Hexa­aqua­manganese(II) dichloride bis­(hexa­methylene­tetr­amine) tetra­hydrate

In the title compound, [Mn(H₂O)₆]Cl₂·2C₆H₁₂N₄·4H₂O, each Mn^II atom, located on a centre of symmetry, is coordinated by six water mol­ecules in a distorted octa­hedral coordination geometry. The hexa­methyl­enetetra­mine (HMTA) mol­ecule does not coordinate to the Mn atom but links with the Mn complex via three O—H...N hydrogen bonds. The remaining N atom of the HMTA is hydrogen-bonded to the solvent water mol­ecule.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](n-O) = 0.002 Å
• R factor = 0.042
• wR factor = 0.111
• Data-to-parameter ratio = 18.9

checkCIF/PLATON results

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Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for         Mn
PLAT601_ALERT_2_C Structure Contains Solvent Accessible VOIDS of .      54.00 A   3  

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

   1 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
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

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S1. Comment

Hexamethylenetetramine (HMTA) has attracted attention because of the desire to construct new supramolecular architectures via hydrogen bonding (Carlucci et al., 1995; Ermer & Eling, 1994; Chopra et al., 2005). In order to investigate in detail the contribution of HMTA to the formation of hydrogen bonds, we report here the X-ray structure of the title compound, (I).

The molecular structure of (I) is shown in Fig. 1. The crystal of (I) consists of the Mn^II complex cations, Cl⁻ anions, solvent water and free HMTA molecules. The Mn^II atom is located on an inversion centre and is coordinated by six water molecules in a distorted octahedral geometry (Table 1). The HMTA molecule is linked to the Mn^II complex cation via three O—H···N hydrogen bonds, while atom N4 of the HMTA is hydrogen-bonded to the solvent water molecule. The Cl⁻ anions link to the Mn^II complex cation via O—H···Cl hydrogen bonding (Table 2).

S2. Experimental

An acetonitrile solution (12 ml) of MnCl₂·4H₂O (0.020 g, 3 mmol) and HMTA (0.042 g, 3 mmol) was transferred into a 23 ml Teflon-lined autoclave and heated at 358 K for 72 h. The autoclave was then cooled over a period of 12 h and the solution was filtered. Pale-yellow single crystals of (I) were obtained from the filtrate after 2 d. Elemental analysis for C₁₂H₄₄Cl₂MnN₈O₁₀, calculated: C 24.50, H 7.71, N 18.64%; found: C 24.78, H 7.51, N 18.72%.

S3. Refinement

Water H atoms were located in a difference Fourier map and refined as riding in their as-found positions relative to the O atoms, with U_iso(H) = 1.5U_eq(O). H atoms on C atoms were placed in calculated positions with C—H = 0.97 Å and refined in riding mode, with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); 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, 1997); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. The molecular structure of (I), with 30% probability displacement ellipsoids. H atoms have been omitted for clarity.

Hexaaquamanganese(II) dichloride bis(hexamethylenetetraamine) tetrahydrate

Crystal data

[Mn(H2O)6]Cl2·2C6H12N4·4H2O	Z = 1
Mr = 586.39	F(000) = 311
Triclinic, P1	Dx = 1.369 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.337 (3) Å	Cell parameters from 1215 reflections
b = 9.531 (2) Å	θ = 2.3–24.6°
c = 9.538 (2) Å	µ = 0.71 mm^−1
α = 119.477 (4)°	T = 294 K
β = 101.018 (5)°	Block, pale yellow
γ = 94.140 (5)°	0.22 × 0.18 × 0.16 mm
V = 711.5 (3) Å^3

Data collection

Bruker SMART CCD area-detector diffractometer	2850 independent reflections
Radiation source: fine-focus sealed tube	1975 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.025
ϕ and ω scans	θmax = 26.4°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −11→10
Tmin = 0.840, Tmax = 0.893	k = −10→11
4034 measured reflections	l = −11→8

