trans-Tetra­chloro­bis{1-[(2,6-diisopropyl­phenyl)­iminiometh­yl]-2-naphtholato-κO}zirconium(IV) dichloro­methane disolvate

The Zr atom in the title disolvate, [ZrCl₄(C₂₃H₂₅NO)₂]·2CH₂Cl₂, lies on a special position of site symmetry in a trans-Cl₄O₂Zr octa­hedral geometry.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.006 Å
• Disorder in solvent or counterion
• R factor = 0.052
• wR factor = 0.161
• Data-to-parameter ratio = 18.9

checkCIF/PLATON results

No syntax errors found



Alert level A
PLAT242_ALERT_2_A Check Low       Ueq as Compared to Neighbors for        C18

Author Response: The atom is the pivot atom of an isopropyl group; there is some disorder in the group but it is not necessary to treat the disorder.

Alert level B
PLAT220_ALERT_2_B Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.83 Ratio
PLAT222_ALERT_3_B Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.48 Ratio
PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for        Zr1

Author Response: The atom is the pivot atom of an isopropyl group; there is some disorder in the group but it is not necessary to treat the disorder.

PLAT242_ALERT_2_B Check Low       Ueq as Compared to Neighbors for        C21

Author Response: The atom is the pivot atom of an isopropyl group; there is some disorder in the group but it is not necessary to treat the disorder.

PLAT431_ALERT_2_B Short Inter HL..A Contact  Cl4    ..  Cl4     ..       3.07 Ang.

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        C24
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for       C24'
PLAT302_ALERT_4_C Anion/Solvent Disorder .........................      50.00 Perc.
PLAT410_ALERT_2_C Short Intra H...H Contact  H8     ..  H11     ..       1.98 Ang.

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   6 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
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

Computing details

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXL97.

trans-Tetrachlorobis{1-[(2,6-diisopropylphenyl)iminiomethyl]-2-naphtholato- κO}zirconium(IV) dichloromethane disolvate

Crystal data

[ZrCl4(C23H25NO)2]·2CH2Cl2	F(000) = 2192
Mr = 1065.75	Dx = 1.363 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5121 reflections
a = 17.700 (1) Å	θ = 2.3–25.6°
b = 16.897 (1) Å	µ = 0.66 mm^−1
c = 18.190 (1) Å	T = 295 K
β = 107.286 (1)°	Block, yellow
V = 5194.6 (5) Å^3	0.25 × 0.20 × 0.16 mm
Z = 4

Data collection

Bruker APEXII area-detector diffractometer	5829 independent reflections
Radiation source: fine-focus sealed tube	4410 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
φ and ω scans	θmax = 27.5°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −22→22
Tmin = 0.852, Tmax = 0.902	k = −10→21
15120 measured reflections	l = −22→23

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.161	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0967P)^2 + 2.9123P] where P = (Fo^2 + 2Fc^2)/3
5829 reflections	(Δ/σ)max = 0.001
309 parameters	Δρmax = 0.53 e Å^−3
43 restraints	Δρmin = −0.36 e Å^−3

