[1,4,12,15,18,26,31,39,42,43,44-Undeca­azapenta­cyclo[13.13.13.1^6,10.1^20,24.1^33,37]tetra­tetra­conta-4,6,8,10(44),11,18,20,22,24(43),25,31,33,35,37(42),38-penta­deca­ene-κ⁹N⁴,N¹¹,N¹⁸,N²⁶,N³¹,N³⁹,N⁴²,N⁴³,N⁴⁴]gadolinium(III) trichloride trihydrate

The Gd atom in the title compound, [Gd(C₃₃H₃₉N₁₁)]Cl₃·3H₂O, lies on a position of 32 point symmetry and exhibits a tricapped trigonal prismatic coordination geometry. A twofold rotation axis passes through the coordinated N atom and the opposite C atom of the pyridyl ring of the ligand, while a threefold rotation axis passes through the aliphatic N atom. The Cl atom and O atom of the uncoordinated water mol­ecule both lie on twofold rotation axes.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.011 Å
• R factor = 0.036
• wR factor = 0.103
• Data-to-parameter ratio = 16.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT342_ALERT_3_C Low Bond Precision on C-C bonds (x 1000) Ang ...         11

Alert level G
REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is
            correct. If it is not, please give the correct count in the
            _publ_section_exptl_refinement section of the submitted CIF.
           From the CIF: _diffrn_reflns_theta_max           26.00
           From the CIF: _reflns_number_total               1328
           Count of symmetry unique reflns          747
           Completeness (_total/calc)            177.78%
           TEST3: Check Friedels for noncentro structure
           Estimate of Friedel pairs measured       581
           Fraction of Friedel pairs measured     0.778
           Are heavy atom types Z>Si present        yes
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

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

   3 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
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

---

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

(I)

Crystal data

[Gd(C33H39N11)]Cl3·3H2O	Dx = 1.499 Mg m^−3
Mr = 907.40	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R32	Cell parameters from 1324 reflections
Hall symbol: R 3 2"	θ = 2.1–25.7°
a = 14.731 (2) Å	µ = 1.90 mm^−1
c = 16.043 (3) Å	T = 293 K
V = 3015.0 (6) Å^3	Block, red
Z = 3	0.30 × 0.24 × 0.22 mm
F(000) = 1377

Data collection

Bruker SMART APEX CCD diffractometer	1328 independent reflections
Radiation source: fine-focus sealed tube	1327 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.045
φ and ω scans	θmax = 26.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −15→18
Tmin = 0.59, Tmax = 0.66	k = −18→17
5619 measured reflections	l = −19→19

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)] = 0.036	H-atom parameters constrained
wR(F^2) = 0.103	w = 1/[σ^2(Fo^2) + (0.08P)^2 + 1.99P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
1328 reflections	Δρmax = 0.74 e Å^−3
80 parameters	Δρmin = −0.50 e Å^−3
0 restraints	Absolute structure: Flack (1983), 581 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (2)

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	Occ. (<1)
Gd1	0.3333	0.6667	0.6667	0.0276 (2)
Cl1	0.7035 (3)	0.6667	0.6667	0.0419 (8)
C1	0.3333	0.3041 (11)	0.6667	0.048 (3)
H1	0.3333	0.2409	0.6667	0.057*
C2	0.4042 (5)	0.3897 (5)	0.7137 (4)	0.0397 (13)
H2	0.4527	0.3824	0.7458	0.048*
C3	0.4073 (5)	0.4856 (5)	0.7157 (4)	0.0412 (14)
C4	0.4716 (6)	0.5750 (6)	0.7677 (5)	0.0560 (18)
H4	0.5267	0.5761	0.7970	0.067*
C5	0.5107 (6)	0.7232 (6)	0.8435 (4)	0.0505 (17)
H5A	0.5248	0.7932	0.8301	0.061*
H5B	0.5766	0.7259	0.8554	0.061*
C6	0.4359 (5)	0.6785 (6)	0.9181 (4)	0.0423 (14)
H6A	0.4273	0.6107	0.9325	0.051*
H6B	0.4674	0.7246	0.9656	0.051*
N1	0.3333	0.4928 (6)	0.6667	0.0420 (18)
N2	0.4566 (4)	0.6516 (4)	0.7753 (3)	0.0406 (12)
N3	0.3333	0.6667	0.9024 (5)	0.0441 (16)
O1	0.5354 (5)	0.3333	0.8333	0.0503 (16)
H1C	0.5426	0.2796	0.8333	0.060*	0.50
H1D	0.5964	0.3871	0.8333	0.060*	0.50

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Gd1	0.0289 (2)	0.0289 (2)	0.0250 (3)	0.01444 (11)	0.000	0.000
Cl1	0.0380 (12)	0.0377 (18)	0.050 (2)	0.0189 (9)	−0.0013 (7)	−0.0026 (15)
C1	0.044 (9)	0.053 (6)	0.043 (7)	0.022 (4)	−0.021 (8)	−0.010 (4)
C2	0.038 (3)	0.042 (3)	0.034 (3)	0.017 (3)	−0.011 (2)	−0.003 (3)
C3	0.043 (4)	0.043 (4)	0.039 (3)	0.022 (3)	0.004 (3)	0.006 (3)
C4	0.033 (3)	0.043 (4)	0.060 (4)	−0.005 (4)	−0.002 (3)	−0.001 (3)
C5	0.050 (4)	0.045 (3)	0.045 (3)	0.015 (3)	0.000 (3)	0.001 (3)
C6	0.037 (3)	0.037 (3)	0.041 (3)	0.010 (3)	−0.004 (2)	−0.002 (3)
N1	0.042 (4)	0.041 (3)	0.043 (4)	0.021 (2)	−0.011 (3)	−0.0055 (16)
N2	0.036 (3)	0.036 (3)	0.032 (2)	0.004 (2)	−0.010 (2)	0.005 (2)
N3	0.043 (2)	0.043 (2)	0.046 (4)	0.0215 (12)	0.000	0.000
O1	0.042 (2)	0.058 (4)	0.057 (4)	0.029 (2)	0.0015 (17)	0.003 (3)

