Acetonitrile­{2-[3-(dimethyl­amino)propyl­imino­meth­yl]-4-nitro­phenolato-κ3N,N′,O}(thio­cyanato-κN)copper(II)

Ye, L.-J.; You, Z.

doi:10.1107/S1600536807025342

Buy article online - an online subscription or single-article purchase is required to access this article.

Acetonitrile{2-[3-(dimethylamino)propyliminomethyl]-4-nitrophenolato-κ³N,N′,O}(thiocyanato-κN)copper(II)

L.-J. Ye and Z. . You

In the title mononuclear copper(II) complex, [Cu(C₁₂H₁₆N₃O₃)(NCS)(C₂H₃N)], the Cu^II atom is five-coordinated in a square-pyramidal geometry, with one O and two N atoms of the Schiff-base ligand and one N atom of the thiocyanate ligand defining the basal plane. The apical position is occupied by the N atom of the acetonitrile molecule. The structure is stabilized by intramolecular C—H

N and intermolecular C—H

O hydrogen-bonding interactions.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025342/rz2144sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025342/rz2144Isup2.hkl Contains datablock I

CCDC reference: 654721

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.003 Å
R factor = 0.037
wR factor = 0.098
Data-to-parameter ratio = 18.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         N3
PLAT241_ALERT_2_C Check High      Ueq as Compared to Neighbors for         N4
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         N5
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C13
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        C14

Alert level G
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       2.19

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   5 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   5 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

Comment top

Recently, we have reported a thiocyanate coordinated zinc(II) complex (Ye & You, 2007). As an extension of the work on the crystal structures of such complexes, we report herein the crystal structure of the title compound, (I).

The Cu^II atom in (I) is five-coordinated in a square-pyramidal geometry, with one O and two N atoms of the Schiff base ligand and one N atom of the thiocyanate ligand defining the basal plane, and the N atom of the acetonitrile group occupying the apical position (Fig. 1). Selected bond distances and angles within the coordination sphere of the metal are given in Table 1. The molecular and crystal structures are stabilized by C—H···N and C—H···O hydrogen bonds (Table 2).

Related literature top

For related literature, see: Ye & You (2007); Hu et al. (2005).

Experimental top

5-Nitrosalicylaldehyde (0.1 mmol, 16.5 mg), N,N-dimethylpropane-1,3-diamine (0.1 mmol, 10.2 mg), ammonium thiocyanate (0.1 mmol, 7.6 mg), and copper acetate monohydrate (0.1 mmol, 20.0 mg) were dissolved in an acetonitrile solution (10 ml). The mixture was stirred at room temperature for 10 min, giving a clear blue solution. Crystals of the title compound were formed by slow evaporation of the solvent over a week at room temperature.

Structure description top

For related literature, see: Ye & You (2007); Hu et al. (2005).

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2002); software used to prepare material for publication: SHELXL97.

Figures top

Fig. 1. The molecular structure of the title compound, shown with 30% probability displacement ellipsoids.

Acetonitrile{2-[3-(dimethylamino)propyliminomethyl]-4-nitrophenolato- κ³N,N',O}(thiocyanato-κN)copper(II) top

Crystal data top

[Cu(C₁₂H₁₆N₃O₃)(NCS)(C₂H₃N)]	F(000) = 852
M_r = 412.95	D_x = 1.487 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3875 reflections
a = 12.507 (2) Å	θ = 2.3–24.5°
b = 11.552 (1) Å	µ = 1.32 mm⁻¹
c = 12.787 (2) Å	T = 298 K
β = 93.543 (1)°	Block, blue
V = 1844.0 (4) Å³	0.23 × 0.21 × 0.20 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	4186 independent reflections
Radiation source: fine-focus sealed tube	3143 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→16
T_min = 0.745, T_max = 0.770	k = −14→14
15401 measured reflections	l = −16→16

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)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.098	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0462P)² + 0.3686P] where P = (F_o² + 2F_c²)/3
4186 reflections	(Δ/σ)_max < 0.001
229 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

[Cu(C₁₂H₁₆N₃O₃)(NCS)(C₂H₃N)]	V = 1844.0 (4) Å³
M_r = 412.95	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.507 (2) Å	µ = 1.32 mm⁻¹
b = 11.552 (1) Å	T = 298 K
c = 12.787 (2) Å	0.23 × 0.21 × 0.20 mm
β = 93.543 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	4186 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3143 reflections with I > 2σ(I)
T_min = 0.745, T_max = 0.770	R_int = 0.035
15401 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	0 restraints
wR(F²) = 0.098	H-atom parameters constrained
S = 1.02	Δρ_max = 0.31 e Å⁻³
4186 reflections	Δρ_min = −0.25 e Å⁻³
229 parameters

