1,4,8,11-Tetra­azoniacyclo­tetradecane diaqua­tetra­chloridomanganese(II) dichloride dihydrate

The title compound, (C₁₀H₂₈N₄)[MnCl₄(H₂O)₂]Cl₂·2H₂O, consists of isolated octa­hedral [MnCl₄(H₂O)₂]^2- anions, tetra­protonated 1,4,8,11-tetra­azoniacyclo­tetradecane cations, chloride anions and water mol­ecules connected by a network of hydrogen bonds. The Mn^II atom is situated on an inversion centre, and the 1,4,8,11-tetra­azoniacyclo­tetradecane cation is located on a mirror plane.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.018
• wR factor = 0.059
• Data-to-parameter ratio = 18.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Mn1    --  O1      ..       6.47 su
PLAT910_ALERT_3_C Missing # of FCF Reflections Below Th(Min) .....          1
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?

   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
   1 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
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The structure contains isolated [MnCl₄(H₂O)₂]^2- octahedron and centrosymmetric tetraprotonated 1,4,8,11-tetraazacyclodecane (cyclamH4⁴⁺) moieties connected by a network of N—H···X (X= O, Cl) hydrogen bonds (Fig. 1). The positive charge of the cyclamH4⁴⁺ is out-balanced beside the octahedral anion with two chloride ions. Two molecules of water participate in the manganese coordination, whereas the third water molecule forms bridge between chloride anion (Cl4), nitrogen atom (N1) in 1,4,8,11-tetraazacyclodecane (cyclam) and water (O1) molecule in [MnCl₄(H₂O)₂]. The cyclam molecules and [MnCl4(H₂O)2] octahedral are arranged into alternating layers parallel with ab. In direction of c axis the cyclam molecules form infinite channels (Fig. 2). The molecules of cyclam are in a distance of 7.877 Å with chloride anion between the middle CH₂ groups in propyl chains (C6···Cl4 3.952 Å, Cl4···C6 3.923Å on one side and C4···Cl3 3.855 Å, Cl3···C4 4.022Å on the other side of channels). The tetra-protonated cyclam (C₁₀H₂₈N₄)⁴⁺ exhibits C—C, C—N bond distances and angles in the range usually found for the cyclam molecule (Melson, 1979). The tetra-protonated macrocycle adopts an endodentate quadrangular (3,4,3,4)-A conformation which is the most stable among the four possible conformations, the exo orientation of the four nitrogen atoms gives rise to the maximal charge separation. The free water molecule participates also in a cyclic system of hydrogen bonds between water (O1) molecule coordinated to manganese and chloride anions (Cl3 and Cl4). The six-membered cycle is formed by hydrogen bonds between O1—H1o···O2—H2o···Cl4···H2o—O2···H1o—O1—H1p···Cl3···H1p—O1 (Fig. 4).

Related literature

For bond distances and angles in the

cyclam molecule, see: Melson (1979).

S2. Experimental

To an acidic solution of cyclam (1 mmol) was added MnCl₂.4H₂O (1 mmol) in 10 ml of distilled water. The mixture was then stirred at room temperature for 3 h after which it was left to evaporate in air. After three weeks, crystals appeared, which were filtered off and washed with 90% ethanol solution.

S3. Refinement

All hydrogen atoms were discernible in difference Fourier maps and could be refined to reasonable geometry. Despite of it the hydrogen atoms bonded to carbon and nitrogen atoms were constrained to ideal positions. The O—H distances were restrained to 0.82 Å with sigma 0.01. The isotropic temperature parameters of hydrogen atoms were calculated as 1.2*U_eq of the parent atom.)

Computing details

Data collection: CrysAlis CCD (Oxford Diffraction, 2005); cell refinement: CrysAlis RED (Oxford Diffraction, 2005); data reduction: CrysAlis RED(Oxford Diffraction, 2005); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: JANA2006 (Petříček et al., 2006); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: JANA2006 (Petříček et al., 2006) and publCIF (Westrip, 2010).

Figures

	Fig. 1. View of the cyclamH4^4+ cation, the [MnCl4(H2O)2]^2- anion, free water molecule and chloride anions, together with atom-labelling scheme. Displacement ellipsoids are shown at the 50% probability level.
	Fig. 2. Projection along the c axis, showing the channels formed by the cyclam cavity.

