Bis[2-(methyl-amino)-troponato]copper(II).

In the title compound, [Cu(C(8)H(8)NO)(2)], a strictly square-planar geometry about the Cu(II) metal atom is observed. Substitution of an O atom with a methyl-functionalized N atom does not significantly alter the bond distances and angles in the copper(II) complex when compared with a similar bis-(troponato)copper(II) complex. π-π stacking is observed between the tropolone rings, with inter-planar distances of 3.5039 (16) and 3.2933 (15) Å, respectively. Additional stabilisation of the structure is accomplished through C-H⋯O hydrogen-bonding interactions.

Related literature

For related literature on values of bond lengths and angles, see: Zhang et al. (2008 ▶); Hill & Steyl (2008 ▶); Kristiansson (2002 ▶). For similar structures, see: Liang et al. (2001 ▶). For other related structures, see: Starikova & Shugam (1969 ▶); Byrn et al. (1993 ▶); Park & Marshall (2005 ▶); Dessy & Fares (1979 ▶); Baidina et al. (2004 ▶). For the synthesis of the title compound, see: Roesky & Burgstein (1999 ▶); Claramunt et al. (2004 ▶). For background and the use of the title compound, see: Roesky (2000 ▶); Nepveu et al. (1993 ▶); Crous et al. (2005 ▶); Roodt et al. (2003 ▶); Steyl (2005 ▶); Steyl et al. (2001 ▶).

Experimental

Crystal data

[Cu(C8H8NO)2]

M = 331.85

Monoclinic,

a = 6.7541 (9) Å

b = 9.1599 (12) Å

c = 22.084 (3) Å

β = 92.108 (5)°

V = 1365.3 (3) Å3

Z = 4

Mo Kα radiation

μ = 1.61 mm−1

T = 100 K

0.34 × 0.32 × 0.17 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.583, T max = 0.760

21665 measured reflections

2985 independent reflections

2804 reflections with I > 2σ(I)

R int = 0.032

Refinement

R[F 2 > 2σ(F 2)] = 0.022

wR(F 2) = 0.066

S = 1.06

2985 reflections

190 parameters

H-atom parameters constrained

Δρmax = 0.36 e Å−3

Δρmin = −0.38 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2004 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenberg & Putz, 2004 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810043503/pk2271sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810043503/pk2271Isup2.hkl

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

[Cu(C8H8NO)2]	F(000) = 684
Mr = 331.85	Dx = 1.614 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6754 reflections
a = 6.7541 (9) Å	θ = 2.4–28.2°
b = 9.1599 (12) Å	µ = 1.61 mm−1
c = 22.084 (3) Å	T = 100 K
β = 92.108 (5)°	Cuboid, black
V = 1365.3 (3) Å3	0.34 × 0.32 × 0.17 mm
Z = 4

Bruker APEXII CCD area-detector diffractometer	2985 independent reflections
graphite	2804 reflections with I > 2σ(I)
Detector resolution: 8.5 pixels mm-1	Rint = 0.032
φ and ω scans	θmax = 27.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −8→8
Tmin = 0.583, Tmax = 0.760	k = −10→11
21665 measured reflections	l = −28→28

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)] = 0.022	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.066	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0363P)2 + 0.8483P] where P = (Fo2 + 2Fc2)/3
2985 reflections	(Δ/σ)max < 0.001
190 parameters	Δρmax = 0.36 e Å−3
0 restraints	Δρmin = −0.38 e Å−3

Experimental. First 80 frames repeated after collection for monitoring possible decay.