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	0.21596 (2)	0.93882 (2)	0.25457 (2)	0.04336 (11)
S1	0.26057 (7)	0.83713 (8)	−0.09663 (6)	0.0811 (3)
O1	0.36548 (13)	0.89111 (16)	0.27255 (15)	0.0596 (5)
O2	0.68408 (15)	1.2638 (2)	0.4508 (2)	0.0856 (7)
O3	0.79311 (14)	1.1489 (2)	0.38151 (18)	0.0819 (7)
N1	0.23620 (14)	1.03387 (16)	0.38324 (14)	0.0414 (4)
N2	0.06710 (15)	1.01357 (17)	0.21204 (15)	0.0452 (5)
N3	0.14008 (19)	0.7828 (2)	0.3335 (2)	0.0679 (6)
N4	0.22514 (18)	0.8813 (2)	0.11039 (18)	0.0656 (6)
N5	0.70235 (15)	1.1749 (2)	0.40349 (17)	0.0544 (5)
C1	0.42878 (17)	1.05305 (18)	0.37335 (17)	0.0387 (5)
C2	0.44268 (19)	0.95528 (19)	0.30748 (19)	0.0448 (5)
C3	0.5498 (2)	0.9310 (2)	0.2819 (2)	0.0561 (7)
H3	0.5630	0.8650	0.2431	0.067*
C4	0.63293 (19)	1.0008 (2)	0.31240 (19)	0.0537 (6)
H4	0.7016	0.9838	0.2929	0.064*
C5	0.61515 (17)	1.0982 (2)	0.37302 (18)	0.0437 (5)
C6	0.51490 (17)	1.1218 (2)	0.40523 (17)	0.0414 (5)
H6	0.5049	1.1847	0.4490	0.050*
C7	0.32677 (18)	1.07729 (19)	0.41476 (18)	0.0408 (5)
H7	0.3266	1.1297	0.4699	0.049*
C8	0.14448 (19)	1.0635 (2)	0.44447 (19)	0.0508 (6)
H8A	0.1690	1.1113	0.5035	0.061*
H8B	0.1146	0.9930	0.4719	0.061*
C9	0.05886 (19)	1.1266 (2)	0.3807 (2)	0.0532 (6)
H9A	0.0908	1.1918	0.3463	0.064*
H9B	0.0072	1.1570	0.4271	0.064*
C10	0.00110 (19)	1.0514 (2)	0.2987 (2)	0.0545 (6)
H10A	−0.0255	0.9831	0.3328	0.065*
H10B	−0.0604	1.0937	0.2687	0.065*
C11	0.0905 (2)	1.1145 (2)	0.1461 (2)	0.0619 (7)
H11A	0.0247	1.1522	0.1234	0.093*
H11B	0.1265	1.0890	0.0860	0.093*
H11C	0.1356	1.1678	0.1860	0.093*
C12	−0.0019 (2)	0.9324 (2)	0.1481 (2)	0.0624 (7)
H12A	−0.0136	0.8636	0.1879	0.094*
H12B	0.0328	0.9124	0.0856	0.094*
H12C	−0.0694	0.9687	0.1294	0.094*
C13	0.24112 (19)	0.8638 (2)	0.0250 (2)	0.0520 (6)
C14	0.1136 (2)	0.7100 (2)	0.3835 (2)	0.0528 (6)
C15	0.0798 (2)	0.6164 (3)	0.4485 (2)	0.0713 (8)
H15A	0.1241	0.6145	0.5125	0.107*
H15B	0.0862	0.5444	0.4120	0.107*
H15C	0.0065	0.6281	0.4641	0.107*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.04219 (18)	0.04213 (18)	0.04608 (18)	−0.00245 (12)	0.00523 (12)	−0.00212 (12)
S1	0.1006 (6)	0.0958 (6)	0.0481 (4)	0.0151 (5)	0.0143 (4)	0.0046 (4)
O1	0.0443 (10)	0.0475 (10)	0.0868 (13)	0.0035 (8)	0.0027 (9)	−0.0201 (9)
O2	0.0455 (11)	0.0814 (15)	0.128 (2)	−0.0016 (10)	−0.0067 (11)	−0.0378 (14)
O3	0.0350 (10)	0.1144 (18)	0.0968 (16)	0.0000 (11)	0.0085 (10)	−0.0257 (14)
N1	0.0392 (10)	0.0449 (11)	0.0406 (10)	0.0004 (8)	0.0073 (8)	0.0032 (8)
N2	0.0432 (11)	0.0459 (11)	0.0465 (11)	−0.0023 (9)	0.0029 (9)	0.0004 (9)
N3	0.0707 (15)	0.0561 (14)	0.0764 (16)	−0.0128 (12)	0.0011 (12)	0.0113 (13)
N4	0.0653 (15)	0.0780 (16)	0.0540 (14)	0.0053 (13)	0.0064 (11)	−0.0135 (12)
N5	0.0352 (11)	0.0694 (15)	0.0578 (13)	0.0048 (10)	−0.0037 (9)	−0.0001 (11)
C1	0.0388 (12)	0.0389 (12)	0.0383 (11)	0.0053 (9)	0.0010 (9)	0.0066 (9)
C2	0.0447 (13)	0.0403 (13)	0.0493 (13)	0.0073 (10)	0.0010 (10)	0.0019 (10)
C3	0.0479 (14)	0.0573 (16)	0.0632 (17)	0.0129 (12)	0.0046 (12)	−0.0134 (13)
C4	0.0382 (13)	0.0689 (17)	0.0543 (15)	0.0120 (12)	0.0053 (11)	0.0003 (13)
C5	0.0350 (12)	0.0511 (13)	0.0446 (13)	0.0048 (10)	−0.0016 (10)	0.0060 (11)
C6	0.0385 (12)	0.0442 (13)	0.0410 (12)	0.0080 (10)	−0.0009 (9)	0.0018 (10)
C7	0.0413 (12)	0.0425 (13)	0.0386 (12)	0.0038 (10)	0.0026 (9)	0.0014 (9)
C8	0.0416 (13)	0.0644 (16)	0.0475 (13)	−0.0065 (12)	0.0121 (11)	−0.0042 (12)
C9	0.0407 (13)	0.0600 (16)	0.0603 (15)	0.0010 (12)	0.0144 (11)	−0.0095 (13)
C10	0.0370 (12)	0.0663 (17)	0.0607 (16)	−0.0002 (11)	0.0069 (11)	−0.0048 (13)
C11	0.0709 (18)	0.0526 (16)	0.0627 (17)	0.0043 (14)	0.0085 (14)	0.0101 (13)
C12	0.0526 (15)	0.0692 (18)	0.0637 (17)	−0.0074 (13)	−0.0101 (13)	−0.0108 (14)
C13	0.0489 (14)	0.0508 (15)	0.0563 (16)	0.0029 (11)	0.0036 (12)	0.0008 (12)
C14	0.0508 (14)	0.0462 (14)	0.0613 (16)	−0.0044 (12)	0.0015 (12)	−0.0010 (13)
C15	0.079 (2)	0.0554 (17)	0.080 (2)	−0.0118 (16)	0.0143 (16)	0.0121 (15)

