Chloro­[N,N'-di­methyl-N,N'-bis(2-pyridyl­methyl)­ethane-1,2-di­amine]oxovanadium(IV) perchlorate

The title vanadium complex, [VClO(C₁₆H₂₂N₄)]ClO₄, of the tetradentate ligand N,N'-di­methyl-N,N'-bis(2-pyridyl­methyl)­ethane-1,2-di­amine was obtained from air oxidation of a mixture of the ligand and VCl₃ in wet methanol.

Key indicators

• Single-crystal X-ray study
• T = 180 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.040
• wR factor = 0.102
• Data-to-parameter ratio = 16.7

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low .......       0.96

Alert level C
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cl2

Alert level G
REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values
           From the CIF: _diffrn_reflns_theta_max           28.30
           From the CIF: _reflns_number_total               4263
           From the CIF: _diffrn_reflns_limit_ max hkl   17.    9.    9.
           From the CIF: _diffrn_reflns_limit_ min hkl  -17.   -9.  -23.
           TEST1: Expected hkl limits for theta max
           Calculated maximum hkl   17.   11.   23.
           Calculated minimum hkl  -17.  -11.  -23.

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

   1 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
   1 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: APEX2 (Bruker–Nonius, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Chloro[N,N'-dimethyl-N,N'-bis(2-pyridylmethyl)ethane-1,2-diamine] oxovanadium(IV) perchlorate

Crystal data

[VClO(C16H22N4)]ClO4	F(000) = 972
Mr = 472.22	Dx = 1.540 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3078 reflections
a = 13.3031 (6) Å	θ = 2.5–27.1°
b = 8.9874 (4) Å	µ = 0.79 mm^−1
c = 17.7551 (9) Å	T = 180 K
β = 106.408 (1)°	Block, blue
V = 2036.35 (17) Å^3	0.34 × 0.20 × 0.20 mm
Z = 4

Data collection

Bruker–Nonius X8APEX-II CCD diffractometer	4263 independent reflections
Radiation source: fine-focus sealed tube	2835 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
thin–slice ω and φ scans	θmax = 28.3°, θmin = 3.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 2003)	h = −17→17
Tmin = 0.719, Tmax = 0.859	k = −9→9
8836 measured reflections	l = −23→9

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.102	H-atom parameters constrained
S = 0.94	w = 1/[σ^2(Fo^2) + (0.0546P)^2] where P = (Fo^2 + 2Fc^2)/3
4263 reflections	(Δ/σ)max = 0.001
255 parameters	Δρmax = 0.82 e Å^−3
0 restraints	Δρmin = −0.42 e Å^−3

Special details

Experimental. Ratio of minimum to maximum apparent transmission: 0.837449

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.

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

5.8286 (0.0111) x - 1.3261 (0.0086) y + 12.9051 (0.0113) z = 3.9044 (0.0072)

* -0.0087 (0.0015) N1 * 0.0008 (0.0017) C1 * 0.0063 (0.0017) C2 * -0.0056 (0.0017) C3 * -0.0022 (0.0017) C4 * 0.0094 (0.0016) C5

Rms deviation of fitted atoms = 0.0063

5.1880 (0.0139) x + 7.4753 (0.0060) y + 4.7733 (0.0191) z = 8.4508 (0.0034)

* -0.0001 (0.0017) N2 * 0.0077 (0.0019) C12 * -0.0107 (0.0021) C13 * 0.0064 (0.0022) C14 * 0.0011 (0.0023) C15 * -0.0044 (0.0021) C16

Rms deviation of fitted atoms = 0.0063

Angle to previous plane (with approximate e.s.d.) = 66.52 (0.09)

