Aqua-chloridobis(2-eth-oxy-6-formyl-phenolato-κO,O)chromium(III) acetonitrile hemisolvate.

In the mononuclear complex mol-ecule of the title compound, [Cr(C(9)H(9)O(3))(2)Cl(H(2)O)]·0.5CH(3)CN, the Cr(III) atom displays an elongated octa-hedral coordination geometry. The dihedral angle between the benzene rings is 12.27 (11)°. Adjacent complex mol-ecules are linked into dimers by O-H⋯O hydrogen bonds, generating rings of R(1) (2)(6) and R(1) (2)(5) graph-set motifs, and by aromatic π-π stacking inter-actions, with a centroid-centroid distance of 3.812 (2) Å. The crystal packing is further stabilized by inter-molecular C-H⋯N hydrogen bonds. The C and N atoms of the acetonitrile solvent mol-ecule are located on a crystallographic twofold axis.

Related literature

For details of hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the structures of tetra­dentate Schiff bases synthesized by our group, see: Kargar et al. (2009 ▶, 2010 ▶).

Experimental

Crystal data

[Cr(C9H9O3)2Cl(H2O)]·0.5C2H3N

M = 456.32

Monoclinic,

a = 19.292 (3) Å

b = 10.1211 (10) Å

c = 20.953 (3) Å

β = 91.824 (11)°

V = 4089.1 (10) Å3

Z = 8

Mo Kα radiation

μ = 0.73 mm−1

T = 291 K

0.25 × 0.15 × 0.12 mm

Data collection

Stoe IPDS 2T Image Plate diffractometer

Absorption correction: multi-scan [MULABS (Blessing, 1995 ▶) in PLATON (Spek, 2009 ▶)] T min = 0.901, T max = 1.000

9374 measured reflections

4371 independent reflections

2108 reflections with I > 2σ(I)

R int = 0.070

Refinement

R[F 2 > 2σ(F 2)] = 0.051

wR(F 2) = 0.078

S = 0.80

4371 reflections

261 parameters

H-atom parameters constrained

Δρmax = 0.27 e Å−3

Δρmin = −0.33 e Å−3

Data collection: X-AREA (Stoe & Cie, 2009 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811037275/rz2636sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811037275/rz2636Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Cr(C9H9O3)2Cl(H2O)]·0.5C2H3N	F(000) = 1888
Mr = 456.32	Dx = 1.482 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1749 reflections
a = 19.292 (3) Å	θ = 2.2–29.5°
b = 10.1211 (10) Å	µ = 0.73 mm−1
c = 20.953 (3) Å	T = 291 K
β = 91.824 (11)°	Block, dark-green
V = 4089.1 (10) Å3	0.25 × 0.15 × 0.12 mm
Z = 8

Stoe IPDS 2T Image Plate diffractometer	4371 independent reflections
Radiation source: fine-focus sealed tube	2108 reflections with I > 2σ(I)
graphite	Rint = 0.070
Detector resolution: 0.15 mm pixels mm-1	θmax = 27.0°, θmin = 1.9°
ω scans	h = −24→24
Absorption correction: multi-scan [MULABS (Blessing, 1995) in PLATON (Spek, 2009)]	k = −11→12
Tmin = 0.901, Tmax = 1.000	l = −23→26
9374 measured reflections

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078	H-atom parameters constrained
S = 0.80	w = 1/[σ2(Fo2) + (0.0193P)2] where P = (Fo2 + 2Fc2)/3
4371 reflections	(Δ/σ)max = 0.001
261 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.33 e Å−3

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.

