Diazido­{(S)-1-phenyl-N,N-bis­[(2-pyrid­yl)meth­yl]ethanamine}­copper(II)

Rowthu, S.R.; Shin, J.W.; Kim, S.-H.; Kim, J.J.; Min, K.S.

doi:10.1107/S1600536811021234

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Pages m873-m874

doi:10.1107/S1600536811021234

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Diazido{(S)-1-phenyl-N,N-bis[(2-pyridyl)methyl]ethanamine}copper(II)

Sankara Rao Rowthu,^a Jong Won Shin,^a Seung-Hui Kim,^a Jong Jin Kim ^b and Kil Sik Min ^c ^*

^aDepartment of Chemistry, Kyungpook National University, Daegu 702-701, Republic of Korea, ^bDepartment of Applied Chemistry, Kyungpook National University, Daegu 702-701, Republic of Korea, and ^cDepartment of Chemistry Education, Kyungpook National University, Daegu 702-701, Republic of Korea
^*Correspondence e-mail: minks@knu.ac.kr

(Received 12 May 2011; accepted 2 June 2011; online 11 June 2011)

In the title compound, [Cu(N₃)₂(C₂₀H₂₁N₃)], the Cu^II ion is coordinated by the three N atoms of the (S)-1-phenyl-N,N-bis[(2-pyridyl)methyl]ethanamine ligand and two N atoms from two azide anions, resulting in a distorted square-pyramidal environment. A weak intermolecular C—H⋯N hydrogen-bonding interaction between one pyridine group of the ligand and an azide N atom of an adjacent complex unit gives a one-dimensional chain structure parallel to the c axis.

Related literature

For the potential applications of chiral complexes in chiral recognition, chiral catalysis and enantioselective sorption, see: Lehn (1995 ); Seo et al. (2000 ). Chiral Ni^II macrocyclic complexes and two-dimensional chiral open-framework compounds have been described by Han et al. (2008 ); Ryoo et al. (2010 ). A homochiral metal–organic framework with a cerium(III) ion has been described by Dang et al. (2010 ). For the preparation of (S)-1-phenyl-N,N-[bis(2-pyridyl)methyl]ethanamine, see: Lucas et al. (2009 ).

Experimental

Crystal data

[Cu(N₃)₂(C₂₀H₂₁N₃)]
M_r = 451.00
Monoclinic, P 2₁
a = 6.9972 (12) Å
b = 14.506 (3) Å
c = 10.2828 (17) Å
β = 98.413 (4)°
V = 1032.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.09 mm⁻¹
T = 296 K
0.23 × 0.19 × 0.04 mm

Data collection

Siemens SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.749, T_max = 0.958
7801 measured reflections
4630 independent reflections
2863 reflections with I > 2σ(I)
R_int = 0.049

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.115
S = 1.09
4630 reflections
272 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.90 e Å⁻³
Absolute structure: Flack (1983 ), 1941 Friedel pairs
Flack parameter: 0.02 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯N6ⁱ	0.93	2.59	3.261 (11)	129
Symmetry code: (i) x, y, z+1.

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SHELXTL (Sheldrick, 2008 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811021234/pk2326sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811021234/pk2326Isup2.hkl

checkCIF report

Comment top

Chiral complexes have attracted considerable interest because of their potential and practical applications, such as chiral recognition, chiral catalysis, and enantioselective sorption (Lehn, 1995; Seo et al., 2000). Very recently, a two-dimensional chiral open framework, [Ni(L^R,^R)]₃[C₆H₃(COO)₃]₂.12H₂O.CH₃CN [L^R^,^R=1,8-bis[(R)-α-methylbenzyl]-1,3,6,8,10,13-\ hexaazacyclotetradecane] has been shown to have selective chiral recognition in rac-1,1'-bi-2-naphthol (Han et al., 2008; Ryoo et al., 2010). Furthermore, a homochiral metal-organic framework composed of a cerium(III) ion and chiral organic building block has large chiral one-dimensional channels and exhibited excellent catalytic activity and high enantioselectivity for the asymmetric cyanosilylation of aromatic aldehydes (Dang et al., 2010). Here, we report the synthesis and crystal structure of a five-coordinated Cu^II complex with (S)-1-phenyl-N,N-[bis(2-pyridyl)methyl]ethanamine (S-ppme), the title compound [Cu(S-ppme)(N₃)₂].

