catena-Poly[[{2-[2-(isopropyl­amino)ethyl­imino­meth­yl]-4-nitro­phenolato}copper(II)]-μ-chlorido]

The title compound, [Cu(C₁₂H₁₆N₃O₃)Cl]_n, is a chloride-bridged polymeric copper(II) complex. The Cu^II atom is five-coordinate in a square-pyramidal geometry, with one O and two N atoms of the Schiff base ligand and one Cl atom defining the basal plane [Cu...Cl = 2.2703 (8) Å] and a symmetry-related Cl atom occupying the apical position [2.8531 (9) Å]. The chloride-bridged polymeric chain runs along the b axis.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.042
• wR factor = 0.096
• Data-to-parameter ratio = 17.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT062_ALERT_4_C Rescale T(min) & T(max) by .....................       0.96
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Cu1    -   Cl1_a   ..       5.93 su

Alert level G
PLAT793_ALERT_1_G Check the Absolute Configuration of N3     .....          S
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
   2 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 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
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

The title compound is a chloride-bridged polynuclear copper(II) complex (Fig. 1). 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 Cl atom defining the basal plane (Cu···Cl = 2.2703 (8) Å), and a symmetry-related Cl atom occupying the apical position (2.8531 (9) Å). Selected bond distances and angles within the coordination sphere of the metal atom are given in Table 1. The crystal structure is stabilized by N—H···O and and C—H···O hydrogen bonds (Table 2).

Related literature

For related literature, see: Ye & You (2007a,b).

S2. Experimental

5-Nitrosalicylaldehyde (0.1 mmol, 16.5 mg), N-isopropylethane-1,2-diamine (0.1 mmol, 10.2 mg), and copper chloride dihydrate (0.1 mmol, 17.0 mg) were dissolved in a methanol solution (10 ml). The mixture was stirred at room temperature for 30 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.

S3. Refinement

Atom H3A was located from a difference Fourier map and refined isotropically, with the N—H distance restrained to 0.90 (1) Å, and with the U_iso(H) value fixed at 0.08 Ų. The remaining 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) = 1.2 or 1.5U_eq(C).

Computing details

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 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. Part of the polymeric structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level. unlabelled atoms are related to labelled atoms by the symmetry operation (3/2 - x, -1/2 + y, 1/2 - z).

catena-Poly[[{2-[2-(isopropylamino)ethyliminomethyl]-4-νitrophenolato}copper(II)]-µ-chlorido]

Crystal data

[Cu(C12H16N3O3)Cl]	F(000) = 716
Mr = 349.27	Dx = 1.643 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3124 reflections
a = 9.762 (1) Å	θ = 2.2–26.0°
b = 6.415 (1) Å	µ = 1.75 mm^−1
c = 22.611 (3) Å	T = 298 K
β = 94.353 (2)°	Block, blue
V = 1411.9 (3) Å^3	0.33 × 0.29 × 0.27 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	3196 independent reflections
Radiation source: fine-focus sealed tube	2607 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
ω scans	θmax = 27.5°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→12
Tmin = 0.597, Tmax = 0.650	k = −8→8
11191 measured reflections	l = −28→29

