Chloro­bis­[4,4-bis(hydroxy­methyl)-2-(2-pyridyl)-4,5-di­hydro­oxazole-N,N']copper(II) chloride hemi­hydrate

The title compound, [CuCl(C₁₀H₁₂N₂O₃)₂]Cl·0.5H₂O, is composed of discrete complex cations, Cl^- anions and water mol­ecules. The O atom of the water mol­ecule lies on a twofold rotation axis. The [CuN₄Cl] coordination polyhedron is intermediate between square pyramidal and trigonal bipy­ramidal.

S1. Comment

The oxazole ring shows an interesting structure and is present in a wide variety of compounds which are of interest in many fields of application (Frump, 1971). The preparation of 2-substituted-2-oxazolines, involving heterocyclic ring-forming processes between nitriles and aminoalcohols, is higly desirable (Brunner & Oberman, 1989; Bolm et al., 1991). The formation of some new 2-pyridinyl-2-oxazolines and their Ni^II, Co^II and Cu^II have been reported (Segĺa & Jamnický, 1993; Segĺa et al., 1998). \sch

The Cu^II centre is five-coordinated by four N donors from two ligands and by and a chloride ligand (Fig. 1). The coordination polyhedron around the Cu^II is intermediate between square-pyramidal and trigonal bipyramidal, and is very similar to that in [CuBr(L)₂]Br.1/2H₂O (Segĺa et al., 1998)·The τ parameter for both complexes is 0.48 (Addison et al., 1984). The Cu—N bond distances in the title complex (see Table 2) are similar to those in the analogues [CuBr(L)₂]Br.1/2H₂O complex [Cu—N1 = 2.018 (4), Cu—N2 = 2.093 (4), Cu—N3 = 2.001 (4), Cu—N4 = 2.201 (5) Å] (Segĺa et al., 1998). The two ligands L in [CuCl(L)₂]⁺ are almost perpendicular, the dihedral angle between the N1,N2,C5,C6,Cu1 and N3,N4,C15,C16,Cu1 planes being 83.44 (6)°. The –OH group (O3—H12) on one oxazoline ring is disordered over two positions with occupation parameters 0.75 for O3—H12 and 0.25 for O3a—H12a (Fig. 1). The chloride anion linked by hydrogen bonds [Cl2···H11 2.30, Cl2···H25ⁱ 2.16 and Cl2···H24ⁱⁱ 2.31 Å; symmetry codes: (i) -x, y, 1/2 - z; (ii) 1/2 + x, 1/2 - y, 1/2 + z]. The O7 atom of water molecule is bonded by hydrogen bond to H23 (O7···H23 1.97 Å].

S2. Experimental

The title compound was obtained by an analogous reaction to that described by Segĺa et al. (1998). Equimolar quantities of pyridine-2-carbonitrile and 2-amino-2-hydroxymethyl-1,3-propandiol were added to an ethanolic solution of anhydrous copper(II) chloride and the mixture was heated for 30 min. at 333 K. After several days blue-green crystals of the title complex appeared. The density of the crystals was measured by flotation in C₆H₆/CHBr₃

S3. Refinement

The H atoms on C10 corresponding to the minor disorder component of O3 have not been included. With the exception of H25 (on water oxygen O7) which was located from a ΔF synthesis and refined as part of a rigid rotating group, other H atoms were placed geometrically and refined as part of a riding model.

Computing details

Data collection: SYNTEX P2₁ software (Syntex, 1973); cell refinement: SYNTEX P2₁ software; data reduction: XP21 (Pavelčík, 1993); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Johnson, 1965); software used to prepare material for publication: SHELXL97.

Figures

Fig. 1. A view of the title complex cation with displacement ellipsoids drawn at the 30% probability level and H atoms shown as spheres of arbitary radii.

(I)

Crystal data

[CuCl(C10H12N2O3)2]Cl·0.5H2O	F(000) = 2304
Mr = 559.88	Dx = 1.621 Mg m^−3 Dm = 1.62 Mg m^−3 Dm measured by flotation in C6 H6 /CHBr3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 17.995 (4) Å	Cell parameters from 25 reflections
b = 16.601 (3) Å	θ = 4.1–11.2°
c = 16.879 (3) Å	µ = 1.23 mm^−1
β = 114.52 (3)°	T = 293 K
V = 4587.6 (15) Å^3	Rectanglular prism, green-blue
Z = 8	0.45 × 0.40 × 0.35 mm

Data collection

Syntex P21 diffractometer	3284 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.021
Graphite monochromator	θmax = 27.6°, θmin = 2.7°
θ–2θ scans	h = −22→0
Absorption correction: ψ scan (North et al., 1968)	k = −21→21
Tmin = 0.565, Tmax = 0.650	l = −19→20
5869 measured reflections	3 standard reflections every 100 reflections
5109 independent reflections	intensity decay: 15%