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
V1	0.32565 (3)	0.76248 (5)	0.22463 (2)	0.02974 (14)
Cl1	0.45080 (5)	0.64760 (9)	0.32580 (4)	0.0499 (2)
O1	0.33757 (13)	0.93676 (19)	0.24415 (10)	0.0414 (5)
N1	0.20724 (15)	0.7375 (2)	0.28407 (11)	0.0288 (5)
N2	0.41997 (16)	0.7453 (2)	0.14671 (12)	0.0325 (5)
N3	0.24933 (15)	0.5305 (2)	0.18843 (11)	0.0305 (5)
N4	0.21611 (15)	0.8098 (2)	0.11067 (11)	0.0306 (5)
C1	0.16784 (19)	0.8531 (3)	0.31447 (14)	0.0334 (6)
H1A	0.1962	0.9493	0.3118	0.040*
C2	0.08846 (19)	0.8383 (3)	0.34922 (14)	0.0340 (6)
H2A	0.0629	0.9225	0.3704	0.041*
C3	0.0466 (2)	0.7001 (3)	0.35302 (14)	0.0351 (6)
H3A	−0.0092	0.6873	0.3761	0.042*
C4	0.08674 (18)	0.5801 (3)	0.32281 (14)	0.0325 (6)
H4A	0.0589	0.4834	0.3250	0.039*
C5	0.16740 (18)	0.6011 (3)	0.28944 (13)	0.0291 (6)
C6	0.2174 (2)	0.4759 (3)	0.25705 (14)	0.0356 (6)
H6A	0.2795	0.4389	0.2979	0.043*
H6B	0.1671	0.3928	0.2409	0.043*
C7	0.3185 (2)	0.4166 (3)	0.16737 (15)	0.0422 (7)
H7A	0.2838	0.3194	0.1613	0.063*
H7B	0.3849	0.4110	0.2091	0.063*
H7C	0.3324	0.4447	0.1179	0.063*
C8	0.15448 (19)	0.5577 (3)	0.12166 (13)	0.0337 (6)
H8A	0.0968	0.5946	0.1418	0.040*
H8B	0.1315	0.4634	0.0931	0.040*
C9	0.17835 (19)	0.6698 (3)	0.06702 (14)	0.0331 (6)
H9A	0.2328	0.6303	0.0442	0.040*
H9B	0.1145	0.6902	0.0236	0.040*
C10	0.12610 (19)	0.9033 (3)	0.11502 (16)	0.0403 (7)
H10A	0.0882	0.9377	0.0623	0.060*
H10B	0.1517	0.9894	0.1489	0.060*
H10C	0.0788	0.8446	0.1368	0.060*
C11	0.27989 (19)	0.8947 (3)	0.06853 (15)	0.0398 (6)
H11A	0.2928	0.9966	0.0902	0.048*
H11B	0.2414	0.9023	0.0121	0.048*
C12	0.38166 (19)	0.8169 (3)	0.07791 (14)	0.0361 (6)
C13	0.4328 (2)	0.8158 (3)	0.02008 (16)	0.0485 (7)
H13A	0.4029	0.8645	−0.0286	0.058*
C14	0.5272 (2)	0.7440 (3)	0.03363 (18)	0.0562 (9)
H14A	0.5645	0.7446	−0.0048	0.067*
C15	0.5670 (2)	0.6706 (4)	0.10414 (17)	0.0561 (9)
H15A	0.6319	0.6190	0.1145	0.067*
C16	0.5123 (2)	0.6727 (3)	0.15918 (15)	0.0448 (7)
H16A	0.5402	0.6216	0.2074	0.054*
Cl2	0.83748 (5)	0.77174 (7)	0.55878 (4)	0.03751 (18)
O2	0.77474 (14)	0.90186 (19)	0.53530 (10)	0.0452 (5)
O3	0.90724 (15)	0.7906 (2)	0.63649 (11)	0.0490 (5)
O4	0.76814 (16)	0.6490 (2)	0.56127 (13)	0.0636 (7)
