Chloro­{2-[tris­(hydroxy­meth­yl)methyl­imino­meth­yl]phenolato}copper(II)

In the title compound, [Cu(C₁₁H₁₄NO₄)Cl], the tridentate Schiff base ligand coordinates to the metal atom through the N and O atoms, forming a square-planar coordination geometry.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.035
• wR factor = 0.077
• Data-to-parameter ratio = 17.7

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT417_ALERT_2_C Short Inter D-H..H-D       H3     ..  H4      ..       2.10 Ang.
PLAT432_ALERT_2_C Short Inter X...Y Contact  O1     ..  C7      ..       2.99 Ang.

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           27.86
           From the CIF: _reflns_number_total               2918
           Count of symmetry unique reflns         1654
           Completeness (_total/calc)            176.42%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1264
           Fraction of Friedel pairs measured     0.764
           Are heavy atom types Z>Si present        yes

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

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   1 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

The chemistry of transition metal ion complexes of hydroxy (aryl and alkyl OH) rich molecules containing imine/amine groups is important in biomimetic chemistry (Cornman et al., 1992). Many complexes of this kind have been reported (Asgedom & Rao, 1996; Dey, Rao, Saarenketo & Rissanen, 2002; Dey, Rao, Saarenketo, Rissanen & Kolehmainen, 2002). We report here a new copper(II) complex, (I), with a tridentate Schiff base ligand.

In compound (I), the Cu^II center is four-coordinated in a square-planar configuration by one N and two O atoms of the Schiff base ligand and one Cl atom. The Cu—O bond lengths are 1.885 (2) and 1.979 (2) Å; the shorter distance between copper and the phenoxy O atom indicates that the electronegativity of atom O1 is stronger than that of the other O atoms of the ligand.

S2. Experimental

The ligand 2-[tris(hydroxymethyl)methyliminomethyl]phenol was prepared according to the literature procedure of Asgedom et al. (1996). Cuprous chloride (0.105 g, 0.5 mmol) was added to a solution of the ligand (0.111 g, 0.5 mmol) in water (10 ml). After stirring for a short time, the solution turned dark green. The filtrate was left for 2 d at room temperature and green needle-shaped crystals were obtained in about 62% yield.

S3. Refinement

H atoms were placed in idealized positions [N—H = 0.82 Å, C—H = 0.93–0.97 Å and U_iso(H) = 1.2U_eq(C)] and were included in the refinement in the riding-model approximation.

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: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. An ORTEPII plot (Johnson, 1976) of (I), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radii.

Chloro{2-[tris(hydroxymethyl)methyliminomethyl]phenolato}copper(II)

Crystal data

[Cu(C11H14NO4)Cl]	Dx = 1.750 Mg m^−3
Mr = 323.22	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P421c	Cell parameters from 1879 reflections
Hall symbol: P -4 2n	θ = 2.4–23.3°
a = 16.7345 (6) Å	µ = 2.00 mm^−1
c = 8.7634 (6) Å	T = 293 K
V = 2454.1 (2) Å^3	Needle, green
Z = 8	0.21 × 0.09 × 0.07 mm
F(000) = 1320

Data collection

Bruker APEX area-dectector diffractometer	2918 independent reflections
Radiation source: fine-focus sealed tube	2661 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.049
ϕ and ω scans	θmax = 27.9°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −21→21
Tmin = 0.679, Tmax = 0.873	k = −21→21
20984 measured reflections	l = −11→11