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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.052	H atoms treated by a mixture of independent and constrained refinement
S = 0.80	w = 1/[σ^2(Fo^2) + (0.0057P)^2] where P = (Fo^2 + 2Fc^2)/3
5109 reflections	(Δ/σ)max = 0.001
323 parameters	Δρmax = 0.22 e Å^−3
0 restraints	Δρmin = −0.19 e Å^−3

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

	x	y	z	Uiso*/Ueq
Cu1	0.356922 (14)	0.104912 (13)	0.198051 (14)	0.03098 (7)
Cl1	0.42411 (3)	0.08467 (4)	0.11286 (3)	0.04889 (14)
Cl2	0.10685 (4)	0.18092 (4)	0.39398 (4)	0.06162 (17)
N1	0.36596 (9)	0.13075 (9)	0.32205 (9)	0.0301 (3)
N2	0.38332 (9)	−0.00537 (9)	0.24976 (10)	0.0318 (3)
N3	0.32367 (9)	0.21452 (9)	0.14967 (9)	0.0308 (3)
N4	0.22298 (9)	0.08912 (9)	0.13065 (9)	0.0300 (3)
O1	0.38145 (10)	0.06855 (8)	0.44558 (9)	0.0496 (4)
O2	0.21160 (10)	0.19540 (11)	0.28777 (10)	0.0600 (5)
H11	0.1894	0.1864	0.3206	0.090*
O3	0.44344 (13)	0.29216 (11)	0.33916 (13)	0.0467 (5)
H12	0.4228	0.3371	0.3328	0.070*
O4	0.11210 (8)	0.16540 (8)	0.06359 (9)	0.0412 (3)
O5	0.08787 (10)	−0.04141 (9)	0.18939 (11)	0.0561 (4)
H23	0.0597	−0.0170	0.2092	0.084*
O6	0.15628 (14)	−0.01503 (10)	−0.01738 (11)	0.0720 (5)
H24	0.1518	−0.0549	−0.0477	0.108*
O7	0.0000	0.05976 (14)	0.2500	0.0603 (6)
C1	0.39217 (12)	−0.07214 (12)	0.21115 (14)	0.0400 (5)
H1	0.3857	−0.0695	0.1536	0.060*
C2	0.41068 (13)	−0.14525 (12)	0.25373 (16)	0.0466 (5)
H2	0.4152	−0.1914	0.2248	0.070*
C3	0.42233 (14)	−0.14912 (12)	0.33864 (16)	0.0492 (6)
H3	0.4354	−0.1978	0.3685	0.074*
C4	0.41451 (13)	−0.08016 (12)	0.37976 (14)	0.0437 (5)
H4	0.4232	−0.0812	0.4381	0.066*
C5	0.39366 (12)	−0.01028 (11)	0.33315 (12)	0.0324 (4)
C6	0.38038 (12)	0.06632 (11)	0.36631 (12)	0.0337 (4)
C7	0.35671 (16)	0.14969 (13)	0.45558 (13)	0.0486 (6)
H5	0.3945	0.1732	0.5101	0.073*
H6	0.3023	0.1498	0.4543	0.073*
C8	0.35815 (12)	0.19637 (11)	0.37763 (12)	0.0355 (4)
C9	0.27991 (13)	0.24441 (13)	0.33002 (14)	0.0447 (5)
H7	0.2704	0.2785	0.3716	0.067*
H8	0.2869	0.2792	0.2875	0.067*
C10	0.43249 (15)	0.25122 (14)	0.40739 (15)	0.0425 (5)
H9	0.4326 (14)	0.2891 (15)	0.4537 (15)	0.064*
H10	0.476 (2)	0.219 (3)	0.429 (2)	0.064*
C11	0.37448 (12)	0.27394 (12)	0.15350 (12)	0.0392 (5)
H13	0.4305	0.2649	0.1811	0.059*
C12	0.34660 (14)	0.34856 (12)	0.11776 (13)	0.0439 (5)
H14	0.3835	0.3896	0.1230	0.066*
C13	0.26472 (14)	0.36203 (12)	0.07465 (13)	0.0433 (5)
H15	0.2452	0.4121	0.0502	0.065*
C14	0.21175 (13)	0.30052 (11)	0.06804 (12)	0.0361 (4)
H16	0.1557	0.3078	0.0381	0.054*
C15	0.24292 (11)	0.22783 (11)	0.10638 (11)	0.0297 (4)
C16	0.19268 (11)	0.15710 (11)	0.10159 (11)	0.0295 (4)
C17	0.07959 (13)	0.08561 (12)	0.06456 (15)	0.0462 (5)
H17	0.0503	0.0654	0.0058	0.069*
H18	0.0429	0.0864	0.0934	0.069*
C18	0.15466 (11)	0.03362 (11)	0.11517 (12)	0.0340 (4)