O5	0.8937 (2)	0.7377 (3)	0.50394 (15)	0.0876 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
V1	0.0304 (2)	0.0366 (3)	0.0247 (2)	−0.00381 (19)	0.01184 (17)	−0.00313 (18)
Cl1	0.0409 (4)	0.0833 (6)	0.0252 (3)	0.0040 (4)	0.0090 (3)	0.0063 (3)
O1	0.0480 (11)	0.0398 (11)	0.0440 (11)	−0.0162 (8)	0.0251 (9)	−0.0097 (8)
N1	0.0331 (11)	0.0281 (13)	0.0275 (11)	−0.0036 (9)	0.0122 (9)	−0.0030 (9)
N2	0.0319 (11)	0.0404 (13)	0.0275 (11)	0.0000 (10)	0.0123 (9)	0.0024 (9)
N3	0.0354 (11)	0.0322 (12)	0.0268 (11)	0.0057 (9)	0.0137 (9)	−0.0003 (9)
N4	0.0319 (11)	0.0308 (12)	0.0310 (11)	0.0009 (9)	0.0120 (9)	0.0030 (9)
C1	0.0410 (14)	0.0283 (15)	0.0344 (14)	−0.0067 (12)	0.0163 (12)	−0.0076 (11)
C2	0.0390 (14)	0.0326 (16)	0.0335 (14)	0.0005 (12)	0.0152 (12)	−0.0080 (11)
C3	0.0335 (13)	0.0426 (16)	0.0321 (14)	−0.0033 (12)	0.0142 (11)	0.0002 (12)
C4	0.0359 (14)	0.0295 (15)	0.0336 (14)	−0.0032 (11)	0.0125 (11)	0.0043 (11)
C5	0.0356 (14)	0.0280 (15)	0.0239 (13)	−0.0005 (11)	0.0085 (10)	0.0021 (10)
C6	0.0451 (15)	0.0324 (15)	0.0336 (14)	0.0032 (12)	0.0182 (12)	0.0033 (11)
C7	0.0538 (17)	0.0369 (16)	0.0418 (16)	0.0107 (13)	0.0230 (13)	−0.0007 (13)
C8	0.0352 (14)	0.0331 (15)	0.0321 (14)	−0.0018 (11)	0.0082 (11)	−0.0083 (11)
C9	0.0365 (14)	0.0356 (15)	0.0271 (13)	0.0027 (11)	0.0089 (11)	−0.0015 (11)
C10	0.0364 (15)	0.0392 (16)	0.0471 (16)	0.0098 (12)	0.0150 (12)	0.0018 (13)
C11	0.0423 (15)	0.0447 (17)	0.0345 (15)	0.0016 (13)	0.0145 (12)	0.0117 (12)
C12	0.0367 (14)	0.0439 (17)	0.0299 (14)	−0.0029 (12)	0.0132 (11)	0.0037 (12)
C13	0.0462 (16)	0.073 (2)	0.0307 (15)	0.0029 (15)	0.0178 (13)	0.0120 (14)
C14	0.0478 (17)	0.086 (3)	0.0434 (17)	0.0022 (17)	0.0278 (14)	0.0061 (16)
C15	0.0405 (16)	0.090 (3)	0.0440 (18)	0.0219 (16)	0.0213 (14)	0.0082 (17)
C16	0.0357 (14)	0.068 (2)	0.0327 (15)	0.0106 (14)	0.0134 (12)	0.0081 (14)
Cl2	0.0426 (4)	0.0362 (4)	0.0334 (3)	0.0049 (3)	0.0102 (3)	0.0026 (3)
O2	0.0499 (11)	0.0371 (11)	0.0485 (12)	0.0097 (9)	0.0139 (9)	0.0108 (9)
O3	0.0552 (12)	0.0396 (11)	0.0418 (11)	−0.0022 (9)	−0.0031 (10)	−0.0012 (9)
O4	0.0669 (14)	0.0388 (13)	0.0723 (16)	−0.0129 (10)	−0.0013 (12)	0.0028 (10)
O5	0.0863 (18)	0.129 (2)	0.0595 (15)	0.0525 (16)	0.0397 (14)	0.0198 (14)

