A dimeric manganese(II) complex bridged by 4-amino­benzoate

The dimeric Mn^II title complex, di-μ-4-amino­benzoato-bis­[(4-amino­benzoato)(2,2′-diamino-4,4′-bithia­zole)manganese(II)] dihydrate, [Mn₂(C₆H₆N₄S₂)₂(C₇H₆NO₂)₄]·2H₂O, bridged by amino­benzoate anions, is located on an inversion center. Each Mn^II atom is coordinated by one diamino­bithia­zole and three amino­benzoate ligands with a distorted octa­hedral geometry.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.032
• wR factor = 0.081
• Data-to-parameter ratio = 12.8

checkCIF/PLATON results

No syntax errors found



Alert level B
PLAT232_ALERT_2_B Hirshfeld Test Diff (M-X)  Mn     -   O2      ..      14.68 su

Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT322_ALERT_2_C Check Hybridisation of  S1     in Main Residue .          ?
PLAT322_ALERT_2_C Check Hybridisation of  S2     in Main Residue .          ?
PLAT420_ALERT_2_C D-H Without Acceptor       N6     -   H6A    ...          ?

   0 ALERT level A = In general: serious problem
   1 ALERT level B = Potentially serious problem
   4 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
   4 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

As part of an ongoing investigation on the nature of π–π stacking in metal complexes (Fu et al., 2005), the title Mn^II complex, (I), was recently prepared and its X-ray structure is presented here.

The dimeric molecule of (I) is located on an inversion center (Fig. 1). Each Mn^II atom is coordinated by three aminobenzoate anions and one diaminobithiazole ligand with a distorted octahedral geometry (Table 1). The diaminobithiazole chelating the Mn^II atom displays a nearly planar configuration, with a dihedral angle of 3.75 (15)° between two thiazole mean planes, which differs from the twisted configuration [dihedral angle = 20.02 (8)°] found in a diaminobithiazole complex of Co^II reported previously (Liu & Xu, 2005).

While the C11 carboxyl group chelates to the Mn^II atom, the C22 carboxyl bridges Mn^II atoms to form the dimeric complex molecule. Although the larger Mn—O3—C21 angle of 157.73 (14)° implies poor overlap between atomic orbitals of the Mn and O3 atoms, the shorter Mn—O3 bond distance (Table 1) shows the normal bonding interaction between them. This is consistent with the situation found in an Mn^II complex with salicylate (Su & Xu, 2005) and in a Mn^II complex with benzenedicarboxylate (Nie et al., 2001), and clearly suggests the significant content of the electrostatic interaction in the Mn—O bond.

As shown in Fig. 2, the partially overlapping arrangement of parallel benzene rings, related by an inversion center, occurs in the crystal structure of (I), but the face-to-face separation of 4.0068 (13) Å shows that there is no π–π stacking between aminobenzoate ligands. The extensive hydrogen-bonding network occurs in the crystal structure of (I) (Table 2).

S2. Experimental

An aqueous solution (20 ml) containing diaminobithiazole (1 mmol) and MnCl₂·2H₂O (1 mmol) was mixed with another aqueous solution (10 ml) of 4-aminobenzoic acid (4 mmol) and NaOH (4 mmol). The mixture was refluxed for 10 h. After cooling to room temperature, the solution was filtered. Yellow single crystals of (I) were obtained from the filtrate after 15 d.

S3. Refinement

H atoms bonded to C atoms were placed in calculated positions, with C—H distances of 0.93 Å, and included in the final cycles of refinement in the riding mode, with U_iso(H) = 1.2U_eq(C). Other H atoms were located in a difference Fourier map and refined as riding in their as found relative positions with U_iso(H) = 1.5U_eq(carrier).

Computing details

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The molecular structure of (I), with 30% probability displacement ellipsoids (arbitrary spheres for H atoms). Dashed lines indicate hydrogen bonds [symmetry code: (i) 2 − x, 1 − y, 1 − z].
	Fig. 2. The unit-cell packing of (I).

di-m-4-aminobenzoato-bis[(4-aminobenzoato)(2,2'-diamino-4,4'- bithiazole)manganese(II)] dihydrate

Crystal data

[Mn2(C6H6N4S2)2(C7H6NO2)4]·2H2O	Z = 1
Mr = 1086.96	F(000) = 558
Triclinic, P1	Dx = 1.597 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.1429 (8) Å	Cell parameters from 4228 reflections
b = 10.6796 (9) Å	θ = 2.2–24.0°
c = 12.0826 (12) Å	µ = 0.82 mm^−1
α = 89.916 (2)°	T = 295 K
β = 74.203 (2)°	Prism, yellow
γ = 84.889 (2)°	0.32 × 0.28 × 0.18 mm
V = 1130.39 (18) Å^3