C19	0.15784 (14)	0.00491 (14)	0.20188 (13)	0.0456 (5)
H19	0.2065	−0.0274	0.2314	0.068*
H20	0.1608	0.0510	0.2383	0.068*
C20	0.16141 (14)	−0.03892 (12)	0.06383 (13)	0.0443 (5)
H21	0.2131	−0.0659	0.0958	0.066*
H22	0.1178	−0.0766	0.0563	0.066*
H25	−0.0200	0.1017	0.2006	0.050*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cu1	0.03417 (12)	0.02802 (11)	0.03326 (12)	0.00355 (11)	0.01649 (9)	0.00244 (10)
Cl1	0.0500 (3)	0.0590 (4)	0.0491 (3)	0.0140 (3)	0.0319 (3)	0.0091 (2)
Cl2	0.0919 (5)	0.0457 (3)	0.0587 (3)	0.0012 (3)	0.0426 (4)	0.0067 (3)
N1	0.0315 (9)	0.0276 (8)	0.0301 (8)	0.0019 (7)	0.0117 (7)	−0.0026 (6)
N2	0.0300 (9)	0.0290 (8)	0.0368 (8)	0.0012 (7)	0.0142 (7)	−0.0014 (7)
N3	0.0347 (9)	0.0291 (8)	0.0291 (8)	−0.0022 (7)	0.0139 (7)	0.0010 (6)
N4	0.0297 (8)	0.0259 (8)	0.0346 (8)	−0.0021 (6)	0.0136 (7)	−0.0007 (6)
O1	0.0795 (11)	0.0375 (8)	0.0364 (7)	0.0095 (8)	0.0286 (8)	0.0063 (6)
O2	0.0449 (9)	0.0682 (11)	0.0672 (11)	0.0007 (9)	0.0237 (8)	−0.0236 (9)
O3	0.0551 (13)	0.0353 (11)	0.0600 (12)	−0.0007 (10)	0.0342 (10)	−0.0031 (10)
O4	0.0286 (7)	0.0343 (7)	0.0560 (8)	0.0009 (6)	0.0129 (7)	0.0074 (7)
O5	0.0654 (11)	0.0415 (9)	0.0796 (11)	−0.0159 (8)	0.0484 (9)	−0.0043 (8)
O6	0.1229 (16)	0.0464 (10)	0.0614 (11)	−0.0230 (11)	0.0530 (11)	−0.0098 (8)
O7	0.0638 (15)	0.0579 (15)	0.0659 (14)	0.000	0.0337 (12)	0.000
C1	0.0390 (11)	0.0350 (11)	0.0483 (12)	−0.0003 (9)	0.0204 (10)	−0.0096 (9)
C2	0.0441 (13)	0.0275 (11)	0.0751 (15)	−0.0035 (10)	0.0315 (12)	−0.0109 (11)
C3	0.0538 (14)	0.0271 (11)	0.0725 (16)	0.0016 (10)	0.0318 (12)	0.0071 (10)
C4	0.0518 (13)	0.0313 (10)	0.0483 (12)	−0.0007 (10)	0.0211 (10)	0.0064 (9)
C5	0.0297 (10)	0.0298 (10)	0.0376 (10)	0.0002 (8)	0.0138 (8)	0.0012 (8)
C6	0.0378 (11)	0.0320 (11)	0.0304 (9)	0.0016 (9)	0.0135 (9)	0.0020 (8)
C7	0.0708 (16)	0.0390 (12)	0.0412 (11)	0.0045 (11)	0.0282 (11)	−0.0055 (9)
C8	0.0436 (12)	0.0308 (10)	0.0338 (10)	0.0039 (9)	0.0176 (9)	−0.0069 (8)
C9	0.0443 (12)	0.0402 (12)	0.0523 (12)	0.0105 (10)	0.0227 (10)	−0.0062 (10)
C10	0.0460 (13)	0.0349 (12)	0.0435 (12)	0.0051 (10)	0.0154 (11)	−0.0059 (10)
C11	0.0397 (12)	0.0399 (11)	0.0395 (11)	−0.0101 (9)	0.0180 (10)	−0.0005 (9)
C12	0.0580 (15)	0.0369 (12)	0.0394 (11)	−0.0141 (11)	0.0229 (11)	−0.0020 (9)
C13	0.0616 (15)	0.0279 (10)	0.0418 (11)	0.0009 (10)	0.0228 (11)	0.0033 (9)
C14	0.0399 (11)	0.0310 (10)	0.0376 (10)	0.0028 (9)	0.0165 (9)	0.0024 (8)
C15	0.0342 (10)	0.0287 (9)	0.0280 (9)	−0.0014 (8)	0.0146 (8)	−0.0013 (8)
C16	0.0292 (10)	0.0301 (10)	0.0285 (9)	0.0002 (8)	0.0111 (8)	0.0002 (8)
C17	0.0342 (11)	0.0354 (12)	0.0627 (13)	−0.0062 (9)	0.0138 (10)	0.0056 (10)
C18	0.0277 (10)	0.0303 (10)	0.0414 (10)	−0.0061 (8)	0.0117 (9)	−0.0003 (8)
C19	0.0469 (13)	0.0456 (12)	0.0469 (12)	−0.0098 (11)	0.0222 (10)	−0.0016 (10)
C20	0.0523 (13)	0.0311 (11)	0.0504 (12)	−0.0085 (10)	0.0222 (11)	−0.0037 (9)

