Add $0.5~\mathrm{mmol}$ $\mathrm{Ce(NO_3)_3\cdot6H_2O}$, $0.5~\mathrm{mmol}$ $\mathrm{Fe(NO_3)_3\cdot9H_2O}$, $1~\mathrm{mmol}$ tiron, $1~\mathrm{mmol}$ phen, $2~\mathrm{mmol}$ $\mathrm{NaOH}$, $5~\mathrm{mL}$ ethanol, and $8~\mathrm{mL}$ distilled water into an $18~\mathrm{mL}$ stainless steel autoclave with a Teflon liner. React at $175~\degree\mathrm{C}$ for $4~$days, then allow to cool naturally to room temperature to obtain black-brown block-shaped single crystals with a yield of approximately $75\%$.

The molecular formula of the tiron ligand is $\mathrm{C_6H_2O_8S_2^{4-}}$, and the molecular formula of the phen ligand is $\mathrm{C_{12}H_8N_2}$. Elemental analysis of the product yielded mass fractions (%) of: $\mathrm{C}$ $47.09$; $\mathrm{N}$ $7.32$; $\mathrm{S}$ $8.38$; $\mathrm{O}$ $20.91$. Thermogravimetric analysis of the obtained crystals showed a weight loss of $4.71\%$ at $122~\degree\mathrm{C}$, corresponding to the loss of all crystalline water. The relative atomic mass of $\mathrm{Ce}$ is known to be $140.1$.

The structure of tiron is:

<MultiModal>![[O-]C1=C(S(=O)([O-])=O)C=C(S(=O)([O-])=O)C=C1[O-]](/media/uploads/25c5331a-813e-4f4d-b354-d34842c013b2.png)</MultiModal>

The structure of phen is:

<MultiModal>![C12=C(N=CC=C3)C3=CC=C1C=CC=N2](/media/uploads/ca29f9eb-283f-4277-b3cf-62dabfcfc963.png)</MultiModal>

The molar conductivity of the complex measured in DMSO solvent is $139~\mathrm{S\cdot cm^2\cdot mol^{-1}}$, indicating that it is a 2:1 type electrolyte. The number of crystalline water molecules in the complex is a positive integer. The anion has a $C_3$ symmetry axis.  

The following statements are correct:  

1. The molecular formula contains $4$ crystalline water molecules.  

2. The molecular formula contains $6$ crystalline water molecules.  

3. The $\mathrm{Ce:Fe}$ ratio in the anion is $1:2$.  

4. The cation has only one stereochemical configuration.  

5. Both sulfonate groups in the anion participate in coordination.  

6. The anion has three mirror planes along the principal axis.
将 $0.5~\mathrm{mmol}$ $\mathrm{Ce(NO_3)_3\cdot6H_2O}$、$0.5~\mathrm{mmol}$ $\mathrm{Fe(NO_3)_3\cdot9H_2O}$、$1~\mathrm{mmol}$ tiron、$1~\mathrm{mmol}$ phen、$2~\mathrm{mmol}$ $\mathrm{NaOH}$、$5~\mathrm{mL}$ 乙醇和 $8~\mathrm{mL}$ 蒸馏水置于 $18~\mathrm{mL}$ 的内衬聚四氟乙烯的不锈钢自升压反应釜中，于 $175~\degree\mathrm{C}$ 下反应 $4~$天后，自然冷却至室温，获得黑褐色块状单晶，产率约为 $75\%$。

已知 tiron 配体的分子式为 $\mathrm{C_6H_2O_8S_2^{4-}}$，phen 配体的分子式为 $\mathrm{C_{12}H_8N_2}$。对产物的元素分析得到质量分数（%）为：$\mathrm{C}$ $47.09$；$\mathrm{N}$ $7.32$；$\mathrm{S}$ $8.38$；$\mathrm{O}$ $20.91$。对所得晶体热重分析表明，$122~\degree\mathrm{C}$ 下该配合物失重 $4.71\%$，对应失去所有结晶水。已知 $\mathrm{Ce}$ 的相对原子质量为 $140.1$。

