Pentaethyl­enehex­amine­manganese(II) pentaborate

The title compound, (pentaethylenehexamine-[kappa]⁶N)manganese(II) 4,4',6,6'-tetrahydroxy-2,2'-spirobi(cyclotriboroxane)(1-), [Mn(C₁₀H₂₈N₆)][B₅O₆(OH)₄]₂, was synthesized under mild solvothermal conditions. The B₅O₆(OH)₄^- units are connected to one another via hydrogen bonds, forming a three-dimensional framework with large channels along the a and c axes, in which the templating [Mn(C₁₀H₂₈N₆)]²⁺ cations are located. The Mn^II complex cation has a twofold axis and the coordination geometry of the MnN₆ group is that of a distorted trigonal prism.

S1. Comment

From the structural point of view, B atoms are easy to condense into clusters, such as [B₄O₅(OH)₄] (Touboul et al., 1999), [B₅O₈] (Penin et al., 2001), [B₈O₁₈] (Li et al., 2003), [B₁₂O₂₄] (Menchetti et al., 1979; Choudhury et al., 2002), [B₁₆O₂₄(OH)₈] (Behm, 1985) etc. Therefore, borates are most complex for compounds containing oxide polyanions, as a result of the flexible coordination of the B atom, from threefold (BO₃, triangular) to fourfold BO₄, tetrahedral). Many inorganic frameworks constructed from BO polyhedra that exhibit one-dimensional chains (Grice et al., 1999; Schubert et al., 2003; Yu et al., 2002), two-dimensional layers (Penin, Seguin et al., 2002; Penin, Touboul et al., 2002, 2003; Bubnova et al., 2002) and three-dimensional open structures (Rowsell et al., 2002; Huppertz et al., 2002, 2003; Harrison et al., 1993; Choudhury et al., 2002; Penin et al., 2001) have been reported in the past few decades. Nevertheless, it is worth pointing out that those borate crystals were usually grown under the templating effect of inorganic cations. Recently, the templating effects of metal–organic complexes have been demonstrated for many inorganic systems (Gray et al., 1997; Yu et al., 2001; Bruce et al., 1995, 1996). However, the formation of metallo-organically templated borates is less well explored, and only one such material, namely [Cu(en)₂][B₇O₁₃H₃] (Sung et al., 2000), has been reported to date. The aim of our work is to construct new borate structures by using common BO clusters as foundamental building blocks (FBBs) in the presence of transition metal coordination complexes. A novel borate, (I), has been successfully isolated.

The title compound is composed of [B₅O₆(OH)₄]⁻ anions and [Mn(C₁₀H₂₈N₆)]²⁺ cations (Fig. 1 and Table 1). The [B₅O₆(OH)₄]⁻ polyanion consists of two B₃O₃ rings, each containing one tetrahedral and two trigonal B atoms. The B—O distances for trigonal B atoms (B1, B2, B4 and B5) are between 1.347 (7) and 1.382 (6) Å, and for the tetrahedral B atom (B3) range from 1.454 (7) to 1.477 (7) Å. The O—B—O angles involving triangular B atoms are 115.6 (5)—123.1 (5)°, and those involving atom B3 are 108.3 (5)—112.0 (4)°. Two of the B₃O₃ rings are connected by sharing their tetrahedral boron vertices. The [B₅O₆(OH)₄]⁻ clusters are further connected by hydrogen-bonding interactions into a three-dimensional structure with large channels along the a (as shown in Fig. 2) and c axes [O—O = 2.717 (6) Å to 3.060 (5) Å]. The Mn atom lies on a twofold axis and is bonded to six N atoms of the ligand. The MnN₆ coordination geometry is a distorted trigonal prism. The Mn—N distances range from 2.256 (5) to 2.332 (5) Å, and the N—Mn—N angles are between 75.1 (3) and 144.1 (2)°. The [Mn(C₁₀H₂₈N₆)]²⁺ cations are located in the inorganic channel and interact with the framework both electrostatically and through hydrogen bonds, with N···O distances in the range 3.059 (6)–3.362 (6) Å (Table 2).

