N3	2.070 (2)	C13—H13	0.9800
Co1—N1	2.094 (2)	C14—H14A	0.9600
Co1—N7	2.154 (2)	C14—H14B	0.9600
P1—C7	1.805 (3)	C14—H14C	0.9600
P1—C1	1.811 (3)	C15—H15A	0.9600
P1—C4	1.814 (3)	C15—H15B	0.9600
C1—C2	1.352 (3)	C15—H15C	0.9600
C1—N1	1.400 (3)	C16—C17	1.508 (4)
C2—N2	1.360 (4)	C16—C18	1.509 (5)
C2—H2	0.9300	C16—H16	0.9800
C3—N1	1.325 (3)	C17—H17A	0.9600
C3—N2	1.347 (3)	C17—H17B	0.9600
C3—C10	1.490 (4)	C17—H17C	0.9600
C4—C5	1.353 (4)	C18—H18A	0.9600
C4—N3	1.389 (3)	C18—H18B	0.9600
C5—N4	1.361 (4)	C18—H18C	0.9600
C5—H5	0.9300	C19—O2	1.229 (3)
C6—N3	1.324 (3)	C19—O1	1.276 (3)
C6—N4	1.337 (4)	C19—C20	1.506 (3)
C6—C13	1.504 (4)	C20—N7	1.334 (3)
C7—C8	1.352 (3)	C20—C21	1.383 (3)
C7—N5	1.397 (3)	C21—C22	1.378 (4)
C8—N6	1.358 (4)	C21—H21	0.9300
C8—H8	0.9300	C22—C23	1.368 (4)
C9—N5	1.323 (3)	C22—H22	0.9300
C9—N6	1.349 (3)	C23—C24	1.381 (4)
C9—C16	1.487 (4)	C23—H23	0.9300
C10—C12	1.501 (5)	C24—N7	1.338 (3)
C10—C11	1.502 (5)	C24—H24	0.9300
C10—H10	0.9800	N2—H02	0.78 (3)
C11—H11A	0.9600	N4—H04	0.82 (3)
C11—H11B	0.9600	N6—H06	0.79 (3)
C11—H11C	0.9600	N8—O4	1.189 (3)
C12—H12A	0.9600	N8—O5	1.229 (4)
C12—H12B	0.9600	N8—O3	1.242 (3)
C12—H12C	0.9600

O1—Co1—N5	118.91 (8)	H14B—C14—H14C	109.5
O1—Co1—N3	139.21 (8)	C13—C15—H15A	109.5
N5—Co1—N3	100.43 (8)	C13—C15—H15B	109.5
O1—Co1—N1	101.22 (7)	H15A—C15—H15B	109.5
N5—Co1—N1	90.61 (8)	C13—C15—H15C	109.5
N3—Co1—N1	87.87 (8)	H15A—C15—H15C	109.5
O1—Co1—N7	78.07 (7)	H15B—C15—H15C	109.5
N5—Co1—N7	92.77 (8)	C9—C16—C17	112.9 (3)
N3—Co1—N7	90.45 (8)	C9—C16—C18	110.8 (3)
N1—Co1—N7	176.45 (8)	C17—C16—C18	111.3 (3)
C7—P1—C1	97.42 (12)	C9—C16—H16	107.2
C7—P1—C4	101.68 (12)	C17—C16—H16	107.2
C1—P1—C4	98.45 (12)	C18—C16—H16	107.2
C2—C1—N1	108.1 (2)	C16—C17—H17A	109.5
C2—C1—P1	128.5 (2)	C16—C17—H17B	109.5
N1—C1—P1	123.43 (18)	H17A—C17—H17B	109.5
C1—C2—N2	107.1 (2)	C16—C17—H17C	109.5
C1—C2—H2	126.5	H17A—C17—H17C	109.5
N2—C2—H2	126.5	H17B—C17—H17C	109.5
N1—C3—N2	109.7 (2)	C16—C18—H18A	109.5
N1—C3—C10	126.1 (2)	C16—C18—H18B	109.5
N2—C3—C10	124.2 (2)	H18A—C18—H18B	109.5
C5—C4—N3	107.8 (2)	C16—C18—H18C	109.5
C5—C4—P1	127.6 (2)	H18A—C18—H18C	109.5
N3—C4—P1	124.27 (19)	H18B—C18—H18C	109.5
C4—C5—N4	106.8 (3)	O2—C19—O1	124.8 (2)
C4—C5—H5	126.6	O2—C19—C20	119.4 (2)
N4—C5—H5	126.6	O1—C19—C20	115.8 (2)
N3—C6—N4	109.4 (2)	N7—C20—C21	122.6 (2)
N3—C6—C13	125.3 (2)	N7—C20—C19	114.4 (2)
N4—C6—C13	125.2 (2)	C21—C20—C19	123.0 (2)
C8—C7—N5	107.8 (2)	C22—C21—C20	118.2 (3)
C8—C7—P1	128.2 (2)	C22—C21—H21	120.9
N5—C7—P1	123.83 (18)	C20—C21—H21	120.9
C7—C8—N6	107.0 (3)	C23—C22—C21	119.7 (3)
C7—C8—H8	126.5	C23—C22—H22	120.2
N6—C8—H8	126.5	C21—C22—H22	120.2
N5—C9—N6	109.2 (3)	C22—C23—C24	118.9 (3)
N5—C9—C16	127.0 (2)	C22—C23—H23	120.5
N6—C9—C16	123.8 (3)	C24—C23—H23	120.5
C3—C10—C12	112.2 (3)	N7—C24—C23	122.0 (3)
C3—C10—C11	110.4 (3)	N7—C24—H24	119.0
C12—C10—C11	111.9 (4)	C23—C24—H24	119.0
C3—C10—H10	107.4	C3—N1—C1	106.6 (2)
C12—C10—H10	107.4	C3—N1—Co1	136.34 (17)
C11—C10—H10	107.4	C1—N1—Co1	116.81 (16)
C10—C11—H11A	109.5	C3—N2—C2	108.5 (2)
C10—C11—H11B	109.5	C3—N2—H02	125 (2)
H11A—C11—H11B	109.5	C2—N2—H02	127 (2)
C10—C11—H11C	109.5	C6—N3—C4	107.1 (2)
H11A—C11—H11C	109.5	C6—N3—Co1	135.34 (18)
H11B—C11—H11C	109.5	C4—N3—Co1	114.51 (16)
C10—C12—H12A	109.5	C6—N4—C5	108.8 (2)
C10—C12—H12B	109.5	C6—N4—H04	131 (2)
H12A—C12—H12B	109.5	C5—N4—H04	120 (2)
C10—C12—H12C	109.5	C9—N5—C7	107.1 (2)
H12A—C12—H12C	109.5	C9—N5—Co1	134.80 (18)
H12B—C12—H12C	109.5	C7—N5—Co1	117.28 (16)
C6—C13—C14	111.1 (2)	C9—N6—C8	108.8 (3)
C6—C13—C15	112.9 (3)	C9—N6—H06	124 (2)
C14—C13—C15	111.1 (3)	C8—N6—H06	127 (2)
C6—C13—H13	107.2	C20—N7—C24	118.6 (2)
C14—C13—H13	107.2	C20—N7—Co1	112.25 (16)
C15—C13—H13	107.2	C24—N7—Co1	129.02 (18)
C13—C14—H14A	109.5	C19—O1—Co1	119.43 (16)
C13—C14—H14B	109.5	O4—N8—O5	125.8 (4)
H14A—C14—H14B	109.5	O4—N8—O3	118.5 (4)
C13—C14—H14C	109.5	O5—N8—O3	115.5 (3)
H14A—C14—H14C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H02···O2ⁱ	0.78 (3)	2.01 (3)	2.786 (3)	174 (3)
N4—H04···O3	0.82 (3)	1.98 (3)	2.791 (3)	169 (3)