其中tiron结构为：

<MultiModal>![[O-]C1=C(S(=O)([O-])=O)C=C(S(=O)([O-])=O)C=C1[O-]](/media/uploads/25c5331a-813e-4f4d-b354-d34842c013b2.png)</MultiModal>

phen结构为：

<MultiModal>![C12=C(N=CC=C3)C3=CC=C1C=CC=N2](/media/uploads/ca29f9eb-283f-4277-b3cf-62dabfcfc963.png)</MultiModal>

该配合物在 DMSO 溶剂中测得的摩尔电导率为 $139~\mathrm{S\cdot cm^2\cdot mol^{-1}}$，表明其属于 2:1 型电解质。配合物中的结晶水数量为正整数。阴离子具有 $C_3$ 对称轴。
以下说法正确的有：

1.该分子式中有$4$个结晶水

2.该分子式中有$6$个结晶水

3.阴离子中 $\mathrm{Ce:Fe}$ 为$1:2$

4.阳离子只有一种立体构型

5.阴离子中两个磺酸根离子均参与配位

6.阴离子中有三个通过主轴的镜面
1,3,4,5
1,3,4,6
2, 3, 4, 5
2,6
2,4,6
1,3,5
1,6
4,6
3,6
2,4,6
None of the above
1,3,4,5
1,3,4,6
2,3,4,5
2,6
2,4,6
1,3,5
1,6
4,6
3,6
2,4,6
以上均不正确
From the known mass fractions:  
$n(\mathrm{C}) : n(\mathrm{S}) = 15.01$,  
$n(\mathrm{C}) : n(\mathrm{N}) = 7.50$  

That is:  
$n(\mathrm{C}) : n(\mathrm{S}) : n(\mathrm{N}) = 15 : 1 : 2$  

<Checkpoint>[$n(\mathrm{C}) : n(\mathrm{S}) : n(\mathrm{N}) = 15 : 1 : 2$](1)</Checkpoint>  

$\mathrm{phen}$ contains $12\mathrm{C}$ and $2\mathrm{N}$, while $\mathrm{tiron}$ contains $6\mathrm{C}$ and $2\mathrm{S}$. Thus:  
$n(\mathrm{phen}) : n(\mathrm{tiron}) = 2 : 1$  

<Checkpoint>[$n(\mathrm{phen}) : n(\mathrm{tiron}) = 2 : 1$](1)</Checkpoint>  

From $n(\mathrm{O}) : n(\mathrm{N}) = 5:2$, we obtain:  
$n(\mathrm{phen}) : n(\mathrm{tiron}) : n(\mathrm{H_2O}) = 2 : 1 : 2$  

<Checkpoint>[$n(\mathrm{phen}) : n(\mathrm{tiron}) : n(\mathrm{H_2O}) = 2 : 1 : 2$](1)</Checkpoint>  

Let the number of $\mathrm{H_2O}$ molecules be $2x$. When $x = 3$ (i.e., $6$ water molecules of crystallization), the remaining metal mass is $307.06~\mathrm{g/mol}$, corresponding to the molar mass of $3$ $\mathrm{Fe}$ and $1$ $\mathrm{Ce}$. Therefore, the chemical formula is:  
$\mathrm{C_{90}H_{66}CeFe_3N_{12}O_{30}S_6}$  

<Checkpoint>[The chemical formula is: $\mathrm{C_{90}H_{66}CeFe_3N_{12}O_{30}S_6}$](2)</Checkpoint>  

The actual structural formula of the complex is:  
$[\mathrm{Fe(phen)_3}]_2[\mathrm{CeFe(tiron)_3}] \cdot 6\mathrm{H_2O}$  

<Checkpoint>[The actual structural formula is: $[\mathrm{Fe(phen)_3}]_2[\mathrm{CeFe(tiron)_3}] \cdot 6\mathrm{H_2O}$](2)</Checkpoint>  

The cation belongs to the $D_3$ point group and is thus chiral.  