S2. Experimental

Compound (I) was prepared from a mixture of NH₄B₅O₈·4H₂O (0.816 g), [Mn(C₁₀N₆H₂₈)](CH₃COO)₂ (0.398 g), pyridine (3.2 ml), distilled water (1.1 ml) and hydrofluoric acid (40%, 0.1 ml) in the molar ratio 3.0:1.0:4.0:4.8:2.0. The mixture was stirred mechanically at room temperature (final pH of 9.0) and then placed in autoclave at 443 K for 7 d. Yellow block-like crystals of (I) were obtained. The powder X-ray diffraction pattern of the bulk product is in a good agreement with the pattern calculated on the basis of the present crystal structure, indicating the phase purity of the sample. Analysis calculated for C₁₀H₃₆B₁₀MnN₆O₂₀: C 15.13, H 7.11, N 10.59%; found: C 15.27, H 7.23, N 10.53%. Thermogravimetric analysis (TGA) was performed in a dry N₂ atmosphere (303–1673 K), with heating rates of 30 K min⁻¹ between 303 and 1273 K, and 15 K min⁻¹ from 1273 to 1673 K. TGA showed that there were two steps of weight loss. The initial weight loss (about 10%; 553– 593 K) corresponds to the total removal of hydroxy groups (calculated 9.7%). The weight loss from 593 to 743 K is assigned to the partial release of organic molecules. When heated further, the organic molecules were fully lost at about 1283 K, and finally the volatile boron oxide phases were partially released from the phase. The IR spectrum of (I) contains the characteristic bands of the BO₃ and BO₄ groups, corresponding to the two strong bands at about 1390 and 1040 cm⁻¹, respectively (Yu, et al., 2002). The peak at 1602 cm⁻¹ corresponds to the bending of NH₂. The stretching bands of the OH and NH₂ groups are observed at about 3435 cm⁻¹ (Yang et al., 2001).

S3. Refinement

H atoms bonded to O atoms were located from difference density maps, and those bonded to C and N atoms were positioned geometrically and allowed to ride on their parent atoms (C—H = 0.97 Å, N—H = 0.91 Å and O—H = 0.82 Å, respectively). In (I), the [B₅O₆(OH)₄]⁻ anions are connected via strong hydrogen-bonding interactions into an open-framework structure, which may give rise to voids of 57 ų. Such voids in the crystal structure are familiar in microporous materials. For example, the 24-MR zinc phosphate (ND-1) (Yang et al., 1999) possesses voids of 285 ų, resulting from the extra-large porous structure.

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997).

Figures

Pentaethylenehexamine manganese(II) pentaborate

Crystal data

[Mn(C10H28N6)][B5O6(OH)4]2	F(000) = 1492.0
Mr = 723.49	Dx = 1.473 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 36 reflections
a = 11.9060 (1) Å	θ = 2.2–25.1°
b = 14.7950 (6) Å	µ = 0.49 mm^−1
c = 18.6611 (7) Å	T = 293 K
β = 97.057 (2)°	Block, yellow
V = 3262.24 (18) Å^3	0.28 × 0.28 × 0.20 mm
Z = 4

Data collection

Siemems SMART CCD diffractometer	2906 independent reflections
Radiation source: fine-focus sealed tube	1738 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
ϕ and ω scans	θmax = 25.1°, θmin = 2.2°
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996)	h = −8→14
Tmin = 0.714, Tmax = 0.907	k = −17→10
5263 measured reflections	l = −21→22