In the title compound (Fig. 1), the Cu^II ion is five-coordinated and shows a distorted square pyramidal geometry, the equatorial plane being defined by the three nitrogen atoms of the S-ppme ligand and one nitrogen atom of an azide ion. The coordination geometry is completed by the axial coordination of the nitrogen atom of the second azide anion. The Cu—L_eq bond lengths are in the range of 1.961 (6) and 2.178 (5) Å and the Cu—N_ax bond length is 1.978 (5) Å. Both azide ions are bonded in η¹-fashion and fully delocalized. The bond angles around the copper atom range from 76.95 (12) to 165.48 (15)°. The packing structure involves a weak C—H···N hydrogen bonding interaction between the one pyridine group of the S-ppme ligand and an azide N atom of an adjacent complex unit (Table 1), giving a one-dimensional chain structure parallel to the c axis (Fig. 2).

Related literature top

For the potential applications of chiral complexes in chiral recognition, chiral catalysis and enantioselective sorption, see: Lehn (1995); Seo et al. (2000). Chiral Ni^II macrocyclic complexes and two-dimensional chiral open-framework compounds have been described by Han et al. (2008); Ryoo et al. (2010). A homochiral metal–organic framework with a cerium(III) ion has been described by Dang et al. (2010). For the preparation of (S)-1-phenyl-N,N-[bis(2-pyridyl)methyl]ethanamine, see: Lucas et al. (2009).

Experimental top

(S)-1-phenyl-N,N-[bis(2-pyridyl)methyl]ethanamine (S-ppme) was prepared according to slightly modified literature procedure (Lucas et al., 2009) except that (S)-(-)-α-methylbenzylamine instead of benzylamine (yield: 0.86 g, 60%). A mixture of MeCN and H₂O (2:1, v/v, 3 ml) solution of CuCl₂.2H₂O (29 mg, 0.17 mmol) was added to an MeCN solution (3 ml) of S-ppme (51 mg, 0.17 mmol) and a MeOH solution (4 ml) of sodium azide (22 mg, 0.34 mmol). The resulting solution was stirred for 1 h at room temperature, resulting in a color change to blue-green. Diffusion of diethyl ether into the mixture gave green crystals of the title compound after a few days. These crystals were filtered and washed with diethyl ether and dried in air (yield: 42 mg, 56%).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. An ellipsoid plot (30% probability) of the title compound. Hydrogen atoms are drawn as small spheres of arbitrary radius.
	Fig. 2. Perspective view of the title compound showing a one-dimensional chain formed by C—H···N hydrogen bonding interactions.

Diazido{(S)-1-phenyl-N,N-bis[(2- pyridyl)methyl]ethanamine}copper(II) top

Crystal data top

[Cu(N₃)₂(C₂₀H₂₁N₃)]	F(000) = 466
M_r = 451.00	D_x = 1.451 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 2059 reflections
a = 6.9972 (12) Å	θ = 2.5–23.1°
b = 14.506 (3) Å	µ = 1.09 mm⁻¹
c = 10.2828 (17) Å	T = 296 K
β = 98.413 (4)°	Plate, green
V = 1032.5 (3) Å³	0.23 × 0.19 × 0.04 mm
Z = 2

Data collection top

Siemens SMART CCD diffractometer	4630 independent reflections
Radiation source: fine-focus sealed tube	2863 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.049
ϕ and ω scans	θ_max = 28.3°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→9
T_min = 0.749, T_max = 0.958	k = −19→16
7801 measured reflections	l = −13→8

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)] = 0.058	H-atom parameters constrained
wR(F²) = 0.115	w = 1/[σ²(F_o²) + 0.2609P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
4630 reflections	Δρ_max = 0.74 e Å⁻³
272 parameters	Δρ_min = −0.90 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1941 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (3)

