Di-μ-oxo-bis­[(histidinato-κ³N,N,O)oxomolybdenum(V)] trihydrate

In the title dinuclear complex, [Mo₂(C₆H₈N₃O₂)₂O₄]·3H₂O, the Mo atoms, bridged by two μ-oxo atoms, have a distorted octa­hedral coordination environment. Besides the two bridging O atoms, the coordination of each Mo atom is completed by a terminal oxo atom and a tridentate histidinate ligand. The short Mo...Mo distance of 2.5458 (4) Å may indicate the existence of an Mo—Mo metal bond. Inter­molecular hydrogen bonding between the uncoordinated carboxyl­ate O atoms and amino groups leads to a layer-like arrangement of the mol­ecules. The uncoordinated water mol­ecules link these layers via O—H...O hydrogen bonds and help to stabilize the crystal packing.

Key indicators

• Single-crystal X-ray study
• T = 292 K
• Mean [sigma](C-C) = 0.005 Å
• R factor = 0.020
• wR factor = 0.049
• Data-to-parameter ratio = 12.0

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?

Alert level G
REFLT03_ALERT_4_G  WARNING: Large fraction of Friedel related reflns may
                     be needed to determine absolute structure
           From the CIF: _diffrn_reflns_theta_max           27.00
           From the CIF: _reflns_number_total               3372
           Count of symmetry unique reflns         2370
           Completeness (_total/calc)            142.28%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured      1002
           Fraction of Friedel pairs measured     0.423
           Are heavy atom types Z>Si present        yes

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 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
   1 ALERT type 4 Improvement, methodology, query or suggestion

---

Computing details

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); 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, 2003); software used to prepare material for publication: SHELXTL.

Di-µ-oxo-bis[(histidinato-κ³N,N,O)oxomolybdenum(V)] trihydrate

Crystal data

[Mo2(C6H8N3O2)2O4]·3H2O	F(000) = 616
Mr = 618.24	Dx = 2.017 Mg m^−3
Monoclinic, P21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 5483 reflections
a = 10.9594 (12) Å	θ = 3.0–28.3°
b = 8.7222 (9) Å	µ = 1.30 mm^−1
c = 11.5783 (12) Å	T = 292 K
β = 113.136 (2)°	Block, yellow
V = 1017.76 (19) Å^3	0.3 × 0.2 × 0.2 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	3372 independent reflections
Radiation source: fine-focus sealed tube	3343 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
φ and ω scans	θmax = 27.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
Tmin = 0.696, Tmax = 0.781	k = −5→11
5964 measured reflections	l = −12→14