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)] = 0.076	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.150	H-atom parameters constrained
S = 1.19	w = 1/[σ^2(Fo^2) + (0.0247P)^2 + 10.2326P] where P = (Fo^2 + 2Fc^2)/3
2890 reflections	(Δ/σ)max < 0.001
213 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.27 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
Mn	0.5000	0.48431 (8)	0.2500	0.0559 (4)
O1	0.6281 (4)	0.0532 (3)	−0.0306 (2)	0.0977 (16)
H1	0.5863	0.0089	−0.0338	0.147*
O2	0.6492 (3)	0.1935 (3)	0.0218 (2)	0.0730 (12)
O3	0.6754 (3)	0.3375 (3)	0.0777 (2)	0.0791 (13)
H2	0.7276	0.3376	0.0528	0.119*
O4	0.5239 (3)	0.2493 (2)	0.10104 (18)	0.0566 (10)
O5	0.3393 (3)	0.1948 (2)	0.06038 (17)	0.0574 (10)
O6	0.1394 (3)	0.1899 (3)	0.05281 (19)	0.0689 (11)
H3	0.1450	0.2243	0.0190	0.103*
O7	0.2464 (3)	0.1272 (2)	0.15227 (18)	0.0580 (10)
O8	0.3459 (3)	0.0865 (3)	0.26201 (18)	0.0659 (11)
H4	0.4065	0.0980	0.2862	0.099*
O9	0.4470 (3)	0.1303 (2)	0.16609 (17)	0.0544 (9)
O10	0.4985 (3)	0.0998 (2)	0.04885 (18)	0.0572 (10)
B1	0.5893 (5)	0.1147 (6)	0.0137 (4)	0.0654 (19)
B2	0.6156 (5)	0.2600 (5)	0.0662 (3)	0.0590 (18)
B3	0.4534 (5)	0.1687 (5)	0.0940 (3)	0.0544 (17)
B4	0.2430 (5)	0.1709 (4)	0.0866 (3)	0.0516 (16)
B5	0.3489 (5)	0.1147 (4)	0.1933 (3)	0.0504 (16)
N1	0.3325 (4)	0.4315 (3)	0.2771 (3)	0.0735 (14)
H1D	0.3416	0.4054	0.3209	0.088*
H1E	0.2830	0.4774	0.2779	0.088*
N2	0.4115 (4)	0.4278 (4)	0.1407 (3)	0.0818 (16)
H2C	0.4472	0.3760	0.1302	0.098*
N3	0.4873 (4)	0.6063 (3)	0.1751 (3)	0.0742 (15)
H3D	0.5564	0.6139	0.1598	0.089*
C1	0.2884 (6)	0.3643 (5)	0.2215 (4)	0.092 (2)
H1B	0.2111	0.3482	0.2275	0.111*
H1C	0.3342	0.3099	0.2264	0.111*
C2	0.2928 (5)	0.4069 (5)	0.1468 (4)	0.087 (2)
H2A	0.2633	0.3650	0.1092	0.104*
H2B	0.2476	0.4616	0.1420	0.104*
C3	0.4229 (6)	0.4940 (6)	0.0834 (3)	0.094 (2)
H3B	0.3666	0.4819	0.0424	0.113*
