catena-Poly[[[2-[(2-methyl­amino­ethyl­imino)methyl]­-4-nitrophenolato]­copper(II)]-μ-thio­cyanato]

The title compound, [Cu(C₁₀H₁₂N₃O₃)(NCS)], is a thio­cyanate-bridged polynuclear copper(II) complex. The Cu^II atom is penta­coordinated by two N atoms and one O atom of the Schiff base ligand, 4-nitro-2-[(2-methyl­amino­ethyl­imino)­meth­yl]phenol (HNP), and by two N atoms from symmetry-related thio­cyanate anions, forming a slightly distorted square-pyramidal coordination configuration. The Cu(NP) units are linked through the bridging thio­cyanate anions, forming chains running along the c direction.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.037
• wR factor = 0.097
• Data-to-parameter ratio = 16.6

checkCIF/PLATON results

No syntax errors found



Alert level C
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        C11
PLAT420_ALERT_2_C D-H Without Acceptor       N2     -   H2     ...          ?

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of N2     = ...          R
PLAT794_ALERT_5_G Check Predicted Bond Valency for Cu1         (2)       2.30
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......          1

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 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

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S1. Comment

Recently, the author has reported the cf.ystal structure of a mononuclear copper(II) complex derived from the Schiff base ligand 1-[3-(cyclohexylamino)propyliminomethyl]-2-naphthol (Zhang, 2004). As an extension of this work, on the structural characterization of Schiff base copper compounds, we report here on the crystal structure of the new title polynuclear complex.

The title compound is a thiocyanato-bridged polynuclear copper(II) complex, as shown in Fig. 1. The Cu^II atom is pentacoordinated by the NNO donor atoms of the Schiff base ligand, 4-nitro-2-[(2-methylaminoethylimino)methyl]phenol(HNP), and by two N atoms from two thiocyanate anions, so forming a slightly distorted square pyramidal coordination configuration. The Cu(NP) units are linked through the bridging thiocyanate anions, forming chains running along the c direction. The bond lengths and angles (Table 1) are within normal ranges and comparable to the values of the complex referred to above.

Related literature

For related literature, see: Zhang (2004).

S2. Experimental

N-Methyl-1,2-diaminoethane (0.1 mmol, 7.4 mg) and 5-nitrosalicylaldehyde (0.1 mmol, 16.7 mg) were dissolved in ethanol (10 cm³). The mixture was stirred for 10 min to give a clear yellow solution. To the solution was added an aqueous solution (2 cm³) of ammonium thiocyanate (0.1 mmol, 7.6 mg) and CuCl₂.2H₂O (0.1 mmol, 17.1 mg), with stirring. The mixture was stirred at room temperature for 1 h and then filtered. After keeping the brown filtrate in air for five days, blue block-shaped crystals were formed with high yield (87% based on 5-nitrosalicylaldehyde).

S3. Refinement

The N—H H-atom was located in a difference Fourier map and refined isotropically, with the N—H distance restrained to 0.90 (1) Å. The other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C—H distances in the range 0.93–0.97 Å, and with U_iso(H) = 1.2U_eq(C) and 1.5U_eq(methyl C).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures

Fig. 1. The structure of the title complex, showing the atom-numbering scheme with displacement ellipsoids drawn at the 30% probability level.

catena-Poly[[[2-[(2- methylaminoethylimino)methyl]-4-nitrophenolato]copper(II)]-µ-thiocyanato]

Crystal data

[Cu(C10H12N3O3)(NCS)]	F(000) = 700
Mr = 343.85	Dx = 1.693 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2670 reflections
a = 10.6144 (12) Å	θ = 2.5–25.9°
b = 11.2212 (13) Å	µ = 1.79 mm^−1
c = 11.7323 (14) Å	T = 298 K
β = 105.160 (2)°	Block, blue
V = 1348.8 (3) Å^3	0.12 × 0.12 × 0.09 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	3073 independent reflections
Radiation source: fine-focus sealed tube	2257 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ω scans	θmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
Tmin = 0.814, Tmax = 0.856	k = −14→14
11164 measured reflections	l = −15→14

