trans-Bis(1,4-butane­di­amine)­di­chloro­cobalt(III) chloride monohydrate

The title compound, [CoCl₂(C₄H₁₂N₂)₂]Cl·H₂O, (I), has an octahedral coordination geometry. The conformations of the seven-membered chelate rings are disordered between the twist-chair and twist-boat forms. The space group of (I) is Cc, although the structure has a pseudo-center of symmetry.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.014 Å
• Disorder in main residue
• R factor = 0.033
• wR factor = 0.082
• Data-to-parameter ratio = 12.7

checkCIF results

No syntax errors found


 Alert Level B:



PLAT_111  Alert B ADDSYM detects (pseudo) centre of symmetry ...         86 Perc Fit

PLAT_113  Alert B ADDSYM suggests Pseudo/New Spacegroup ........       C2/c


 Alert Level C:



PLAT_301  Alert C Main Residue Disorder ........................      12.00 Perc.

PLAT_420  Alert C D-H Without Acceptor       N1     -   H1B               ?

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           29.98
         From the CIF: _reflns_number_total               2259
         Count of symmetry unique reflns         2230
         Completeness (_total/calc)            101.30%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured        29
         Fraction of Friedel pairs measured     0.013
         Are heavy atom types Z>Si present          yes
          WARNING: Large fraction of Friedel related reflns may
                   be needed to determine absolute structure


 0 Alert Level A = Potentially serious problem

 2 Alert Level B = Potential problem

 2 Alert Level C = Please check

---

S1. Comment

1,4-Butanediamine (tmd: putrescin or tetramethylenediamine) is a biogenic diamine. The interaction between transition metals and tmd is of interest from the viewpoint of bioinorganic chemistry (Gasowska et al., 2000). However, only a few structures have been reported for transition metal complexes of tmd (Sato et al., 1974; Shimoi et al., 1988; Kurachi & Ohba, 1992). We report here the structure of the title compound, trans-[Co^IIICl₂(tmd)₂]Cl·H₂O, (I).

The complex cation (Fig. 1) has a pseudosymmetry of inversion and thus the conformations of the seven-membered chelate rings are almost identical. One of the C atoms of the two tmd chelates (C3 and C7, respectively) is disordered with equal occupancy factors. The C3b and C7a positions correspond to the twist-chair conformation of the cycloheptane ring, and the C3a and C7b positions to the twist-boat conformation (Fig. 2), though the observed conformations deviate from the ideal conformations to a considerable extent (Hendrickson, 1961).

The Co—N bond distances range from 1.978 (4) to 2.003 (4) Å and are comparable with those found in [Co(NO₂)₂(tmd)₂]NO₃ (Shimoi et al., 1988). The bite angles of the seven-membered chelate rings are 91.4 (2) and 89.59 (18)° and are also normal.

S2. Experimental

The title compound was prepared by adapting the procedures described by Nagata et al. (1985) and Nagata & Kanamori (2001). Crystals of (I) were obtained by a spontaneous evaporation of an aqueous solution at room temperature.

S3. Refinement

Systematic absences showed the space group of either C2/c or Cc. The former case could not locate non-coordinating anions and water molecules successfully, whereas the latter case gave a satisfactory result (C2/c, R = 8.0%; Cc, R = 3.3%). Comparison of the two solutions revealed that the [CoCl₂(tmd)₂]⁺ moiety has a pseudosymmetry of inversion but that the non-coordinating Cl^- and water lower the lattice symmetry down to Cc (Fig. 3). The Flack (1983) parameter [0.13 (3)] is also consistent with the absence of inversion symmetry. Disorder of the two C atoms (C3 and C7) was suggested by their highly anisotropic displacement parameters, so that two positions for each atom were calculated by moving along the direction of the largest eigenvalue of the displacement tensor, with a fixed site occupation factor of 0.5. H atoms bonded to C and N atoms were placed geometrically and refined using a riding model via the SHELXL97 HFIX/AFIX 23 facility. The displacement parameter was set as 1.2 times that of the parent atom. H atoms of water were refined with a fixed O—H distance and H—O—H angle via SHELXL97 DFIX facility.

