[Diphenyldi(pyrazol-1-yl)methane]­dinitratocobalt(II)

Shaw, J.L.; Noll, B.C.

doi:10.1107/S1600536810000565

metal-organic compounds

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Volume 66| Part 2| February 2010| Page m140

https://doi.org/10.1107/S1600536810000565

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[Diphenyldi(pyrazol-1-yl)methane]dinitratocobalt(II)

Janet L. Shaw ^a ^* and Bruce C. Noll ^b

^aKennesaw State University, 1000 Chastain Road, Kennesaw, GA 30144-5591, USA, and ^bBruker AXS Inc., 5465 East Cheryl Parkway, Madison, WI 53711, USA
^*Correspondence e-mail: jshaw22@kennesaw.edu

(Received 24 November 2009; accepted 5 January 2010; online 13 January 2010)

In the title compound, [Co(NO₃)₂(C₁₉H₁₆N₄)], the diphenyldipyrazolylmethane ligand coordinates to Co^II in a bidentate fashion forming a six-membered ring with an approximate boat configuration. The mean planes of the two pyrazolyl rings are separated by an angle of 39.6 (2)°. The coordination at the Co^II center is best described as distorted octahedral with two NO₃⁻ anions serving as bidentate ligands for charge balance. The dihedral angle between the mean planes of the two nitrate rings is 85.0 (1)° and that between the mean planes of the two phenyl rings is 73.7 (1)°. The crystal structure is stabilized by weak intermolecular C—H⋯O and intramolecular C—H⋯N hydrogen-bond interactions.

Related literature

For related structures incorporating diphenyldipyrazolylmethane ligands, see: Shiu et al. (1993 ); Tsuji et al. (1999 ); Reger et al. (2004 ); Shaw et al. (2004 , 2005 , 2009 ); Baho & Zargarian (2007a ,b ).

Experimental

Crystal data

[Co(NO₃)₂(C₁₉H₁₆N₄)]
M_r = 483.31
Monoclinic, P 2₁ /n
a = 8.5476 (14) Å
b = 14.8058 (17) Å
c = 16.818 (3) Å
β = 103.383 (4)°
V = 2070.6 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.88 mm⁻¹
T = 200 K
0.50 × 0.30 × 0.30 mm

Data collection

Bruker SMART X2S benchtop diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ) T_min = 0.668, T_max = 0.778
13223 measured reflections
3666 independent reflections
3042 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.118
S = 0.96
3666 reflections
289 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.45 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17⋯O5ⁱ	0.93	2.54	3.413 (3)	157
C10—H10⋯O3ⁱⁱ	0.93	2.59	3.399 (4)	146
C3—H3⋯O4ⁱⁱⁱ	0.93	2.50	3.313 (3)	146
C19—H19⋯N1	0.93	2.46	2.799 (3)	102
Symmetry codes: (i) $[-x+{\script{5\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2009 ); cell refinement: APEX2 and SAINT (Bruker, 2009); data reduction: SAINT and XPREP (Bruker, 2008 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810000565/jj2017sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810000565/jj2017Isup2.hkl

checkCIF report

Comment top

The metal chemistry of diphenyldipyrazolylmethane ligands was first explored by Shiu et al. (1993) who crystallized two complexes of the 3,5-dimethylpyrazolyl variant with molybdenum. Similar complexes with Pd^II were synthesized by Tsuji et al. (1999) and Reger et al. (2004) who generated complexes with Ag^I . More recently, compounds with diphenyldipyrazolylmethane ligands complexed with Cu^I/II (Shaw et al. 2004;2005), Ni^II (Baho & Zargarian, 2007a; 2007b), and Zn^II (Shaw et al. 2009) have appeared in the literature.

In the title compound, Co(C₁₉H₁₆N₄)(NO₃)₂, the diphenyldipyrazolylmethane ligand coordinates to the Co^II in a bidentate fashion forming a six-membered ring with an approximate boat configuration (Fig. 1). The mean planes of the two pyrazolyl rings are separated by 39.55 (12)°. The geometry at the Co^II is best described as a distorted octahedral with two NO₃^- anions serving as bidentate ligands for charge balance. The N2 and N4 atoms are the bidentate groups that form a heteroscorpionate type structure coordinated to a d²sp³ hybridized Co^IIion. The dihedral angle between the mean planes of the two nitrato rings is 84.52 (10)° and between the mean planes of the two phenyl rings is 73.71 (6)°. The crystal structure is stabilized by weak intermolecular C—H···O and intramolecular C—H···N hydrogen bond interactions (Fig. 2; Table 1).