Crystal data top

[Cu(N₃)₂(C₂₀H₂₁N₃)]	V = 1032.5 (3) Å³
M_r = 451.00	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 6.9972 (12) Å	µ = 1.09 mm⁻¹
b = 14.506 (3) Å	T = 296 K
c = 10.2828 (17) Å	0.23 × 0.19 × 0.04 mm
β = 98.413 (4)°

Data collection top

Siemens SMART CCD diffractometer	4630 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2863 reflections with I > 2σ(I)
T_min = 0.749, T_max = 0.958	R_int = 0.049
7801 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	H-atom parameters constrained
wR(F²) = 0.115	Δρ_max = 0.74 e Å⁻³
S = 1.09	Δρ_min = −0.90 e Å⁻³
4630 reflections	Absolute structure: Flack (1983), 1941 Friedel pairs
272 parameters	Absolute structure parameter: 0.02 (3)
1 restraint

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
Cu1	0.97299 (8)	0.03627 (6)	0.09599 (6)	0.03987 (19)
N1	0.9182 (6)	0.1005 (4)	0.2601 (5)	0.0397 (13)
N2	1.1219 (6)	−0.0557 (3)	0.2383 (5)	0.0352 (12)
N3	0.7954 (6)	−0.0873 (4)	0.0636 (5)	0.0391 (13)
N4	0.8063 (8)	0.1251 (5)	−0.0106 (6)	0.0594 (18)
N5	0.7529 (8)	0.1156 (4)	−0.1229 (7)	0.0571 (16)
N6	0.6948 (12)	0.1098 (6)	−0.2324 (7)	0.113 (3)
N7	1.1556 (7)	0.0125 (5)	−0.0299 (6)	0.056 (2)
N8	1.1260 (9)	−0.0280 (5)	−0.1291 (7)	0.0662 (19)
N9	1.1054 (13)	−0.0689 (8)	−0.2243 (9)	0.150 (5)
C1	0.8573 (8)	0.1875 (5)	0.2688 (7)	0.0476 (17)
H1	0.8397	0.2237	0.1934	0.057*
C2	0.8202 (9)	0.2249 (5)	0.3835 (8)	0.061 (2)
H2	0.7774	0.2854	0.3864	0.073*
C3	0.8470 (10)	0.1716 (7)	0.4955 (8)	0.071 (2)
H3	0.8182	0.1951	0.5745	0.085*
C4	0.9162 (9)	0.0839 (5)	0.4894 (7)	0.055 (2)
H4	0.9390	0.0474	0.5645	0.066*
C5	0.9513 (7)	0.0509 (5)	0.3707 (5)	0.0375 (17)
C6	1.0194 (8)	−0.0470 (5)	0.3535 (6)	0.0433 (16)
H6A	1.1050	−0.0656	0.4319	0.052*
H6B	0.9088	−0.0881	0.3428	0.052*
C7	1.0910 (8)	−0.1481 (4)	0.1814 (6)	0.0412 (15)
H7A	1.1169	−0.1934	0.2512	0.049*
H7B	1.1829	−0.1583	0.1207	0.049*
C8	0.8881 (8)	−0.1635 (4)	0.1091 (6)	0.0376 (14)
C9	0.8111 (8)	−0.2496 (5)	0.0895 (6)	0.0518 (18)
H9	0.8782	−0.3010	0.1257	0.062*
C10	0.6315 (10)	−0.2587 (6)	0.0148 (7)	0.066 (2)
H10	0.5770	−0.3167	−0.0025	0.079*
C11	0.5346 (10)	−0.1809 (6)	−0.0334 (6)	0.059 (2)
H11	0.4125	−0.1853	−0.0828	0.071*
C12	0.6200 (8)	−0.0968 (5)	−0.0079 (6)	0.0535 (19)
H12	0.5541	−0.0442	−0.0413	0.064*
C13	1.3354 (8)	−0.0333 (5)	0.2654 (6)	0.0376 (17)
H13	1.3882	−0.0501	0.1855	0.045*
C14	1.4474 (7)	−0.0887 (5)	0.3751 (6)	0.0397 (15)
C15	1.4879 (9)	−0.0563 (5)	0.5031 (6)	0.0551 (18)
H15	1.4398	0.0005	0.5249	0.066*
