Bis{2-[bis-(3,5-dimethyl-1H-pyrazol-1-yl-κN)meth-yl]pyridine-κN}copper(II) dinitrate.

In the mononuclear title complex, [Cu(C(16)H(19)N(5))(2)](NO(3))(2), the Cu(II) ion is located on a twofold rotation axis and is six-coordinated by six N atoms from two 2-[bis-(3,5-dimethyl-1H-pyrazol-1-yl)meth-yl]pyridine ligands, forming a distorted octa-hedral geometry. In the crystal, mol-ecules are linked by weak C-H⋯O inter-actions.

Related literature

For background to complexes based on rigid ligands containing pyrazole, see: Zhang et al. (2009 ▶); Otten et al. (2009 ▶); Arroyo et al. (2000 ▶); Morin et al. (2011 ▶). For the bioinorganic chemistry of cooper complexes, see: Turski & Thiele (2009 ▶); Finney et al. (2009 ▶); Tardito & Marchiò (2009 ▶).

Experimental

Crystal data

[Cu(C16H19N5)2](NO3)2

M = 750.28

Monoclinic,

a = 24.819 (6) Å

b = 10.918 (3) Å

c = 17.592 (4) Å

β = 132.348 (2)°

V = 3523.0 (14) Å3

Z = 4

Mo Kα radiation

μ = 0.68 mm−1

T = 296 K

0.23 × 0.22 × 0.16 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.859, T max = 0.899

12411 measured reflections

3266 independent reflections

2601 reflections with I > 2σ(I)

R int = 0.022

Refinement

R[F 2 > 2σ(F 2)] = 0.036

wR(F 2) = 0.104

S = 1.07

3266 reflections

235 parameters

H-atom parameters constrained

Δρmax = 0.37 e Å−3

Δρmin = −0.32 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; 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/S1600536811045636/ff2036sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811045636/ff2036Isup2.hkl

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

[Cu(C16H19N5)2](NO3)2	F(000) = 1564
Mr = 750.28	Dx = 1.415 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 4634 reflections
a = 24.819 (6) Å	θ = 2.2–25.8°
b = 10.918 (3) Å	µ = 0.68 mm−1
c = 17.592 (4) Å	T = 296 K
β = 132.348 (2)°	Block, blue
V = 3523.0 (14) Å3	0.23 × 0.22 × 0.16 mm
Z = 4

Bruker APEXII CCD diffractometer	3266 independent reflections
Radiation source: fine-focus sealed tube	2601 reflections with I > 2σ(I)
graphite	Rint = 0.022
φ and ω scans	θmax = 25.5°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −30→29
Tmin = 0.859, Tmax = 0.899	k = −13→13
12411 measured reflections	l = −20→21

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.104	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0412P)2 + 5.0393P] where P = (Fo2 + 2Fc2)/3
3266 reflections	(Δ/σ)max < 0.001
235 parameters	Δρmax = 0.37 e Å−3
0 restraints	Δρmin = −0.32 e Å−3