Geometric parameters (Å, º) top

Cu1—O1	1.950 (2)	C4—C5	1.391 (4)
Cu1—N4	1.970 (2)	C4—H4	0.9300
Cu1—N1	1.981 (2)	C5—C6	1.371 (3)
Cu1—N2	2.093 (2)	C6—H6	0.9300
Cu1—N3	2.299 (2)	C7—H7	0.9300
S1—C13	1.618 (3)	C8—C9	1.495 (3)
O1—C2	1.276 (3)	C8—H8A	0.9700
O2—N5	1.220 (3)	C8—H8B	0.9700
O3—N5	1.224 (3)	C9—C10	1.511 (3)
N1—C7	1.281 (3)	C9—H9A	0.9700
N1—C8	1.469 (3)	C9—H9B	0.9700
N2—C11	1.479 (3)	C10—H10A	0.9700
N2—C12	1.485 (3)	C10—H10B	0.9700
N2—C10	1.487 (3)	C11—H11A	0.9600
N3—C14	1.119 (3)	C11—H11B	0.9600
N4—C13	1.140 (3)	C11—H11C	0.9600
N5—C5	1.441 (3)	C12—H12A	0.9600
C1—C6	1.379 (3)	C12—H12B	0.9600
C1—C2	1.426 (3)	C12—H12C	0.9600
C1—C7	1.439 (3)	C14—C15	1.443 (4)
C2—C3	1.427 (3)	C15—H15A	0.9600
C3—C4	1.354 (4)	C15—H15B	0.9600
C3—H3	0.9300	C15—H15C	0.9600