Data collection

Rigaku R-AXIS RAPID diffractometer	3923 independent reflections
Radiation source: fine-focus sealed tube	3582 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.013
Detector resolution: 10.00 pixels mm^-1	θmax = 25.0°, θmin = 1.9°
ω scans	h = −4→10
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −12→12
Tmin = 0.775, Tmax = 0.862	l = −14→14
5976 measured reflections

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.081	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.043P)^2 + 0.3658P] where P = (Fo^2 + 2Fc^2)/3
3923 reflections	(Δ/σ)max = 0.001
307 parameters	Δρmax = 0.24 e Å^−3
0 restraints	Δρmin = −0.31 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	0.85122 (3)	0.32431 (3)	0.57384 (2)	0.02791 (11)
S1	0.74404 (7)	−0.09561 (5)	0.48027 (5)	0.04253 (16)
S2	0.57384 (7)	0.44529 (5)	0.30110 (5)	0.04342 (16)
N1	0.78057 (18)	0.13106 (14)	0.53138 (13)	0.0289 (4)
N2	0.8731 (2)	−0.02364 (15)	0.64220 (15)	0.0363 (4)
H2A	0.9209	0.0362	0.6640	0.050*
H2B	0.9146	−0.1039	0.6347	0.050*
N3	0.70916 (18)	0.36521 (14)	0.45201 (13)	0.0293 (4)
N4	0.7076 (2)	0.58314 (16)	0.42513 (16)	0.0461 (5)
H4A	0.7553	0.5870	0.4767	0.050*
H4B	0.6697	0.6560	0.3994	0.050*
N5	0.4861 (2)	0.02057 (17)	1.20158 (15)	0.0414 (4)
H5A	0.5253	−0.0618	1.2109	0.050*
H5B	0.3740	0.0307	1.2281	0.050*
N6	0.8788 (2)	0.6542 (2)	1.11964 (16)	0.0514 (5)
H6A	0.8624	0.5755	1.1588	0.050*
H6B	0.9519	0.7005	1.1333	0.050*
O1	0.67552 (16)	0.31267 (13)	0.73888 (11)	0.0343 (3)
O2	0.90758 (16)	0.23124 (13)	0.73307 (12)	0.0377 (3)
O3	0.86053 (18)	0.51921 (13)	0.60791 (12)	0.0383 (3)
O4	0.95741 (15)	0.70272 (12)	0.57683 (11)	0.0318 (3)
O1W	0.40246 (18)	0.23202 (14)	0.72123 (13)	0.0446 (4)
H1A	0.4779	0.2736	0.7339	0.050*
H1B	0.3160	0.2676	0.7825	0.050*
C1	0.8077 (2)	0.01377 (17)	0.55820 (16)	0.0297 (4)
C2	0.6765 (3)	0.02561 (19)	0.4087 (2)	0.0418 (5)
H2	0.6278	0.0154	0.3514	0.050*
C3	0.7035 (2)	0.13724 (18)	0.44663 (17)	0.0307 (4)
C4	0.6724 (2)	0.46892 (18)	0.40294 (17)	0.0322 (4)
C5	0.5879 (3)	0.2862 (2)	0.32614 (19)	0.0413 (5)
H5	0.5493	0.2260	0.2892	0.050*
C6	0.6626 (2)	0.26150 (18)	0.40666 (17)	0.0308 (4)
C11	0.7671 (2)	0.25022 (17)	0.78570 (17)	0.0309 (4)
C12	0.7034 (2)	0.19747 (18)	0.89991 (17)	0.0320 (4)
C13	0.7791 (2)	0.09624 (19)	0.94077 (18)	0.0365 (5)
H13	0.8784	0.0679	0.9003	0.044*
C14	0.7088 (3)	0.0374 (2)	1.04036 (18)	0.0389 (5)
H14	0.7609	−0.0302	1.0663	0.047*
C16	0.4869 (3)	0.1837 (2)	1.06441 (18)	0.0380 (5)
H16	0.3897	0.2151	1.1069	0.046*
C17	0.5571 (3)	0.24113 (19)	0.96499 (18)	0.0371 (5)
H17	0.5062	0.3105	0.9405	0.045*
C21	0.9062 (2)	0.61454 (17)	0.64322 (16)	0.0270 (4)
C22	0.8982 (2)	0.62733 (17)	0.76746 (16)	0.0292 (4)
C23	0.9828 (2)	0.7105 (2)	0.80679 (18)	0.0383 (5)
H23	1.0433	0.7617	0.7547	0.046*
C24	0.9788 (3)	0.7184 (2)	0.92144 (19)	0.0456 (6)
H24	1.0371	0.7742	0.9455	0.055*