1,4,8,11-Tetraazoniacyclotetradecane diaquatetrachloridomanganese(II) dichloride dihydrate

Crystal data

(C10H28N4)[MnCl4(H2O)2]Cl2·2H2O	F(000) = 1132
Mr = 544.1	Dx = 1.596 Mg m^−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ac 2n	Cell parameters from 16479 reflections
a = 14.8492 (2) Å	θ = 2.5–26.5°
b = 19.3511 (3) Å	µ = 1.31 mm^−1
c = 7.8772 (1) Å	T = 292 K
V = 2263.50 (5) Å^3	Prism, colourless
Z = 4	0.36 × 0.22 × 0.16 mm

Data collection

Oxford Diffraction CCD diffractometer	2429 independent reflections
Radiation source: X-ray tube	1999 reflections with I > 3σ(I)
Graphite monochromator	Rint = 0.026
Detector resolution: 8.3438 pixels mm^-1	θmax = 26.5°, θmin = 2.7°
Rotation method data acquisition using ω scans	h = −18→18
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2005)	k = −24→24
Tmin = 0.721, Tmax = 0.840	l = −9→9
26200 measured reflections

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
R[F > 3σ(F)] = 0.018	Hydrogen site location: difference Fourier map
wR(F) = 0.059	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	Weighting scheme based on measured s.u.'s w = 1/[σ^2(I) + 0.0016I^2]
2429 reflections	(Δ/σ)max = 0.010
133 parameters	Δρmax = 0.14 e Å^−3
Primary atom site location: structure-invariant direct methods	Δρmin = −0.10 e Å^−3

Special details

Experimental. CrysAlis RED, Oxford Diffraction Ltd., Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid.

Refinement. The refinement was carried out against all reflections. The conventional R-factor is always based on F. The goodness of fit as well as the weighted R-factor are based on F and F² for refinement carried out on F and F², respectively. The threshold expression is used only for calculating R-factors etc. and it is not relevant to the choice of reflections for refinement.

All the H atoms were discrenible in difference Fourier maps and could be refined to reasonable geometry. Despite of it the H atoms bonded to catbon and nitrogen atoms were constrained to ideal positions. The O—H distances were restrained to 0.82 Å with σ 0.01. The isotropic temperature parameters of hydrogen atoms were calculated as 1.2*U_eq of the parent atom.

The program used for refinement, Jana2006, uses the weighting scheme based on the experimental expectations, see _refine_ls_weighting_details,