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
Cu1	0.5000	−0.01320 (4)	0.7500	0.03860 (15)
C1	0.48707 (15)	−0.2377 (2)	0.8338 (2)	0.0508 (7)
H1	0.5351	−0.2502	0.8646	0.061*
C2	0.45590 (17)	−0.3194 (3)	0.8536 (2)	0.0595 (8)
H2	0.4828	−0.3849	0.8980	0.071*
C3	0.38457 (16)	−0.3035 (3)	0.8069 (2)	0.0598 (8)
H3	0.3621	−0.3586	0.8183	0.072*
C4	0.34694 (15)	−0.2046 (2)	0.7430 (2)	0.0492 (6)
H4	0.2985	−0.1920	0.7102	0.059*
C5	0.38190 (13)	−0.1246 (2)	0.72802 (18)	0.0368 (5)
C6	0.34211 (13)	−0.0120 (2)	0.66153 (19)	0.0389 (5)
H6	0.2941	−0.0109	0.6403	0.047*
C7	0.26736 (15)	−0.0142 (3)	0.4692 (2)	0.0554 (7)
C8	0.28709 (17)	−0.0194 (3)	0.4136 (2)	0.0611 (8)
H8	0.2559	−0.0196	0.3423	0.073*
C9	0.36269 (16)	−0.0244 (2)	0.4835 (2)	0.0498 (7)
C10	0.4118 (2)	−0.0301 (4)	0.4627 (3)	0.0755 (10)
H10A	0.4604	−0.0078	0.5237	0.113*
H10B	0.3947	0.0257	0.4082	0.113*
H10C	0.4119	−0.1119	0.4427	0.113*
C11	0.19391 (19)	−0.0068 (5)	0.4360 (3)	0.1009 (15)
H11A	0.1859	−0.0785	0.4588	0.151*
H11B	0.1570	−0.0018	0.3623	0.151*
H11C	0.1916	0.0647	0.4655	0.151*
C12	0.35339 (18)	0.1970 (3)	0.7337 (2)	0.0553 (7)
C13	0.4112 (2)	0.2737 (3)	0.7987 (3)	0.0666 (9)
H13	0.4104	0.3487	0.8230	0.080*
C14	0.47163 (17)	0.2200 (2)	0.8223 (2)	0.0540 (7)
C15	0.2759 (2)	0.2089 (3)	0.6840 (4)	0.0882 (12)
H15A	0.2455	0.2171	0.6110	0.132*
H15B	0.2705	0.2800	0.7105	0.132*
H15C	0.2617	0.1373	0.6985	0.132*
C16	0.54737 (19)	0.2688 (3)	0.8906 (3)	0.0773 (10)
H16A	0.5811	0.2021	0.9172	0.116*
H16B	0.5580	0.3130	0.9465	0.116*
H16C	0.5518	0.3228	0.8520	0.116*
N1	0.45132 (11)	−0.14066 (18)	0.77218 (15)	0.0392 (5)
N2	0.38955 (12)	−0.0231 (2)	0.57884 (16)	0.0463 (5)
N3	0.33024 (11)	−0.01645 (19)	0.56902 (16)	0.0416 (5)
N4	0.37949 (12)	0.09956 (18)	0.71912 (16)	0.0420 (5)
N5	0.45224 (12)	0.11305 (19)	0.77316 (17)	0.0448 (5)
N6	0.35109 (14)	0.5779 (2)	0.41294 (19)	0.0512 (6)
O1	0.35080 (16)	0.6715 (3)	0.4505 (2)	0.1132 (11)
O2	0.29475 (13)	0.5446 (3)	0.3289 (2)	0.0896 (8)
O3	0.40686 (15)	0.5216 (2)	0.4542 (2)	0.1047 (10)