Computing details

Data collection: AFC-7R Diffractometer Control Software (Rigaku, 1999); cell refinement: AFC-7R Diffractometer Control Software; data reduction: AFC-7R Diffractometer Control Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

	Fig. 1. The molecular structure of (I) showing the labelling of the non-H atoms. Displacement ellipsoids are shown at 50% probability levels.
	Fig. 2. The conformation of the chelate rings projected along the bisector of the N—Co—N angle.
	Fig. 3. A packing diagram of (I). H atoms have been omitted for clarity.

trans-dichlorobis(1,4-butanediamine)cobalt(III) chloride monohydrate

Crystal data

[CoCl2(C4H12N2)2]Cl·H2O	F(000) = 752
Mr = 359.61	Dx = 1.561 Mg m^−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
a = 14.914 (5) Å	Cell parameters from 25 reflections
b = 13.560 (6) Å	θ = 14.2–14.9°
c = 8.994 (4) Å	µ = 1.64 mm^−1
β = 122.75 (2)°	T = 296 K
V = 1529.8 (11) Å^3	Prism, green
Z = 4	0.20 × 0.20 × 0.20 mm

Data collection

Rigaku AFC-7R diffractometer	2097 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.000
Graphite monochromator	θmax = 30.0°, θmin = 2.7°
ω–2θ scans	h = 0→20
Absorption correction: ψ scan (North et al., 1968)	k = 0→19
Tmin = 0.735, Tmax = 0.735	l = −12→10
2259 measured reflections	3 standard reflections every 60 min
2259 independent reflections	intensity decay: 2.8%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.033	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.082	w = 1/[σ^2(Fo^2) + (0.0335P)^2 + 2.6779P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max < 0.001
2259 reflections	Δρmax = 1.00 e Å^−3
178 parameters	Δρmin = −0.55 e Å^−3
5 restraints	Absolute structure: (Flack, 1983), 29 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.13 (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	Occ. (<1)
Co	0.42289 (14)	0.25059 (5)	0.0390 (2)	0.02536 (10)
Cl1	0.30277 (14)	0.18861 (11)	−0.2308 (2)	0.0383 (3)
Cl2	0.54476 (14)	0.30961 (12)	0.3100 (2)	0.0400 (3)
N1	0.4330 (4)	0.1178 (4)	0.1442 (7)	0.0414 (12)
H1A	0.4566	0.0757	0.0953	0.050*
H1B	0.4847	0.1219	0.2597	0.050*
N2	0.3023 (4)	0.2882 (4)	0.0608 (6)	0.0333 (10)
H2A	0.2846	0.3502	0.0192	0.040*
H2B	0.2472	0.2497	−0.0158	0.040*
C1	0.3404 (7)	0.0699 (5)	0.1336 (11)	0.0577 (19)
H1C	0.3497	−0.0010	0.1375	0.069*
H1D	0.2765	0.0861	0.0207	0.069*
C2	0.3246 (9)	0.1000 (6)	0.2800 (13)	0.086 (3)
H2C	0.2519	0.0837	0.2419	0.103*
H2D	0.3710	0.0591	0.3820	0.103*
C3A	0.3418 (17)	0.1945 (12)	0.335 (2)	0.057 (4)	0.50
H3AA	0.4187	0.2009	0.4085	0.068*	0.50
H3AB	0.3168	0.1991	0.4139	0.068*	0.50