	x	y	z	Uiso*/Ueq	Occ. (<1)
Cr1	0.64593 (2)	1.32691 (7)	0.04499 (3)	0.03258 (17)
Cl1	0.61724 (4)	1.48966 (12)	0.11688 (5)	0.0500 (3)
O1	0.72440 (10)	1.2660 (3)	0.09641 (12)	0.0352 (7)
O2	0.58449 (11)	1.2011 (3)	0.08794 (13)	0.0421 (8)
O3	0.70720 (10)	1.4377 (3)	−0.00154 (12)	0.0343 (7)
O4	0.56652 (10)	1.3822 (3)	−0.01146 (13)	0.0395 (7)
O5	0.84236 (11)	1.2384 (3)	0.15669 (13)	0.0506 (8)
O6	0.80992 (11)	1.5786 (3)	−0.04008 (14)	0.0460 (8)
C1	0.72533 (16)	1.1870 (4)	0.14529 (18)	0.0325 (9)
C2	0.78879 (17)	1.1670 (4)	0.18084 (19)	0.0386 (10)
C3	0.7924 (2)	1.0838 (5)	0.2312 (2)	0.0556 (13)
H3A	0.8347	1.0717	0.2528	0.067*
C4	0.7343 (2)	1.0156 (5)	0.2516 (2)	0.0632 (14)
H4A	0.7378	0.9601	0.2870	0.076*
C5	0.6731 (2)	1.0311 (5)	0.2196 (2)	0.0543 (13)
H5A	0.6345	0.9839	0.2323	0.065*
C6	0.66667 (19)	1.1183 (4)	0.16681 (19)	0.0385 (10)
C7	0.60077 (19)	1.1291 (4)	0.1337 (2)	0.0455 (12)
H7A	0.5658	1.0750	0.1485	0.055*
C8	0.90836 (18)	1.2297 (5)	0.1897 (2)	0.0581 (14)
H8A	0.9267	1.1407	0.1870	0.070*
H8B	0.9039	1.2522	0.2344	0.070*
C9	0.95559 (18)	1.3257 (6)	0.1581 (2)	0.0790 (17)
H9A	1.0012	1.3198	0.1775	0.118*
H9B	0.9381	1.4138	0.1630	0.118*
H9C	0.9576	1.3050	0.1135	0.118*
C10	0.69152 (17)	1.5300 (4)	−0.04271 (19)	0.0330 (10)
C11	0.74590 (19)	1.6113 (4)	−0.0648 (2)	0.0415 (11)
C12	0.7323 (2)	1.7116 (5)	−0.1067 (2)	0.0640 (15)
H12A	0.7684	1.7646	−0.1200	0.077*
C13	0.6644 (2)	1.7360 (5)	−0.1301 (2)	0.0764 (17)
H13A	0.6555	1.8044	−0.1589	0.092*
C14	0.6121 (2)	1.6586 (5)	−0.1102 (2)	0.0625 (14)
H14A	0.5671	1.6753	−0.1255	0.075*
C15	0.62361 (17)	1.5546 (4)	−0.06753 (19)	0.0381 (11)
C16	0.56650 (17)	1.4756 (5)	−0.04983 (19)	0.0400 (11)
H16A	0.5239	1.4965	−0.0693	0.048*
C17	0.86615 (18)	1.6679 (5)	−0.0508 (2)	0.0595 (13)
H17A	0.8541	1.7563	−0.0371	0.071*
H17B	0.8761	1.6707	−0.0958	0.071*
C18	0.92803 (19)	1.6186 (5)	−0.0130 (2)	0.0718 (17)
H18A	0.9666	1.6765	−0.0192	0.108*
H18B	0.9395	1.5312	−0.0269	0.108*
H18C	0.9176	1.6166	0.0315	0.108*
O1W	0.66200 (9)	1.1806 (3)	−0.01853 (11)	0.0375 (7)
H1W1	0.6804	1.1980	−0.0537	0.056*
H2W1	0.6804	1.1082	−0.0071	0.056*
N1	0.5000	1.8521 (9)	−0.2500	0.123 (3)
C19	0.5000	1.5944 (10)	−0.2500	0.137 (4)
H19A	0.5241	1.5628	−0.2864	0.206*	0.50
H19B	0.4531	1.5628	−0.2520	0.206*	0.50
H19C	0.5229	1.5628	−0.2116	0.206*	0.50
C20	0.5000	1.7396 (12)	−0.2500	0.076 (3)