Geometric parameters (Å, º)

V1—O1	1.6024 (18)	C7—H7A	0.980
V1—N2	2.120 (2)	C7—H7B	0.980
V1—N1	2.141 (2)	C7—H7C	0.980
V1—N4	2.1755 (19)	C8—C9	1.494 (3)
V1—Cl1	2.3184 (8)	C8—H8A	0.990
V1—N3	2.329 (2)	C8—H8B	0.990
N1—C1	1.343 (3)	C9—H9A	0.990
N1—C5	1.350 (3)	C9—H9B	0.990
N2—C12	1.347 (3)	C10—H10A	0.980
N2—C16	1.353 (3)	C10—H10B	0.980
N3—C6	1.482 (3)	C10—H10C	0.980
N3—C8	1.487 (3)	C11—C12	1.491 (3)
N3—C7	1.493 (3)	C11—H11A	0.990
N4—C10	1.483 (3)	C11—H11B	0.990
N4—C9	1.489 (3)	C12—C13	1.383 (3)
N4—C11	1.490 (3)	C13—C14	1.371 (4)
C1—C2	1.372 (3)	C13—H13A	0.950
C1—H1A	0.950	C14—C15	1.381 (4)
C2—C3	1.370 (3)	C14—H14A	0.950
C2—H2A	0.950	C15—C16	1.374 (4)
C3—C4	1.378 (3)	C15—H15A	0.950
C3—H3A	0.950	C16—H16A	0.950
C4—C5	1.377 (3)	Cl2—O5	1.419 (2)
C4—H4A	0.950	Cl2—O2	1.4288 (18)
C5—C6	1.502 (3)	Cl2—O3	1.4387 (18)
C6—H6A	0.990	Cl2—O4	1.446 (2)
C6—H6B	0.990
O1—V1—N2	99.88 (8)	H6A—C6—H6B	108.3
O1—V1—N1	92.14 (8)	N3—C7—H7A	109.5
N2—V1—N1	165.39 (8)	N3—C7—H7B	109.5
O1—V1—N4	90.54 (8)	H7A—C7—H7B	109.5
N2—V1—N4	76.80 (8)	N3—C7—H7C	109.5
N1—V1—N4	94.94 (7)	H7A—C7—H7C	109.5
O1—V1—Cl1	105.20 (7)	H7B—C7—H7C	109.5
N2—V1—Cl1	92.60 (6)	N3—C8—C9	109.92 (19)
N1—V1—Cl1	92.22 (6)	N3—C8—H8A	109.7
N4—V1—Cl1	162.45 (6)	C9—C8—H8A	109.7
O1—V1—N3	160.69 (8)	N3—C8—H8B	109.7
N2—V1—N3	92.70 (7)	C9—C8—H8B	109.7
N1—V1—N3	73.63 (7)	H8A—C8—H8B	108.2
N4—V1—N3	78.06 (7)	N4—C9—C8	109.54 (19)
Cl1—V1—N3	88.67 (5)	N4—C9—H9A	109.8
C1—N1—C5	117.9 (2)	C8—C9—H9A	109.8
C1—N1—V1	122.83 (16)	N4—C9—H9B	109.8
C5—N1—V1	119.22 (15)	C8—C9—H9B	109.8
C12—N2—C16	118.2 (2)	H9A—C9—H9B	108.2
C12—N2—V1	114.53 (16)	N4—C10—H10A	109.5
C16—N2—V1	127.28 (17)	N4—C10—H10B	109.5
C6—N3—C8	109.52 (19)	H10A—C10—H10B	109.5
C6—N3—C7	108.62 (18)	N4—C10—H10C	109.5
C8—N3—C7	110.94 (19)	H10A—C10—H10C	109.5
C6—N3—V1	105.85 (14)	H10B—C10—H10C	109.5
C8—N3—V1	106.15 (14)	N4—C11—C12	109.4 (2)
C7—N3—V1	115.54 (15)	N4—C11—H11A	109.8
C10—N4—C9	110.32 (19)	C12—C11—H11A	109.8
C10—N4—C11	108.59 (19)	N4—C11—H11B	109.8
C9—N4—C11	109.13 (19)	C12—C11—H11B	109.8
C10—N4—V1	113.64 (15)	H11A—C11—H11B	108.2
C9—N4—V1	110.97 (14)	N2—C12—C13	122.0 (2)
C11—N4—V1	103.90 (14)	N2—C12—C11	115.1 (2)
N1—C1—C2	122.9 (2)	C13—C12—C11	122.8 (2)
N1—C1—H1A	118.6	C14—C13—C12	119.4 (3)
C2—C1—H1A	118.6	C14—C13—H13A	120.3
C3—C2—C1	119.0 (2)	C12—C13—H13A	120.3
C3—C2—H2A	120.5	C13—C14—C15	118.8 (3)
C1—C2—H2A	120.5	C13—C14—H14A	120.6
C2—C3—C4	118.8 (2)	C15—C14—H14A	120.6
C2—C3—H3A	120.6	C16—C15—C14	119.6 (3)
C4—C3—H3A	120.6	C16—C15—H15A	120.2