C3B	0.2687 (8)	0.1950 (8)	0.2691 (11)	0.0320 (19)	0.50
H3BA	0.1936	0.1868	0.1792	0.038*	0.50
H3BB	0.2745	0.2041	0.3809	0.038*	0.50
C4	0.3048 (6)	0.2863 (5)	0.2297 (9)	0.0472 (16)
H4A	0.3505	0.3397	0.3040	0.057*
H4B	0.2335	0.3003	0.2015	0.057*
N3	0.4171 (4)	0.3824 (3)	−0.0629 (6)	0.0320 (9)
H3C	0.3703	0.3776	−0.1804	0.038*
H3D	0.3883	0.4241	−0.0221	0.038*
N4	0.5462 (4)	0.2143 (4)	0.0190 (6)	0.0331 (10)
H4C	0.5992	0.2562	0.0901	0.040*
H4D	0.5676	0.1542	0.0682	0.040*
C5	0.5146 (6)	0.4322 (4)	−0.0365 (9)	0.0448 (13)
H5A	0.5745	0.4176	0.0819	0.054*
H5B	0.5034	0.5030	−0.0443	0.054*
C6	0.5438 (7)	0.4019 (5)	−0.1691 (11)	0.0579 (16)
H6A	0.4864	0.4265	−0.2827	0.069*
H6B	0.6062	0.4407	−0.1386	0.069*
C7A	0.564 (3)	0.3123 (16)	−0.200 (4)	0.106 (9)	0.50
H7AA	0.6399	0.3125	−0.1520	0.127*	0.50
H7AB	0.5296	0.3097	−0.3272	0.127*	0.50
C7B	0.5020 (7)	0.3022 (9)	−0.2556 (12)	0.0244 (19)	0.50
H7BA	0.4254	0.3028	−0.3096	0.029*	0.50
H7BB	0.5141	0.2971	−0.3509	0.029*	0.50
C8	0.5428 (6)	0.2105 (4)	−0.1508 (9)	0.0436 (15)
H8A	0.4734	0.1871	−0.2449	0.052*
H8B	0.5961	0.1643	−0.1386	0.052*
Cl3	0.25888 (14)	0.47305 (13)	0.5027 (2)	0.0576 (3)
O	0.0882 (5)	0.4928 (4)	0.0955 (8)	0.0846 (19)
H1WA	0.138 (3)	0.497 (7)	0.199 (3)	0.101*
H1WB	0.111 (5)	0.484 (7)	0.031 (7)	0.101*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co	0.02508 (17)	0.02802 (18)	0.02302 (16)	0.00227 (13)	0.01304 (13)	0.00186 (12)
Cl1	0.0326 (7)	0.0460 (7)	0.0301 (7)	−0.0009 (6)	0.0129 (6)	−0.0062 (6)
Cl2	0.0357 (8)	0.0487 (8)	0.0289 (6)	0.0007 (6)	0.0130 (6)	−0.0048 (6)
N1	0.053 (3)	0.035 (2)	0.045 (3)	0.005 (2)	0.033 (3)	0.010 (2)
N2	0.035 (3)	0.033 (2)	0.039 (3)	0.0050 (17)	0.025 (2)	0.0056 (17)
C1	0.083 (5)	0.036 (3)	0.083 (5)	−0.010 (3)	0.064 (5)	0.000 (3)
C2	0.147 (9)	0.064 (4)	0.118 (7)	0.031 (5)	0.117 (7)	0.034 (5)
C3A	0.082 (13)	0.061 (9)	0.043 (8)	0.004 (8)	0.043 (9)	0.003 (7)
C3B	0.022 (4)	0.056 (6)	0.019 (3)	0.004 (4)	0.012 (3)	0.004 (3)
C4	0.060 (4)	0.061 (4)	0.039 (3)	−0.008 (3)	0.039 (3)	−0.012 (3)
N3	0.034 (2)	0.0303 (19)	0.034 (2)	0.0063 (17)	0.021 (2)	0.0040 (17)
N4	0.030 (3)	0.036 (2)	0.034 (3)	0.0069 (17)	0.018 (2)	0.0050 (17)
C5	0.058 (4)	0.033 (2)	0.063 (3)	−0.004 (2)	0.046 (3)	0.000 (2)
C6	0.080 (4)	0.049 (3)	0.079 (4)	−0.013 (3)	0.065 (4)	−0.005 (3)
C7A	0.18 (3)	0.083 (14)	0.122 (19)	0.048 (17)	0.13 (2)	0.048 (13)
C7B	0.016 (4)	0.044 (5)	0.017 (4)	0.002 (4)	0.011 (3)	−0.001 (4)
C8	0.050 (4)	0.040 (3)	0.055 (4)	0.009 (2)	0.038 (4)	0.000 (3)
Cl3	0.0700 (9)	0.0500 (6)	0.0695 (8)	−0.0165 (7)	0.0487 (8)	−0.0096 (7)
O	0.092 (4)	0.067 (3)	0.123 (5)	0.031 (3)	0.077 (4)	0.042 (4)