Related literature top

For related structures incorporating diphenyldipyrazolylmethane ligands, see: Shiu et al. (1993); Tsuji et al. (1999); Reger et al. (2004); Shaw et al. (2004, 2005, 2009); Baho & Zargarian (2007a,b).

Experimental top

The title compound was prepared by reacting cobalt(II) nitrate hexahydrate (1.64 mmoles) with diphenyldipyrazolylmethane (1.97 mmoles) in ethanol (100 ml). After 24 h of stirring, the solution was evaporated under reduced pressure to afford a red solid. Crystals were isolated by redissolving the solid in dichloromethane and layering with hexanes.

Structure description top

For related structures incorporating diphenyldipyrazolylmethane ligands, see: Shiu et al. (1993); Tsuji et al. (1999); Reger et al. (2004); Shaw et al. (2004, 2005, 2009); Baho & Zargarian (2007a,b).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: APEX2 and SAINT (Bruker, 2008); data reduction: SAINT and XPREP (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

	Fig. 1. The molecular structure of Co(C₁₉H₁₆N₄)(NO₃)₂ with 50% thermal ellipsoids. Hydrogen atoms have been omitted for clarity.
	Fig. 2. The packing diagram for Co(C₁₉H₁₆N₄)(NO₃)₂ viewed along the a axis. Dashed lines indicate weak C—H···O intermolecular hydrogen bond interactions.

[Diphenyldi(pyrazol-1-yl)methane]dinitratocobalt(II) top

Crystal data top

[Co(NO₃)₂(C₁₉H₁₆N₄)]	F(000) = 988
M_r = 483.31	D_x = 1.550 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5780 reflections
a = 8.5476 (14) Å	θ = 2.5–24.7°
b = 14.8058 (17) Å	µ = 0.88 mm⁻¹
c = 16.818 (3) Å	T = 200 K
β = 103.383 (4)°	Block, red
V = 2070.6 (5) Å³	0.50 × 0.30 × 0.30 mm
Z = 4

Data collection top

Bruker SMART X2S benchtop diffractometer	3666 independent reflections
Radiation source: microfocus sealed tube	3042 reflections with I > 2σ(I)
Doubly curved silicon crystal monochromator	R_int = 0.035
ω scans	θ_max = 25.1°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	h = −10→10
T_min = 0.668, T_max = 0.778	k = −13→17
13223 measured reflections	l = −19→19

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 0.96	w = 1/[σ²(F_o²) + (0.0648P)² + 0.2696P] where P = (F_o² + 2F_c²)/3
3666 reflections	(Δ/σ)_max = 0.001
289 parameters	Δρ_max = 0.42 e Å⁻³
0 restraints	Δρ_min = −0.45 e Å⁻³

Crystal data top

[Co(NO₃)₂(C₁₉H₁₆N₄)]	V = 2070.6 (5) Å³
M_r = 483.31	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.5476 (14) Å	µ = 0.88 mm⁻¹
b = 14.8058 (17) Å	T = 200 K
c = 16.818 (3) Å	0.50 × 0.30 × 0.30 mm
β = 103.383 (4)°