	U11	U22	U33	U12	U13	U23
Cu1	0.0389 (3)	0.0372 (2)	0.0438 (3)	0.000	0.0295 (2)	0.000
C1	0.0402 (15)	0.0482 (15)	0.0480 (16)	0.0088 (12)	0.0232 (14)	0.0131 (12)
C2	0.0570 (19)	0.0490 (16)	0.0591 (19)	0.0058 (13)	0.0337 (16)	0.0185 (14)
C3	0.0576 (19)	0.0546 (17)	0.0637 (19)	−0.0056 (14)	0.0394 (17)	0.0134 (14)
C4	0.0440 (15)	0.0497 (15)	0.0526 (16)	−0.0009 (12)	0.0320 (14)	0.0070 (13)
C5	0.0368 (13)	0.0370 (12)	0.0341 (13)	0.0017 (10)	0.0229 (12)	0.0016 (10)
C6	0.0371 (13)	0.0431 (13)	0.0409 (13)	0.0054 (11)	0.0280 (12)	0.0068 (11)
C7	0.0431 (16)	0.0669 (18)	0.0400 (15)	0.0112 (14)	0.0215 (14)	0.0093 (13)
C8	0.0593 (19)	0.075 (2)	0.0334 (14)	0.0083 (16)	0.0248 (15)	0.0067 (14)
C9	0.0621 (18)	0.0511 (15)	0.0426 (15)	0.0026 (13)	0.0378 (15)	0.0022 (12)
C10	0.085 (2)	0.103 (3)	0.061 (2)	0.004 (2)	0.059 (2)	0.0016 (19)
C11	0.0434 (19)	0.176 (5)	0.057 (2)	0.017 (2)	0.0226 (18)	0.004 (2)
C12	0.078 (2)	0.0428 (15)	0.078 (2)	0.0118 (14)	0.0658 (19)	0.0078 (14)
C13	0.108 (3)	0.0402 (15)	0.096 (3)	−0.0011 (17)	0.086 (2)	−0.0072 (16)
C14	0.076 (2)	0.0427 (15)	0.0636 (19)	−0.0079 (14)	0.0553 (18)	−0.0085 (13)
C15	0.093 (3)	0.062 (2)	0.147 (4)	0.0158 (19)	0.096 (3)	0.001 (2)
C16	0.088 (3)	0.062 (2)	0.090 (3)	−0.0267 (18)	0.063 (2)	−0.0329 (18)
N1	0.0345 (11)	0.0405 (11)	0.0383 (12)	0.0020 (9)	0.0227 (10)	0.0039 (9)
N2	0.0425 (12)	0.0615 (14)	0.0384 (12)	0.0045 (10)	0.0286 (11)	0.0039 (10)
N3	0.0368 (11)	0.0503 (12)	0.0366 (11)	0.0080 (9)	0.0243 (10)	0.0077 (9)
N4	0.0501 (13)	0.0391 (11)	0.0494 (13)	0.0049 (9)	0.0386 (12)	0.0045 (9)
N5	0.0505 (13)	0.0415 (12)	0.0508 (13)	−0.0030 (10)	0.0374 (12)	−0.0043 (10)
N6	0.0515 (15)	0.0467 (13)	0.0554 (15)	−0.0091 (11)	0.0361 (14)	−0.0065 (11)
O1	0.103 (2)	0.098 (2)	0.116 (2)	−0.0088 (17)	0.065 (2)	−0.0504 (18)
O2	0.0583 (15)	0.0995 (19)	0.0702 (16)	−0.0095 (14)	0.0268 (14)	−0.0291 (14)
O3	0.0630 (16)	0.0806 (18)	0.098 (2)	0.0121 (14)	0.0247 (16)	−0.0141 (15)