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
C11	0.0756 (2)	0.73761 (16)	−0.03802 (6)	0.0123 (3)
C12	−0.1170 (2)	0.68077 (16)	−0.01916 (6)	0.0117 (3)
C13	−0.2292 (2)	0.57152 (18)	−0.05113 (7)	0.0152 (3)
H13	−0.3515	0.5479	−0.0336	0.018*
C14	−0.1913 (2)	0.49449 (18)	−0.10280 (7)	0.0172 (3)
H14	−0.2907	0.4259	−0.1147	0.021*
C15	−0.0299 (2)	0.50069 (18)	−0.14071 (7)	0.0171 (3)
H15	−0.0326	0.4366	−0.1746	0.02*
C16	0.1324 (2)	0.59075 (18)	−0.13361 (7)	0.0157 (3)
H16	0.2282	0.5813	−0.1638	0.019*
C17	0.1773 (2)	0.69413 (17)	−0.08858 (7)	0.0141 (3)
H17	0.2993	0.7436	−0.0934	0.017*
C18	−0.3658 (2)	0.70243 (17)	0.05564 (6)	0.0136 (3)
H18A	−0.3873	0.7593	0.0924	0.02*
H18B	−0.364	0.5982	0.0656	0.02*
H18C	−0.4732	0.7221	0.0257	0.02*
C21	−0.0559 (2)	1.02279 (16)	0.17475 (6)	0.0119 (3)
C22	0.1447 (2)	1.06912 (16)	0.15765 (6)	0.0113 (3)
C23	0.2695 (2)	1.16602 (17)	0.19214 (7)	0.0145 (3)
H23	0.3988	1.1773	0.1773	0.017*
C24	0.2340 (2)	1.24600 (17)	0.24341 (7)	0.0172 (3)
H24	0.3422	1.3042	0.2578	0.021*
C25	0.0645 (2)	1.25541 (17)	0.27773 (7)	0.0176 (3)
H25	0.0693	1.3219	0.3108	0.021*
C26	−0.1089 (2)	1.17780 (18)	0.26841 (7)	0.0167 (3)
H26	−0.2094	1.1981	0.2962	0.02*
C27	−0.1587 (2)	1.07348 (18)	0.22402 (7)	0.0146 (3)
H27	−0.2848	1.0296	0.2283	0.018*
C28	0.3903 (2)	1.04390 (17)	0.08191 (7)	0.0136 (3)
H28A	0.4064	0.9896	0.0442	0.02*
H28B	0.4966	1.0171	0.1112	0.02*
H28C	0.3965	1.1489	0.0737	0.02*
N1	−0.17729 (18)	0.74362 (14)	0.03074 (5)	0.0117 (2)
N2	0.19904 (18)	1.00838 (14)	0.10669 (5)	0.0117 (2)
O1	0.15352 (16)	0.83831 (13)	−0.00342 (5)	0.0158 (2)
O2	−0.14060 (15)	0.92738 (13)	0.13907 (5)	0.0142 (2)
Cu	0.00529 (2)	0.881953 (19)	0.067482 (7)	0.01073 (8)

	U11	U22	U33	U12	U13	U23
C11	0.0124 (7)	0.0115 (7)	0.0126 (6)	0.0001 (5)	−0.0022 (5)	0.0015 (5)
C12	0.0118 (7)	0.0108 (7)	0.0122 (6)	0.0004 (5)	−0.0013 (5)	0.0018 (5)
C13	0.0146 (7)	0.0149 (8)	0.0161 (7)	−0.0032 (6)	0.0009 (5)	−0.0008 (6)
C14	0.0190 (7)	0.0146 (8)	0.0178 (7)	−0.0037 (6)	−0.0027 (6)	−0.0030 (6)
C15	0.0222 (8)	0.0142 (8)	0.0147 (7)	0.0012 (6)	−0.0007 (6)	−0.0048 (6)
C16	0.0183 (7)	0.0160 (8)	0.0128 (7)	0.0034 (6)	0.0016 (6)	−0.0005 (6)
C17	0.0137 (7)	0.0136 (8)	0.0150 (7)	−0.0007 (6)	0.0004 (5)	0.0005 (5)
C18	0.0122 (7)	0.0146 (8)	0.0142 (7)	−0.0020 (6)	0.0019 (5)	−0.0006 (5)
C21	0.0135 (7)	0.0103 (7)	0.0116 (6)	0.0000 (5)	−0.0024 (5)	0.0028 (5)
C22	0.0120 (7)	0.0094 (7)	0.0123 (6)	0.0013 (5)	−0.0016 (5)	0.0024 (5)
C23	0.0134 (7)	0.0143 (8)	0.0158 (7)	−0.0009 (6)	−0.0013 (5)	0.0000 (6)
C24	0.0210 (8)	0.0134 (8)	0.0166 (7)	−0.0028 (6)	−0.0048 (6)	−0.0014 (6)
C25	0.0274 (8)	0.0133 (8)	0.0120 (7)	−0.0008 (6)	−0.0006 (6)	−0.0026 (5)
C26	0.0224 (8)	0.0162 (8)	0.0118 (7)	0.0015 (6)	0.0030 (6)	0.0001 (6)
C27	0.0160 (7)	0.0150 (8)	0.0128 (7)	−0.0010 (6)	0.0006 (5)	0.0017 (6)
C28	0.0106 (7)	0.0151 (8)	0.0152 (7)	−0.0013 (5)	0.0006 (5)	−0.0007 (5)
N1	0.0115 (6)	0.0115 (6)	0.0122 (6)	−0.0012 (5)	0.0000 (4)	0.0008 (5)
N2	0.0114 (6)	0.0110 (6)	0.0127 (6)	−0.0007 (5)	−0.0011 (4)	−0.0003 (5)
O1	0.0145 (5)	0.0185 (6)	0.0143 (5)	−0.0058 (4)	0.0019 (4)	−0.0048 (4)
O2	0.0137 (5)	0.0167 (6)	0.0123 (5)	−0.0035 (4)	0.0008 (4)	−0.0027 (4)
Cu	0.01051 (11)	0.01176 (12)	0.00990 (11)	−0.00228 (6)	−0.00007 (7)	−0.00182 (6)