H3C	0.4972	0.4886	0.0676	0.113*
C4	0.4068 (6)	0.5901 (5)	0.1115 (4)	0.097 (2)
H4A	0.4182	0.6338	0.0743	0.117*
H4B	0.3303	0.5971	0.1235	0.117*
C5	0.4626 (5)	0.6886 (4)	0.2132 (3)	0.089 (2)
H5A	0.3832	0.6902	0.2202	0.107*
H5B	0.4790	0.7413	0.1854	0.107*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn	0.0511 (7)	0.0565 (8)	0.0603 (8)	0.000	0.0086 (6)	0.000
O1	0.083 (3)	0.105 (4)	0.119 (4)	−0.019 (3)	0.068 (3)	−0.032 (3)
O2	0.051 (2)	0.088 (3)	0.088 (3)	−0.010 (2)	0.038 (2)	−0.007 (3)
O3	0.058 (2)	0.099 (3)	0.086 (3)	−0.025 (2)	0.032 (2)	−0.002 (3)
O4	0.0421 (19)	0.071 (3)	0.060 (2)	−0.0047 (19)	0.0203 (17)	0.003 (2)
O5	0.0363 (18)	0.088 (3)	0.050 (2)	0.0032 (18)	0.0143 (16)	0.017 (2)
O6	0.037 (2)	0.104 (3)	0.066 (2)	−0.003 (2)	0.0071 (18)	0.020 (2)
O7	0.0355 (19)	0.088 (3)	0.051 (2)	−0.0082 (19)	0.0068 (16)	0.014 (2)
O8	0.045 (2)	0.105 (3)	0.048 (2)	−0.019 (2)	0.0076 (17)	0.014 (2)
O9	0.0377 (19)	0.084 (3)	0.0432 (19)	0.0009 (18)	0.0126 (15)	0.0110 (19)
O10	0.0394 (19)	0.077 (3)	0.060 (2)	−0.0006 (18)	0.0248 (17)	0.001 (2)
B1	0.044 (4)	0.095 (6)	0.061 (4)	0.003 (4)	0.021 (3)	0.005 (4)
B2	0.041 (4)	0.086 (5)	0.049 (4)	0.005 (4)	0.005 (3)	0.014 (4)
B3	0.041 (3)	0.075 (5)	0.049 (4)	0.010 (3)	0.015 (3)	0.007 (3)
B4	0.044 (4)	0.066 (4)	0.046 (4)	−0.001 (3)	0.011 (3)	0.004 (3)
B5	0.048 (4)	0.061 (4)	0.044 (4)	−0.008 (3)	0.011 (3)	0.000 (3)
N1	0.068 (3)	0.066 (3)	0.087 (4)	0.011 (3)	0.012 (3)	0.014 (3)
N2	0.071 (4)	0.087 (4)	0.087 (4)	0.010 (3)	0.009 (3)	−0.019 (3)
N3	0.058 (3)	0.078 (4)	0.090 (4)	0.003 (3)	0.024 (3)	0.019 (3)
C1	0.086 (5)	0.073 (5)	0.115 (6)	−0.027 (4)	0.002 (4)	−0.008 (5)
C2	0.066 (4)	0.088 (5)	0.102 (6)	−0.009 (4)	−0.006 (4)	−0.021 (4)
C3	0.096 (5)	0.126 (7)	0.060 (4)	−0.001 (5)	0.007 (4)	0.008 (5)
C4	0.081 (5)	0.123 (7)	0.085 (5)	−0.011 (5)	−0.001 (4)	0.032 (5)
C5	0.083 (5)	0.054 (4)	0.136 (7)	0.007 (3)	0.039 (4)	0.000 (4)