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.020	H-atom parameters constrained
wR(F^2) = 0.049	w = 1/[σ^2(Fo^2) + (0.0218P)^2] where P = (Fo^2 + 2Fc^2)/3
S = 1.13	(Δ/σ)max = 0.001
3372 reflections	Δρmax = 0.33 e Å^−3
280 parameters	Δρmin = −0.69 e Å^−3
1 restraint	Absolute structure: Flack (1983), with 1006 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (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
Mo1	0.84113 (2)	0.47077 (3)	0.58675 (2)	0.02049 (7)
Mo2	0.60843 (2)	0.52951 (3)	0.42698 (2)	0.02015 (6)
O1	0.9534 (2)	0.0052 (3)	0.6463 (2)	0.0343 (5)
O2	0.83566 (18)	0.2183 (3)	0.57700 (18)	0.0262 (5)
O3	0.3375 (2)	0.2042 (3)	0.2237 (2)	0.0363 (5)
O4	0.52055 (19)	0.3008 (3)	0.37024 (19)	0.0262 (5)
O5	0.76353 (18)	0.4547 (3)	0.40437 (17)	0.0248 (5)
O6	0.67035 (19)	0.4624 (3)	0.59928 (17)	0.0264 (4)
O7	0.6098 (2)	0.7245 (3)	0.4264 (2)	0.0321 (5)
O8	0.9057 (2)	0.6498 (3)	0.6190 (2)	0.0339 (5)
O9	0.8483 (2)	0.3550 (4)	0.1685 (2)	0.0449 (7)
H9A	0.9085	0.3877	0.2360	0.054*
H9B	0.8339	0.2612	0.1787	0.054*
O10	0.7517 (2)	0.1325 (3)	0.2968 (2)	0.0411 (6)
H10C	0.6823	0.0783	0.2795	0.049*
H10D	0.7571	0.1935	0.3559	0.049*
O11	0.5041 (2)	0.9766 (4)	0.2157 (2)	0.0454 (6)
H11A	0.4593	1.0413	0.2377	0.055*
H11B	0.5010	0.8907	0.2491	0.055*
N1	0.9250 (2)	0.4029 (3)	0.7868 (2)	0.0251 (5)
N2	0.9300 (3)	0.3579 (4)	0.9738 (2)	0.0321 (6)
H2	0.9073	0.3575	1.0369	0.039*
N3	1.0342 (2)	0.3858 (3)	0.5867 (2)	0.0268 (6)
H3A	1.0265	0.3715	0.5071	0.032*
H3B	1.0980	0.4561	0.6227	0.032*
N4	0.5089 (2)	0.5407 (4)	0.2183 (2)	0.0264 (5)
N5	0.4759 (3)	0.5350 (5)	0.0202 (2)	0.0434 (7)
H5	0.4914	0.5315	−0.0470	0.052*
N6	0.4094 (2)	0.5204 (4)	0.4346 (2)	0.0263 (5)
H6A	0.4140	0.4705	0.5043	0.032*
H6B	0.3794	0.6160	0.4367	0.032*
C1	0.8636 (3)	0.4229 (4)	0.8639 (3)	0.0290 (7)
H1	0.7842	0.4758	0.8433	0.035*
C2	1.0414 (3)	0.2910 (4)	0.9695 (3)	0.0334 (7)
H2A	1.1059	0.2364	1.0335	0.040*
C3	1.0390 (3)	0.3203 (4)	0.8534 (3)	0.0265 (6)
C4	1.1346 (3)	0.2688 (4)	0.7981 (3)	0.0305 (7)
H4A	1.1771	0.1752	0.8398	0.037*
H4B	1.2030	0.3462	0.8151	0.037*
C5	1.0715 (3)	0.2398 (4)	0.6567 (3)	0.0260 (6)
H5A	1.1346	0.1847	0.6309	0.031*
C6	0.9450 (3)	0.1432 (4)	0.6242 (3)	0.0249 (6)
C7	0.5670 (3)	0.5272 (5)	0.1374 (3)	0.0355 (7)
H7	0.6576	0.5142	0.1593	0.043*
C8	0.3538 (3)	0.5496 (5)	0.0250 (3)	0.0381 (8)
H8	0.2726	0.5562	−0.0429	0.046*
C9	0.3746 (3)	0.5526 (4)	0.1477 (3)	0.0274 (7)
C10	0.2760 (3)	0.5476 (4)	0.2090 (3)	0.0319 (7)
H10A	0.1905	0.5153	0.1475	0.038*
H10B	0.2658	0.6499	0.2368	0.038*
