Bis(1-carbamoyl­guanidinium) di­aqua­tetra­chloro­manganate(II)

The title compound, (C₂H₇N₄O)₂[MnCl₄(H₂O)₂], contains a molecular network of C₂H₇N₄O⁺ cations and [Mn(H₂O)₂Cl₄]²⁻ trans-octahedral anions (Mn site symmetry 2/m). An extensive network of N—H...Cl, N—H...(Cl,Cl), N—H...O, O—H...O and O—H...Cl links results in a structure with a three-dimensional hydrogen-bonding network. The compound is isostructural with its copper- and cobalt-containing congeners.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](Mn-O) = 0.001 Å
• R factor = 0.031
• wR factor = 0.078
• Data-to-parameter ratio = 30.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

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Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: isostructural with Co complex; program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and ATOMS (Shape Software, 1999); software used to prepare material for publication: SHELXL97.

(I)

Crystal data

(C2H7N4O)2[Mn(H2O)2Cl4]	F(000) = 446
Mr = 439.00	Dx = 1.773 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 6.4106 (3) Å	Cell parameters from 2931 reflections
b = 11.4036 (6) Å	θ = 2.5–32.3°
c = 11.5775 (6) Å	µ = 1.48 mm^−1
β = 103.640 (1)°	T = 293 K
V = 822.49 (7) Å^3	Block, colourless
Z = 2	0.33 × 0.23 × 0.19 mm

Data collection

Bruker SMART1000 CCD diffractometer	2947 independent reflections
Radiation source: fine-focus sealed tube	2122 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.023
ω scans	θmax = 32.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −9→9
Tmin = 0.644, Tmax = 0.768	k = −11→17
8334 measured reflections	l = −17→16

Refinement

Refinement on F^2	Primary atom site location: from isostructural phase
Least-squares matrix: full	Hydrogen site location: difmap (O-H) and geom (N-H)
R[F^2 > 2σ(F^2)] = 0.031	H-atom parameters constrained
wR(F^2) = 0.078	w = 1/[σ^2(Fo^2) + (0.0411P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 0.95	(Δ/σ)max < 0.001
2947 reflections	Δρmax = 0.40 e Å^−3
97 parameters	Δρmin = −0.23 e Å^−3
0 restraints

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
Mn1	0.0000	0.5000	0.0000	0.02798 (8)
Cl1	0.00427 (7)	0.49621 (3)	0.21671 (3)	0.03772 (10)
Cl2	0.31918 (6)	0.64019 (3)	0.04754 (3)	0.03472 (10)
O1	0.24682 (17)	0.36239 (9)	0.03072 (9)	0.0312 (2)
H1	0.2170	0.2977	0.0093	0.037*
H2	0.3590	0.3809	0.0045	0.037*
O2	0.70236 (19)	0.35420 (10)	0.44553 (10)	0.0438 (3)
N1	0.4764 (2)	0.29980 (12)	0.27397 (11)	0.0419 (3)
H3	0.4965	0.2262	0.2887	0.050*
H4	0.3906	0.3223	0.2090	0.050*
N2	0.5298 (2)	0.49315 (10)	0.31684 (11)	0.0334 (3)
H5	0.4304	0.5044	0.2535	0.040*
N3	0.5662 (2)	0.69142 (12)	0.32318 (12)	0.0437 (3)
H6	0.6207	0.7552	0.3570	0.052*
H7	0.4733	0.6942	0.2562	0.052*
N4	0.7653 (2)	0.58247 (13)	0.47515 (11)	0.0398 (3)
H8	0.8218	0.6452	0.5105	0.048*
H9	0.8016	0.5150	0.5068	0.048*
C1	0.5773 (2)	0.37802 (13)	0.35087 (13)	0.0326 (3)
C2	0.6251 (2)	0.58967 (13)	0.37387 (13)	0.0309 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn1	0.02756 (16)	0.02426 (15)	0.03128 (15)	0.00143 (11)	0.00524 (11)	0.00018 (12)
Cl1	0.0396 (2)	0.0422 (2)	0.03286 (17)	0.00100 (16)	0.01143 (15)	0.00047 (16)
Cl2	0.03229 (18)	0.03009 (18)	0.04105 (18)	−0.00478 (14)	0.00721 (13)	0.00079 (15)
O1	0.0314 (5)	0.0233 (5)	0.0402 (5)	−0.0002 (4)	0.0112 (4)	−0.0022 (4)
O2	0.0500 (7)	0.0292 (6)	0.0433 (6)	0.0001 (5)	−0.0068 (5)	0.0078 (5)
N1	0.0525 (8)	0.0259 (7)	0.0408 (7)	−0.0029 (6)	−0.0020 (6)	0.0020 (6)
N2	0.0338 (7)	0.0263 (6)	0.0355 (6)	0.0021 (5)	−0.0009 (5)	0.0031 (5)
N3	0.0603 (9)	0.0256 (7)	0.0397 (7)	0.0024 (6)	0.0006 (6)	0.0003 (6)
N4	0.0423 (7)	0.0303 (7)	0.0408 (6)	−0.0008 (6)	−0.0022 (5)	−0.0020 (6)
C1	0.0326 (8)	0.0272 (8)	0.0374 (7)	−0.0004 (5)	0.0068 (6)	0.0041 (6)
C2	0.0312 (7)	0.0286 (7)	0.0336 (7)	0.0003 (6)	0.0088 (5)	−0.0011 (6)