C25	0.8886 (2)	0.6439 (2)	1.00149 (18)	0.0401 (5)
C26	0.8029 (3)	0.5620 (2)	0.96354 (18)	0.0391 (5)
H26	0.7413	0.5120	1.0162	0.047*
C27	0.8075 (2)	0.55326 (18)	0.84849 (17)	0.0338 (5)
H27	0.7493	0.4972	0.8248	0.041*
C15	0.5596 (2)	0.07887 (19)	1.10242 (17)	0.0341 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mn	0.03612 (19)	0.02381 (16)	0.02449 (17)	−0.00675 (12)	−0.00821 (13)	0.00329 (11)
S1	0.0564 (4)	0.0222 (3)	0.0541 (4)	−0.0080 (2)	−0.0223 (3)	0.0001 (2)
S2	0.0597 (4)	0.0357 (3)	0.0437 (3)	−0.0026 (3)	−0.0296 (3)	0.0062 (2)
N1	0.0337 (9)	0.0231 (8)	0.0291 (9)	−0.0028 (7)	−0.0072 (7)	0.0015 (6)
N2	0.0448 (10)	0.0246 (8)	0.0405 (10)	−0.0004 (7)	−0.0142 (8)	0.0030 (7)
N3	0.0355 (9)	0.0241 (8)	0.0294 (8)	−0.0013 (7)	−0.0110 (7)	0.0010 (6)
N4	0.0725 (14)	0.0255 (9)	0.0525 (12)	−0.0068 (9)	−0.0368 (11)	0.0081 (8)
N5	0.0505 (11)	0.0406 (10)	0.0337 (10)	−0.0129 (9)	−0.0099 (8)	0.0095 (8)
N6	0.0519 (12)	0.0700 (14)	0.0316 (10)	0.0044 (10)	−0.0131 (9)	−0.0031 (9)
O1	0.0394 (8)	0.0334 (7)	0.0300 (7)	−0.0050 (6)	−0.0085 (6)	0.0071 (6)
O2	0.0369 (8)	0.0408 (8)	0.0338 (8)	−0.0055 (6)	−0.0064 (7)	0.0035 (6)
O3	0.0538 (9)	0.0290 (7)	0.0330 (8)	−0.0141 (7)	−0.0102 (7)	−0.0009 (6)
O4	0.0376 (8)	0.0259 (7)	0.0299 (7)	−0.0048 (6)	−0.0052 (6)	0.0046 (6)
O1W	0.0461 (9)	0.0421 (9)	0.0478 (9)	−0.0043 (7)	−0.0166 (7)	0.0045 (7)
C1	0.0305 (10)	0.0241 (9)	0.0309 (10)	−0.0048 (8)	−0.0013 (8)	0.0002 (8)
C2	0.0531 (14)	0.0308 (11)	0.0494 (13)	−0.0068 (10)	−0.0267 (11)	−0.0007 (9)
C3	0.0333 (11)	0.0274 (10)	0.0317 (10)	−0.0043 (8)	−0.0090 (9)	0.0002 (8)
C4	0.0380 (11)	0.0294 (10)	0.0292 (10)	−0.0023 (8)	−0.0094 (9)	0.0020 (8)
C5	0.0549 (14)	0.0312 (11)	0.0448 (13)	−0.0046 (10)	−0.0251 (11)	−0.0010 (9)
C6	0.0342 (11)	0.0275 (10)	0.0316 (10)	−0.0043 (8)	−0.0100 (9)	−0.0002 (8)
C11	0.0391 (12)	0.0245 (9)	0.0304 (10)	−0.0085 (8)	−0.0097 (9)	0.0000 (8)
C12	0.0385 (11)	0.0300 (10)	0.0280 (10)	−0.0058 (9)	−0.0089 (9)	0.0004 (8)
C13	0.0361 (11)	0.0382 (11)	0.0356 (11)	−0.0016 (9)	−0.0109 (9)	0.0033 (9)
C14	0.0470 (13)	0.0357 (11)	0.0369 (12)	−0.0025 (10)	−0.0166 (10)	0.0070 (9)
C16	0.0394 (12)	0.0401 (12)	0.0306 (11)	−0.0002 (9)	−0.0040 (9)	0.0009 (9)
C17	0.0456 (13)	0.0310 (10)	0.0334 (11)	0.0016 (9)	−0.0102 (10)	0.0037 (9)
C21	0.0259 (10)	0.0238 (9)	0.0295 (10)	0.0002 (8)	−0.0053 (8)	0.0006 (8)
C22	0.0315 (10)	0.0254 (9)	0.0297 (10)	0.0002 (8)	−0.0077 (8)	0.0001 (8)
C23	0.0367 (12)	0.0439 (12)	0.0338 (11)	−0.0110 (10)	−0.0064 (9)	0.0003 (9)
C24	0.0426 (13)	0.0562 (14)	0.0415 (13)	−0.0100 (11)	−0.0156 (10)	−0.0085 (11)
C25	0.0388 (12)	0.0483 (13)	0.0304 (11)	0.0116 (10)	−0.0098 (9)	−0.0036 (9)
C26	0.0453 (13)	0.0350 (11)	0.0314 (11)	0.0004 (10)	−0.0022 (10)	0.0059 (9)
C27	0.0400 (12)	0.0270 (10)	0.0324 (11)	−0.0033 (9)	−0.0065 (9)	−0.0001 (8)
C15	0.0445 (12)	0.0331 (10)	0.0270 (10)	−0.0101 (9)	−0.0116 (9)	0.0008 (8)