Data collection top

Bruker SMART X2S benchtop diffractometer	3666 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a)	3042 reflections with I > 2σ(I)
T_min = 0.668, T_max = 0.778	R_int = 0.035
13223 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 0.96	Δρ_max = 0.42 e Å⁻³
3666 reflections	Δρ_min = −0.45 e Å⁻³
289 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	1.03355 (4)	0.17196 (2)	0.34055 (2)	0.02457 (16)
N1	0.7926 (2)	0.22829 (13)	0.18460 (12)	0.0213 (5)
N2	0.9396 (3)	0.24461 (14)	0.23606 (13)	0.0235 (5)
N3	0.6768 (2)	0.14506 (15)	0.28100 (13)	0.0237 (5)
N4	0.8088 (2)	0.13421 (15)	0.34433 (13)	0.0265 (5)
C1	1.0006 (3)	0.31437 (17)	0.20321 (17)	0.0291 (6)
H1	1.0991	0.3413	0.2258	0.035*
C2	0.8968 (4)	0.34157 (18)	0.13031 (18)	0.0318 (6)
H2	0.9123	0.3885	0.0961	0.038*
C3	0.7677 (3)	0.28493 (17)	0.11973 (16)	0.0278 (6)
H3	0.6786	0.2852	0.0758	0.033*
C4	0.7511 (3)	0.1164 (2)	0.40996 (17)	0.0337 (7)
H4	0.8141	0.1070	0.4623	0.040*
C5	0.5849 (4)	0.1140 (2)	0.38961 (18)	0.0393 (7)
H5	0.5170	0.1029	0.4244	0.047*
C6	0.5413 (3)	0.1313 (2)	0.30753 (17)	0.0311 (6)
H6	0.4368	0.1331	0.2757	0.037*
C7	0.6991 (3)	0.14624 (17)	0.19537 (15)	0.0220 (5)
C8	0.5318 (3)	0.15306 (17)	0.13787 (15)	0.0229 (6)
C9	0.4379 (3)	0.22968 (18)	0.14071 (17)	0.0292 (6)
H9	0.4780	0.2764	0.1766	0.035*
C10	0.2851 (3)	0.23643 (19)	0.09023 (16)	0.0316 (6)
H10	0.2225	0.2874	0.0923	0.038*
C11	0.2264 (3)	0.16684 (19)	0.03673 (18)	0.0325 (7)
H11	0.1240	0.1710	0.0027	0.039*
C12	0.3187 (3)	0.0916 (2)	0.03361 (17)	0.0329 (6)
H12	0.2783	0.0450	−0.0023	0.039*
C13	0.4716 (3)	0.08490 (18)	0.08371 (16)	0.0267 (6)
H13	0.5339	0.0341	0.0808	0.032*
C14	0.7942 (3)	0.06191 (17)	0.18337 (15)	0.0212 (5)
C15	0.7524 (3)	−0.02053 (18)	0.21221 (17)	0.0288 (6)
H15	0.6694	−0.0235	0.2394	0.035*
C16	0.8343 (3)	−0.09812 (19)	0.20048 (18)	0.0356 (7)
H16	0.8047	−0.1533	0.2190	0.043*
C17	0.9592 (3)	−0.0945 (2)	0.16159 (16)	0.0314 (7)
H17	1.0155	−0.1466	0.1550	0.038*
C18	1.0000 (3)	−0.01311 (18)	0.13258 (16)	0.0291 (6)
H18	1.0840	−0.0105	0.1061	0.035*
C19	0.9174 (3)	0.06503 (17)	0.14234 (15)	0.0248 (6)
H19	0.9445	0.1195	0.1214	0.030*
N5	1.2003 (3)	0.03089 (17)	0.38553 (19)	0.0432 (7)
O1	1.1748 (2)	0.06871 (14)	0.31497 (13)	0.0377 (5)
O2	1.1390 (3)	0.07016 (16)	0.43733 (14)	0.0486 (6)
O3	1.2805 (3)	−0.03780 (16)	0.4002 (2)	0.0696 (8)
N6	1.1981 (3)	0.29851 (17)	0.42180 (14)	0.0350 (6)
O4	1.0646 (2)	0.26855 (14)	0.43302 (12)	0.0370 (5)
O5	1.2473 (2)	0.26008 (14)	0.36490 (13)	0.0382 (5)