Geometric parameters (Å, º)

Gd1—N1^i	2.562 (8)	C3—C4	1.442 (10)
Gd1—N1^ii	2.562 (8)	C4—N2	1.259 (12)
Gd1—N1	2.562 (8)	C4—H4	0.930
Gd1—N2^ii	2.606 (5)	C5—N2	1.450 (8)
Gd1—N2^i	2.606 (5)	C5—C6	1.534 (10)
Gd1—N2^iii	2.606 (5)	C5—H5A	0.970
Gd1—N2^iv	2.606 (5)	C5—H5B	0.970
Gd1—N2	2.606 (5)	C6—N3	1.454 (7)
Gd1—N2^v	2.606 (5)	C6—H6A	0.970
C1—C2	1.391 (10)	C6—H6B	0.970
C1—C2^iv	1.391 (10)	N1—C3^iv	1.390 (8)
C1—H1	0.930	N3—C6^ii	1.454 (7)
C2—C3	1.391 (10)	N3—C6^i	1.454 (7)
C2—H2	0.930	O1—H1C	0.850
C3—N1	1.390 (8)	O1—H1D	0.850
N1^i—Gd1—N1^ii	120.000 (1)	N2—Gd1—N2^v	84.6 (3)
N1^i—Gd1—N1	120.000 (3)	C2—C1—C2^iv	115.7 (13)
N1^ii—Gd1—N1	120.000 (2)	C2—C1—H1	122.1
N1^i—Gd1—N2^ii	72.19 (11)	C2^iv—C1—H1	122.1
N1^ii—Gd1—N2^ii	64.30 (13)	C3—C2—C1	124.2 (8)
N1—Gd1—N2^ii	137.69 (13)	C3—C2—H2	117.9
N1^i—Gd1—N2^i	64.30 (13)	C1—C2—H2	117.9
N1^ii—Gd1—N2^i	137.69 (13)	N1—C3—C2	115.8 (6)
N1—Gd1—N2^i	72.19 (11)	N1—C3—C4	116.1 (7)
N2^ii—Gd1—N2^i	80.1 (2)	C2—C3—C4	127.9 (7)
N1^i—Gd1—N2^iii	64.30 (13)	N2—C4—C3	123.0 (8)
N1^ii—Gd1—N2^iii	72.19 (11)	N2—C4—H4	118.5
N1—Gd1—N2^iii	137.69 (13)	C3—C4—H4	118.5
N2^ii—Gd1—N2^iii	84.6 (3)	N2—C5—C6	105.1 (6)
N2^i—Gd1—N2^iii	128.6 (3)	N2—C5—H5A	110.7
N1^i—Gd1—N2^iv	72.19 (11)	C6—C5—H5A	110.7
N1^ii—Gd1—N2^iv	137.69 (13)	N2—C5—H5B	110.7
N1—Gd1—N2^iv	64.30 (13)	C6—C5—H5B	110.7
N2^ii—Gd1—N2^iv	144.4 (2)	H5A—C5—H5B	108.8
N2^i—Gd1—N2^iv	84.6 (3)	N3—C6—C5	113.5 (6)
N2^iii—Gd1—N2^iv	80.1 (2)	N3—C6—H6A	108.9
N1^i—Gd1—N2	137.69 (13)	C5—C6—H6A	108.9
N1^ii—Gd1—N2	72.19 (11)	N3—C6—H6B	108.9
N1—Gd1—N2	64.30 (13)	C5—C6—H6B	108.9
N2^ii—Gd1—N2	80.1 (2)	H6A—C6—H6B	107.7
N2^i—Gd1—N2	80.1 (2)	C3^iv—N1—C3	124.2 (9)
N2^iii—Gd1—N2	144.4 (2)	C3^iv—N1—Gd1	117.9 (4)
N2^iv—Gd1—N2	128.6 (3)	C3—N1—Gd1	117.9 (4)
N1^i—Gd1—N2^v	137.69 (13)	C4—N2—C5	116.5 (6)
N1^ii—Gd1—N2^v	64.30 (13)	C4—N2—Gd1	117.0 (5)
N1—Gd1—N2^v	72.19 (11)	C5—N2—Gd1	126.6 (5)
N2^ii—Gd1—N2^v	128.6 (3)	C6^ii—N3—C6^i	117.1 (2)
N2^i—Gd1—N2^v	144.4 (2)	C6^ii—N3—C6	117.1 (2)
N2^iii—Gd1—N2^v	80.1 (2)	C6^i—N3—C6	117.1 (2)
N2^iv—Gd1—N2^v	80.1 (2)	H1C—O1—H1D	107.5

Symmetry codes: (i) −x+y, −x+1, z; (ii) −y+1, x−y+1, z; (iii) y−1/3, x+1/3, −z+4/3; (iv) −x+2/3, −x+y+1/3, −z+4/3; (v) x−y+2/3, −y+4/3, −z+4/3.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1C···O1^vi	0.85	2.59	3.349 (11)	149
O1—H1D···O1^vii	0.85	2.59	3.349 (11)	149
C2—H2···O1	0.93	2.20	3.117 (8)	167

Symmetry codes: (vi) −y+1, x−y, z; (vii) −x+y+1, −x+1, z.