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Mn1	0	0	0	0.01920 (9)
Cl1	−0.06104 (2)	0.040619 (17)	0.28548 (4)	0.02344 (10)
Cl3	0.03588 (3)	0.25	0.10590 (6)	0.02742 (14)
Cl2	0.14001 (2)	−0.046308 (19)	0.14869 (4)	0.03195 (11)
Cl4	0.27203 (4)	0.25	0.80690 (7)	0.03300 (16)
O1	0.06526 (7)	0.10208 (5)	−0.04773 (13)	0.0246 (3)
O2	0.24961 (7)	0.11049 (6)	−0.02640 (14)	0.0323 (3)
N1	0.25833 (7)	0.12044 (5)	0.33251 (14)	0.0211 (3)
N2	0.04152 (7)	0.12050 (5)	0.59062 (14)	0.0203 (3)
C1	0.15939 (9)	0.11683 (7)	0.36796 (16)	0.0212 (4)
C2	0.14089 (8)	0.11699 (7)	0.55731 (17)	0.0206 (4)
C3	−0.00618 (8)	0.18592 (7)	0.54150 (17)	0.0217 (4)
C4	0.03729 (16)	0.25	0.6165 (3)	0.0314 (6)
C5	0.30646 (9)	0.18591 (6)	0.38037 (17)	0.0228 (4)
C6	0.26338 (16)	0.25	0.3046 (3)	0.0329 (7)
H1m	0.268045	0.111373	0.225895	0.0253*
H1n	0.285152	0.085355	0.379572	0.0253*
H2m	0.031159	0.111526	0.697062	0.0244*
H2n	0.015046	0.085424	0.542836	0.0244*
H1a	0.134992	0.075561	0.318388	0.0254*
H1b	0.129816	0.155584	0.31619	0.0254*
H2a	0.165029	0.07569	0.607205	0.0247*
H2b	0.169981	0.156082	0.608522	0.0247*
H3a	−0.067928	0.183451	0.577083	0.026*
H3n	−0.007609	0.18981	0.420039	0.026*
H4a	0.100476	0.25	0.590704	0.0377*
H4b	0.029252	0.25	0.737419	0.0377*
H5a	0.368181	0.18312	0.344749	0.0273*
H5b	0.308095	0.190111	0.50176	0.0273*
H6a	0.200057	0.25	0.329167	0.0394*
H6b	0.272047	0.25	0.183783	0.0394*
H2o	0.2545 (12)	0.1474 (6)	−0.080 (2)	0.0387*
H2p	0.2810 (10)	0.0859 (8)	−0.085 (2)	0.0387*
H1o	0.1201 (6)	0.1002 (8)	−0.042 (2)	0.0296*
H1p	0.0475 (11)	0.1365 (6)	0.0039 (18)	0.0296*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.02119 (16)	0.01807 (15)	0.01834 (15)	0.00097 (11)	−0.00088 (10)	0.00132 (11)
Cl1	0.0257 (2)	0.02367 (17)	0.02098 (17)	0.00260 (12)	−0.00054 (12)	−0.00266 (13)
Cl3	0.0298 (3)	0.0235 (2)	0.0290 (3)	0	−0.0005 (2)	0
Cl2	0.0316 (2)	0.0361 (2)	0.02823 (19)	0.01481 (15)	−0.00806 (14)	−0.00686 (15)
Cl4	0.0394 (3)	0.0291 (3)	0.0305 (3)	0	−0.0040 (2)	0
O1	0.0262 (5)	0.0217 (5)	0.0260 (5)	−0.0011 (4)	0.0017 (4)	−0.0027 (4)
O2	0.0351 (6)	0.0327 (6)	0.0290 (6)	0.0005 (5)	0.0060 (4)	0.0008 (5)
N1	0.0225 (6)	0.0184 (5)	0.0224 (6)	0.0031 (4)	0.0018 (4)	−0.0012 (5)
N2	0.0223 (6)	0.0179 (5)	0.0207 (6)	−0.0024 (4)	0.0023 (4)	0.0014 (4)
C1	0.0198 (6)	0.0208 (6)	0.0230 (7)	−0.0017 (5)	−0.0010 (5)	−0.0022 (5)
C2	0.0186 (6)	0.0221 (6)	0.0210 (6)	0.0009 (5)	−0.0010 (5)	0.0026 (5)
C3	0.0191 (7)	0.0200 (7)	0.0259 (7)	0.0011 (5)	−0.0014 (5)	0.0002 (6)
C4	0.0448 (13)	0.0191 (9)	0.0304 (11)	0	−0.0135 (10)	0
C5	0.0185 (7)	0.0214 (7)	0.0285 (7)	−0.0010 (5)	−0.0013 (5)	0.0002 (6)
C6	0.0451 (13)	0.0208 (10)	0.0327 (12)	0	−0.0135 (9)	0

Geometric parameters (Å, º)