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0355P)^2 + 1.0385P] where P = (Fo^2 + 2Fc^2)/3
3196 reflections	(Δ/σ)max = 0.001
186 parameters	Δρmax = 0.47 e Å^−3
1 restraint	Δρmin = −0.50 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	0.76386 (4)	0.83895 (5)	0.181248 (15)	0.02930 (12)
Cl1	0.87605 (8)	1.08051 (11)	0.24016 (3)	0.03700 (19)
O1	0.1740 (3)	0.9670 (5)	−0.04462 (13)	0.0726 (9)
O2	0.1089 (3)	1.2464 (5)	−0.00250 (13)	0.0774 (9)
O3	0.6076 (2)	1.0252 (3)	0.17348 (9)	0.0350 (5)
N1	0.1850 (3)	1.0962 (5)	−0.00511 (14)	0.0507 (7)
N2	0.6771 (3)	0.6547 (4)	0.11980 (11)	0.0323 (5)
N3	0.9188 (2)	0.6230 (4)	0.18510 (11)	0.0303 (5)
C1	0.4874 (3)	0.8788 (4)	0.08619 (13)	0.0315 (6)
C2	0.5112 (3)	1.0351 (4)	0.13091 (13)	0.0305 (6)
C3	0.4235 (3)	1.2127 (5)	0.12726 (15)	0.0382 (7)
H3	0.4372	1.3183	0.1553	0.046*
C4	0.3191 (3)	1.2319 (5)	0.08343 (15)	0.0415 (8)
H4	0.2629	1.3490	0.0821	0.050*
C5	0.2974 (3)	1.0762 (5)	0.04096 (14)	0.0388 (7)
C6	0.3792 (3)	0.9025 (5)	0.04230 (14)	0.0365 (7)
H6	0.3627	0.7991	0.0138	0.044*
C7	0.5695 (3)	0.6920 (4)	0.08538 (13)	0.0328 (7)
H7	0.5422	0.5905	0.0576	0.039*
C8	0.7463 (3)	0.4534 (4)	0.11834 (15)	0.0401 (8)
H8A	0.7286	0.3895	0.0796	0.048*
H8B	0.7124	0.3609	0.1479	0.048*
C9	0.8987 (3)	0.4889 (5)	0.13117 (14)	0.0370 (7)
H9A	0.9455	0.3567	0.1380	0.044*
H9B	0.9363	0.5571	0.0977	0.044*
C10	1.0653 (3)	0.6924 (5)	0.19822 (14)	0.0347 (7)
H10	1.0672	0.7827	0.2332	0.042*
C11	1.1140 (4)	0.8217 (6)	0.14826 (17)	0.0536 (9)
H11A	1.1254	0.7339	0.1146	0.080*
H11B	1.2003	0.8856	0.1608	0.080*
H11C	1.0474	0.9279	0.1376	0.080*
C12	1.1584 (4)	0.5073 (6)	0.21439 (17)	0.0523 (9)
H12A	1.1618	0.4174	0.1806	0.078*
H12B	1.1229	0.4314	0.2465	0.078*
H12C	1.2492	0.5563	0.2263	0.078*
H3A	0.893 (4)	0.546 (6)	0.2159 (12)	0.080*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.0326 (2)	0.02052 (18)	0.0340 (2)	0.00192 (14)	−0.00242 (14)	−0.00460 (14)
Cl1	0.0400 (4)	0.0272 (4)	0.0427 (4)	−0.0004 (3)	−0.0037 (3)	−0.0090 (3)
O1	0.071 (2)	0.074 (2)	0.0672 (19)	0.0107 (16)	−0.0334 (15)	−0.0090 (16)
O2	0.0700 (19)	0.092 (2)	0.0670 (19)	0.0411 (18)	−0.0155 (15)	0.0043 (17)
O3	0.0360 (11)	0.0289 (11)	0.0385 (12)	0.0066 (9)	−0.0067 (9)	−0.0082 (9)
N1	0.0459 (18)	0.0576 (19)	0.0476 (18)	0.0078 (15)	−0.0037 (14)	0.0140 (16)
N2	0.0373 (14)	0.0217 (12)	0.0370 (14)	0.0000 (10)	−0.0036 (11)	−0.0020 (10)
N3	0.0318 (13)	0.0247 (12)	0.0343 (14)	−0.0002 (10)	0.0011 (10)	−0.0004 (10)
C1	0.0332 (16)	0.0267 (15)	0.0341 (16)	−0.0016 (12)	−0.0004 (12)	0.0028 (12)
C2	0.0302 (15)	0.0251 (14)	0.0363 (16)	0.0003 (11)	0.0040 (12)	0.0040 (12)
C3	0.0424 (18)	0.0287 (16)	0.0432 (18)	0.0053 (13)	0.0016 (14)	−0.0010 (13)
C4	0.0407 (18)	0.0356 (17)	0.0485 (19)	0.0125 (14)	0.0055 (15)	0.0114 (15)
C5	0.0348 (17)	0.0464 (19)	0.0349 (17)	0.0031 (14)	−0.0004 (13)	0.0121 (15)
C6	0.0397 (17)	0.0340 (16)	0.0351 (17)	−0.0017 (13)	−0.0014 (13)	0.0002 (13)
C7	0.0420 (17)	0.0235 (14)	0.0319 (15)	−0.0022 (12)	−0.0030 (13)	−0.0046 (12)
C8	0.050 (2)	0.0201 (15)	0.0480 (19)	0.0028 (13)	−0.0091 (15)	−0.0089 (13)
C9	0.0436 (18)	0.0237 (15)	0.0429 (18)	0.0070 (13)	−0.0018 (14)	−0.0083 (13)
C10	0.0320 (16)	0.0322 (16)	0.0393 (17)	0.0009 (12)	−0.0020 (13)	−0.0027 (13)
C11	0.044 (2)	0.058 (2)	0.059 (2)	−0.0113 (17)	0.0042 (17)	0.0095 (19)
C12	0.042 (2)	0.049 (2)	0.064 (2)	0.0144 (16)	−0.0056 (17)	−0.0030 (18)

Geometric parameters (Å, º)