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.077	w = 1/[σ^2(Fo^2) + (0.0354P)^2 + 1.812P] where P = (Fo^2 + 2Fc^2)/3
S = 1.01	(Δ/σ)max = 0.001
2918 reflections	Δρmax = 0.36 e Å^−3
165 parameters	Δρmin = −0.21 e Å^−3
0 restraints	Absolute structure: Flack (1983), 1265 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.007 (15)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.18286 (2)	0.741879 (19)	0.09321 (5)	0.02794 (11)
Cl1	0.28495 (5)	0.76534 (5)	−0.06532 (11)	0.0405 (2)
N1	0.09148 (14)	0.73905 (15)	0.2314 (3)	0.0234 (5)
O1	0.21555 (13)	0.63628 (13)	0.1344 (3)	0.0335 (5)
O2	0.13204 (14)	0.84338 (13)	0.0301 (3)	0.0351 (5)
H2A	0.1380	0.8636	−0.0544	0.053*
O3	−0.08821 (14)	0.86992 (15)	0.2373 (2)	0.0337 (5)
H3	−0.1088	0.8869	0.3158	0.051*
O4	0.07400 (15)	0.84538 (14)	0.5015 (3)	0.0337 (5)
H4	0.1005	0.8046	0.5127	0.051*
C1	0.1834 (2)	0.58627 (18)	0.2323 (3)	0.0289 (6)
C2	0.2141 (2)	0.5080 (2)	0.2414 (4)	0.0376 (8)
H2	0.2556	0.4931	0.1770	0.045*
C3	0.1843 (2)	0.4534 (2)	0.3426 (4)	0.0439 (9)
H3A	0.2054	0.4020	0.3446	0.053*
C4	0.1232 (2)	0.4736 (2)	0.4422 (4)	0.0421 (9)
H4A	0.1051	0.4370	0.5140	0.051*
C5	0.0901 (2)	0.54798 (19)	0.4334 (4)	0.0354 (7)
H5	0.0483	0.5611	0.4987	0.043*
C6	0.11758 (19)	0.60572 (18)	0.3277 (4)	0.0278 (6)
C7	0.07552 (17)	0.68002 (18)	0.3202 (3)	0.0249 (6)
H7	0.0324	0.6862	0.3860	0.030*
C8	0.04322 (17)	0.81324 (18)	0.2348 (3)	0.0234 (6)
C9	0.05021 (18)	0.84912 (19)	0.0741 (4)	0.0298 (7)
H9A	0.0167	0.8198	0.0031	0.036*
H9B	0.0333	0.9046	0.0747	0.036*
C10	−0.04503 (17)	0.79829 (18)	0.2701 (3)	0.0273 (6)
H10A	−0.0651	0.7547	0.2080	0.033*
H10B	−0.0515	0.7840	0.3766	0.033*
C11	0.0808 (2)	0.87221 (18)	0.3487 (4)	0.0295 (7)
H11A	0.1368	0.8793	0.3239	0.035*
H11B	0.0547	0.9237	0.3390	0.035*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.02737 (19)	0.02232 (17)	0.03414 (19)	0.00267 (14)	0.00942 (16)	0.00233 (16)
Cl1	0.0386 (4)	0.0303 (4)	0.0527 (5)	0.0000 (3)	0.0219 (4)	0.0010 (4)
N1	0.0232 (12)	0.0231 (12)	0.0239 (12)	−0.0004 (10)	0.0004 (9)	−0.0011 (10)
O1	0.0352 (11)	0.0274 (10)	0.0378 (13)	0.0095 (10)	0.0115 (10)	0.0053 (9)
O2	0.0352 (12)	0.0351 (12)	0.0350 (12)	0.0087 (10)	0.0143 (10)	0.0136 (10)
O3	0.0281 (11)	0.0502 (14)	0.0228 (11)	0.0163 (11)	0.0025 (9)	0.0021 (10)
O4	0.0450 (14)	0.0304 (12)	0.0258 (12)	0.0083 (10)	−0.0084 (10)	−0.0055 (9)
C1	0.0315 (16)	0.0292 (15)	0.0261 (15)	0.0050 (13)	−0.0033 (13)	−0.0009 (12)
C2	0.0416 (19)	0.0308 (16)	0.0404 (19)	0.0082 (15)	0.0033 (16)	0.0012 (15)
C3	0.050 (2)	0.0251 (16)	0.056 (2)	0.0072 (16)	−0.0002 (19)	0.0070 (15)
C4	0.044 (2)	0.0311 (17)	0.051 (2)	−0.0064 (15)	0.0007 (17)	0.0187 (16)
C5	0.0349 (16)	0.0338 (16)	0.0376 (19)	−0.0021 (14)	0.0031 (15)	0.0046 (14)
C6	0.0310 (17)	0.0234 (15)	0.0291 (16)	−0.0039 (12)	−0.0021 (13)	0.0024 (13)
C7	0.0228 (14)	0.0268 (15)	0.0251 (14)	−0.0017 (12)	0.0024 (11)	−0.0033 (13)
C8	0.0231 (13)	0.0272 (14)	0.0197 (13)	0.0033 (13)	0.0002 (11)	−0.0003 (12)
C9	0.0282 (14)	0.0331 (15)	0.0282 (16)	0.0081 (12)	0.0063 (13)	0.0062 (14)
C10	0.0235 (14)	0.0352 (17)	0.0232 (14)	0.0031 (13)	−0.0003 (11)	0.0002 (13)
C11	0.0331 (16)	0.0210 (14)	0.0344 (17)	0.0042 (13)	−0.0034 (13)	−0.0021 (13)

Geometric parameters (Å, º)

