Di-μ-chloro-bis­[trichloro­(4-chloro­aniline)zirconium(IV)]

The title compound, [Zr₂Cl₈(C₆H₆ClN)₂], is centrosymmetric. Each Zr^IV ion has distorted octa­hedral coordination geometry, formed by one N atom from a 4-chloro­aniline ligand, three terminal Cl⁻ ions and two bridging Cl⁻ ions. The Zr—μ-Cl bond distances are much longer than the other Zr—Cl bond distances.

Key indicators

• Single-crystal X-ray study
• T = 153 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.028
• wR factor = 0.065
• Data-to-parameter ratio = 17.9

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.90

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

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

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Computing details

Data collection: CrystalClear (Rigaku, 2001); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2004); 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.

Di-µ-chloro-bis[trichloro(4-chloroaniline)zirconium(IV)]

Crystal data

[Zr2Cl8(C6H6ClN)2]	F(000) = 696
Mr = 721.18	Dx = 2.051 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ybc	Cell parameters from 3816 reflections
a = 7.8434 (14) Å	θ = 3.1–25.3°
b = 9.4373 (14) Å	µ = 2.04 mm^−1
c = 15.989 (3) Å	T = 153 K
β = 99.372 (5)°	Block, colourless
V = 1167.7 (3) Å^3	0.42 × 0.35 × 0.30 mm
Z = 2

Data collection

Rigaku Mercury diffractometer	2134 independent reflections
Radiation source: fine-focus sealed tube	1971 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
Detector resolution: 7.31 pixels mm^-1	θmax = 25.3°, θmin = 3.3°
ω scans	h = −9→9
Absorption correction: multi-scan (Jacobson, 1998)	k = −11→11
Tmin = 0.385, Tmax = 0.543	l = −18→19
10883 measured reflections

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) = 0.065	H-atom parameters constrained
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0268P)^2 + 1.743P] where P = (Fo^2 + 2Fc^2)/3
2134 reflections	(Δ/σ)max = 0.001
119 parameters	Δρmax = 0.47 e Å^−3
0 restraints	Δρmin = −0.77 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
Zr1	0.13383 (3)	0.15643 (3)	0.567187 (17)	0.01486 (10)
Cl1	−0.18274 (9)	0.08348 (7)	0.50328 (4)	0.01709 (16)
Cl2	0.43176 (9)	0.19634 (8)	0.59165 (5)	0.02277 (18)
Cl3	0.03184 (11)	0.38304 (8)	0.59853 (5)	0.02812 (19)
Cl4	0.10244 (9)	0.04146 (8)	0.69563 (4)	0.02190 (17)
Cl5	0.75766 (9)	0.32270 (8)	0.27930 (5)	0.02437 (18)
N1	0.1142 (3)	0.2422 (3)	0.42535 (15)	0.0195 (5)
H1A	0.0452	0.1803	0.3905	0.023*
H1B	0.0569	0.3276	0.4225	0.023*
C1	0.2717 (4)	0.2631 (3)	0.38943 (18)	0.0173 (6)
C2	0.3622 (4)	0.3890 (3)	0.40333 (19)	0.0204 (6)
H2	0.3210	0.4626	0.4353	0.025*
C3	0.5139 (4)	0.4067 (3)	0.37018 (19)	0.0199 (6)
H3	0.5777	0.4925	0.3793	0.024*
C4	0.5708 (4)	0.2982 (3)	0.32384 (18)	0.0185 (6)
C5	0.4815 (4)	0.1716 (3)	0.30996 (19)	0.0201 (6)
H5	0.5225	0.0979	0.2780	0.024*
C6	0.3309 (4)	0.1548 (3)	0.34367 (19)	0.0198 (6)
H6	0.2682	0.0685	0.3353	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zr1	0.01379 (16)	0.01531 (16)	0.01537 (17)	0.00013 (11)	0.00206 (11)	−0.00130 (10)
Cl1	0.0125 (3)	0.0179 (3)	0.0209 (4)	0.0020 (3)	0.0027 (3)	−0.0034 (3)
Cl2	0.0149 (3)	0.0293 (4)	0.0233 (4)	−0.0025 (3)	0.0004 (3)	−0.0005 (3)
Cl3	0.0316 (4)	0.0197 (4)	0.0327 (4)	0.0062 (3)	0.0042 (4)	−0.0056 (3)
Cl4	0.0228 (4)	0.0260 (4)	0.0173 (4)	−0.0009 (3)	0.0047 (3)	0.0008 (3)
Cl5	0.0164 (4)	0.0292 (4)	0.0279 (4)	−0.0025 (3)	0.0047 (3)	0.0074 (3)
N1	0.0180 (12)	0.0203 (13)	0.0206 (13)	0.0013 (11)	0.0046 (11)	0.0012 (10)
C1	0.0177 (14)	0.0203 (15)	0.0142 (14)	0.0024 (12)	0.0035 (12)	0.0039 (11)
C2	0.0240 (16)	0.0168 (15)	0.0203 (15)	0.0004 (13)	0.0028 (13)	0.0002 (12)
C3	0.0237 (16)	0.0142 (14)	0.0203 (15)	−0.0076 (12)	−0.0010 (13)	−0.0008 (12)
C4	0.0135 (14)	0.0257 (16)	0.0160 (15)	−0.0015 (12)	0.0018 (12)	0.0068 (12)
C5	0.0218 (16)	0.0190 (15)	0.0198 (15)	0.0005 (12)	0.0039 (13)	−0.0015 (12)
C6	0.0217 (15)	0.0190 (15)	0.0184 (15)	−0.0028 (12)	0.0028 (13)	0.0012 (12)