Geometric parameters (Å, º)

Co—Cl1	2.2582 (19)	C4—H4A	0.9700
Co—Cl2	2.2571 (19)	C4—H4B	0.9700
Co—N1	2.002 (5)	N3—H3C	0.9000
Co—N2	1.978 (4)	N3—H3D	0.9000
Co—N3	1.989 (4)	N3—C5	1.501 (7)
Co—N4	2.003 (4)	N4—H4C	0.9000
N1—H1A	0.9000	N4—H4D	0.9000
N1—H1B	0.9000	N4—C8	1.501 (7)
N1—C1	1.482 (8)	C5—H5A	0.9700
N2—H2A	0.9000	C5—H5B	0.9700
N2—H2B	0.9000	C5—C6	1.531 (8)
N2—C4	1.500 (7)	C6—H6A	0.9700
C1—H1C	0.9700	C6—H6B	0.9700
C1—H1D	0.9700	C6—C7A	1.32 (2)
C1—C2	1.513 (9)	C6—C7B	1.516 (13)
C2—H2C	0.9700	C7A—H7AA	0.9700
C2—H2D	0.9700	C7A—H7AB	0.9700
C2—C3A	1.346 (18)	C7A—C8	1.53 (2)
C2—C3B	1.509 (14)	C7B—H7BA	0.9700
C3A—H3AA	0.9700	C7B—H7BB	0.9700
C3A—H3AB	0.9700	C7B—C8	1.477 (13)
C3A—C4	1.476 (17)	C8—H8A	0.9700
C3B—H3BA	0.9700	C8—H8B	0.9700
C3B—H3BB	0.9700	O—H1WA	0.82 (5)
C3B—C4	1.468 (13)	O—H1WB	0.83 (8)
Co···C1	3.062 (8)	N1···C4	3.325 (9)
Co···C4	3.090 (7)	N1···N4	2.808 (7)
Co···C5	3.066 (6)	N1···O^iii	3.086 (8)
Co···C8	3.116 (7)	N2···C1	3.018 (8)
Cl1···N1	2.997 (6)	N2···C2	3.130 (10)
Cl1···N2	2.953 (5)	N2···N3	2.804 (6)
Cl1···C1	3.414 (8)	N2···Cl3^iv	3.288 (5)
Cl1···N3	3.051 (5)	C1···C4	3.184 (10)
Cl1···N4	3.086 (5)	C3A···C7B^v	3.450 (19)
Cl1···N4^i	3.482 (5)	C3B···C7A^vi	3.21 (3)
Cl1···C7B	3.459 (10)	N3···N4	2.813 (7)
Cl1···C8	3.262 (8)	N3···C7A	3.18 (3)
Cl2···N1	3.013 (5)	N3···C7B	2.857 (11)
Cl2···N2	3.068 (5)	N3···C8	3.343 (8)
Cl2···N2^ii	3.497 (5)	N3···Cl3^iv	3.356 (5)
Cl2···C4	3.260 (8)	N4···C5	2.992 (8)
Cl2···N3	2.990 (5)	N4···C6	3.045 (9)
Cl2···N4	2.930 (5)	N4···O^iii	3.070 (8)
Cl2···C5	3.341 (7)	C5···C8	3.277 (9)
N1···N2	2.849 (7)	Cl3···O	3.143 (6)
N1···C3A	2.895 (19)	Cl3···O^vii	3.113 (6)
N1···C3B	3.368 (11)
Cl1—Co—Cl2	178.83 (8)	N2—C4—H4A	108.0
Cl1—Co—N1	89.22 (16)	N2—C4—H4B	108.0
Cl1—Co—N2	88.11 (15)	C3A—C4—H4A	108.0
Cl1—Co—N3	91.62 (14)	C3A—C4—H4B	108.0
Cl1—Co—N4	92.61 (15)	C3B—C4—H4A	132.5
Cl2—Co—N1	89.85 (17)	C3B—C4—H4B	74.5
Cl2—Co—N2	92.61 (15)	H4A—C4—H4B	107.2
Cl2—Co—N3	89.30 (14)	Co—N3—H3C	106.8
Cl2—Co—N4	86.68 (14)	Co—N3—H3D	106.8
N1—Co—N2	91.4 (2)	Co—N3—C5	122.3 (4)
N1—Co—N3	178.4 (3)	H3C—N3—H3D	106.6
N1—Co—N4	89.0 (2)	H3C—N3—C5	106.8
N2—Co—N3	89.94 (18)	H3D—N3—C5	106.8
N2—Co—N4	179.1 (3)	Co—N4—H4C	106.1
N3—Co—N4	89.59 (18)	Co—N4—H4D	106.1
Co—N1—H1A	106.8	Co—N4—C8	124.9 (4)
Co—N1—H1B	106.8	H4C—N4—H4D	106.3
Co—N1—C1	122.3 (4)	H4C—N4—C8	106.1