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.111	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0517P)^2] where P = (Fo^2 + 2Fc^2)/3
2850 reflections	(Δ/σ)max < 0.001
151 parameters	Δρmax = 0.28 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	0.5000	0.5000	0.03063 (18)
Cl	0.81455 (9)	0.06236 (10)	0.32135 (10)	0.0601 (3)
N1	0.6664 (3)	0.0410 (3)	0.8491 (3)	0.0384 (6)
N2	0.6603 (3)	0.3259 (3)	1.0453 (3)	0.0369 (5)
N3	0.6652 (2)	0.2412 (3)	0.7604 (3)	0.0357 (5)
N4	0.8857 (2)	0.2548 (3)	0.9556 (3)	0.0390 (6)
O1	0.6255 (2)	0.5573 (2)	0.3598 (2)	0.0462 (5)
H1C	0.7148	0.6405	0.4000	0.069*
H1D	0.6341	0.4855	0.2575	0.069*
O2	0.6263 (2)	0.7040 (2)	0.7362 (2)	0.0504 (6)
H2C	0.6201	0.8057	0.7599	0.076*
H2D	0.6795	0.7012	0.8204	0.076*
O3	0.6372 (2)	0.3333 (3)	0.5208 (2)	0.0545 (6)
H3C	0.6914	0.2776	0.4647	0.082*
H3D	0.6393	0.2991	0.5866	0.082*
O4	0.8039 (2)	0.7197 (2)	1.0046 (2)	0.0502 (5)
H4C	0.7856	0.8207	1.0842	0.075*
H4D	0.8979	0.7228	1.0016	0.075*
O5	0.8512 (3)	0.8047 (3)	0.4465 (3)	0.0850 (9)
H5C	0.8409	0.8754	0.4055	0.127*
H5D	0.9363	0.8478	0.5201	0.127*
C1	0.6090 (3)	0.1522 (3)	0.9890 (3)	0.0400 (7)
H1A	0.6415	0.1349	1.0812	0.048*
H1B	0.5012	0.1265	0.9551	0.048*
C2	0.6077 (3)	0.3474 (3)	0.9030 (3)	0.0398 (7)
H2A	0.6394	0.4613	0.9371	0.048*
H2B	0.4998	0.3220	0.8690	0.048*
C3	0.6145 (3)	0.0698 (3)	0.7107 (3)	0.0400 (7)
H3A	0.6517	−0.0022	0.6169	0.048*
H3B	0.5067	0.0431	0.6750	0.048*
C4	0.8232 (3)	0.3615 (4)	1.0938 (3)	0.0428 (7)
H4A	0.8583	0.3464	1.1871	0.051*
H4B	0.8584	0.4754	1.1303	0.051*
C5	0.8291 (3)	0.0828 (3)	0.9014 (4)	0.0438 (7)
H5A	0.8680	0.0107	0.8092	0.053*
H5B	0.8647	0.0646	0.9924	0.053*
C6	0.8291 (3)	0.2793 (4)	0.8161 (3)	0.0425 (7)
H6A	0.8685	0.2097	0.7233	0.051*
H6B	0.8641	0.3926	0.8502	0.051*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn	0.0398 (4)	0.0265 (3)	0.0278 (3)	0.0094 (3)	0.0106 (3)	0.0147 (3)
Cl	0.0645 (6)	0.0589 (5)	0.0519 (5)	0.0294 (4)	0.0167 (4)	0.0222 (4)
N1	0.0468 (15)	0.0290 (12)	0.0361 (12)	0.0069 (11)	0.0053 (11)	0.0164 (10)
N2	0.0429 (14)	0.0332 (13)	0.0342 (12)	0.0074 (11)	0.0156 (11)	0.0151 (10)
N3	0.0404 (14)	0.0400 (13)	0.0363 (12)	0.0145 (11)	0.0154 (10)	0.0239 (11)
N4	0.0351 (13)	0.0395 (14)	0.0387 (13)	0.0084 (11)	0.0091 (10)	0.0175 (11)
O1	0.0568 (13)	0.0406 (12)	0.0372 (10)	0.0003 (10)	0.0224 (9)	0.0148 (9)
O2	0.0725 (15)	0.0274 (11)	0.0357 (11)	0.0040 (10)	−0.0072 (10)	0.0130 (9)
O3	0.0804 (16)	0.0651 (15)	0.0563 (13)	0.0499 (12)	0.0410 (12)	0.0466 (12)
O4	0.0405 (12)	0.0491 (13)	0.0502 (12)	0.0088 (10)	0.0041 (9)	0.0205 (10)
O5	0.0710 (18)	0.084 (2)	0.100 (2)	−0.0210 (15)	−0.0019 (15)	0.0605 (17)
C1	0.0472 (18)	0.0367 (16)	0.0407 (16)	0.0042 (13)	0.0107 (13)	0.0240 (14)
C2	0.0462 (18)	0.0337 (15)	0.0491 (17)	0.0161 (13)	0.0212 (14)	0.0243 (14)
C3	0.0469 (18)	0.0373 (16)	0.0318 (14)	0.0123 (13)	0.0078 (12)	0.0152 (13)
C4	0.0451 (18)	0.0371 (17)	0.0361 (15)	0.0023 (14)	0.0100 (13)	0.0126 (13)
C5	0.0502 (19)	0.0420 (17)	0.0429 (16)	0.0206 (14)	0.0099 (14)	0.0239 (14)
C6	0.0494 (18)	0.0432 (17)	0.0458 (17)	0.0163 (14)	0.0264 (14)	0.0253 (14)

