Bis(piperazinium) di-μ-chloro-bis­[diaqua­dichloro­manganate(II)] dichloride

Jin, Z.-M.; Li, L.; Li, M.-C.; Hu, M.-L.; Shen, L.

doi:10.1107/S1600536805024530

Bis(piperazinium) di-μ-chloro-bis[diaquadichloromanganate(II)] dichloride

Z.-M. Jin, L. Li, M.-C. Li, M.-L. Hu and L. Shen

The title compound, (C₄H₁₂N₂)₂[Mn₂Cl₆(H₂O)₄]Cl₂, consists of two piperazinium cations, two chloride anions and a dimanganese complex anion, which lies on a center of symmetry. Each Mn^II atom is located in a distorted octahedral environment. The cations and the anions are held together by O—H

Cl and N—H

Cl hydrogen bonds. The structure features the formation of inorganic and organic ionic layers, which interpenetrate each other and which are linked by hydrogen bonds.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805024530/is6108sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536805024530/is6108Isup2.hkl Contains datablock I

CCDC reference: 262895

checkCIF report

Key indicators

Single-crystal X-ray study
T = 299 K
Mean (C-C) = 0.003 Å
R factor = 0.023
wR factor = 0.057
Data-to-parameter ratio = 14.8

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  Mn     -   Cl1_a   ..       9.56 su
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....       2.04
PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... #          2
            O1  -MN  -CL1 -MN    -16.60  0.60   1.555   1.555   1.555   3.556
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          8
PLAT731_ALERT_1_C Bond    Calc     0.82(3), Rep   0.813(10) ......       3.00 su-Rat
              O1   -H1OA    1.555   1.555
PLAT731_ALERT_1_C Bond    Calc     0.82(3), Rep   0.811(10) ......       3.00 su-Rat
              O1   -H1OB    1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.82(3), Rep   0.813(10) ......       3.00 su-Rat
              O1   -H1#     1.555   1.555
PLAT735_ALERT_1_C D-H     Calc     0.82(3), Rep   0.811(10) ......       3.00 su-Rat
              O1   -H2#     1.555   1.555
PLAT736_ALERT_1_C H...A   Calc     2.40(3), Rep   2.400(13) ......       2.31 su-Rat
              H1#  -CL4     1.555   1.555

Alert level G
FORMU01_ALERT_1_G  There is a discrepancy between the atom counts in the
            _chemical_formula_sum and _chemical_formula_moiety. This is
            usually due to the moiety formula being in the wrong format.
            Atom count from _chemical_formula_sum:   C8 H32 Cl8 Mn2 N4 O4
            Atom count from _chemical_formula_moiety:C8 H28 Cl8 Mn2 N4 O2

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

   8 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
   2 ALERT type 4 Improvement, methodology, query or suggestion

Computing details top

Data collection: XSCANS (Siemens, 1994); cell refinement: XSCANS; data reduction: SHELXTL (Siemens, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Bis(piperazinium) di-µ-chloro-bis[diaquadichloromanganese(II)] dichloride top

Crystal data top

(C₄H₁₂N₂)₂[Mn₂Cl₆(H₂O)₄]Cl₂	F(000) = 652
M_r = 641.86	D_x = 1.733 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 36 reflections
a = 9.865 (2) Å	θ = 5.2–15.1°
b = 9.429 (1) Å	µ = 1.92 mm⁻¹
c = 13.506 (2) Å	T = 299 K
β = 101.74 (1)°	Block, pink
V = 1230.0 (3) Å³	0.56 × 0.56 × 0.26 mm
Z = 2

Data collection top

Siemens P4 diffractometer	1931 reflections with I > 2σ(I)
Radiation source: normal-focus sealed tube	R_int = 0.012
Graphite monochromator	θ_max = 25.3°, θ_min = 2.1°
ω scans	h = 0→11
Absorption correction: ψ scan (North et al., 1968)	k = 0→11
T_min = 0.356, T_max = 0.608	l = −16→15
2623 measured reflections	3 standard reflections every 97 reflections
2235 independent reflections	intensity decay: 1.2%

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.023	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.057	w = 1/[σ²(F_o²) + (0.0296P)²] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max = 0.001
2235 reflections	Δρ_max = 0.26 e Å⁻³
151 parameters	Δρ_min = −0.23 e Å⁻³
8 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0331 (10)

