Acetonitrile­dichloro­(1,4,7-triaza­cyclo­decane)cobalt(III) perchlorate

In the title compound, [CoCl₂(C₇H₁₇N₃)(C₂H₃N)]ClO₄, the Co³⁺ ion is six-coordinated by three N atoms from the 1,4,7-triaza­cyclo­deca­ne (tacd) ligand, two chloride anions and one N atom of the acetonitrile group, giving a distorted octa­hedral geometry. The cation and anion both have crystallographic mirror symmetry. Inter­molecular hydrogen bonds link the ions into a three-dimensional network.

Key indicators

• Single-crystal X-ray study
• T = 273 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.041
• wR factor = 0.118
• Data-to-parameter ratio = 19.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT213_ALERT_2_C Atom C6      has ADP max/min Ratio .............       3.10 prolat
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.20 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       4.00 Ratio
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         C5
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        Cl2
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.32

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   8 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
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

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

Acetonitriledichloro(1,4,7-triazacyclodecane)cobalt(III) perchlorate

Crystal data

[CoCl2(C7H17N3)(C2H3N)]ClO4	Dx = 1.657 Mg m^−3
Mr = 413.57	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pnma	Cell parameters from 1445 reflections
a = 20.863 (4) Å	θ = 2.7–23.6°
b = 10.7899 (19) Å	µ = 1.54 mm^−1
c = 7.3630 (13) Å	T = 273 K
V = 1657.5 (5) Å^3	Block, purple
Z = 4	0.21 × 0.10 × 0.03 mm
F(000) = 848

Data collection

Bruker SMART CCD area-detector diffractometer	2199 independent reflections
Radiation source: fine-focus sealed tube	1526 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.044
ω scans	θmax = 28.7°, θmin = 2.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −28→27
Tmin = 0.735, Tmax = 0.955	k = −14→14
10135 measured reflections	l = −9→7

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.118	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ^2(Fo^2) + (0.0583P)^2 + 0.6755P] where P = (Fo^2 + 2Fc^2)/3
2199 reflections	(Δ/σ)max < 0.001
114 parameters	Δρmax = 0.80 e Å^−3
0 restraints	Δρmin = −0.44 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
Co1	0.13348 (2)	0.7500	0.74666 (6)	0.02646 (17)
Cl1	0.15073 (4)	0.90132 (8)	0.95415 (10)	0.0480 (2)
N1	0.22291 (16)	0.7500	0.6855 (5)	0.0379 (8)
N2	0.12308 (11)	0.8802 (2)	0.5629 (3)	0.0332 (6)
N3	0.04449 (17)	0.7500	0.8113 (5)	0.0433 (9)
C1	0.23902 (15)	0.8657 (3)	0.5881 (4)	0.0483 (8)
H1A	0.2779	0.8541	0.5180	0.058*
H1B	0.2463	0.9320	0.6747	0.058*
C2	0.18429 (15)	0.8995 (3)	0.4632 (4)	0.0415 (7)
H2A	0.1880	0.9855	0.4260	0.050*
H2B	0.1853	0.8479	0.3554	0.050*
C3	0.06684 (15)	0.8685 (3)	0.4388 (4)	0.0441 (8)
H3A	0.0668	0.9383	0.3557	0.053*
H3B	0.0279	0.8732	0.5105	0.053*
C4	0.0657 (2)	0.7500	0.3294 (6)	0.0438 (11)
H4A	0.1023	0.7500	0.2484	0.053*
H4B	0.0274	0.7500	0.2547	0.053*
C5	−0.0063 (2)	0.7500	0.8654 (7)	0.0657 (16)
C6	−0.0718 (3)	0.7500	0.9363 (8)	0.133 (4)
H6A	−0.0761	0.8215	1.0132	0.200*
H6C	−0.1029	0.7500	0.8407	0.200*
H1	0.244 (4)	0.7500	0.789 (11)	0.160*
H2	0.120 (3)	0.945 (6)	0.640 (10)	0.160*
Cl2	0.36534 (5)	0.7500	0.07996 (16)	0.0451 (3)
O1	0.3196 (3)	0.7500	0.2078 (9)	0.212 (5)
O2	0.3357 (3)	0.7500	−0.0860 (6)	0.135 (2)
O3	0.40513 (18)	0.8522 (3)	0.1021 (7)	0.1336 (17)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0303 (3)	0.0272 (3)	0.0219 (3)	0.000	0.0017 (2)	0.000
Cl1	0.0713 (6)	0.0415 (5)	0.0311 (4)	−0.0093 (4)	0.0012 (4)	−0.0083 (3)
N1	0.0330 (18)	0.048 (2)	0.0325 (18)	0.000	0.0004 (14)	0.000
N2	0.0437 (14)	0.0286 (13)	0.0274 (12)	0.0042 (10)	0.0037 (10)	0.0030 (10)
N3	0.040 (2)	0.062 (3)	0.0282 (18)	0.000	0.0040 (16)	0.000
C1	0.0436 (18)	0.057 (2)	0.0441 (18)	−0.0212 (15)	0.0068 (14)	0.0029 (15)
C2	0.0563 (19)	0.0325 (16)	0.0356 (16)	−0.0087 (14)	0.0096 (14)	0.0067 (13)
C3	0.0472 (18)	0.053 (2)	0.0324 (16)	0.0153 (15)	−0.0039 (13)	0.0080 (14)
C4	0.045 (2)	0.060 (3)	0.026 (2)	0.000	−0.0071 (19)	0.000
C5	0.046 (3)	0.117 (5)	0.033 (3)	0.000	0.006 (2)	0.000
C6	0.037 (3)	0.306 (13)	0.056 (4)	0.000	0.011 (3)	0.000
Cl2	0.0494 (6)	0.0390 (6)	0.0469 (6)	0.000	−0.0072 (5)	0.000
O1	0.112 (5)	0.421 (15)	0.101 (4)	0.000	0.050 (4)	0.000
O2	0.099 (4)	0.245 (8)	0.062 (3)	0.000	−0.039 (3)	0.000
O3	0.097 (2)	0.0440 (18)	0.260 (5)	−0.0102 (17)	−0.065 (3)	0.014 (3)