O6	1.2721 (3)	0.35837 (17)	0.46355 (14)	0.0579 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Co1	0.0188 (2)	0.0290 (3)	0.0254 (2)	−0.00224 (13)	0.00403 (16)	−0.00001 (14)
N1	0.0205 (11)	0.0212 (11)	0.0222 (11)	−0.0004 (8)	0.0047 (9)	−0.0017 (8)
N2	0.0210 (11)	0.0229 (11)	0.0272 (11)	−0.0030 (9)	0.0067 (9)	−0.0025 (9)
N3	0.0207 (11)	0.0298 (11)	0.0210 (11)	−0.0023 (9)	0.0058 (9)	−0.0030 (9)
N4	0.0220 (11)	0.0344 (12)	0.0223 (11)	−0.0030 (10)	0.0032 (9)	−0.0003 (9)
C1	0.0282 (15)	0.0282 (14)	0.0326 (15)	−0.0059 (11)	0.0102 (12)	−0.0035 (11)
C2	0.0368 (16)	0.0267 (14)	0.0337 (16)	−0.0023 (12)	0.0123 (13)	0.0057 (12)
C3	0.0329 (15)	0.0267 (14)	0.0240 (14)	0.0036 (11)	0.0072 (12)	0.0009 (11)
C4	0.0313 (15)	0.0478 (18)	0.0224 (14)	−0.0073 (13)	0.0076 (12)	−0.0004 (12)
C5	0.0329 (16)	0.059 (2)	0.0305 (16)	−0.0096 (15)	0.0170 (13)	−0.0008 (14)
C6	0.0218 (14)	0.0407 (16)	0.0330 (15)	−0.0029 (12)	0.0109 (12)	−0.0035 (13)
C7	0.0207 (13)	0.0245 (13)	0.0209 (13)	−0.0034 (10)	0.0048 (10)	−0.0021 (10)
C8	0.0206 (13)	0.0260 (13)	0.0228 (13)	0.0004 (10)	0.0065 (11)	0.0006 (10)
C9	0.0270 (14)	0.0292 (15)	0.0316 (15)	0.0006 (11)	0.0070 (12)	−0.0032 (11)
C10	0.0240 (14)	0.0357 (15)	0.0358 (16)	0.0083 (12)	0.0081 (12)	0.0009 (12)
C11	0.0221 (14)	0.0448 (18)	0.0289 (15)	−0.0013 (12)	0.0025 (12)	0.0013 (12)
C12	0.0291 (15)	0.0357 (16)	0.0319 (15)	−0.0050 (12)	0.0029 (12)	−0.0092 (12)
C13	0.0264 (14)	0.0253 (13)	0.0280 (14)	0.0016 (11)	0.0054 (11)	−0.0025 (11)
C14	0.0193 (12)	0.0233 (13)	0.0206 (12)	0.0001 (10)	0.0035 (10)	−0.0017 (10)
C15	0.0274 (14)	0.0293 (15)	0.0311 (15)	0.0018 (11)	0.0100 (12)	0.0050 (11)
C16	0.0411 (17)	0.0235 (14)	0.0426 (17)	0.0040 (12)	0.0106 (14)	0.0090 (12)
C17	0.0324 (15)	0.0278 (15)	0.0314 (15)	0.0090 (11)	0.0022 (13)	−0.0019 (11)
C18	0.0241 (13)	0.0350 (15)	0.0291 (14)	0.0019 (11)	0.0082 (12)	−0.0069 (12)
C19	0.0257 (13)	0.0238 (13)	0.0247 (13)	−0.0027 (11)	0.0055 (11)	−0.0012 (10)
N5	0.0272 (13)	0.0356 (14)	0.0631 (19)	−0.0012 (11)	0.0030 (13)	0.0115 (13)
O1	0.0304 (11)	0.0371 (11)	0.0450 (12)	0.0022 (9)	0.0073 (9)	−0.0004 (10)
O2	0.0457 (13)	0.0550 (14)	0.0452 (13)	0.0062 (11)	0.0108 (11)	0.0152 (11)
O3	0.0546 (16)	0.0409 (14)	0.112 (2)	0.0174 (12)	0.0161 (16)	0.0256 (14)
N6	0.0356 (14)	0.0373 (14)	0.0293 (13)	−0.0105 (11)	0.0020 (11)	−0.0006 (11)
O4	0.0335 (11)	0.0477 (12)	0.0304 (11)	−0.0102 (9)	0.0087 (9)	−0.0085 (9)
O5	0.0325 (11)	0.0439 (12)	0.0383 (12)	−0.0100 (9)	0.0081 (9)	−0.0036 (9)
O6	0.0704 (17)	0.0561 (14)	0.0429 (13)	−0.0357 (13)	0.0045 (12)	−0.0139 (11)