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.037	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0487P)^2 + 0.1747P] where P = (Fo^2 + 2Fc^2)/3
3073 reflections	(Δ/σ)max < 0.001
185 parameters	Δρmax = 0.56 e Å^−3
1 restraint	Δρmin = −0.39 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.36112 (3)	0.75795 (3)	0.17031 (3)	0.04190 (13)
S1	0.57494 (8)	0.78609 (8)	0.57534 (6)	0.0540 (2)
O1	0.3209 (2)	0.59558 (17)	0.20010 (15)	0.0497 (5)
O2	0.0453 (2)	0.1542 (2)	−0.0731 (2)	0.0775 (7)
O3	−0.0014 (3)	0.2839 (2)	−0.2116 (2)	0.0934 (9)
N1	0.2374 (2)	0.76051 (18)	0.01592 (19)	0.0381 (5)
N2	0.3757 (2)	0.9355 (2)	0.1417 (2)	0.0499 (6)
N3	0.0476 (3)	0.2569 (2)	−0.1091 (3)	0.0563 (7)
N4	0.4606 (3)	0.7728 (2)	0.3345 (2)	0.0584 (7)
C1	0.1869 (2)	0.5502 (2)	0.0052 (2)	0.0345 (5)
C2	0.2510 (2)	0.5216 (2)	0.1262 (2)	0.0394 (6)
C3	0.2321 (3)	0.4050 (3)	0.1644 (2)	0.0461 (7)
H3	0.2665	0.3859	0.2436	0.055*
C4	0.1658 (3)	0.3198 (3)	0.0900 (3)	0.0479 (7)
H4	0.1558	0.2437	0.1179	0.057*
C5	0.1131 (2)	0.3482 (2)	−0.0283 (2)	0.0415 (6)
C6	0.1200 (2)	0.4613 (2)	−0.0692 (2)	0.0388 (6)
H6	0.0795	0.4792	−0.1477	0.047*
C7	0.1822 (2)	0.6689 (2)	−0.0415 (2)	0.0386 (6)
H7	0.1354	0.6803	−0.1196	0.046*
C8	0.2156 (3)	0.8792 (2)	−0.0400 (2)	0.0472 (7)
H8A	0.1386	0.9158	−0.0251	0.057*
H8B	0.2024	0.8720	−0.1247	0.057*
C9	0.3341 (3)	0.9543 (3)	0.0121 (2)	0.0502 (7)
H9A	0.4043	0.9323	−0.0226	0.060*
H9B	0.3138	1.0378	−0.0050	0.060*
C10	0.2983 (4)	1.0049 (3)	0.2052 (3)	0.0852 (12)
H10A	0.3056	1.0882	0.1894	0.128*
H10B	0.3302	0.9907	0.2885	0.128*
H10C	0.2084	0.9811	0.1793	0.128*
C11	0.5081 (3)	0.7796 (2)	0.4342 (2)	0.0393 (6)
H2	0.4577 (16)	0.964 (3)	0.171 (3)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0555 (2)	0.0438 (2)	0.02492 (17)	−0.00736 (15)	0.00780 (14)	−0.00031 (13)
S1	0.0494 (4)	0.0807 (6)	0.0288 (3)	−0.0122 (4)	0.0044 (3)	−0.0053 (3)
O1	0.0690 (13)	0.0490 (12)	0.0253 (9)	−0.0143 (10)	0.0019 (9)	0.0051 (8)
O2	0.0818 (17)	0.0491 (15)	0.102 (2)	−0.0157 (12)	0.0242 (15)	−0.0172 (14)
O3	0.118 (2)	0.0742 (18)	0.0644 (18)	−0.0119 (16)	−0.0183 (16)	−0.0234 (14)
N1	0.0433 (12)	0.0406 (13)	0.0305 (10)	0.0012 (9)	0.0101 (9)	0.0043 (9)
N2	0.0591 (16)	0.0448 (14)	0.0450 (13)	−0.0032 (11)	0.0118 (12)	−0.0030 (11)
N3	0.0482 (15)	0.0514 (18)	0.0671 (19)	−0.0020 (12)	0.0114 (14)	−0.0173 (14)
N4	0.0746 (18)	0.0677 (18)	0.0312 (12)	−0.0234 (14)	0.0108 (12)	−0.0012 (11)
C1	0.0330 (13)	0.0420 (15)	0.0291 (12)	0.0026 (10)	0.0090 (10)	0.0008 (10)
C2	0.0418 (15)	0.0458 (16)	0.0301 (13)	0.0004 (12)	0.0084 (11)	0.0034 (11)
C3	0.0516 (17)	0.0473 (17)	0.0360 (14)	0.0005 (13)	0.0053 (12)	0.0092 (12)
C4	0.0451 (16)	0.0401 (17)	0.0570 (18)	0.0025 (12)	0.0107 (14)	0.0084 (13)
C5	0.0321 (14)	0.0432 (16)	0.0491 (16)	0.0005 (11)	0.0103 (12)	−0.0106 (13)
C6	0.0326 (13)	0.0501 (16)	0.0328 (13)	0.0056 (11)	0.0068 (10)	−0.0021 (12)
C7	0.0388 (14)	0.0484 (17)	0.0274 (12)	0.0058 (12)	0.0063 (11)	0.0048 (11)
C8	0.0551 (18)	0.0446 (17)	0.0411 (15)	0.0043 (13)	0.0109 (13)	0.0113 (12)
C9	0.0621 (19)	0.0406 (16)	0.0507 (17)	0.0011 (13)	0.0195 (14)	0.0058 (13)
C10	0.121 (3)	0.073 (3)	0.060 (2)	0.021 (2)	0.023 (2)	−0.0222 (19)
C11	0.0426 (15)	0.0452 (16)	0.0315 (13)	−0.0097 (11)	0.0119 (11)	−0.0017 (11)