Geometric parameters (Å, º)

Mn1—O1	2.1971 (10)	N1—H4	0.860
Mn1—O1^i	2.1971 (10)	N2—C2	1.3529 (19)
Mn1—Cl1^i	2.5031 (4)	N2—C1	1.3839 (18)
Mn1—Cl1	2.5031 (4)	N2—H5	0.860
Mn1—Cl2^i	2.5523 (4)	N3—C2	1.3147 (19)
Mn1—Cl2	2.5523 (4)	N3—H6	0.860
O1—H1	0.787	N3—H7	0.860
O1—H2	0.870	N4—C2	1.3011 (18)
O2—C1	1.2260 (17)	N4—H8	0.860
N1—C1	1.317 (2)	N4—H9	0.860
N1—H3	0.860
O1—Mn1—O1^i	180.0	C1—N1—H3	120.0
O1—Mn1—Cl1^i	90.68 (3)	C1—N1—H4	120.0
O1^i—Mn1—Cl1^i	89.32 (3)	H3—N1—H4	120.0
O1—Mn1—Cl1	89.32 (3)	C2—N2—C1	126.10 (13)
O1^i—Mn1—Cl1	90.68 (3)	C2—N2—H5	117.0
Cl1^i—Mn1—Cl1	180.0	C1—N2—H5	117.0
O1—Mn1—Cl2^i	95.60 (3)	C2—N3—H6	120.0
O1^i—Mn1—Cl2^i	84.40 (3)	C2—N3—H7	120.0
Cl1^i—Mn1—Cl2^i	88.622 (12)	H6—N3—H7	120.0
Cl1—Mn1—Cl2^i	91.378 (12)	C2—N4—H8	120.0
O1—Mn1—Cl2	84.40 (3)	C2—N4—H9	120.0
O1^i—Mn1—Cl2	95.60 (3)	H8—N4—H9	120.0
Cl1^i—Mn1—Cl2	91.378 (12)	O2—C1—N1	124.57 (14)
Cl1—Mn1—Cl2	88.622 (12)	O2—C1—N2	121.22 (14)
Cl2^i—Mn1—Cl2	180.0	N1—C1—N2	114.21 (13)
Mn1—O1—H1	120.4	N4—C2—N3	121.50 (15)
Mn1—O1—H2	113.2	N4—C2—N2	121.67 (14)
H1—O1—H2	106.1	N3—C2—N2	116.82 (14)

Symmetry code: (i) −x, −y+1, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2^ii	0.79	1.88	2.6499 (15)	167
O1—H2···Cl2^iii	0.87	2.29	3.1227 (11)	159
N1—H3···Cl1^iv	0.86	2.62	3.4649 (14)	166
N1—H4···O1	0.86	2.10	2.9415 (17)	165
N2—H5···Cl1	0.86	2.67	3.2944 (14)	131
N2—H5···Cl2	0.86	2.79	3.5170 (13)	143
N3—H6···Cl2^v	0.86	2.57	3.3282 (15)	148
N3—H6···Cl1^vi	0.86	2.93	3.5213 (14)	127
N3—H7···Cl2	0.86	2.46	3.2635 (14)	155
N4—H8···Cl2^v	0.86	2.49	3.2692 (15)	152
N4—H9···O2	0.86	2.01	2.6441 (18)	129

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