C11	0.3183 (3)	0.4387 (4)	0.3211 (3)	0.0274 (7)
H11	0.2400	0.4032	0.3345	0.033*
C12	0.3944 (3)	0.3018 (4)	0.3023 (3)	0.0248 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Mo1	0.01965 (11)	0.01993 (12)	0.02006 (11)	−0.00022 (10)	0.00585 (9)	−0.00066 (10)
Mo2	0.01999 (11)	0.02074 (12)	0.01889 (11)	0.00110 (10)	0.00673 (8)	−0.00040 (10)
O1	0.0365 (12)	0.0246 (15)	0.0453 (12)	0.0047 (10)	0.0198 (10)	0.0017 (10)
O2	0.0222 (10)	0.0228 (12)	0.0302 (11)	0.0003 (9)	0.0068 (8)	−0.0017 (9)
O3	0.0312 (11)	0.0285 (13)	0.0423 (13)	−0.0079 (11)	0.0070 (10)	−0.0033 (11)
O4	0.0209 (10)	0.0234 (12)	0.0327 (11)	0.0004 (9)	0.0088 (8)	0.0006 (10)
O5	0.0221 (9)	0.0331 (13)	0.0200 (9)	−0.0021 (10)	0.0091 (7)	−0.0006 (10)
O6	0.0256 (10)	0.0332 (11)	0.0208 (9)	0.0033 (11)	0.0095 (8)	0.0014 (10)
O7	0.0372 (13)	0.0214 (12)	0.0343 (12)	0.0012 (10)	0.0104 (10)	−0.0002 (9)
O8	0.0318 (12)	0.0236 (12)	0.0394 (13)	−0.0027 (10)	0.0064 (10)	−0.0019 (11)
O9	0.0499 (15)	0.0533 (18)	0.0353 (13)	−0.0127 (15)	0.0209 (11)	−0.0090 (13)
O10	0.0369 (12)	0.0483 (16)	0.0402 (13)	−0.0018 (13)	0.0175 (10)	−0.0116 (13)
O11	0.0542 (15)	0.0463 (16)	0.0445 (13)	0.0002 (14)	0.0288 (12)	−0.0005 (14)
N1	0.0243 (12)	0.0263 (13)	0.0226 (11)	0.0045 (11)	0.0069 (10)	−0.0007 (11)
N2	0.0377 (14)	0.0373 (16)	0.0224 (12)	0.0042 (13)	0.0129 (11)	−0.0019 (12)
N3	0.0254 (12)	0.0271 (16)	0.0284 (13)	−0.0015 (11)	0.0111 (10)	0.0000 (11)
N4	0.0262 (12)	0.0291 (14)	0.0222 (11)	−0.0014 (13)	0.0075 (9)	0.0032 (12)
N5	0.0480 (16)	0.063 (2)	0.0233 (12)	−0.0087 (18)	0.0180 (12)	−0.0009 (16)
N6	0.0254 (11)	0.0302 (14)	0.0248 (11)	0.0065 (13)	0.0116 (9)	0.0011 (12)
C1	0.0287 (15)	0.0300 (16)	0.0268 (14)	0.0054 (13)	0.0093 (12)	−0.0030 (13)
C2	0.0337 (16)	0.0338 (19)	0.0273 (15)	0.0055 (15)	0.0062 (13)	0.0016 (14)
C3	0.0257 (14)	0.0262 (16)	0.0227 (13)	0.0016 (13)	0.0044 (11)	−0.0023 (12)
C4	0.0223 (14)	0.0338 (18)	0.0310 (16)	0.0021 (14)	0.0058 (12)	−0.0024 (14)
C5	0.0248 (14)	0.0247 (16)	0.0278 (14)	0.0016 (12)	0.0097 (12)	−0.0033 (12)
C6	0.0291 (14)	0.0260 (16)	0.0220 (13)	0.0033 (13)	0.0127 (11)	−0.0025 (12)
C7	0.0313 (15)	0.0478 (19)	0.0296 (15)	−0.0045 (18)	0.0143 (12)	−0.0010 (18)
C8	0.0351 (16)	0.047 (2)	0.0269 (15)	−0.0031 (17)	0.0064 (13)	0.0011 (16)
C9	0.0275 (14)	0.0258 (18)	0.0254 (13)	0.0029 (13)	0.0066 (11)	0.0051 (13)
C10	0.0233 (14)	0.036 (2)	0.0305 (15)	0.0082 (15)	0.0040 (12)	0.0051 (15)
C11	0.0194 (13)	0.033 (2)	0.0313 (15)	0.0005 (12)	0.0114 (11)	0.0023 (13)
C12	0.0234 (13)	0.0248 (16)	0.0267 (14)	−0.0025 (13)	0.0104 (11)	0.0059 (12)

