N,N-Diethyl­pyrrolidinium penta­chloro­(tetra­hydro­furan)­zirconate(IV)

Both ions of the title compound, (C₈H₁₈N)[ZrCl₅(C₄H₈O)], exhibit approximate C_s symmetry. The equatorial Cl atoms of the anion display an umbrella effect with significant bending towards the tetra­hydro­furan fragment, as observed before for similar anions. The cation exhibits bond lengths and angles in the expected range.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.034
• wR factor = 0.108
• Data-to-parameter ratio = 21.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Zr1    -   Cl2     ..       9.63 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Zr1    -   Cl4     ..       6.08 su
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Zr1    -   Cl5     ..       6.81 su

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 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
   3 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

Computing details

Data collection: SMART-NT (Bruker, 2003); cell refinement: SAINT-NT (Bruker, 2003); data reduction: SAINT-NT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: XP in SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: XP in SHELXTL.

N,N-Diethylpyrrolidinium pentachloro(tetrahydrofuran)zirconate

Crystal data

(C8H18N)[ZrCl5(C4H8O)]	F(000) = 1904.0
Mr = 468.81	Dx = 1.581 Mg m^−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 7412 reflections
a = 15.4148 (17) Å	θ = 2.6–26.1°
b = 14.9772 (17) Å	µ = 1.23 mm^−1
c = 17.0633 (19) Å	T = 173 K
V = 3939.4 (8) Å^3	Block, yellow
Z = 8	0.35 × 0.18 × 0.14 mm

Data collection

Bruker SMART CCD area-detector diffractometer	3922 independent reflections
Radiation source: fine-focus sealed tube	3440 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
φ and ω scans	θmax = 26.2°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	h = −19→19
Tmin = 0.668, Tmax = 0.841	k = −18→18
54795 measured reflections	l = −21→21