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zr1	0.2500	0.2500	0.5000	0.0560 (2)
Cl1	0.17909 (8)	0.34234 (7)	0.55970 (7)	0.1043 (4)
Cl2	0.36778 (6)	0.33501 (7)	0.54233 (6)	0.1013 (4)
Cl3	0.2228 (3)	0.6999 (3)	0.3078 (3)	0.157 (1)	0.73 (1)
Cl4	0.0685 (3)	0.7432 (5)	0.2146 (4)	0.295 (4)	0.73 (1)
Cl3'	0.1842 (9)	0.6919 (5)	0.3192 (5)	0.141 (3)	0.27 (1)
Cl4'	0.1058 (9)	0.8132 (7)	0.2206 (8)	0.242 (7)	0.27 (1)
O1	0.2166 (1)	0.3172 (1)	0.4012 (1)	0.0605 (5)
N1	0.2629 (1)	0.4701 (1)	0.4078 (1)	0.0516 (5)
C1	0.1683 (2)	0.3320 (2)	0.3328 (2)	0.050 (1)
C2	0.1268 (2)	0.2694 (2)	0.2869 (2)	0.065 (1)
C3	0.0760 (2)	0.2839 (2)	0.2170 (2)	0.067 (1)
C4	0.0598 (2)	0.3611 (2)	0.1868 (2)	0.057 (1)
C5	0.0023 (2)	0.3748 (2)	0.1147 (2)	0.071 (1)
C6	−0.0138 (2)	0.4492 (3)	0.0873 (2)	0.083 (1)
C7	0.0264 (2)	0.5126 (3)	0.1297 (2)	0.089 (1)
C8	0.0821 (2)	0.5020 (2)	0.1997 (2)	0.075 (1)
C9	0.1006 (2)	0.4256 (2)	0.2301 (2)	0.053 (1)
C10	0.1591 (2)	0.4098 (2)	0.3038 (1)	0.047 (1)
C11	0.2072 (2)	0.4718 (2)	0.3433 (2)	0.051 (1)
C12	0.3124 (2)	0.5380 (2)	0.4385 (2)	0.052 (1)
C13	0.3744 (2)	0.5560 (2)	0.4085 (2)	0.060 (1)
C14	0.4187 (2)	0.6229 (2)	0.4376 (2)	0.071 (1)
C15	0.4022 (2)	0.6685 (2)	0.4930 (2)	0.079 (1)
C16	0.3420 (2)	0.6491 (2)	0.5215 (2)	0.078 (1)
C17	0.2949 (2)	0.5824 (2)	0.4951 (2)	0.063 (1)
C18	0.3943 (2)	0.5054 (2)	0.3486 (2)	0.075 (1)
C19	0.3932 (5)	0.5521 (4)	0.2778 (3)	0.159 (3)
C20	0.4747 (4)	0.4682 (5)	0.3799 (4)	0.179 (4)
C21	0.2276 (3)	0.5623 (2)	0.5271 (3)	0.086 (1)
C22	0.2556 (5)	0.5527 (5)	0.6126 (4)	0.176 (3)
C23	0.1610 (3)	0.6208 (4)	0.5000 (5)	0.143 (2)
C24	0.1698 (6)	0.7627 (8)	0.2337 (6)	0.168 (5)	0.73 (1)
C24'	0.169 (2)	0.732 (1)	0.2259 (9)	0.113 (8)	0.27 (1)
H1	0.275 (2)	0.427 (1)	0.432 (2)	0.06 (1)*
H2	0.1346	0.2177	0.3052	0.078*
H3	0.0505	0.2415	0.1874	0.080*
H5	−0.0244	0.3323	0.0862	0.085*
H6	−0.0517	0.4579	0.0402	0.099*
H7	0.0153	0.5635	0.1101	0.106*
H8	0.1078	0.5457	0.2271	0.090*
H11	0.1975	0.5210	0.3196	0.061*
H14	0.4604	0.6370	0.4190	0.085*
H15	0.4325	0.7133	0.5113	0.094*
H16	0.3318	0.6807	0.5593	0.093*
H18	0.3549	0.4630	0.3335	0.090*
H19a	0.3419	0.5757	0.2566	0.238*
H19b	0.4042	0.5176	0.2404	0.238*
H19c	0.4326	0.5929	0.2914	0.238*
H20a	0.4860	0.4366	0.3406	0.269*
H20b	0.4754	0.4353	0.4232	0.269*
H20c	0.5139	0.5090	0.3960	0.269*
H21	0.2069	0.5108	0.5056	0.103*
H22a	0.2115	0.5399	0.6309	0.264*
H22b	0.2793	0.6012	0.6359	0.264*
H22c	0.2940	0.5109	0.6259	0.264*
H23a	0.1190	0.6068	0.5209	0.215*
H23b	0.1418	0.6199	0.4448	0.215*