Geometric parameters (Å, º)

Mo1—O8	1.695 (2)	N3—H3A	0.9000
Mo1—O6	1.9347 (19)	N3—H3B	0.9000
Mo1—O5	1.9470 (19)	N4—C7	1.329 (4)
Mo1—O2	2.205 (2)	N4—C9	1.378 (4)
Mo1—N1	2.210 (2)	N5—C7	1.334 (4)
Mo1—N3	2.242 (2)	N5—C8	1.367 (4)
Mo1—Mo2	2.5458 (4)	N5—H5	0.8600
Mo2—O7	1.701 (3)	N6—C11	1.483 (4)
Mo2—O6	1.9286 (19)	N6—H6A	0.9000
Mo2—O5	1.932 (2)	N6—H6B	0.9000
Mo2—O4	2.201 (2)	C1—H1	0.9300
Mo2—N6	2.219 (2)	C2—C3	1.359 (4)
Mo2—N4	2.228 (2)	C2—H2A	0.9300
O1—C6	1.226 (4)	C3—C4	1.495 (4)
O2—C6	1.284 (4)	C4—C5	1.528 (4)
O3—C12	1.223 (4)	C4—H4A	0.9700
O4—C12	1.295 (3)	C4—H4B	0.9700
O9—H9A	0.8500	C5—C6	1.538 (4)
O9—H9B	0.8499	C5—H5A	0.9800
O10—H10C	0.8500	C7—H7	0.9300
O10—H10D	0.8500	C8—C9	1.348 (4)
O11—H11A	0.8501	C8—H8	0.9300
O11—H11B	0.8500	C9—C10	1.508 (4)
N1—C1	1.324 (4)	C10—C11	1.526 (4)
N1—C3	1.384 (4)	C10—H10A	0.9700
N2—C1	1.320 (4)	C10—H10B	0.9700
N2—C2	1.371 (4)	C11—C12	1.520 (4)
N2—H2	0.8600	C11—H11	0.9800
N3—C5	1.478 (4)
O8—Mo1—O6	110.53 (11)	C7—N4—C9	106.5 (2)
O8—Mo1—O5	105.78 (11)	C7—N4—Mo2	126.4 (2)
O6—Mo1—O5	93.18 (8)	C9—N4—Mo2	126.89 (19)
O8—Mo1—O2	158.82 (9)	C7—N5—C8	108.5 (2)
O6—Mo1—O2	87.62 (10)	C7—N5—H5	125.8
O5—Mo1—O2	83.17 (9)	C8—N5—H5	125.8
O8—Mo1—N1	92.88 (11)	C11—N6—Mo2	108.16 (16)
O6—Mo1—N1	85.85 (9)	C11—N6—H6A	110.1
O5—Mo1—N1	160.33 (11)	Mo2—N6—H6A	110.1
O2—Mo1—N1	77.16 (9)	C11—N6—H6B	110.1
O8—Mo1—N3	89.56 (11)	Mo2—N6—H6B	110.1
O6—Mo1—N3	158.19 (10)	H6A—N6—H6B	108.4
O5—Mo1—N3	89.20 (9)	N2—C1—N1	111.1 (3)
O2—Mo1—N3	71.12 (9)	N2—C1—H1	124.5
N1—Mo1—N3	84.70 (9)	N1—C1—H1	124.5
O8—Mo1—Mo2	100.78 (8)	C3—C2—N2	106.5 (3)
O6—Mo1—Mo2	48.67 (6)	C3—C2—H2A	126.7
O5—Mo1—Mo2	48.73 (6)	N2—C2—H2A	126.7
O2—Mo1—Mo2	99.47 (5)	C2—C3—N1	108.2 (3)
N1—Mo1—Mo2	134.48 (6)	C2—C3—C4	128.5 (3)
N3—Mo1—Mo2	137.94 (7)	N1—C3—C4	123.2 (3)
O7—Mo2—O6	107.89 (11)	C3—C4—C5	114.3 (2)
O7—Mo2—O5	109.13 (11)	C3—C4—H4A	108.7
O6—Mo2—O5	93.84 (8)	C5—C4—H4A	108.7
O7—Mo2—O4	155.36 (9)	C3—C4—H4B	108.7