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
Mn	0.10145 (3)	0.16818 (3)	0.54958 (2)	0.02268 (12)
Cl1	0.00813 (5)	0.05235 (6)	0.37480 (4)	0.02493 (14)
Cl2	0.32378 (5)	0.04614 (5)	0.56086 (4)	0.02290 (14)
Cl3	−0.10924 (5)	0.32075 (5)	0.53620 (4)	0.02716 (15)
Cl4	0.44336 (6)	0.19574 (6)	0.87221 (4)	0.03084 (15)
O1	0.1695 (2)	0.2557 (2)	0.70523 (14)	0.0430 (5)
O2	0.1939 (2)	0.34665 (19)	0.48525 (19)	0.0554 (6)
N1	0.6250 (2)	0.17909 (19)	0.60178 (13)	0.0249 (4)
N2	0.72344 (19)	0.2685 (2)	0.80598 (12)	0.0233 (4)
C1	0.5773 (2)	0.3155 (2)	0.63850 (16)	0.0282 (5)
H1A	0.4923	0.3002	0.6626	0.034*
H1B	0.5584	0.3832	0.5833	0.034*
C2	0.6870 (2)	0.3743 (2)	0.72301 (15)	0.0268 (5)
H2A	0.7689	0.3981	0.6972	0.032*
H2B	0.6531	0.4603	0.7491	0.032*
C3	0.7730 (2)	0.1330 (2)	0.76860 (16)	0.0293 (5)
H3A	0.7934	0.0652	0.8236	0.035*
H3B	0.8574	0.1500	0.7441	0.035*
C4	0.6636 (2)	0.0734 (2)	0.68447 (15)	0.0281 (5)
H4A	0.6984	−0.0119	0.6580	0.034*
H4B	0.5824	0.0480	0.7107	0.034*
H1OA	0.237 (3)	0.226 (4)	0.745 (2)	0.096 (14)*
H1OB	0.113 (3)	0.292 (3)	0.734 (2)	0.069 (11)*
H2OA	0.259 (2)	0.345 (3)	0.457 (2)	0.071 (11)*
H2OB	0.159 (3)	0.4249 (19)	0.478 (3)	0.090 (13)*
H1NA	0.5566 (18)	0.146 (2)	0.5541 (13)	0.032 (7)*
H1NB	0.6938 (18)	0.197 (2)	0.5705 (16)	0.036 (7)*
H2NA	0.790 (2)	0.307 (2)	0.8542 (15)	0.054 (8)*
H2NB	0.6479 (16)	0.251 (2)	0.8337 (15)	0.031 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Mn	0.01830 (19)	0.02262 (19)	0.02741 (19)	0.00175 (14)	0.00534 (14)	0.00018 (13)
Cl1	0.0209 (3)	0.0297 (3)	0.0242 (3)	0.0013 (2)	0.0046 (2)	0.0008 (2)
Cl2	0.0170 (3)	0.0263 (3)	0.0255 (3)	0.0017 (2)	0.0046 (2)	0.0013 (2)
Cl3	0.0231 (3)	0.0262 (3)	0.0340 (3)	0.0055 (2)	0.0101 (2)	0.0018 (2)
Cl4	0.0271 (3)	0.0373 (3)	0.0299 (3)	−0.0048 (2)	0.0101 (2)	−0.0044 (2)
O1	0.0338 (11)	0.0546 (12)	0.0376 (11)	0.0097 (10)	0.0003 (9)	−0.0163 (9)
O2	0.0499 (13)	0.0280 (10)	0.1039 (17)	0.0117 (9)	0.0522 (13)	0.0193 (11)
N1	0.0238 (10)	0.0301 (10)	0.0210 (9)	−0.0045 (9)	0.0046 (8)	−0.0064 (8)
N2	0.0220 (10)	0.0286 (10)	0.0191 (9)	−0.0020 (8)	0.0039 (8)	−0.0039 (7)
C1	0.0326 (13)	0.0257 (11)	0.0241 (11)	0.0025 (10)	0.0006 (10)	−0.0031 (9)
C2	0.0358 (13)	0.0247 (11)	0.0198 (10)	−0.0034 (10)	0.0054 (9)	−0.0027 (9)
C3	0.0267 (12)	0.0298 (12)	0.0301 (12)	0.0065 (10)	0.0027 (10)	−0.0041 (10)
C4	0.0308 (13)	0.0238 (11)	0.0285 (11)	−0.0007 (10)	0.0036 (10)	−0.0044 (9)

Geometric parameters (Å, º) top

Mn—O2	2.1776 (18)	N2—C2	1.488 (3)
Mn—O1	2.2308 (18)	N2—C3	1.492 (3)
Mn—Cl2	2.4540 (7)	N2—H2NA	0.903 (10)
Mn—Cl3	2.5038 (7)	N2—H2NB	0.914 (10)
Mn—Cl1	2.5939 (7)	C1—C2	1.509 (3)
Mn—Cl1ⁱ	2.6429 (6)	C1—H1A	0.9700
Cl1—Mnⁱ	2.6429 (6)	C1—H1B	0.9700
O1—H1OA	0.813 (10)	C2—H2A	0.9700
O1—H1OB	0.811 (10)	C2—H2B	0.9700
O2—H2OA	0.812 (10)	C3—C4	1.507 (3)
O2—H2OB	0.812 (10)	C3—H3A	0.9700
N1—C4	1.488 (3)	C3—H3B	0.9700
N1—C1	1.489 (3)	C4—H4A	0.9700
N1—H1NA	0.891 (10)	C4—H4B	0.9700
N1—H1NB	0.885 (10)