H23c	0.1799	0.6729	0.5171	0.215*
H24a	0.1807	0.8175	0.2490	0.201*	0.73 (1)
H24b	0.1857	0.7535	0.1877	0.201*	0.73 (1)
H24c	0.2191	0.7483	0.2189	0.135*	0.27 (1)
H24d	0.1450	0.6926	0.1869	0.135*	0.27 (1)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zr1	0.0492 (2)	0.0424 (2)	0.0687 (3)	−0.0059 (2)	0.0054 (2)	0.0147 (2)
Cl1	0.1287 (9)	0.0858 (7)	0.1056 (8)	0.0366 (6)	0.0458 (7)	0.0212 (6)
Cl2	0.0748 (6)	0.0985 (7)	0.1088 (8)	−0.0415 (5)	−0.0063 (5)	0.0293 (6)
Cl3	0.186 (3)	0.129 (2)	0.162 (3)	0.001 (2)	0.063 (2)	0.029 (2)
Cl4	0.222 (5)	0.285 (7)	0.393 (7)	0.062 (4)	0.115 (5)	0.091 (5)
Cl3'	0.225 (9)	0.082 (3)	0.116 (4)	0.007 (5)	0.050 (5)	−0.012 (3)
Cl4'	0.26 (1)	0.137 (7)	0.29 (1)	0.043 (7)	0.017 (7)	0.053 (6)
O1	0.061 (1)	0.046 (1)	0.066 (1)	−0.006 (1)	0.004 (1)	0.012 (1)
N1	0.057 (1)	0.038 (1)	0.057 (1)	−0.006 (1)	0.012 (1)	0.006 (1)
C1	0.051 (1)	0.044 (1)	0.055 (1)	0.000 (1)	0.017 (1)	0.001 (1)
C2	0.073 (2)	0.046 (1)	0.071 (2)	−0.001 (1)	0.015 (2)	−0.004 (1)
C3	0.071 (2)	0.059 (2)	0.067 (2)	−0.008 (2)	0.017 (2)	−0.016 (2)
C4	0.053 (2)	0.072 (2)	0.048 (1)	−0.005 (1)	0.018 (1)	−0.003 (1)
C5	0.062 (2)	0.098 (3)	0.052 (2)	−0.014 (2)	0.016 (1)	−0.003 (2)
C6	0.068 (2)	0.114 (3)	0.057 (2)	−0.009 (2)	0.004 (2)	0.020 (2)
C7	0.084 (2)	0.085 (3)	0.081 (2)	−0.003 (2)	0.001 (2)	0.032 (2)
C8	0.074 (2)	0.068 (2)	0.070 (2)	−0.008 (2)	0.000 (2)	0.016 (2)
C9	0.051 (1)	0.057 (2)	0.051 (1)	−0.003 (1)	0.016 (1)	0.005 (1)
C10	0.048 (1)	0.043 (1)	0.051 (1)	0.000 (1)	0.017 (1)	0.002 (1)
C11	0.052 (1)	0.044 (1)	0.057 (2)	0.000 (1)	0.018 (1)	0.008 (1)
C12	0.053 (2)	0.040 (1)	0.060 (2)	−0.006 (1)	0.010 (1)	0.006 (1)
C13	0.059 (2)	0.049 (2)	0.069 (2)	−0.004 (1)	0.016 (1)	0.007 (1)
C14	0.062 (2)	0.058 (2)	0.090 (2)	−0.016 (2)	0.018 (2)	0.007 (2)
C15	0.077 (2)	0.052 (2)	0.097 (3)	−0.017 (2)	0.012 (2)	−0.008 (2)
C16	0.092 (2)	0.057 (2)	0.083 (2)	−0.011 (2)	0.024 (2)	−0.015 (2)
C17	0.069 (2)	0.051 (2)	0.071 (2)	−0.006 (1)	0.021 (2)	−0.003 (1)
C18	0.075 (2)	0.062 (2)	0.097 (3)	−0.014 (2)	0.041 (2)	−0.006 (2)
C19	0.276 (9)	0.126 (5)	0.094 (4)	0.052 (5)	0.084 (5)	0.018 (3)
C20	0.180 (7)	0.228 (8)	0.115 (4)	0.126 (6)	0.022 (4)	−0.015 (5)
C21	0.108 (3)	0.065 (2)	0.102 (3)	−0.018 (2)	0.058 (3)	−0.017 (2)
C22	0.208 (8)	0.236 (9)	0.105 (4)	−0.073 (7)	0.078 (5)	−0.007 (5)
C23	0.105 (4)	0.119 (4)	0.233 (7)	0.010 (3)	0.092 (4)	0.011 (5)
C24	0.175 (8)	0.20 (1)	0.162 (8)	0.006 (8)	0.103 (7)	−0.022 (7)
C24'	0.13 (1)	0.09 (1)	0.12 (1)	0.014 (8)	0.035 (8)	−0.003 (8)