Geometric parameters (Å, º) top

Co1—N4	2.015 (2)	C8—C9	1.397 (4)
Co1—O1	2.054 (2)	C9—C10	1.387 (4)
Co1—N2	2.058 (2)	C9—H9	0.9300
Co1—O4	2.0841 (19)	C10—C11	1.383 (4)
Co1—O5	2.205 (2)	C10—H10	0.9300
Co1—O2	2.248 (2)	C11—C12	1.372 (4)
N1—C3	1.353 (3)	C11—H11	0.9300
N1—N2	1.372 (3)	C12—C13	1.385 (4)
N1—C7	1.488 (3)	C12—H12	0.9300
N2—C1	1.333 (3)	C13—H13	0.9300
N3—C6	1.350 (3)	C14—C19	1.387 (3)
N3—N4	1.370 (3)	C14—C15	1.390 (4)
N3—C7	1.496 (3)	C15—C16	1.383 (4)
N4—C4	1.335 (3)	C15—H15	0.9300
C1—C2	1.396 (4)	C16—C17	1.376 (4)
C1—H1	0.9300	C16—H16	0.9300
C2—C3	1.364 (4)	C17—C18	1.375 (4)
C2—H2	0.9300	C17—H17	0.9300
C3—H3	0.9300	C18—C19	1.385 (4)
C4—C5	1.382 (4)	C18—H18	0.9300
C4—H4	0.9300	C19—H19	0.9300
C5—C6	1.368 (4)	N5—O3	1.219 (3)
C5—H5	0.9300	N5—O2	1.258 (4)
C6—H6	0.9300	N5—O1	1.284 (3)
C7—C14	1.528 (3)	N6—O6	1.214 (3)
C7—C8	1.533 (3)	N6—O5	1.266 (3)
C8—C13	1.377 (4)	N6—O4	1.278 (3)

N4—Co1—O1	114.25 (9)	N3—C7—C8	107.4 (2)
N4—Co1—N2	89.17 (9)	C14—C7—C8	114.7 (2)
O1—Co1—N2	110.01 (8)	C13—C8—C9	119.2 (2)
N4—Co1—O4	97.15 (8)	C13—C8—C7	121.4 (2)
O1—Co1—O4	133.44 (8)	C9—C8—C7	119.4 (2)
N2—Co1—O4	103.62 (8)	C10—C9—C8	120.3 (2)
N4—Co1—O5	155.92 (9)	C10—C9—H9	119.8
O1—Co1—O5	88.71 (8)	C8—C9—H9	119.8
N2—Co1—O5	89.55 (8)	C11—C10—C9	119.5 (3)
O4—Co1—O5	59.90 (8)	C11—C10—H10	120.2
N4—Co1—O2	90.96 (9)	C9—C10—H10	120.2
O1—Co1—O2	59.74 (9)	C12—C11—C10	120.3 (3)
N2—Co1—O2	168.60 (9)	C12—C11—H11	119.9
O4—Co1—O2	87.67 (9)	C10—C11—H11	119.9
O5—Co1—O2	94.93 (8)	C11—C12—C13	120.3 (3)
C3—N1—N2	110.5 (2)	C11—C12—H12	119.8
C3—N1—C7	128.0 (2)	C13—C12—H12	119.8
N2—N1—C7	120.40 (19)	C8—C13—C12	120.3 (2)
C1—N2—N1	105.3 (2)	C8—C13—H13	119.8
C1—N2—Co1	130.24 (18)	C12—C13—H13	119.8
N1—N2—Co1	124.46 (15)	C19—C14—C15	119.3 (2)
C6—N3—N4	109.9 (2)	C19—C14—C7	121.8 (2)
C6—N3—C7	129.1 (2)	C15—C14—C7	118.9 (2)
N4—N3—C7	119.0 (2)	C16—C15—C14	120.0 (2)
C4—N4—N3	105.7 (2)	C16—C15—H15	120.0
C4—N4—Co1	128.17 (18)	C14—C15—H15	120.0
N3—N4—Co1	124.22 (16)	C17—C16—C15	120.6 (3)
N2—C1—C2	110.9 (2)	C17—C16—H16	119.7
N2—C1—H1	124.5	C15—C16—H16	119.7
C2—C1—H1	124.5	C18—C17—C16	119.4 (2)
C3—C2—C1	105.5 (2)	C18—C17—H17	120.3
C3—C2—H2	127.2	C16—C17—H17	120.3
C1—C2—H2	127.2	C17—C18—C19	120.8 (2)
N1—C3—C2	107.7 (2)	C17—C18—H18	119.6
N1—C3—H3	126.1	C19—C18—H18	119.6
C2—C3—H3	126.1	C18—C19—C14	119.9 (2)
N4—C4—C5	110.8 (2)	C18—C19—H19	120.1
N4—C4—H4	124.6	C14—C19—H19	120.1
C5—C4—H4	124.6	O3—N5—O2	123.3 (3)
C6—C5—C4	105.6 (3)	O3—N5—O1	121.2 (3)
C6—C5—H5	127.2	O2—N5—O1	115.4 (2)
C4—C5—H5	127.2	N5—O1—Co1	96.51 (17)
N3—C6—C5	107.9 (2)	N5—O2—Co1	88.28 (16)
N3—C6—H6	126.0	O6—N6—O5	123.1 (3)
C5—C6—H6	126.0	O6—N6—O4	122.1 (3)
N1—C7—N3	108.57 (19)	O5—N6—O4	114.8 (2)
N1—C7—C14	109.52 (19)	N6—O4—Co1	95.26 (15)
N3—C7—C14	107.9 (2)	N6—O5—Co1	90.03 (15)
N1—C7—C8	108.6 (2)