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.108	H-atom parameters constrained
S = 1.10	w = 1/[σ^2(Fo^2) + (0.0622P)^2 + 4.0936P] where P = (Fo^2 + 2Fc^2)/3
3922 reflections	(Δ/σ)max = 0.027
183 parameters	Δρmax = 1.02 e Å^−3
96 restraints	Δρmin = −0.52 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	1.048908 (18)	0.746204 (17)	0.396971 (17)	0.02940 (12)
Cl2	1.05252 (4)	0.91068 (4)	0.37741 (5)	0.03458 (18)
Cl3	1.03538 (5)	0.58741 (5)	0.42745 (5)	0.03987 (19)
Cl4	0.90238 (5)	0.74390 (5)	0.33967 (5)	0.03805 (19)
Cl5	1.18131 (5)	0.75453 (5)	0.47640 (6)	0.0460 (2)
Cl6	1.12565 (7)	0.71663 (6)	0.27546 (5)	0.0560 (3)
O1	0.98246 (13)	0.77316 (14)	0.51104 (12)	0.0344 (4)
C9	0.2038 (2)	0.9009 (2)	0.1561 (2)	0.0429 (7)
H9A	0.2320	0.8689	0.1122	0.051*
H9B	0.2169	0.8677	0.2049	0.051*
N1	0.24286 (15)	0.99312 (15)	0.16222 (16)	0.0328 (5)
C5	0.2134 (2)	1.0400 (2)	0.23508 (19)	0.0452 (6)
H5A	0.1506	1.0301	0.2439	0.054*
H5B	0.2241	1.1050	0.2310	0.054*
C7	0.3495 (3)	0.9670 (3)	0.2614 (3)	0.0663 (9)
H7A	0.4006	0.9989	0.2826	0.080*
H7B	0.3573	0.9022	0.2705	0.080*
C4	0.9081 (2)	0.7231 (3)	0.5415 (2)	0.0537 (9)
H4A	0.9202	0.6582	0.5407	0.064*
H4B	0.8558	0.7349	0.5095	0.064*
C11	0.2223 (3)	1.0490 (2)	0.0914 (2)	0.0481 (7)
H11A	0.2498	1.1083	0.0979	0.058*
H11B	0.1588	1.0583	0.0890	0.058*
C3	0.8948 (3)	0.7546 (3)	0.6237 (3)	0.0644 (10)
H3A	0.8323	0.7563	0.6370	0.077*
H3B	0.9252	0.7153	0.6614	0.077*
C12	0.2521 (3)	1.0093 (3)	0.0146 (2)	0.0693 (13)
H12A	0.3130	0.9912	0.0191	0.104*
H12B	0.2462	1.0538	−0.0271	0.104*
H12C	0.2165	0.9570	0.0021	0.104*
C10	0.1068 (2)	0.8998 (3)	0.1432 (2)	0.0527 (9)
H10A	0.0780	0.9313	0.1863	0.079*
H10B	0.0863	0.8378	0.1414	0.079*
H10C	0.0931	0.9294	0.0935	0.079*
C1	1.0060 (2)	0.8434 (2)	0.5671 (2)	0.0503 (8)
H1A	1.0124	0.9017	0.5403	0.060*
H1B	1.0612	0.8288	0.5939	0.060*
C6	0.2659 (3)	1.0001 (3)	0.3011 (2)	0.0621 (9)
H6A	0.2344	0.9500	0.3260	0.075*
H6B	0.2791	1.0456	0.3414	0.075*
C8	0.3392 (2)	0.9859 (2)	0.1753 (2)	0.0508 (7)
H8A	0.3641	0.9368	0.1435	0.061*
H8B	0.3686	1.0424	0.1609	0.061*
C2	0.9327 (3)	0.8457 (3)	0.6240 (3)	0.0703 (11)
H2A	0.9538	0.8614	0.6770	0.084*
H2B	0.8888	0.8903	0.6077	0.084*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zr1	0.02996 (19)	0.02775 (18)	0.03049 (19)	0.00009 (10)	0.00494 (10)	0.00206 (10)
Cl2	0.0329 (4)	0.0243 (3)	0.0466 (4)	−0.0015 (2)	0.0023 (3)	0.0047 (3)
Cl3	0.0517 (4)	0.0285 (3)	0.0395 (4)	−0.0030 (3)	0.0011 (3)	0.0060 (3)
Cl4	0.0408 (4)	0.0366 (4)	0.0368 (4)	−0.0055 (3)	−0.0121 (3)	0.0027 (3)
Cl5	0.0236 (3)	0.0484 (4)	0.0660 (5)	−0.0015 (3)	−0.0053 (3)	0.0080 (4)
Cl6	0.0815 (6)	0.0423 (4)	0.0442 (4)	0.0158 (4)	0.0332 (4)	0.0093 (3)
O1	0.0286 (8)	0.0447 (9)	0.0299 (7)	−0.0060 (8)	0.0031 (6)	−0.0048 (6)
C9	0.0439 (14)	0.0328 (12)	0.0519 (19)	−0.0077 (11)	−0.0055 (14)	0.0055 (10)
N1	0.0321 (10)	0.0281 (11)	0.0381 (9)	0.0006 (8)	0.0058 (9)	0.0001 (8)
C5	0.0436 (15)	0.0544 (17)	0.0375 (11)	0.0026 (13)	0.0051 (11)	−0.0080 (11)
C7	0.0586 (17)	0.053 (2)	0.087 (2)	0.0016 (16)	−0.0330 (15)	−0.002 (2)
C4	0.0335 (16)	0.083 (2)	0.0440 (16)	−0.0185 (14)	0.0132 (12)	−0.0070 (15)
C11	0.068 (2)	0.0380 (15)	0.0388 (11)	−0.0070 (15)	0.0024 (13)	0.0064 (11)
C3	0.052 (2)	0.097 (2)	0.0440 (16)	−0.0100 (18)	0.0187 (16)	−0.0076 (18)
C12	0.100 (4)	0.070 (3)	0.0389 (12)	−0.027 (3)	0.0146 (19)	−0.0033 (16)
C10	0.0455 (14)	0.058 (2)	0.055 (2)	−0.0169 (14)	−0.0109 (16)	0.0091 (17)
C1	0.061 (2)	0.0498 (18)	0.0406 (15)	−0.0066 (13)	0.0061 (13)	−0.0149 (12)
C6	0.068 (2)	0.077 (3)	0.0418 (11)	−0.0221 (18)	−0.0102 (12)	0.0115 (16)
C8	0.0311 (10)	0.0449 (18)	0.0765 (16)	−0.0019 (11)	0.0051 (12)	−0.0086 (16)
C2	0.095 (3)	0.0655 (19)	0.0500 (19)	0.0151 (18)	0.0286 (18)	−0.0106 (15)