Geometric parameters (Å, º)

Zr1—O1	2.058 (2)	C21—C22	1.494 (7)
Zr1—Cl2	2.459 (1)	C21—C23	1.503 (7)
Zr1—Cl1	2.449 (1)	N1—H1	0.84 (1)
Cl3—C24	1.752 (9)	C2—H2	0.93
Cl4—C24	1.753 (9)	C3—H3	0.93
Cl3'—C24'	1.77 (1)	C5—H5	0.93
Cl4'—C24'	1.76 (1)	C6—H6	0.93
O1—C1	1.308 (3)	C7—H7	0.93
N1—C11	1.289 (4)	C8—H8	0.93
N1—C12	1.451 (3)	C11—H11	0.93
C1—C2	1.410 (4)	C14—H14	0.93
C1—C10	1.409 (4)	C15—H15	0.93
C2—C3	1.344 (5)	C16—H16	0.93
C3—C4	1.411 (5)	C18—H18	0.98
C4—C9	1.411 (4)	C19—H19a	0.96
C4—C5	1.419 (4)	C19—H19b	0.96
C5—C6	1.351 (5)	C19—H19c	0.96
C6—C7	1.386 (6)	C20—H20a	0.96
C7—C8	1.371 (5)	C20—H20b	0.96
C8—C9	1.405 (4)	C20—H20c	0.96
C9—C10	1.454 (4)	C21—H21	0.98
C10—C11	1.405 (4)	C22—H22a	0.96
C12—C17	1.381 (4)	C22—H22b	0.96
C12—C13	1.396 (4)	C22—H22c	0.96
C13—C14	1.387 (4)	C23—H23a	0.96
C13—C18	1.508 (5)	C23—H23b	0.96
C14—C15	1.368 (5)	C23—H23c	0.96
C15—C16	1.357 (5)	C24—H24a	0.97
C16—C17	1.398 (5)	C24—H24b	0.97
C17—C21	1.512 (5)	C24'—H24c	0.97
C18—C20	1.504 (7)	C24'—H24d	0.97
C18—C19	1.505 (6)
O1—Zr1—O1^i	180	C6—C5—H5	119.7
O1—Zr1—Cl1	89.09 (7)	C4—C5—H5	119.7
O1—Zr1—Cl1^i	90.91 (7)	C5—C6—H6	120.1
O1—Zr1—Cl2	87.02 (6)	C7—C6—H6	120.1
O1—Zr1—Cl2^i	92.98 (6)	C8—C7—H7	119.2
Cl1—Zr1—Cl1^i	180	C6—C7—H7	119.2
Cl1—Zr1—Cl2	89.28 (5)	C7—C8—H8	119.9
Cl1—Zr1—Cl2^i	90.72 (5)	C9—C8—H8	119.9
Cl2—Zr1—Cl2^i	180	N1—C11—H11	115.4
C1—O1—Zr1	150.8 (2)	C10—C11—H11	115.4
C11—N1—C12	123.0 (2)	C15—C14—H14	119.3
O1—C1—C2	119.9 (2)	C13—C14—H14	119.3
O1—C1—C10	120.3 (2)	C16—C15—H15	119.7
C2—C1—C10	119.8 (3)	C14—C15—H15	119.7
C3—C2—C1	120.5 (3)	C15—C16—H16	119.4
C2—C3—C4	122.6 (3)	C17—C16—H16	119.4
C3—C4—C9	119.0 (3)	C20—C18—H18	108.4
C3—C4—C5	121.2 (3)	C13—C18—H18	108.4
C9—C4—C5	119.8 (3)	C19—C18—H18	108.4
C6—C5—C4	120.6 (3)	C18—C19—H19a	109.5
C5—C6—C7	119.7 (3)	C18—C19—H19b	109.5
C8—C7—C6	121.7 (4)	H19a—C19—H19b	109.5
C7—C8—C9	120.3 (4)	C18—C19—H19c	109.5
C8—C9—C4	118.0 (3)	H19a—C19—H19c	109.5
C8—C9—C10	123.4 (3)	H19b—C19—H19c	109.5
C4—C9—C10	118.7 (3)	C18—C20—H20a	109.5
C11—C10—C1	121.3 (2)	C18—C20—H20b	109.5
C11—C10—C9	119.5 (2)	H20a—C20—H20b	109.5
C1—C10—C9	119.2 (2)	C18—C20—H20c	109.5
N1—C11—C10	129.3 (2)	H20a—C20—H20c	109.5
C17—C12—C13	123.4 (3)	H20b—C20—H20c	109.5
C17—C12—N1	118.2 (3)	C22—C21—H21	106.8
C13—C12—N1	118.4 (3)	C23—C21—H21	106.8
C14—C13—C12	116.7 (3)	C17—C21—H21	106.8