C3—N1—N2—C1	2.5 (3)	C14—C7—C8—C13	3.7 (4)
C7—N1—N2—C1	171.1 (2)	N1—C7—C8—C9	−53.9 (3)
C3—N1—N2—Co1	−177.56 (16)	N3—C7—C8—C9	63.3 (3)
C7—N1—N2—Co1	−8.9 (3)	C14—C7—C8—C9	−176.7 (2)
N4—Co1—N2—C1	157.3 (2)	C13—C8—C9—C10	0.8 (4)
O1—Co1—N2—C1	−87.1 (2)	C7—C8—C9—C10	−178.8 (2)
O4—Co1—N2—C1	60.2 (2)	C8—C9—C10—C11	−0.3 (4)
O5—Co1—N2—C1	1.4 (2)	C9—C10—C11—C12	0.0 (4)
O2—Co1—N2—C1	−111.9 (4)	C10—C11—C12—C13	−0.3 (4)
N4—Co1—N2—N1	−22.63 (19)	C9—C8—C13—C12	−1.0 (4)
O1—Co1—N2—N1	92.95 (19)	C7—C8—C13—C12	178.6 (2)
O4—Co1—N2—N1	−119.78 (18)	C11—C12—C13—C8	0.8 (4)
O5—Co1—N2—N1	−178.58 (19)	N1—C7—C14—C19	−19.7 (3)
O2—Co1—N2—N1	68.1 (5)	N3—C7—C14—C19	−137.7 (2)
C6—N3—N4—C4	−1.9 (3)	C8—C7—C14—C19	102.6 (3)
C7—N3—N4—C4	−167.1 (2)	N1—C7—C14—C15	162.4 (2)
C6—N3—N4—Co1	−167.12 (19)	N3—C7—C14—C15	44.4 (3)
C7—N3—N4—Co1	27.7 (3)	C8—C7—C14—C15	−75.3 (3)
O1—Co1—N4—C4	99.7 (3)	C19—C14—C15—C16	0.5 (4)
N2—Co1—N4—C4	−148.7 (3)	C7—C14—C15—C16	178.6 (2)
O4—Co1—N4—C4	−45.1 (3)	C14—C15—C16—C17	1.1 (4)
O5—Co1—N4—C4	−61.7 (3)	C15—C16—C17—C18	−1.5 (4)
O2—Co1—N4—C4	42.7 (3)	C16—C17—C18—C19	0.3 (4)
O1—Co1—N4—N3	−98.5 (2)	C17—C18—C19—C14	1.4 (4)
N2—Co1—N4—N3	13.1 (2)	C15—C14—C19—C18	−1.8 (4)
O4—Co1—N4—N3	116.75 (19)	C7—C14—C19—C18	−179.7 (2)
O5—Co1—N4—N3	100.1 (3)	O3—N5—O1—Co1	178.8 (2)
O2—Co1—N4—N3	−155.5 (2)	O2—N5—O1—Co1	−2.1 (3)
N1—N2—C1—C2	−1.5 (3)	N4—Co1—O1—N5	−74.82 (17)
Co1—N2—C1—C2	178.50 (18)	N2—Co1—O1—N5	−173.28 (15)
N2—C1—C2—C3	0.1 (3)	O4—Co1—O1—N5	53.1 (2)
N2—N1—C3—C2	−2.5 (3)	O5—Co1—O1—N5	97.67 (16)
C7—N1—C3—C2	−170.1 (2)	O2—Co1—O1—N5	1.20 (15)
C1—C2—C3—N1	1.4 (3)	O3—N5—O2—Co1	−179.0 (3)
N3—N4—C4—C5	1.1 (3)	O1—N5—O2—Co1	1.9 (2)
Co1—N4—C4—C5	165.6 (2)	N4—Co1—O2—N5	116.54 (17)
N4—C4—C5—C6	0.0 (4)	O1—Co1—O2—N5	−1.22 (15)
N4—N3—C6—C5	1.9 (3)	N2—Co1—O2—N5	26.0 (5)
C7—N3—C6—C5	165.2 (3)	O4—Co1—O2—N5	−146.35 (17)
C4—C5—C6—N3	−1.1 (3)	O5—Co1—O2—N5	−86.83 (17)
C3—N1—C7—N3	−138.1 (2)	O6—N6—O4—Co1	−178.9 (3)
N2—N1—C7—N3	55.4 (3)	O5—N6—O4—Co1	0.1 (2)
C3—N1—C7—C14	104.3 (3)	N4—Co1—O4—N6	−172.34 (16)
N2—N1—C7—C14	−62.2 (3)	O1—Co1—O4—N6	54.13 (19)
C3—N1—C7—C8	−21.6 (3)	N2—Co1—O4—N6	−81.46 (17)
N2—N1—C7—C8	171.9 (2)	O5—Co1—O4—N6	−0.08 (14)
C6—N3—C7—N1	131.7 (3)	O2—Co1—O4—N6	96.98 (16)
N4—N3—C7—N1	−66.4 (3)	O6—N6—O5—Co1	178.9 (3)
C6—N3—C7—C14	−109.7 (3)	O4—N6—O5—Co1	−0.1 (2)
N4—N3—C7—C14	52.3 (3)	N4—Co1—O5—N6	19.2 (3)
C6—N3—C7—C8	14.4 (4)	O1—Co1—O5—N6	−143.82 (16)
N4—N3—C7—C8	176.4 (2)	N2—Co1—O5—N6	106.16 (16)
N1—C7—C8—C13	126.5 (2)	O4—Co1—O5—N6	0.08 (14)
N3—C7—C8—C13	−116.3 (3)	O2—Co1—O5—N6	−84.34 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···O5ⁱ	0.93	2.54	3.413 (3)	157
C10—H10···O3ⁱⁱ	0.93	2.59	3.399 (4)	146
C3—H3···O4ⁱⁱⁱ	0.93	2.50	3.313 (3)	146
C19—H19···N1	0.93	2.46	2.799 (3)	102