Cu1—N5i	2.030 (2)	C9—C10	1.491 (4)
Cu1—N5	2.030 (2)	C10—H10A	0.9600
Cu1—N1	2.045 (2)	C10—H10B	0.9600
Cu1—N1i	2.045 (2)	C10—H10C	0.9600
Cu1—N2i	2.339 (2)	C11—H11A	0.9600
Cu1—N2	2.339 (2)	C11—H11B	0.9600
C1—N1	1.337 (3)	C11—H11C	0.9600
C1—C2	1.370 (4)	C12—N4	1.358 (3)
C1—H1	0.9300	C12—C13	1.363 (4)
C2—C3	1.371 (4)	C12—C15	1.488 (4)
C2—H2	0.9300	C13—C14	1.388 (4)
C3—C4	1.374 (4)	C13—H13	0.9300
C3—H3	0.9300	C14—N5	1.334 (3)
C4—C5	1.376 (3)	C14—C16	1.490 (4)
C4—H4	0.9300	C15—H15A	0.9600
C5—N1	1.341 (3)	C15—H15B	0.9600
C5—C6	1.516 (3)	C15—H15C	0.9600
C6—N3	1.446 (3)	C16—H16A	0.9600
C6—N4	1.451 (3)	C16—H16B	0.9600
C6—H6	0.9800	C16—H16C	0.9600
C7—N3	1.352 (3)	N2—N3	1.363 (3)
C7—C8	1.359 (4)	N4—N5	1.369 (3)
C7—C11	1.495 (5)	N6—O3	1.211 (3)
C8—C9	1.388 (4)	N6—O2	1.219 (3)
C8—H8	0.9300	N6—O1	1.220 (3)
C9—N2	1.324 (3)
N5i—Cu1—N5	94.48 (12)	C9—C10—H10C	109.5
N5i—Cu1—N1	179.57 (9)	H10A—C10—H10C	109.5
N5—Cu1—N1	85.63 (8)	H10B—C10—H10C	109.5
N5i—Cu1—N1i	85.63 (8)	C7—C11—H11A	109.5
N5—Cu1—N1i	179.57 (9)	C7—C11—H11B	109.5
N1—Cu1—N1i	94.26 (12)	H11A—C11—H11B	109.5
N5i—Cu1—N2i	87.32 (8)	C7—C11—H11C	109.5
N5—Cu1—N2i	96.28 (8)	H11A—C11—H11C	109.5
N1—Cu1—N2i	93.08 (8)	H11B—C11—H11C	109.5
N1i—Cu1—N2i	83.31 (8)	N4—C12—C13	105.8 (3)
N5i—Cu1—N2	96.28 (8)	N4—C12—C15	123.3 (3)
N5—Cu1—N2	87.32 (8)	C13—C12—C15	130.8 (3)
N1—Cu1—N2	83.31 (8)	C12—C13—C14	107.9 (3)
N1i—Cu1—N2	93.08 (8)	C12—C13—H13	126.1
N2i—Cu1—N2	174.72 (11)	C14—C13—H13	126.1
N1—C1—C2	122.8 (3)	N5—C14—C13	109.3 (3)
N1—C1—H1	118.6	N5—C14—C16	123.0 (3)
C2—C1—H1	118.6	C13—C14—C16	127.7 (3)
C1—C2—C3	119.2 (3)	C12—C15—H15A	109.5
C1—C2—H2	120.4	C12—C15—H15B	109.5
C3—C2—H2	120.4	H15A—C15—H15B	109.5
C2—C3—C4	118.8 (3)	C12—C15—H15C	109.5
C2—C3—H3	120.6	H15A—C15—H15C	109.5
C4—C3—H3	120.6	H15B—C15—H15C	109.5
C3—C4—C5	119.2 (3)	C14—C16—H16A	109.5
C3—C4—H4	120.4	C14—C16—H16B	109.5
C5—C4—H4	120.4	H16A—C16—H16B	109.5
N1—C5—C4	122.4 (2)	C14—C16—H16C	109.5
N1—C5—C6	117.9 (2)	H16A—C16—H16C	109.5
C4—C5—C6	119.7 (2)	H16B—C16—H16C	109.5
N3—C6—N4	111.33 (19)	C1—N1—C5	117.7 (2)
N3—C6—C5	111.97 (19)	C1—N1—Cu1	122.61 (17)
N4—C6—C5	111.4 (2)	C5—N1—Cu1	119.60 (15)
N3—C6—H6	107.3	C9—N2—N3	105.1 (2)
N4—C6—H6	107.3	C9—N2—Cu1	141.70 (19)
C5—C6—H6	107.3	N3—N2—Cu1	112.94 (15)
N3—C7—C8	105.9 (3)	C7—N3—N2	111.6 (2)
N3—C7—C11	123.1 (3)	C7—N3—C6	130.0 (2)
C8—C7—C11	131.1 (3)	N2—N3—C6	118.4 (2)
C7—C8—C9	107.0 (3)	C12—N4—N5	111.0 (2)
C7—C8—H8	126.5	C12—N4—C6	128.9 (2)
C9—C8—H8	126.5	N5—N4—C6	119.95 (19)