Cu1—O1	1.885 (2)	C3—C4	1.386 (5)
Cu1—N1	1.951 (2)	C3—H3A	0.93
Cu1—O2	1.979 (2)	C4—C5	1.365 (5)
Cu1—Cl1	2.2366 (8)	C4—H4A	0.93
N1—C7	1.286 (4)	C5—C6	1.415 (4)
N1—C8	1.481 (4)	C5—H5	0.93
O1—C1	1.313 (4)	C6—C7	1.430 (4)
O2—C9	1.426 (3)	C7—H7	0.93
O2—H2A	0.82	C8—C11	1.538 (4)
O3—C10	1.429 (4)	C8—C10	1.529 (4)
O3—H3	0.82	C8—C9	1.535 (4)
O4—C11	1.417 (4)	C9—H9A	0.97
O4—H4	0.82	C9—H9B	0.97
C1—C2	1.408 (4)	C10—H10A	0.97
C1—C6	1.421 (4)	C10—H10B	0.97
C2—C3	1.367 (5)	C11—H11A	0.97
C2—H2	0.93	C11—H11B	0.97
O1—Cu1—N1	94.92 (10)	C5—C6—C1	118.7 (3)
O1—Cu1—O2	169.50 (10)	C5—C6—C7	117.6 (3)
N1—Cu1—O2	81.81 (10)	C1—C6—C7	123.6 (3)
O1—Cu1—Cl1	93.56 (7)	N1—C7—C6	126.4 (3)
N1—Cu1—Cl1	171.25 (8)	N1—C7—H7	116.8
O2—Cu1—Cl1	90.22 (7)	C6—C7—H7	116.8
C7—N1—C8	121.2 (2)	N1—C8—C11	109.1 (2)
C7—N1—Cu1	123.9 (2)	N1—C8—C10	113.2 (2)
C8—N1—Cu1	114.80 (18)	C11—C8—C10	111.6 (2)
C1—O1—Cu1	127.2 (2)	N1—C8—C9	105.5 (2)
C9—O2—Cu1	113.26 (17)	C11—C8—C9	108.3 (3)
C9—O2—H2A	109.5	C10—C8—C9	108.9 (2)
Cu1—O2—H2A	123.7	O2—C9—C8	107.2 (2)
C10—O3—H3	109.5	O2—C9—H9A	110.3
C11—O4—H4	109.5	C8—C9—H9A	110.3
O1—C1—C2	118.7 (3)	O2—C9—H9B	110.3
O1—C1—C6	123.7 (3)	C8—C9—H9B	110.3
C2—C1—C6	117.5 (3)	H9A—C9—H9B	108.5
C3—C2—C1	121.7 (3)	O3—C10—C8	108.1 (2)
C3—C2—H2	119.1	O3—C10—H10A	110.1
C1—C2—H2	119.1	C8—C10—H10A	110.1
C2—C3—C4	120.9 (3)	O3—C10—H10B	110.1
C2—C3—H3A	119.5	C8—C10—H10B	110.1
C4—C3—H3A	119.5	H10A—C10—H10B	108.4
C5—C4—C3	119.1 (3)	O4—C11—C8	112.2 (2)
C5—C4—H4A	120.5	O4—C11—H11A	109.2
C3—C4—H4A	120.5	C8—C11—H11A	109.2
C4—C5—C6	121.9 (3)	O4—C11—H11B	109.2
C4—C5—H5	119.1	C8—C11—H11B	109.2
C6—C5—H5	119.1	H11A—C11—H11B	107.9
O1—Cu1—N1—C7	5.2 (2)	C2—C1—C6—C7	−173.8 (3)
O2—Cu1—N1—C7	175.2 (2)	C8—N1—C7—C6	−179.9 (3)
O1—Cu1—N1—C8	−178.54 (19)	Cu1—N1—C7—C6	−3.9 (4)
O2—Cu1—N1—C8	−8.59 (19)	C5—C6—C7—N1	−179.7 (3)
N1—Cu1—O1—C1	−2.7 (3)	C1—C6—C7—N1	−1.6 (5)
O2—Cu1—O1—C1	−74.0 (6)	C7—N1—C8—C11	91.1 (3)
Cl1—Cu1—O1—C1	175.1 (3)	Cu1—N1—C8—C11	−85.3 (2)
O1—Cu1—O2—C9	54.0 (6)	C7—N1—C8—C10	−33.9 (4)
N1—Cu1—O2—C9	−18.4 (2)	Cu1—N1—C8—C10	149.79 (18)
Cl1—Cu1—O2—C9	165.2 (2)	C7—N1—C8—C9	−152.8 (3)
Cu1—O1—C1—C2	176.9 (2)	Cu1—N1—C8—C9	30.9 (3)
Cu1—O1—C1—C6	−1.4 (4)	Cu1—O2—C9—C8	39.6 (3)
O1—C1—C2—C3	178.9 (3)	N1—C8—C9—O2	−43.8 (3)
C6—C1—C2—C3	−2.8 (5)	C11—C8—C9—O2	72.9 (3)
C1—C2—C3—C4	−1.0 (6)	C10—C8—C9—O2	−165.6 (2)
C2—C3—C4—C5	3.1 (6)	N1—C8—C10—O3	−167.3 (2)
C3—C4—C5—C6	−1.4 (6)	C11—C8—C10—O3	69.1 (3)
C4—C5—C6—C1	−2.4 (5)	C9—C8—C10—O3	−50.3 (3)
C4—C5—C6—C7	175.9 (3)	N1—C8—C11—O4	−68.1 (3)
O1—C1—C6—C5	−177.4 (3)	C10—C8—C11—O4	57.7 (3)
C2—C1—C6—C5	4.4 (5)	C9—C8—C11—O4	177.5 (2)
O1—C1—C6—C7	4.5 (5)