O1—Cu1—N4	84.49 (9)	C1—C6—H6	119.7
O1—Cu1—N1	89.22 (7)	N1—C7—C1	126.5 (2)
N4—Cu1—N1	162.26 (9)	N1—C7—H7	116.7
O1—Cu1—N2	168.09 (8)	C1—C7—H7	116.7
N4—Cu1—N2	89.91 (9)	N1—C8—C9	112.3 (2)
N1—Cu1—N2	93.04 (7)	N1—C8—H8A	109.1
O1—Cu1—N3	98.37 (8)	C9—C8—H8A	109.1
N4—Cu1—N3	101.30 (10)	N1—C8—H8B	109.1
N1—Cu1—N3	96.01 (8)	C9—C8—H8B	109.1
N2—Cu1—N3	93.03 (8)	H8A—C8—H8B	107.9
C2—O1—Cu1	125.21 (15)	C8—C9—C10	113.2 (2)
C7—N1—C8	116.47 (19)	C8—C9—H9A	108.9
C7—N1—Cu1	122.92 (15)	C10—C9—H9A	108.9
C8—N1—Cu1	120.52 (15)	C8—C9—H9B	108.9
C11—N2—C12	108.2 (2)	C10—C9—H9B	108.9
C11—N2—C10	109.4 (2)	H9A—C9—H9B	107.8
C12—N2—C10	105.38 (19)	N2—C10—C9	115.0 (2)
C11—N2—Cu1	105.60 (15)	N2—C10—H10A	108.5
C12—N2—Cu1	111.08 (16)	C9—C10—H10A	108.5
C10—N2—Cu1	116.96 (15)	N2—C10—H10B	108.5
C14—N3—Cu1	170.0 (2)	C9—C10—H10B	108.5
C13—N4—Cu1	168.5 (3)	H10A—C10—H10B	107.5
O2—N5—O3	121.7 (2)	N2—C11—H11A	109.5
O2—N5—C5	119.4 (2)	N2—C11—H11B	109.5
O3—N5—C5	118.9 (2)	H11A—C11—H11B	109.5
C6—C1—C2	120.6 (2)	N2—C11—H11C	109.5
C6—C1—C7	118.2 (2)	H11A—C11—H11C	109.5
C2—C1—C7	121.0 (2)	H11B—C11—H11C	109.5
O1—C2—C1	123.3 (2)	N2—C12—H12A	109.5
O1—C2—C3	120.4 (2)	N2—C12—H12B	109.5
C1—C2—C3	116.2 (2)	H12A—C12—H12B	109.5
C4—C3—C2	122.1 (2)	N2—C12—H12C	109.5
C4—C3—H3	118.9	H12A—C12—H12C	109.5
C2—C3—H3	118.9	H12B—C12—H12C	109.5
C3—C4—C5	119.7 (2)	N4—C13—S1	178.4 (3)
C3—C4—H4	120.1	N3—C14—C15	179.7 (3)
C5—C4—H4	120.1	C14—C15—H15A	109.5
C6—C5—C4	120.6 (2)	C14—C15—H15B	109.5
C6—C5—N5	119.2 (2)	H15A—C15—H15B	109.5
C4—C5—N5	120.2 (2)	C14—C15—H15C	109.5
C5—C6—C1	120.6 (2)	H15A—C15—H15C	109.5
C5—C6—H6	119.7	H15B—C15—H15C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12B···N4	0.96	2.43	2.969 (3)	115
C10—H10B···O3ⁱ	0.97	2.48	3.082 (3)	120

Symmetry code: (i) x−1, y, z.

Experimental details

Crystal data
Chemical formula	[Cu(C₁₂H₁₆N₃O₃)(NCS)(C₂H₃N)]
M_r	412.95
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	12.507 (2), 11.552 (1), 12.787 (2)
β (°)	93.543 (1)
V (Å³)	1844.0 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	1.32
Crystal size (mm)	0.23 × 0.21 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.745, 0.770
No. of measured, independent and observed [I > 2σ(I)] reflections	15401, 4186, 3143
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.098, 1.02
No. of reflections	4186
No. of parameters	229
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.25

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2002), SHELXL97.

Selected geometric parameters (Å, º) top

Cu1—O1	1.950 (2)	Cu1—N2	2.093 (2)
Cu1—N4	1.970 (2)	Cu1—N3	2.299 (2)
Cu1—N1	1.981 (2)

O1—Cu1—N4	84.49 (9)	N1—Cu1—N2	93.04 (7)
O1—Cu1—N1	89.22 (7)	O1—Cu1—N3	98.37 (8)
N4—Cu1—N1	162.26 (9)	N4—Cu1—N3	101.30 (10)
O1—Cu1—N2	168.09 (8)	N1—Cu1—N3	96.01 (8)
N4—Cu1—N2	89.91 (9)	N2—Cu1—N3	93.03 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12B···N4	0.96	2.43	2.969 (3)	114.9
C10—H10B···O3ⁱ	0.97	2.48	3.082 (3)	119.7

Symmetry code: (i) x−1, y, z.

Subscribe to Acta Crystallographica Section E: Crystallographic Communications

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.

E-mail address*
Repeat e-mail address* (for error checking)

Format*	PDF (US $40)
	HTML (US $40)
	PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number (non-UK EC countries only)
Country*

Terms and conditions of use
Contact us

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page