Geometric parameters (Å, º)

Mn—N1^i	2.256 (5)	O10—B1	1.350 (7)
Mn—N1	2.256 (5)	O10—B3	1.466 (7)
Mn—N3^i	2.277 (5)	N1—C1	1.485 (7)
Mn—N3	2.277 (5)	N1—H1D	0.9000
Mn—N2	2.332 (5)	N1—H1E	0.9000
Mn—N2^i	2.332 (5)	N2—C2	1.465 (7)
O1—B1	1.349 (8)	N2—C3	1.468 (8)
O1—H1	0.8200	N2—H2C	0.9100
O2—B1	1.365 (8)	N3—C4	1.451 (7)
O2—B2	1.377 (8)	N3—C5	1.458 (7)
O3—B2	1.353 (8)	N3—H3D	0.9100
O3—H2	0.8200	C1—C2	1.536 (9)
O4—B2	1.347 (7)	C1—H1B	0.9700
O4—B3	1.454 (7)	C1—H1C	0.9700
O5—B4	1.348 (6)	C2—H2A	0.9700
O5—B3	1.477 (7)	C2—H2B	0.9700
O6—B4	1.345 (6)	C3—C4	1.536 (9)
O6—H3	0.8200	C3—H3B	0.9700
O7—B5	1.372 (7)	C3—H3C	0.9700
O7—B4	1.382 (6)	C4—H4A	0.9700
O8—B5	1.352 (6)	C4—H4B	0.9700
O8—H4	0.8200	C5—C5^i	1.543 (13)
O9—B5	1.349 (6)	C5—H5A	0.9700
O9—B3	1.471 (6)	C5—H5B	0.9700
N1^i—Mn—N1	139.5 (2)	C1—N1—H1E	109.9
N1^i—Mn—N3^i	114.71 (17)	Mn—N1—H1E	109.9
N1—Mn—N3^i	97.53 (17)	H1D—N1—H1E	108.3
N1^i—Mn—N3	97.53 (17)	C2—N2—C3	111.9 (5)
N1—Mn—N3	114.71 (17)	C2—N2—Mn	110.1 (4)
N3^i—Mn—N3	75.1 (3)	C3—N2—Mn	109.0 (4)
N1^i—Mn—N2	89.83 (17)	C2—N2—H2C	108.5
N1—Mn—N2	75.81 (19)	C3—N2—H2C	108.5
N3^i—Mn—N2	144.1 (2)	Mn—N2—H2C	108.5
N3—Mn—N2	76.0 (2)	C4—N3—C5	112.6 (5)
N1^i—Mn—N2^i	75.81 (19)	C4—N3—Mn	111.0 (4)
N1—Mn—N2^i	89.83 (17)	C5—N3—Mn	111.4 (4)
N3^i—Mn—N2^i	76.0 (2)	C4—N3—H3D	107.2
N3—Mn—N2^i	144.1 (2)	C5—N3—H3D	107.2
N2—Mn—N2^i	138.0 (3)	Mn—N3—H3D	107.2
B1—O1—H1	109.5	N1—C1—C2	108.1 (5)
B1—O2—B2	119.4 (5)	N1—C1—H1B	110.1
B2—O3—H2	109.5	C2—C1—H1B	110.1
B2—O4—B3	123.1 (5)	N1—C1—H1C	110.1
B4—O5—B3	123.8 (4)	C2—C1—H1C	110.1
B4—O6—H3	109.5	H1B—C1—H1C	108.4
B5—O7—B4	119.1 (4)	N2—C2—C1	107.3 (5)
B5—O8—H4	109.5	N2—C2—H2A	110.2
B5—O9—B3	123.7 (4)	C1—C2—H2A	110.2
B1—O10—B3	122.5 (5)	N2—C2—H2B	110.2
O1—B1—O10	122.8 (7)	C1—C2—H2B	110.2
O1—B1—O2	115.6 (5)	H2A—C2—H2B	108.5
O10—B1—O2	121.6 (6)	N2—C3—C4	110.0 (5)
O4—B2—O3	117.8 (6)	N2—C3—H3B	109.7
O4—B2—O2	121.2 (6)	C4—C3—H3B	109.7
O3—B2—O2	120.9 (5)	N2—C3—H3C	109.7
O4—B3—O10	112.0 (4)	C4—C3—H3C	109.7
O4—B3—O9	109.1 (5)	H3B—C3—H3C	108.2
O10—B3—O9	108.7 (5)	N3—C4—C3	109.5 (6)
O4—B3—O5	108.3 (5)	N3—C4—H4A	109.8
O10—B3—O5	108.7 (5)	C3—C4—H4A	109.8
O9—B3—O5	109.9 (4)	N3—C4—H4B	109.8
O6—B4—O5	123.1 (5)	C3—C4—H4B	109.8
O6—B4—O7	116.1 (5)	H4A—C4—H4B	108.2
O5—B4—O7	120.7 (5)	N3—C5—C5^i	107.8 (4)
O9—B5—O8	122.3 (5)	N3—C5—H5A	110.2
O9—B5—O7	121.2 (5)	C5^i—C5—H5A	110.2
O8—B5—O7	116.5 (5)	N3—C5—H5B	110.2
C1—N1—Mn	108.8 (4)	C5^i—C5—H5B	110.2
C1—N1—H1D	109.9	H5A—C5—H5B	108.5
Mn—N1—H1D	109.9

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O10^ii	0.82	1.90	2.717 (6)	173
O3—H2···O2^iii	0.82	2.19	2.995 (5)	166
O3—H2···O1^iii	0.82	2.43	3.060 (5)	134
O6—H3···O5^iv	0.82	1.93	2.751 (5)	179
O8—H4···O9^i	0.82	1.92	2.736 (4)	174
N1—H1D···O3^i	0.90	2.17	3.059 (6)	168
N1—H1E···O8^v	0.90	2.29	3.150 (6)	160
N1—H1E···O7^v	0.90	2.62	3.362 (6)	141
N2—H2C···O4	0.91	2.18	3.092 (6)	177
N3—H3D···O7^vi	0.91	2.29	3.181 (5)	165
N3—H3D···O6^vi	0.91	2.59	3.321 (6)	138

Symmetry codes: (i) −x+1, y, −z+1/2; (ii) −x+1, −y, −z; (iii) −x+3/2, −y+1/2, −z; (iv) −x+1/2, −y+1/2, −z; (v) −x+1/2, y+1/2, −z+1/2; (vi) x+1/2, y+1/2, z.