C16	1.6004 (11)	−0.1086 (6)	0.5992 (7)	0.072 (2)
H16	1.6268	−0.0864	0.6848	0.087*
C17	1.6718 (10)	−0.1919 (7)	0.5691 (9)	0.077 (3)
H17	1.7478	−0.2257	0.6341	0.092*
C18	1.6329 (10)	−0.2265 (6)	0.4442 (8)	0.068 (2)
H18	1.6803	−0.2838	0.4238	0.082*
C19	1.5211 (8)	−0.1742 (5)	0.3486 (6)	0.0508 (18)
H19	1.4948	−0.1975	0.2635	0.061*
C20	1.3706 (8)	0.0698 (5)	0.2839 (8)	0.050 (2)
H20A	1.3169	0.0905	0.3595	0.075*
H20B	1.3102	0.1021	0.2074	0.075*
H20C	1.5070	0.0817	0.2966	0.075*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0360 (3)	0.0420 (4)	0.0411 (4)	0.0039 (5)	0.0038 (2)	0.0023 (5)
N1	0.034 (3)	0.048 (4)	0.036 (3)	−0.002 (2)	0.001 (2)	−0.005 (3)
N2	0.033 (3)	0.029 (3)	0.044 (3)	0.000 (2)	0.005 (2)	−0.001 (2)
N3	0.029 (2)	0.042 (4)	0.046 (3)	−0.004 (2)	0.005 (2)	−0.005 (3)
N4	0.063 (4)	0.070 (5)	0.042 (4)	0.017 (3)	−0.002 (3)	0.001 (3)
N5	0.062 (4)	0.058 (5)	0.051 (4)	0.014 (3)	0.006 (3)	0.012 (3)
N6	0.169 (8)	0.112 (7)	0.050 (5)	0.037 (6)	−0.012 (5)	0.006 (4)
N7	0.044 (3)	0.074 (6)	0.052 (3)	0.008 (3)	0.009 (2)	−0.003 (3)
N8	0.064 (4)	0.075 (5)	0.057 (4)	0.022 (3)	0.002 (3)	−0.017 (4)
N9	0.134 (8)	0.207 (12)	0.103 (7)	0.055 (7)	−0.002 (6)	−0.088 (8)
C1	0.039 (3)	0.039 (5)	0.065 (5)	0.006 (3)	0.008 (3)	−0.009 (3)
C2	0.052 (4)	0.052 (6)	0.079 (6)	0.004 (4)	0.013 (4)	−0.032 (5)
C3	0.059 (5)	0.099 (8)	0.058 (5)	−0.008 (5)	0.021 (4)	−0.034 (5)
C4	0.054 (4)	0.062 (6)	0.052 (4)	0.005 (3)	0.015 (3)	−0.010 (3)
C5	0.031 (2)	0.043 (5)	0.039 (3)	0.002 (3)	0.007 (2)	−0.008 (4)
C6	0.043 (4)	0.042 (5)	0.048 (4)	−0.009 (3)	0.017 (3)	0.007 (3)
C7	0.034 (3)	0.035 (4)	0.053 (4)	0.001 (3)	0.002 (3)	−0.004 (3)
C8	0.035 (3)	0.027 (4)	0.051 (4)	−0.001 (3)	0.008 (3)	−0.012 (3)
C9	0.037 (3)	0.052 (5)	0.067 (5)	−0.005 (3)	0.011 (3)	−0.021 (4)
C10	0.055 (5)	0.065 (6)	0.081 (6)	−0.016 (4)	0.023 (4)	−0.032 (5)
C11	0.048 (4)	0.068 (7)	0.058 (5)	−0.012 (4)	−0.002 (3)	−0.019 (4)
C12	0.038 (3)	0.067 (6)	0.054 (4)	−0.002 (4)	0.002 (3)	−0.003 (4)
C13	0.032 (3)	0.038 (5)	0.042 (4)	−0.003 (3)	0.002 (3)	0.006 (3)
C14	0.029 (3)	0.039 (4)	0.049 (4)	0.002 (3)	−0.001 (3)	0.003 (3)
C15	0.053 (4)	0.058 (5)	0.052 (4)	0.003 (4)	−0.001 (3)	0.003 (4)
C16	0.076 (5)	0.085 (8)	0.051 (5)	−0.017 (5)	−0.007 (4)	0.020 (5)
C17	0.055 (5)	0.078 (8)	0.089 (7)	−0.003 (4)	−0.017 (4)	0.048 (5)
C18	0.050 (4)	0.059 (6)	0.091 (6)	0.003 (4)	−0.002 (4)	0.020 (5)
C19	0.041 (3)	0.057 (5)	0.053 (4)	−0.004 (3)	0.002 (3)	0.003 (3)
C20	0.027 (3)	0.054 (6)	0.067 (5)	−0.005 (3)	−0.003 (3)	0.010 (3)