C14—C13—C18	120.7 (3)	C21—C22—H22a	109.5
C12—C13—C18	122.6 (3)	C21—C22—H22b	109.5
C15—C14—C13	121.3 (3)	H22a—C22—H22b	109.5
C16—C15—C14	120.6 (3)	C21—C22—H22c	109.5
C15—C16—C17	121.3 (3)	H22a—C22—H22c	109.5
C12—C17—C16	116.8 (3)	H22b—C22—H22c	109.5
C12—C17—C21	122.8 (3)	C21—C23—H23a	109.5
C16—C17—C21	120.4 (3)	C21—C23—H23b	109.5
C20—C18—C13	111.2 (4)	H23a—C23—H23b	109.5
C20—C18—C19	108.3 (5)	C21—C23—H23c	109.5
C13—C18—C19	111.9 (3)	H23a—C23—H23c	109.5
C22—C21—C23	113.4 (5)	H23b—C23—H23c	109.5
C22—C21—C17	111.7 (4)	Cl4—C24—H24a	109.9
C23—C21—C17	110.9 (4)	Cl3—C24—H24a	109.9
Cl4—C24—Cl3	108.7 (6)	Cl4—C24—H24b	109.9
Cl4'—C24'—Cl3'	105.1 (8)	Cl3—C24—H24b	109.9
C11—N1—H1	120 (2)	H24a—C24—H24b	108.3
C12—N1—H1	116 (2)	Cl4'—C24'—H24c	110.7
C3—C2—H2	119.8	Cl3'—C24'—H24c	110.7
C1—C2—H2	119.8	Cl4'—C24'—H24d	110.7
C2—C3—H3	118.7	Cl3'—C24'—H24d	110.7
C4—C3—H3	118.7	H24c—C24'—H24d	108.8
Cl1^i—Zr1—O1—C1	85.6 (4)	C4—C9—C10—C1	−5.5 (4)
Cl1—Zr1—O1—C1	−94.4 (4)	C12—N1—C11—C10	174.5 (3)
Cl2—Zr1—O1—C1	176.3 (4)	C1—C10—C11—N1	−0.9 (4)
Cl2^i—Zr1—O1—C1	−3.7 (4)	C9—C10—C11—N1	−178.5 (3)
Zr1—O1—C1—C2	−29.6 (5)	C11—N1—C12—C17	100.0 (3)
Zr1—O1—C1—C10	152.2 (3)	C11—N1—C12—C13	−78.9 (4)
O1—C1—C2—C3	179.0 (3)	C17—C12—C13—C14	−0.9 (5)
C10—C1—C2—C3	−2.8 (5)	N1—C12—C13—C14	177.9 (3)
C1—C2—C3—C4	−1.7 (5)	C17—C12—C13—C18	178.0 (3)
C2—C3—C4—C9	2.5 (5)	N1—C12—C13—C18	−3.2 (4)
C2—C3—C4—C5	−176.2 (3)	C12—C13—C14—C15	0.2 (5)
C3—C4—C5—C6	178.5 (3)	C18—C13—C14—C15	−178.8 (3)
C9—C4—C5—C6	−0.2 (5)	C13—C14—C15—C16	0.4 (6)
C4—C5—C6—C7	0.3 (6)	C14—C15—C16—C17	−0.3 (6)
C5—C6—C7—C8	−0.6 (6)	C13—C12—C17—C16	1.1 (5)
C6—C7—C8—C9	0.7 (6)	N1—C12—C17—C16	−177.8 (3)
C7—C8—C9—C4	−0.5 (5)	C13—C12—C17—C21	−180.0 (3)
C7—C8—C9—C10	179.9 (3)	N1—C12—C17—C21	1.2 (5)
C3—C4—C9—C8	−178.4 (3)	C15—C16—C17—C12	−0.4 (5)
C5—C4—C9—C8	0.3 (4)	C15—C16—C17—C21	−179.4 (4)
C3—C4—C9—C10	1.1 (4)	C14—C13—C18—C20	63.9 (5)
C5—C4—C9—C10	179.8 (3)	C12—C13—C18—C20	−115.0 (5)
O1—C1—C10—C11	6.9 (4)	C14—C13—C18—C19	−57.3 (5)
C2—C1—C10—C11	−171.3 (3)	C12—C13—C18—C19	123.8 (5)
O1—C1—C10—C9	−175.5 (2)	C12—C17—C21—C22	124.1 (5)
C2—C1—C10—C9	6.3 (4)	C16—C17—C21—C22	−57.0 (6)
C8—C9—C10—C11	−8.3 (4)	C12—C17—C21—C23	−108.3 (5)
C4—C9—C10—C11	172.2 (2)	C16—C17—C21—C23	70.6 (6)
C8—C9—C10—C1	174.1 (3)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.84 (1)	2.12 (3)	2.703 (3)	126 (3)