	U11	U22	U33	U12	U13	U23
Cr1	0.0213 (2)	0.0403 (4)	0.0361 (4)	−0.0020 (3)	−0.0004 (2)	0.0045 (4)
Cl1	0.0440 (5)	0.0546 (8)	0.0511 (7)	0.0016 (5)	−0.0026 (5)	−0.0124 (7)
O1	0.0267 (11)	0.0417 (18)	0.0369 (17)	−0.0002 (11)	−0.0029 (11)	0.0143 (15)
O2	0.0327 (13)	0.050 (2)	0.0435 (18)	−0.0103 (13)	0.0052 (13)	0.0062 (17)
O3	0.0236 (11)	0.0380 (18)	0.0412 (17)	0.0020 (11)	−0.0011 (11)	0.0118 (15)
O4	0.0241 (12)	0.052 (2)	0.0426 (18)	0.0052 (12)	−0.0045 (12)	0.0019 (16)
O5	0.0360 (13)	0.067 (2)	0.0477 (18)	0.0003 (13)	−0.0122 (13)	0.0142 (18)
O6	0.0334 (13)	0.0396 (18)	0.065 (2)	−0.0062 (12)	0.0060 (13)	0.0103 (17)
C1	0.0390 (18)	0.030 (3)	0.029 (2)	0.0044 (19)	0.0030 (17)	−0.005 (2)
C2	0.0449 (19)	0.038 (3)	0.033 (2)	0.007 (2)	−0.0006 (18)	0.003 (2)
C3	0.064 (3)	0.058 (3)	0.045 (3)	0.015 (2)	−0.001 (2)	0.009 (3)
C4	0.098 (4)	0.049 (3)	0.042 (3)	0.017 (3)	0.004 (3)	0.021 (3)
C5	0.071 (3)	0.042 (3)	0.050 (3)	−0.006 (2)	0.018 (2)	0.008 (3)
C6	0.050 (2)	0.037 (3)	0.029 (2)	−0.0024 (19)	0.008 (2)	−0.001 (2)
C7	0.047 (2)	0.044 (3)	0.047 (3)	−0.017 (2)	0.021 (2)	−0.003 (3)
C8	0.047 (2)	0.069 (4)	0.057 (3)	0.013 (2)	−0.018 (2)	−0.015 (3)
C9	0.043 (2)	0.113 (5)	0.080 (4)	−0.012 (3)	−0.011 (2)	0.000 (4)
C10	0.0368 (19)	0.029 (2)	0.033 (2)	0.0052 (17)	0.0041 (18)	−0.003 (2)
C11	0.048 (2)	0.032 (3)	0.044 (3)	−0.0016 (19)	0.005 (2)	0.004 (2)
C12	0.064 (3)	0.054 (4)	0.075 (4)	0.004 (2)	0.017 (3)	0.020 (3)
C13	0.083 (3)	0.065 (4)	0.081 (4)	0.015 (3)	0.003 (3)	0.047 (3)
C14	0.061 (3)	0.066 (4)	0.059 (3)	0.017 (3)	−0.011 (2)	0.015 (3)
C15	0.039 (2)	0.044 (3)	0.031 (2)	0.0149 (18)	−0.0003 (18)	0.009 (2)
C16	0.0324 (19)	0.056 (3)	0.031 (3)	0.013 (2)	−0.0046 (18)	−0.008 (3)
C17	0.055 (2)	0.041 (3)	0.084 (4)	−0.012 (2)	0.025 (2)	−0.007 (3)
C18	0.045 (2)	0.072 (4)	0.098 (4)	−0.022 (2)	0.006 (3)	−0.023 (3)
O1W	0.0300 (11)	0.0395 (17)	0.0432 (16)	0.0016 (12)	0.0049 (11)	0.0037 (16)
N1	0.144 (6)	0.099 (8)	0.129 (8)	0.000	0.057 (5)	0.000
C19	0.216 (11)	0.097 (10)	0.100 (9)	0.000	0.009 (7)	0.000
C20	0.078 (5)	0.107 (8)	0.043 (5)	0.000	0.023 (4)	0.000