Geometric parameters (Å, º) top

Cu1—N4	1.961 (6)	C7—H7A	0.9700
Cu1—N7	1.978 (5)	C7—H7B	0.9700
Cu1—N1	2.013 (5)	C8—C9	1.363 (8)
Cu1—N2	2.135 (5)	C9—C10	1.380 (8)
Cu1—N3	2.178 (5)	C9—H9	0.9300
N1—C5	1.337 (7)	C10—C11	1.371 (10)
N1—C1	1.339 (8)	C10—H10	0.9300
N2—C7	1.466 (7)	C11—C12	1.367 (9)
N2—C6	1.477 (6)	C11—H11	0.9300
N2—C13	1.514 (7)	C12—H12	0.9300
N3—C8	1.332 (7)	C13—C14	1.508 (9)
N3—C12	1.342 (7)	C13—C20	1.522 (8)
N4—N5	1.169 (8)	C13—H13	0.9800
N5—N6	1.144 (7)	C14—C19	1.386 (8)
N7—N8	1.168 (7)	C14—C15	1.388 (8)
N8—N9	1.137 (8)	C15—C16	1.395 (9)
C1—C2	1.357 (9)	C15—H15	0.9300
C1—H1	0.9300	C16—C17	1.360 (11)
C2—C3	1.377 (10)	C16—H16	0.9300
C2—H2	0.9300	C17—C18	1.369 (10)
C3—C4	1.366 (10)	C17—H17	0.9300
C3—H3	0.9300	C18—C19	1.389 (9)
C4—C5	1.366 (8)	C18—H18	0.9300
C4—H4	0.9300	C19—H19	0.9300
C5—C6	1.517 (10)	C20—H20A	0.9600
C6—H6A	0.9700	C20—H20B	0.9600
C6—H6B	0.9700	C20—H20C	0.9600
C7—C8	1.520 (7)