Symmetry code: (i) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Co(C₆H₄NO₂)(C₁₈H₂₇N₆P)]NO₃
M_r	601.47
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	292
a, b, c (Å)	15.4012 (5), 10.7035 (3), 17.8548 (5)
β (°)	90.491 (3)
V (Å³)	2943.21 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.68
Crystal size (mm)	0.60 × 0.58 × 0.30

Data collection
Diffractometer	Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction	Gaussian (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.67, 0.82
No. of measured, independent and observed [I > 2σ(I)] reflections	12068, 5760, 4526
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.086, 1.01
No. of reflections	5760
No. of parameters	370
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.43, −0.30

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 2010), publCIF (Westrip, 2010).

Selected geometric parameters (Å, º) top

Co1—O1	1.9885 (17)	Co1—N1	2.094 (2)
Co1—N5	2.060 (2)	Co1—N7	2.154 (2)
Co1—N3	2.070 (2)

O1—Co1—N5	118.91 (8)	N3—Co1—N1	87.87 (8)
O1—Co1—N3	139.21 (8)	O1—Co1—N7	78.07 (7)
N5—Co1—N3	100.43 (8)	N5—Co1—N7	92.77 (8)
O1—Co1—N1	101.22 (7)	N3—Co1—N7	90.45 (8)
N5—Co1—N1	90.61 (8)	N1—Co1—N7	176.45 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H02···O2ⁱ	0.78 (3)	2.01 (3)	2.786 (3)	174 (3)
N4—H04···O3	0.82 (3)	1.98 (3)	2.791 (3)	169 (3)

Symmetry code: (i) −x+1, y−1/2, −z+1/2.

References

Brandenburg, K. (2010). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Kunz, P. C., Börgardts, M. & Mohr, F. (2011). Inorg. Chim. Acta, 380, 392–398. Web of Science CrossRef Google Scholar
Kunz, P. C., Huber, W., Rojas, A., Schatzschneider, U. & Spingler, B. (2009). Eur. J. Inorg. Chem. pp. 5358–5366. Web of Science CSD CrossRef Google Scholar
Kunz, P. C. & Kläui, W. (2007). Collect. Czech. Chem. Commun. 72, 492–502. Web of Science CrossRef CAS Google Scholar
Kunz, P. C., Reiss, G. J., Frank, W. & Kläui, W. (2003). Eur. J. Inorg. Chem. pp. 3945–3951. Web of Science CSD CrossRef Google Scholar
Kunz, P. C., Zribi, A., Frank, W. & Kläui, W. (2007). Z. Anorg. Allg. Chem. 633, 955–960. Web of Science CSD CrossRef CAS Google Scholar
Kunz, P. C., Zribi, A., Frank, W. & Kläui, W. (2008). Z. Anorg. Allg. Chem. 634, 724–729. Web of Science CSD CrossRef CAS Google Scholar
Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, Oxfordshire, England. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Steiner, T. (2002). Angew. Chem. Int. Ed. 41, 48–76. Web of Science CrossRef CAS Google Scholar
Tekeste, T. & Vahrenkamp, H. (2006). Eur. J. Inorg. Chem. pp. 5158–5164. Web of Science CSD CrossRef Google Scholar
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Volume 68| Part 3| March 2012| Pages m265-m266

doi:10.1107/S1600536812004485

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