Cr1—O3	1.918 (2)	C9—H9A	0.9600
Cr1—O1	1.931 (2)	C9—H9B	0.9600
Cr1—O2	1.976 (3)	C9—H9C	0.9600
Cr1—O4	1.986 (3)	C10—C15	1.416 (5)
Cr1—O1W	2.021 (3)	C10—C11	1.422 (5)
Cr1—Cl1	2.3112 (13)	C11—C12	1.361 (6)
O1—C1	1.299 (4)	C12—C13	1.406 (6)
O2—C7	1.237 (5)	C12—H12A	0.9300
O3—C10	1.301 (4)	C13—C14	1.354 (6)
O4—C16	1.242 (4)	C13—H13A	0.9300
O5—C2	1.371 (4)	C14—C15	1.395 (6)
O5—C8	1.433 (4)	C14—H14A	0.9300
O6—C11	1.365 (4)	C15—C16	1.420 (5)
O6—C17	1.435 (4)	C16—H16A	0.9300
C1—C6	1.414 (5)	C17—C18	1.497 (6)
C1—C2	1.427 (5)	C17—H17A	0.9700
C2—C3	1.349 (5)	C17—H17B	0.9700
C3—C4	1.395 (5)	C18—H18A	0.9600
C3—H3A	0.9300	C18—H18B	0.9600
C4—C5	1.349 (6)	C18—H18C	0.9600
C4—H4A	0.9300	O1W—H1W1	0.8475
C5—C6	1.418 (6)	O1W—H2W1	0.8459
C5—H5A	0.9300	N1—C20	1.138 (11)
C6—C7	1.433 (5)	C19—C20	1.470 (12)
C7—H7A	0.9300	C19—H19A	0.9600
C8—C9	1.501 (6)	C19—H19B	0.9600
C8—H8A	0.9700	C19—H19C	0.9600
C8—H8B	0.9700
O3—Cr1—O1	89.17 (10)	C8—C9—H9B	109.5
O3—Cr1—O2	175.31 (12)	H9A—C9—H9B	109.5
O1—Cr1—O2	90.64 (11)	C8—C9—H9C	109.5
O3—Cr1—O4	90.51 (11)	H9A—C9—H9C	109.5
O1—Cr1—O4	176.86 (12)	H9B—C9—H9C	109.5
O2—Cr1—O4	89.43 (11)	O3—C10—C15	124.2 (3)
O3—Cr1—O1W	89.06 (10)	O3—C10—C11	118.2 (3)
O1—Cr1—O1W	89.98 (10)	C15—C10—C11	117.6 (4)
O2—Cr1—O1W	86.25 (10)	C12—C11—O6	125.4 (4)
O4—Cr1—O1W	86.89 (10)	C12—C11—C10	120.8 (4)
O3—Cr1—Cl1	94.52 (9)	O6—C11—C10	113.9 (4)
O1—Cr1—Cl1	93.64 (9)	C11—C12—C13	121.0 (4)
O2—Cr1—Cl1	90.16 (8)	C11—C12—H12A	119.5
O4—Cr1—Cl1	89.50 (8)	C13—C12—H12A	119.5
O1W—Cr1—Cl1	174.93 (6)	C14—C13—C12	119.1 (5)
C1—O1—Cr1	128.9 (2)	C14—C13—H13A	120.5
C7—O2—Cr1	126.3 (2)	C12—C13—H13A	120.5
C10—O3—Cr1	128.5 (2)	C13—C14—C15	121.9 (4)
C16—O4—Cr1	125.8 (2)	C13—C14—H14A	119.0
C2—O5—C8	117.3 (3)	C15—C14—H14A	119.0
C11—O6—C17	117.9 (3)	C14—C15—C10	119.7 (4)
O1—C1—C6	124.3 (3)	C14—C15—C16	118.9 (4)
O1—C1—C2	119.3 (3)	C10—C15—C16	121.5 (4)
C6—C1—C2	116.5 (4)	O4—C16—C15	127.9 (4)
C3—C2—O5	126.6 (4)	O4—C16—H16A	116.1
C3—C2—C1	121.2 (4)	C15—C16—H16A	116.1
O5—C2—C1	112.1 (3)	O6—C17—C18	107.5 (4)
C2—C3—C4	121.8 (4)	O6—C17—H17A	110.2
C2—C3—H3A	119.1	C18—C17—H17A	110.2
C4—C3—H3A	119.1	O6—C17—H17B	110.2
C5—C4—C3	119.3 (4)	C18—C17—H17B	110.2
C5—C4—H4A	120.4	H17A—C17—H17B	108.5
C3—C4—H4A	120.4	C17—C18—H18A	109.5
C4—C5—C6	120.9 (4)	C17—C18—H18B	109.5
C4—C5—H5A	119.6	H18A—C18—H18B	109.5
C6—C5—H5A	119.6	C17—C18—H18C	109.5
C1—C6—C5	120.3 (4)	H18A—C18—H18C	109.5