N4—Cu1—N7	97.9 (2)	C8—C7—H7A	108.8
N4—Cu1—N1	89.6 (2)	N2—C7—H7B	108.8
N7—Cu1—N1	148.2 (2)	C8—C7—H7B	108.8
N4—Cu1—N2	169.7 (2)	H7A—C7—H7B	107.7
N7—Cu1—N2	92.4 (2)	N3—C8—C9	123.2 (5)
N1—Cu1—N2	81.3 (2)	N3—C8—C7	115.0 (5)
N4—Cu1—N3	100.1 (2)	C9—C8—C7	121.8 (6)
N7—Cu1—N3	99.5 (2)	C8—C9—C10	118.6 (7)
N1—Cu1—N3	109.55 (19)	C8—C9—H9	120.7
N2—Cu1—N3	78.53 (19)	C10—C9—H9	120.7
C5—N1—C1	117.9 (6)	C11—C10—C9	118.9 (7)
C5—N1—Cu1	115.7 (5)	C11—C10—H10	120.5
C1—N1—Cu1	126.4 (4)	C9—C10—H10	120.5
C7—N2—C6	109.7 (5)	C12—C11—C10	119.1 (7)
C7—N2—C13	110.7 (4)	C12—C11—H11	120.5
C6—N2—C13	114.5 (5)	C10—C11—H11	120.5
C7—N2—Cu1	105.6 (3)	N3—C12—C11	122.4 (7)
C6—N2—Cu1	104.5 (3)	N3—C12—H12	118.8
C13—N2—Cu1	111.2 (4)	C11—C12—H12	118.8
C8—N3—C12	117.8 (6)	C14—C13—N2	114.5 (5)
C8—N3—Cu1	113.0 (4)	C14—C13—C20	111.9 (6)
C12—N3—Cu1	128.6 (5)	N2—C13—C20	111.8 (6)
N5—N4—Cu1	123.6 (5)	C14—C13—H13	106.0
N6—N5—N4	176.8 (8)	N2—C13—H13	106.0
N8—N7—Cu1	127.6 (5)	C20—C13—H13	106.0
N9—N8—N7	176.9 (8)	C19—C14—C15	117.3 (6)
N1—C1—C2	122.5 (7)	C19—C14—C13	119.9 (6)
N1—C1—H1	118.7	C15—C14—C13	122.7 (6)
C2—C1—H1	118.7	C14—C15—C16	120.3 (7)
C1—C2—C3	118.8 (8)	C14—C15—H15	119.9
C1—C2—H2	120.6	C16—C15—H15	119.9
C3—C2—H2	120.6	C17—C16—C15	120.7 (8)
C4—C3—C2	119.4 (7)	C17—C16—H16	119.7
C4—C3—H3	120.3	C15—C16—H16	119.7
C2—C3—H3	120.3	C16—C17—C18	120.7 (7)
C5—C4—C3	118.5 (7)	C16—C17—H17	119.7
C5—C4—H4	120.7	C18—C17—H17	119.7
C3—C4—H4	120.7	C17—C18—C19	118.6 (8)
N1—C5—C4	122.7 (7)	C17—C18—H18	120.7
N1—C5—C6	115.0 (5)	C19—C18—H18	120.7
C4—C5—C6	122.2 (6)	C14—C19—C18	122.4 (7)
N2—C6—C5	111.8 (5)	C14—C19—H19	118.8
N2—C6—H6A	109.3	C18—C19—H19	118.8
C5—C6—H6A	109.3	C13—C20—H20A	109.5
N2—C6—H6B	109.3	C13—C20—H20B	109.5
C5—C6—H6B	109.3	H20A—C20—H20B	109.5
H6A—C6—H6B	107.9	C13—C20—H20C	109.5
N2—C7—C8	113.7 (5)	H20A—C20—H20C	109.5
N2—C7—H7A	108.8	H20B—C20—H20C	109.5

