Di-μ₂-methano­lato-bis­[tetra­kis(pyrimidin-2-amine-κN¹)cobalt(II)] bis­(tetra­fluoro­borate)

The title compound, [Co₂(CH₃O)₂(C₄H₅N₃)₄](BF₄)₂, consists of a discrete dimeric Co^II complex. The asymmetric unit consists of one pyrimidin-2-amine ligand, which occupies a general position, and one methano­late group, as well as one Co^II cation and one tetra­fluoro­borate anion, which are located in special positions. The Co^II cation lies on a twofold rotation axis, whereas the tetra­fluoro­borate anion and the methano­late group lie on mirror planes. The N atoms of the pyrimidin-2-amine ligand are involved in inter­molecular hydrogen bonding. From this arrangement, large channels are formed, which elongate in the direction of the crystallographic c axis.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.009 Å
• R factor = 0.064
• wR factor = 0.207
• Data-to-parameter ratio = 23.3

checkCIF/PLATON results

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Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT199_ALERT_1_C Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_C Check the Reported _diffrn_ambient_temperature .        293 K
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Co1    -   O1      ..       5.35 su
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for         B1
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.23
PLAT341_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         10
PLAT602_ALERT_4_C VERY LARGE Solvent Accessible VOID(S) in Structure        !
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          3
            N1  -CO1 -O1  -C5   -164.40  0.90   2.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          6
            N1  -CO1 -O1  -CO1    52.10  1.10   2.555   1.555   1.555   5.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          7
            O1  -CO1 -N1  -C1   -116.10  1.00   5.555   1.555   1.555   1.555
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #         11
            O1  -CO1 -N1  -C4     66.40  1.10   5.555   1.555   1.555   1.555
PLAT731_ALERT_1_C Bond    Calc   1.365(14), Rep    1.365(6) ......       2.33 su-Rat
              B1   -F2      1.555   1.555
PLAT764_ALERT_4_C Overcomplete CIF Bond List Detected (Rep/Expd) .       1.20 Ratio

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

   4 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   2 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
   7 ALERT type 4 Improvement, methodology, query or suggestion

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Computing details

Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); 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-µ₂-methanolato-bis[tetrakis(pyrimidin-2-amine-κN¹)cobalt(II)] bis(tetrafluoroborate)

Crystal data

[Co2(CH3O)2(C4H5N3)4](BF4)2	F(000) = 740
Mr = 733.99	Dx = 1.140 Mg m^−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 1625 reflections
a = 16.338 (6) Å	θ = 2.9–26.4°
b = 14.704 (2) Å	µ = 0.84 mm^−1
c = 12.040 (4) Å	T = 293 K
β = 132.34 (1)°	Block, red
V = 2138.0 (11) Å^3	0.32 × 0.28 × 0.20 mm
Z = 2

Data collection

Bruker APEX area-detector diffractometer	2541 independent reflections
Radiation source: fine-focus sealed tube	2010 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
φ and ω scans	θmax = 27.5°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = 0→21
Tmin = 0.775, Tmax = 0.850	k = 0→19
2626 measured reflections	l = −15→11

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.207	H-atom parameters constrained
S = 1.11	w = 1/[σ^2(Fo^2) + (0.1252P)^2 + 2.7158P] where P = (Fo^2 + 2Fc^2)/3
2541 reflections	(Δ/σ)max = 0.003
109 parameters	Δρmax = 0.86 e Å^−3
0 restraints	Δρmin = −0.60 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	Occ. (<1)
Co1	0.0000	0.10015 (4)	0.0000	0.0410 (3)
O1	0.0973 (3)	0.0000	0.1198 (4)	0.0508 (9)
C5	0.2121 (5)	0.0000	0.2001 (8)	0.0722 (18)
H5A	0.2415	−0.0600	0.2379	0.108*	0.50
H5B	0.2495	0.0419	0.2825	0.108*	0.50
H5C	0.2230	0.0180	0.1342	0.108*	0.50
N1	0.1166 (3)	0.1969 (2)	0.1248 (4)	0.0580 (9)
N2	0.1491 (4)	0.1670 (3)	0.3384 (5)	0.0886 (16)
H2A	0.0904	0.1295	0.2879	0.133*
H2B	0.1843	0.1797	0.4346	0.133*
N3	0.2423 (4)	0.2852 (3)	0.3459 (5)	0.0798 (13)
C1	0.1687 (4)	0.2155 (3)	0.2684 (5)	0.0615 (11)
C2	0.2640 (5)	0.3337 (4)	0.2768 (6)	0.0862 (17)
H2	0.3130	0.3823	0.3280	0.103*
C3	0.2181 (6)	0.3164 (4)	0.1337 (7)	0.0940 (19)
H3	0.2383	0.3493	0.0895	0.113*
C4	0.1409 (5)	0.2485 (3)	0.0580 (6)	0.0744 (14)
H4	0.1042	0.2378	−0.0421	0.089*
B1	0.0628 (4)	0.0000	0.7771 (5)	0.0281 (9)
F1	−0.0454 (5)	0.0000	0.6403 (6)	0.1115 (17)
F2	0.1392 (6)	0.0000	0.7634 (9)	0.121 (2)
F3	0.0765 (3)	0.0786 (2)	0.8565 (4)	0.0821 (9)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Co1	0.0441 (4)	0.0311 (4)	0.0335 (4)	0.000	0.0203 (3)	0.000
O1	0.0439 (19)	0.047 (2)	0.0447 (19)	0.000	0.0230 (16)	0.000
C5	0.050 (3)	0.069 (4)	0.070 (4)	0.000	0.030 (3)	0.000
N1	0.069 (2)	0.0437 (17)	0.0520 (18)	−0.0099 (16)	0.0369 (17)	−0.0050 (14)
N2	0.110 (3)	0.086 (3)	0.063 (2)	−0.057 (3)	0.056 (3)	−0.025 (2)
N3	0.096 (3)	0.072 (3)	0.066 (2)	−0.041 (2)	0.053 (2)	−0.024 (2)
C1	0.070 (3)	0.052 (2)	0.055 (2)	−0.019 (2)	0.039 (2)	−0.0125 (19)
C2	0.103 (4)	0.072 (3)	0.082 (3)	−0.041 (3)	0.062 (3)	−0.017 (3)
C3	0.132 (5)	0.080 (4)	0.092 (4)	−0.045 (4)	0.085 (4)	−0.017 (3)
C4	0.098 (4)	0.057 (3)	0.066 (3)	−0.019 (3)	0.054 (3)	−0.004 (2)
B1	0.042 (2)	0.0159 (18)	0.044 (2)	0.000	0.036 (2)	0.000
F1	0.114 (4)	0.097 (4)	0.094 (3)	0.000	0.058 (3)	0.000
F2	0.174 (6)	0.071 (3)	0.229 (7)	0.000	0.181 (6)	0.000
F3	0.101 (2)	0.0579 (16)	0.103 (2)	0.0020 (15)	0.075 (2)	−0.0080 (15)