Geometric parameters (Å, º)

Cu1—N3	1.9825 (15)	O5—C19	1.415 (2)
Cu1—N2	1.9988 (15)	O6—C20	1.393 (2)
Cu1—N1	2.0757 (15)	C1—C2	1.379 (3)
Cu1—N4	2.2127 (17)	C2—C3	1.361 (3)
Cu1—Cl1	2.2552 (7)	C3—C4	1.376 (3)
N1—C6	1.268 (2)	C4—C5	1.364 (3)
N1—C8	1.482 (2)	C5—C6	1.449 (3)
N2—C1	1.329 (2)	C7—C8	1.536 (3)
N2—C5	1.343 (2)	C8—C9	1.525 (3)
N3—C11	1.328 (2)	C8—C10	1.521 (3)
N3—C15	1.346 (2)	C11—C12	1.378 (3)
N4—C16	1.261 (2)	C12—C13	1.364 (3)
N4—C18	1.470 (2)	C13—C14	1.369 (3)
O1—C6	1.331 (2)	C14—C15	1.374 (2)
O1—C7	1.450 (2)	C15—C16	1.464 (3)
O2—C9	1.398 (3)	C17—C18	1.530 (3)
O3—C10	1.420 (3)	C18—C20	1.518 (3)
O4—C16	1.327 (2)	C18—C19	1.517 (3)
O4—C17	1.451 (2)
N3—Cu1—N2	175.54 (6)	N1—C6—O1	118.87 (17)
N3—Cu1—N1	96.29 (6)	N1—C6—C5	122.62 (16)
N2—Cu1—N1	81.03 (6)	O1—C6—C5	118.49 (16)
N3—Cu1—N4	79.56 (6)	O1—C7—C8	104.69 (15)
N2—Cu1—N4	97.28 (6)	N1—C8—C9	111.12 (15)
N1—Cu1—N4	98.96 (6)	N1—C8—C10	110.34 (17)
N3—Cu1—Cl1	91.38 (5)	C9—C8—C10	110.73 (17)
N2—Cu1—Cl1	92.80 (5)	N1—C8—C7	102.19 (15)
N1—Cu1—Cl1	146.65 (5)	C9—C8—C7	112.03 (18)
N4—Cu1—Cl1	114.35 (5)	C10—C8—C7	110.14 (17)
C6—N1—C8	107.28 (14)	O2—C9—C8	112.86 (18)
C6—N1—Cu1	109.32 (12)	O3—C10—C8	114.70 (19)
C8—N1—Cu1	143.32 (12)	N3—C11—C12	121.87 (19)
C1—N2—C5	118.07 (16)	C13—C12—C11	119.8 (2)
C1—N2—Cu1	127.24 (13)	C12—C13—C14	118.84 (19)
C5—N2—Cu1	114.68 (12)	C13—C14—C15	118.83 (19)
C11—N3—C15	118.07 (16)	N3—C15—C14	122.50 (17)
C11—N3—Cu1	125.28 (13)	N3—C15—C16	113.65 (16)
C15—N3—Cu1	116.58 (12)	C14—C15—C16	123.81 (17)
C16—N4—C18	107.27 (15)	N4—C16—O4	119.37 (16)
C16—N4—Cu1	107.27 (12)	N4—C16—C15	122.62 (17)
C18—N4—Cu1	144.85 (12)	O4—C16—C15	118.00 (16)
C6—O1—C7	105.41 (14)	O4—C17—C18	104.75 (15)
C16—O4—C17	105.34 (14)	N4—C18—C20	109.84 (16)
N2—C1—C2	122.07 (19)	N4—C18—C19	109.35 (15)
C3—C2—C1	119.24 (19)	C20—C18—C19	108.75 (16)
C2—C3—C4	119.3 (2)	N4—C18—C17	103.01 (15)
C5—C4—C3	118.54 (19)	C20—C18—C17	112.96 (17)
N2—C5—C4	122.77 (18)	C19—C18—C17	112.76 (18)
N2—C5—C6	112.22 (16)	O5—C19—C18	110.61 (17)
C4—C5—C6	125.01 (17)	O6—C20—C18	110.35 (17)