Geometric parameters (Å, º)

Zr1—O1	2.236 (2)	C4—H4A	0.9900
Zr1—Cl6	2.4279 (8)	C4—H4B	0.9900
Zr1—Cl3	2.4434 (8)	C11—C12	1.510 (5)
Zr1—Cl5	2.4532 (9)	C11—H11A	0.9900
Zr1—Cl4	2.4615 (8)	C11—H11B	0.9900
Zr1—Cl2	2.4865 (8)	C3—C2	1.484 (6)
O1—C4	1.465 (4)	C3—H3A	0.9900
O1—C1	1.468 (4)	C3—H3B	0.9900
C9—C10	1.511 (5)	C12—H12A	0.9800
C9—N1	1.511 (4)	C12—H12B	0.9800
C9—H9A	0.9900	C12—H12C	0.9800
C9—H9B	0.9900	C10—H10A	0.9800
N1—C5	1.499 (4)	C10—H10B	0.9800
N1—C11	1.503 (4)	C10—H10C	0.9800
N1—C8	1.506 (4)	C1—C2	1.491 (5)
C5—C6	1.511 (5)	C1—H1A	0.9900
C5—H5A	0.9900	C1—H1B	0.9900
C5—H5B	0.9900	C6—H6A	0.9900
C7—C8	1.505 (6)	C6—H6B	0.9900
C7—C6	1.537 (6)	C8—H8A	0.9900
C7—H7A	0.9900	C8—H8B	0.9900
C7—H7B	0.9900	C2—H2A	0.9900
C4—C3	1.492 (5)	C2—H2B	0.9900
O1—Zr1—Cl6	178.08 (6)	N1—C11—C12	114.4 (3)
O1—Zr1—Cl3	87.21 (6)	N1—C11—H11A	108.7
Cl6—Zr1—Cl3	92.63 (3)	C12—C11—H11A	108.7
O1—Zr1—Cl5	83.74 (6)	N1—C11—H11B	108.7
Cl6—Zr1—Cl5	94.34 (4)	C12—C11—H11B	108.7
Cl3—Zr1—Cl5	90.17 (3)	H11A—C11—H11B	107.6
O1—Zr1—Cl4	85.87 (6)	C2—C3—C4	103.9 (4)
Cl6—Zr1—Cl4	96.05 (4)	C2—C3—H3A	111.0
Cl3—Zr1—Cl4	89.57 (3)	C4—C3—H3A	111.0
Cl5—Zr1—Cl4	169.61 (3)	C2—C3—H3B	111.0
O1—Zr1—Cl2	87.03 (6)	C4—C3—H3B	111.0
Cl6—Zr1—Cl2	93.16 (3)	H3A—C3—H3B	109.0
Cl3—Zr1—Cl2	174.14 (3)	C11—C12—H12A	109.5
Cl5—Zr1—Cl2	90.29 (3)	C11—C12—H12B	109.5
Cl4—Zr1—Cl2	88.92 (2)	H12A—C12—H12B	109.5
C4—O1—C1	109.2 (2)	C11—C12—H12C	109.5
C4—O1—Zr1	125.12 (19)	H12A—C12—H12C	109.5
C1—O1—Zr1	125.68 (18)	H12B—C12—H12C	109.5
C10—C9—N1	114.5 (3)	C9—C10—H10A	109.5
C10—C9—H9A	108.6	C9—C10—H10B	109.5
N1—C9—H9A	108.6	H10A—C10—H10B	109.5