Cu1—O3	1.935 (2)	C4—C5	1.390 (5)
Cu1—N2	1.966 (3)	C4—H4	0.93
Cu1—N3	2.048 (3)	C5—C6	1.370 (4)
Cu1—Cl1	2.2703 (8)	C6—H6	0.93
Cu1—Cl1^i	2.8531 (9)	C7—H7	0.93
O1—N1	1.217 (4)	C8—C9	1.511 (4)
O2—N1	1.221 (4)	C8—H8A	0.97
O3—C2	1.296 (3)	C8—H8B	0.97
N1—C5	1.460 (4)	C9—H9A	0.97
N2—C7	1.281 (4)	C9—H9B	0.97
N2—C8	1.459 (4)	C10—C11	1.507 (5)
N3—C9	1.493 (4)	C10—C12	1.523 (4)
N3—C10	1.506 (4)	C10—H10	0.98
N3—H3A	0.91 (3)	C11—H11A	0.96
C1—C6	1.402 (4)	C11—H11B	0.96
C1—C2	1.431 (4)	C11—H11C	0.96
C1—C7	1.443 (4)	C12—H12A	0.96
C2—C3	1.424 (4)	C12—H12B	0.96
C3—C4	1.372 (4)	C12—H12C	0.96
C3—H3	0.93
O3—Cu1—N2	90.74 (10)	C4—C5—N1	119.8 (3)
O3—Cu1—N3	174.91 (9)	C5—C6—C1	120.7 (3)
N2—Cu1—N3	84.29 (11)	C5—C6—H6	119.7
O3—Cu1—Cl1	88.48 (8)	C1—C6—H6	119.7
N2—Cu1—Cl1	171.01 (8)	N2—C7—C1	125.3 (3)
N3—Cu1—Cl1	96.60 (9)	N2—C7—H7	117.3
O3—Cu1—Cl1^i	90.23 (7)	C1—C7—H7	117.3
N2—Cu1—Cl1^i	83.67 (8)	N2—C8—C9	108.3 (2)
N3—Cu1—Cl1^i	88.13 (7)	N2—C8—H8A	110.0
Cl1—Cu1—Cl1^i	105.28 (2)	C9—C8—H8A	110.0
C2—O3—Cu1	128.38 (18)	N2—C8—H8B	110.0
O1—N1—O2	123.6 (3)	C9—C8—H8B	110.0
O1—N1—C5	118.9 (3)	H8A—C8—H8B	108.4
O2—N1—C5	117.5 (3)	N3—C9—C8	108.0 (2)
C7—N2—C8	120.8 (2)	N3—C9—H9A	110.1
C7—N2—Cu1	127.3 (2)	C8—C9—H9A	110.1
C8—N2—Cu1	111.87 (19)	N3—C9—H9B	110.1
C9—N3—C10	113.3 (2)	C8—C9—H9B	110.1
C9—N3—Cu1	107.72 (18)	H9A—C9—H9B	108.4
C10—N3—Cu1	119.73 (18)	N3—C10—C11	111.3 (3)
C9—N3—H3A	107 (3)	N3—C10—C12	110.9 (3)
C10—N3—H3A	109 (3)	C11—C10—C12	113.1 (3)
Cu1—N3—H3A	99 (3)	N3—C10—H10	107.0
C6—C1—C2	119.8 (3)	C11—C10—H10	107.0
C6—C1—C7	118.1 (3)	C12—C10—H10	107.0
C2—C1—C7	122.0 (3)	C10—C11—H11A	109.5
O3—C2—C3	118.8 (3)	C10—C11—H11B	109.5
O3—C2—C1	124.1 (3)	H11A—C11—H11B	109.5
C3—C2—C1	117.1 (3)	C10—C11—H11C	109.5
C4—C3—C2	121.6 (3)	H11A—C11—H11C	109.5
C4—C3—H3	119.2	H11B—C11—H11C	109.5
C2—C3—H3	119.2	C10—C12—H12A	109.5
C3—C4—C5	120.1 (3)	C10—C12—H12B	109.5
C3—C4—H4	120.0	H12A—C12—H12B	109.5
C5—C4—H4	120.0	C10—C12—H12C	109.5
C6—C5—C4	120.7 (3)	H12A—C12—H12C	109.5
C6—C5—N1	119.5 (3)	H12B—C12—H12C	109.5

Symmetry code: (i) −x+3/2, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O3^i	0.91 (3)	2.51 (3)	3.288 (4)	145 (3)
C8—H8B···O3^ii	0.97	2.47	3.345 (3)	150
C9—H9B···O2^iii	0.97	2.50	3.365 (4)	148

Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) x, y−1, z; (iii) −x+1, −y+2, −z.