Geometric parameters (Å, º)

Mn—O1	2.2053 (14)	O4—C21	1.273 (2)
Mn—O2	2.3233 (15)	O1W—H1A	0.8993
Mn—O3	2.1361 (13)	O1W—H1B	0.9732
Mn—O4^i	2.1532 (13)	C2—C3	1.345 (3)
Mn—N1	2.3154 (15)	C2—H2	0.9300
Mn—N3	2.2321 (16)	C3—C6	1.464 (3)
Mn—C11	2.608 (2)	C5—C6	1.346 (3)
S1—C2	1.718 (2)	C5—H5	0.9300
S1—C1	1.735 (2)	C11—C12	1.476 (3)
S2—C5	1.725 (2)	C12—C13	1.394 (3)
S2—C4	1.742 (2)	C12—C17	1.394 (3)
N1—C1	1.312 (2)	C13—C14	1.380 (3)
N1—C3	1.391 (3)	C13—H13	0.9300
N2—C1	1.355 (3)	C14—C15	1.399 (3)
N2—H2A	0.8839	C14—H14	0.9300
N2—H2B	0.9004	C16—C17	1.371 (3)
N3—C4	1.316 (2)	C16—C15	1.392 (3)
N3—C6	1.386 (2)	C16—H16	0.9300
N4—C4	1.335 (3)	C17—H17	0.9300
N4—H4A	0.8556	C21—C22	1.489 (3)
N4—H4B	0.9119	C22—C23	1.391 (3)
N5—C15	1.382 (3)	C22—C27	1.395 (3)
N5—H5A	0.9376	C23—C24	1.378 (3)
N5—H5B	0.9836	C23—H23	0.9300
N6—C25	1.410 (3)	C24—C25	1.389 (3)
N6—H6A	0.9670	C24—H24	0.9300
N6—H6B	0.9153	C25—C26	1.381 (3)
O1—C11	1.274 (2)	C26—C27	1.382 (3)
O2—C11	1.267 (2)	C26—H26	0.9300
O3—C21	1.251 (2)	C27—H27	0.9300
O3—Mn—O4^i	99.14 (5)	N3—C4—N4	124.79 (18)
O3—Mn—O1	90.01 (5)	N3—C4—S2	113.88 (14)
O4^i—Mn—O1	167.61 (5)	N4—C4—S2	121.32 (15)
O3—Mn—N3	92.75 (6)	C6—C5—S2	110.47 (16)
O4^i—Mn—N3	86.13 (6)	C6—C5—H5	124.8
O1—Mn—N3	101.85 (6)	S2—C5—H5	124.8
O3—Mn—N1	165.34 (6)	C5—C6—N3	115.57 (18)
O4^i—Mn—N1	87.98 (5)	C5—C6—C3	126.54 (18)
O1—Mn—N1	85.04 (5)	N3—C6—C3	117.84 (17)
N3—Mn—N1	74.85 (6)	O2—C11—O1	120.23 (18)
O3—Mn—O2	102.07 (5)	O2—C11—C12	121.66 (19)
O4^i—Mn—O2	111.33 (5)	O1—C11—C12	118.07 (18)
O1—Mn—O2	58.15 (5)	O2—C11—Mn	62.92 (10)
N3—Mn—O2	154.57 (6)	O1—C11—Mn	57.59 (10)
N1—Mn—O2	87.03 (5)	C12—C11—Mn	171.48 (14)
O3—Mn—C11	98.54 (6)	C13—C12—C17	118.16 (19)
O4^i—Mn—C11	139.66 (6)	C13—C12—C11	121.92 (19)
O1—Mn—C11	29.19 (6)	C17—C12—C11	119.63 (18)
N3—Mn—C11	128.78 (6)	C14—C13—C12	121.0 (2)
N1—Mn—C11	83.78 (6)	C14—C13—H13	119.5
O2—Mn—C11	29.05 (6)	C12—C13—H13	119.5