<Checkpoint>[The cation is chiral](1)</Checkpoint>  

The anion has a $C_3$ symmetry axis and lacks a mirror plane perpendicular to this axis. Therefore, in the anion, tiron acts as a bidentate ligand, with $\mathrm{Fe}$ and $\mathrm{Ce}$ lying on the $C_3$ symmetry axis. Consequently, both hydroxyl anions in the anion participate in coordination, while only one sulfonate ion is involved in coordination. There are three mirror planes passing through the principal axis.  

<Checkpoint>[The anion has three mirror planes passing through the principal axis](1)</Checkpoint>  

<Checkpoint>[Only one sulfonate ion participates in coordination](1)</Checkpoint>  

Thus, the correct answer is option D.
由已知的质量分数可知：  
$n(\mathrm{C}) : n(\mathrm{S}) = 15.01$，  
$n(\mathrm{C}) : n(\mathrm{N}) = 7.50$  

即：  
$n(\mathrm{C}) : n(\mathrm{S}) : n(\mathrm{N}) = 15 : 1 : 2$  

<Checkpoint>[$n(\mathrm{C}) : n(\mathrm{S}) : n(\mathrm{N}) = 15 : 1 : 2$  ](1)</Checkpoint>

$\mathrm{phen}$ 含 $12\mathrm{C}$、$2\mathrm{N}$，$\mathrm{tiron}$ 含 $6\mathrm{C}$、$2\mathrm{S}$，可得：  
$n(\mathrm{phen}) : n(\mathrm{tiron}) = 2 : 1$  

<Checkpoint>[$n(\mathrm{phen}) : n(\mathrm{tiron}) = 2 : 1$ ](1)</Checkpoint>

由 $n(\mathrm{O}) : n(\mathrm{N}) = 5:2$，可得：  
$n(\mathrm{phen}) : n(\mathrm{tiron}) : n(\mathrm{H_2O}) = 2 : 1 : 2$  

<Checkpoint>[$n(\mathrm{phen}) : n(\mathrm{tiron}) : n(\mathrm{H_2O}) = 2 : 1 : 2$](1)</Checkpoint>

设 $\mathrm{H_2O}$ 个数为 $2x$，当 $x = 3$ 时（即 $6$ 个结晶水），剩余金属质量为 $307.06~\mathrm{g/mol}$，对应 $3$ 个 $\mathrm{Fe}$ 和 $1$ 个 $\mathrm{Ce}$ 的摩尔质量，故化学式为：  
$\mathrm{C_{90}H_{66}CeFe_3N_{12}O_{30}S_6}$  

<Checkpoint>[化学式为：   $\mathrm{C_{90}H_{66}CeFe_3N_{12}O_{30}S_6}$](2)</Checkpoint>

该配合物实际结构的化学式为：  
$[\mathrm{Fe(phen)_3}]_2[\mathrm{CeFe(tiron)_3}] \cdot 6\mathrm{H_2O}$ 

<Checkpoint>[实际结构化学式为：  $[\mathrm{Fe(phen)_3}]_2[\mathrm{CeFe(tiron)_3}] \cdot 6\mathrm{H_2O}$](2)</Checkpoint> 

阳离子为$D_3$点群，所以有手型。

<Checkpoint>[阳离子有手性](1)</Checkpoint>

阴离子具有 $C_3$ 对称轴，且不存在垂直于该轴的镜面。所以阴离子中tiron作双齿配体，且$Fe$和$Ce$处在$C_3$ 对称轴上，因此阴离子中两个羟基负离子均参与配位，只有一个磺酸根离子参与配位，存在通过主轴的三个镜面。

<Checkpoint>[阴离子中存在通过主轴的三个镜面](1)</Checkpoint>

<Checkpoint>[只有一个磺酸根离子参与配位](1)</Checkpoint>

因此正确答案为选项D