O2—Mn—O1	91.14 (9)	C2—N2—H2NA	107.4 (17)
O2—Mn—Cl2	86.86 (5)	C3—N2—H2NA	110.6 (17)
O1—Mn—Cl2	91.21 (5)	C2—N2—H2NB	109.8 (14)
O2—Mn—Cl3	86.35 (5)	C3—N2—H2NB	109.4 (15)
O1—Mn—Cl3	86.66 (5)	H2NA—N2—H2NB	108 (2)
Cl2—Mn—Cl3	172.84 (2)	N1—C1—C2	110.04 (18)
O2—Mn—Cl1	93.56 (7)	N1—C1—H1A	109.7
O1—Mn—Cl1	175.12 (6)	C2—C1—H1A	109.7
Cl2—Mn—Cl1	90.36 (2)	N1—C1—H1B	109.7
Cl3—Mn—Cl1	92.32 (2)	C2—C1—H1B	109.7
O2—Mn—Cl1ⁱ	178.71 (6)	H1A—C1—H1B	108.2
O1—Mn—Cl1ⁱ	89.74 (6)	N2—C2—C1	110.49 (17)
Cl2—Mn—Cl1ⁱ	92.17 (2)	N2—C2—H2A	109.6
Cl3—Mn—Cl1ⁱ	94.65 (2)	C1—C2—H2A	109.6
Cl1—Mn—Cl1ⁱ	85.59 (2)	N2—C2—H2B	109.6
Mn—Cl1—Mnⁱ	94.41 (2)	C1—C2—H2B	109.6
Mn—O1—H1OA	123 (3)	H2A—C2—H2B	108.1
Mn—O1—H1OB	120 (2)	N2—C3—C4	109.95 (18)
H1OA—O1—H1OB	112 (3)	N2—C3—H3A	109.7
Mn—O2—H2OA	128 (2)	C4—C3—H3A	109.7
Mn—O2—H2OB	123 (3)	N2—C3—H3B	109.7
H2OA—O2—H2OB	108 (3)	C4—C3—H3B	109.7
C4—N1—C1	112.27 (16)	H3A—C3—H3B	108.2
C4—N1—H1NA	110.2 (15)	N1—C4—C3	110.54 (17)
C1—N1—H1NA	107.7 (15)	N1—C4—H4A	109.5
C4—N1—H1NB	112.3 (15)	C3—C4—H4A	109.5
C1—N1—H1NB	108.8 (15)	N1—C4—H4B	109.5
H1NA—N1—H1NB	105 (2)	C3—C4—H4B	109.5
C2—N2—C3	111.37 (16)	H4A—C4—H4B	108.1

O2—Mn—Cl1—Mnⁱ	179.03 (5)	C3—N2—C2—C1	57.9 (2)
O1—Mn—Cl1—Mnⁱ	−16.6 (6)	N1—C1—C2—N2	−56.0 (2)
Cl2—Mn—Cl1—Mnⁱ	92.14 (2)	C2—N2—C3—C4	−57.7 (2)
Cl3—Mn—Cl1—Mnⁱ	−94.49 (2)	C1—N1—C4—C3	−56.3 (2)
Cl1ⁱ—Mn—Cl1—Mnⁱ	0.0	N2—C3—C4—N1	56.1 (2)
C4—N1—C1—C2	56.0 (2)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1OA···Cl4	0.81 (1)	2.40 (1)	3.197 (2)	167 (4)
O1—H1OB···Cl1ⁱⁱ	0.81 (1)	2.77 (2)	3.5411 (19)	160 (3)
O2—H2OB···Cl3ⁱⁱⁱ	0.81 (1)	2.45 (1)	3.2433 (19)	167 (3)
O2—H2OA···Cl4^iv	0.81 (1)	2.37 (1)	3.174 (2)	172 (3)
N1—H1NA···Cl2	0.89 (1)	2.50 (2)	3.168 (2)	132 (2)
N1—H1NB···Cl3^v	0.89 (1)	2.39 (1)	3.223 (2)	156 (2)
N2—H2NB···Cl4	0.91 (1)	2.25 (1)	3.148 (2)	169 (2)
N2—H2NA···Cl1^vi	0.90 (1)	2.49 (2)	3.247 (2)	141 (2)

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

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Bis(piperazinium) di-μ-chloro-bis­[diaqua­dichloro­manganate(II)] dichloride

Supporting information

Key indicators

checkCIF/PLATON results

Bis(piperazinium) di-μ-chloro-bis[diaquadichloromanganate(II)] dichloride