Geometric parameters (Å, º)

Mn—O1	2.1642 (17)	O2—H2C	0.8899
Mn—O1^i	2.1642 (17)	O2—H2D	0.8730
Mn—O2^i	2.1421 (18)	O3—H3C	0.8292
Mn—O2	2.1421 (18)	O3—H3D	0.8358
Mn—O3	2.1707 (19)	O4—H4C	0.9419
Mn—O3^i	2.1707 (19)	O4—H4D	0.8823
N1—C5	1.464 (4)	O5—H5C	0.9338
N1—C1	1.467 (3)	O5—H5D	0.8656
N1—C3	1.478 (3)	C1—H1A	0.9700
N2—C4	1.465 (4)	C1—H1B	0.9700
N2—C2	1.470 (3)	C2—H2A	0.9700
N2—C1	1.473 (3)	C2—H2B	0.9700
N3—C3	1.469 (3)	C3—H3A	0.9700
N3—C2	1.471 (3)	C3—H3B	0.9700
N3—C6	1.475 (3)	C4—H4A	0.9700
N4—C6	1.470 (3)	C4—H4B	0.9700
N4—C5	1.473 (4)	C5—H5A	0.9700
N4—C4	1.475 (3)	C5—H5B	0.9700
O1—H1C	0.9771	C6—H6A	0.9700
O1—H1D	0.8988	C6—H6B	0.9700
O2^i—Mn—O2	180.0	H5C—O5—H5D	103.6
O2^i—Mn—O1	86.17 (8)	N1—C1—N2	111.9 (2)
O2—Mn—O1	93.83 (8)	N1—C1—H1A	109.2
O2^i—Mn—O1^i	93.83 (8)	N2—C1—H1A	109.2
O2—Mn—O1^i	86.17 (8)	N1—C1—H1B	109.2
O1—Mn—O1^i	180.000 (1)	N2—C1—H1B	109.2
O2^i—Mn—O3	87.53 (8)	H1A—C1—H1B	107.9
O2—Mn—O3	92.47 (8)	N2—C2—N3	111.8 (2)
O1—Mn—O3	94.45 (8)	N2—C2—H2A	109.2
O1^i—Mn—O3	85.55 (8)	N3—C2—H2A	109.2
O2^i—Mn—O3^i	92.47 (8)	N2—C2—H2B	109.2
O2—Mn—O3^i	87.53 (8)	N3—C2—H2B	109.2
O1—Mn—O3^i	85.55 (8)	H2A—C2—H2B	107.9
O1^i—Mn—O3^i	94.45 (8)	N3—C3—N1	111.7 (2)
O3—Mn—O3^i	180.000 (1)	N3—C3—H3A	109.3
C5—N1—C1	108.6 (2)	N1—C3—H3A	109.3
C5—N1—C3	108.3 (2)	N3—C3—H3B	109.3
C1—N1—C3	107.9 (2)	N1—C3—H3B	109.3
C4—N2—C2	108.9 (2)	H3A—C3—H3B	107.9
C4—N2—C1	108.3 (2)	N2—C4—N4	112.2 (2)
C2—N2—C1	107.6 (2)	N2—C4—H4A	109.2
C3—N3—C2	108.1 (2)	N4—C4—H4A	109.2
C3—N3—C6	108.2 (2)	N2—C4—H4B	109.2