C11—O1	1.2970 (18)	C21—C22	1.482 (2)
C11—C17	1.390 (2)	C22—N2	1.3196 (19)
C11—C12	1.475 (2)	C22—C23	1.425 (2)
C12—N1	1.3210 (19)	C23—C24	1.377 (2)
C12—C13	1.426 (2)	C23—H23	0.95
C13—C14	1.374 (2)	C24—C25	1.399 (2)
C13—H13	0.95	C24—H24	0.95
C14—C15	1.400 (2)	C25—C26	1.379 (2)
C14—H14	0.95	C25—H25	0.95
C15—C16	1.376 (2)	C26—C27	1.401 (2)
C15—H15	0.95	C26—H26	0.95
C16—C17	1.398 (2)	C27—H27	0.95
C16—H16	0.95	C28—N2	1.4582 (18)
C17—H17	0.95	C28—H28A	0.98
C18—N1	1.4551 (18)	C28—H28B	0.98
C18—H18A	0.98	C28—H28C	0.98
C18—H18B	0.98	N1—Cu	1.9263 (12)
C18—H18C	0.98	N2—Cu	1.9287 (12)
C21—O2	1.2958 (18)	O1—Cu	1.9312 (11)
C21—C27	1.392 (2)	O2—Cu	1.9385 (11)
O1—C11—C17	118.36 (13)	C24—C23—H23	114.6
O1—C11—C12	115.32 (13)	C22—C23—H23	114.6
C17—C11—C12	126.32 (14)	C23—C24—C25	130.46 (15)
N1—C12—C13	122.96 (13)	C23—C24—H24	114.8
N1—C12—C11	112.57 (13)	C25—C24—H24	114.8
C13—C12—C11	124.46 (13)	C26—C25—C24	126.51 (15)
C14—C13—C12	131.26 (14)	C26—C25—H25	116.7
C14—C13—H13	114.4	C24—C25—H25	116.7
C12—C13—H13	114.4	C25—C26—C27	129.55 (15)
C13—C14—C15	130.47 (15)	C25—C26—H26	115.2
C13—C14—H14	114.8	C27—C26—H26	115.2
C15—C14—H14	114.8	C21—C27—C26	131.35 (15)
C16—C15—C14	126.19 (15)	C21—C27—H27	114.3
C16—C15—H15	116.9	C26—C27—H27	114.3
C14—C15—H15	116.9	N2—C28—H28A	109.5
C15—C16—C17	129.65 (15)	N2—C28—H28B	109.5
C15—C16—H16	115.2	H28A—C28—H28B	109.5
C17—C16—H16	115.2	N2—C28—H28C	109.5
C11—C17—C16	131.64 (15)	H28A—C28—H28C	109.5
C11—C17—H17	114.2	H28B—C28—H28C	109.5
C16—C17—H17	114.2	C12—N1—C18	120.21 (12)
N1—C18—H18A	109.5	C12—N1—Cu	115.20 (10)
N1—C18—H18B	109.5	C18—N1—Cu	124.54 (10)
H18A—C18—H18B	109.5	C22—N2—C28	120.26 (12)
N1—C18—H18C	109.5	C22—N2—Cu	115.52 (10)
H18A—C18—H18C	109.5	C28—N2—Cu	124.15 (10)
H18B—C18—H18C	109.5	C11—O1—Cu	114.43 (9)