C1—C6—C7	121.0 (4)	H18B—C18—H18C	109.5
C5—C6—C7	118.6 (4)	Cr1—O1W—H1W1	119.9
O2—C7—C6	128.3 (4)	Cr1—O1W—H2W1	121.3
O2—C7—H7A	115.9	H1W1—O1W—H2W1	104.1
C6—C7—H7A	115.9	C20—C19—H19A	109.5
O5—C8—C9	106.8 (4)	C20—C19—H19B	109.5
O5—C8—H8A	110.4	H19A—C19—H19B	109.5
C9—C8—H8A	110.4	C20—C19—H19C	109.5
O5—C8—H8B	110.4	H19A—C19—H19C	109.5
C9—C8—H8B	110.4	H19B—C19—H19C	109.5
H8A—C8—H8B	108.6	N1—C20—C19	180.000 (5)
C8—C9—H9A	109.5
O3—Cr1—O1—C1	175.8 (3)	O1—C1—C6—C7	1.9 (6)
O2—Cr1—O1—C1	−8.9 (3)	C2—C1—C6—C7	−178.6 (4)
O1W—Cr1—O1—C1	−95.1 (3)	C4—C5—C6—C1	2.4 (6)
Cl1—Cr1—O1—C1	81.3 (3)	C4—C5—C6—C7	178.8 (4)
O1—Cr1—O2—C7	5.5 (3)	Cr1—O2—C7—C6	0.1 (6)
O4—Cr1—O2—C7	−177.6 (3)	C1—C6—C7—O2	−5.5 (6)
O1W—Cr1—O2—C7	95.5 (3)	C5—C6—C7—O2	178.2 (4)
Cl1—Cr1—O2—C7	−88.1 (3)	C2—O5—C8—C9	−174.6 (3)
O1—Cr1—O3—C10	−169.9 (3)	Cr1—O3—C10—C15	−8.8 (5)
O4—Cr1—O3—C10	13.2 (3)	Cr1—O3—C10—C11	171.7 (3)
O1W—Cr1—O3—C10	100.1 (3)	C17—O6—C11—C12	10.1 (6)
Cl1—Cr1—O3—C10	−76.3 (3)	C17—O6—C11—C10	−169.6 (3)
O3—Cr1—O4—C16	−12.4 (3)	O3—C10—C11—C12	−178.4 (4)
O2—Cr1—O4—C16	172.3 (3)	C15—C10—C11—C12	2.1 (6)
O1W—Cr1—O4—C16	−101.4 (3)	O3—C10—C11—O6	1.4 (5)
Cl1—Cr1—O4—C16	82.1 (3)	C15—C10—C11—O6	−178.1 (3)
Cr1—O1—C1—C6	6.6 (5)	O6—C11—C12—C13	179.1 (4)
Cr1—O1—C1—C2	−172.9 (3)	C10—C11—C12—C13	−1.2 (7)
C8—O5—C2—C3	−3.3 (6)	C11—C12—C13—C14	0.3 (8)
C8—O5—C2—C1	178.0 (3)	C12—C13—C14—C15	−0.5 (8)
O1—C1—C2—C3	−178.7 (4)	C13—C14—C15—C10	1.5 (7)
C6—C1—C2—C3	1.7 (6)	C13—C14—C15—C16	−178.6 (5)
O1—C1—C2—O5	0.0 (5)	O3—C10—C15—C14	178.2 (4)
C6—C1—C2—O5	−179.5 (3)	C11—C10—C15—C14	−2.3 (6)
O5—C2—C3—C4	−179.8 (4)	O3—C10—C15—C16	−1.6 (6)
C1—C2—C3—C4	−1.2 (7)	C11—C10—C15—C16	177.9 (4)
C2—C3—C4—C5	1.2 (7)	Cr1—O4—C16—C15	7.5 (6)
C3—C4—C5—C6	−1.8 (7)	C14—C15—C16—O4	−177.8 (4)
O1—C1—C6—C5	178.2 (4)	C10—C15—C16—O4	2.0 (6)
C2—C1—C6—C5	−2.3 (5)	C11—O6—C17—C18	173.5 (4)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W1···O1i	0.85	2.10	2.826 (3)	143.
O1W—H1W1···O5i	0.85	2.28	3.007 (4)	144.
O1W—H2W1···O3i	0.85	2.22	2.813 (3)	127.
O1W—H2W1···O6i	0.85	2.14	2.940 (4)	158.
C7—H7A···N1ii	0.93	2.62	3.171 (4)	119
C19—H19A···Cl1iii	0.96	2.80	3.745 (3)	167

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W1⋯O1i	0.85	2.10	2.826 (3)	143
O1W—H1W1⋯O5i	0.85	2.28	3.007 (4)	144
O1W—H2W1⋯O3i	0.85	2.22	2.813 (3)	127
O1W—H2W1⋯O6i	0.85	2.14	2.940 (4)	158
C7—H7A⋯N1ii	0.93	2.62	3.171 (4)	119

Symmetry codes: (i) ; (ii) .