N2—C9—C8	110.4 (2)	C14—N5—N4	106.0 (2)
N2—C9—C10	121.0 (3)	C14—N5—Cu1	136.0 (2)
C8—C9—C10	128.7 (3)	N4—N5—Cu1	117.58 (15)
C9—C10—H10A	109.5	O3—N6—O2	119.3 (3)
C9—C10—H10B	109.5	O3—N6—O1	121.5 (3)
H10A—C10—H10B	109.5	O2—N6—O1	119.1 (3)
N1—C1—C2—C3	1.4 (5)	N5—Cu1—N2—N3	−38.62 (17)
C1—C2—C3—C4	−1.0 (5)	N1—Cu1—N2—N3	47.29 (16)
C2—C3—C4—C5	−0.2 (4)	N1i—Cu1—N2—N3	141.22 (17)
C3—C4—C5—N1	1.3 (4)	C8—C7—N3—N2	0.0 (3)
C3—C4—C5—C6	−177.2 (3)	C11—C7—N3—N2	−179.8 (3)
N1—C5—C6—N3	67.1 (3)	C8—C7—N3—C6	179.4 (2)
C4—C5—C6—N3	−114.3 (3)	C11—C7—N3—C6	−0.4 (5)
N1—C5—C6—N4	−58.3 (3)	C9—N2—N3—C7	0.2 (3)
C4—C5—C6—N4	120.3 (2)	Cu1—N2—N3—C7	175.91 (18)
N3—C7—C8—C9	−0.2 (3)	C9—N2—N3—C6	−179.3 (2)
C11—C7—C8—C9	179.6 (4)	Cu1—N2—N3—C6	−3.6 (3)
C7—C8—C9—N2	0.3 (3)	N4—C6—N3—C7	−114.3 (3)
C7—C8—C9—C10	−179.5 (3)	C5—C6—N3—C7	120.3 (3)
N4—C12—C13—C14	−0.1 (3)	N4—C6—N3—N2	65.1 (3)
C15—C12—C13—C14	−179.6 (3)	C5—C6—N3—N2	−60.3 (3)
C12—C13—C14—N5	0.3 (3)	C13—C12—N4—N5	−0.1 (3)
C12—C13—C14—C16	−179.8 (3)	C15—C12—N4—N5	179.4 (3)
C2—C1—N1—C5	−0.4 (4)	C13—C12—N4—C6	176.1 (2)
C2—C1—N1—Cu1	176.1 (2)	C15—C12—N4—C6	−4.4 (4)
C4—C5—N1—C1	−1.0 (4)	N3—C6—N4—C12	110.1 (3)
C6—C5—N1—C1	177.6 (2)	C5—C6—N4—C12	−124.1 (3)
C4—C5—N1—Cu1	−177.61 (19)	N3—C6—N4—N5	−74.0 (3)
C6—C5—N1—Cu1	1.0 (3)	C5—C6—N4—N5	51.8 (3)
N5—Cu1—N1—C1	−133.1 (2)	C13—C14—N5—N4	−0.4 (3)
N1i—Cu1—N1—C1	46.47 (18)	C16—C14—N5—N4	179.8 (3)
N2i—Cu1—N1—C1	−37.0 (2)	C13—C14—N5—Cu1	171.5 (2)
N2—Cu1—N1—C1	139.1 (2)	C16—C14—N5—Cu1	−8.3 (5)
N5—Cu1—N1—C5	43.32 (18)	C12—N4—N5—C14	0.3 (3)
N1i—Cu1—N1—C5	−137.1 (2)	C6—N4—N5—C14	−176.3 (2)
N2i—Cu1—N1—C5	139.39 (18)	C12—N4—N5—Cu1	−173.37 (17)
N2—Cu1—N1—C5	−44.48 (18)	C6—N4—N5—Cu1	10.0 (3)
C8—C9—N2—N3	−0.4 (3)	N5i—Cu1—N5—C14	−40.8 (2)
C10—C9—N2—N3	179.5 (3)	N1—Cu1—N5—C14	139.7 (3)
C8—C9—N2—Cu1	−173.9 (2)	N2i—Cu1—N5—C14	47.0 (3)
C10—C9—N2—Cu1	5.9 (5)	N2—Cu1—N5—C14	−136.9 (3)
N5i—Cu1—N2—C9	40.4 (3)	N5i—Cu1—N5—N4	130.4 (2)
N5—Cu1—N2—C9	134.6 (3)	N1—Cu1—N5—N4	−49.17 (17)
N1—Cu1—N2—C9	−139.5 (3)	N2i—Cu1—N5—N4	−141.80 (17)
N1i—Cu1—N2—C9	−45.6 (3)	N2—Cu1—N5—N4	34.32 (17)
N5i—Cu1—N2—N3	−132.84 (17)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O3ii	0.93	2.39	3.245 (4)	153
C8—H8···O2iii	0.93	2.46	3.338 (4)	158
C15—H15c···O2iv	0.96	2.29	3.202 (6)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O3i	0.93	2.39	3.245 (4)	153
C8—H8⋯O2ii	0.93	2.46	3.338 (4)	158
C15—H15c⋯O2iii	0.96	2.29	3.202 (6)	159

Symmetry codes: (i) ; (ii) ; (iii) .