O2—C21—C27	118.58 (13)	C21—O2—Cu	114.48 (9)
O2—C21—C22	115.20 (13)	N1—Cu—N2	175.77 (5)
C27—C21—C22	126.21 (14)	N1—Cu—O1	82.26 (5)
N2—C22—C23	122.75 (13)	N2—Cu—O1	97.17 (5)
N2—C22—C21	112.46 (13)	N1—Cu—O2	98.51 (5)
C23—C22—C21	124.78 (13)	N2—Cu—O2	82.06 (5)
C24—C23—C22	130.81 (14)	O1—Cu—O2	179.23 (4)
O1—C11—C12—N1	−0.08 (18)	C13—C12—N1—C18	0.0 (2)
C17—C11—C12—N1	−179.70 (14)	C11—C12—N1—C18	179.21 (12)
O1—C11—C12—C13	179.09 (14)	C13—C12—N1—Cu	177.49 (11)
C17—C11—C12—C13	−0.5 (2)	C11—C12—N1—Cu	−3.32 (16)
N1—C12—C13—C14	−179.73 (16)	C23—C22—N2—C28	−2.6 (2)
C11—C12—C13—C14	1.2 (3)	C21—C22—N2—C28	178.48 (12)
C12—C13—C14—C15	−0.7 (3)	C23—C22—N2—Cu	−179.61 (11)
C13—C14—C15—C16	−0.3 (3)	C21—C22—N2—Cu	1.49 (16)
C14—C15—C16—C17	0.5 (3)	C17—C11—O1—Cu	−176.94 (11)
O1—C11—C17—C16	−179.83 (16)	C12—C11—O1—Cu	3.41 (16)
C12—C11—C17—C16	−0.2 (3)	C27—C21—O2—Cu	173.51 (11)
C15—C16—C17—C11	0.1 (3)	C22—C21—O2—Cu	−5.60 (16)
O2—C21—C22—N2	2.74 (18)	C12—N1—Cu—O1	4.09 (10)
C27—C21—C22—N2	−176.28 (14)	C18—N1—Cu—O1	−178.57 (12)
O2—C21—C22—C23	−176.13 (14)	C12—N1—Cu—O2	−175.85 (10)
C27—C21—C22—C23	4.8 (2)	C18—N1—Cu—O2	1.49 (12)
N2—C22—C23—C24	175.20 (16)	C22—N2—Cu—O1	176.53 (11)
C21—C22—C23—C24	−6.0 (3)	C28—N2—Cu—O1	−0.34 (12)
C22—C23—C24—C25	0.7 (3)	C22—N2—Cu—O2	−3.48 (11)
C23—C24—C25—C26	3.1 (3)	C28—N2—Cu—O2	179.66 (12)
C24—C25—C26—C27	0.0 (3)	C11—O1—Cu—N1	−4.09 (10)
O2—C21—C27—C26	−177.74 (16)	C11—O1—Cu—N2	171.68 (10)
C22—C21—C27—C26	1.3 (3)	C21—O2—Cu—N1	−179.20 (10)
C25—C26—C27—C21	−4.0 (3)	C21—O2—Cu—N2	5.04 (10)

D—H···A	D—H	H···A	D···A	D—H···A
C18—H18A···O2	0.98	2.47	3.1222 (18)	124
C28—H28A···O1	0.98	2.41	3.0715 (18)	124

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C18—H18A⋯O2	0.98	2.47	3.1222 (18)	124
C28—H28A⋯O1	0.98	2.41	3.0715 (18)	124