Mn1—Cl1	2.5488 (3)	N2—H2n	0.8700
Mn1—Cl1^i	2.5488 (3)	C1—C2	1.5166 (18)
Mn1—Cl2	2.5490 (4)	C1—H1a	0.9600
Mn1—Cl2^i	2.5490 (4)	C1—H1b	0.9600
Mn1—O1	2.2322 (10)	C2—H2a	0.9600
Mn1—O1^i	2.2322 (10)	C2—H2b	0.9600
O1—H1o	0.817 (9)	C3—C4	1.5176 (18)
O1—H1p	0.824 (13)	C3—H3a	0.9600
O2—H2o	0.833 (13)	C3—H3n	0.9600
O2—H2p	0.812 (15)	C4—H4a	0.960
N1—C1	1.4971 (17)	C4—H4b	0.960
N1—C5	1.5026 (16)	C5—C6	1.5179 (18)
N1—H1m	0.8700	C5—H5a	0.9600
N1—H1n	0.8700	C5—H5b	0.9600
N2—C2	1.5004 (16)	C6—H6a	0.960
N2—C3	1.5013 (17)	C6—H6b	0.960
N2—H2m	0.8700
Cl1—Mn1—Cl1^i	180	C2—C1—H1b	109.47
Cl1—Mn1—Cl2	89.601 (11)	H1a—C1—H1b	107.72
Cl1—Mn1—Cl2^i	90.399 (11)	N2—C2—C1	110.50 (10)
Cl1—Mn1—O1	91.72 (3)	N2—C2—H2a	109.47
Cl1—Mn1—O1^i	88.28 (3)	N2—C2—H2b	109.47
Cl1^i—Mn1—Cl2	90.399 (11)	C1—C2—H2a	109.47
Cl1^i—Mn1—Cl2^i	89.601 (11)	C1—C2—H2b	109.47
Cl1^i—Mn1—O1	88.28 (3)	H2a—C2—H2b	108.42
Cl1^i—Mn1—O1^i	91.72 (3)	N2—C3—C4	112.83 (11)
Cl2—Mn1—Cl2^i	180	N2—C3—H3a	109.47
Cl2—Mn1—O1	91.97 (3)	N2—C3—H3n	109.47
Cl2—Mn1—O1^i	88.03 (3)	C4—C3—H3a	109.47
Cl2^i—Mn1—O1	88.03 (3)	C4—C3—H3n	109.47
Cl2^i—Mn1—O1^i	91.97 (3)	H3a—C3—H3n	105.89
O1—Mn1—O1^i	180	C3—C4—C3^ii	109.58 (15)
H1o—O1—H1p	109.3 (16)	C3—C4—H4a	109.47
H2o—O2—H2p	99.4 (15)	C3—C4—H4b	109.47
C1—N1—C5	117.34 (10)	C3^ii—C4—H4a	109.47
C1—N1—H1m	109.47	C3^ii—C4—H4b	109.47
C1—N1—H1n	109.47	H4a—C4—H4b	109.4
C5—N1—H1m	109.47	N1—C5—C6	112.94 (12)
C5—N1—H1n	109.47	N1—C5—H5a	109.47
H1m—N1—H1n	100.26	N1—C5—H5b	109.47
C2—N2—C3	117.20 (10)	C6—C5—H5a	109.47
C2—N2—H2m	109.47	C6—C5—H5b	109.47
C2—N2—H2n	109.47	H5a—C5—H5b	105.77
C3—N2—H2m	109.47	C5—C6—C5^ii	109.58 (16)
C3—N2—H2n	109.47	C5—C6—H6a	109.47
H2m—N2—H2n	100.45	C5—C6—H6b	109.47
N1—C1—C2	111.17 (10)	C5^ii—C6—H6a	109.47
N1—C1—H1a	109.47	C5^ii—C6—H6b	109.47
N1—C1—H1b	109.47	H6a—C6—H6b	109.4
C2—C1—H1a	109.47

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1M···O2	0.87	2.01	2.8367 (16)	159
N1—H1N···Cl2^iii	0.87	2.51	3.2465 (11)	143
N1—H1N···Cl1^iv	0.87	2.77	3.2317 (11)	115
O1—H1O···O2	0.82 (1)	1.94 (1)	2.7474 (15)	172 (2)
O1—H1P···Cl3	0.82 (1)	2.35 (1)	3.1382 (10)	162 (1)
N2—H2M···O1^v	0.87	2.08	2.8926 (15)	155
N2—H2N···Cl1	0.87	2.48	3.2383 (11)	146
O2—H2O···Cl4^vi	0.83 (1)	2.19 (1)	3.0205 (12)	173 (1)
O2—H2P···Cl2^vii	0.81 (2)	2.52 (2)	3.2832 (11)	157 (1)
C1—H1A···Cl2	0.96	2.71	3.6100 (14)	156
C3—H3N···Cl3	0.96	2.81	3.7016 (14)	155
C5—H5B···Cl4	0.96	2.72	3.6178 (14)	156

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