Symmetry codes: (i) −x+5/2, y−1/2, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2; (iii) x−1/2, −y+1/2, z−1/2.

Experimental details

Crystal data
Chemical formula	[Co(NO₃)₂(C₁₉H₁₆N₄)]
M_r	483.31
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	200
a, b, c (Å)	8.5476 (14), 14.8058 (17), 16.818 (3)
β (°)	103.383 (4)
V (Å³)	2070.6 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.88
Crystal size (mm)	0.50 × 0.30 × 0.30

Data collection
Diffractometer	Bruker SMART X2S benchtop diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 2008a)
T_min, T_max	0.668, 0.778
No. of measured, independent and observed [I > 2σ(I)] reflections	13223, 3666, 3042
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.118, 0.96
No. of reflections	3666
No. of parameters	289
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.42, −0.45

Computer programs: APEX2 (Bruker, 2008), APEX2 and SAINT (Bruker, 2008), SAINT and XPREP (Bruker, 2008), SHELXS97 (Sheldrick, 2008b), SHELXL97 (Sheldrick, 2008b), SHELXTL (Sheldrick, 2008b), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···O5ⁱ	0.93	2.54	3.413 (3)	156.8
C10—H10···O3ⁱⁱ	0.93	2.59	3.399 (4)	145.5
C3—H3···O4ⁱⁱⁱ	0.93	2.50	3.313 (3)	145.7
C19—H19···N1	0.93	2.46	2.799 (3)	101.7

Symmetry codes: (i) −x+5/2, y−1/2, −z+1/2; (ii) −x+3/2, y+1/2, −z+1/2; (iii) x−1/2, −y+1/2, z−1/2.

References

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