Geometric parameters (Å, º)

Co1—O1^i	1.920 (2)	N2—H2A	0.8999
Co1—O1	1.920 (2)	N2—H2B	0.9000
Co1—N1	2.014 (3)	N3—C2	1.313 (7)
Co1—N1^ii	2.014 (3)	N3—C1	1.362 (6)
Co1—Co1^i	2.9452 (13)	C2—C3	1.362 (8)
O1—C5	1.418 (8)	C2—H2	0.9300
O1—Co1^i	1.920 (2)	C3—C4	1.367 (7)
C5—H5A	0.9600	C3—H3	0.9300
C5—H5B	0.9600	C4—H4	0.9300
C5—H5C	0.9600	B1—F2	1.365 (6)
N1—C1	1.344 (5)	B1—F1	1.384 (7)
N1—C4	1.345 (6)	B1—F3	1.419 (4)
N2—C1	1.297 (6)	B1—F3^iii	1.419 (4)
O1^i—Co1—O1	79.86 (17)	C1—N2—H2A	121.0
O1^i—Co1—N1	172.23 (15)	C1—N2—H2B	120.0
O1—Co1—N1	95.33 (14)	H2A—N2—H2B	117.5
O1^i—Co1—N1^ii	95.33 (14)	C2—N3—C1	117.7 (4)
O1—Co1—N1^ii	172.23 (15)	N2—C1—N1	120.3 (4)
N1—Co1—N1^ii	90.1 (2)	N2—C1—N3	117.2 (4)
O1^i—Co1—Co1^i	39.93 (8)	N1—C1—N3	122.5 (4)
O1—Co1—Co1^i	39.93 (8)	N3—C2—C3	123.1 (5)
N1—Co1—Co1^i	134.96 (11)	N3—C2—H2	118.5
N1^ii—Co1—Co1^i	134.96 (11)	C3—C2—H2	118.5
C5—O1—Co1^i	123.92 (19)	C2—C3—C4	117.1 (5)
C5—O1—Co1	123.92 (19)	C2—C3—H3	121.5
Co1^i—O1—Co1	100.14 (17)	C4—C3—H3	121.5
O1—C5—H5A	109.5	N1—C4—C3	121.6 (5)
O1—C5—H5B	109.5	N1—C4—H4	119.2
H5A—C5—H5B	109.5	C3—C4—H4	119.2
O1—C5—H5C	109.5	F2—B1—F1	113.3 (5)
H5A—C5—H5C	109.5	F2—B1—F3	109.9 (3)
H5B—C5—H5C	109.5	F1—B1—F3	107.3 (3)
C1—N1—C4	117.9 (4)	F2—B1—F3^iii	109.9 (3)
C1—N1—Co1	124.4 (3)	F1—B1—F3^iii	107.3 (3)
C4—N1—Co1	117.7 (3)	F3—B1—F3^iii	109.1 (4)
O1^i—Co1—O1—C5	143.5 (5)	Co1^i—Co1—N1—C4	112.1 (4)
N1—Co1—O1—C5	−30.4 (5)	C4—N1—C1—N2	−179.2 (5)
N1^ii—Co1—O1—C5	−164.4 (9)	Co1—N1—C1—N2	3.3 (7)
Co1^i—Co1—O1—C5	143.5 (5)	C4—N1—C1—N3	1.5 (8)
N1—Co1—O1—Co1^i	−173.85 (16)	Co1—N1—C1—N3	−176.0 (4)
N1^ii—Co1—O1—Co1^i	52.1 (11)	C2—N3—C1—N2	179.0 (6)
O1^i—Co1—N1—C1	−116.1 (10)	C2—N3—C1—N1	−1.7 (8)
O1—Co1—N1—C1	−64.8 (4)	C1—N3—C2—C3	−1.3 (10)
N1^ii—Co1—N1—C1	109.6 (4)	N3—C2—C3—C4	4.2 (11)
Co1^i—Co1—N1—C1	−70.4 (4)	C1—N1—C4—C3	1.7 (8)
O1^i—Co1—N1—C4	66.4 (11)	Co1—N1—C4—C3	179.3 (5)
O1—Co1—N1—C4	117.7 (4)	C2—C3—C4—N1	−4.4 (10)
N1^ii—Co1—N1—C4	−67.9 (4)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···N3^iv	0.90	2.10	3.001 (6)	176
N2—H2A···F3^v	0.90	2.15	3.022 (6)	163
N2—H2A···F1^vi	0.90	2.40	3.091 (6)	134

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