C2—N3—C6	108.3 (2)	N4—C4—H4B	109.2
C6—N4—C5	108.0 (2)	H4A—C4—H4B	107.9
C6—N4—C4	107.7 (2)	N1—C5—N4	112.2 (2)
C5—N4—C4	108.0 (2)	N1—C5—H5A	109.2
Mn—O1—H1C	129.5	N4—C5—H5A	109.2
Mn—O1—H1D	125.6	N1—C5—H5B	109.2
H1C—O1—H1D	100.1	N4—C5—H5B	109.2
Mn—O2—H2C	119.3	H5A—C5—H5B	107.9
Mn—O2—H2D	127.6	N4—C6—N3	112.3 (2)
H2C—O2—H2D	112.8	N4—C6—H6A	109.1
Mn—O3—H3C	133.5	N3—C6—H6A	109.1
Mn—O3—H3D	126.1	N4—C6—H6B	109.1
H3C—O3—H3D	100.0	N3—C6—H6B	109.1
H4C—O4—H4D	113.3	H6A—C6—H6B	107.9
C5—N1—C1—N2	58.1 (3)	C2—N2—C4—N4	−58.3 (3)
C3—N1—C1—N2	−59.1 (3)	C1—N2—C4—N4	58.4 (3)
C4—N2—C1—N1	−58.1 (3)	C6—N4—C4—N2	58.3 (3)
C2—N2—C1—N1	59.4 (3)	C5—N4—C4—N2	−58.2 (3)
C4—N2—C2—N3	57.9 (3)	C1—N1—C5—N4	−58.2 (3)
C1—N2—C2—N3	−59.4 (3)	C3—N1—C5—N4	58.8 (3)
C3—N3—C2—N2	59.4 (3)	C6—N4—C5—N1	−58.3 (3)
C6—N3—C2—N2	−57.6 (3)	C4—N4—C5—N1	58.0 (3)
C2—N3—C3—N1	−58.8 (3)	C5—N4—C6—N3	57.9 (3)
C6—N3—C3—N1	58.3 (3)	C4—N4—C6—N3	−58.5 (3)
C5—N1—C3—N3	−58.7 (3)	C3—N3—C6—N4	−58.3 (3)
C1—N1—C3—N3	58.7 (3)	C2—N3—C6—N4	58.6 (3)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1C···O5	0.98	1.75	2.717 (4)	167
O1—H1D···N2^ii	0.90	1.92	2.817 (3)	176
O2—H2C···N1^iii	0.89	1.94	2.808 (4)	163
O2—H2D···O4	0.87	1.83	2.700 (3)	173
O3—H3C···Cl	0.83	2.36	3.165 (3)	163
O3—H3D···N3	0.84	1.97	2.800 (4)	173
O4—H4C···Cl^iv	0.94	2.25	3.151 (2)	161
O4—H4D···N4^v	0.88	1.96	2.827 (3)	168
O5—H5C···Cl^iii	0.93	2.30	3.228 (3)	176
O5—H5D···Cl^vi	0.87	2.35	3.205 (3)	170

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