O6—Mo2—O4	88.20 (10)	C5—C4—H4B	108.7
O5—Mo2—O4	87.62 (9)	H4A—C4—H4B	107.6
O7—Mo2—N6	92.66 (12)	N3—C5—C4	110.9 (3)
O6—Mo2—N6	84.24 (9)	N3—C5—C6	108.0 (2)
O5—Mo2—N6	157.55 (11)	C4—C5—C6	109.7 (2)
O4—Mo2—N6	69.98 (10)	N3—C5—H5A	109.4
O7—Mo2—N4	87.35 (12)	C4—C5—H5A	109.4
O6—Mo2—N4	163.38 (11)	C6—C5—H5A	109.4
O5—Mo2—N4	87.13 (9)	O1—C6—O2	124.7 (3)
O4—Mo2—N4	75.25 (10)	O1—C6—C5	120.1 (3)
N6—Mo2—N4	88.54 (8)	O2—C6—C5	115.2 (3)
O7—Mo2—Mo1	101.31 (7)	N4—C7—N5	109.8 (3)
O6—Mo2—Mo1	48.88 (6)	N4—C7—H7	125.1
O5—Mo2—Mo1	49.24 (6)	N5—C7—H7	125.1
O4—Mo2—Mo1	103.32 (5)	C9—C8—N5	106.4 (3)
N6—Mo2—Mo1	133.12 (6)	C9—C8—H8	126.8
N4—Mo2—Mo1	136.11 (6)	N5—C8—H8	126.8
C6—O2—Mo1	119.0 (2)	C8—C9—N4	108.8 (3)
C12—O4—Mo2	114.4 (2)	C8—C9—C10	129.8 (3)
Mo2—O5—Mo1	82.03 (8)	N4—C9—C10	120.9 (2)
Mo2—O6—Mo1	82.44 (7)	C9—C10—C11	112.6 (2)
H9A—O9—H9B	108.4	C9—C10—H10A	109.1
H10C—O10—H10D	108.1	C11—C10—H10A	109.1
H11A—O11—H11B	108.5	C9—C10—H10B	109.1
C1—N1—C3	106.2 (3)	C11—C10—H10B	109.1
C1—N1—Mo1	124.0 (2)	H10A—C10—H10B	107.8
C3—N1—Mo1	129.49 (19)	N6—C11—C12	106.8 (2)
C1—N2—C2	108.0 (3)	N6—C11—C10	109.2 (3)
C1—N2—H2	126.0	C12—C11—C10	111.5 (2)
C2—N2—H2	126.0	N6—C11—H11	109.8
C5—N3—Mo1	110.04 (18)	C12—C11—H11	109.8
C5—N3—H3A	109.7	C10—C11—H11	109.8
Mo1—N3—H3A	109.7	O3—C12—O4	123.9 (3)
C5—N3—H3B	109.7	O3—C12—C11	120.4 (3)
Mo1—N3—H3B	109.7	O4—C12—C11	115.7 (3)
H3A—N3—H3B	108.2

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O9—H9A···O1^i	0.85	1.89	2.716 (3)	163
O9—H9B···O10	0.85	2.22	2.885 (4)	136
O10—H10C···O11^ii	0.85	2.00	2.844 (4)	170
O10—H10D···O5	0.85	2.34	3.056 (4)	142
O11—H11A···O3^iii	0.85	1.91	2.724 (4)	159
O11—H11B···O7	0.85	2.41	3.148 (4)	145
N2—H2···O9^iv	0.86	1.88	2.735 (4)	177
N3—H3A···O1^i	0.90	2.21	2.944 (3)	139
N3—H3B···O10^i	0.90	2.18	3.077 (4)	178
N5—H5···O11^v	0.86	2.03	2.869 (3)	165
N6—H6A···O7^vi	0.90	2.34	3.091 (4)	141
N6—H6B···O2^vii	0.90	2.47	3.150 (3)	133

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