C5—C4—C3	119.7 (2)	C14—C15—H15A	120.2
C5—C4—H4A	120.2	N2—C16—C15	122.0 (2)
C3—C4—H4A	120.2	N2—C16—H16A	119.0
N1—C5—C4	121.6 (2)	C15—C16—H16A	119.0
N1—C5—C6	115.4 (2)	O5—Cl2—O2	110.73 (13)
C4—C5—C6	123.0 (2)	O5—Cl2—O3	111.17 (14)
N3—C6—C5	109.13 (19)	O2—Cl2—O3	110.40 (11)
N3—C6—H6A	109.9	O5—Cl2—O4	108.72 (16)
C5—C6—H6A	109.9	O2—Cl2—O4	107.94 (12)
N3—C6—H6B	109.9	O3—Cl2—O4	107.76 (12)
C5—C6—H6B	109.9
O1—V1—N1—C1	4.77 (19)	O1—V1—N4—C11	63.72 (16)
N2—V1—N1—C1	−140.7 (3)	N2—V1—N4—C11	−36.30 (15)
N4—V1—N1—C1	−85.96 (19)	N1—V1—N4—C11	155.91 (15)
Cl1—V1—N1—C1	110.08 (18)	Cl1—V1—N4—C11	−90.4 (2)
N3—V1—N1—C1	−162.0 (2)	N3—V1—N4—C11	−131.99 (16)
O1—V1—N1—C5	−177.42 (17)	C5—N1—C1—C2	−1.1 (4)
N2—V1—N1—C5	37.1 (4)	V1—N1—C1—C2	176.77 (18)
N4—V1—N1—C5	91.85 (17)	N1—C1—C2—C3	−0.4 (4)
Cl1—V1—N1—C5	−72.11 (16)	C1—C2—C3—C4	1.0 (4)
N3—V1—N1—C5	15.85 (16)	C2—C3—C4—C5	−0.2 (4)
O1—V1—N2—C12	−66.81 (19)	C1—N1—C5—C4	1.9 (3)
N1—V1—N2—C12	78.1 (4)	V1—N1—C5—C4	−176.02 (17)
N4—V1—N2—C12	21.41 (18)	C1—N1—C5—C6	−177.8 (2)
Cl1—V1—N2—C12	−172.73 (17)	V1—N1—C5—C6	4.2 (3)
N3—V1—N2—C12	98.48 (18)	C3—C4—C5—N1	−1.3 (4)
O1—V1—N2—C16	112.7 (2)	C3—C4—C5—C6	178.4 (2)
N1—V1—N2—C16	−102.4 (4)	C8—N3—C6—C5	−70.6 (2)
N4—V1—N2—C16	−159.1 (2)	C7—N3—C6—C5	168.06 (19)
Cl1—V1—N2—C16	6.8 (2)	V1—N3—C6—C5	43.4 (2)
N3—V1—N2—C16	−82.0 (2)	N1—C5—C6—N3	−33.9 (3)
O1—V1—N3—C6	−75.7 (3)	C4—C5—C6—N3	146.3 (2)
N2—V1—N3—C6	153.43 (14)	C6—N3—C8—C9	155.42 (19)
N1—V1—N3—C6	−31.83 (14)	C7—N3—C8—C9	−84.7 (2)
N4—V1—N3—C6	−130.67 (15)	V1—N3—C8—C9	41.6 (2)
Cl1—V1—N3—C6	60.89 (14)	C10—N4—C9—C8	−84.1 (2)
O1—V1—N3—C8	40.6 (3)	C11—N4—C9—C8	156.66 (19)
N2—V1—N3—C8	−90.23 (14)	V1—N4—C9—C8	42.8 (2)
N1—V1—N3—C8	84.52 (14)	N3—C8—C9—N4	−57.6 (3)
N4—V1—N3—C8	−14.33 (14)	C10—N4—C11—C12	168.3 (2)
Cl1—V1—N3—C8	177.23 (14)	C9—N4—C11—C12	−71.4 (2)
O1—V1—N3—C7	164.0 (2)	V1—N4—C11—C12	47.1 (2)
N2—V1—N3—C7	33.19 (16)	C16—N2—C12—C13	1.1 (4)
N1—V1—N3—C7	−152.06 (17)	V1—N2—C12—C13	−179.4 (2)
N4—V1—N3—C7	109.09 (16)	C16—N2—C12—C11	−179.8 (2)
Cl1—V1—N3—C7	−59.35 (15)	V1—N2—C12—C11	−0.3 (3)
O1—V1—N4—C10	−54.11 (17)	N4—C11—C12—N2	−32.9 (3)
N2—V1—N4—C10	−154.14 (17)	N4—C11—C12—C13	146.2 (3)
N1—V1—N4—C10	38.08 (17)	N2—C12—C13—C14	−2.1 (4)
Cl1—V1—N4—C10	151.81 (17)	C11—C12—C13—C14	178.8 (3)
N3—V1—N4—C10	110.18 (17)	C12—C13—C14—C15	1.9 (5)
O1—V1—N4—C9	−179.12 (15)	C13—C14—C15—C16	−0.8 (5)
N2—V1—N4—C9	80.85 (15)	C12—N2—C16—C15	0.1 (4)
N1—V1—N4—C9	−86.93 (15)	V1—N2—C16—C15	−179.4 (2)
Cl1—V1—N4—C9	26.8 (3)	C14—C15—C16—N2	−0.2 (5)
N3—V1—N4—C9	−14.83 (14)