H1A—N1—H1B	106.6	H4D—N4—C8	106.1
H1A—N1—C1	106.8	N3—C5—H5A	108.6
H1B—N1—C1	106.8	N3—C5—H5B	108.6
Co—N2—H2A	106.1	N3—C5—C6	114.5 (5)
Co—N2—H2B	106.1	H5A—C5—H5B	107.6
Co—N2—C4	124.8 (4)	H5A—C5—C6	108.6
H2A—N2—H2B	106.3	H5B—C5—C6	108.6
H2A—N2—C4	106.1	C5—C6—H6A	105.5
H2B—N2—C4	106.1	C5—C6—H6B	105.5
N1—C1—H1C	108.8	C5—C6—C7A	127.2 (10)
N1—C1—H1D	108.8	C5—C6—C7B	115.3 (5)
N1—C1—C2	113.8 (7)	H6A—C6—H6B	106.1
H1C—C1—H1D	107.7	H6A—C6—C7A	105.5
H1C—C1—C2	108.8	H6A—C6—C7B	83.3
H1D—C1—C2	108.8	H6B—C6—C7A	105.5
C1—C2—H2C	107.6	H6B—C6—C7B	134.0
C1—C2—H2D	107.6	C6—C7A—H7AA	104.3
C1—C2—C3A	119.0 (8)	C6—C7A—H7AB	104.3
C1—C2—C3B	120.9 (7)	C6—C7A—C8	131.7 (15)
H2C—C2—H2D	107.0	H7AA—C7A—H7AB	105.6
H2C—C2—C3A	107.6	H7AA—C7A—C8	104.3
H2C—C2—C3B	72.5	H7AB—C7A—C8	104.3
H2D—C2—C3A	107.6	C6—C7B—H7BA	107.2
H2D—C2—C3B	129.5	C6—C7B—H7BB	107.2
C2—C3A—H3AA	104.9	C6—C7B—C8	120.7 (8)
C2—C3A—H3AB	104.9	H7BA—C7B—H7BB	106.8
C2—C3A—C4	129.7 (13)	H7BA—C7B—C8	107.2
H3AA—C3A—H3AB	105.8	H7BB—C7B—C8	107.2
H3AA—C3A—C4	104.9	N4—C8—C7A	111.3 (10)
H3AB—C3A—C4	104.9	N4—C8—C7B	113.3 (5)
C2—C3B—H3BA	107.7	N4—C8—H8A	109.4
C2—C3B—H3BB	107.7	N4—C8—H8B	109.4
C2—C3B—C4	118.3 (8)	C7A—C8—H8A	109.4
H3BA—C3B—H3BB	107.1	C7A—C8—H8B	109.4
H3BA—C3B—C4	107.7	C7B—C8—H8A	80.9
H3BB—C3B—C4	107.7	C7B—C8—H8B	130.2
N2—C4—C3A	117.2 (7)	H8A—C8—H8B	108.0
N2—C4—C3B	116.6 (6)	H1WA—O—H1WB	109 (7)
Co—N1—C1—C2	−86.0 (7)	N1—C1—C2—C3B	81.6 (11)
Co—N2—C4—C3A	−51.0 (12)	N2—Co—N1—C1	26.0 (5)
Co—N2—C4—C3B	−91.9 (8)	N2—Co—N3—C5	148.9 (4)
Co—N3—C5—C6	85.2 (6)	C1—C2—C3A—C4	47 (2)
Co—N4—C8—C7A	85.4 (14)	C1—C2—C3B—C4	−50.9 (13)
Co—N4—C8—C7B	52.6 (8)	C2—C3A—C4—N2	−38 (2)
Cl1—Co—N1—C1	−62.1 (5)	C2—C3B—C4—N2	57.6 (11)
Cl1—Co—N2—C4	144.9 (5)	N3—Co—N2—C4	−123.5 (5)
Cl1—Co—N3—C5	−123.0 (4)	N3—Co—N4—C8	−60.6 (5)
Cl1—Co—N4—C8	31.0 (4)	N3—C5—C6—C7A	−58 (2)
Cl2—Co—N1—C1	118.6 (5)	N3—C5—C6—C7B	−23.4 (9)
Cl2—Co—N2—C4	−34.2 (5)	N4—Co—N1—C1	−154.7 (5)
Cl2—Co—N3—C5	56.3 (4)	N4—Co—N3—C5	−30.4 (4)
Cl2—Co—N4—C8	−149.9 (5)	C5—C6—C7A—C8	15 (4)
N1—Co—N2—C4	55.7 (5)	C5—C6—C7B—C8	−67.6 (10)
N1—Co—N4—C8	120.2 (5)	C6—C7A—C8—N4	−30 (4)
N1—C1—C2—C3A	38.8 (15)	C6—C7B—C8—N4	47.7 (9)

Symmetry codes: (i) x−1/2, −y+1/2, z−1/2; (ii) x+1/2, −y+1/2, z+1/2; (iii) x+1/2, y−1/2, z; (iv) x, −y+1, z−1/2; (v) x, y, z+1; (vi) x−1/2, −y+1/2, z+1/2; (vii) x, −y+1, z+1/2.