C2—S1—C1	89.11 (10)	C13—C14—C15	120.3 (2)
C5—S2—C4	89.24 (10)	C13—C14—H14	119.9
C1—N1—C3	110.47 (16)	C15—C14—H14	119.9
C1—N1—Mn	136.21 (14)	C17—C16—C15	120.7 (2)
C3—N1—Mn	112.87 (11)	C17—C16—H16	119.7
C1—N2—H2A	112.4	C15—C16—H16	119.7
C1—N2—H2B	114.6	C16—C17—C12	121.2 (2)
H2A—N2—H2B	120.3	C16—C17—H17	119.4
C4—N3—C6	110.82 (16)	C12—C17—H17	119.4
C4—N3—Mn	132.75 (13)	O3—C21—O4	122.32 (17)
C6—N3—Mn	115.96 (12)	O3—C21—C22	119.31 (16)
C4—N4—H4A	115.6	O4—C21—C22	118.36 (16)
C4—N4—H4B	124.3	C23—C22—C27	117.60 (18)
H4A—N4—H4B	119.0	C23—C22—C21	121.78 (17)
C15—N5—H5A	116.0	C27—C22—C21	120.60 (17)
C15—N5—H5B	119.2	C24—C23—C22	121.3 (2)
H5A—N5—H5B	111.9	C24—C23—H23	119.3
C25—N6—H6A	112.9	C22—C23—H23	119.3
C25—N6—H6B	112.3	C23—C24—C25	120.7 (2)
H6A—N6—H6B	118.0	C23—C24—H24	119.7
C11—O1—Mn	93.22 (12)	C25—C24—H24	119.7
C11—O2—Mn	88.04 (12)	C26—C25—C24	118.46 (19)
C21—O3—Mn	157.73 (14)	C26—C25—N6	120.1 (2)
C21—O4—Mn^i	123.83 (12)	C24—C25—N6	121.4 (2)
H1A—O1W—H1B	100.8	C25—C26—C27	121.0 (2)
N1—C1—N2	125.05 (18)	C25—C26—H26	119.5
N1—C1—S1	114.36 (15)	C27—C26—H26	119.5
N2—C1—S1	120.53 (14)	C26—C27—C22	120.95 (19)
C3—C2—S1	110.81 (16)	C26—C27—H27	119.5
C3—C2—H2	124.6	C22—C27—H27	119.5
S1—C2—H2	124.6	N5—C15—C16	120.0 (2)
C2—C3—N1	115.23 (18)	N5—C15—C14	121.38 (19)
C2—C3—C6	126.77 (19)	C16—C15—C14	118.62 (19)
N1—C3—C6	117.99 (16)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1A···O1	0.90	1.91	2.774 (2)	161
O1W—H1B···N6^ii	0.97	1.96	2.923 (3)	168
N2—H2A···O2	0.88	2.23	3.011 (2)	148
N2—H2B···O4^iii	0.90	2.15	3.006 (2)	159
N4—H4A···O3	0.86	2.16	2.967 (2)	157
N4—H4B···O1W^iv	0.91	2.09	2.940 (2)	155
N5—H5A···O1W^v	0.94	2.12	3.034 (2)	165
N5—H5B···N2^v	0.98	2.38	3.310 (3)	157
N6—H6B···O2^vi	0.92	2.47	3.287 (2)	149
C2—H2···N5^vii	0.93	2.49	3.418 (3)	172
C27—H27···O1	0.93	2.46	3.353 (2)	162

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