C10—C9—H9B	108.6	C9—C10—H10C	109.5
N1—C9—H9B	108.6	H10A—C10—H10C	109.5
H9A—C9—H9B	107.6	H10B—C10—H10C	109.5
C5—N1—C11	110.0 (2)	O1—C1—C2	104.6 (3)
C5—N1—C8	102.2 (3)	O1—C1—H1A	110.8
C11—N1—C8	111.5 (3)	C2—C1—H1A	110.8
C5—N1—C9	111.4 (3)	O1—C1—H1B	110.8
C11—N1—C9	111.7 (3)	C2—C1—H1B	110.8
C8—N1—C9	109.8 (2)	H1A—C1—H1B	108.9
N1—C5—C6	105.7 (3)	C5—C6—C7	104.4 (3)
N1—C5—H5A	110.6	C5—C6—H6A	110.9
C6—C5—H5A	110.6	C7—C6—H6A	110.9
N1—C5—H5B	110.6	C5—C6—H6B	110.9
C6—C5—H5B	110.6	C7—C6—H6B	110.9
H5A—C5—H5B	108.7	H6A—C6—H6B	108.9
C8—C7—C6	106.3 (3)	C7—C8—N1	105.1 (3)
C8—C7—H7A	110.5	C7—C8—H8A	110.7
C6—C7—H7A	110.5	N1—C8—H8A	110.7
C8—C7—H7B	110.5	C7—C8—H8B	110.7
C6—C7—H7B	110.5	N1—C8—H8B	110.7
H7A—C7—H7B	108.7	H8A—C8—H8B	108.8
O1—C4—C3	106.2 (3)	C3—C2—C1	106.0 (3)
O1—C4—H4A	110.5	C3—C2—H2A	110.5
C3—C4—H4A	110.5	C1—C2—H2A	110.5
O1—C4—H4B	110.5	C3—C2—H2B	110.5
C3—C4—H4B	110.5	C1—C2—H2B	110.5
H4A—C4—H4B	108.7	H2A—C2—H2B	108.7
Cl3—Zr1—O1—C4	−41.4 (3)	Zr1—O1—C4—C3	171.3 (3)
Cl5—Zr1—O1—C4	−131.9 (3)	C5—N1—C11—C12	178.1 (3)
Cl4—Zr1—O1—C4	48.3 (3)	C8—N1—C11—C12	65.5 (4)
Cl2—Zr1—O1—C4	137.5 (3)	C9—N1—C11—C12	−57.7 (4)
Cl3—Zr1—O1—C1	138.6 (2)	O1—C4—C3—C2	25.2 (5)
Cl5—Zr1—O1—C1	48.1 (2)	C4—O1—C1—C2	−11.2 (4)
Cl4—Zr1—O1—C1	−131.6 (2)	Zr1—O1—C1—C2	168.8 (3)
Cl2—Zr1—O1—C1	−42.5 (2)	N1—C5—C6—C7	26.0 (4)
C10—C9—N1—C5	67.4 (4)	C8—C7—C6—C5	−2.2 (4)
C10—C9—N1—C11	−56.0 (4)	C6—C7—C8—N1	−22.1 (4)
C10—C9—N1—C8	179.8 (3)	C5—N1—C8—C7	37.8 (3)
C11—N1—C5—C6	−158.1 (3)	C11—N1—C8—C7	155.3 (3)
C8—N1—C5—C6	−39.7 (3)	C9—N1—C8—C7	−80.4 (3)
C9—N1—C5—C6	77.4 (3)	C4—C3—C2—C1	−32.3 (5)
C1—O1—C4—C3	−8.7 (4)	O1—C1—C2—C3	27.1 (5)