N4—Cu1—N1—C5	159.9 (4)	Cu1—N1—C5—C4	−178.2 (4)
N7—Cu1—N1—C5	−95.6 (6)	C1—N1—C5—C6	179.8 (5)
N2—Cu1—N1—C5	−15.2 (4)	Cu1—N1—C5—C6	−1.7 (6)
N3—Cu1—N1—C5	59.3 (4)	C3—C4—C5—N1	−0.9 (9)
N4—Cu1—N1—C1	−21.8 (5)	C3—C4—C5—C6	−177.1 (6)
N7—Cu1—N1—C1	82.7 (6)	C7—N2—C6—C5	−148.8 (5)
N2—Cu1—N1—C1	163.1 (5)	C13—N2—C6—C5	86.0 (6)
N3—Cu1—N1—C1	−122.4 (5)	Cu1—N2—C6—C5	−35.9 (5)
N4—Cu1—N2—C7	114.6 (13)	N1—C5—C6—N2	27.1 (7)
N7—Cu1—N2—C7	−68.0 (4)	C4—C5—C6—N2	−156.5 (5)
N1—Cu1—N2—C7	143.3 (4)	C6—N2—C7—C8	72.5 (6)
N3—Cu1—N2—C7	31.2 (3)	C13—N2—C7—C8	−160.1 (5)
N4—Cu1—N2—C6	−1.1 (15)	Cu1—N2—C7—C8	−39.6 (5)
N7—Cu1—N2—C6	176.3 (4)	C12—N3—C8—C9	−1.9 (9)
N1—Cu1—N2—C6	27.6 (3)	Cu1—N3—C8—C9	−174.1 (5)
N3—Cu1—N2—C6	−84.5 (4)	C12—N3—C8—C7	176.1 (5)
N4—Cu1—N2—C13	−125.2 (13)	Cu1—N3—C8—C7	3.9 (6)
N7—Cu1—N2—C13	52.2 (4)	N2—C7—C8—N3	24.9 (7)
N1—Cu1—N2—C13	−96.5 (4)	N2—C7—C8—C9	−157.1 (5)
N3—Cu1—N2—C13	151.4 (4)	N3—C8—C9—C10	2.5 (9)
N4—Cu1—N3—C8	170.0 (4)	C7—C8—C9—C10	−175.4 (6)
N7—Cu1—N3—C8	70.2 (4)	C8—C9—C10—C11	−2.0 (10)
N1—Cu1—N3—C8	−96.7 (4)	C9—C10—C11—C12	1.0 (10)
N2—Cu1—N3—C8	−20.4 (4)	C8—N3—C12—C11	0.8 (9)
N4—Cu1—N3—C12	−1.1 (6)	Cu1—N3—C12—C11	171.6 (5)
N7—Cu1—N3—C12	−101.0 (5)	C10—C11—C12—N3	−0.4 (10)
N1—Cu1—N3—C12	92.1 (5)	C7—N2—C13—C14	−68.9 (7)
N2—Cu1—N3—C12	168.5 (5)	C6—N2—C13—C14	55.8 (7)
N7—Cu1—N4—N5	43.4 (7)	Cu1—N2—C13—C14	174.0 (4)
N1—Cu1—N4—N5	−167.6 (6)	C7—N2—C13—C20	162.5 (6)
N2—Cu1—N4—N5	−139.2 (11)	C6—N2—C13—C20	−72.8 (7)
N3—Cu1—N4—N5	−57.8 (6)	Cu1—N2—C13—C20	45.4 (7)
N4—Cu1—N7—N8	−71.0 (7)	N2—C13—C14—C19	86.4 (7)
N1—Cu1—N7—N8	−173.1 (6)	C20—C13—C14—C19	−145.1 (6)
N2—Cu1—N7—N8	109.5 (7)	N2—C13—C14—C15	−96.2 (7)
N3—Cu1—N7—N8	30.7 (7)	C20—C13—C14—C15	32.3 (9)
C5—N1—C1—C2	−3.1 (9)	C13—C14—C15—C16	−176.8 (6)
Cu1—N1—C1—C2	178.7 (5)	C15—C16—C17—C18	−0.7 (12)
N1—C1—C2—C3	0.3 (10)	C16—C17—C18—C19	0.8 (11)
C1—C2—C3—C4	2.2 (10)	C15—C14—C19—C18	−0.6 (9)
C2—C3—C4—C5	−1.9 (10)	C13—C14—C19—C18	177.0 (6)
C1—N1—C5—C4	3.4 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N6ⁱ	0.93	2.59	3.261 (11)	129

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

Experimental details

Crystal data
Chemical formula	[Cu(N₃)₂(C₂₀H₂₁N₃)]
M_r	451.00
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	6.9972 (12), 14.506 (3), 10.2828 (17)
β (°)	98.413 (4)
V (Å³)	1032.5 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.09
Crystal size (mm)	0.23 × 0.19 × 0.04

Data collection
Diffractometer	Siemens SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.749, 0.958
No. of measured, independent and observed [I > 2σ(I)] reflections	7801, 4630, 2863
R_int	0.049
(sin θ/λ)_max (Å⁻¹)	0.668

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.115, 1.09
No. of reflections	4630
No. of parameters	272
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.90
Absolute structure	Flack (1983), 1941 Friedel pairs
Absolute structure parameter	0.02 (3)

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXTL (Sheldrick, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N6ⁱ	0.93	2.59	3.261 (11)	129

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

Acknowledgements

This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (grant No. R01-2008-000-20955-0). The authors acknowledge the Korea Basic Science Institute for the X-ray data collection.

References

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