Geometric parameters (Å, º)

Cu1—O1	1.9240 (19)	C1—C2	1.441 (3)
Cu1—N1	1.940 (2)	C2—C3	1.413 (4)
Cu1—N4	1.947 (3)	C3—C4	1.361 (4)
Cu1—N2	2.033 (3)	C3—H3	0.9300
S1—C11	1.623 (3)	C4—C5	1.392 (4)
O1—C2	1.287 (3)	C4—H4	0.9300
O2—N3	1.231 (3)	C5—C6	1.366 (4)
O3—N3	1.217 (4)	C6—H6	0.9300
N1—C7	1.284 (3)	C7—H7	0.9300
N1—C8	1.476 (3)	C8—C9	1.505 (4)
N2—C10	1.468 (4)	C8—H8A	0.9700
N2—C9	1.484 (3)	C8—H8B	0.9700
N2—H2	0.906 (10)	C9—H9A	0.9700
N3—C5	1.444 (3)	C9—H9B	0.9700
N4—C11	1.149 (4)	C10—H10A	0.9600
C1—C6	1.392 (3)	C10—H10B	0.9600
C1—C7	1.435 (4)	C10—H10C	0.9600
O1—Cu1—N1	93.18 (8)	C3—C4—H4	120.5
O1—Cu1—N4	89.43 (9)	C5—C4—H4	120.5
N1—Cu1—N4	169.22 (11)	C6—C5—C4	121.3 (3)
O1—Cu1—N2	171.14 (9)	C6—C5—N3	119.3 (3)
N1—Cu1—N2	83.89 (9)	C4—C5—N3	119.4 (3)
N4—Cu1—N2	91.96 (10)	C5—C6—C1	120.7 (2)
C2—O1—Cu1	127.24 (16)	C5—C6—H6	119.6
C7—N1—C8	119.5 (2)	C1—C6—H6	119.6
C7—N1—Cu1	125.64 (18)	N1—C7—C1	125.3 (2)
C8—N1—Cu1	114.68 (17)	N1—C7—H7	117.4
C10—N2—C9	112.9 (3)	C1—C7—H7	117.4
C10—N2—Cu1	111.0 (2)	N1—C8—C9	107.9 (2)
C9—N2—Cu1	107.05 (17)	N1—C8—H8A	110.1
C10—N2—H2	104 (2)	C9—C8—H8A	110.1
C9—N2—H2	109 (2)	N1—C8—H8B	110.1
Cu1—N2—H2	113 (2)	C9—C8—H8B	110.1
O3—N3—O2	122.0 (3)	H8A—C8—H8B	108.4
O3—N3—C5	118.7 (3)	N2—C9—C8	109.2 (2)
O2—N3—C5	119.3 (3)	N2—C9—H9A	109.8
C11—N4—Cu1	173.4 (3)	C8—C9—H9A	109.8
C6—C1—C7	117.6 (2)	N2—C9—H9B	109.8
C6—C1—C2	119.4 (2)	C8—C9—H9B	109.8
C7—C1—C2	122.9 (2)	H9A—C9—H9B	108.3
O1—C2—C3	119.2 (2)	N2—C10—H10A	109.5
O1—C2—C1	124.1 (2)	N2—C10—H10B	109.5
C3—C2—C1	116.7 (2)	H10A—C10—H10B	109.5
C4—C3—C2	122.7 (2)	N2—C10—H10C	109.5
C4—C3—H3	118.7	H10A—C10—H10C	109.5
C2—C3—H3	118.7	H10B—C10—H10C	109.5
C3—C4—C5	118.9 (3)	N4—C11—S1	178.8 (3)