Geometric parameters (Å, º)

Co1—N3	1.917 (4)	C2—H2A	0.9700
Co1—N1	1.919 (3)	C2—H2B	0.9700
Co1—N2^i	1.963 (2)	C3—C4	1.511 (4)
Co1—N2	1.963 (2)	C3—H3A	0.9700
Co1—Cl1	2.2648 (9)	C3—H3B	0.9700
Co1—Cl1^i	2.2648 (9)	C4—C3^i	1.511 (4)
N1—C1^i	1.478 (4)	C4—H4A	0.9700
N1—C1	1.478 (4)	C4—H4B	0.9700
N1—H1	0.87 (8)	C5—C6	1.463 (7)
N2—C2	1.487 (4)	C6—H6A	0.9612
N2—C3	1.492 (4)	C6—H6C	0.9584
N2—H2	0.90 (6)	Cl2—O1	1.340 (6)
N3—C5	1.132 (6)	Cl2—O2	1.369 (4)
C1—C2	1.511 (4)	Cl2—O3	1.390 (3)
C1—H1A	0.9700	Cl2—O3^i	1.390 (3)
C1—H1B	0.9700
N3—Co1—N1	179.20 (15)	N1—C1—H1B	109.9
N3—Co1—N2^i	93.67 (10)	C2—C1—H1B	109.9
N1—Co1—N2^i	86.89 (10)	H1A—C1—H1B	108.3
N3—Co1—N2	93.67 (10)	N2—C2—C1	108.4 (2)
N1—Co1—N2	86.89 (10)	N2—C2—H2A	110.0
N2^i—Co1—N2	91.41 (14)	C1—C2—H2A	110.0
N3—Co1—Cl1	89.22 (8)	N2—C2—H2B	110.0
N1—Co1—Cl1	90.22 (8)	C1—C2—H2B	110.0
N2^i—Co1—Cl1	177.09 (7)	H2A—C2—H2B	108.4
N2—Co1—Cl1	88.09 (8)	N2—C3—C4	114.2 (3)
N3—Co1—Cl1^i	89.22 (8)	N2—C3—H3A	108.7
N1—Co1—Cl1^i	90.22 (8)	C4—C3—H3A	108.7
N2^i—Co1—Cl1^i	88.09 (8)	N2—C3—H3B	108.7
N2—Co1—Cl1^i	177.09 (7)	C4—C3—H3B	108.7
Cl1—Co1—Cl1^i	92.26 (5)	H3A—C3—H3B	107.6
C1^i—N1—C1	115.2 (4)	C3—C4—C3^i	115.6 (3)
C1^i—N1—Co1	109.57 (19)	C3—C4—H4A	108.4
C1—N1—Co1	109.57 (19)	C3^i—C4—H4A	108.4
C1^i—N1—H1	108 (3)	C3—C4—H4B	108.4
C1—N1—H1	108 (3)	C3^i—C4—H4B	108.4
Co1—N1—H1	106 (6)	H4A—C4—H4B	107.4
C2—N2—C3	112.6 (2)	N3—C5—C6	179.7 (5)
C2—N2—Co1	110.21 (18)	C5—C6—H6A	107.4
C3—N2—Co1	116.67 (18)	C5—C6—H6C	111.8
C2—N2—H2	105 (4)	H6A—C6—H6C	111.6
C3—N2—H2	113 (4)	O1—Cl2—O2	107.8 (4)
Co1—N2—H2	97 (4)	O1—Cl2—O3	110.0 (3)
C5—N3—Co1	173.8 (4)	O2—Cl2—O3	112.0 (2)
N1—C1—C2	109.1 (3)	O1—Cl2—O3^i	110.0 (3)
N1—C1—H1A	109.9	O2—Cl2—O3^i	112.0 (2)
C2—C1—H1A	109.9	O3—Cl2—O3^i	105.0 (3)

Symmetry code: (i) x, −y+3/2, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···Cl1	0.90 (6)	2.45 (7)	2.947 (3)	115 (5)
N2—H2···O3^ii	0.90 (6)	2.27 (6)	2.961 (4)	133 (6)
N1—H1···O2^iii	0.87 (8)	2.13 (9)	2.893 (6)	145 (8)

Symmetry codes: (ii) −x+1/2, −y+2, z+1/2; (iii) x, y, z+1.