Geometric parameters (Å, º)

Zr1—Cl1	2.6186 (8)	C1—C6	1.381 (4)
Zr1—Cl1^i	2.5852 (8)	C1—C2	1.383 (4)
Zr1—Cl2	2.3362 (9)	C2—C3	1.389 (4)
Zr1—Cl3	2.3655 (8)	C2—H2	0.9500
Zr1—Cl4	2.3707 (8)	C3—C4	1.380 (4)
Zr1—N1	2.389 (2)	C3—H3	0.9500
Cl5—C4	1.746 (3)	C4—C5	1.384 (4)
N1—C1	1.458 (4)	C5—C6	1.384 (4)
N1—H1A	0.9200	C5—H5	0.9500
N1—H1B	0.9200	C6—H6	0.9500
Cl2—Zr1—Cl3	100.51 (3)	Zr1—N1—H1B	107.5
Cl2—Zr1—Cl4	99.84 (3)	H1A—N1—H1B	107.0
Cl3—Zr1—Cl4	98.27 (3)	C6—C1—C2	120.8 (3)
Cl2—Zr1—N1	90.71 (6)	C6—C1—N1	119.3 (3)
Cl3—Zr1—N1	85.58 (7)	C2—C1—N1	119.9 (3)
Cl4—Zr1—N1	167.85 (7)	C1—C2—C3	119.4 (3)
Cl2—Zr1—Cl1^i	89.93 (3)	C1—C2—H2	120.3
Cl3—Zr1—Cl1^i	164.45 (3)	C3—C2—H2	120.3
Cl4—Zr1—Cl1^i	91.17 (3)	C4—C3—C2	119.1 (3)
N1—Zr1—Cl1^i	82.78 (7)	C4—C3—H3	120.4
Cl2—Zr1—Cl1	165.19 (3)	C2—C3—H3	120.4
Cl3—Zr1—Cl1	89.34 (3)	C3—C4—C5	121.8 (3)
Cl4—Zr1—Cl1	89.54 (3)	C3—C4—Cl5	119.1 (2)
N1—Zr1—Cl1	78.95 (6)	C5—C4—Cl5	119.0 (2)
Cl1^i—Zr1—Cl1	78.36 (2)	C4—C5—C6	118.5 (3)
Zr1^i—Cl1—Zr1	101.64 (2)	C4—C5—H5	120.7
C1—N1—Zr1	119.47 (17)	C6—C5—H5	120.7
C1—N1—H1A	107.5	C1—C6—C5	120.2 (3)
Zr1—N1—H1A	107.5	C1—C6—H6	119.9
C1—N1—H1B	107.5	C5—C6—H6	119.9
Cl2—Zr1—Cl1—Zr1^i	38.39 (11)	Zr1—N1—C1—C2	−85.5 (3)
Cl3—Zr1—Cl1—Zr1^i	170.43 (3)	C6—C1—C2—C3	0.5 (4)
Cl4—Zr1—Cl1—Zr1^i	−91.29 (3)	N1—C1—C2—C3	178.8 (3)
N1—Zr1—Cl1—Zr1^i	84.80 (7)	C1—C2—C3—C4	0.1 (4)
Cl1^i—Zr1—Cl1—Zr1^i	0.0	C2—C3—C4—C5	−0.5 (4)
Cl2—Zr1—N1—C1	12.3 (2)	C2—C3—C4—Cl5	178.0 (2)
Cl3—Zr1—N1—C1	112.8 (2)	C3—C4—C5—C6	0.1 (4)
Cl4—Zr1—N1—C1	−138.1 (3)	Cl5—C4—C5—C6	−178.3 (2)
Cl1^i—Zr1—N1—C1	−77.5 (2)	C2—C1—C6—C5	−0.9 (5)
Cl1—Zr1—N1—C1	−157.0 (2)	N1—C1—C6—C5	−179.1 (3)
Zr1—N1—C1—C6	92.8 (3)	C4—C5—C6—C1	0.5 (4)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl4^i	0.92	2.66	3.567 (3)	167
N1—H1B···Cl3^ii	0.92	2.82	3.718 (3)	164

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